@phdthesis{Fischer2008, author = {Fischer, Anna}, title = {"Reactive hard templating" : from carbon nitrides to metal nitrides}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-19777}, school = {Universit{\"a}t Potsdam}, year = {2008}, abstract = {Nanostructured inorganic materials are routinely synthesized by the use of templates. Depending on the synthesis conditions of the product material, either "soft" or "hard" templates can be applied. For sol-gel processes, usually "soft" templating techniques are employed, while "hard" templates are used for high temperature synthesis pathways. In classical templating approaches, the template has the unique role of structure directing agent, in the sense that it is not participating to the chemical formation of the resulting material. This work investigates a new templating pathway to nanostructured materials, where the template is also a reagent in the formation of the final material. This concept is described as "reactive templating" and opens a synthetic path toward materials which cannot be synthesised on a nanometre scale by classical templating approaches. Metal nitrides are such kind of materials. They are usually produced by the conversion of metals or metal oxides in ammonia flow at high temperature (T > 1000°C), which make the application of classical templating techniques difficult. Graphitic carbon nitride, g-C3N4, despite its fundamental and theoretical importance, is probably one of the most promising materials to complement carbon in material science and many efforts are put in the synthesis of this material. A simple polyaddition/elimination reaction path at high temperature (T = 550°C) allows the polymerisation of cyanamide toward graphitic carbon nitride solids. By hard templating, using nanostructured silica or aluminium oxide as nanotemplates, a variety of nanostructured graphitic carbon nitrides such as nanorods, nanotubes, meso- and macroporous powders could be obtained by nanocasting or nanocoating. Due to the special semi-conducting properties of the graphitic carbon nitride matrix, the nanostructured graphitic carbon nitrides show unexpected catalytic activity for the activation of benzene in Friedel-Crafts type reactions, making this material an interesting metal free catalyst. Furthermore, due to the chemical composition of g-C3N4 and the fact that it is totally decomposed at temperatures between 600°C and 800°C even under inert atmosphere, g-C3N4 was shown to be a good nitrogen donor for the synthesis of early transition metal nitrides at high temperatures. Thus using the nanostructured carbon nitrides as "reactive templates" or "nanoreactors", various metal nitride nanostructures, such as nanoparticles and porous frameworks could be obtained at high temperature. In this approach the carbon nitride nanostructure played both the role of the nitrogen source and of the exotemplate, imprinting its size and shape to the resulting metal nitride nanostructure.}, language = {en} } @phdthesis{Vranic2019, author = {Vranic, Marija}, title = {3D Structure of the biomarker hepcidin-25 in its native state}, doi = {10.25932/publishup-45929}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-459295}, school = {Universit{\"a}t Potsdam}, pages = {xii, 135}, year = {2019}, abstract = {Hepcidin-25 (Hep-25) plays a crucial role in the control of iron homeostasis. Since the dysfunction of the hepcidin pathway leads to multiple diseases as a result of iron imbalance, hepcidin represents a potential target for the diagnosis and treatment of disorders of iron metabolism. Despite intense research in the last decade targeted at developing a selective immunoassay for iron disorder diagnosis and treatment and better understanding the ferroportin-hepcidin interaction, questions remain. The key to resolving these underlying questions is acquiring exact knowledge of the 3D structure of native Hep-25. Since it was determined that the N-terminus, which is responsible for the bioactivity of Hep-25, contains a small Cu(II)-binding site known as the ATCUN motif, it was assumed that the Hep-25-Cu(II) complex is the native, bioactive form of the hepcidin. This structure has thus far not been elucidated in detail. Owing to the lack of structural information on metal-bound Hep-25, little is known about its possible biological role in iron metabolism. Therefore, this work is focused on structurally characterizing the metal-bound Hep-25 by NMR spectroscopy and molecular dynamics simulations. For the present work, a protocol was developed to prepare and purify properly folded Hep-25 in high quantities. In order to overcome the low solubility of Hep-25 at neutral pH, we introduced the C-terminal DEDEDE solubility tag. The metal binding was investigated through a series of NMR spectroscopic experiments to identify the most affected amino acids that mediate metal coordination. Based on the obtained NMR data, a structural calculation was performed in order to generate a model structure of the Hep-25-Ni(II) complex. The DEDEDE tag was excluded from the structural calculation due to a lack of NMR restraints. The dynamic nature and fast exchange of some of the amide protons with solvent reduced the overall number of NMR restraints needed for a high-quality structure. The NMR data revealed that the 20 Cterminal Hep-25 amino acids experienced no significant conformational changes, compared to published results, as a result of a pH change from pH 3 to pH 7 and metal binding. A 3D model of the Hep-25-Ni(II) complex was constructed from NMR data recorded for the hexapeptideNi(II) complex and Hep-25-DEDEDE-Ni(II) complex in combination with the fixed conformation of 19 C-terminal amino acids. The NMR data of the Hep-25-DEDEDE-Ni(II) complex indicates that the ATCUN motif moves independently from the rest of the structure. The 3D model structure of the metal-bound Hep-25 allows for future works to elucidate hepcidin's interaction with its receptor ferroportin and should serve as a starting point for the development of antibodies with improved selectivity.}, language = {en} } @phdthesis{VillatoroLeal2018, author = {Villatoro Leal, Jos{\´e} Andr{\´e}s}, title = {A combined approach for the analysis of biomolecules using IR-MALDI ion mobility spectrometry and molecular dynamics simulations of peptide ions in the gas phase}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-419723}, school = {Universit{\"a}t Potsdam}, pages = {133}, year = {2018}, abstract = {The aim of this doctoral thesis was to establish a technique for the analysis of biomolecules with infrared matrix-assisted laser dispersion (IR-MALDI) ion mobility (IM) spectrometry. The main components of the work were the characterization of the IR-MALDI process, the development and characterization of different ion mobility spectrometers, the use of IR-MALDI-IM spectrometry as a robust, standalone spectrometer and the development of a collision cross-section estimation approach for peptides based on molecular dynamics and thermodynamic reweighting. First, the IR-MALDI source was studied with atmospheric pressure ion mobility spectrometry and shadowgraphy. It consisted of a metal capillary, at the tip of which a self-renewing droplet of analyte solution was met by an IR laser beam. A relationship between peak shape, ion desolvation, diffusion and extraction pulse delay time (pulse delay) was established. First order desolvation kinetics were observed and related to peak broadening by diffusion, both influenced by the pulse delay. The transport mechanisms in IR-MALDI were then studied by relating different laser impact positions on the droplet surface to the corresponding ion mobility spectra. Two different transport mechanisms were determined: phase explosion due to the laser pulse and electrical transport due to delayed ion extraction. The velocity of the ions stemming from the phase explosion was then measured by ion mobility and shadowgraphy at different time scales and distances from the source capillary, showing an initially very high but rapidly decaying velocity. Finally, the anatomy of the dispersion plume was observed in detail with shadowgraphy and general conclusions over the process were drawn. Understanding the IR-MALDI process enabled the optimization of the different IM spectrometers at atmospheric and reduced pressure (AP and RP, respectively). At reduced pressure, both an AP and an RP IR-MALDI source were used. The influence of the pulsed ion extraction parameters (pulse delay, width and amplitude) on peak shape, resolution and area was systematically studied in both AP and RP IM spectrometers and discussed in the context of the IR-MALDI process. Under RP conditions, the influence of the closing field and of the pressure was also examined for both AP and RP sources. For the AP ionization RP IM spectrometer, the influence of the inlet field (IF) in the source region was also examined. All of these studies led to the determination of the optimal analytical parameters as well as to a better understanding of the initial ion cloud anatomy. The analytical performance of the spectrometer was then studied. Limits of detection (LOD) and linear ranges were determined under static and pulsed ion injection conditions and interpreted in the context of the IR-MALDI mechanism. Applications in the separation of simple mixtures were also illustrated, demonstrating good isomer separation capabilities and the advantages of singly charged peaks. The possibility to couple high performance liquid chromatography (HPLC) to IR-MALDI-IM spectrometry was also demonstrated. Finally, the reduced pressure spectrometer was used to study the effect of high reduced field strength on the mobility of polyatomic ions in polyatomic gases. The last focus point was on the study of peptide ions. A dataset obtained with electrospray IM spectrometry was characterized and used for the calibration of a collision cross-section (CCS) determination method based on molecular dynamics (MD) simulations at high temperature. Instead of producing candidate structures which are evaluated one by one, this semi-automated method uses the simulation as a whole to determine a single average collision cross-section value by reweighting the CCS of a few representative structures. The method was compared to the intrinsic size parameter (ISP) method and to experimental results. Additional MD data obtained from the simulations was also used to further analyze the peptides and understand the experimental results, an advantage with regard to the ISP method. Finally, the CCS of peptide ions analyzed by IR-MALDI were also evaluated with both ISP and MD methods and the results compared to experiment, resulting in a first validation of the MD method. Thus, this thesis brings together the soft ionization technique that is IR-MALDI, which produces mostly singly charged peaks, with ion mobility spectrometry, which can distinguish between isomers, and a collision cross-section determination method which also provides structural information on the analyte at hand.}, language = {en} } @phdthesis{DereseYenesewMidiwoetal.2003, author = {Derese, Solomon and Yenesew, Abiy and Midiwo, Jacob O. and Heydenreich, Matthias and Peter, Martin G.}, title = {A new isoflavone from stem bark of Millettia dura}, issn = {1011-3924}, year = {2003}, language = {en} } @phdthesis{Rackwitz2016, author = {Rackwitz, Jenny}, title = {A novel approach to study low-energy electron-induced damage to DNA oligonucleotides}, school = {Universit{\"a}t Potsdam}, pages = {137}, year = {2016}, language = {en} } @phdthesis{Gebauer2008, author = {Gebauer, Denis}, title = {A novel view on the early stage of crystallization}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-19818}, school = {Universit{\"a}t Potsdam}, year = {2008}, abstract = {This thesis provides a novel view on the early stage of crystallization utilizing calcium carbonate as a model system. Calcium carbonate is of great economical, scientific and ecological importance, because it is a major part of water hardness, the most abundant Biomineral and forms huge amounts of geological sediments thus binding large amounts of carbon dioxide. The primary experiments base on the evolution of supersaturation via slow addition of dilute calcium chloride solution into dilute carbonate buffer. The time-dependent measurement of the Ca2+ potential and concurrent pH = constant titration facilitate the calculation of the amount of calcium and carbonate ions bound in pre-nucleation stage clusters, which have never been detected experimentally so far, and in the new phase after nucleation, respectively. Analytical Ultracentrifugation independently proves the existence of pre-nucleation stage clusters, and shows that the clusters forming at pH = 9.00 have a proximately time-averaged size of altogether 70 calcium and carbonate ions. Both experiments show that pre-nucleation stage cluster formation can be described by means of equilibrium thermodynamics. Effectively, the cluster formation equilibrium is physico-chemically characterized by means of a multiple-binding equilibrium of calcium ions to a 'lattice' of carbonate ions. The evaluation gives GIBBS standard energy for the formation of calcium/carbonate ion pairs in clusters, which exhibits a maximal value of approximately 17.2 kJ mol^-1 at pH = 9.75 and relates to a minimal binding strength in clusters at this pH-value. Nucleated calcium carbonate particles are amorphous at first and subsequently become crystalline. At high binding strength in clusters, only calcite (the thermodynamically stable polymorph) is finally obtained, while with decreasing binding strength in clusters, vaterite (the thermodynamically least stable polymorph) and presumably aragonite (the thermodynamically intermediate stable polymorph) are obtained additionally. Concurrently, two different solubility products of nucleated amorphous calcium carbonate (ACC) are detected at low binding strength and high binding strength in clusters (ACC I 3.1EE-8 M^2, ACC II 3.8EE-8 M^2), respectively, indicating the precipitation of at least two different ACC species, while the clusters provide the precursor species of ACC. It is proximate that ACC I may relate to calcitic ACC -i.e. ACC exhibiting short range order similar to the long range order of calcite and that ACC II may relate to vateritic ACC, which will subsequently transform into the particular crystalline polymorph as discussed in the literature, respectively. Detailed analysis of nucleated particles forming at minimal binding strength in clusters (pH = 9.75) by means of SEM, TEM, WAXS and light microscopy shows that predominantly vaterite with traces of calcite forms. The crystalline particles of early stages are composed of nano-crystallites of approximately 5 to 10 nm size, respectively, which are aligned in high mutual order as in mesocrystals. The analyses of precipitation at pH = 9.75 in presence of additives -polyacrylic acid (pAA) as a model compound for scale inhibitors and peptides exhibiting calcium carbonate binding affinity as model compounds for crystal modifiers- shows that ACC I and ACC II are precipitated in parallel: pAA stabilizes ACC II particles against crystallization leading to their dissolution for the benefit of crystals that form from ACC I and exclusively calcite is finally obtained. Concurrently, the peptide additives analogously inhibit the formation of calcite and exclusively vaterite is finally obtained in case of one of the peptide additives. These findings show that classical nucleation theory is hardly applicable for the nucleation of calcium carbonate. The metastable system is stabilized remarkably due to cluster formation, while clusters forming by means of equilibrium thermodynamics are the nucleation relevant species and not ions. Most likely, the concept of cluster formation is a common phenomenon occurring during the precipitation of hardly soluble compounds as qualitatively shown for calcium oxalate and calcium phosphate. This finding is important for the fundamental understanding of crystallization and nucleation-inhibition and modification by additives with impact on materials of huge scientific and industrial importance as well as for better understanding of the mass transport in crystallization. It can provide a novel basis for simulation and modelling approaches. New mechanisms of scale formation in Bio- and Geomineralization and also in scale inhibition on the basis of the newly reported reaction channel need to be considered.}, language = {en} } @phdthesis{Jehannin2015, author = {Jehannin, Marie}, title = {About the role of physico-chemical properties and hydrodynamics on the progress of a precipitation reaction}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-88364}, school = {Universit{\"a}t Potsdam}, pages = {xii, 130}, year = {2015}, abstract = {The size and morphology control of precipitated solid particles is a major economic issue for numerous industries. For instance, it is interesting for the nuclear industry, concerning the recovery of radioactive species from used nuclear fuel. The precipitates features, which are a key parameter from the post-precipitate processing, depend on the process local mixing conditions. So far, the relationship between precipitation features and hydrodynamic conditions have not been investigated. In this study, a new experimental configuration consisting of coalescing drops is set to investigate the link between reactive crystallization and hydrodynamics. Two configurations of aqueous drops are examined. The first one corresponds to high contact angle drops (>90°) in oil, as a model system for flowing drops, the second one correspond to sessile drops in air with low contact angle (<25°). In both cases, one reactive is dissolved in each drop, namely oxalic acid and cerium nitrate. When both drops get into contact, they may coalesce; the dissolved species mix and react to produce insoluble cerium oxalate. The precipitates features and effect on hydrodynamics are investigated depending on the solvent. In the case of sessile drops in air, the surface tension difference between the drops generates a gradient which induces a Marangoni flow from the low surface tension drop over the high surface tension drop. By setting the surface tension difference between the two drops and thus the Marangoni flow, the hydrodynamics conditions during the drop coalescence could be modified. Diols/water mixtures are used as solvent, in order to fix the surface tension difference between the liquids of both drops regardless from the reactant concentration. More precisely, the used diols, 1,2-propanediol and 1,3-propanediol, are isomer with identical density and close viscosity. By keeping the water volume fraction constant and playing with the 1,2-propanediol and 1,3-propanediol volume fractions of the solvents, the mixtures surface tensions differ up to 10 mN/m for identical/constant reactant concentration, density and viscosity. 3 precipitation behaviors were identified for the coalescence of water/diols/recatants drops depending on the oxalic excess. The corresponding precipitates patterns are visualized by optical microscopy and the precipitates are characterized by confocal microscopy SEM, XRD and SAXS measurements. In the intermediate oxalic excess regime, formation of periodic patterns can be observed. These patterns consist in alternating cerium oxalate precipitates with distinct morphologies, namely needles and "microflowers". Such periodic fringes can be explained by a feedback mechanism between convection, reaction and the diffusion.}, language = {en} } @phdthesis{Bai2010, author = {Bai, Shuo}, title = {Active hydrogels with nanocomposites}, address = {Potsdam}, pages = {VI, 109 Bl. : Ill., graph. Darst.}, year = {2010}, language = {en} } @phdthesis{Asfaw2005, author = {Asfaw, Mesfin}, title = {Adhesion of multi-component membbranes and strings}, address = {Potsdam}, pages = {102 S. : graph. Darst.}, year = {2005}, language = {en} } @phdthesis{Steeples2016, author = {Steeples, Elliot}, title = {Amino acid-derived imidazolium salts: platform molecules for N-Heterocyclic carbene metal complexes and organosilica materials}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-101861}, school = {Universit{\"a}t Potsdam}, pages = {139}, year = {2016}, abstract = {In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes. The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC-Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer. The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts.}, language = {en} } @phdthesis{Kristen2011, author = {Kristen, Juliane Ute}, title = {Amphiphilic BAB-triblock copolymers bearing fluorocarbon groups : synthesis and self-organization in aqueous media}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-61782}, school = {Universit{\"a}t Potsdam}, year = {2011}, abstract = {In this work new fluorinated and non-fluorinated mono- and bifunctional trithiocarbonates of the structure Z-C(=S)-S-R and Z-C(=S)-S-R-S-C(=S)-Z were synthesized for the use as chain transfer agents (CTAs) in the RAFT-process. All newly synthesized CTAs were tested for their efficiency to moderate the free radical polymerization process by polymerizing styrene (M3). Besides characterization of the homopolymers by GPC measurements, end- group analysis of the synthesized block copolymers via 1H-, 19F-NMR, and in some cases also UV-vis spectroscopy, were performed attaching suitable fluorinated moieties to the Z- and/or R-groups of the CTAs. Symmetric triblock copolymers of type BAB and non-symmetric fluorine end- capped polymers were accessible using the RAFT process in just two or one polymerization step. In particular, the RAFT-process enabled the controlled polymerization of hydrophilic monomers such as N-isopropylacrylamide (NIPAM) (M1) as well as N-acryloylpyrrolidine (NAP) (M2) for the A-blocks and of the hydrophobic monomers styrene (M3), 2-fluorostyrene (M4), 3-fluorostyrene (M5), 4-fluorostyrene (M6) and 2,3,4,5,6-pentafluorostyrene (M7) for the B-blocks. The properties of the BAB-triblock copolymers were investigated in dilute, concentrated and highly concentrated aqueous solutions using DLS, turbidimetry, 1H- and 19F-NMR, rheology, determination of the CMC, foam height- and surface tension measurements and microscopy. Furthermore, their ability to stabilize emulsions and microemulsions and the wetting behaviour of their aqueous solutions on different substrates was investigated. The behaviour of the fluorine end-functionalized polymers to form micelles was studied applying DLS measurements in diluted organic solution. All investigated BAB-triblock copolymers were able to form micelles and show surface activity at room temperature in dilute aqueous solution. The aqueous solutions displayed moderate foam formation. With different types and concentrations of oils, the formation of emulsions could be detected using a light microscope. A boosting effect in microemulsions could not be found adding BAB-triblock copolymers. At elevated polymer concentrations, the formation of hydrogels was proved applying rheology measurements.}, language = {en} } @phdthesis{Stocco2007, author = {Stocco, Antonio}, title = {Amphiphilic block copolymers at the liquid-fluid interface, invesrigated by evanescent light scattering and ellipsometry}, address = {Potsdam}, pages = {iii, 108 S. : Ill., graph. Darst.}, year = {2007}, language = {en} } @phdthesis{Ambrogi2015, author = {Ambrogi, Martina}, title = {Application of Poly(Ionic Liquid)s for the synthesis of functional carbons}, school = {Universit{\"a}t Potsdam}, pages = {125}, year = {2015}, language = {en} } @phdthesis{Moya2001, author = {Moya, Sergio Enrique}, title = {Architecture, permeability, electrical and mechanical properties of polyelectrolyte lipid composite capsules}, pages = {138 S.}, year = {2001}, language = {en} } @phdthesis{Luedecke2022, author = {L{\"u}decke, Nils}, title = {Bio-sourced adsorbing poly(2-oxazoline)s mimicking mussel glue proteins for antifouling applications}, doi = {10.25932/publishup-54983}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-549836}, school = {Universit{\"a}t Potsdam}, pages = {iii, 224}, year = {2022}, abstract = {Nature developed countless systems for many applications. In maritime environments, several organisms established extra-ordinary mechanisms to attach to surfaces. Over the past years, the scientific interest to employ those mechanisms for coatings and long-lasting adhering materials gained significant attention. This work describes the synthesis of bio-inspired adsorbing copoly(2-oxazoline)s for surface coatings with protein repelling effects, mimicking mussel glue proteins. From a set of methoxy substituted phenyl, benzyl, and cinnamyl acids, 2-oxazoline monomers were synthesized. All synthesized 2-oxazolines were analyzed by FT-IR spectroscopy, NMR spectroscopy, and EI mass spectrometry. With those newly synthesized 2-oxazoline monomers and 2-ethyl-2-oxazoline, kinetic studies concerning homo- and copolymerization in a microwave reactor were conducted. The success of the polymerization reactions was demonstrated by FT-IR spectroscopy, NMR spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography (SEC). The copolymerization of 2-ethyl-2-oxazoline with a selection of methoxy-substituted 2-oxazolines resulted in water-soluble copolymers. To release the adsorbing catechol and cationic units, the copoly(2-oxazoline)s were modified. The catechol units were (partially) released by a methyl aryl ether cleavage reaction. A subsequent partial acidic hydrolysis of the ethyl unit resulted in mussel glue protein-inspired catechol and cation-containing copolymers. The modified copolymers were analyzed by NMR spectroscopy, UV-VIS spectroscopy, and SEC. The catechol- and cation-containing copolymers and their precursors were examined by a Quartz Crystal Microbalance with Dissipation (QCM-D), so study the adsorption performance on gold, borosilicate, iron, and polystyrene surfaces. An exemplary study revealed that a catechol and cation-containing copoly(2-oxazoline)-coated gold surface exhibits strong protein repelling properties.}, language = {en} } @phdthesis{Tang2022, author = {Tang, Jo Sing Julia}, title = {Biofunctional polymers for medical applications}, doi = {10.25932/publishup-56363}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-563639}, school = {Universit{\"a}t Potsdam}, pages = {III, 150, V}, year = {2022}, abstract = {Carbohydrates are found in every living organism, where they are responsible for numerous, essential biological functions and processes. Synthetic polymers with pendant saccharides, called glycopolymers, mimic natural glycoconjugates in their special properties and functions. Employing such biomimetics furthers the understanding and controlling of biological processes. Hence, glycopolymers are valuable and interesting for applications in the medical and biological field. However, the synthesis of carbohydrate-based materials can be very challenging. In this thesis, the synthesis of biofunctional glycopolymers is presented, with the focus on aqueous-based, protecting group free and short synthesis routes to further advance in the field of glycopolymer synthesis. A practical and versatile precursor for glycopolymers are glycosylamines. To maintain biofunctionality of the saccharides after their amination, regioselective functionalization was performed. This frequently performed synthesis was optimized for different sugars. The optimization was facilitated using a design of experiment (DoE) approach to enable a reduced number of necessary experiments and efficient procedure. Here, the utility of using DoE for optimizing the synthesis of glycosylamines is discussed. The glycosylamines were converted to glycomonomers which were then polymerized to yield biofunctional glycopolymers. Here, the glycopolymers were aimed to be applicable as layer-by-layer (LbL) thin film coatings for drug delivery systems. To enable the LbL technique, complimentary glycopolymer electrolytes were synthesized by polymerization of the glycomonomers and subsequent modification or by post-polymerization modification. For drug delivery, liposomes were embedded into the glycopolymer coating as potential cargo carriers. The stability as well as the integrity of the glycopolymer layers and liposomes were investigated at physiological pH range. Different glycopolymers were also synthesized to be applicable as anti-adhesion therapeutics by providing advanced architectures with multivalent presentations of saccharides, which can inhibit the binding of pathogene lectins. Here, the synthesis of glycopolymer hydrogel particles based on biocompatible poly(N-isopropylacrylamide) (NiPAm) was established using the free-radical precipitation polymerization technique. The influence of synthesis parameters on the sugar content in the gels and on the hydrogel morphology is discussed. The accessibility of the saccharides to model lectins and their enhanced, multivalent interaction were investigated. At the end of this work, the synthesis strategies for the glycopolymers are generally discussed as well as their potential application in medicine.