@misc{KortPeterKoopmanschap1983, author = {Kort, C. A. D. de and Peter, Martin G. and Koopmanschap, A. B.}, title = {Binding and degradation of juvenile hormone III by haemolymph proteins of the Colorado potato beetle: a re-examination}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-16777}, year = {1983}, abstract = {The haemolymph of the adult Colorado potato beetle, Lepinotarsa decemlineata Say, contains a high molecular weight (MW > 200,000) JH-III specific binding protein. The Kd value of the protein for racemic JH-III is 1.3 ± 0.2 × 10-7 M. It has a lower affinity for racemic JH-I and it does not bind JH-III-diol or JH-III-acid. The binding protein does discriminate between the enantiomers of synthetic, racemic JH-III as was determined by stereochemical anaysis of the bound and the free JH-III. Incubation of racemic JH-III with crude haemolymph results in preferential formation of (10S)-JH-III-acid, the unnatural configuration. The JH-esterase present in L. decemlineata haemolymph is not enantioselective. It is concluded that the most important function of the binding protein is that of a specific carrier, protecting the natural hormone against degradation by esterases. The carrier does not protect JH-I as efficiently as the lower homologue.}, 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{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} } @misc{PeterAndersenHartmannetal.1992, author = {Peter, Martin G. and Andersen, Svend Olav and Hartmann, Rudolf and Miessner, Merle and Roepstorff, Peter}, title = {Catecholamine-protein conjugates : isolation of 4-phenylphenoxazin-2-ones from oxidative coupling of N-acetyldopamine with alipathic amino acids}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-17571}, year = {1992}, abstract = {4-Phenylphenoxazinones were isolated after biomimetic oxidation, using diphenoloxidases of insect cuticle, mushroom tyrosinase, or after autoxidation of N-acetyldopamine (Image ) in the presence of β-alanine, β-alanine methyl ester or N-acetyl-L-lysine. They are formed presumably by addition of 2-aminoalkyl-5-alkylphenols to the o-quinone of biphenyltetrol which, in turn, arises from oxidative coupling of. The structures of present the first examples for the assembly of reasonably stable intermediates in the rather complex process of chemical modifications of aliphatic amino acid residues by o-quinones.}, language = {en} } @article{FigueroaCamposGKTKruizengaSaguTchewonpietal.2022, author = {Figueroa Campos, Gustavo Adolfo and G. K. T. Kruizenga, Johannes and Sagu Tchewonpi, Sorel and Schwarz, Steffen and Homann, Thomas and Taubert, Andreas and Rawel, Harshadrai Manilal}, title = {Effect of the post-harvest processing on protein modification in green coffee beans by phenolic compounds}, series = {Foods : open access journal}, volume = {11}, journal = {Foods : open access journal}, edition = {2}, publisher = {MDPI}, address = {Basel, Schweiz}, issn = {2304-8158}, doi = {10.3390/foods11020159}, pages = {19}, year = {2022}, abstract = {The protein fraction, important for coffee cup quality, is modified during post-harvest treatment prior to roasting. Proteins may interact with phenolic compounds, which constitute the major metabolites of coffee, where the processing affects these interactions. This allows the hypothesis that the proteins are denatured and modified via enzymatic and/or redox activation steps. The present study was initiated to encompass changes in the protein fraction. The investigations were limited to major storage protein of green coffee beans. Fourteen Coffea arabica samples from various processing methods and countries were used. Different extraction protocols were compared to maintain the status quo of the protein modification. The extracts contained about 4-8 µg of chlorogenic acid derivatives per mg of extracted protein. High-resolution chromatography with multiple reaction monitoring was used to detect lysine modifications in the coffee protein. Marker peptides were allocated for the storage protein of the coffee beans. Among these, the modified peptides K.FFLANGPQQGGK.E and R.LGGK.T of the α-chain and R.ITTVNSQK.I and K.VFDDEVK.Q of β-chain were detected. Results showed a significant increase (p < 0.05) of modified peptides from wet processed green beans as compared to the dry ones. The present study contributes to a better understanding of the influence of the different processing methods on protein quality and its role in the scope of coffee cup quality and aroma. View Full-Text}, 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{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{Boerner2009, author = {B{\"o}rner, Hans Gerhard}, title = {Exploiting self-organization and functionality of peptides for polymer science}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-29066}, school = {Universit{\"a}t Potsdam}, year = {2009}, abstract = {Controlling interactions in synthetic polymers as precisely as in proteins would have a strong impact on polymer science. Advanced structural and functional control can lead to rational design of, integrated nano- and microstructures. To achieve this, properties of monomer sequence defined oligopeptides were exploited. Through their incorporation as monodisperse segments into synthetic polymers we learned in recent four years how to program the structure formation of polymers, to adjust and exploit interactions in such polymers, to control inorganic-organic interfaces in fiber composites and induce structure in Biomacromolecules like DNA for biomedical applications.