@phdthesis{Fechler2012,
  author    = {Fechler, Nina},
  title     = {Salts as highly diverse porogens : functional ionic liquid-derived carbons and carbon-based composites for energy-related applications},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-64775},
  school      = {Universit{\"a}t Potsdam},
  year      = {2012},
  abstract  = {The present thesis is to be brought into line with the current need for alternative and sustainable approaches toward energy management and materials design. In this context, carbon in particular has become the material of choice in many fields such as energy conversion and storage. Herein, three main topics are covered: 1)An alternative synthesis strategy toward highly porous functional carbons with tunable porosity using ordinary salts as porogen (denoted as "salt templating") 2)The one-pot synthesis of porous metal nitride containing functional carbon composites 3)The combination of both approaches, enabling the generation of highly porous composites with finely tunable properties All approaches have in common that they are based on the utilization of ionic liquids, salts which are liquid below 100 °C, as precursors. Just recently, ionic liquids were shown to be versatile precursors for the generation of heteroatom-doped carbons since the liquid state and a negligible vapor pressure are highly advantageous properties. However, in most cases the products do not possess any porosity which is essential for many applications. In the first part, "salt templating", the utilization of salts as diverse and sustainable porogens, is introduced. Exemplarily shown for ionic liquid derived nitrogen- and nitrogen-boron-co-doped carbons, the control of the porosity and morphology on the nanometer scale by salt templating is presented. The studies within this thesis were conducted with the ionic liquids 1-Butyl-3-methyl-pyridinium dicyanamide (Bmp-dca), 1-Ethyl-3-methyl-imidazolium dicyanamide (Emim-dca) and 1 Ethyl 3-methyl-imidazolium tetracyanoborate (Emim-tcb). The materials are generated through thermal treatment of precursor mixtures containing one of the ionic liquids and a porogen salt. By simple removal of the non-carbonizable template salt with water, functional graphitic carbons with pore sizes ranging from micro- to mesoporous and surface areas up to 2000 m2g-1 are obtained. The carbon morphologies, which presumably originate from different onsets of demixing, mainly depend on the nature of the porogen salt whereas the nature of the ionic liquid plays a minor role. Thus, a structural effect of the porogen salt rather than activation can be assumed. This offers an alternative to conventional activation and templating methods, enabling to avoid multiple-step and energy-consuming synthesis pathways as well as employment of hazardous chemicals for the template removal. The composition of the carbons can be altered via the heat-treatment procedure, thus at lower synthesis temperatures rather polymeric carbonaceous materials with a high degree of functional groups and high surface areas are accessible. First results suggest the suitability of the materials for CO2 utilization. In order to further illustrate the potential of ionic liquids as carbon precursors and to expand the class of carbons which can be obtained, the ionic liquid 1-Ethyl-3-methyl-imidazolium thiocyanate (Emim-scn) is introduced for the generation of nitrogen-sulfur-co-doped carbons in combination with the already studied ionic liquids Bmp-dca and Emim-dca. Here, the salt templating approach should also be applicable eventually further illustrating the potential of salt templating, too. In the second part, a one-pot and template-free synthesis approach toward inherently porous metal nitride nanoparticle containing nitrogen-doped carbon composites is presented. Since ionic liquids also offer outstanding solubility properties, the materials can be generated through the carbonization of homogeneous solutions of an ionic liquid acting as nitrogen as well as carbon source and the respective metal precursor. The metal content and surface area are easily tunable via the initial metal precursor amount. Furthermore, it is also possible to synthesize composites with ternary nitride nanoparticles whose composition is adjustable by the metal ratio in the precursor solution. Finally, both approaches are combined into salt templating of the one-pot composites. This opens the way to the one-step synthesis of composites with tunable composition, particle size as well as precisely controllable porosity and morphology. Thereby, common synthesis strategies where the product composition is often negatively affected by the template removal procedure can be avoided. The composites are further shown to be suitable as electrodes for supercapacitors. Here, different properties such as porosity, metal content and particle size are investigated and discussed with respect to their influence on the energy storage performance. Because a variety of ionic liquids, metal precursors and salts can be combined and a simple closed-loop process including salt recycling is imaginable, the approaches present a promising platform toward sustainable materials design.},
  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{Zenichowski2012,
  author    = {Zenichowski, Karl},
  title     = {Quantum dynamical study of Si(100) surface-mounted, STM-driven switches at the atomic and molecular scale},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-62156},