}, language = {en} } @phdthesis{Zhou2022, author = {Zhou, Shuo}, title = {Biological evaluation and sulfation of polymer networks from glycerol glycidyl ether}, school = {Universit{\"a}t Potsdam}, pages = {96}, year = {2022}, abstract = {Cardiovascular diseases are the main cause of death worldwide, and their prevalence is expected to rise in the coming years. Polymer-based artificial replacements have been widely used for the treatment of cardiovascular diseases. Coagulation and thrombus formation on the interfaces between the materials and the human physiological environment are key issues leading to the failure of the medical device in clinical implantation. The surface properties of the materials have a strong influence on the protein adsorption and can direct the blood cell adhesion behavior on the interfaces. Furthermore, implant-associated infections will be induced by bacterial adhesion and subsequent biofilm formation at the implantation site. Thus, it is important to improve the hemocompatibility of an implant by altering the surface properties. One of the effective strategies is surface passivation to achieve protein/cell repelling ability to reduce the risk of thrombosis. This thesis consists of synthesis, functionalization, sterilization, and biological evaluation of bulk poly(glycerol glycidyl ether) (polyGGE), which is a highly crosslinked polyether-based polymer synthesized by cationic ring-opening polymerization. PolyGGE is hypothesized to be able to resist plasma protein adsorption and bacterial adhesion due to analogous chemical structure as polyethylene glycol and hyperbranched polyglycerol. Hydroxyl end groups of polyGGE provide possibilities to be functionalized with sulfates to mimic the anti-thrombogenic function of the endothelial glycocalyx. PolyGGE was synthesized by polymerization of the commercially available monomer glycerol glycidyl ether, which was characterized as a mixture of mono-, di- and tri-glycidyl ether. Cationic ring opening-polymerization of this monomer was carried out by ultraviolet (UV) initiation of the photo-initiator diphenyliodonium hexafluorophosphate. With the increased UV curing time, more epoxides in the side chains of the monomers participated in chemical crosslinking, resulting in an increase of Young's modulus, while the value of elongation at break of polyGGE first increased due to the propagation of the polymer chains then decreased with the increase of crosslinking density. Eventually, the chain propagation can be effectively terminated by potassium hydroxide aqueous solution. PolyGGE exhibited different tensile properties in hydrated conditions at body temperature compared to the values in the dry state at room temperature. Both Young's modulus and values of elongation at break were remarkably reduced when tested in water at 37 °C, which was above the glass transition temperature of polyGGE. At physiological conditions, entanglements of the ployGGE networks unfolded and the free volume of networks were replaced by water molecules as softener, which increased the mobility of the polymer chains, resulting in a lower Young's modulus. Protein adsorption analysis was performed on polyGGE films with 30 min UV curing using an enzyme-linked immunosorbent assay. PolyGGE could effectively prevent the adsorption of human plasma fibrinogen, albumin, and fibronectin at the interface of human plasma and polyGGE films. The protein resistance of polyGGE was comparable to the negative controls: the hemocompatible polydimethylsiloxane (PDMS), showing its potential as a coating material for cardiovascular implants. Moreover, antimicrobial tests of bacterial activity using isothermal microcalorimetry and the microscopic image of direct bacteria culturing demonstrated that polyGGE could directly interfere biofilm formation and growth of both Gram-negative and antibiotic-resistant Gram-positive bacteria, indicating the potential application of polyGGE for combating the risk of hospital-acquired infections and preventing drug-resistant superbug spreading. To investigate its cell compatibility, polyGGE films were extracted by different solvents (ethanol, chloroform, acetone) and cell culture medium. Indirect cytotoxicity tests showed extracted polyGGE films still had toxic effects on L929 fibroblast cells. High-performance liquid chromatography/electrospray ionization mass spectrometry revealed the occurrence of organochlorine-containing compounds released during the polymer-cell culture medium interaction. A constant level of those organochlorine-containing compounds was confirmed from GGE monomer by a specific peak of C-Cl stretching in infrared spectra of GGE. This is assumed to be the main reason causing the increased cell membrane permeability and decreased metabolic activity, leading to cell death. Attempts as changing solvents were made to remove toxic substances, however, the release of these small molecules seems to be sluggish. The densely crosslinked polyGGE networks can possibly contribute to the trapping of organochlorine-containing compounds. These results provide valuable information for exploring the potentially toxic substances, leaching from polyGGE networks, and propose a feasible strategy for minimizing the cytotoxicity via reducing their crosslinking density. Sulfamic acid/ N-Methyl-2-pyrrolidone (NMP) were selected as the reagents for the sulfation of polyGGE surfaces. Fourier transform attenuated total reflection infrared spectroscopy (ATR-FT-IR) was used to monitor the functionalization kinetics and the results confirmed the successful sulfate grafting on the surface of polyGGE with the covalent bond -C-O-S-. X-ray photoelectron spectroscopy was used to determine the element composition on the surface and the cross-section of the functionalized polyGGE and sulfation within 15 min guarantees the sulfation only takes place on the surface while not occurring in the bulk of the polymer. The concentration of grafted sulfates increased with the increasing reaction time. The hydrophilicity of the surface of polyGGE was highly increased due to the increase of negatively charged end groups. Three sterilization techniques including autoclaving, gamma irradiation, and ethylene oxide (EtO) sterilization were used for polyGGE sulfates. Results from ATR-FT-IR and Toluidine Blue O quantitative assay demonstrated the total loss of the sulfates after autoclave sterilization, which was also confirmed by the increased water contact angle. Little influence on the concentration of sulfates was found for gamma-irradiated and autoclaving sterilized polyGGE sulfates. To investigate the thermal influence on polyGGE sulfates, one strategy was to use poly(hydroxyethyl acrylate) sulfates (PHEAS) for modeling. The thermogravimetric analysis profile of PHEAS demonstrated that sulfates are not thermally stable independent of the substrate materials and decomposition of sulfates occurs at around 100 °C. Although gamma irradiation also showed little negative effect on the sulfate content, the color change in the polyGGE sulfates indicates chemical or physical change might occur in the polymer. EtO sterilization was validated as the most suitable sterilization technique to maintain the chemical structure of polyGGE sulfates. In conclusion, the conducted work proved that bulk polyGGE can be used as an antifouling coating material and shows its antimicrobial potential. Sulfates functionalization can be effectively realized using sulfamic acid/NMP. EtO sterilization is the most suitable sterilization technique for grafted sulfates. Besides, this thesis also offers a good strategy for the analysis of toxic leachable substances using suitable physicochemical characterization techniques. Future work will focus on minimizing/eliminating the release of toxic substances via reducing the crosslinking density. Another interesting aspect is to study whether grafted sulfates can meet the need for anti-thrombogenicity.}, language = {en} } @phdthesis{Bhaskar2020, author = {Bhaskar, Thanga Bhuvanesh Vijaya}, title = {Biomimetic layers of extracellular matrix glycoproteins as designed biointerfaces}, school = {Universit{\"a}t Potsdam}, year = {2020}, abstract = {The goal of regenerative medicine is to guide biological systems towards natural healing outcomes using a combination of niche-specific cells, bioactive molecules and biomaterials. In this regard, mimicking the extracellular matrix (ECM) surrounding cells and tissues in vivo is an effective strategy to modulate cell behaviors. Cellular function and phenotype is directed by the biochemical and biophysical signals present in the complex 3D network of ECMs composed mainly of glycoproteins and hydrophilic proteoglycans. While cellular modulation in response to biophysical cues emulating ECM features has been investigated widely, the influence of biochemical display of ECM glycoproteins mimicking their presentation in vivo is not well characterized. It remains a significant challenge to build artificial biointerfaces using ECM glycoproteins that precisely match their presentation in nature in terms of morphology, orientation and conformation. This challenge becomes clear, when one understands how ECM glycoproteins self-assemble in the body. Glycoproteins produced inside the cell are secreted in the extra-cellular space, where they are bound to the cell membrane or other glycoproteins by specific interactions. This leads to elevated local concentration and 2Dspatial confinement, resulting in self-assembly by the reciprocal interactions arising from the molecular complementarity encoded in the glycoprotein domains. In this thesis, air-water (A-W) interface is presented as a suitable platform, where self-assembly parameters of ECM glycoproteins such as pH, temperature and ionic strength can be controlled to simulate in vivo conditions (Langmuir technique), resulting in the formation of glycoprotein layers with defined characteristics. The layer can be further compressed with surface barriers to enhance glycoprotein-glycoprotein contacts and defined layers of glycoproteins can be immobilized on substrates by horizontal lift and touch method, called Langmuir-Sch{\"a}fer (LS) method. Here, the benefit of Langmuir and LS methods in achieving ECM glycoprotein biointerfaces with controlled network morphology and ligand density on substrates is highlighted and contrasted with the commonly used (glyco)protein solution deposition (SO) method on substrates. In general, the (glyco)protein layer formation by SO is rather uncontrolled, influenced strongly by (glyco)protein-substrate interactions and it results in multilayers and aggregations on substrates, while the LS method results in (glyco)proteins layers with a more homogenous presentation. To achieve the goal of realizing defined ECM layers on substrates, ECM glycoproteins having the ability to self-assemble were selected: Collagen-IV (Col-IV) and fibronectin (FN). Highly packed FN layer with uniform presentation of ligands was deposited on polydimethysiloxane VIII (PDMS) by LS method, while a heterogeneous layer was formed on PDMS by SO with prominent aggregations visible. Mesenchymal stem cells (MSC) on PDMS equipped with FN by LS exhibited more homogeneous and elevated vinculin expression and weaker stress fiber formation than on PDMS equipped with FN by SO and these divergent responses could be attributed to the differences in glycoprotein presentation at the interface. Col-IV are scaffolding components of specialized ECM called basement membranes (BM), and have the propensity to form 2D networks by self-polymerization associated with cells. Col- IV behaves as a thin-disordered network at the A-W interface. As the Col-IV layer was compressed at the A-W interface using trough barriers, there was negligible change in thickness (layer thickness ~ 50 nm) or orientation of molecules. The pre-formed organization of Col-IV was transferred by LS method in a controlled fashion onto substrates meeting the wettability criterion (CA ≤ 80°). MSC adhesion (24h) on PET substrates deposited with Col-IV LS films at 10, 15 and 20 mN·m-1 surface pressures was (12269.0 ± 5856.4) cells for LS10, (16744.2 ± 1280.1) cells for LS15 and (19688.3 ± 1934.0) cells for LS20 respectively. Remarkably, by selecting the surface areal density of Col-IV on the Langmuir trough on PET, there is a linear increase between the number of adherent MSCs and the Col-IV ligand density. Further, FN has the ability to self-stabilize and form 2D networks (even without compression) while preserving native β-sheet structure at the A-W interface on a defined subphase (pH = 2). This provides the possibility to form such layers on any vessel (even on standard six-well culture plates) and the cohesive FN layers can be deposited by LS transfer, without the need for expensive LB instrumentation. Multilayers of FN can be immobilized on substrates by this approach, as easily as Layer-by-Layer method, even without the need for secondary adlayer or activated bare substrate. Thus, this facile glycoprotein coating strategy approach is accessible to many researchers to realize defined FN films on substrates for cell culture. In conclusion, Langmuir and LS methods can create biomimetic glycoprotein biointerfaces on substrates controlling aspects of presentation such as network morphology and ligand density. These methods will be utilized to produce artificial BM mimics and interstitial ECM mimics composed of more than one ECM glycoprotein layer on substrates, serving as artificial niches instructing stem cells for cell-replacement therapies in the future.}, language = {en} } @phdthesis{Coelfen2000, author = {C{\"o}lfen, Helmut}, title = {Biomimetric mineralisation using hydrophilic copolymers : synthesis of hybrid colloids with complex from and pathways towards their analysis in solution}, pages = {155 S.}, year = {2000}, language = {en} } @phdthesis{Peh2017, author = {Peh, Eddie K.W.}, title = {Calcium carbonate formation}, school = {Universit{\"a}t Potsdam}, pages = {133}, year = {2017}, language = {en} } @phdthesis{Esen2023, author = {Esen, Cansu}, title = {Carbon nitride incorporation in polymer networks}, doi = {10.25932/publishup-57625}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-576253}, school = {Universit{\"a}t Potsdam}, pages = {xvi, 175}, year = {2023}, abstract = {The urge of light utilization in fabrication of materials is as encouraging as challenging. Steadily increasing energy consumption in accordance with rapid population growth, is requiring a corresponding solution within the same rate of occurrence speed. Therefore, creating, designing and manufacturing materials that can interact with light and in further be applicable as well as disposable in photo-based applications are very much under attention of researchers. In the era of sustainability for renewable energy systems, semiconductor-based photoactive materials have received great attention not only based on solar and/or hydrocarbon fuels generation from solar energy, but also successful stimulation of photocatalytic reactions such as water splitting, pollutant degradation and organic molecule synthesisThe turning point had been reached for water splitting with an electrochemical cell consisting of TiO2-Pt electrode illuminated by UV light as energy source rather than an external voltage, that successfully pursued water photolysis by Fujishima and Honda in 1972. Ever since, there has been a great deal of interest in research of semiconductors (e.g. metal oxide, metal-free organic, noble-metal complex) exhibiting effective band gap for photochemical reactions. In the case of environmental friendliness, toxicity of metal-based semiconductors brings some restrictions in possible applications. Regarding this, very robust and 'earth-abundant' organic semiconductor, graphitic carbon nitride has been synthesized and successfully applied in photoinduced applications as novel photocatalyst. Properties such as suitable band gap, low charge carrier recombination and feasibility for scaling up, pave the way of advance combination with other catalysts to gather higher photoactivity based on compatible heterojunction. This dissertation aims to demonstrate a series of combinations between organic semiconductor g-CN and polymer materials that are forged through photochemistry, either in synthesis or in application. Fabrication and design processes as well as applications performed in accordance to the scope of thesis will be elucidated in detail. In addition to UV light, more attention is placed on visible light as energy source with a vision of more sustainability and better scalability in creation of novel materials and solar energy based applications.}, language = {en} } @phdthesis{Galushchinskiy2023, author = {Galushchinskiy, Alexey}, title = {Carbon nitride: a flexible platform for net-oxidative and net-neutral photocatalysis}, doi = {10.25932/publishup-61092}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-610923}, school = {Universit{\"a}t Potsdam}, pages = {351}, year = {2023}, abstract = {Solar photocatalysis is the one of leading concepts of research in the current paradigm of sustainable chemical industry. For actual practical implementation of sunlight-driven catalytic processes in organic synthesis, a cheap, efficient, versatile and robust heterogeneous catalyst is necessary. Carbon nitrides are a class of organic semiconductors who are known to fulfill these requirements. First, current state of solar photocatalysis in economy, industry and lab research is overviewed, outlining EU project funding, prospective synthetic and reforming bulk processes, small scale solar organic chemistry, and existing reactor designs and prototypes, concluding feasibility of the approach. Then, the photocatalytic aerobic cleavage of oximes to corresponding aldehydes and ketones by anionic poly(heptazine imide) carbon nitride is discussed. The reaction provides a feasible method of deprotection and formation of carbonyl compounds from nitrosation products and serves as a convenient model to study chromoselectivity and photophysics of energy transfer in heterogeneous photocatalysis. Afterwards, the ability of mesoporous graphitic carbon nitride to conduct proton-coupled electron transfer was utilized for the direct oxygenation of 1,3-oxazolidin-2-ones to corresponding 1,3-oxazlidine-2,4-diones. This reaction provides an easier access to a key scaffold of diverse types of drugs and agrochemicals. Finally, a series of novel carbon nitrides based on poly(triazine imide) and poly(heptazine imide) structure was synthesized from cyanamide and potassium rhodizonate. These catalysts demonstrated a good performance in a set of photocatalytic benchmark reactions, including aerobic oxidation, dual nickel photoredox catalysis, hydrogen peroxide evolution and chromoselective transformation of organosulfur precursors. Concluding, the scope of carbon nitride utilization for net-oxidative and net-neutral photocatalytic processes was expanded, and a new tunable platform for catalyst synthesis was discovered.}, language = {en} } @phdthesis{Stark2008, author = {Stark, Arne Henning}, title = {CCD based ellipsometric light scattering}, pages = {xv, 99, XVI S.: Ill., graph. Darst.}, year = {2008}, language = {en} } @phdthesis{Stark2008, author = {Stark, Arne Henning}, title = {CCD based ellipsometric light scattering}, address = {Potsdam}, pages = {99 S., vi-xv, : graph. Darst.}, year = {2008}, language = {en} } @phdthesis{Glatzel2012, author = {Glatzel, Stefan}, title = {Cellulose based transition metal nano-composites : structuring and development}, address = {Potsdam}, pages = {102, XXIII S.}, year = {2012}, language = {en} } @phdthesis{Glatzel2013, author = {Glatzel, Stefan}, title = {Cellulose based transition metal nano-composites : structuring and development}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-64678}, school = {Universit{\"a}t Potsdam}, year = {2013}, abstract = {Cellulose is the most abundant biopolymer on earth. In this work it has been used, in various forms ranging from wood to fully processed laboratory grade microcrystalline cellulose, to synthesise a variety of metal and metal carbide nanoparticles and to establish structuring and patterning methodologies that produce highly functional nano-hybrids. To achieve this, the mechanisms governing the catalytic processes that bring about graphitised carbons in the presence of iron have been investigated. It was found that, when infusing cellulose with an aqueous iron salt solution and heating this mixture under inert atmosphere to 640 °C and above, a liquid eutectic mixture of iron and carbon with an atom ratio of approximately 1:1 forms. The eutectic droplets were monitored with in-situ TEM at the reaction temperature where they could be seen dissolving amorphous carbon and leaving behind a trail of graphitised carbon sheets and subsequently iron carbide nanoparticles. These transformations turned ordinary cellulose into a conductive and porous matrix that is well suited for catalytic applications. Despite these significant changes on the nanometre scale the shape of the matrix as a whole was retained with remarkable precision. This was exemplified by folding a sheet of cellulose paper into origami cranes and converting them via the temperature treatment in to magnetic facsimiles of those cranes. The study showed that the catalytic mechanisms derived from controlled systems and described in the literature can be transferred to synthetic concepts beyond the lab without loss of generality. Once the processes determining the transformation of cellulose into functional materials were understood, the concept could be extended to other metals and metal-combinations. Firstly, the procedure was utilised to produce different ternary iron carbides in the form of MxFeyC (M = W, Mn). None of those ternary carbides have thus far been produced in a nanoparticle form. The next part of this work encompassed combinations of iron with cobalt, nickel, palladium and copper. All of those metals were also probed alone in combination with cellulose. This produced elemental metal and metal alloy particles of low polydispersity and high stability. Both features are something that is typically not associated with high temperature syntheses and enables to connect the good size control with a scalable process. Each of the probed reactions resulted in phase pure, single crystalline, stable materials. After showing that cellulose is a good stabilising and separating agent for all the investigated types of nanoparticles, the focus of the work at hand is shifted towards probing the limits of the structuring and pattering capabilities of cellulose. Moreover possible post-processing techniques to further broaden the applicability of the materials are evaluated. This showed that, by choosing an appropriate paper, products ranging from stiff, self-sustaining monoliths to ultra-thin and very flexible cloths can be obtained after high temperature treatment. Furthermore cellulose has been demonstrated to be a very good substrate for many structuring and patterning techniques from origami folding to ink-jet printing. The thereby resulting products have been employed as electrodes, which was exemplified by electrodepositing copper onto them. Via ink-jet printing they have additionally been patterned and the resulting electrodes have also been post functionalised by electro-deposition of copper onto the graphitised (printed) parts of the samples. Lastly in a preliminary test the possibility of printing several metals simultaneously and thereby producing finely tuneable gradients from one metal to another have successfully been made. Starting from these concepts future experiments were outlined. The last chapter of this thesis concerned itself with alternative synthesis methods of the iron-carbon composite, thereby testing the robustness of the devolved reactions. By performing the synthesis with partly dissolved scrap metal and pieces of raw, dry wood, some progress for further use of the general synthesis technique were made. For example by using wood instead of processed cellulose all the established shaping techniques available for wooden objects, such as CNC milling or 3D prototyping, become accessible for the synthesis path. Also by using wood its intrinsic well defined porosity and the fact that large monoliths are obtained help expanding the prospect of using the composite. It was also demonstrated in this chapter that the resulting material can be applied for the environmentally important issue of waste water cleansing. Additionally to being made from renewable resources and by a cheap and easy one-pot synthesis, the material is recyclable, since the pollutants can be recovered by washing with ethanol. Most importantly this chapter covered experiments where the reaction was performed in a crude, home-built glass vessel, fuelled - with the help of a Fresnel lens - only by direct concentrated sunlight irradiation. This concept carries the thus far presented synthetic procedures from being common laboratory syntheses to a real world application. Based on cellulose, transition metals and simple equipment, this work enabled the easy one-pot synthesis of nano-ceramic and metal nanoparticle composites otherwise not readily accessible. Furthermore were structuring and patterning techniques and synthesis routes involving only renewable resources and environmentally benign procedures established here. Thereby it has laid the foundation for a multitude of applications and pointed towards several future projects reaching from fundamental research, to application focussed research and even and industry relevant engineering project was envisioned.