}, 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} } @misc{NiederkruegerSalbBecketal.2006, author = {Niederkr{\"u}ger, Matthias and Salb, Christian and Beck, Michael and Hildebrandt, Niko and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Marowsky, Gerd}, title = {Improvement of a fluorescence immunoassay with a compact diode-pumped solid state laser at 315 nm}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-10150}, year = {2006}, abstract = {We demonstrate the improvement of fluorescence immunoassay (FIA) diagnostics in deploying a newly developed compact diode-pumped solid state (DPSS) laser with emission at 315 nm. The laser is based on the quasi-three-level transition in Nd:YAG at 946 nm. The pulsed operation is either realized by an active Q-switch using an electro-optical device or by introduction of a Cr4+:YAG saturable absorber as passive Q-switch element. By extra-cavity second harmonic generation in different nonlinear crystal media we obtained blue light at 473 nm. Subsequent mixing of the fundamental and the second harmonic in a β-barium-borate crystal provided pulsed emission at 315 nm with up to 20 μJ maximum pulse energy and 17 ns pulse duration. Substitution of a nitrogen laser in a FIA diagnostics system by the DPSS laser succeeded in considerable improvement of the detection limit. Despite significantly lower pulse energies (7 μJ DPSS laser versus 150 μJ nitrogen laser), in preliminary investigations the limit of detection was reduced by a factor of three for a typical FIA.}, subject = {Immunoassay}, language = {en} } @phdthesis{Simsek2022, author = {Simsek, Ibrahim}, title = {Ink-based preparation of chalcogenide perovskites as thin films for PV applications}, doi = {10.25932/publishup-57271}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-572711}, school = {Universit{\"a}t Potsdam}, pages = {iv, 113}, year = {2022}, abstract = {The increasing demand for energy in the current technological era and the recent political decisions about giving up on nuclear energy diverted humanity to focus on alternative environmentally friendly energy sources like solar energy. Although silicon solar cells are the product of a matured technology, the search for highly efficient and easily applicable materials is still ongoing. These properties made the efficiency of halide perovskites comparable with silicon solar cells for single junctions within a decade of research. However, the downside of halide perovskites are poor stability and lead toxicity for the most stable ones. On the other hand, chalcogenide perovskites are one of the most promising absorber materials for the photovoltaic market, due to their elemental abundance and chemical stability against moisture and oxygen. In the search of the ultimate solar absorber material, combining the good optoelectronic properties of halide perovskites with the stability of chalcogenides could be the promising candidate. Thus, this work investigates new techniques for the synthesis and design of these novel chalcogenide perovskites, that contain transition metals as cations, e.g., BaZrS3, BaHfS3, EuZrS3, EuHfS3 and SrHfS3. There are two stages in the deposition techniques of this study: In the first stage, the binary compounds are deposited via a solution processing method. In the second stage, the deposited materials are annealed in a chalcogenide atmosphere to form the perovskite structure by using solid-state reactions. The research also focuses on the optimization of a generalized recipe for a molecular ink to deposit precursors of chalcogenide perovskites with different binaries. The implementation of the precursor sulfurization resulted in either binaries without perovskite formation or distorted perovskite structures, whereas some of these materials are reported in the literature as they are more favorable in the needle-like non-perovskite configuration. Lastly, there are two categories for the evaluation of the produced materials: The first category is about the determination of the physical properties of the deposited layer, e.g., crystal structure, secondary phase formation, impurities, etc. For the second category, optoelectronic properties are measured and compared to an ideal absorber layer, e.g., band gap, conductivity, surface photovoltage, etc.}, language = {en} } @phdthesis{Gaebert2022, author = {G{\"a}bert, Chris}, title = {Light-responsive polymer systems aiming towards programmable friction}, doi = {10.25932/publishup-55338}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-553380}, school = {Universit{\"a}t Potsdam}, pages = {XVI, 108, XXVI}, year = {2022}, abstract = {The development of novel programmable materials aiming to control friction in real-time holds potential to facilitate innovative lubrication solutions for reducing wear and energy losses. This work describes the integration of light-responsiveness into two lubricating materials, silicon oils and polymer brush surfaces. The first part focusses on the assessment on 9-anthracene ester-terminated polydimethylsiloxanes (PDMS-A) and, in particular, on the variability of rheological properties and the implications that arise with UV-light as external trigger. The applied rheometer setup contains an UV-transparent quartz-plate, which enables radiation and simultaneous measurement of the dynamic moduli. UV-A radiation (354 nm) triggers the cycloaddition reaction between the terminal functionalities of linear PDMS, resulting in chain extension. The newly-formed anthracene dimers cleave by UV-C radiation (254 nm) or at elevated temperatures (T > 130 °C). The sequential UV-A radiation and thermal reprogramming over three cycles demonstrate high conversions and reproducible programming of rheological properties. In contrast, the photochemical back reaction by UV-C is incomplete and can only partially restore the initial rheological properties. The dynamic moduli increase with each cycle in photochemical programming, presumably resulting from a chain segment re-arrangement as a result of the repeated partial photocleavage and subsequent chain length-dependent dimerization. In addition, long periods of radiation cause photooxidative degradation, which damages photo-responsive functions and consequently reduces the programming range. The absence of oxygen, however, reduces undesired side reactions. Anthracene-functionalized PDMS and native PDMS mix depending on the anthracene ester content and chain length, respectively, and allow fine-tuning of programmable rheological