  school      = {Universit{\"a}t Potsdam},
  year      = {2012},
  abstract  = {The aim of this thesis is the quantum dynamical study of two examples of scanning tunneling microscope (STM)-controllable, Si(100)(2x1) surface-mounted switches of atomic and molecular scale. The first example considers the switching of single H-atoms between two dangling-bond chemisorption sites on a Si-dimer of the Si(100) surface (Grey et al., 1996). The second system examines the conformational switching of single 1,5-cyclooctadiene molecules chemisorbed on the Si(100) surface (Nacci et al., 2008). The temporal dynamics are provided by the propagation of the density matrix in time via an according set of equations of motion (EQM). The latter are based on the open-system density matrix theory in Lindblad form. First order perturbation theory is used to evaluate those transition rates between vibrational levels of the system part. In order to account for interactions with the surface phonons, two different dissipative models are used, namely the bilinear, harmonic and the Ohmic bath model. IET-induced vibrational transitions in the system are due to the dipole- and the resonance-mechanism. A single surface approach is used to study the influence of dipole scattering and resonance scattering in the below-threshold regime. Further, a second electronic surface was included to study the resonance-induced switching in the above-threshold regime. Static properties of the adsorbate, e.g., potentials and dipole function and potentials, are obtained from quantum chemistry and used within the established quantum dynamical models.},
  language  = {en}
}
@phdthesis{Jeromenok2012,
  author    = {Jeromenok, Jekaterina},
  title     = {Polymers from the natural product betulin : a microstructural investigation},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-61380},
  school      = {Universit{\"a}t Potsdam},
  year      = {2012},
  abstract  = {Porous materials (e.g. zeolites, activated carbon, etc.) have found various applications in industry, such as the use as sorbents, catalyst supports and membranes for separation processes. Recently, much attention has been focused on synthesizing porous polymer materials. A vast amount of tailor-made polymeric systems with tunable properties has been investigated. Very often, however, the starting substances for these polymers are of petrochemical origin, and the processes are all in all not sustainable. Moreover, the new polymers have challenged existing characterizing methodologies. These have to be further developed to address the upcoming demands of the novel materials. Some standard techniques for the analysis of porous substances like nitrogen sorption at 77 K do not seem to be sufficient to answer all arising questions about the microstructure of such materials. In this thesis, microporous polymers from an abundant natural resource, betulin, will be presented. Betulin is a large-scale byproduct of the wood industry, and its content in birch bark can reach 30 wt.\%. Based on its rigid structure, polymer networks with intrinsic microporosity could be synthesized and characterized. Apart from standard nitrogen and carbon dioxide sorption at 77 K and 273 K, respectively, gas sorption has been examined not only with various gases (hydrogen and argon) but also at various temperatures. Additional techniques such as X-ray scattering and xenon NMR have been utilized to enable insight into the microporous structure of the material. Starting from insoluble polymer networks with promising gas selectivities, soluble polyesters have been synthesized and processed to a cast film. Such materials are feasible for membrane applications in gas separation. Betulin as a starting compound for polyester synthesis has aided to prepare, and for the first time to thoroughly analyse a microporous polyester with respect to its pores and microstructure. It was established that nitrogen adsorption at 87 K can be a better method to solve the microstructure of the material. In addition to that, other betulin-based polymers such as polyurethanes and polyethylene glycol bioconjugates are presented. Altogether, it has been shown that as an abundant natural resource betulin is a suitable and cheap starting compound for some polymers with various potential applications.},
  language  = {en}
}
@phdthesis{Latnikova2012,
  author    = {Latnikova, Alexandra},
  title     = {Polymeric capsules for self-healing anticorrosion coatings},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-60432},
  school      = {Universit{\"a}t Potsdam},
  year      = {2012},
  abstract  = {The present work is devoted to establishing of a new generation of self-healing anti-corrosion coatings for protection of metals. The concept of self-healing anticorrosion coatings is based on the combination of the passive part, represented by the matrix of conventional coating, and the active part, represented by micron-sized capsules loaded with corrosion inhibitor. Polymers were chosen as the class of compounds most suitable for the capsule preparation. The morphology of capsules made of crosslinked polymers, however, was found to be dependent on the nature of the encapsulated liquid. Therefore, a systematic analysis of the morphology of capsules consisting of a crosslinked polymer and a solvent was performed. Three classes of polymers such as polyurethane, polyurea and polyamide were chosen. Capsules made of these polymers and