}, language = {en} } @phdthesis{Debsharma2019, author = {Debsharma, Tapas}, title = {Cellulose derived polymers}, doi = {10.25932/publishup-44131}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-441312}, school = {Universit{\"a}t Potsdam}, pages = {x, 103}, year = {2019}, abstract = {Plastics, such as polyethylene, polypropylene, and polyethylene terephthalate are part of our everyday lives in the form of packaging, household goods, electrical insulation, etc. These polymers are non-degradable and create many environmental problems and public health concerns. Additionally, these polymers are produced from finite fossils resources. With the continuous utilization of these limited resources, it is important to look towards renewable sources along with biodegradation of the produced polymers, ideally. Although many bio-based polymers are known, such as polylactic acid, polybutylene succinate adipate or polybutylene succinate, none have yet shown the promise of replacing conventional polymers like polyethylene, polypropylene and polyethylene terephthalate. Cellulose is one of the most abundant renewable resources produced in nature. It can be transformed into various small molecules, such as sugars, furans, and levoglucosenone. The aim of this research is to use the cellulose derived molecules for the synthesis of polymers. Acid-treated cellulose was subjected to thermal pyrolysis to obtain levoglucosenone, which was reduced to levoglucosenol. Levoglucosenol was polymerized, for the first time, by ring-opening metathesis polymerization (ROMP) yielding high molar mass polymers of up to ~150 kg/mol. The poly(levoglucosenol) is thermally stable up to ~220 ℃, amorphous, and is exhibiting a relatively high glass transition temperature of ~100 ℃. The poly(levoglucosenol) can be converted to a transparent film, resembling common plastic, and was found to degrade in a moist acidic environment. This means that poly(levoglucosenol) may find its use as an alternative to conventional plastic, for instance, polystyrene. Levoglucosenol was also converted into levoglucosenyl methyl ether, which was polymerized by cationic ring-opening metathesis polymerization (CROP). Polymers were obtained with molar masses up to ~36 kg/mol. These polymers are thermally stable up to ~220 ℃ and are semi-crystalline thermoplastics, having a glass transition temperature of ~35 ℃ and melting transition of 70-100 ℃. Additionally, the polymers underwent cross-linking, hydrogenation and thiol-ene click chemistry.}, language = {en} } @phdthesis{Zarafshani2012, author = {Zarafshani, Zoya}, title = {Chain-end functionalization and modification of polymers using modular chemical reactions}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-59723}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {Taking advantage of ATRP and using functionalized initiators, different functionalities were introduced in both α and ω chain-ends of synthetic polymers. These functionalized polymers could then go through modular synthetic pathways such as click cycloaddition (copper-catalyzed or copper-free) or amidation to couple synthetic polymers to other synthetic polymers, biomolecules or silica monoliths. Using this general strategy and designing these co/polymers so that they are thermoresponsive, yet bioinert and biocompatible with adjustable cloud point values (as it is the case in the present thesis), the whole generated system becomes "smart" and potentially applicable in different branches. The applications which were considered in the present thesis were in polymer post-functionalization (in situ functionalization of micellar aggregates with low and high molecular weight molecules), hydrophilic/hydrophobic tuning, chromatography and bioconjugation (enzyme thermoprecipitation and recovery, improvement of enzyme activity). Different α-functionalized co/polymers containing cholesterol moiety, aldehyde, t-Boc protected amine, TMS-protected alkyne and NHS-activated ester were designed and synthesized in this work.}, language = {en} } @phdthesis{Sapei2007, author = {Sapei, Lanny}, title = {Characterisation of silica in Equisetum hyemale and its transformation into biomorphous ceramics}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-15883}, school = {Universit{\"a}t Potsdam}, year = {2007}, abstract = {Equisetum spp. (horsetail / "Schachtelhalm") is the only surviving genus of the primitive Sphenopsids vascular plants which reached their zenith during the Carboniferous era. It is an herbaceous plant and is distinguished by jointed stems with fused whorl of nodal leaves. The plant has been used for scouring kitchen utensils and polishing wood during the past time due to its high silica encrustations in the epidermis. Equisetum hyemale (scouring rush) can accumulate silica up to 16\% dry weight in its tissue, which makes this plant an interesting candidate as a renewable resource of silica for the synthesis of biomorphous ceramics. The thesis comprises a comprehensive experimental study of silica accumulations in E.hyemale using different characterisation techniques at all hierarchical levels. The obtained results shed light on the local distribution, chemical form, crystallinity, and nanostructure of biogenic silica in E.hyemale which were quite unclear until now. Furthermore, isolation of biogenic silica from E.hyemale to obtain high grade mesoporous silica with high purity is investigated. Finally, syntheses of silicon carbide (b-SiC) by a direct thermoconversion process of E.hyemale is attempted, which is a promising material for high performance ceramics. It is found that silica is deposited continuously on the entire epidermal layer with the highest concentration on the knobs. The highest silicon content is at the knob tips (≈ 33\%), followed by epidermal flank (≈ 17\%), and inner lower knob (≈ 6\%), whereas there is almost no silicon found in the interior parts. Raman spectroscopy reveals the presence of at least two silica modifications in E.hyemale. The first type is pure hydrated amorphous silica restricted to the knob tips. The second type is accumulated on the entire continuous outer layer adjacent to the epidermis cell walls. It is lacking silanol groups and is intimately associated with polysaccharides (cellulose, hemicellulose, pectin) and inorganic compounds. Silica deposited in E.hyemale is found to be mostly amorphous with almost negligible amounts of crystalline silica in the form of a-quartz (< 7\%). The silica primary particles have a plate-like shape with a thickness of about 2 nm. Pure mesoporous amorphous silica with an open surface area up to 400 m2/g can be obtained from E.hyemale after leaching the plant with HCl to remove the inorganic impurities followed by a calcination treatment. The optimum calcination temperature appears to be around 500°C. Calcination of untreated E.hyemale causes a collapse of the biogenic silica structure which is mainly attributed to the detrimental action of alkali ions present in the native plant. Finally, pure b-SiC with a surface area of about 12 m2/g is obtained upon direct pyrolysis of HCl-treated E.hyemale samples in argon atmosphere. The original structure of native E.hyemale is substantially retained in the biomorphous b-SiC. The results of this thesis lead to a better understanding of the silicification process and allow to draw conclusions about the role of silica in E.hyemale. In particular, a templating role of the plant biopolymers for the synthesis of the nanostructured silica within the plant body can be deduced. Moreover, the high grade ultrafine amorphous silica isolated from E.hyemale promises applications as adsorbent and catalyst support and as silica source for the fabrication of silica-based composites. The synthesis of biomorphous b-SiC from sustainable and low-cost E.hyemale is still in its initial stage. The present thesis demonstrates the principal possibility of carbothermal synthesis of SiC from E.hyemale with the prospect of potential applications, for instance as refractory materials, catalyst supports, or high performance advanced ceramics.}, language = {en} } @phdthesis{Schneider2012, author = {Schneider, Julia}, title = {Characterisation of single and multibubble cavitation through analysis of molecular, atomic and ionic line emissions}, address = {Potsdam}, pages = {117 S.}, year = {2012}, language = {en} } @phdthesis{BahrkeEinarssonGislasonetal.2003, author = {Bahrke, Sven and Einarsson, Jon M. and Gislason, Johannes and Haebel, Sophie and Peter-Katalinic, Jasna and Peter, Martin G.}, title = {Characterization of chitooligosaccharides by mass spectrometry}, isbn = {82-47-15901-5}, year = {2003}, language = {en} } @phdthesis{Qin2019, author = {Qin, Qing}, title = {Chemical functionalization of porous carbon-based materials to enable novel modes for efficient electrochemical N2 fixation}, doi = {10.25932/publishup-44339}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-443397}, school = {Universit{\"a}t Potsdam}, pages = {146}, year = {2019}, abstract = {The central motivation of the thesis was to provide possible solutions and concepts to improve the performance (e.g. activity and selectivity) of electrochemical N2 reduction reaction (NRR). Given that porous carbon-based materials usually exhibit a broad range of structural properties, they could be promising NRR catalysts. Therefore, the advanced design of novel porous carbon-based materials and the investigation of their application in electrocatalytic NRR including the particular reaction mechanisms are the most crucial points to be addressed. In this regard, three main topics were investigated. All of them are related to the functionalization of porous carbon for electrochemical NRR or other electrocatalytic reactions. In chapter 3, a novel C-TixOy/C nanocomposite has been described that has been obtained via simple pyrolysis of MIL-125(Ti). A novel mode for N2 activation is achieved by doping carbon atoms from nearby porous carbon into the anion lattice of TixOy. By comparing the NRR performance of M-Ts and by carrying out DFT calculations, it is found that the existence of (O-)Ti-C bonds in C-doped TixOy can largely improve the ability to activate and reduce N2 as compared to unoccupied OVs in TiO2. The strategy of rationally doping heteroatoms into the anion lattice of transition metal oxides to create active centers may open many new opportunities beyond the use of noble metal-based catalysts also for other reactions that require the activation of small molecules as well. In chapter 4, a novel catalyst construction composed of Au single atoms decorated on the surface of NDPCs was reported. The introduction of Au single atoms leads to active reaction sites, which are stabilized by the N species present in NDPCs. Thus, the interaction within as-prepared AuSAs-NDPCs catalysts enabled promising performance for electrochemical NRR. For the reaction mechanism, Au single sites and N or C species can act as Frustrated Lewis pairs (FLPs) to enhance the electron donation and back-donation process to activate N2 molecules. This work provides new opportunities for catalyst design in order to achieve efficient N2 fixation at ambient conditions by utilizing recycled electric energy. The last topic described in chapter 5 mainly focused on the synthesis of dual heteroatom-doped porous carbon from simple precursors. The introduction of N and B heteroatoms leads to the construction of N-B motives and Frustrated Lewis pairs in a microporous architecture which is also rich in point defects. This can improve the strength of adsorption of different reactants (N2 and HMF) and thus their activation. As a result, BNC-2 exhibits a desirable electrochemical NRR and HMF oxidation performance. Gas adsorption experiments have been used as a simple tool to elucidate the relationship between the structure and catalytic activity. This work provides novel and deep insights into the rational design and the origin of activity in metal-free electrocatalysts and enables a physically viable discussion of the active motives, as well as the search for their further applications. Throughout this thesis, the ubiquitous problems of low selectivity and activity of electrochemical NRR are tackled by designing porous carbon-based catalysts with high efficiency and exploring their catalytic mechanisms. The structure-performance relationships and mechanisms of activation of the relatively inert N2 molecules are revealed by either experimental results or DFT calculations. These fundamental understandings pave way for a future optimal design and targeted promotion of NRR catalysts with porous carbon-based structure, as well as study of new N2 activation modes.}, language = {en} } @phdthesis{Giusto2020, author = {Giusto, Paolo}, title = {Chemical vapor deposition of carbon-based thin films}, school = {Universit{\"a}t Potsdam}, pages = {165}, year = {2020}, language = {en} } @phdthesis{Appajaiah2004, author = {Appajaiah, Anilkumar}, title = {Climatic stability of polymer optical fibers (POF)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0001661}, school = {Universit{\"a}t Potsdam}, year = {2004}, abstract = {Optische Polymerfasern stellen ein relativ neues Medium zur Hochgeschwindigkeitsdaten{\"u}bertragung mittels moduliertem Licht dar. Sie gestatten die Verbreitung großer Datenmengen {\"u}ber Entfernungen bis zu ca. 100 m, ohne eine Beeinflussung durch externe elektromagnetischen Feldern. Jedoch reagieren die Fasern und somit auch ihre optischen Eigenschaften aufgrund des organischchemischen Faseraufbaus empfindlich auf das Klima ihrer Umgebung. Die Ursachen f{\"u}r die Abnahme der optischen Transmission aufgrund von klimatischen Einfl{\"u}ssen (Alterung, Degradation) werden mittels chemisch analytischer Verfahren wie Chemilumineszenz (CL) und Fourier Transform Infrarot (FTIR) Spektroskopie untersucht. Dabei kommen f{\"u}nf, von verschiedenen Herstellern bezogene, Multimode- POFs aus PMMA in sieben verschiedenen Klimaten zum Einsatz. Drei dieser f{\"u}nf POFs werden genauer untersucht, um den Einfluss einzelner Parameter festzustellen und optische Langzeitstabilit{\"a}t aufgrund von Kurzzeittests vorherzusagen. Als erstes erfolgt eine Kennzeichnung unbeanspruchter POF Komponenten (Kern, Mantel und nackte POF als Kombination von Kern und Mantel) {\"u}ber ihre physikalischen und chemischen Eigenschaften. Die Glas- und die Schmelztemperaturen liegen im Bereich von 120 °C bis 140 °C, das Molekulargewicht des Kerns bei gr{\"o}ßenordnungsm{\"a}ßig 105 g mol-1 ;. FTIR-Messungen zeigen zwar Unterschiede in der chemischen Zusammensetzung der M{\"a}ntel aber keine Unterschiede bei den Kernen. Bei zwei der POF Proben , die als Kabel (Kern, Mantel und Schutzh{\"u}lle) f{\"u}r 3300 Stunden einem Klima aus 92 °C und 95 \% relativer Feuchte (r.F.) ausgesetzt waren, verringern sich daraufhin die optische Transmissionen in unterschiedlicher Weise. Die Untersuchung der zugeh{\"o}rigen nackten POFs mittels CL, FTIR, Thermogravimetrie (TG), UV/VIS und Gel Permeation Chromatographie (GPC) l{\"a}sst eine st{\"a}rkere Sch{\"a}digung der M{\"a}ntel als der Kerne vermuten. Wahrscheinlich f{\"u}hrt eine starke Manteldegradation zu einer erh{\"o}hten Absorption und Fehlstellen im Mantel und damit zu einer Transmissionsabnahme. Daher scheint die optische Stabilit{\"a}t der POF st{\"a}rker durch die thermo-oxidative Stabilit{\"a}t des Mantels bestimmt zu sein als durch die des Kernes. Drei nackte POFs (Kern und Mantel) sind unterschiedlich lang (30 Stunden bis 3000 Stunden) folgenden Klimaten ausgesetzt: 92 °C / 95 \% r.F., 92 °C / 50 \% r.F., 50 °C / 95 \% r.F., 90 °C / geringe Feuchte, 100 °C / geringe Feuchte, 110 °C / geringe Feuchte and 120 °C / geringe Feuchte. Auch in diesen Klimaten ergaben sich probenbedingte unterschiedliche Transmissions{\"a}nderungen. Die Ergebnisse deuten stark darauf hin, dass bei gleichzeitig hoher Temperatur und hoher Feuchte physikalische {\"A}nderungen wie die Volumenausdehnung die Hauptursachen f{\"u}r die Abnahme der optischen Transmission bilden. Ein weiterer Einflussfaktor ist die chemische Zusammensetzung der M{\"a}ntel. Bei Kombination von hoher Temperatur und geringer Feuchte erzeugen in den Anfangsstadien der Alterung physikalische {\"A}nderungen Transmissionsabnahmen, vermutlich entstehen Fehlstellen in der Kern-Mantel-Grenzschicht. Hinzukommen in den sp{\"a}teren Stadien wahrscheinlich zunehmende Lichtabsorption in Kern und Mantel. L. Jankowski (Doktorand in der BAM) best{\"a}tigt diese Annahme durch parallel ausgef{\"u}hrte optische Simulationsrechnungen. Auch f{\"u}r nackte POFs scheint also die thermo-oxidative Stabilit{\"a}t die optische Stabilit{\"a}t zu bestimmen. Kurzzeitalterungstests sollen Aufschluss {\"u}ber den Einfluss individueller Klimaparameter auf die POF Eigenschaften geben. Es zeigt sich bei dauerhaft hoher Temperatur und variabler Feuchte aufgrund des physikalisch absorbierten Wassers bis zu einem gewissen Grad ein reversibles Verhalten des Transmissionsverlustes. Dieses Verhalten tritt aber nur kaum merkbar auf, wenn bei konstanter hoher Feuchte die Temperatur variiert wird. Bei Raumtemperatur und variabler Feuchte stellt sich jedoch ein voll reversibles Verhalten des Transmissionsverlustes ein. Die hier beschriebenen Untersuchungen sind als Ausgangspunkt f{\"u}r weitergehende Forschungen zu verstehen. Die begrenzte Zurverf{\"u}gungstellung von POF Basisdaten durch die Hersteller und der zeitaufwendige klimabedingte Alterungsprozess beschr{\"a}nken die Ergebnisse mehr oder weniger auf die untersuchten Proben. Signifikante allgemeine Aussagen erfordern aber beispielsweise zus{\"a}tzliche statistische Daten der Produktionsschwankungen von POF Eigenschaften. Dennoch besitzen die hier beschriebenen Tests das Potential f{\"u}r eine Ann{\"a}herung an die optische Langzeitstabilit{\"a}t und deren Vorhersage.}, language = {en} } @phdthesis{Dechtrirat2013, author = {Dechtrirat, Decha}, title = {Combination of self-assembled monolayers (SAMs) and molecularly imprinted polymers (MIPs) in biomimetic sensors}, address = {Potsdam}, pages = {107 S.}, year = {2013}, language = {en} } @phdthesis{Jelicic2011, author = {Jelicic, Aleksandra}, title = {Combining polymethacrylates and ionic liquids : a way to create and understand}, address = {Potsdam}, pages = {161 S.}, year = {2011}, language = {en} } @phdthesis{Frank2023, author = {Frank, Bradley D.}, title = {Complex and adaptive soft colloids}, school = {Universit{\"a}t Potsdam}, pages = {XIV, 154}, year = {2023}, language = {en} } @phdthesis{Gentsch2010, author = {Gentsch, Rafael}, title = {Complex bioactive fiber systems by means of electrospinning}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-44900}, school = {Universit{\"a}t Potsdam}, year = {2010}, abstract = {Nanofibrous mats are interesting scaffold materials for biomedical applications like tissue engineering due to their interconnectivity and their size dimension which mimics the native cell environment. Electrospinning provides a simple route to access such fiber meshes. This thesis addresses the structural and functional control of electrospun fiber mats. In the first section, it is shown that fiber meshes with bimodal size distribution could be obtained in a single-step process by electrospinning. A standard single syringe set-up was used to spin concentrated poly(ε-caprolactone) (PCL) and poly(lactic-co-glycolic acid) (PLGA) solutions in chloroform and meshes with bimodal-sized fiber distribution could be directly obtained by reducing the spinning rate at elevated humidity. Scanning electron microscopy (SEM) and mercury porosity of the meshes suggested a suitable pore size distribution for effective cell infiltration. The bimodal fiber meshes together with unimodal fiber meshes were evaluated for cellular infiltration. While the micrometer fibers in the mixed meshes generate an open pore structure, the submicrometer fibers support cell adhesion and facilitate cell bridging on the large pores. This was revealed by initial cell penetration studies, showing superior ingrowth of epithelial cells into the bimodal meshes compared to a mesh composed of unimodal 1.5 μm fibers. The bimodal fiber meshes together with electrospun nano- and microfiber meshes were further used for the inorganic/organic hybrid fabrication of PCL with calcium carbonate or calcium phosphate, two biorelevant minerals. Such composite structures are attractive for the potential improvement of properties such as stiffness or bioactivity. It was possible to encapsulate nano and mixed sized plasma-treated PCL meshes to areas > 1 mm2 with calcium carbonate using three different mineralization methods including the use of poly(acrylic acid). The additive seemed to be useful in stabilizing amorphous calcium carbonate to effectively fill the space between the electrospun fibers resulting in composite structures. Micro-, nano- and mixed sized fiber meshes were successfully coated within hours by fiber directed crystallization of calcium phosphate using a ten-times concentrated simulated body fluid. It was shown that nanofibers accelerated the calcium phosphate crystallization, as compared to microfibers. In addition, crystallizations performed at static conditions led to hydroxyapatite formations whereas in dynamic conditions brushite coexisted. In the second section, nanofiber functionalization strategies are investigated. First, a one-step process was introduced where a peptide-polymer-conjugate (PLLA-b-CGGRGDS) was co-spun with PLGA in such a way that the peptide is enriched on the surface. It was shown that by adding methanol to the chloroform/blend solution, a dramatic increase of the peptide concentration at the fiber surface could be achieved as determined by X-ray photoelectron spectroscopy (XPS). Peptide accessibility was demonstrated via a contact angle comparison of pure PLGA and RGD-functionalized fiber meshes. In addition, the electrostatic attraction between a RGD-functionalized fiber and a silica bead at pH ~ 4 confirmed the accessibility of the peptide. The bioactivity of these RGD-functionalized fiber meshes was demonstrated using blends containing 18 wt\% bioconjugate. These meshes promoted adhesion behavior of fibroblast compared to pure PLGA meshes. In a second functionalization approach, a modular strategy was investigated. In a single step, reactive fiber meshes were fabricated and then functionalized with bioactive molecules. While the electrospinning of the pure reactive polymer poly(pentafluorophenyl methacrylate) (PPFPMA) was feasible, the inherent brittleness of PPFPMA required to spin a PCL blend. Blends and pure PPFPMA showed a two-step functionalization kinetics. An initial fast reaction of the pentafluorophenyl esters with aminoethanol as a model substance was followed by a slow conversion upon further hydrophilization. This was analysed by UV/Vis-spectroscopy of the pentaflurorophenol release upon nucleophilic substitution with the amines. The conversion was confirmed by increased hydrophilicity of the resulting meshes. The PCL/PPFPMA fiber meshes were then used for functionalization with more complex molecules such as saccharides. Aminofunctionalized D-Mannose or D-Galactose was reacted with the active pentafluorophenyl esters as followed by UV/Vis spectroscopy and XPS. The functionality was shown to be bioactive using macrophage cell culture. The meshes functionalized with D-Mannose specifically stimulated the cytokine production of macrophages when lipopolysaccharides were added. This was in contrast to D-Galactose- or aminoethanol-functionalized and unfunctionalized PCL/PPFPMA fiber mats.}, language = {en} } @phdthesis{Belova2010, author = {Belova, Valentina}, title = {Composite fabrication and surface modification via high intensity ultrasound}, address = {Potsdam}, pages = {113, XII S. : zahlr. Ill. und graph. Darst.}, year = {2010}, language = {en} } @phdthesis{Rusu2004, author = {Rusu, Viorel Marin}, title = {Composite materials made of chitosan and nanosized apatite : preparation and physicochemical characterization}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-2316}, school = {Universit{\"a}t Potsdam}, year = {2004}, abstract = {Taking inspiration from nature, where composite materials made of a polymer matrix and inorganic fillers are often found, e.g. bone, shell of crustaceans, shell of eggs, etc., the feasibility on making composite materials containing chitosan and nanosized hydroxyapatite were investigated. A new preparation approach based on a co-precipitation method has been developed. In its earlier stage of formation, the composite occurs as hydrogel as suspended in aqueous alkaline solution. In order to get solid composites various drying procedures including freeze-drying technique, air-drying at room temperature and at moderate temperatures, between 50oC and 100oC were used. Physicochemical studies showed that the composites exhibit different properties with respect to their structure and composition. IR and Raman spectroscopy probed the presence of both chitosan and hydroxyapatite in the composites. Hydroxyapatite as dispersed in the chitosan matrix was found to be in the nanosize range (15-50 nm) and occurs in a bimodal distribution with respect to its crystallite length. Two types of distribution domains of hydroxyapatite crystallites in the composite matrix such as cluster-like (200-400 nm) and scattered-like domains were identified by the transmission electron microscopy (TEM), X-ray diffraction (XRD) and by confocal scanning laser microscopy (CSLM) measurements. Relaxation NMR experiments on composite hydrogels showed the presence of two types of water sites in their gel networks, such as free and bound water. Mechanical tests showed that the mechanical properties of composites are one order of magnitude less than those of compact bone but comparable to those of porous bone. The enzymatic degradation rates of composites showed slow degradation processes. The yields of degradation were estimated to be less than 10\% by loss of mass, after incubation with lysozyme, for a period of 50 days. Since the composite materials were found biocompatible by the in vivo tests, the simple mode of their fabrication and their properties recommend them as potential candidates for the non-load bearing bone substitute materials.}, language = {en} } @phdthesis{Pimthon2009, author = {Pimthon, Jutarat}, title = {Computational modeling of anionic and zwitterionic lipid bilayers for investigating interfacial activities of antimicrobial peptide NK-2}, address = {Potsdam}, pages = {151 S.}, year = {2009}, language = {en} } @phdthesis{You2017, author = {You, Zewang}, title = {Conformational transition of peptide-functionalized cryogels enabling shape-memory capability}, school = {Universit{\"a}t Potsdam}, pages = {144}, year = {2017}, language = {en} } @phdthesis{Kossmann2021, author = {Kossmann, Janina}, title = {Controlled condensation to functional materials - synergetic effect of nitrogen content and pore structure}, doi = {10.25932/publishup-53693}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-536935}, school = {Universit{\"a}t Potsdam}, pages = {vi, 148}, year = {2021}, abstract = {The development and optimization of carbonaceous materials is of great interest for several applications including gas sorption, electrochemical storage and conversion, or heterogeneous catalysis. In this thesis, the exploration and optimization of nitrogen containing carbonaceous materials by direct condensation of smart chosen, molecular precursors will be presented. As suggested with the concept of noble carbons, the choice of a stable, nitrogen-containing precursor will lead to an even more stable, nitrogen doped carbonaceous material with a controlled structure and electronic properties. Molecules fulfilling this requirement are for example nucleobases. The direct condensation of nucleobases leads to highly nitrogen containing carbonaceous materials without any further post or pretreatment. By using salt melt templating, pore structure adjustment is possible without the use of hazardous or toxic reagents and the template can be reused. Using these simple tools, the synergetic effect of the pore structure and nitrogen content of the materials can be explored. Within this thesis, the influence of the condensation parameters will be correlated to the structure and performance of the materials. First, the influence of the condensation temperature to the porosity and nitrogen content of guanine will be discussed and the exploration of highly CO2 selective structural pores in C1N1 materials will be shown. Further tuning the pore structure of the materials by salt melt templating will be then explored, the potential of the prepared materials as heterogeneous catalysts and their basic catalytic strength will be correlated to their nitrogen content and pore morphology. A similar approach is used to explore the water sorption behavior of uric acid derived carbonaceous materials as potential sorbents for heat transformation applications. Changes in maximum water uptake and hydrophilicity of the prepared materials will be correlated to the nitrogen content and pore architecture. Due to the high thermal stability, porosity, and nitrogen content of ionic liquid derived nitrogen doped carbonaceous materials, a simple impregnation and calcination route can be conducted to obtain copper nano cluster decorated nitrogen-doped carbonaceous materials. The activity as catalyst for the oxygen reduction reaction of the obtained materials will be shown and structure performance relations are discussed. In conclusion, the versatility of nitrogen doped carbonaceous materials with a nitrogen to carbon ratio of up to one will be shown. The possibility to tune the pore structure as well as the nitrogen content by using a simple procedure including salt melt templating as well as the use of molecular precursors and their effect on the performance will be discussed.