properties. The work shows the influence of mixing conditions during the photoprogramming step on the rheological properties, indicating that material property gradients induced by light attenuation along the beam have to be considered. Accordingly, thin lubricant films are suggested as potential application for light-programmable silicon fluids. The second part compares strategies for the grafting of spiropyran (SP) containing copolymer brushes from Si wafers and evaluates the light-responsiveness of the surfaces. Pre-experiments on the kinetics of the thermally initiated RAFT copolymerization of 2-hydroxyethyl acrylate (HEA) and spiropyran acrylate (SPA) in solution show, first, a strong retardation by SP and, second, the dependence of SPA polymerization on light. Surprisingly, the copolymerization of SPA is inhibited in the dark. These findings contribute to improve the synthesis of polar, spiropyran-containing copolymers. The comparison between initiator systems for the grafting-from approach indicates PET-RAFT superior to thermally initiated RAFT, suggesting a more efficient initiation of surface-bound CTA by light. Surface-initiated polymerization via PET-RAFT with an initiator system of EosinY (EoY) and ascorbic acid (AscA) facilitates copolymer synthesis from HEA and 5-25 mol\% SPA. The resulting polymer film with a thickness of a few nanometers was detected by atomic force microscopy (AFM) and ellipsometry. Water contact angle (CA) measurements demonstrate photo-switchable surface polarity, which is attributed to the photoisomerization between non-polar spiropyran and zwitterionic merocyanine isomer. Furthermore, the obtained spiropyran brushes show potential for further studies on light-programmable properties. In this context, it would be interesting to investigate whether swollen spiropyran-containing polymers change their configuration and thus their film thickness under the influence of light. In addition, further experiments using an AFM or microtribometer should evaluate whether light-programmable solvation enables a change in frictional properties between polymer brush surfaces.}, language = {en} } @phdthesis{Weber2007, author = {Weber, Jens}, title = {Meso- und mikropor{\"o}se Hochleistungspolymere : Synthese, Analytik und Anwendungen}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-15994}, school = {Universit{\"a}t Potsdam}, year = {2007}, abstract = {Die Arbeit beschreibt die Synthese, Charakterisierung und Anwendung von meso- und mikropor{\"o}sen Hochleistungspolymeren. Im ersten Teil wird die Synthese von mesopor{\"o}sen Polybenzimidazol (PBI) auf der Basis einer Templatierungsmethode vorgestellt. Auf der Grundlage kommerzieller Monomere und Silikatnanopartikel sowie eines neuen Vernetzers wurde ein Polymer-Silikat-Hybridmaterial aufgebaut. Das Herausl{\"o}sen des Silikats mit Ammoniumhydrogendifluorid f{\"u}hrt zu mesopor{\"o}sen Polybenzimidazolen mit spherischen Poren von 9 bis 11 nm Durchmesser. Die Abh{\"a}ngigkeit der beobachteten Porosit{\"a}t vom Massenverh{\"a}ltnis Silikat zu Polymer wurde ebenso untersucht wie die Abh{\"a}ngigkeit der Porosit{\"a}t vom Vernetzergehalt. Die Porosit{\"a}t vollvernetzter Proben zeigt eine lineare Abh{\"a}ngigkeit vom Verh{\"a}ltnis Silikat zu Polymer bis zu einem Grenzwert von 1. Wird der Grenzwert {\"u}berschritten, ist teilweiser Porenkollaps zu beobachten. Die Abh{\"a}ngigkeit der Porosit{\"a}t vom Vernetzergehalt bei festem Silikatgehalt ist nichtlinear. Oberhalb einer kritischen Vernetzerkonzentration wird eine komplette Replikation der Nanopartikel gefunden. Ist die Vernetzerkonzentration dagegen kleiner als der kritische Wert, so ist der v{\"o}llige Kollaps einiger Poren bei Stabilit{\"a}t der verbleibenden Poren zu beobachten. Ein komplett unpor{\"o}ses PBI resultiert bei Abwesenheit des Vernetzers. Die mesopor{\"o}sen PBI-Netzwerke konnten kontrolliert mit Phosphors{\"a}ure beladen werden. Die erhaltenen Addukte wurden auf ihre Protonenleitf{\"a}higkeit untersucht. Es kann gezeigt werden, dass die Nutzung der vordefinierten Morphologie im Vergleich zu einem unstrukturierten PBI in h{\"o}heren Leitf{\"a}higkeiten resultiert. Durch die vernetzte Struktur war des Weiteren gen{\"u}gend mechanische Stabilit{\"a}t gegeben, um die Addukte reversibel und bei sehr guten Leitf{\"a}higkeiten bis zu Temperaturen von 190°C bei 0\% relativer Feuchtigkeit zu untersuchen. Dies ist f{\"u}r unstrukturierte Phosphors{\"a}ure/PBI - Addukte aus linearem PBI nicht m{\"o}glich. Im zweiten Teil der Arbeit wird die Synthese intrinsisch mikropor{\"o}ser Polyamide und Polyimide vorgestellt. Das Konzept intrinsisch mikropor{\"o}ser Polymere konnte damit auf weitere Polymerklassen ausgeweitet werden. Als zentrales, strukturinduzierendes Motiv wurde 9,9'-Spirobifluoren gew{\"a}hlt. Dieses Molek{\"u}l ist leicht und vielf{\"a}ltig zu di- bzw. tetrafunktionellen Monomeren modifizierbar. Dabei wurden bestehende Synthesevorschriften modifiziert bzw. neue Vorschriften entwickelt. Ein erster Schwerpunkt innerhalb des Kapitels lag in der Synthese und Charakterisierung von l{\"o}slichen, intrinsisch mikropor{\"o}sen, aromatischen Polyamid und Polyimid. Es konnte gezeigt werden, dass das Beobachten von Mikroporosit{\"a}t stark von der molekularen Architektur und der Verarbeitung der Polymere abh{\"a}ngig ist. Die Charakterisierung der Porosit{\"a}t erfolgte unter Nutzung von Stickstoffsorption, Kleinwinkelr{\"o}ntgenstreuung und Molecular Modeling. Es konnte gezeigt werden, dass die Proben stark vom Umgebungsdruck abh{\"a}ngigen Deformationen unterliegen. Die starke Quellung der Proben w{\"a}hrend des Sorptionsvorgangs konnte durch Anwendung des "dual sorption" Modells, also dem Auftreten von Porenf{\"u}llung und dadurch induzierter Henry-Sorption, erkl{\"a}rt werden. Der zweite Schwerpunkt des Kapitels beschreibt die Synthese und Charakterisierung mikropor{\"o}ser Polyamid- und Polyimidnetzwerke. W{\"a}hrend Polyimidnetzwerke auf Spirobifluorenbasis ausgepr{\"a}gte Mikroporosit{\"a}t und spezifische