eight solvents of different polarity were synthesized via interfacial polymerization. It was shown that the morphology of the resulting capsules is specific for every polymer-solvent pair. Formation of capsules with three general types of morphology, such as core-shell, compact and multicompartment, was demonstrated by means of Scanning Electron Microscopy. Compact morphology was assumed to be a result of the specific polymer-solvent interactions and be analogues to the process of swelling. In order to verify the hypothesis, pure polyurethane, polyurea and polyamide were synthesized; their swelling behavior in the solvents used as the encapsulated material was investigated. It was shown that the swelling behavior of the polymers in most cases correlates with the capsules morphology. Different morphologies (compact, core-shell and multicompartment) were therefore attributed to the specific polymer-solvent interactions and discussed in terms of "good" and "poor" solvent. Capsules with core-shell morphology are formed when the encapsulated liquid is a "poor" solvent for the chosen polymer while compact morphologies are formed when the solvent is "good". Multicompartment morphology is explained by the formation of infinite networks or gelation of crosslinked polymers. If gelation occurs after the phase separation in the system is achieved, core-shell morphology is present. If gelation of the polymer occurs far before crosslinking is accomplished, further condensation of the polymer due to the crosslinking may lead to the formation of porous or multicompartment morphologies. It was concluded that in general, the morphology of capsules consisting of certain polymer-solvent pairs can be predicted on the basis of polymer-solvent behavior. In some cases, the swelling behavior and morphology may not match. The reasons for that are discussed in detail in the thesis. The discussed approach is only capable of predicting capsule morphology for certain polymer-solvent pairs. In practice, the design of the capsules assumes the trial of a great number of polymer-solvent combinations; more complex systems consisting of three, four or even more components are often used. Evaluation of the swelling behavior of each component pair of such systems becomes unreasonable. Therefore, exploitation of the solubility parameter approach was found to be more useful. The latter allows consideration of the properties of each single component instead of the pair of components. In such a manner, the Hansen Solubility Parameter (HSP) approach was used for further analysis. Solubility spheres were constructed for polyurethane, polyurea and polyamide. For this a three-dimensional graph is plotted with dispersion, polar and hydrogen bonding components of solubility parameter, obtained from literature, as the orthogonal axes. The HSP of the solvents are used as the coordinates for the points on the HSP graph. Then a sphere with a certain radius is located on a graph, and the "good" solvents would be located inside the sphere, while the "poor" ones are located outside. Both the location of the sphere center and the sphere radius should be fitted according to the information on polymer swelling behavior in a number of solvents. According to the existing correlation between the capsule morphology and swelling behavior of polymers, the solvents located inside the solubility sphere of a polymer give capsules with compact morphologies. The solvents located outside the solubility sphere of the solvent give either core-shell or multicompartment capsules in combination with the chosen polymer. Once the solubility sphere of a polymer is found, the solubility/swelling behavior is approximated to all possible substances. HSP theory allows therefore prediction of polymer solubility/swelling behavior and consequently the capsule morphology for any given substance with known HSP parameters on the basis of limited data. The latter makes the theory so attractive for application in chemistry and technology, since the choice of the system components is usually performed on the basis of a large number of different parameters that should mutually match. Even slight change of the technology sometimes leads to the necessity to find the analogue of this or that solvent in a sense of solvency but carrying different chemistry. Usage of the HSP approach in this case is indispensable. In the second part of the work examples of the HSP application for the fabrication of capsules with on-demand-morphology are presented. Capsules with compact or core-shell morphology containing corrosion inhibitors were synthesized. Thus, alkoxysilanes possessing long hydrophobic tail, combining passivating and water-repelling properties, were encapsulated in polyurethane shell. The mechanism of action of the active material required core-shell morphology of the capsules. The new hybrid corrosion inhibitor, cerium diethylhexyl phosphate, was encapsulated in polyamide shells in order to facilitate the dispersion of the substance and improve its adhesion to the coating matrix. The encapsulation of commercially available antifouling agents in polyurethane shells was carried out in order to control its release behavior and colloidal stability. Capsules with compact morphology made of polyurea containing the liquid corrosion inhibitor 2-methyl benzothiazole were synthesized in order to improve the colloidal stability of the substance. Capsules with compact morphology allow slower release of