}, language = {en} } @phdthesis{Cheng2018, author = {Cheng, Xiao}, title = {Controlled solvent vapor annealing of block copolymer films}, doi = {10.25932/publishup-42417}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-424179}, school = {Universit{\"a}t Potsdam}, pages = {X, 166}, year = {2018}, abstract = {This project was focused on exploring the phase behavior of poly(styrene)187000-block-poly(2-vinylpyridine)203000 (SV390) with high molecular weight (390 kg/mol) in thin films, in which the self-assembly of block copolymers (BCPs) was realized via thermo-solvent annealing. The advanced processing technique of solvent vapor treatment provides controlled and stable conditions. In Chapter 3, the factors to influence the annealing process and the swelling behavior of homopolymers are presented and discussed. The swelling behavior of BCP in films is controlled by the temperature of the vapor and of the substrate, on one hand, and variation of the saturation of the solvent vapor atmosphere (different solvents), on the other hand. Additional factors like the geometry and material of the chamber, the type of flow inside the chamber etc. also influence the reproducibility and stability of the processing. The slightly selective solvent vapor of chloroform gives 10\% more swelling of P2VP than PS in films with thickness of ~40 nm. The tunable morphology in ultrathin films of high molecular weight BCP (SV390) was investigated in Chapter 4. First, the swelling behavior can be precisely tuned by temperature and/or vapor flow separately, which provided information for exploring the multiple-parameter-influenced segmental chain mobility of polymer films. The equilibrium state of SV390 in thin films influenced by temperature was realized at various temperatures with the same degree of swelling. Various methods including characterization with SFM, metallization and RIE were used to identify the morphology of films as porous half-layer with PS dots and P2VP matrix. The kinetic investigations demonstrate that on substrates with either weak or strong interaction the original morphology of the BCP with high molecular weight is changed very fast within 5 min, and the further annealing serves for annihilation of defects. The morphological development of symmetric BCP in films with thickness increasing from half-layer to one-layer influenced by confinement factors of gradient film thicknesses and various surface properties of substrates was studied in Chapter 5. SV390 and SV99 films show bulk lamella-forming morphology after slightly selective solvent vapor (chloroform) treatment. SV99 films show cylinder-forming morphology under strongly selective solvent vapor (toluene) treatment since the asymmetric structure (caused by toluene uptake in PS blocks only) of SV99 block copolymer during annealing. Both kinds of morphology (lamella and cylinder) are influenced by the film thickness. The annealed morphology of SV390 and SV99 influenced by the combination of confined film and substrate property is similar to the morphology on flat silicon wafers. In this chapter the gradients in the film thickness and surface properties of the substrates with regard to their influence on the morphological development in thin BCP films are presented. Directed self-assembly (graphoepitaxy) of this SV390 was also investigated to compare with systematically reported SV99. In Chapter 6 an approach to induced oriented microphase separation in thick block copolymer films via treatment with the oriented vapor flow using mini-extruder is envisaged to be an alternative to existing methodologies, e.g. via non-solvent-induced phase separation. The preliminary tests performed in this study confirm potential perspective of this method, which alters the structure through the bulk of the film (as revealed by SAXS measurements), but more detailed studies have to be conducted in order to optimize the preparation.}, language = {en} } @phdthesis{IbarzRic2003, author = {Ibarz-Ric, Gemma}, title = {Controlling internal structure and permeability of polyelectrolyte multilayer microcapsules}, pages = {96 S.}, year = {2003}, language = {en} } @phdthesis{Moeller2010, author = {M{\"o}ller, El{\´e}onore}, title = {Copolymerizations of vinylidene fluoride and hexafluoropropene in supercritical carbon dioxide (scCO2)}, address = {Potsdam}, pages = {121 S. : graph. Darst.}, year = {2010}, language = {en} } @phdthesis{Bastian2022, author = {Bastian, Philipp U.}, title = {Core-shell upconversion nanoparticles - investigation of dopant intermixing and surface modification}, doi = {10.25932/publishup-55160}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-551607}, school = {Universit{\"a}t Potsdam}, pages = {XII, 108, xxiii}, year = {2022}, abstract = {Frequency upconversion nanoparticles (UCNPs) are inorganic nanocrystals capable to up-convert incident photons of the near-infrared electromagnetic spectrum (NIR) into higher energy photons. These photons are re-emitted in the range of the visible (Vis) and even ultraviolet (UV) light. The frequency upconversion process (UC) is realized with nanocrystals doped with trivalent lanthanoid ions (Ln(III)). The Ln(III) ions provide the electronic (excited) states forming a ladder-like electronic structure for the Ln(III) electrons in the nanocrystals. The absorption of at least two low energy photons by the nanoparticle and the subsequent energy transfer to one Ln(III) ion leads to the promotion of one Ln(III) electron into higher excited electronic states. One high energy photon will be emitted during the radiative relaxation of the electron in the excited state back into the electronic ground state of the Ln(III) ion. The excited state electron is the result of the previous absorption of at least two low energy photons. The UC process is very interesting in the biological/medical context. Biological samples (like organic tissue, blood, urine, and stool) absorb high-energy photons (UV and blue light) more strongly than low-energy photons (red and NIR light). Thanks to a naturally occurring optical window, NIR light can penetrate deeper than UV light into biological samples. Hence, UCNPs in bio-samples can be excited by NIR light. This possibility opens a pathway for in vitro as well as in vivo applications, like optical imaging by cell labeling or staining of specific organic tissue. Furthermore, early detection and diagnosis of diseases by predictive and diagnostic biomarkers can be realized with bio-recognition elements being labeled to the UCNPs. Additionally, "theranostic" becomes possible, in which the identification and the treatment of a disease are tackled simultaneously. For this to succeed, certain parameters for the UCNPs must be met: high upconversion efficiency, high photoluminescence quantum yield, dispersibility, and dispersion stability in aqueous media, as well as availability of functional groups to introduce fast and easy bio-recognition elements. The UCNPs used in this work were prepared with a solvothermal decomposition synthesis yielding in particles with NaYF4 or NaGdF4 as host lattice. They have been doped with the Ln(III) ions Yb3+ and Er3+, which is only one possible upconversion pair. Their upconversion efficiency and photoluminescence quantum yield were improved by adding a passivating shell to reduce surface quenching. However, the brightness of core-shell UCNPs stays behind the expectations compared to their bulk material (being at least μm-sized particles). The core-shell structures are not clearly separated from each other, which is a topic in literature. Instead, there is a transition layer between the core and the shell structure, which relates to the migration of the dopants within the host lattice during the synthesis. The ion migration has been examined by time-resolved laser spectroscopy and the interlanthanoid resonance energy transfer (LRET) in the two different host lattices from above. The results are presented in two publications, which dealt with core-shell-shell structured nanoparticles. The core is doped with the LRET-acceptor (either Nd3+ or Pr3+). The intermediate shell serves as an insulation shell of pure host lattice material, whose shell thickness has been varied within one set of samples having the same composition, so that the spatial separation of LRET-acceptor and -donor changes. The outer shell with the same host lattice is doped with the LRET-donor (Eu3+). The effect of the increasing insulation shell thickness is significant, although the LRET cannot be suppressed completely. Next to the Ln(III) migration within a host lattice, various phase transfer reactions were investigated in order to subsequently perform surface modifications for bioapplications. One result out of this research has been published using a promising ligand, that equips the UCNP with bio-modifiable groups and has good potential for bio-medical applications. This particular ligand mimics natural occurring mechanisms of mussel protein adhesion and of blood coagulation, which is why the UCNPs are encapsulated very effectively. At the same time, bio-functional groups are introduced. In a proof-of-concept, the encapsulated UCNP has been coupled successfully with a dye (which is representative for a biomarker) and the system's photoluminescence properties have been investigated.}, language = {en} } @phdthesis{Eren2024, author = {Eren, Enis Oğuzhan}, title = {Covalent anode materials for high-energy sodium-ion batteries}, doi = {10.25932/publishup-62258}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-622585}, school = {Universit{\"a}t Potsdam}, pages = {xi, 153}, year = {2024}, abstract = {The reliance on fossil fuels has resulted in an abnormal increase in the concentration of greenhouse gases, contributing to the global climate crisis. In response, a rapid transition to renewable energy sources has begun, particularly lithium-ion batteries, playing a crucial role in the green energy transformation. However, concerns regarding the availability and geopolitical implications of lithium have prompted the exploration of alternative rechargeable battery systems, such as sodium-ion batteries. Sodium is significantly abundant and more homogeneously distributed in the crust and seawater, making it easier and less expensive to extract than lithium. However, because of the mysterious nature of its components, sodium-ion batteries are not yet sufficiently advanced to take the place of lithium-ion batteries. Specifically, sodium exhibits a more metallic character and a larger ionic radius, resulting in a different ion storage mechanism utilized in lithium-ion batteries. Innovations in synthetic methods, post-treatments, and interface engineering clearly demonstrate the significance of developing high-performance carbonaceous anode materials for sodium-ion batteries. The objective of this dissertation is to present a systematic approach for fabricating efficient, high-performance, and sustainable carbonaceous anode materials for sodium-ion batteries. This will involve a comprehensive investigation of different chemical environments and post-modification techniques as well. This dissertation focuses on three main objectives. Firstly, it explores the significance of post-synthetic methods in designing interfaces. A conformal carbon nitride coating is deposited through chemical vapor deposition on a carbon electrode as an artificial solid-electrolyte interface layer, resulting in improved electrochemical performance. The interaction between the carbon nitride artificial interface and the carbon electrode enhances initial Coulombic efficiency, rate performance, and total capacity. Secondly, a novel process for preparing sulfur-rich carbon as a high-performing anode material for sodium-ion batteries is presented. The method involves using an oligo-3,4-ethylenedioxythiophene precursor for high sulfur content hard carbon anode to investigate the sulfur heteroatom effect on the electrochemical sodium storage mechanism. By optimizing the condensation temperature, a significant transformation in the materials' nanostructure is achieved, leading to improved electrochemical performance. The use of in-operando small-angle X-ray scattering provides valuable insights into the interaction between micropores and sodium ions during the electrochemical processes. Lastly, the development of high-capacity hard carbon, derived from 5-hydroxymethyl furfural, is examined. This carbon material exhibits exceptional performance at both low and high current densities. Extensive electrochemical and physicochemical characterizations shed light on the sodium storage mechanism concerning the chemical environment, establishing the material's stability and potential applications in sodium-ion batteries.}, language = {en} } @phdthesis{ElamparuthiLinkerKellingetal.2009, author = {Elamparuthi, Elangovan and Linker, Torsten and Kelling, Alexandra and Schilde, Uwe}, title = {Crystal structure of methyl 3,4,6-tri-O-benzyl-2-deoxy-2-C-nitromethyl-beta-D-galactopyranoside, C29H33NO7}, issn = {1433-7266}, doi = {10.1524/ncrs.2009.0054}, year = {2009}, language = {en} } @phdthesis{Montenegro2003, author = {Montenegro, Rivelino V. D.}, title = {Crystallization, biomimetics and semiconducting polymers in confined systems}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0000726}, school = {Universit{\"a}t Potsdam}, year = {2003}, abstract = {popul{\"a}rwissenschaftlicher Abstract: Kristallisation, Biomimetik und halbleitende Polymere in r{\"a}umlich begrenzten Systemen: {\"O}l und Wasser mischen sich nicht, man kann aber aus beiden Fl{\"u}ssigkeiten Emulsionen herstellen, bei denen Tr{\"o}pfchen der einen Fl{\"u}ssigkeit in der anderen Fl{\"u}ssigkeit vorliegen. Das heißt, es k{\"o}nnen entweder {\"O}ltr{\"o}pfchen in Wasser oder Wassertr{\"o}pfchen in {\"O}l erzeugt werden. Aus t{\"a}glichen Erfahrungen, z.B. beim Kochen weiß man jedoch, dass sich eine Emulsion durch Sch{\"u}tteln oder R{\"u}hren herstellen l{\"a}sst, diese jedoch nicht besonders stabil ist. Mit Hilfe von hohen Scherenergien kann man nun sehr kleine, in ihrer Gr{\"o}ße sehr einheitliche und außerdem sehr stabile Tr{\"o}pfchen von 1/10000 mm erhalten. Eine solche Emulsion wird Miniemulsion genannt. In der Dissertation wurden nun z.B. Miniemulsionen untersucht, die aus kleinen Wassertr{\"o}pfchen in einem {\"O}l bestehen. Es konnte gezeigt werden, dass das Wasser in diesen Tr{\"o}pfchen, also in den r{\"a}umlich begrenzten Systemen, nicht bei 0 \&\#176;C, sondern bei -22 \&\#176;C kristallisierte. Wie l{\"a}sst sich das erkl{\"a}ren? Wenn man einen Eimer Wasser hat, dann bildet sich normalerweise bei 0 \&\#176;C Eis, da n{\"a}mlich in dem Wasser einige (manchmal ganz wenige) Keime (z.B. Schutzteilchen, ein Fussel etc.) vorhanden sind, an denen sich die ersten Kristalle bilden. Wenn sich dann einmal ein Kristall gebildet hat, kann das Wasser im gesamten Eimer schnell zu Eis werden. Ultrareines Wasser w{\"u}rde bei -22 \&\#176;C kristallisieren. Wenn man jetzt die Menge Wasser aus dem Eimer in kleine Tr{\"o}pfchen bringt, dann hat man eine sehr, sehr große Zahl, n{\"a}mlich 1017 Tr{\"o}pfchen, in einem Liter Emulsion vorliegen. Die wenigen Schmutzpartikel verteilen auf sehr wenige Tr{\"o}pfchen, die anderen Tr{\"o}pfchen sind ultrarein. Daher kristallisieren sie erst bei -22 \&\#176;C. Im Rahmen der Arbeit konnte auch gezeigt werden, dass die Miniemulsionen genutzt werden k{\"o}nnen, um kleine Gelatine-Partikel, also Nanogummib{\"a}rchen, herzustellen. Diese Nanogummib{\"a}rchen quellen bei Erh{\"o}hung der Temperatur auf ca. 38 \&\#176;C an. Das kann ausgenutzt werden, um zum Beispiel Medikamente zun{\"a}chst in den Partikeln im menschlichen K{\"o}rper zu transportieren, die Medikamente werden dann an einer gew{\"u}nschten Stelle freigelassen. In der Arbeit wurde auch gezeigt, dass die Gelatine-Partikel genutzt werden k{\"o}nnen, um die Natur nachzuahnen (Biomimetik). Innerhalb der Partikel kann n{\"a}mlich gezielt Knochenmaterial aufgebaut werden kann. Die Gelatine-Knochen-Partikel k{\"o}nnen dazu genutzt werden, um schwer heilende oder komplizierte Knochenbr{\"u}che zu beheben. Gelatine wird n{\"a}mlich nach einigen Tagen abgebaut, das Knochenmaterial kann in den Knochen eingebaut werden. LEDs werden heute bereits vielf{\"a}ltig verwendet. LEDs bestehen aus Halbleitern, wie z.B. Silizium. Neuerdings werden dazu auch halbleitende Polymere eingesetzt. Das große Problem bei diesen Materialien ist, dass sie aus L{\"o}sungsmitteln aufgebracht werden. Im Rahmen der Doktorarbeit wurde gezeigt, dass der Prozess der Miniemulsionen genutzt werden kann, um umweltfreundlich diese LEDs herzustellen. Man stellt dazu nun w{\"a}ssrige Dispersionen mit den Polymerpartikeln her. Damit hat man nicht nur das L{\"o}sungsmittel vermieden, das hat nun noch einen weiteren Vorteil: man kann n{\"a}mlich diese Dispersion auf sehr einfache Art verdrucken, im einfachsten Fall verwendet man einfach einen handels{\"u}blichen Tintenstrahldrucker.}, language = {en} } @phdthesis{Jordan2017, author = {Jordan, Thomas}, title = {CxNy-materials from supramolecular precursors for "All-Carbon" composite materials}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-398855}, school = {Universit{\"a}t Potsdam}, pages = {157}, year = {2017}, abstract = {Among modern functional materials, the class of nitrogen-containing carbons combines non-toxicity and sustainability with outstanding properties. The versatility of this materials class is based on the opportunity to tune electronic and catalytic properties via the nitrogen content and -motifs: This ranges from the electronically conducting N-doped carbon, where few carbon atoms in the graphitic lattice are substituted by nitrogen, to the organic semiconductor graphitic carbon nitride (g-C₃N₄), with a structure based on tri-s-triazine units. In general, composites can reveal outstanding catalytic properties due to synergistic behavior, e.g. the formation of electronic heterojunctions. In this thesis, the formation of an "all-carbon" heterojunction was targeted, i.e. differences in the electronic properties of the single components were achieved by the introduction of different nitrogen motives into the carbon lattice. Such composites are promising as metal-free catalysts for the photocatalytic water splitting. Here, hydrogen can be generated from water by light irradiation with the use of a photocatalyst. As first part of the heterojunction, the organic semiconductor g-C₃N₄ was employed, because of its suitable band structure for photocatalytic water splitting, high stability and non-toxicity. The second part was chosen as C₂N, a recently discovered semiconductor. Compared to g-C₃N₄, the less nitrogen containing C₂N has a smaller band gap and a higher absorption coefficient in the visible light range, which is expected to increase the optical absorption in the composite eventually leading to an enhanced charge carrier separation due to the formation of an electronic heterojunction. The aim of preparing an "all-carbon" composite included the research on appropriate precursors for the respective components g-C₃N₄ and C₂N, as well as strategies for appropriate structuring. This was targeted by applying precursors which can form supramolecular pre-organized structures. This allows for more control over morphology and atom patterns during the carbonization process. In the first part of this thesis, it was demonstrated how the photocatalytic activity of g-C₃N₄ can be increased by the targeted introduction of defects or surface terminations. This was achieved by using caffeine as a "growth stopping" additive during the formation of the hydrogen-bonded supramolecular precursor complexes. The increased photocatalytic activity of the obtained materials was demonstrated with dye degradation experiments. The second part of this thesis was focused on the synthesis of the second component C₂N. Here, a deep eutectic mixture from hexaketocyclohexane and urea was structured using the biopolymer chitosan. This scaffolding resulted in mesoporous nitrogen-doped carbon monoliths and beads. CO₂- and dye-adsorption experiments with the obtained monolith material revealed a high isosteric heat of CO₂-adsorption and showed the accessibility of the monolithic pore system to larger dye molecules. Furthermore, a novel precursor system for C₂N was explored, based on organic crystals from squaric acid and urea. The respective C₂N carbon with an unusual sheet-like morphology could be synthesized by carbonization of the crystals at 550 °C. With this precursor system, also microporous C₂N carbon with a BET surface area of 865 m²/g was obtained by "salt-templating" with ZnCl₂. Finally, the preparation of a g-C₃N₄/C₂N "all carbon" composite heterojunction was attempted by the self-assembly of g-C₃N₄ and C₂N nanosheets and tested for photocatalytic water splitting. Indeed, the composites revealed high rates of hydrogen evolution when compared to bulk g-C₃N₄. However, the increased catalytic activity was mainly attributed to the high surface area of the nanocomposites rather than to the composition. With regard to alternative composite synthesis ways, first experiments indicated N-Methyl-2-pyrrolidon to be suitable for higher concentrated dispersion of C₂N nanosheets. Eventually, the results obtained in this thesis provide precious synthetic contributions towards the preparation and processing of carbon/nitrogen compounds for energy applications.}, language = {en} } @phdthesis{Phung2020, author = {Phung, Thi Thuy Nga}, title = {Defect chemistry in halide perovskites}, doi = {10.25932/publishup-47652}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-476529}, school = {Universit{\"a}t Potsdam}, pages = {vi, 231}, year = {2020}, abstract = {Metallhalogenid-Perowskite haben sich aufgrund ihrer hervorragenden optoelektronischen Eigenschaften zu einer attraktiven Materialklasse f{\"u}r die Photovoltaikindustrie entwickelt. Die Langzeitstabilit{\"a}t ist jedoch noch immer ein Hindernis f{\"u}r die industrielle Realisierung dieser Materialklasse. Zunehmend zeigen sich Hinweise daf{\"u}r, dass intrinsische Defekte im Perowskit die Material-Degradation f{\"o}rdern. Das Verst{\"a}ndnis der Defekte im Perowskit ist wichtig, um seine Stabilit{\"a}t und optoelektronische Qualit{\"a}t weiter zu verbessern. Diese Dissertation konzentriert sich daher auf das Thema Defektchemie im Perowskit. Der erste Teil der Dissertation gibt einen kurzen {\"U}berblick {\"u}ber die Defekteigenschaften von Halogenid-Perowskiten. Anschließend zeigt der zweite Teil, dass das Dotieren von Methylammoniumbleiiodid mit einer kleinen Menge von Erdalkalimetallen (Sr und Mg) ein h{\"o}herwertiges, weniger fehlerhaftes Material erzeugt, was zu hohen Leerlaufspannungen sowohl in der n-i-p als auch in der p-i-n Architektur von Solarzellen f{\"u}hrt. Es wurde beobachtet, dass die Dotierung in zwei Dom{\"a}nen stattfindet: eine niedrige Dotierungskonzentration f{\"u}hrt zum Einschluss der entsprechenden Elemente in das Kristallgitter erm{\"o}glicht, w{\"a}hrend eine hohe Dotierungskonzentration zu einer Phasentrennung f{\"u}hrt. Das Material kann im Niedrigdotierungsbereich mehr n-dotiert sein, w{\"a}hrend es im Hochdotierungsbereich weniger n-dotiert ist. Die Schwelle dieser beiden Regime h{\"a}ngt von der Atomgr{\"o}ße der Dotierelemente ab. Der n{\"a}chste Teil der Dissertation untersucht die photoinduzierte Degradation von Methylammonium-Bleiiodid. Dieser Abbaumechanismus h{\"a}ngt eng mit der Bildung und Migration von defekten zusammen. Nach der Bildung k{\"o}nnen sich diese in Abh{\"a}ngigkeit von der Defektdichte und ihrer Verteilung bewegen. Demnach kann eine hohe Defektdichte wie an den Korngrenzen eines Perowskitfilms die Beweglichkeit von ionischen Punktdefekten hemmen. Diese Erkenntnis ließe sich auf das zuk{\"u}nftige Materialdesign in der Photovoltaikindustrie anwenden, da die Perowskit-Solarzellen normalerweise einen polykristallinen D{\"u}nnfilm mit hoher Korngrenzendichte verwenden. Die abschließende Studie, die in dieser Dissertation vorgestellt wird, konzentriert sich auf die Stabilit{\"a}t der neuesten „dreifach-kationen" Perowskit-basierten Solarzellen unter dem Einfluss einer permanent angelegten elektrischen Spannung. Eine l{\"a}ngere Betriebsdauer (mehr als drei Stunden permanente Spannung) f{\"o}rdert die Amorphisierung im Halogenid-Perowskiten. Es wird hierbei vermutet, dass sich eine amorphe Phase an den Grenzfl{\"a}chen bildet, insbesondere zwischen der lochselektiven Schicht und dem Perowskit. Diese amorphe Phase hemmt den Ladungstransport und beeintr{\"a}chtigt die Leistung der Perowskit-Solarzelle erheblich. Sobald jedoch keine Spannung mehr anliegt k{\"o}nnen sich die Perowskitschichten im Dunkeln bereits nach einer kurzen Pause regenerieren. Die Amorphisierung wird auf die Migration von ionischen Fehlordnungen zur{\"u}ckgef{\"u}hrt, h{\"o}chstwahrscheinlich auf die Migration von Halogeniden. Dieser Ansatz zeigt ein neues Verst{\"a}ndnis des Abbau-Mechanismus in Perowskit-Solarzellen unter Betriebsbedingungen.}, language = {en} } @phdthesis{Kulkarni2007, author = {Kulkarni, Amit Narahari}, title = {Degradation kinetics studies of polymers for biomedical applications}, address = {Potsdam}, pages = {vi, 144, viii S. : graph. Darst.}, year = {2007}, language = {en} } @phdthesis{Flehr2012, author = {Flehr, Roman}, title = {Design and development of novel three color-FRET systems in synthetic peptides and oligonucleotides}, address = {Potsdam}, pages = {VII, 149 S.