Oberfl{\"a}chen von ca. 1100 m²/g aufwiesen, war die Situation f{\"u}r entsprechende Polyamidnetzwerke abweichend. Mittels Stickstoffsorption konnte keine Mikroporosit{\"a}t nachgewiesen werden, jedoch konnte mittels SAXS eine innere Grenzfl{\"a}che von ca. 300 m²/g nachgewiesen werden. Durch die in dieser Arbeit gezeigten Experimente kann die Grenze zwischen Polymeren mit hohem freien Volumen und mikropor{\"o}sen Polymeren somit etwas genauer gezogen werden. ausgepr{\"a}gte Mikroporosit{\"a}t kann nur in extrem steifen Strukturen nachgewiesen werden. Die Kombination der Konzepte "Mesoporosit{\"a}t durch Templatierung" und "Mikroporosit{\"a}t durch strukturierte Monomere" hatte ein hierarchisch strukturiertes Polybenzimidazol zum Ergebnis. Die Pr{\"a}senz einer Strukturierung im molekularen Maßstab konnte SAXS bewiesen werden. Das so strukturierte Polybenzimidazol zeichnete sich durch eine h{\"o}here Protonenleitf{\"a}higkeit im Vergleich zu einem rein mesopor{\"o}sen PBI aus. Der letzte Teil der Arbeit besch{\"a}ftigte sich mit der Entwicklung einer neuen Synthesemethode zur Herstellung von Polybenzimidazol. Es konnte gezeigt werden, dass lineares PBI in einer eutektischen Salzschmelze aus Lithium- und Kaliumchlorid synthetisiert werden kann. Die Umsetzung der spirobifluorenbasierten Monomere zu l{\"o}slichem oder vernetztem PBI ist in der Salzschmelze m{\"o}glich.}, language = {de} } @phdthesis{Ulaganathan2016, author = {Ulaganathan, Vamseekrishna}, title = {Molecular fundamentals of foam fractionation}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-94263}, school = {Universit{\"a}t Potsdam}, pages = {ix, 136}, year = {2016}, abstract = {Foam fractionation of surfactant and protein solutions is a process dedicated to separate surface active molecules from each other due to their differences in surface activities. The process is based on forming bubbles in a certain mixed solution followed by detachment and rising of bubbles through a certain volume of this solution, and consequently on the formation of a foam layer on top of the solution column. Therefore, systematic analysis of this whole process comprises of at first investigations dedicated to the formation and growth of single bubbles in solutions, which is equivalent to the main principles of the well-known bubble pressure tensiometry. The second stage of the fractionation process includes the detachment of a single bubble from a pore or capillary tip and its rising in a respective aqueous solution. The third and final stage of the process is the formation and stabilization of the foam created by these bubbles, which contains the adsorption layers formed at the growing bubble surface, carried up and gets modified during the bubble rising and finally ends up as part of the foam layer. Bubble pressure tensiometry and bubble profile analysis tensiometry experiments were performed with protein solutions at different bulk concentrations, solution pH and ionic strength in order to describe the process of accumulation of protein and surfactant molecules at the bubble surface. The results obtained from the two complementary methods allow understanding the mechanism of adsorption, which is mainly governed by the diffusional transport of the adsorbing protein molecules to the bubble surface. This mechanism is the same as generally discussed for surfactant molecules. However, interesting peculiarities have been observed for protein adsorption kinetics at sufficiently short adsorption times. First of all, at short adsorption times the surface tension remains constant for a while before it decreases as expected due to the adsorption of proteins at the surface. This time interval is called induction time and it becomes shorter with increasing protein bulk concentration. Moreover, under special conditions, the surface tension does not stay constant but even increases over a certain period of time. This so-called negative surface pressure was observed for BCS and BLG and discussed for the first time in terms of changes in the surface conformation of the adsorbing protein molecules. Usually, a negative surface pressure would correspond to a negative adsorption, which is of course impossible for the studied protein solutions. The phenomenon, which amounts to some mN/m, was rather explained by simultaneous changes in the molar area required by the adsorbed proteins and the non-ideality of entropy of the interfacial layer. It is a transient phenomenon and exists only under dynamic conditions. The experiments dedicated to the local velocity of rising air bubbles in solutions were performed in a broad range of BLG concentration, pH and ionic strength. Additionally, rising bubble experiments were done for surfactant solutions in order to validate the functionality of the instrument. It turns out that the velocity of a rising bubble is much more sensitive to adsorbing molecules than classical dynamic surface tension measurements. At very low BLG or surfactant concentrations, for example, the measured local velocity profile of an air bubble is changing dramatically in time scales of seconds while dynamic surface tensions still do not show any measurable changes at this time scale. The solution's pH and ionic strength are important parameters that govern the measured rising velocity for protein solutions. A general theoretical description of rising bubbles in surfactant and protein solutions is not available at present due to the complex situation of the adsorption process at a bubble surface in a liquid flow field with simultaneous Marangoni effects. However, instead of modelling the complete velocity profile, new theoretical work has been started to evaluate the maximum values in the profile as characteristic parameter for dynamic adsorption layers at the bubble surface more quantitatively. The studies with protein-surfactant mixtures demonstrate in an impressive way that the complexes formed by the two compounds change the surface activity as compared to the original native protein molecules and therefore lead to