the liquid encapsulated material compared to the core-shell ones. If the "in-situ" encapsulation is not possible due to the reaction of the oil-soluble monomer with the encapsulated material, a solution was proposed: loading of the capsules should be performed after monomer deactivation due to the accomplishment of the polymerization reaction. Capsules of desired morphologies should be preformed followed by the loading step. In this way, compact polyurea capsules containing the highly effective but chemically active corrosion inhibitors 8-hydroxyquinoline and benzotriazole were fabricated. All the resulting capsules were successfully introduced into model coatings. The efficiency of the resulting "smart" self-healing anticorrosion coatings on steel and aluminium alloy of the AA-2024 series was evaluated using characterization techniques such as Scanning Vibrating Electron Spectroscopy, Electrochemical Impedance Spectroscopy and salt-spray chamber tests.},
  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{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{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{Miasnikova2012,
  author    = {Miasnikova, Anna},
  title     = {New hydrogel forming thermo-responsive block copolymers of increasing structural complexity},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-59953},
  school      = {Universit{\"a}t Potsdam},
  year      = {2012},
  abstract  = {This work describes the synthesis and characterization of stimuli-responsive polymers made by reversible addition-fragmentation chain transfer (RAFT) polymerization and the investigation of their self-assembly into "smart" hydrogels. In particular the hydrogels were designed to swell at low temperature and could be reversibly switched to a collapsed hydrophobic state by rising the temperature. Starting from two constituents, a short permanently hydrophobic polystyrene (PS) block and a thermo-responsive poly(methoxy diethylene glycol acrylate) (PMDEGA) block, various gelation behaviors and switching temperatures were achieved. New RAFT agents bearing tert-butyl benzoate or benzoic acid groups, were developed for the synthesis of diblock, symmetrical triblock and 3-arm star block copolymers. Thus, specific end groups were attached to the polymers that facilitate efficient macromolecular characterization, e.g by routine 1H-NMR spectroscopy. Further, the carboxyl end-groups allowed functionalizing the various polymers by a fluorophore. Because reports on PMDEGA have been extremely rare, at first, the thermo-responsive behavior of the polymer was investigated and the influence of factors such as molar mass, nature of the end-groups, and architecture, was studied. The use of special RAFT agents enabled the design of polymer with specific hydrophobic and hydrophilic end-groups. Cloud points (CP) of the polymers proved to be sensitive to all molecular variables studied, namely molar mass, nature and number of the end-groups, up to relatively high molar masses. Thus, by changing molecular parameters, CPs of the PMDEGA could be easily adjusted within the physiological interesting range of 20 to 40°C. A second responsivity, namely to light, was added to the PMDEGA system via random copolymerization of MDEGA with a specifically designed photo-switchable azobenzene acrylate. The composition of the copolymers was varied in order to determine the optimal conditions for an isothermal cloud point variation triggered by light. Though reversible light-induced solubility changes were achieved, the differences between the cloud points before and after the irradiation were small. Remarkably, the response to light differed from common observations for azobenzene-based systems, as CPs decreased after UV-irradiation, i.e with increasing content of cis-azobenzene units. The viscosifying and gelling abilities of the various block copolymers made from PS and PMDEGA blocks were studied by rheology. Important differences were observed between diblock copolymers, containing one hydrophobic PS block only, the telechelic symmetrical triblock copolymers made of two associating PS termini, and the star block copolymers having three associating end blocks. Regardless of their hydrophilic block length, diblock copolymers PS11 PMDEGAn were freely flowing even at concentrations as high as 40 wt. \%. In contrast, all studied symmetrical triblock copolymers PS8-PMDEGAn-PS8 formed gels at low temperatures and at concentrations as low as 3.5 wt. \% at best. When heated, these gels underwent a gel-sol transition at intermediate temperatures, well below the cloud point where phase separation occurs. The gel-sol transition shifted to markedly higher transition temperatures with increasing length of the hydrophilic inner block. This effect increased also with the number of arms, and with the length of the hydrophobic end blocks. The mechanical properties of the gels were significantly altered at the cloud point and liquid-like dispersions were formed. These could be reversibly transformed into hydrogels by cooling. This thesis demonstrates that high molar mass PMDEGA is an easily accessible, presumably also biocompatible and at ambient temperature well water-soluble, non-ionic thermo-responsive polymer. PMDEGA can be easily molecularly engineered via the RAFT method, implementing defined end-groups, and producing different, also complex, architectures, such as amphiphilic triblock and star block copolymers, having an analogous structure to associative telechelics. With appropriate design, such amphiphilic copolymers give way to efficient, "smart" viscosifiers and gelators displaying tunable gelling and mechanical properties.},