}, year = {2012}, language = {en} } @phdthesis{Altabal2021, author = {Altabal, Osamah}, title = {Design and fabrication of geometry-assisted on-demand dosing systems}, doi = {10.25932/publishup-53244}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-532441}, school = {Universit{\"a}t Potsdam}, pages = {xxiv, 122}, year = {2021}, abstract = {The controlled dosage of substances from a device to its environment, such as a tissue or an organ in medical applications or a reactor, room, machinery or ecosystem in technical, should ideally match the requirements of the applications, e.g. in terms of the time point at which the cargo is released. On-demand dosage systems may enable such a desired release pattern, if the device contain suitable features that can translate external signals into a release function. This study is motivated by the opportunities arising from microsystems capable of an on-demand release and the contributions that geometrical design may have in realizing such features. The goals of this work included the design, fabrication, characterization and experimental proof-of-concept of geometry-assisted triggerable dosing effect (a) with a sequential dosing release and (b) in a self-sufficient dosage system. Structure-function relationships were addressed on the molecular, morphological and, with a particular attention, the device design level, which is on the micrometer scale. Models and/or computational tools were used to screen the parameter space and provide guidance for experiments.}, language = {en} } @phdthesis{Ast2013, author = {Ast, Cindy}, title = {Design and photophysical characterization of single fluorophore-based ammonium sensors}, address = {Potsdam}, pages = {90 S.}, year = {2013}, language = {en} } @phdthesis{Cataldo2020, author = {Cataldo, Vincenzo Alessandro}, title = {Design and synthesis of alkylating ionic liquids and their application in synthesis, materials and proteomics}, school = {Universit{\"a}t Potsdam}, pages = {153}, year = {2020}, language = {en} } @phdthesis{Heyne2022, author = {Heyne, Benjamin}, title = {Design and Synthesis of Highly Efficient InPZnS/ZnSe/ZnS Multishell Quantum Dots and Phase Transfer via Ligand Exchange}, school = {Universit{\"a}t Potsdam}, pages = {102,LII}, year = {2022}, language = {en} } @phdthesis{Piluso2012, author = {Piluso, Susanna}, title = {Design of biopolymer-based networks with defined molecular architecture}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-59865}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {In this work, the synthesis of biopolymer-based hydrogel networks with defined architecture is presented. In order to obtain materials with defined properties, the chemoselective copper-catalyzed azide-alkyne cycloaddition (or Click Chemistry) was used for the synthesis of gelatin-based hydrogels. Alkyne-functionalized gelatin was reacted with four different diazide crosslinkers above its sol-gel transition to suppress the formation of triple helices. By variation of the crosslinking density and the crosslinker flexibility, the swelling (Q: 150-470 vol.-\%;) and the Young's and shear moduli (E: 50 kPa - 635 kPa, G': 0.1 kPa - 16 kPa) could be tuned in the kPa range. In order to understand the network structure, a method based on the labelling of free functional groups within the hydrogel was developed. Gelatin-based hydrogels were incubated with alkyne-functionalized fluorescein to detect the free azide groups, resulting from the formation of dangling chains. Gelatin hydrogels were also incubated with azido-functionalized fluorescein to check the presence of alkyne groups available for the attachment of bioactive molecules. By using confocal laser scanning microscopy and fluorescence spectroscopy, the amount of crosslinking, grafting and free alkyne groups could be determined. Dangling chains were observed in samples prepared by using an excess of crosslinker and also when using equimolar amounts of alkyne:azide. In the latter case the amount of dangling chains was affected by the crosslinker structure. Specifically, 0.1\% of dangling chains were found using 4,4'-diazido-2,2'-stilbene-disulfonic acid as cosslinker, 0.06\% with 1,8-diazidooctane, 0.05\% with 1,12-diazidododecane and 0.022 \% with PEG-diazide. This observation could be explained considering the structure of the crosslinkers. During network formation, the movements of the gelatin chains are restricted due to the formation of covalent netpoints. A further crosslinking will be possible only in the case of crosslinker that are flexible and long enough to reach another chain. The method used to obtain defined gelatin-based hydrogels enabled also the synthesis of hyaluronic acid-based hydrogels with tailorable properties. Alkyne-functionalized hyaluronic acid was crosslinked with three different linkers having two terminal azide functionalities. By variation of the crosslinking density and crosslinker type, hydrogels with elastic moduli in the range of 0.5-3 kPa have been prepared. The variation of the crosslinking density and crosslinker type had furthermore an influence also on the hydrolytic and enzymatic degradation of gelatin-based hydrogels. Hydrogels with a low crosslinker amount experienced a faster decrease in mass loss and elastic modulus compared to hydrogels with higher crosslinker content. Moreover, the structure of the crosslinker had a strong influence on the enzymatic degradation. Hydrogels containing a crosslinker with a rigid structure were much more resistant to enzymatic degradation than hydrogels containing a flexible crosslinker. During hydrolytic degradation, the hydrogel became softer while maintaining the same outer dimensions. These observations are in agreement with a bulk degradation mechanism, while the decrease in size of the hydrogels during enzymatic degradation suggested a surface erosion mechanism. Because of the use of small amount of crosslinker (0.002 mol.\% 0.02 mol.\%) the networks synthesized can still be defined as biopolymer-based hydrogels. However, they contain a small percentage of synthetic residues. Alternatively, a possible method to obtain biopolymer-based telechelics, which could be used as crosslinkers, was investigated. Gelatin-based fragments with defined molecular weight were obtained by controlled degradation of gelatin with hydroxylamine, due to its specific action on asparaginyl-glycine bonds. The reaction of gelatin with hydroxylamine resulted in fragments with molecular weights of 15, 25, 37, and 50 kDa (determined by SDS-PAGE) independently of the reaction time and conditions. Each of these fragments could be potentially used for the synthesis of hydrogels in which all components are biopolymer-based materials.}, language = {en} } @phdthesis{Mondal2013, author = {Mondal, Suvendu Sekhar}, title = {Design of isostructural metal-imidazolate frameworks : application for gas storage}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-69692}, school = {Universit{\"a}t Potsdam}, year = {2013}, abstract = {The sharply rising level of atmospheric carbon dioxide resulting from anthropogenic emissions is one of the greatest environmental concerns facing our civilization today. Metal-organic frameworks (MOFs) are a new class of materials that constructed by metal-containing nodes bonded to organic bridging ligands. MOFs could serve as an ideal platform for the development of next generation CO2 capture materials owing to their large capacity for the adsorption of gases and their structural and chemical tunability. The ability to rationally select the framework components is expected to allow the affinity of the internal pore surface toward CO2 to be precisely controlled, facilitating materials properties that are optimized for the specific type of CO2 capture to be performed (post-combustion capture, precombustion capture, or oxy-fuel combustion) and potentially even for the specific power plant in which the capture system is to be installed. For this reason, significant effort has been made in recent years in improving the gas separation performance of MOFs and some studies evaluating the prospects of deploying these materials in real-world CO2 capture systems have begun to emerge. We have developed six new MOFs, denoted as IFPs (IFP-5, -6, -7, -8, -9, -10, IFP = Imidazolate Framework Potsdam) and two hydrogen-bonded molecular building block (MBB, named as 1 and 2 for Zn and Co based, respectively) have been synthesized, characterized and applied for gas storage. The structure of IFP possesses 1D hexagonal channels. Metal centre and the substituent groups of C2 position of the linker protrude into the open channels and determine their accessible diameter. Interestingly, the channel diameters (range : 0.3 to 5.2 {\AA}) for IFP structures are tuned by the metal centre (Zn, Co and Cd) and substituent of C2 position of the imidazolate linker. Moreover hydrogen bonded MBB of 1 and 2 is formed an in situ functionalization of a ligand under solvothermal condition. Two different types of channels are observed for 1 and 2. Materials contain solvent accessible void space. Solvent could be easily removed by under high vacuum. The porous framework has maintained the crystalline integrity even without solvent molecules. N2, H2, CO2 and CH4 gas sorption isotherms were performed. Gas uptake capacities are comparable with other frameworks. Gas uptake capacity is reduced when the channel diameter is narrow. For example, the channel diameter of IFP-5 (channel diameter: 3.8 {\AA}) is slightly lower than that of IFP-1 (channel diameter: 4.2 {\AA}); hence, the gas uptake capacity and Brunauer-Emmett-Teller (BET) surface area are slightly lower than IFP-1. The selectivity does not depend only on the size of the gas components (kinetic diameter: CO2 3.3 {\AA}, N2 3.6 {\AA} and CH4 3.8 ) but also on the polarizability of the surface and of the gas components. IFP-5 and-6 have the potential applications for the separation of CO2 and CH4 from N2-containing gas mixtures and CO2 and CH4 containing gas mixtures. Gas sorption isotherms of IFP-7, -8, -9, -10 exhibited hysteretic behavior due to flexible alkoxy (e.g., methoxy and ethoxy) substituents. Such phenomenon is a kind of gate effects which is rarely observed in microporous MOFs. IFP-7 (Zn-centred) has a flexible methoxy substituent. This is the first example where a flexible methoxy substituent shows the gate opening behavior in a MOF. Presence of methoxy functional group at the hexagonal channels, IFP-7 acted as molecular gate for N2 gas. Due to polar methoxy group and channel walls, wide hysteretic isotherm was observed during gas uptake. The N2 The estimated BET surface area for 1 is 471 m2 g-1 and the Langmuir surface area is 570 m2 g-1. However, such surface area is slightly higher than azolate-based hydrogen-bonded supramolecular assemblies and also comparable and higher than some hydrogen-bonded porous organic molecules.}, language = {en} } @phdthesis{Ilic2020, author = {Ilic, Ivan}, title = {Design of sustainable cathodes for Li-ion batteries}, doi = {10.25932/publishup-48368}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-483689}, school = {Universit{\"a}t Potsdam}, pages = {iv, 154}, year = {2020}, abstract = {In recent years people have realised non-renewability of our modern society which relays on spending huge amounts of energy mostly produced from fosil fuels, such as oil and coal, and the shift towards more sustainable energy sources has started. However, sustainable sources of energy, such as wind-, solar- and hydro-energy, produce primarily electrical energy and can not just be poured in canister like many fosil fuels, creating necessity for rechragable batteries. However, modern Li-ion batteries are made from toxic heavy metals and sustainable alternatives are needed. Here we show that naturally abundant catecholic and guaiacyl groups can be utilised to replace heavy metals in Li-ion batteries. Foremost vanillin, a naturally occurring food additive that can be sustainably synthesised from industrial biowaste, lignin, was utilised to synthesise materials that showed extraordinary performance as cathodes in Li-ion batteries. Furthermore, behaviour of catecholic and guiacyl groups in Li-ion system was compared, confirming usability of guiacayl containing biopolymers as cathodes in Li-ion batteries. Lastly, naturally occurring polyphenol, tannic acid, was incorporated in fully bioderived hybrid material that shows performance comparable to commercial Li-ion batteries and good stability. This thesis presents an important advancement in understanding of biowaste derived cathode materials for Li-ion batteries. Further research should be conducted to better understand behaviour of guaiacyl groups during Li-ion battery cycling. Lastly, challenges of incorporation of lignin, an industrial biowaste, have to be addressed and lignin should be incorporated as a cathode material in Li-ion batteries.}, language = {en} } @phdthesis{BivigouKoumba2009, author = {Bivigou Koumba, Achille Mayelle}, title = {Design, Synthesis and Characterisation of Amphiphilic Symmetrical triblock copolymers by the RAFT process : their self-organisation in dilute and concentrated aqueous solutions}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-39549}, school = {Universit{\"a}t Potsdam}, year = {2009}, abstract = {This work presents the synthesis and the self-assembly of symmetrical amphiphilic ABA and BAB triblock copolymers in dilute, semi-concentrated and highly concentrated aqueous solution. A series of new bifunctional bistrithiocarbonates as RAFT agents was used to synthesise these triblock copolymers, which are characterised by a long hydrophilic middle block and relatively small, but strongly hydrophobic end blocks. As hydrophilic A blocks, poly(N-isopropylacrylamide) (PNIPAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) were employed, while as hydrophobic B blocks, poly(4-tert-butyl styrene), polystyrene, poly(3,5-dibromo benzyl acrylate), poly(2-ethylhexyl acrylate), and poly(octadecyl acrylate) were explored as building blocks with different hydrophobicities and glass transition temperatures. The five bifunctional trithiocarbonates synthesised belong to two classes: the first are RAFT agents, which position the active group of the growing polymer chain at the outer ends of the polymer (Z-C(=S)-S-R-S-C(=S)-Z, type I). The second class places the active groups in the middle of the growing polymer chain (R-S-C(=S)-Z-C(=S)-S-R, type II). These RAFT agents enable the straightforward synthesis of amphiphilic triblock copolymers in only two steps, allowing to vary the nature of the hydrophobic blocks as well as the length of the hydrophobic and hydrophilic blocks broadly with good molar mass control and narrow polydispersities. Specific side reactions were observed among some RAFT agents including the elimination of ethylenetrithiocarbonate in the early stage of the polymerisation of styrene mediated by certain agents of the type II, while the use of the RAFT agents of type I resulted in retardation of the chain extension of PNIPAM with styrene. These results underline the need of a careful choice of RAFT agents for a given task. The various copolymers self-assemble in dilute and semi-concentrated aqueous solution into small flower-like micelles. No indication for the formation of micellar clusters was found, while only at high concentration, physical hydrogels are formed. The reversible thermoresponsive behaviour of the ABA and BAB type copolymer solutions in water with A made of PNIPAM was examined by turbidimetry and dynamic light scattering (DLS). The cloud point of the copolymers was nearly identical to the cloud point of the homopolymer and varied between 28-32 °C with concentrations from 0.01 to 50 wt\%. This is attributed to the formation of micelles where the hydrophobic blocks are shielded from a direct contact with water, so that the hydrophobic interactions of the copolymers are nearly the same as for pure PNIPAM. Dynamic light scattering measurements showed the presence of small micelles at ambient temperature. The aggregate size dramatically increased above the cloud point, indicating a change of aggregate morphology into clusters due to the thermosensitivity of the PNIPAM block. The rheological behaviour of the amphiphilic BAB triblock copolymers demonstrated the formation of hydrogels at high concentrations, typically above 30-35 wt\%. The minimum concentration to induce hydrogels decreased with the increasing glass transition temperatures and increasing length of the end blocks. The weak tendency to form hydrogels was attributed to a small share of bridged micelles only, due to the strong segregation regime occurring. In order to learn about the role of the nature of the thermoresponsive block for the aggregation, a new BAB triblock copolymer consisting of short polystyrene end blocks and PMDEGA as stimuli-responsive middle block was prepared and investigated. Contrary to PNIPAM, dilute aqueous solutions of PMDEGA and of its block copolymers showed reversible phase transition temperatures characterised by a strong dependence on the polymer composition. Moreover, the PMDEGA block copolymer allowed the formation of physical hydrogels at lower concentration, i.e. from 20 wt\%. This result suggests that PMDEGA has a higher degree of water-swellability than PNIPAM.}, language = {en} } @phdthesis{Meiling2017, author = {Meiling, Till Thomas}, title = {Development of a reliable and environmentally friendly synthesis for fluorescence carbon nanodots}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-410160}, school = {Universit{\"a}t Potsdam}, pages = {198}, year = {2017}, abstract = {Carbon nanodots (CNDs) have generated considerable attention due to their promising properties, e.g. high water solubility, chemical inertness, resistance to photobleaching, high biocompatibility and ease of functionalization. These properties render them ideal for a wide range of functions, e.g. electrochemical applications, waste water treatment, (photo)catalysis, bio-imaging and bio-technology, as well as chemical sensing, and optoelectronic devices like LEDs. In particular, the ability to prepare CNDs from a wide range of accessible organic materials makes them a potential alternative for conventional organic dyes and semiconductor quantum dots (QDs) in various applications. However, current synthesis methods are typically expensive and depend on complex and time-consuming processes or severe synthesis conditions and toxic chemicals. One way to reduce overall preparation costs is the use of biological waste as starting material. Hence, natural carbon sources such as pomelo peal, egg white and egg yolk, orange juice, and even eggshells, to name a few; have been used for the preparation of CNDs. While the use of waste is desirable, especially to avoid competition with essential food production, most starting-materials lack the essential purity and structural homogeneity to obtain homogeneous carbon dots. Furthermore, most synthesis approaches reported to date require extensive purification steps and have resulted in carbon dots with heterogeneous photoluminescent properties and indefinite composition. For this reason, among others, the relationship between CND structure (e.g. size, edge shape, functional groups and overall composition) and photophysical properties is yet not fully understood. This is particularly true for carbon dots displaying selective luminescence (one of their most intriguing properties), i.e. their PL emission wavelength can be tuned by varying the excitation wavelength. In this work, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain CNDs with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch, carboxylic acids and Tris-EDTA (TE) buffer as carbon- and nitrogen source, respectively. The presented microwave-assisted hydrothermal precursor carbonization (MW-hPC) is characterized by its cost-efficiency, simplicity, short reaction times, low environmental footprint, and high yields of approx. 80\% (w/w). Furthermore, only a single synthesis step is necessary to obtain homogeneous water-soluble CNDs with no need for further purification. Depending on starting materials and reaction conditions different types of CNDs have been prepared. The as-prepared CNDs exhibit reproducible, highly homogeneous and favourable PL properties with narrow emission bands (approx. 70nm FWHM), are non-blinking, and are ready to use without need for further purification, modification or surface passivation agents. Furthermore, the CNDs are comparatively small (approx. 2.0nm to 2.4nm) with narrow size distributions; are stable over a long period of time (at least one year), either in solution or as a dried solid; and maintain their PL properties when re-dispersed in solution. Depending on CND type, the PL quantum yield (PLQY) can be adjusted from as low as 1\% to as high as 90\%; one of the highest reported PLQY values (for CNDs) so far. An essential part of this work was the utilization of a microwave synthesis reactor, allowing various batch sizes and precise control over reaction temperature and -time, pressure, and heating- and cooling rate, while also being safe to operate at elevated reaction conditions (e.g. 230 ±C and 30 bar). The hereby-achieved high sample throughput allowed, for the first time, the thorough investigation of a wide range of synthesis parameters, providing valuable insight into the CND formation. The influence of carbon- and nitrogen source, precursor concentration and -combination, reaction time and -temperature, batch size, and post-synthesis purification steps were carefully investigated regarding their influence on the optical properties of as-synthesized CNDs. In addition, the change in photophysical properties resulting from the conversion of CND solution into solid and back into the solution was investigated. Remarkably, upon freeze-drying the initial brown CND-solution turns into a non-fluorescent white/slightly yellow to brown solid which recovers PL in aqueous solution. Selected CND samples were also subject to EDX, FTIR, NMR, PL lifetime (TCSPC), particle size (TEM), TGA and XRD analysis. Besides structural characterization, the pH- and excitation dependent PL characteristics (i.e. selective luminescence) were examined; giving inside into the origin of photophysical properties and excitation dependent behaviour of CNDs. The obtained results support the notion that for CNDs the nature of the surface states determines the PL properties and that excitation dependent behaviour is caused by the "Giant Red-Edge Excitation Shift" (GREES).}, language = {en} } @phdthesis{Bhattacharryya2006, author = {Bhattacharryya, Saroj Kumar}, title = {Development of detector for analytical ultracentrifuge. - [korr. Fassung]}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-8215}, school = {Universit{\"a}t Potsdam}, year = {2006}, abstract = {In this work approaches for new detection system development for an Analytical Ultracentrifuge (AUC) were explored. Unlike its counterpart in chromatography fractionation techniques, the use of a Multidetection system for AUC has not yet been implemented to full extent despite its potential benefit. In this study we tried to couple existing fundamental spectroscopic and scattering techniques that are used in day to day science as tool for extracting analyte information. Trials were performed for adapting Raman, Light scattering and UV/Vis (with possibility to work with the whole range of wavelengths) to AUC. Conclusions were drawn for Raman and Light scattering to be a possible detection system for AUC, while the development for a fast fiber optics based multiwavelength detector was completed. The multiwavelength detector demonstrated the capability of data generation matching the literature and reference measurement data and faster data collection than that of the commercial instrument. It became obvious that with the generation of data in 3-D space in the UV/Vis detection system, the user can select the wavelength for the evaluation of experimental results as the data set contains the whole range of information from UV/Vis wavelength. The detector showed the data generation with much faster speed unlike the commercial instruments. The advantage of fast data generation was exemplified with the evaluation of data for a mixture of three colloids. These data were in conformity with measurement results from normal radial experiments and without significant diffusion broadening. Thus conclusions were drawn that with our designed Multiwavelength detector, meaningful data in 3-D space can be collected with much faster speed of data generation.}, subject = {Ultrazentrifuge}, language = {en} } @phdthesis{Dippel2017, author = {Dippel, Sandor}, title = {Development of functional hydrogels for sensor applications}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-398252}, school = {Universit{\"a}t Potsdam}, pages = {127}, year = {2017}, abstract = {In this work, a sensor system based on thermoresponsive materials is developed by utilizing a modular approach. By synthesizing three different key monomers containing either a carboxyl, alkene or alkyne end group connected with a spacer to the methacrylic polymerizable unit, a flexible copolymerization strategy has been set up with oligo ethylene glycol methacrylates. This allows to tune the lower critical solution temperature (LCST) of the polymers in aqueous media. The molar masses are variable thanks to the excurse taken in polymerization in ionic liquids thus stretching molar masses from 25 to over 1000 kDa. The systems that were shown shown to be effective in aqueous solution could be immobilized on surfaces by copolymerizing photo crosslinkable units. The immobilized systems were formulated to give different layer thicknesses, swelling ratios and mesh sizes depending on the demand of the coupling reaction. The coupling of detector units or model molecules is approached via reactions of the click chemistry pool, and the reactions are evaluated on their efficiency under those aspects, too. These coupling reactions are followed by surface plasmon resonance spectroscopy (SPR) to judge efficiency. With these tools at hand, Salmonella saccharides could be selectively detected by SPR. Influenza viruses were detected in solution by turbidimetry in solution as well as by a copolymerized solvatochromic dye to track binding via the changes of the polymers' fluorescence by said binding event. This effect could also be achieved by utilizing the thermoresponsive behavior. Another demonstrator consists of the detection system bound to a quartz surface, thus allowing the virus detection on a solid carrier. The experiments show the great potential of combining the concepts of thermoresponsive materials and click chemistry to develop technically simple sensors for large biomolecules and viruses.