a completely different retardation behavior of rising bubbles. Changes in the velocity profile can be interpreted qualitatively in terms of increased or decreased surface activity of the formed protein-surfactant complexes. It was also observed that the pH and ionic strength of a protein solution have strong effects on the surface activity of the protein molecules, which however, could be different on the rising bubble velocity and the equilibrium adsorption isotherms. These differences are not fully understood yet but give rise to discussions about the structure of protein adsorption layer under dynamic conditions or in the equilibrium state. The third main stage of the discussed process of fractionation is the formation and characterization of protein foams from BLG solutions at different pH and ionic strength. Of course a minimum BLG concentration is required to form foams. This minimum protein concentration is a function again of solution pH and ionic strength, i.e. of the surface activity of the protein molecules. Although at the isoelectric point, at about pH 5 for BLG, the hydrophobicity and hence the surface activity should be the highest, the concentration and ionic strength effects on the rising velocity profile as well as on the foamability and foam stability do not show a maximum. This is another remarkable argument for the fact that the interfacial structure and behavior of BLG layers under dynamic conditions and at equilibrium are rather different. These differences are probably caused by the time required for BLG molecules to adapt respective conformations once they are adsorbed at the surface. All bubble studies described in this work refer to stages of the foam fractionation process. Experiments with different systems, mainly surfactant and protein solutions, were performed in order to form foams and finally recover a solution representing the foamed material. As foam consists to a large extent of foam lamella - two adsorption layers with a liquid core - the concentration in a foamate taken from foaming experiments should be enriched in the stabilizing molecules. For determining the concentration of the foamate, again the very sensitive bubble rising velocity profile method was applied, which works for any type of surface active materials. This also includes technical surfactants or protein isolates for which an accurate composition is unknown.}, language = {en} } @misc{AlbrechtCummingKreuderetal.1986, author = {Albrecht, O. and Cumming, W. and Kreuder, W. and Laschewsky, Andr{\´e} and Ringsdorf, Helmut}, title = {Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-17124}, year = {1986}, abstract = {Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data are discussed.}, language = {en} } @phdthesis{Stoermann2023, author = {St{\"o}rmann, Florian Konstantin}, title = {Multifunctional Microballoons for the active and passive control of fluid-flows}, school = {Universit{\"a}t Potsdam}, pages = {XVI, 104, A24}, year = {2023}, abstract = {Functional materials, also called "Smart Materials", are described by their ability to fulfill a desired task through targeted interaction with its environment. Due to this functional integration, such materials are of increased interest, especially in areas where the increasing micronization of components is required. Modern manufacturing processes (e.g. microfluidics) and the availability of a wide variety of functional materials (e.g. shape memory materials) now enable the production of particle-based switching components. This category includes micropumps and microvalves, whose basic function is the active control of liquid flows. One approach in realizing those microcomponents as pursued by this work, enables variable size-switching of water-filled microballoons by implementing a stimulus-sensitive switching motif in the capsule's membrane shell, while being under the influence of a constant driving force. The switching motif with its gatekeeper function has a critical influence on one or more material parameters, which modulate the capsule's resistance against the driving force in microballoon expansion process. The advantage of this concept is that even non-variable analyte conditions, such as concentration levels of ions, can be capitalized to generate external force fields that, under the control of the membrane, cause an inflation of the microballoon by an osmotically driven water influx. In case of osmotic pressure gradients as the driving force for the capsule expansion, material parameters associated with the gatekeeper function are specifically the permeability and the mechanical stiffness of the shell material. While a modulation of the shell permeability could be utilized to kinetically impede the water influx on large time scales, a modulation of the shell's mechanical stiffness even might be utilized to completely prevent the capsule inflation due to a possible non-deformability beneath a certain threshold pressure. In polymer networks, which are a suitable material class for the demanded capsule shell because of their excellent elasticity, both the permeability and the mechanical properties are strongly influenced by the crystallinity of the material. Since the permeability is effectively reduced with increasing crystallinity, while the mechanical stiffness is simultaneously greatly increased, both effects point in the same direction in terms of their functional relationship. For this reason and due to a reversible and contactless modulation of the membrane crystallinity by heat input, crystallites may be suitable switching motifs for controlling the capsule expansion. As second design element of reversible expandable microballoons, the capsule geometry, defined by an aqueous core enveloped by the temperature-sensitive polymer network membrane, should allow an osmotic pressure gradient across the membrane layer. The strength of the inflation pressure and the associated inflation velocity upon membrane melting should be controlled by the salt concentration within the aqueous