  language  = {en}
}
@phdthesis{Falco2012,
  author    = {Falco, Camillo},
  title     = {Sustainable biomass-derived hydrothermal carbons for energy applications},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-59785},
  school      = {Universit{\"a}t Potsdam},
  year      = {2012},
  abstract  = {The need to reduce humankind reliance on fossil fuels by exploiting sustainably the planet renewable resources is a major driving force determining the focus of modern material research. For this reason great interest is nowadays focused on finding alternatives to fossil fuels derived products/materials. For the short term the most promising substitute is undoubtedly biomass, since it is the only renewable and sustainable alternative to fossil fuels as carbon source. As a consequence efforts, aimed at finding new synthetic approaches to convert biomass and its derivatives into carbon-based materials, are constantly increasing. In this regard, hydrothermal carbonisation (HTC) has shown to be an effective means of conversion of biomass-derived precursors into functional carbon materials. However the attempts to convert raw biomass, in particular lignocellulosic one, directly into such products have certainly been rarer. Unlocking the direct use of these raw materials as carbon precursors would definitely be beneficial in terms of HTC sustainability. For this reason, in this thesis the HTC of carbohydrate and protein-rich biomass was systematically investigated, in order to obtain more insights on the potentials of this thermochemical processing technique in relation to the production of functional carbon materials from crude biomass. First a detailed investigation on the HTC conversion mechanism of lignocellulosic biomass and its single components (i.e. cellulose, lignin) was developed based on a comparison with glucose HTC, which was adopted as a reference model. In the glucose case it was demonstrated that varying the HTC temperature allowed tuning the chemical structure of the synthesised carbon materials from a highly cross-linked furan-based structure (T = 180oC) to a carbon framework composed of polyaromatic arene-like domains. When cellulose or lignocellulosic biomass was used as carbon precursor, the furan rich structure could not be isolated at any of the investigated processing conditions. These evidences were indicative of a different HTC conversion mechanism for cellulose, involving reactions that are commonly observed during pyrolytic processes. The evolution of glucose-derived HTC carbon chemical structure upon pyrolysis was also investigated. These studies revealed that upon heat treatment (Investigated temperatures 350 - 900 oC) the furan-based structure was progressively converted into highly curved aromatic pre-graphenic domains. This thermal degradation process was observed to produce an increasingly more hydrophobic surface and considerable microporosity within the HTC carbon structure. In order to introduce porosity in the HTC carbons derived from lignocellulosic biomass, KOH chemical activation was investigated as an HTC post-synthesis functionalisation step. These studies demonstrated that HTC carbons are excellent precursors for the production of highly microporous activated carbons (ACs) and that the porosity development upon KOH chemical activation is dependent on the chemical structure of the HTC carbon, tuned by employing different HTC temperatures. Preliminary testing of the ACs for CO2 capture or high pressure CH4 storage yielded very promising results, since the measured uptakes of both adsorbates (i.e. CO2 and CH4) were comparable to top-performing and commercially available adsorbents, usually employed for these end-applications. The combined use of HTC and KOH chemical activation was also employed to produce highly microporous N-doped ACs from microalgae. The hydrothermal treatment of the microalgae substrate was observed to cause the depletion of the protein and carbohydrate fractions and the near complete loss (i.e. 90\%) of the microalgae N-content, as liquid hydrolysis/degradation products. The obtained carbonaceous product showed a predominantly aliphatic character indicating the presence of alkyl chains presumably derived from the lipid fractions. Addition of glucose to the initial reaction mixture was found out to be extremely beneficial, because it allowed the fixation of a higher N amount, in the algae derived HTC carbons (i.e.  60\%), and the attainment of higher product yields (50\%). Both positive effects were attributed to Maillard type cascade reactions taking place between the monosaccharides and the microalgae derived liquid hydrolysis/degradation products, which were in this way recovered from the liquid phase. KOH chemical activation of the microalgae/glucose mixture derived HTC carbons produced highly microporous N-doped carbons. Although the activation process led to a major reduction of the N-content, the retained N-amount in the ACs was still considerable. These features render these materials ideal candidates for supercapacitors electrodes, since they provide extremely high surface areas, for the formation of electric double-layer, coupled to abundant heteroatom doping (i.e. N and O) necessary to obtain a pseudocapacitance contribution.},
  language  = {en}
}