}, language = {en} } @phdthesis{Neumann2022, author = {Neumann, Christian}, title = {Development of functionalized waterborne coatings for the production of multifunctional microapsules}, pages = {127}, year = {2022}, language = {en} } @phdthesis{Karabudak2009, author = {Karabudak, Engin}, title = {Development of MWL-AUC / CCD-C-AUC / SLS-AUC detectors for the analytical ultracentrifuge}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-39921}, school = {Universit{\"a}t Potsdam}, year = {2009}, abstract = {Analytical ultracentrifugation (AUC) has made an important contribution to polymer and particle characterization since its invention by Svedberg (Svedberg and Nichols 1923; Svedberg and Pederson 1940) in 1923. In 1926, Svedberg won the Nobel price for his scientific work on disperse systems including work with AUC. The first important discovery performed with AUC was to show the existence of macromolecules. Since that time AUC has become an important tool to study polymers in biophysics and biochemistry. AUC is an absolute technique that does not need any standard. Molar masses between 200 and 1014 g/mol and particle size between 1 and 5000 nm can be detected by AUC. Sample can be fractionated into its components due to its molar mass, particle size, structure or density without any stationary phase requirement as it is the case in chromatographic techniques. This very property of AUC earns it an important status in the analysis of polymers and particles. The distribution of molar mass, particle sizes and densities can be measured with the fractionation. Different types of experiments can give complementary physicochemical parameters. For example, sedimentation equilibrium experiments can lead to the study of pure thermodynamics. For complex mixtures, AUC is the main method that can analyze the system. Interactions between molecules can be studied at different concentrations without destroying the chemical equilibrium (Kim et al. 1977). Biologically relevant weak interactions can also be monitored (K ≈ 10-100 M-1). An analytical ultracentrifuge experiment can yield the following information: • Molecular weight of the sample • Number of the components in the sample if the sample is not a single component • Homogeneity of the sample • Molecular weight distribution if the sample is not a single component • Size and shape of macromolecules \& particles • Aggregation \& interaction of macromolecules • Conformational changes of macromolecules • Sedimentation coefficient and density distribution Such an extremely wide application area of AUC allows the investigation of all samples consisting of a solvent and a dispersed or dissolved substance including gels, micro gels, dispersions, emulsions and solutions. Another fact is that solvent or pH limitation does not exist for this method. A lot of new application areas are still flourishing, although the technique is 80 years old. In 1970s, 1500 AUC were operational throughout the world. At those times, due to the limitation in detection technologies, experimental results were obtained with photographic records. As time passed, faster techniques such as size exclusion chromatography (SEC), light scattering (LS) or SDS-gel electrophoresis occupied the same research fields with AUC. Due to these relatively new techniques, AUC began to loose its importance. In the 1980s, only a few AUC were in use throughout the world. In the beginning of the 1990s a modern AUC -the Optima XL-A - was released by Beckman Instruments (Giebeler 1992). The Optima XL-A was equipped with a modern computerized scanning absorption detector. The addition of Rayleigh Interference Optics is introduced which is called XL-I AUC. Furthermore, major development in computers made the analysis easier with the help of new analysis software. Today, about 400 XL-I AUC exist worldwide. It is usually applied in the industry of pharmacy, biopharmacy and polymer companies as well as in academic research fields such as biochemistry, biophysics, molecular biology and material science. About 350 core scientific publications which use analytical ultracentrifugation are published every year (source: SciFinder 2008 ) with an increasing number of references (436 reference in 2008). A tremendous progress has been made in method and analysis software after digitalization of experimental data with the release of XL-I. In comparison to the previous decade, data analysis became more efficient and reliable. Today, AUC labs can routinely use sophisticated data analysis methods for determination of sedimentation coefficient distributions (Demeler and van Holde 2004; Schuck 2000; Stafford 1992), molar mass distributions (Brookes and Demeler 2008; Brookes et al. 2006; Brown and Schuck 2006), interaction constants (Cao and Demeler 2008; Schuck 1998; Stafford and Sherwood 2004), particle size distributions with Angstrom resolution (C{\"o}lfen and Pauck 1997) and the simulations determination of size and shape distributions from sedimentation velocity experiments (Brookes and Demeler 2005; Brookes et al. 2006). These methods are also available in powerful software packages that combines various methods, such as, Ultrascan (Demeler 2005), Sedift/Sedphat (Schuck 1998; Vistica et al. 2004) and Sedanal (Stafford and Sherwood 2004). All these powerful packages are free of charge. Furthermore, Ultrascans source code is licensed under the GNU Public License (http://www.gnu.org/copyleft/gpl.html). Thus, Ultrascan can be further improved by any research group. Workshops are organized to support these software packages. Despite of the tremendous developments in data analysis, hardware for the system has not developed much. Although there are various user developed detectors in research laboratories, they are not commercially available. Since 1992, only one new optical system called "the fluorescence optics" (Schmidt and Reisner, 1992, MacGregor et al. 2004, MacGregor, 2006, Laue and Kroe, in press) has been commercialized. However, except that, there has been no commercially available improvement in the optical system. The interesting fact about the current hardware of the XL-I is that it is 20 years old, although there has been an enormous development in microelectronics, software and in optical systems in the last 20 years, which could be utilized for improved detectors. As examples of user developed detector, Bhattacharyya (Bhattacharyya 2006) described a Multiwavelength-Analytical Ultracentrifuge (MWL-AUC), a Raman detector and a small angle laser light scattering detector in his PhD thesis. MWL-AUC became operational, but a very high noise level prevented to work with real samples. Tests with the Raman detector were not successful due to the low light intensity and thus high integration time is required. The small angle laser light scattering detector could only detect latex particles but failed to detect smaller particles and molecules due to low sensitivity of the detector (a photodiode was used as detector). The primary motivation of this work is to construct a detector which can measure new physico-chemical properties with AUC with a nicely fractionated sample in the cell. The final goal is to obtain a multiwavelength detector for the AUC that measures complementary quantities. Instrument development is an option for a scientist only when there is a huge potential benefit but there is no available commercial enterprise developing appropriate equipment, or if there is not enough financial support to buy it. The first case was our motivation for developing detectors for AUC. Our aim is to use today's technological advances in microelectronics, programming, mechanics in order to develop new detectors for AUC and improve the existing MWL detector to routine operation mode. The project has multiple aspects which can be listed as mechanical, electronical, optical, software, hardware, chemical, industrial and biological. Hence, by its nature it is a multidisciplinary project. Again by its nature it contains the structural problem of its kind; the problem of determining the exact discipline to follow at each new step. It comprises the risk of becoming lost in some direction. Having that fact in mind, we have chosen the simplest possible solution to any optical, mechanical, electronic, software or hardware problem we have encountered and we have always tried to see the overall picture. In this research, we have designed CCD-C-AUC (CCD Camera UV/Vis absorption detector for AUC) and SLS-AUC (Static Light Scattering detector for AUC) and tested them. One of the SLS-AUC designs produced successful test results, but the design could not be brought to the operational stage. However, the operational state Multiwavelength Analytical Ultracentrifuge (MWL-AUC) AUC has been developed which is an important detector in the fields of chemistry, biology and industry. In this thesis, the operational state Multiwavelength Analytical Ultracentrifuge (MWL-AUC) AUC is to be introduced. Consequently, three different applications of MWL-AUC to the aforementioned disciplines shall be presented. First of all, application of MWL-AUC to a biological system which is a mixture of proteins lgG, aldolase and BSA is presented. An application of MWL-AUC to a mass-produced industrial sample (β-carotene gelatin composite particles) which is manufactured by BASF AG, is presented. Finally, it is shown how MWL-AUC will impact on nano-particle science by investigating the quantum size effect of CdTe and its growth mechanism. In this thesis, mainly the relation between new technological developments and detector development for AUC is investigated. Pioneering results are obtained that indicate the possible direction to be followed for the future of AUC. As an example, each MWL-AUC data contains thousands of wavelengths. MWL-AUC data also contains spectral information at each radial point. Data can be separated to its single wavelength files and can be analyzed classically with existing software packages. All the existing software packages including Ultrascan, Sedfit, Sedanal can analyze only single wavelength data, so new extraordinary software developments are needed. As a first attempt, Emre Brookes and Borries Demeler have developed mutliwavelength module in order to analyze the MWL-AUC data. This module analyzes each wavelength separately and independently. We appreciate Emre Brookes and Borries Demeler for their important contribution to the development of the software. Unfortunately, this module requires huge amount of computer power and does not take into account the spectral information during the analysis. New software algorithms are needed which take into account the spectral information and analyze all wavelengths accordingly. We would like also invite the programmers of Ultrascan, Sedfit, Sedanal and the other programs, to develop new algorithms in this direction.}, language = {en} } @phdthesis{Lutz2008, author = {Lutz, Jean-Fran{\c{c}}ois}, title = {Development of versatile chemical platforms to access new generations of "smart" polymer materials}, address = {Potsdam}, pages = {104 S.}, year = {2008}, language = {en} } @phdthesis{Kovach2016, author = {Kovach, Ildiko}, title = {Development, characterization of Janus emulsions, and their usage as a template phase for fabricating biopolymer scaffolds}, school = {Universit{\"a}t Potsdam}, year = {2016}, language = {en} } @phdthesis{Baeckemo2022, author = {B{\"a}ckemo, Johan Dag Valentin}, title = {Digital tools and bioinspiration for the implementation in science and medicine}, doi = {10.25932/publishup-57145}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-571458}, school = {Universit{\"a}t Potsdam}, pages = {xiv, 108}, year = {2022}, abstract = {Diese Doktorarbeit untersucht anhand dreier Beispiele, wie digitale Werkzeuge wie Programmierung, Modellierung, 3D-Konstruktions-Werkzeuge und additive Fertigung in Verbindung mit einer auf Biomimetik basierenden Design\-strategie zu neuen Analysemethoden und Produkten f{\"u}hren k{\"o}nnen, die in Wissenschaft und Medizin Anwendung finden. Das Verfahren der Funkenerosion (EDM) wird h{\"a}ufig angewandt, um harte Metalle zu verformen oder zu formen, die mit normalen Maschinen nur schwer zu bearbeiten sind. In dieser Arbeit wird eine neuartige Kr{\"u}mmungsanalysemethode als Alternative zur Rauheitsanalyse vorgestellt. Um besser zu verstehen, wie sich die Oberfl{\"a}che w{\"a}hrend der Bearbeitungszeit des EDM-Prozesses ver{\"a}ndert, wurde außerdem ein digitales Schlagmodell erstellt, das auf einem urspr{\"u}nglich flachen Substrat Krater auf Erhebungen erzeugte. Es wurde festgestellt, dass ein Substrat bei etwa 10.000 St{\"o}ßen ein Gleichgewicht erreicht. Die vorgeschlagene Kr{\"u}mmungsanalysemethode hat das Potenzial, bei der Entwicklung neuer Zellkultursubstrate f{\"u}r die Stammzellenforschung eingesetzt zu werden. Zwei Arten, die in dieser Arbeit aufgrund ihrer interessanten Mechanismen analysiert wurden, sind die Venusfliegenfalle und der Bandwurm. Die Venusfliegenfalle kann ihr Maul mit einer erstaunlichen Geschwindigkeit schließen. Der Schließmechanismus kann f{\"u}r die Wissenschaft interessant sein und ist ein Beispiel f{\"u}r ein so genanntes mechanisch bi-stabiles System - es gibt zwei stabile Zust{\"a}nde. Der Bandwurm ist bei S{\"a}ugetieren meist im unteren Darm zu finden und heftet sich mit seinen Saugn{\"a}pfen an die Darmw{\"a}nde. Wenn der Bandwurm eine geeignete Stelle gefunden hat, st{\"o}ßt er seine Haken aus und heftet sich dauerhaft an die Wand. Diese Funktion k{\"o}nnte in der minimalinvasiven Medizin genutzt werden, um eine bessere Kontrolle der Implantate w{\"a}hrend des Implantationsprozesses zu erm{\"o}glichen. F{\"u}r beide Projekte wurde ein mathematisches Modell, das so genannte Chained Beam Constraint Model (CBCM), verwendet, um das nichtlineare Biegeverhalten zu modellieren und somit vorherzusagen, welche Strukturen ein mechanisch bi-stabiles Verhalten aufweisen k{\"o}nnten. Daraufhin konnten zwei Prototypen mit einem 3D-Drucker gedruckt und durch Experimente veranschaulicht werden, dass sie beide ein bi-stabiles Verhalten aufweisen. Diese Arbeit verdeutlicht das hohe Anwendungspotenzial f{\"u}r neue Analysenmethoden in der Wissenschaft und f{\"u}r neue Medizinprodukte in der minimalinvasiven Medizin.}, language = {en} } @phdthesis{ChandrakanthShetty2021, author = {Chandrakanth Shetty, Sunidhi}, title = {Directed chemical communication in artificial eukaryotic cells}, doi = {10.25932/publishup-53364}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-533642}, school = {Universit{\"a}t Potsdam}, year = {2021}, abstract = {Eukaryotic cells can be regarded as complex microreactors capable of performing various biochemical reactions in parallel which are necessary to sustain life. An essential prerequisite for these complex metabolic reactions to occur is the evolution of lipid membrane-bound organelles enabling compartmental- ization of reactions and biomolecules. This allows for a spatiotemporal control over the metabolic reactions within the cellular system. Intracellular organi- zation arising due to compartmentalization is a key feature of all living cells and has inspired synthetic biologists to engineer such systems with bottom-up approaches. Artificial cells provide an ideal platform to isolate and study specific re- actions without the interference from the complex network of biomolecules present in biological cells. To mimic the hierarchical architecture of eukaryotic cells, multi-compartment assemblies with nested liposomal structures also re- ferred to as multi-vesicular vesicles (MVVs) have been widely adopted. Most of the previously reported multi-compartment systems adopt bulk method- ologies which suffer from low yield and poor control over size. Microfluidic strategies help circumvent these issues and facilitate a high-throughput and robust technique to assemble MVVs of uniform size distribution. In this thesis, firstly, the bulk methodologies are explored to build MVVs and implement a synthetic signalling cascade. Next, a polydimethylsiloxane (PDMS)-based microfluidic platform is introduced to build MVVs and the significance of PEGylated lipids for the successful encapsulation of inner com- partments to generate stable multi-compartment systems is highlighted. Next, a novel two-inlet channel PDMS-based microfluidic device to create MVVs encompassing a three-step enzymatic reaction cascade is presented. A directed reaction pathway comprising of the enzymes α-glucosidase (α-Glc), glucose oxidase (GOx), and horseradish peroxidase (HRP) spanning across three compartments via reconstitution of size-selective membrane proteins is described. Furthermore, owing to the monodispersity of our MVVs due to microfluidic strategies, this platform is employed to study the effect of com- partmentalization on reaction kinetics. Further integration of cell-free expression module into the MVVs would allow for gene-mediated signal transduction within artificial eukaryotic cells. Therefore, the chemically inducible cell-free expression of a membrane protein alpha-hemolysin and its further reconstitution into liposomes is carried out. In conclusion, the present thesis aims to build artificial eukaryotic cells to achieve size-selective chemical communication that also show potential for applications as micro reactors and as vehicles for drug delivery.}, language = {en} } @phdthesis{Choi2018, author = {Choi, Youngeun}, title = {DNA origami structures as versatile platforms for nanophotonics}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-421483}, school = {Universit{\"a}t Potsdam}, pages = {125}, year = {2018}, abstract = {Nanophotonics is the field of science and engineering aimed at studying the light-matter interactions on the nanoscale. One of the key aspects in studying such optics at the nanoscale is the ability to assemble the material components in a spatially controlled manner. In this work, DNA origami nanostructures were used to self-assemble dye molecules and DNA coated plasmonic nanoparticles. Optical properties of dye nanoarrays, where the dyes were arranged at distances where they can interact by F{\"o}rster resonance energy transfer (FRET), were systematically studied according to the size and arrangement of the dyes using fluorescein (FAM) as the donor and cyanine 3 (Cy 3) as the acceptor. The optimized design, based on steady-state and time-resolved fluorometry, was utilized in developing a ratiometric pH sensor with pH-inert coumarin 343 (C343) as the donor and pH-sensitive FAM as the acceptor. This design was further applied in developing a ratiometric toxin sensor, where the donor C343 is unresponsive and FAM is responsive to thioacetamide (TAA) which is a well-known hepatotoxin. The results indicate that the sensitivity of the ratiometric sensor can be improved by simply arranging the dyes into a well-defined array. The ability to assemble multiple fluorophores without dye-dye aggregation also provides a strategy to amplify the signal measured from a fluorescent reporter, and was utilized here to develop a reporter for sensing oligonucleotides. By incorporating target capturing sequences and multiple fluorophores (ATTO 647N dye molecules), a reporter for microbead-based assay for non-amplified target oligonucleotide sensing was developed. Analysis of the assay using VideoScan, a fluorescence microscope-based technology capable of conducting multiplex analysis, showed the DNA origami nanostructure based reporter to have a lower limit of detection than a single stranded DNA reporter. Lastly, plasmonic nanostructures were assembled on DNA origami nanostructures as substrates to study interesting optical behaviors of molecules in the near-field. Specifically, DNA coated gold nanoparticles, silver nanoparticles, and gold nanorods, were placed on the DNA origami nanostructure aiming to study surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS) of molecules placed in the hotspot of coupled plasmonic structures.}, language = {en} } @phdthesis{Prinz2016, author = {Prinz, Julia}, title = {DNA origami substrates as a versatile tool for surface-enhanced Raman scattering (SERS)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-104089}, school = {Universit{\"a}t Potsdam}, pages = {xviii, 184 Seiten}, year = {2016}, abstract = {Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called "hot spots", have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information. Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA (dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules. In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami substrates very well, which enables the monitoring of structural alterations by AFM imaging. In this way, it is shown that graphene encapsulation significantly increases the structural stability of bare DNA origami substrates towards mechanical force and prolonged exposure to deionized water. Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a 40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice. Although SLG can significantly influence the SERS substrate in the aforementioned ways, all those effects are strongly related to the extent of contact with the underlying AuNP dimer.}, language = {en} } @phdthesis{Won2016, author = {Won, Jooyoung}, title = {Dynamic and equilibrium adsorption behaviour of ß-lactoglobulin at the solution/tetradecane interface: Effect of solution concentration, pH and ionic strength}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-99167}, school = {Universit{\"a}t Potsdam}, pages = {ix, 106}, year = {2016}, abstract = {Proteins are amphiphilic and adsorb at liquid interfaces. Therefore, they can be efficient stabilizers of foams and emulsions. β-lactoglobulin (BLG) is one of the most widely studied proteins due to its major industrial applications, in particular in food technology. In the present work, the influence of different bulk concentration, solution pH and ionic strength on the dynamic and equilibrium pressures of BLG adsorbed layers at the solution/tetradecane (W/TD) interface has been investigated. Dynamic interfacial pressure (Π) and interfacial dilational elastic modulus (E') of BLG solutions for various concentrations at three different pH values of 3, 5 and 7 at a fixed ionic strength of 10 mM and for a selected fixed concentration at three different ionic strengths of 1 mM, 10 mM and 100 mM are measured by Profile Analysis Tensiometer PAT-1 (SINTERFACE Technologies, Germany). A quantitative data analysis requires additional consideration of depletion due to BLG adsorption at the interface at low protein bulk concentrations. This fact makes experiments more efficient when oil drops are studied in the aqueous protein solutions rather than solution drops formed in oil. On the basis of obtained experimental data, concentration dependencies and the effect of solution pH on the protein surface activity was qualitatively analysed. In the presence of 10 mM buffer, we observed that generally the adsorbed amount is increasing with increasing BLG bulk concentration for all three pH values. The adsorption kinetics at pH 5 result in the highest Π values at any time of adsorption while it exhibits a less active behaviour at pH 3. Since the experimental data have not been in a good agreement with the classical diffusion controlled model due to the conformational changes which occur when the protein molecules get in contact with the hydrophobic oil phase in order to adapt to the interfacial environment, a new theoretical model is proposed here. The adsorption kinetics data were analysed with the newly proposed model, which is the classical diffusion model but modified by assuming an additional change in the surface activity of BLG molecules when adsorbing at the interface. This effect can be expressed through the adsorption activity constant in the corresponding equation of state. The dilational visco-elasticity of the BLG adsorbed interfacial layers is determined from measured dynamic interfacial tensions during sinusoidal drop area variations. The interfacial tension responses to these harmonic drop oscillations are interpreted with the same thermodynamic model which is used for the corresponding adsorption isotherm. At a selected BLG concentration of 2×10-6 mol/l, the influence of the ionic strength using different buffer concentration of 1, 10 and 100 mM on the interfacial pressure was studied. It is affected weakly at pH 5, whereas it has a strong impact by increasing buffer concentration at pH 3 and 7. In conclusion, the structure formation of BLG adsorbed layer in the early stage of adsorption at the W/TD interface is similar to those of the solution/air (W/A) surface. However, the equation of state at the W/TD interface provides an adsorption activity constant which is almost two orders of magnitude higher than that for the solution/air surface. At the end of this work, a new experimental tool called Drop and Bubble Micro Manipulator DBMM (SINTERFACE Technologies, Germany) has been introduced to study the stability of protein covered bubbles against coalescence. Among the available protocols the lifetime between the moment of contact and coalescence of two contacting bubble is determined for different BLG concentrations. The adsorbed amount of BLG is determined as a function of time and concentration and correlates with the observed coalescence behaviour of the contacting bubbles.}, language = {en} } @phdthesis{Lian2023, author = {Lian, Tingting}, title = {Efficient activation of peroxymonosulfate by carbon-based catalysts for water purification}, school = {Universit{\"a}t Potsdam}, pages = {167}, year = {2023}, abstract = {The increasing global population has led to a growing demand for cost-effective and eco-friendly methods of water purification. This demand has reached a peak due to the increasing presence of impurities and pollutants in water and a growing awareness of waterborne diseases. Advanced oxidation processes (AOPs) are effective methods to address these challenges, due to the generation of highly reactive radicals, such as sulfate radical (SO4•-), hydroxyl radical (•OH), and/or superoxide radical (•O2-) in oxidation reactions. Relative to conventional hydrogen peroxide (H2O2)-based AOPs for wastewater treatment, the persulfate-related AOPs are receiving increasing attention over the past decades, due to their stronger oxidizing capability and a wider pH working window. Further deployment of the seemingly plausible technology as an alternative for the well-established one in industry, however, necessitates a careful evaluation of compounding factors, such as water matrix effects, toxicological consequences, costs, and engineering challenges, etc. To this end, rational design of efficient and environmentally friendly catalysts constitutes an indispensable pathway to advance persulfate activation efficacy and to elucidate the mechanisms in AOPs, the combined endeavors are expected to provide insightful understanding and guidelines for future studies in wastewater treatment. A dozens of transition metal-based catalysts have been developed for persulfate-related AOPs, while the undesirable metal leaching and poor stability in acidic conditions have been identified as major obstacles. Comparatively, the carbonaceous materials are emerging as alternative candidates, which are characterized by metal-free nature, wide availability, and exceptional resistance to acid and alkali, as well as tunable physicochemical and electronic properties, the combined merits make them an attractive option to overcome the aforementioned limitations in metal-based catalytic systems. This dissertation aims at developing novel carbonaceous materials to boost the activity in peroxymonosulfate (PMS) activation processes. Functionalized carbon materials with metal particles or heteroatoms were constructed and further evaluated in terms of their ability to activate PMS for AOPs. The main contents of this thesis are summarized as follows: (1) Iron oxide-loaded biochar: improving stability and alleviating metal leakage Metal leaching constitutes one of the main drawbacks in using transition metals as PMS activators, which is accompanied by the generation of metal-containing sludge, potentially leading to secondary pollution. Meanwhile, the metal nanoparticles are prone to aggregate, causing rapid decay of catalytic performance. The use of carbons as supports for transition metals could mitigate these deficiencies, because the interaction between metals and carbons could in turn disperse and stabilize metal nanoparticles, thus suppressing the metal leaching. In this work, the environmentally benign lignin with its abundant phenolic groups, which is well known to serve as carbon source with high yields and flexibility, was utilized to load Fe ions. The facile low-temperature pre-treatment pyrolytic strategy was employed to construct a green catalyst with iron oxides embedded in Kraft-lignin-derived biochar (termed as γ-Fe2O3@KC). The γ-Fe2O3@KC was capable of activating PMS to generate stable non-radical species (1O2 and Fe (V)=O) and to enhance electron transfer efficiency. A surface-bound reactive complex (catalyst-PMS*) was identified by electrochemical characterizations and discussed with primary surface-bound radical pairs to explain the contradictions between quenching and EPR detection results. The system also showed encouraging reusability for at least 5 times and high stability at pH 3-9. The low concentration of iron in γ-Fe2O3@KC/PMS system implied that the carbon scaffold of biochar substantially alleviated metal leakage. (2) MOF-derived nanocarbon: new carbon crystals Traditional carbon materials are of rather moderate performance in activation PMS, due to the poor electron transfer capacity within the amorphous structure and limited active sites for PMS adsorption. Herein, we established crystalline nanocarbon materials via a simple NaCl-templated strategy using the monoclinic zeolitic imidazolate framework-8 (ZIF-8) sealed with NaCl crystals as the precursors. Specifically, NaCl captured dual advantages in serving as structure-directing agent during hydrolysis and protective salt reactor to facilitate phase transformation during carbonization. The structure-directing agent NaCl provided a protective and confined space for the evolution of MOF upon carbonization, which led to high doping amounts of nitrogen (N) and oxygen elements (O) in carbon framework (N: 14.16 wt\%, O: 9.6 wt\%) after calcination at a high temperature of 950 oC. We found that N-O co-doping can activate the chemically inert carbon network and the nearby sp2-hybridized carbon atoms served as active sites for adsorption and activation. Besides, the highly crystallized structure with well-established carbon channels around activated carbon atoms could significantly accelerate electron transfer process after initial adsorption of PMS. As such, this crystalline nanocarbon exhibited excellent catalytic kinetics for various pollutants. (3) MOF-derived 2D carbon layers: enhanced mass/electron transfer The two-dimensional (2D) configuration of carbon-based nanosheets with inherent nanochannels and abundant active sites residing on the layer edges or in between the layers, allowed the accessible interaction and close contact between the substrates and reactants, as well as the dramatically improved electron- and mass-transfer kinetics. In this regard, we developed dual-templating strategy to afford 2D assembly of the crystalline carbons, which found efficiency in reinforcing the interactions between the catalyst surface and foreign pollutants. Specifically, we found that the ice crystals and NaCl promoted the evolution of MOF in a 2D fashion during the freezing casting stage, while the later further allowed the formation of a graphitic surface at high calcination temperature, by virtue of the templating effect of molten salt. Due to the highly retained co-doping amounts, N and O heteroatoms created abundant active sites for PMS activation, the 2D configuration of carbon-based nanosheets enable efficient interaction of PMS and pollutants on the surface, which further boosted the kinetics of degradation.