core, while a turn in the osmotic gradient should furthermore allow the reversible process of capsule deflation. Therefore, it should be possible to build either microvalves and micropumps, while their intended action of either pumping or valving is determined by their state of expansion and the direction of the osmotic pressure gradient.. Microballoons of approximately 300 µm in diameter were formed via droplet-based microfluidics from double-emulsion templates (w/o/w). The elastomeric capsule membrane was formed by photo-crosslinking of methacrylate (MA) functionalized oligo(ε-caprolactone) precursors (≈ 3.8 MA-arms, Mn ≈ 12000 g mol-1) within the organic medium layer (o) via UV-exposure after droplet-formation. After removal of the toluene/chloroform mixture by slow extraction via the continuous aqueous phase, the capsules solidified under the development of a characteristic "mushroom"-like shape at specific experimental conditions (e.g. λ = 308 nm, 57 mJ·s-1·cm-2, 16 min). It could be furthermore shown that in dependency to the process parameters: oligomer concentration and curing-time also spherical capsules were accessible. Long curing-times and high oligomer concentrations at a fixed light-intensity favored the formation of "mushroom"-like capsules, whereas the contrary led to spherical shaped capsules. A comparative study on thin polymer network films of same composition and equal treatment proved a correlation between the film's crosslink density and their contraction capability, while stronger crosslinked polymer networks showed a stronger contraction after solvent removal. In combination with observations during capsule solidification via light-microscopy, where a continuous shaping from almost spherical crosslinked templates to "mushroom"-shaped and solidified capsules was stated, the following mechanism was proposed. In case of low oligomer contents and short curing-times, the contraction of the capsule shell during solvent removal is strongly diminished due to a low degree of crosslinking. Therefore, the solidifying shell could freely collapse onto the aqueous core. In the other case, high oligomer concentrations and long curing-times will favor the formation of highly crosslinked capsule membranes with a strong contraction capability. Due to an observed decentered location of the aqueous core within the swollen polymer network, an uneven radial stress along the capsule's circumference is exerted to the incompressible core. This lead to an uneven contraction during solvent removal and a directed flow of the core fluid into the direction of the minimal stress vector. In consequence, the initially thicker spherical cap contracts, whereas the opposing thinner spherical cap get stretched. The "mushroom"-shape over some advantages over their spherical shaped counterparts, why they were selected for the further experiments. Besides the necessity of a high density of crosslinking for the purpose of extraordinary elasticity and toughness, the form-anisotropy promotes a faster microballoon expandability due to a partial reduction of the membrane thickness. Additionally, pre-stretched regions of thin thickness might provide a better resistance against inflation pressure than spherical but non-stretched capsules of equal membrane thickness. The resulting "mushroom"-shaped microcapsules exhibited a melting point of Tm ≈ 50 - 60 °C and a degree of crystallinity of Xc ≈ 29 - 38 \% depending on the membrane thickness and internal salt content, which is slightly lower than for the non-crosslinked oligomer and reasoned by a limited chain mobility upon crosslinking. Nonetheless, the melting transition of the polymer network was associated with a strong drop in its mechanical stiffness, which was shown to have a strong influence on the osmotic driven expansion of the microcapsules. Capsules that were subjected to osmotic pressures between 1.5 and 4.7 MPa did not expand if the temperature was well below the melting point of the capsule's membrane, i.e. at room temperature. In contrast, a continuous expansion, while approaching asymptotically to a final capsule size, was observed if the temperature exceeded the melting point, i.e. 60 °C. Microballoons, which were kept for 56 days at ∆Π = 1.5 MPa and room temperature, did not change significantly in diameter, why the impact of the mechanical stiffness on the expansion behavior is considered to be the greater than the influence of the shell permeability. The time-resolved expansion behavior of the microballoons above their Tm was subsequently modeled, using difusion equations that were corrected for shape anisotropy and elastic restoring forces. A shape-related and expansion dependent pre-factor was used to dynamically address the influence of the shell thickness differences along the circumference on the inflation velocity, whereas the microballoon's elastic contraction upon inflation was rendered by the inclusion of a hyperelastic constitutive model. An important finding resulting from this model was the pronounced increase in inflation velocity compared to hypothetical capsules with a homogeneous shell thickness, which stresses the benefit of employing shape anisotropic balloon-like capsules in this study. Furthermore, the model was able to predict the finite expandability on basis of entropy-elastic recovery forces and strain-hardening effects. A comparison of six different microballoons with different shell thicknesses and internal salt contents showed the linear relationship between the volumetric expansion, the shell thickness and the applied osmotic pressure, as represented by the model. As the proposed model facilitates the prediction of the expansion kinetics depending on the membranes mechanical and diffusional characteristics, it might be a screening tool for future material selections. In course of the microballoon expansion process, capsules of intermediate diameters could be isolated by recrystallization of the membrane, which is mainly caused by a restoration of the membrane's mechanical