}, language = {en} } @phdthesis{Schutjajew2021, author = {Schutjajew, Konstantin}, title = {Electrochemical sodium storage in non-graphitizing carbons - insights into mechanisms and synthetic approaches towards high-energy density materials}, doi = {10.25932/publishup-54189}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-541894}, school = {Universit{\"a}t Potsdam}, pages = {v, 148}, year = {2021}, abstract = {To achieve a sustainable energy economy, it is necessary to turn back on the combustion of fossil fuels as a means of energy production and switch to renewable sources. However, their temporal availability does not match societal consumption needs, meaning that renewably generated energy must be stored in its main generation times and allocated during peak consumption periods. Electrochemical energy storage (EES) in general is well suited due to its infrastructural independence and scalability. The lithium ion battery (LIB) takes a special place, among EES systems due to its energy density and efficiency, but the scarcity and uneven geological occurrence of minerals and ores vital for many cell components, and hence the high and fluctuating costs will decelerate its further distribution. The sodium ion battery (SIB) is a promising successor to LIB technology, as the fundamental setup and cell chemistry is similar in the two systems. Yet, the most widespread negative electrode material in LIBs, graphite, cannot be used in SIBs, as it cannot store sufficient amounts of sodium at reasonable potentials. Hence, another carbon allotrope, non-graphitizing or hard carbon (HC) is used in SIBs. This material consists of turbostratically disordered, curved graphene layers, forming regions of graphitic stacking and zones of deviating layers, so-called internal or closed pores. The structural features of HC have a substantial impact of the charge-potential curve exhibited by the carbon when it is used as the negative electrode in an SIB. At defects and edges an adsorption-like mechanism of sodium storage is prevalent, causing a sloping voltage curve, ill-suited for the practical application in SIBs, whereas a constant voltage plateau of relatively high capacities is found immediately after the sloping region, which recent research attributed to the deposition of quasimetallic sodium into the closed pores of HC. Literature on the general mechanism of sodium storage in HCs and especially the role of the closed pore is abundant, but the influence of the pore geometry and chemical nature of the HC on the low-potential sodium deposition is yet in an early stage. Therefore, the scope of this thesis is to investigate these relationships using suitable synthetic and characterization methods. Materials of precisely known morphology, porosity, and chemical structure are prepared in clear distinction to commonly obtained ones and their impact on the sodium storage characteristics is observed. Electrochemical impedance spectroscopy in combination with distribution of relaxation times analysis is further established as a technique to study the sodium storage process, in addition to classical direct current techniques, and an equivalent circuit model is proposed to qualitatively describe the HC sodiation mechanism, based on the recorded data. The obtained knowledge is used to develop a method for the preparation of closed porous and non-porous materials from open porous ones, proving not only the necessity of closed pores for efficient sodium storage, but also providing a method for effective pore closure and hence the increase of the sodium storage capacity and efficiency of carbon materials. The insights obtained and methods developed within this work hence not only contribute to the better understanding of the sodium storage mechanism in carbon materials of SIBs, but can also serve as guidance for the design of efficient electrode materials.}, language = {en} } @phdthesis{Krabi1996, author = {Krabi, Astrid}, title = {Electrophoretic and hydrodynamik characterization of neutral polymer depletion layers}, pages = {114 S.}, year = {1996}, language = {en} } @phdthesis{Ledendecker2016, author = {Ledendecker, Marc}, title = {En route towards advanced catalyst materials for the electrocatalytic water splitting reaction}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-93296}, school = {Universit{\"a}t Potsdam}, pages = {II, 148}, year = {2016}, abstract = {The thesis on hand deals with the development of new types of catalysts based on pristine metals and ceramic materials and their application as catalysts for the electrocatalytic water splitting reaction. In order to breathe life into this technology, cost-efficient, stable and efficient catalysts are imploringly desired. In this manner, the preparation of Mn-, N-, S-, P-, and C-containing nickel materials has been investigated together with the theoretical and electrochemical elucidation of their activity towards the hydrogen (and oxygen) evolution reaction. The Sabatier principle has been used as the principal guideline towards successful tuning of catalytic sites. Furthermore, two pathways have been chosen to ameliorate the electrocatalytic performance, namely, the direct improvement of intrinsic properties through appropriate material selection and secondly the increase of surface area of the catalytic material with an increased amount of active sites. In this manner, bringing materials with optimized hydrogen adsorption free energy onto high surface area support, catalytic performances approaching the golden standards of noble metals were feasible. Despite varying applied synthesis strategies (wet chemistry in organic solvents, ionothermal reaction, gas phase reaction), one goal has been systematically pursued: to understand the driving mechanism of the growth. Moreover, deeper understanding of inherent properties and kinetic parameters of the catalytic materials has been gained.}, language = {en} } @phdthesis{Kar, author = {Kar, Manaswita}, title = {Energy band gap tuning of halide perovskite materials from first principles}, school = {Universit{\"a}t Potsdam}, abstract = {Solar cells based on hybrid perovskites materials have become significantly important among the third generation photovoltaics over the last few years. The first solid state solar cell was reported in 2012. Over the years, the power conversion efficiencies of these devices have increased at a tremendous pace and this has made the perovskite solar cell devices a serious competitor in the well-established market of thin-film and wafer technologies. Over time, a large number of articles on this topic has been published in peer-reviewed journals. The presence of lead in the most efficient hybrid perovskite materials have raised questions about the possible toxicity of these devices and the extent of their environmental impact. Therefore, a lot of research has been devoted to finding alternative perovskite materials with similar or even better opto-electronic properties. An alternative strategy to improve the efficiency of thin film solar cells is to build efficient tandem cells by combining two or more perovskite materials with specifically tailored band gaps. The first step towards the development of perovskite-only tandem solar cells is to identify complementary hybrid perovskite materials with specific band gaps that maximize the efficiency of tandem solar cells. The optimal set of optical gaps for a tandem structure made of two materials is 1.9 eV and 1.0 eV. Since the electronic properties of hybrid perovskites are known to be strongly dependent on the composition and distortion of the crystal lattice, strong focus has been made towards the structure optimisation as well as the calculation of the energy band gaps of the materials using density functional theory (DFT). In an attempt to study the structure-property relationship of these perovskite materials and to find novel perovskite materials for future applications, researchers have employed computational screening procedures to study a large range of these materials by systematic replacement of the cations and anions from the prototypical perovskite. Density functional theory in particular is used as a theoretical tool, because of it's precision to determine the properties of materials and also it's computational viability in dealing with complex systems. In this thesis, the main focus is to do a systematic screening of the perovskite materials, of the composition ABX3 again by replacing the A-site, B-site and the X-site elements to find novel materials with band gaps suitable for application in tandem solar cells. As a first step towards contributing to this vibrant field of research, a high-throughput computational screening has been performed by replacing the metal and the halogen in the conventional CH3NH3PbI3 perovskites with homovalent metals and halogens to find materials in the desired range of band gaps that has already been mentioned earlier. This is achieved by performing a geometry optimisation on all the simulated structures followed by calculating their energy band gaps at the semilocal and the hybrid levels of theory. However, it is well known that the rotation of the organic cation CH3NH3 hinders the stability of these devices by the formation of hydrogen bonds between the hydrogen atoms of the cation and the halogens. This causes the materials to degrade under normal temperature and pressure conditions. As an attempt to prevent these devices from being unstable, a next step has been taken where the CH3NH3 cation has been replaced by inorganic cations of similar ionic radius. This is followed by another thorough screening, similar to the previous step. The stability of the materials has been determined by using the empirical Goldschmidt tolerance factor. As a last part of the thesis, a small proportion of the inorganic cation is mixed with CH3NH3 in order to form mixed-halide perovskites. These structures are optimised and their band gaps are calculated using density functional theory in order to predict materials suitable for single junction as well as tandem solar cell devices. It is expected that the contribution made through this thesis will be helpful for the progress of perovskite solar cells in terms of efficiencies and will also allow the community to explore the different properties these materials for further progress and development.}, language = {en} } @phdthesis{CruzLemus2020, author = {Cruz Lemus, Saul Daniel}, title = {Enhancing Efficiency of Inverted Perovskite Solar Cells}, school = {Universit{\"a}t Potsdam}, pages = {117}, year = {2020}, abstract = {Carbon nitride and poly(ionic liquid)s (PILs) have been successfully applied in various fields of materials science owing to their outstanding properties. This thesis aims at the successful application of these polymers as innovative materials in the interfaces of hybrid organic-inorganic perovskite solar cells. A critical problem in harnessing the full thermodynamic potential of halide perovskites in solar cells is the design and modification of interfaces to reduce carrier recombination. Therefore, the interface must be properly studied and improved. This work investigated the effect of applying carbon nitride and PILs on a perovskite surface on the device performance. The facile synthetic method for modifying carbon nitride with vinyl thiazole and barbituric acid (CMB-vTA) yields 2.3 nm layers when solution processing is performed using isopropanol. The nanosheets were applied as a metal-free electron transport layer in inverted perovskite solar cells. The application of carbon nitride layers (CMB-vTA) resulted in negligible current-voltage hysteresis with a high open circuit voltage (Voc) of 1.1 V and a short-circuit current (Jsc) of 20.28 mA cm-2, which afforded efficiencies of up to 17\%. Thus, the successful implementation of a carbon nitride-based structure enabled good charge extraction with minimized interface recombination between the perovskite and PCBM. Similarly, PILs represent a new strategy of interfacial modification using an ionic polymer in an n-i-p perovskite architecture.. The application of PILs as an interfacial modifier resulted in solar cell devices with an extraordinarily high efficiency of 21.8\% and a Voc of 1.17 V. The implementation reduced non-radiative recombination at the perovskite surface through defect passivation. Finally, our work proposes a novel method to efficiently suppress non-radiative charge recombination using the unexplored properties of carbon nitride and PILs in the solar cell field. Additionally, the method for interfacial modification has general applicability because of the simplicity of the post-treatment approach, and therefore has potential applicability in other solar cells. Thus, this work opens the door to a new class of materials to be implemented.}, language = {en} } @phdthesis{Riebe2016, author = {Riebe, Daniel}, title = {Experimental and theoretical investigations of molecular ions by spectroscopy as well as ion mobility and mass spectrometry}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-94632}, school = {Universit{\"a}t Potsdam}, pages = {143}, year = {2016}, abstract = {The aim of this thesis was the elucidation of different ionization methods (resonance-enhanced multiphoton ionization - REMPI, electrospray ionization - ESI, atmospheric pressure chemical ionization - APCI) in ion mobility (IM) spectrometry. In order to gain a better understanding of the ionization processes, several spectroscopic, mass spectrometric and theoretical methods were also used. Another focus was the development of experimental techniques, including a high resolution spectrograph and various combinations of IM and mass spectrometry. The novel high resolution 2D spectrograph facilitates spectroscopic resolutions in the range of commercial echelle spectrographs. The lowest full width at half maximum of a peak achieved was 25 pm. The 2D spectrograph is based on the wavelength separation of light by the combination of a prism and a grating in one dimension, and an etalon in the second dimension. This instrument was successfully employed for the acquisition of Raman and laser-induced breakdown spectra. Different spectroscopic methods (light scattering and fluorescence spectroscopy) permitting a spatial as well as spectral resolution, were used to investigate the release of ions in the electrospray. The investigation is based on the 50 nm shift of the fluorescence band of rhodamine 6G ions of during the transfer from the electrospray droplets to the gas phase. A newly developed ionization chamber operating at reduced pressure (0.5 mbar) was coupled to a time-of-flight mass spectrometer. After REMPI of H2S, an ionization chemistry analogous to H2O was observed with this instrument. Besides H2S+ and its fragments, H3S+ and protonated analyte ions could be observed as a result of proton-transfer reactions. For the elucidation of the peaks in IM spectra, a combination of IM spectrometer and linear quadrupole ion trap mass spectrometer was developed. The instrument can be equipped with various ionization sources (ESI, REMPI, APCI) and was used for the characterization of the peptide bradykinin and the neuroleptic promazine. The ionization of explosive compounds in an APCI source based on soft x-radiation was investigated in a newly developed ionization chamber attached to the ion trap mass spectrometer. The major primary and secondary reactions could be characterized and explosive compound ions could be identified and assigned to the peaks in IM spectra. The assignment is based on the comparison of experimentally determined and calculated IM. The methods of calculation currently available exhibit large deviations, especially in the case of anions. Therefore, on the basis of an assessment of available methods, a novel hybrid method was developed and characterized.}, language = {en} } @phdthesis{Alahverdjieva2007, author = {Alahverdjieva, Veneta}, title = {Experimental study of mixed protein/surfactant systems at the aqueous solution/air interface}, address = {Potsdam}, pages = {XIV, 146 S., X : graph. Darst.}, year = {2007}, language = {en} } @phdthesis{Kopetzki2011, author = {Kopetzki, Daniel}, title = {Exploring hydrothermal reactions : from prebiotic synthesis to green chemistry}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-52581}, school = {Universit{\"a}t Potsdam}, year = {2011}, abstract = {In this thesis chemical reactions under hydrothermal conditions were explored, whereby emphasis was put on green chemistry. Water at high temperature and pressure acts as a benign solvent. Motivation to work under hydrothermal conditions was well-founded in the tunability of physicochemical properties with temperature, e.g. of dielectric constant, density or ion product, which often resulted in surprising reactivity. Another cornerstone was the implementation of the principles of green chemistry. Besides the use of water as solvent, this included the employment of a sustainable feedstock and the sensible use of resources by minimizing waste and harmful intermediates and additives. To evaluate the feasibility of hydrothermal conditions for chemical synthesis, exemplary reactions were performed. These were carried out in a continuous flow reactor, allowing for precise control of reaction conditions and kinetics measurements. In most experiments a temperature of 200 °C in combination with a pressure of 100 bar was chosen. In some cases the temperature was even raised to 300 °C. Water in this subcritical range can also be found in nature at hydrothermal vents on the ocean floor. On the primitive earth, environments with such conditions were however present in larger numbers. Therefore we tested whether biologically important carbohydrates could be formed at high temperature from the simple, probably prebiotic precursor formaldehyde. Indeed, this formose reaction could be carried out successfully, although the yield was lower compared to the counterpart reaction under ambient conditions. However, striking differences regarding selectivity and necessary catalysts were observed. At moderate temperatures bases and catalytically active cations like Ca2+ are necessary and the main products are hexoses and pentoses, which accumulate due to their higher stability. In contrast, in high-temperature water no catalyst was necessary but a slightly alkaline solution was sufficient. Hexoses were only formed in negligible amounts, whereas pentoses and the shorter carbohydrates accounted for the major fraction. Amongst the pentoses there was some preference for the formation of ribose. Even deoxy sugars could be detected in traces. The observation that catalysts can be avoided was successfully transferred to another reaction. In a green chemistry approach platform chemicals must be produced from sustainable resources. Carbohydrates can for instance be employed as a basis. They can be transformed to levulinic acid and formic acid, which can both react via a transfer hydrogenation to the green solvent and biofuel gamma-valerolactone. This second reaction usually requires catalysis by Ru or Pd, which are neither sustainable nor low-priced. Under hydrothermal conditions these heavy metals could be avoided and replaced by cheap salts, taking advantage of the temperature dependence of the acid dissociation constant. Simple sulfate was recognized as a temperature switchable base. With this additive high yield could be achieved by simultaneous prevention of waste. In contrast to conventional bases, which create salt upon neutralization, a temperature switchable base becomes neutral again when cooled down and thus can be reused. This adds another sustainable feature to the high atom economy of the presented hydrothermal synthesis. In a last study complex decomposition pathways of biomass were investigated. Gas chromatography in conjunction with mass spectroscopy has proven to be a powerful tool for the identification of unknowns. It was observed that several acids were formed when carbohydrates were treated with bases at high temperature. This procedure was also applied to digest wood. Afterwards it was possible to fermentate the solution and a good yield of methane was obtained. This has to be regarded in the light of the fact that wood practically cannot be used as a feedstock in a biogas factory. Thus the hydrothermal pretreatment is an efficient means to employ such materials as well. Also the reaction network of the hydrothermal decomposition of glycine was investigated using isotope-labeled compounds as comparison for the unambiguous identification of unknowns. This refined analysis allowed the identification of several new molecules and pathways, not yet described in literature. In summary several advantages could be taken from synthesis in high-temperature water. Many catalysts, absolutely necessary under ambient conditions, could either be completely avoided or replaced by cheap, sustainable alternatives. In this respect water is not only a green solvent, but helps to prevent waste and preserves resources.}, language = {en} } @phdthesis{Deshpande2004, author = {Deshpande, Atul Suresh}, title = {Fabrication of porous metal oxides for catalytic application using templating techniques}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0001324}, school = {Universit{\"a}t Potsdam}, year = {2004}, abstract = {Nanostrukturierte Materialien zeichnen sich dadurch aus, dass sie aus sehr kleinen Baueinheiten zusammengesetzt sind. Typischerweise liegt die Gr{\"o}ssenordnung dieser Bausteine im Bereich von einigen Nanometern. Ein Nanometer entspricht 10-9 Meter. Dadurch bekommen nanostrukturierte Materialien oft verbesserte, vielfach sogar ganz neue Eigenschaften, die f{\"u}r viele heutige wie auch zuk{\"u}nftige Anwendungen von Vorteil sind. Ein Weg, um solche nanostrukturierte Materialien herzustellen, ist die sogenannte \„Templatierungsmethode\“. Das Templat besteht aus einem einzelnen Molek{\"u}l, einer Ansammlung von Molek{\"u}len oder aus einem festen Objekt. Beim Aufbau des nanostrukturierten Materials wirkt das Templat als Schablone oder als Gussform und beeinflusst damit die Struktur des Endproduktes. Normalerweise besteht dieser Prozess aus mehreren Schritten. Zuerst wird der Raum um das Templat mit dem Ausgangsstoff umh{\"u}llt oder ausgef{\"u}llt, dann wird der Ausgangsstoff chemisch in das gew{\"u}nschte Endprodukt umgewandelt, wobei das Templat die Endform kontrolliert und am Schluss wird das Templat entfernt. Das geschieht meistens durch Erhitzen. Als Ausgangsstoff k{\"o}nnen dabei einzelne Molek{\"u}le verwendet werden, die sich leicht in das Endprodukt umwandeln lassen, oder aber vorgeformte Partikelchen, die nur noch zur entsprechenden Form angeordnet werden m{\"u}ssen. In dieser Arbeit wurden por{\"o}se Metalloxid-K{\"u}gelchen hergestellt, die aus einem Gemisch aus Titanoxid und entweder Aluminium-, Gallium- oder Indiumoxid bestehen. Als Template wurden por{\"o}se Kunststoffk{\"u}gelchen eingesetzt, die man sonst f{\"u}r Chromatographiezwecke braucht. Bei der Synthese wurden die Poren der Kunststoffk{\"u}gelchen mit dem Ausgangsmaterial gef{\"u}llt und mit Wasser in ein amorphes Netzwerk umgewandelt. Danach werden die K{\"u}gelchen erhitzt, wobei das Kunststofftemplat zersetzt wird. Gleichzeitig wird das amorphe Ger{\"u}st in stabile, kristalline W{\"a}nde umgewandelt, die die Form der K{\"u}gelchen auch dann noch behalten, wenn das Templat verschwunden ist. Mit einem {\"a}hnlichen Prozess wurden auch K{\"u}gelchen aus Cer-Zirkonoxid erhalten. Als Ausgangsstoff wurden dabei aber vorgeformte Cer-Zirkonoxid-Nanopartikel eingesetzt, die in die Poren der Kunststofftemplatk{\"u}gelchen hinein diffundieren. Diese Cer-Zirkonoxid-Nanopartikel lassen sich auch f{\"u}r die Herstellung von por{\"o}sen Pulvern verwenden, wobei dann nicht Polymerk{\"u}gelchen, sondern hochgeordnete Ansammlungen von Block Copolymeren als Template verwendet werden. Form, Struktur und Eigenschaften all dieser Materialien wurden systematisch unter Anwendung verschiedenster Analysemethoden untersucht. Die auf Titanoxid-basierten K{\"u}gelchen wurden auch auf ihre photokatalytische Verwendung zum Abbau von umweltsch{\"a}dlichem 2-Chlorophenol untersucht. Die Cer-Zirkonoxid-K{\"u}gelchen wurden f{\"u}r die Herstellung von Wasserstoff aus Methanol getestet. Wasserstoff gilt als hoffungsvoller, sauberer Energietr{\"a}ger der Zukunft und kommt in Brennstoffzellen zum Einsatz.}, language = {en} } @phdthesis{Borisova2012, author = {Borisova, Dimitriya}, title = {Feedback active coatings based on mesoporous silica containers}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-63505}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {Metalle werden oft w{\"a}hrend ihrer Anwendung korrosiven Bedingungen ausgesetzt, was ihre Alterungsbest{\"a}ndigkeit reduziert. Deswegen werden korrosionsanf{\"a}llige Metalle, wie Aluminiumlegierungen mit Schutzbeschichtungen versehen, um den Korrosionsprozess aktiv oder passiv zu verhindern. Die klassischen Schutzbeschichtungen funktionieren als physikalische Barriere zwischen Metall und korrosiver Umgebung und bieten einen passiven Korrosionsschutz nur, wenn sie unbesch{\"a}digt sind. Im Gegensatz dazu kann die Korrosion auch im Fall einer Besch{\"a}digung mittels aktiver Schutzbeschichtungen gehemmt werden. Chromathaltige Beschichtungen bieten heutzutage den besten aktiven Korrosionsschutz f{\"u}r Aluminiumlegierungen. Aufgrund ihrer Giftigkeit wurden diese weltweit verboten und m{\"u}ssen durch neue umweltfreundliche Schutzbeschichtungen ersetzt werden. Ein potentieller Ersatz sind Schutzbeschichtungen mit integrierten Nano- und Mikrobeh{\"a}ltern, die mit ungiftigem Inhibitor gef{\"u}llt sind. In dieser Arbeit werden die Entwicklung und Optimierung solcher aktiver Schutzbeschichtungen f{\"u}r die industriell wichtige Aluminiumlegierung AA2024-T3 dargestellt Mesopor{\"o}se Silika-Beh{\"a}lter wurden mit dem ungiftigen Inhibitor (2-Mercaptobenzothiazol) beladen und dann in die Matrix anorganischer (SiOx/ZrOx) oder organischer (wasserbasiert) Schichten dispergiert. Zwei Sorten von Silika-Beh{\"a}ltern mit unterschiedlichen Gr{\"o}ßen (d ≈ 80 and 700 nm) wurden verwendet. Diese haben eine große spezifische Oberfl{\"a}che (≈ 1000 m² g-1), eine enge Porengr{\"o}ßenverteilung mit mittlerer Porenweite ≈ 3 nm und ein großes Porenvolumen (≈ 1 mL g-1). Dank dieser Eigenschaften k{\"o}nnen große Inhibitormengen im Beh{\"a}lterinneren adsorbiert und gehalten werden. Die Inhibitormolek{\"u}le werden bei korrosionsbedingter Erh{\"o}hung des pH-Wertes gel{\"o}st und freigegeben. Die Konzentration, Position und Gr{\"o}ße der integrierten Beh{\"a}lter wurden variiert um die besten Bedingungen f{\"u}r einen optimalen Korrosionsschutz zu bestimmen. Es wurde festgestellt, dass eine gute Korrosionsschutzleistung durch einen Kompromiss zwischen ausreichender Inhibitormenge und guten Barriereeigenschaften hervorgerufen wird. Diese Studie erweitert das Wissen {\"u}ber die wichtigsten Faktoren, die den Korrosionsschutz beeinflussen. Somit wurde die Entwicklung effizienter, aktiver Schutzbeschichtungen erm{\"o}glicht, die auf mit Inhibitor beladenen Beh{\"a}ltern basieren.}, language = {en} } @phdthesis{Netz1999, author = {Netz, Roland R.}, title = {Field-theoretic approaches to clasical charged systems}, pages = {123 S.}, year = {1999}, language = {en} } @phdthesis{Unterlass2011, author = {Unterlass, Miriam Margarethe}, title = {From monomer salts and their tectonic crystals to aromatic polyimides : development of neoteric synthesis routes}, address = {Potsdam}, pages = {147 S.}, year = {2011}, language = {en} } @phdthesis{Melani2019, author = {Melani, Giacomo}, title = {From structural fluctuations to vibrational spectroscopy of adsorbates on surfaces}, doi = {10.25932/publishup-44182}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-441826}, school = {Universit{\"a}t Potsdam}, pages = {119}, year = {2019}, abstract = {Aluminum oxide is an Earth-abundant geological material, and its interaction with water is of crucial importance for geochemical and environmental processes. Some aluminum oxide surfaces are also known to be useful in heterogeneous catalysis, while the surface chemistry of aqueous oxide interfaces determines the corrosion, growth and dissolution of such materials. In this doctoral work, we looked mainly at the (0001) surface of α-Al 2 O 3 and its reactivity towards water. In particular, a great focus of this work is dedicated to simulate and address the vibrational spectra of water adsorbed on the α-alumina(0001) surface in various conditions and at different coverages. In fact, the main source of comparison and inspiration for this work comes from the collaboration with the "Interfacial Molecular Spectroscopy" group led by Dr. R. Kramer Campen at the Fritz-Haber Institute of the MPG in Berlin. The expertise of our project partners in surface-sensitive Vibrational Sum Frequency (VSF) generation spectroscopy was crucial to develop and adapt specific simulation schemes used in this work. Methodologically, the main approach employed in this thesis is Ab Initio Molecular Dynamics (AIMD) based on periodic Density Functional Theory (DFT) using the PBE functional with D2 dispersion correction. The analysis of vibrational frequencies from both a static and a dynamic, finite-temperature perspective offers the ability to investigate the water / aluminum oxide interface in close connection to experiment. The first project presented in this work considers the characterization of dissociatively adsorbed deuterated water on the Al-terminated (0001) surface. This particular structure is known from both experiment and theory to be the thermodynamically most stable surface termination of α-alumina in Ultra-High Vacuum (UHV) conditions. Based on experiments performed by our colleagues at FHI, different adsorption sites and products have been proposed and identified for D 2 O. While previous theoretical investigations only looked at vibrational frequencies of dissociated OD groups by staticNormal Modes Analysis (NMA), we rather employed a more sophisticated approach to directly assess vibrational spectra (like IR and VSF) at finite temperature from AIMD. In this work, we have employed a recent implementation which makes use of velocity-velocity autocorrelation functions to simulate such spectral responses of O-H(D) bonds. This approach allows for an efficient and qualitatively accurate estimation of Vibrational Densities of States (VDOS) as well as IR and VSF spectra, which are then tested against experimental spectra from our collaborators. In order to extend previous work on unimolecularly dissociated water on α-Al 2 O 3 , we then considered a different system, namely, a fully hydroxylated (0001) surface, which results from the reconstruction of the UHV-stable Al-terminated surface at high water contents. This model is then further extended by considering a hydroxylated surface with additional water molecules, forming a two-dimensional layer which serves as a potential template to simulate an aqueous interface in environmental conditions. Again, employing finite-temperature AIMD trajectories at the PBE+D2 level, we investigated the behaviour of both hydroxylated surface (HS) and the water-covered structure derived from it (known as HS+2ML). A full range of spectra, from VDOS to IR and VSF, is then calculated using the same methodology, as described above. This is the main focus of the second project, reported in Chapter 5. In this case, comparison between theoretical spectra and experimental data is definitely good. In particular, we underline the nature of high-frequency resonances observed above 3700 cm -1 in VSF experiments to be associated with surface OH-groups, known as "aluminols" which are a key fingerprint of the fully hydroxylated surface. In the third and last project, which is presented in Chapter 6, the extension of VSF spectroscopy experiments to the time-resolved regime offered us the opportunity to investigate vibrational energy relaxation at the α-alumina / water interface. Specifically, using again DFT-based AIMD simulations, we simulated vibrational lifetimes for surface aluminols as experimentally detected via pump-probe VSF. We considered the water-covered HS model as a potential candidate to address this problem. The vibrational (IR) excitation and subsequent relaxation is performed by means of a non-equilibrium molecular dynamics scheme. In such a scheme, we specifically looked at the O-H stretching mode of surface aluminols. Afterwards, the analysis of non-equilibrium trajectories allows for an estimation of relaxation times in the order of 2-4 ps which are in overall agreement with measured ones. The aim of this work has been to provide, within a consistent theoretical framework, a better understanding of vibrational spectroscopy and dynamics for water on the α-alumina(0001) surface,ranging from very low water coverage (similar to the UHV case) up to medium-high coverages, resembling the hydroxylated oxide in environmental moist conditions.}, language = {en} } @phdthesis{Makowski2009, author = {Makowski, Philippe Denis}, title = {From Supported Paladium to Metal free Catalysts : different approaches in heterogeneous catalysis}, address = {Potsdam}, pages = {144 S.}, year = {2009}, language = {en} } @phdthesis{Xie2012, author = {Xie, Zai-Lai}, title = {Functional materials in metal-containing ionic liquids}, address = {Potsdam}, pages = {108 S.}, year = {2012}, language = {en} } @phdthesis{Diehl2009, author = {Diehl, Christina}, title = {Functional microspheres through crystallization of thermoresponsive poly(2-oxazoline)s}, address = {Potsdam}, pages = {125 S. : Ill., graph. Darst.}, year = {2009}, language = {en} } @phdthesis{Duan2005, author = {Duan, Hongwei}, title = {Functional Nanoparticles as Self-Assembling Building Block and Synthetic Templates}, address = {Potsdam}, pages = {III, 107 S. : Ill., graph. Darst.}, year = {2005}, language = {en} } @phdthesis{MbayaMani2017, author = {Mbaya Mani, Christian}, title = {Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-407866}, school = {Universit{\"a}t Potsdam}, pages = {IV, 135}, year = {2017}, abstract = {Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures. In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges. These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure. Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67\% of this specific capacitance when the scan rate is increased to 200 mV s-1. In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking. Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.}, language = {en} } @phdthesis{Wohlgemuth2012, author = {Wohlgemuth, Stephanie-Angelika}, title = {Functional nanostructured hydrothermal carbons for sustainable technologies : heteroatom doping and superheated vapor}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-60120}, school = {Universit{\"a}t Potsdam}, year = {2012}, abstract = {The underlying motivation for the work carried out for this thesis was the growing need for more sustainable technologies. The aim was to synthesize a "palette" of functional nanomaterials using the established technique of hydrothermal carbonization (HTC). The incredible diversity of HTC was demonstrated together with small but steady advances in how HTC can be manipulated to tailor material properties for specific applications. Two main strategies were used to modify the materials obtained by HTC of glucose, a model precursor representing biomass. The first approach was the introduction of heteroatoms, or "doping" of the carbon framework. Sulfur was for the first time introduced as a dopant in hydrothermal carbon. The synthesis of sulfur and sulfur/nitrogen doped microspheres was presented whereby it was shown that the binding state of sulfur could be influenced by varying the type of sulfur source. Pyrolysis may additionally be used to tune the heteroatom binding states which move to more stable motifs with increasing pyrolysis temperature. Importantly, the presence of aromatic binding states in the as synthesized hydrothermal carbon allows for higher heteroatom retention levels after pyrolysis and hence more efficient use of dopant sources. In this regard, HTC may be considered as an "intermediate" step in the formation of conductive heteroatom doped carbon. To assess the novel hydrothermal carbons in terms of their potential for electrochemical applications, materials with defined nano-architectures and high surface areas were synthesized via templated, as well as template-free routes. Sulfur and/or nitrogen doped carbon hollow spheres (CHS) were synthesized using a polystyrene hard templating approach and doped carbon aerogels (CA) were synthesized using either the albumin directed or borax-mediated hydrothermal carbonization of glucose. Electrochemical testing showed that S/N dual doped CHS and aerogels derived via the albumin approach exhibited superior catalytic performance compared to solely nitrogen or sulfur doped counterparts in the oxygen reduction reaction (ORR) relevant to fuel cells. Using the borax mediated aerogel formation, nitrogen content and surface area could be tuned and a carbon aerogel was engineered to maximize electrochemical performance. The obtained sample exhibited drastically improved current densities compared to a platinum catalyst (but lower onset potential), as well as excellent long term stability. In the second approach HTC was carried out at elevated temperatures (550 °C) and pressure (50 bar), corresponding to the superheated vapor regime (htHTC). It was demonstrated that the carbon materials obtained via htHTC are distinct from those obtained via ltHTC and subsequent pyrolysis at 550 °C. No difference in htHTC-derived material properties could be observed between pentoses and hexoses. The material obtained from a polysaccharide exhibited a slightly lower degree of carbonization but was otherwise similar to the monosaccharide derived samples. It was shown that in addition to thermally induced carbonization at 550 °C, the SHV environment exhibits a catalytic effect on the carbonization process. The resulting materials are chemically inert (i.e. they contain a negligible amount of reactive functional groups) and possess low surface area and electronic conductivity which distinguishes them from carbon obtained from pyrolysis. Compared to the materials presented in the previous chapters on chemical modifications of hydrothermal carbon, this makes them ill-suited candidates for electronic applications like lithium ion batteries or electrocatalysts. However, htHTC derived materials could be interesting for applications that require chemical inertness but do not require specific electronic properties. The final section of this thesis therefore revisited the latex hard templating approach to synthesize carbon hollow spheres using htHTC. However, by using htHTC it was possible to carry out template removal in situ because the second heating step at 550 °C was above the polystyrene latex decomposition temperature. Preliminary tests showed that the CHS could be dispersed in an aqueous polystyrene latex without monomer penetrating into the hollow sphere voids. This leaves the stagnant air inside the CHS intact which in turn is promising for their application in heat and sound insulating coatings. Overall the work carried out in this thesis represents a noteworthy development in demonstrating the great potential of sustainable carbon materials.}, language = {en} } @phdthesis{Zhang2017, author = {Zhang, Weiyi}, title = {Functional Poly(ionic liquid) Materials based on Poly(1,2,4-triazolium)s}, school = {Universit{\"a}t Potsdam}, pages = {108}, year = {2017}, language = {en} } @phdthesis{Perovic2020, author = {Perovic, Milena}, title = {Functionalization of nanoporous carbon materials for chiral separation and heterogeneous oxidation catalysis}, doi = {10.25932/publishup-48659}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-486594}, school = {Universit{\"a}t Potsdam}, pages = {140}, year = {2020}, abstract = {The impact that catalysis has on global economy and environment is substantial, since 85\% of all chemical industrial processes are catalytic. Among those, 80\% of the processes are heterogeneously catalyzed, 17\% make use of homogeneous catalysts, and 3\% are biocatalytic processes. Especially in the pharmaceutical and agrochemical industry, a significant part of these processes involves chiral compounds. Obtaining enantiomerically pure compounds is necessary and it is usually accomplished by asymmetric synthesis and catalysis, as well as chiral separation. The efficiency of these processes may be vastly improved if the chiral selectors are positioned on a porous solid support, thereby increasing the available surface area for chiral recognition. Similarly, the majority of commercial catalysts are also supported, usually comprising of metal nanoparticles (NPs) dispersed on highly porous oxide or nanoporous carbon material. Materials that have exceptional thermal and chemical stability, and are electrically conductive are porous carbons. Their stability in extreme pH regions and temperatures, the possibility to tailor their pore architecture and chemical functionalization, and their electric conductivity have already established these materials in the fields of separation and catalysis. However, their heterogeneous chemical structure with abundant defects make it challenging to develop reliable models for the investigation of structure-performance relationships. Therefore, there is a necessity for expanding the fundamental understanding of these robust materials under experimental conditions to allow for their further optimization for particular applications. This thesis gives a contribution to our knowledge about carbons, through different aspects, and in different applications. On the one hand, a rather exotic novel application was investigated by attempts in synthesizing porous carbon materials with an enantioselective surface. Chapter 4.1 described an approach for obtaining mesoporous carbons with an enantioselective surface by direct carbonization of a chiral precursor. Two enantiomers of chiral ionic liquids (CIL) based on amino acid tyrosine were used as carbon precursors and ordered mesoporous silica SBA-15 served as a hard template for obtaining porosity. The chiral recognition of the prepared carbons has been tested in the solution by isothermal titration calorimetry with enantiomers of Phenylalanine as probes, as well as chiral vapor adsorption with 2-butanol enantiomers. Measurements in both solution and the gas phase revealed the differences in the affinity of carbons towards two enantiomers. The atomic efficiency of the CIL precursors was increased in Chapter 4.2, and the porosity was developed independently from the development of chiral carbons, through the formation of stable composites of pristine carbon and CIL-derived coating. After the same set of experiments for the investigation of chirality, the enantiomeric ratios of the composites reported herein were even higher than in the previous chapter. On the other hand, the structure‒activity relationship of carbons as supports for gold nanoparticles in a rather traditional catalytic model reaction, on the interface between gas, liquid, and solid, was studied. In Chapter 5.1 it was shown on the series of catalysts with different porosities that the kinetics of ᴅ-glucose oxidation reaction can be enhanced by increasing the local concentration of the reactants around the active phase of the catalyst. A large amount of uniform narrow mesopores connected to the surface of the Au catalyst supported on ordered mesoporous carbon led to the water confinement, which increased the solubility of the oxygen in the proximity of the catalyst and thereby increased the apparent catalytic activity of this catalyst. After increasing the oxygen concentration in the internal area of the catalyst, in Chapter 5.2 the concentration of oxygen was increased in the external environment of the catalyst, by the introduction of less cohesive liquids that serve as efficient solvent for oxygen, perfluorinated compounds, near the active phase of the catalyst. This was achieved by a formation of catalyst particle-stabilized emulsions of perfluorocarbon in aqueous ᴅ-glucose solution, that further promoted the catalytic activity of gold-on-carbon catalyst. The findings reported within this thesis are an important step in the understanding of the structure-related properties of carbon materials.}, language = {en} } @phdthesis{Lama2018, author = {Lama, Sandy M. G.}, title = {Functionalization of Porous Carbon Materials with Heteroatoms and Application as Supports in Industrial Heterogeneous Catalysis}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-415797}, school = {Universit{\"a}t Potsdam}, pages = {124}, year = {2018}, abstract = {Due to a challenging population growth and environmental changes, a need for new routes to provide required chemicals for human necessities arises. An effective solution discussed in this thesis is industrial heterogeneous catalysis. The development of an advanced industrial heterogeneous catalyst is investigated herein by considering porous carbon nano-material as supports and modifying their surface chemistry structure with heteroatoms. Such modifications showed a significant influence on the performance of the catalyst and provided a deeper insight regarding the interaction between the surface structure of the catalyst and the surrounding phase. This thesis contributes to the few present studies about heteroatoms effect on the catalyst performance and emphasizes on the importance of understanding surface structure functionalization in a catalyst in different phases (liquid and gaseous) and for different reactions (hydrogenolysis, oxidation, and hydrogenation/ polymerization). Herein, the heteroatoms utilized for the modifications are hydrogen (H), oxygen (O), and nitrogen (N). The heteroatoms effect on the metal particle size, on the polarity of the support/ the catalyst, on the catalytic performance (activity, selectivity, and stability), and on the interaction with the surrounding phase has been explored. First hierarchical porous carbon nanomaterials functionalized with heteroatoms (N) is synthesized and applied as supports for nickel nanoparticles for hydrogenolysis process of kraft lignin in liquid phase. This reaction has been performed in batch and flow reactors for three different catalysts, two of comparable hierarchical porosity, yet one is modified with N and the other is not, and a third is a prepared catalyst from a commercial carbon support. The reaction production and analyses show that the catalysts with hierarchical porosity perform catalytically much better than in presence of a commercial carbon support with lower surface area. Moreover, the modification with N-heteroatoms enhanced the catalytic performance because the heteroatom modified porous carbon material with nickel nanoparticles catalyst (Ni-NDC) performed highest among the other catalysts. In the flow reactor, Ni-NDC selectively degraded the ether bonds (β-O-4) in kraft lignin with an activity of 2.2 x10^-4 mg lignin mg Ni-1 s-1 for 50 h at 350°C and 3.5 mL min-1 flow, providing ~99 \% conversion to shorter chained chemicals (mainly guaiacol derivatives). Then, the functionalization of carbon surface was further studied in selective oxidation of glucose to gluconic acid using < 1 wt. \% of gold (Au) deposited on the previously-mentioned synthesized carbon (C) supports with different functionalities (Au-CGlucose, Au-CGlucose-H, Au-CGlucose-O, Au-CGlucoseamine). Except for Au-CGlucose-O, the other catalysts achieved full glucose conversion within 40-120 min and 100\% selectivity towards gluconic acid with a maximum activity of 1.5 molGlucose molAu-1 s-1 in an aqueous phase at 45 °C and pH 9. Each heteroatom influenced the polarity of the carbon differently, affecting by that the deposition of Au on the support and thus the activity of the catalyst and its selectivity. The heteroatom effect was further investigated in a gas phase. The Fischer-Tropsch reaction was applied to convert synthetic gas (CO and H2) to short olefins and paraffins using surface-functionalized carbon nanotubes (CNTs) with heteroatoms as supports for ion (Fe) deposition in presence and absence of promoters (Na and S). The results showed the promoted Fe-CNT doped with nitrogen catalyst to be stable up to 180 h and selective to the formation of olefins (~ 47 \%) and paraffins (~6 \%) with a conversion of CO ~ 92 \% at a maximum activity of 94 *10^-5 mol CO g Fe-1 s-1. The more information given regarding this topic can open wide range of applications not only in catalysis, but in other approaches as well. In conclusion, incorporation of heteroatoms can be the next approach for an advanced industrial heterogeneous catalyst, but also for other applications (e.g. electrocatalysis, gas adsorption, or supercapacitors).}, language = {en} } @phdthesis{Lai2019, author = {Lai, Feili}, title = {Functionalized ordered mesoporous carbon materials for enhancing the energy density of supercapacitors}, school = {Universit{\"a}t Potsdam}, pages = {115}, year = {2019}, language = {en} } @phdthesis{Kupstat2012, author = {Kupstat, Annette}, title = {F{\"o}rster resonance energy transfer (FRET)-based detection of molecular binding interactions - from fundamental research to application in life science}, address = {Potsdam}, pages = {129 S.}, year = {2012}, language = {en} } @phdthesis{Olejko2017, author = {Olejko, Lydia}, title = {F{\"o}rster resonance energy transfer (FRET)-based nanophotonics using DNA origami structures}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-396747}, school = {Universit{\"a}t Potsdam}, year = {2017}, abstract = {The field of nanophotonics focuses on the interaction between electromagnetic radiation and matter on the nanometer scale. The elements of nanoscale photonic devices can transfer excitation energy non-radiatively from an excited donor molecule to an acceptor molecule by F{\"o}rster resonance energy transfer (FRET). The efficiency of this energy transfer is highly dependent on the donor-acceptor distance. Hence, in these nanoscale photonic devices it is of high importance to have a good control over the spatial assembly of used fluorophores. Based on molecular self-assembly processes, various nanostructures can be produced. Here, DNA nanotechnology and especially the DNA origami technique are auspicious self-assembling methods. By using DNA origami nanostructures different fluorophores can be introduced with a high local control to create a variety of nanoscale photonic objects. The applications of such nanostructures range from photonic wires and logic gates for molecular computing to artificial light harvesting systems for artificial photosynthesis. In the present cumulative doctoral thesis, different FRET systems on DNA origami structures have been designed and thoroughly analyzed. Firstly, the formation of guanine (G) quadruplex structures from G rich DNA sequences has been studied based on a two-color FRET system (Fluorescein (FAM)/Cyanine3 (Cy3)). Here, the influences of different cations (Na+ and K+), of the DNA origami structure and of the DNA sequence on the G-quadruplex formation have been analyzed. In this study, an ion-selective K+ sensing scheme based on the G-quadruplex formation on DNA origami structures has been developed. Subsequently, the reversibility of the G-quadruplex formation on DNA origami structures has been evaluated. This has been done for the simple two-color FRET system which has then been advanced to a switchable photonic wire by introducing additional fluorophores (FAM/Cy3/Cyanine5 (Cy5)/IRDye®700). In the last part, the emission intensity of the acceptor molecule (Cy5) in a three-color FRET cascade has been tuned by arranging multiple donor (FAM) and transmitter (Cy3) molecules around the central acceptor molecule. In such artificial light harvesting systems, the excitation energy is absorbed by several donor and transmitter molecules followed by an energy transfer to the acceptor leading to a brighter Cy5 emission. Furthermore, the range of possible excitation wavelengths is extended by using several different fluorophores (FAM/Cy3/Cy5). In this part of the thesis, the light harvesting efficiency (antenna effect) and the FRET efficiency of different donor/transmitter/acceptor assemblies have been analyzed and the artificial light harvesting complex has been optimized in this respect.}, language = {en} }