stiffness and is otherwise difficult to achieve with other stimuli-sensitive systems. The capsule's crystallinity of intermediate expansion states was nearly unchanged, whereas the lamellar crystal size tends to decreased with the expansion ratio. Therefore, it was assumed that the elastic modulus was only minimally altered and might increased due to the networks segment-chain extension. In addition to the volume increase achieved by inflation, a turn in the osmotic gradient also facilitated the reversible deflation, which was shown in inflation/deflation cycles. These both characteristics of the introduced microballoons are important parameter regarding the realization of micropumps and microvalves. The fixation of expanded microcapsules via recrystallization enabled the storage of entropy-elastic strain-energy, which could be utilized for pumping actions in non-aqueous media. Here, the pumping velocity depended on both, the type of surrounding medium and the applied temperature. Surrounding media that supported the fast transport of pumped liquid showed an accelerated deflation, while high temperatures further accelerate the pumping velocity. Very fast rejection of the incorporated payload was furthermore realized with pierced expanded microballoons, which were subjected to temperatures above their Tm. The possible fixation of intermediate particle sizes provide opportunities for vent constructions that allowed the precise adjustment of specific flow-rates and multiple valve openings and closings. A valve construction was realized by the insertion of a single or multiple microballoons in a microfluidic channel. A complete and a partial closing of the microballoon-valves was demonstrated as a function of the heating period. In this context, a difference between the inflation and deflation velocity was stated, summarizing slower expansion kinetics. Overall, microballoons, which presented both on-demand pumping and reversible valving by a temperature-triggered change in the capsule's volume, might be suitable components that help to design fully integrated LOC devices, due to the implementation of the control switch and controllable inflation/deflation kinetics. In comparison to other state of the art stimuli-sensitive materials, one has to highlight the microballoons capability of stabilizing almost continuously intermediate capsule sizes by simple recrystallization of the microballoon's membrane.}, language = {en} } @phdthesis{Djalali2023, author = {Djalali, Saveh Arman}, title = {Multiresponsive complex emulsions: Concepts for the design of active and adaptive liquid colloidal systems}, doi = {10.25932/publishup-57520}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-575203}, school = {Universit{\"a}t Potsdam}, pages = {151}, year = {2023}, abstract = {Complex emulsions are dispersions of kinetically stabilized multiphasic emulsion droplets comprised of two or more immiscible liquids that provide a novel material platform for the generation of active and dynamic soft materials. In recent years, the intrinsic reconfigurable morphological behavior of complex emulsions, which can be attributed to the unique force equilibrium between the interfacial tensions acting at the various interfaces, has become of fundamental and applied interest. As such, particularly biphasic Janus droplets have been investigated as structural templates for the generation of anisotropic precision objects, dynamic optical elements or as transducers and signal amplifiers in chemo- and bio-sensing applications. In the present thesis, switchable internal morphological responses of complex droplets triggered by stimuli-induced alterations of the balance of interfacial tensions have been explored as a universal building block for the design of multiresponsive, active, and adaptive liquid colloidal systems. A series of underlying principles and mechanisms that influence the equilibrium of interfacial tensions have been uncovered, which allowed the targeted design of emulsion bodies that can alter their shape, bind and roll on surfaces, or change their geometrical shape in response to chemical stimuli. Consequently, combinations of the unique triggerable behavior of Janus droplets with designer surfactants, such as a stimuli-responsive photosurfactant (AzoTAB) resulted for instance in shape-changing soft colloids that exhibited a jellyfish inspired buoyant motion behavior, holding great promise for the design of biological inspired active material architectures and transformable soft robotics. In situ observations of spherical Janus emulsion droplets using a customized side-view microscopic imaging setup with accompanying pendant dropt measurements disclosed the sensitivity regime of the unique chemical-morphological coupling inside complex emulsions and enabled the recording of calibration curves for the extraction of critical parameters of surfactant effectiveness. The deduced new "responsive drop" method permitted a convenient and cost-efficient quantification and comparison of the critical micelle concentrations (CMCs) and effectiveness of various cationic, anionic, and nonionic surfactants. Moreover, the method allowed insightful characterization of stimuli-responsive surfactants and monitoring of the impact of inorganic salts on the CMC and surfactant effectiveness of ionic and nonionic surfactants. Droplet functionalization with synthetic crown ether surfactants yielded a synthetically minimal material platform capable of autonomous and reversible adaptation to its chemical environment through different supramolecular host-guest recognition events. Addition of metal or ammonium salts resulted in the uptake of the resulting hydrophobic complexes to the hydrocarbon hemisphere, whereas addition of hydrophilic ammonium compounds such as amino acids or polypeptides resulted in supramolecular assemblies at the hydrocarbon-water interface of the droplets. The multiresponsive material platform enabled interfacial complexation and thus triggered responses of the droplets to a variety of chemical triggers including metal ions, ammonium compounds, amino acids, antibodies, carbohydrates as well as amino-functionalized solid surfaces. In the final chapter, the first documented optical logic gates and combinatorial logic circuits based on complex emulsions are presented. More specifically, the unique reconfigurable and multiresponsive properties of complex emulsions were exploited to realize droplet-based logic gates of varying complexity using different stimuli-responsive surfactants in combination with diverse readout methods. In summary, different designs for multiresponsive, active, and adaptive liquid colloidal systems were presented and investigated, enabling the design of novel transformative chemo-intelligent soft material platforms.}, language = {en} } @phdthesis{Schulze2017, author = {Schulze, Nicole}, title = {Neue Templatphasen zur anisotropen Goldnanopartikelherstellung durch den Einsatz strukturbildender Polymere}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-409515}, school = {Universit{\"a}t Potsdam}, pages = {VI, 117, xv}, year = {2017}, abstract = {Ziel der vorliegenden Arbeit war die Synthese und Charakterisierung von anisotropen Goldnanopartikeln in einer geeigneten Polyelektrolyt-modifizierten Templatphase. Der Mittelpunkt bildet dabei die Auswahl einer geeigneten Templatphase, zur Synthese von einheitlichen und reproduzierbaren anisotropen Goldnanopartikeln mit den daraus resultierenden besonderen Eigenschaften. Bei der Synthese der anisotropen Goldnanopartikeln lag der Fokus in der Verwendung von Vesikeln als Templatphase, wobei hier der Einfluss unterschiedlicher strukturbildender Polymere (stark alternierende Maleamid-Copolymere PalH, PalPh, PalPhCarb und PalPhBisCarb mit verschiedener Konformation) und Tenside (SDS, AOT - anionische Tenside) bei verschiedenen Synthese- und Abtrennungsbedingungen untersucht werden sollte. Im ersten Teil der Arbeit konnte gezeigt werden, dass PalPhBisCarb bei einem pH-Wert von 9 die Bedingungen eines R{\"o}hrenbildners f{\"u}r eine morphologische Transformation von einer vesikul{\"a}ren Phase in eine r{\"o}hrenf{\"o}rmige Netzwerkstruktur erf{\"u}llt und somit als Templatphase zur formgesteuerten Bildung von Nanopartikeln genutzt werden kann. Im zweiten Teil der Arbeit wurde dargelegt, dass die Templatphase PalPhBisCarb (pH-Wert von 9, Konzentration von 0,01 wt.\%) mit AOT als Tensid und PL90G als Phospholipid (im Verh{\"a}ltnis 1:1) die effektivste Wahl einer Templatphase f{\"u}r die Bildung von anisotropen Strukturen in einem einstufigen Prozess darstellt. Bei einer konstanten Synthesetemperatur von 45 °C wurden die besten Ergebnisse bei einer Goldchloridkonzentration von 2 mM, einem Gold-Templat-Verh{\"a}ltnis von 3:1 und einer Synthesezeit von 30 Minuten erzielt. Ausbeute an anisotropen Strukturen lag bei 52 \% (Anteil an dreieckigen Nanopl{\"a}ttchen von 19 \%). Durch Erh{\"o}hung der Synthesetemperatur konnte die Ausbeute auf 56 \% (29 \%) erh{\"o}ht werden. Im dritten Teil konnte durch zeitabh{\"a}ngige Untersuchungen gezeigt werden, dass bei Vorhandensein von PalPhBisCarb die Bildung der energetisch nicht bevorzugten Pl{\"a}ttchen-Strukturen bei Raumtemperatur initiiert wird und bei 45 °C ein Optimum annimmt. Kintetische Untersuchungen haben gezeigt, dass die Bildung dreieckiger Nanopl{\"a}ttchen bei schrittweiser Zugabe der Goldchlorid-Pr{\"a}kursorl{\"o}sung zur PalPhBisCarb enthaltenden Templatphase durch die Dosierrate der vesikul{\"a}ren Templatphase gesteuert werden kann. In umgekehrter Weise findet bei Zugabe der Templatphase zur Goldchlorid-Pr{\"a}kursorl{\"o}sung bei 45 °C ein {\"a}hnlicher, kinetisch gesteuerter Prozess der Bildung von Nanodreiecken statt mit einer maximalen Ausbeute dreieckigen Nanopl{\"a}ttchen von 29 \%. Im letzten Kapitel erfolgten erste Versuche zur Abtrennung dreieckiger Nanopl{\"a}ttchen von den {\"u}brigen Geometrien der gemischten Nanopartikell{\"o}sung mittels tensidinduzierter Verarmungsf{\"a}llung. Bei Verwendung von AOT mit einer Konzentration von 0,015 M wurde eine Ausbeute an Nanopl{\"a}ttchen von 99 \%, wovon 72 \% dreieckiger Geometrien hatten, erreicht.}, language = {de} } @misc{LoehmannsroebenBeckHildebrandtetal.2006, author = {L{\"o}hmannsr{\"o}ben, Hans-Gerd and Beck, Michael and Hildebrandt, Niko and Schm{\"a}lzlin, Elmar and van Dongen, Joost T.}, title = {New challenges in biophotonics : laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-10120}, year = {2006}, abstract = {Two examples of our biophotonic research utilizing nanoparticles are presented, namely laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring. Results of the work include significantly enhanced sensitivity of a homogeneous fluorescence immunoassay and markedly improved spatial resolution of oxygen gradients in root nodules of a legume species.}, subject = {Sauerstoff}, language = {en} } @phdthesis{Lepre2023, author = {Lepre, Enrico}, title = {Nitrogen-doped carbonaceous materials for energy and catalysis}, doi = {10.25932/publishup-57739}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-577390}, school = {Universit{\"a}t Potsdam}, pages = {153}, year = {2023}, abstract = {Facing the environmental crisis, new technologies are needed to sustain our society. In this context, this thesis aims to describe the properties and applications of carbon-based sustainable materials. In particular, it reports the synthesis and characterization of a wide set of porous carbonaceous materials with high nitrogen content obtained from nucleobases. These materials are used as cathodes for Li-ion capacitors, and a major focus is put on the cathode preparation, highlighting the oxidation resistance of nucleobase-derived materials. Furthermore, their catalytic properties for acid/base and redox reactions are described, pointing to the role of nitrogen speciation on their surfaces. Finally, these materials are used as supports for highly dispersed nickel loading, activating the materials for carbon dioxide electroreduction.}, language = {en} }