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The time-dependent approach to electronic spectroscopy, as popularized by Heller and coworkers in the 1980's, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption, emission and resonance Raman spectra of several diamondoids. Two-state models, the harmonic and the Condon approximations, are used for the calculations, making them easily applicable to larger molecules. The method is applied to nine pristine lower and higher diamondoids: adamantane, diamantane, triamantane, and three isomers each of tetramantane and pentamantane. We also consider a hybrid species “Dia = Dia” – a shorthand notation for a recently synthesized molecule comprising two diamantane units connected by a C[double bond, length as m-dash]C double bond. We resolve and interpret trends in optical and vibrational properties of these molecules as a function of their size, shape, and symmetry, as well as effects of “blending” with sp2-hybridized C-atoms. Time-dependent correlation functions facilitate the computations and shed light on the vibrational dynamics following electronic transitions.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
A Co(II)–imidazolate-4-amide-5-imidate based MOF, IFP-5, is synthesized by using an imidazolate anion-based novel ionic liquid as a linker precursor under solvothermal conditions. IFP-5 shows significant amounts of gas (N2, CO2, CH4 and H2) uptake capacities. IFP-5 exhibits an independent high spin Co(II) centre and antiferromagnetic coupling.
It was the goal of this work to explore two different synthesis pathways using green chemistry. The first part of this thesis is focusing on the use of the urea-glass route towards single phase manganese nitride and manganese nitride/oxide nano-composites embedded in carbon, while the second part of the thesis is focusing on the use of the “saccharide route” (namely cellulose, sucrose, glucose and lignin) towards metal (Ni0), metal alloy (Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5, Cu0.5Ni0.5 and W0.15Ni0.85) and ternary carbide (Mn0.75Fe2.25C) nanoparticles embedded in carbon. In the interest of battery application, MnN0.43 nanoparticles surrounded by a graphitic shell and embedded in carbon with a high surface area (79 m^2/g) were synthesized, following a previously set route.The comparison of the material characteristics before and after the discharge showed no remarkable difference in terms of composition and just slight differences in the morphological point of view, meaning the particles are stable but agglomerate. The graphitic shell is contributing to the resistance of the material and leads to a fine cyclic stability over 140 cycles of 230 mAh/g after the first charge/discharge and coulombic efficiencies close to 100%. Due to the low voltage towards Li/Li+ and the low polarization, it might be an attractive anode material for lithium ion batteries. However, the capacity is still noticeably lower than the theoretical value for MnN0.43. A mixture of MnN0.43 and MnO nanoparticles embedded in carbon (surface area 93 m^2/g) was able to improve the cyclic stability to over 160 cycles giving a capacity of 811 mAh/g, which is considerably higher than the capacity of the conventional material graphite (372 mAh/g). This nano-composite seems to agglomerate less during the process of discharge. Interestingly, although the capacity is much higher than of the single phase manganese nitride, the nano-composite seems to only contain MnN0.43 nanoparticles after the process of discharge with no oxide phase to be found. Concerning catalysis application, different metal, metal alloy, and metal carbide nanoparticles were synthesized using the saccharide route. At first, systems that were already investigated before, being Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5 and Mn0.75Fe2.25C using cellulose as the carbon source were prepared and tested in an alkylation reaction of toluene with benzylchloride. Unexpectedly, the metal alloys did not show any catalytic activity, but the ternary carbide Mn0.75Fe2.25C showed fine catalytic activity of 98% conversion after 9 hour reaction time (110 °C). In a second step, the saccharide route was modified towards other carbon sources and carbon to metal ratios in order to improve the homogeneity of the samples and accessibility of the particle surfaces. The used carbon sources sucrose and glucose are similar in their basic structure of carbohydrates, but reducing the (polymeric) chain length. Indeed, the cellulose could be successfully replaced by sucrose and glucose. A lower carbon to metal ratio was found to influence the size, homogeneity and accessibility (as evidenced by TEM) of the samples. Since sucrose is an aliment, glucose is the better choice as a carbon source. Using glucose, the synthesis of Cu0.5Ni0.5 and W0.15Ni0.85 nano-composites was also possible, although the later was never obtained as pure phase. These alloy nano-composites were tested, along with nickel0 nanoparticles also prepared with glucose and on their catalytic activity towards the reduction of phenylacetylene. The results obtained let believe that any (poly) saccharide, including lignin, could be used as carbon source. The nickel0 nano-composites prepared with lignin as a carbon source were tested along with those prepared with cellulose and sucrose for their catalytic activity in the transfer hydrogenation of nitrobenzene (results compared with exposed nickel nanoparticles and nickel supported on carbon) leading to very promising results. Based on the urea-glass route and the saccharide route, simple equipment and transition metals, it was possible to have a one-pot synthesize with scale-up possibilities towards new material that can be applied in catalysis and battery systems.
In this work, thermosensitive hydrogels having tunable thermo-mechanical properties were synthesized. Generally the thermal transition of thermosensitive hydrogels is based on either a lower critical solution temperature (LCST) or critical micelle concentration/ temperature (CMC/ CMT). The temperature dependent transition from sol to gel with large volume change may be seen in the former type of thermosensitive hydrogels and is negligible in CMC/ CMT dependent systems. The change in volume leads to exclusion of water molecules, resulting in shrinking and stiffening of system above the transition temperature. The volume change can be undesired when cells are to be incorporated in the system. The gelation in the latter case is mainly driven by micelle formation above the transition temperature and further colloidal packing of micelles around the gelation temperature. As the gelation mainly depends on concentration of polymer, such a system could undergo fast dissolution upon addition of solvent. Here, it was envisioned to realize a thermosensitive gel based on two components, one responsible for a change in mechanical properties by formation of reversible netpoints upon heating without volume change, and second component conferring degradability on demand. As first component, an ABA triblockcopolymer (here: Poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEPE) with thermosensitive properties, whose sol-gel transition on the molecular level is based on micellization and colloidal jamming of the formed micelles was chosen, while for the additional macromolecular component crosslinking the formed micelles biopolymers were employed. The synthesis of the hydrogels was performed in two ways, either by physical mixing of compounds showing electrostatic interactions, or by covalent coupling of the components. Biopolymers (here: the polysaccharides hyaluronic acid, chondroitin sulphate, or pectin, as well as the protein gelatin) were employed as additional macromolecular crosslinker to simultaneously incorporate an enzyme responsiveness into the systems. In order to have strong ionic/electrostatic interactions between PEPE and polysaccharides, PEPE was aminated to yield predominantly mono- or di-substituted PEPEs. The systems based on aminated PEPE physically mixed with HA showed an enhancement in the mechanical properties such as, elastic modulus (G′) and viscous modulus (G′′) and a decrease of the gelation temperature (Tgel) compared to the PEPE at same concentration. Furthermore, by varying the amount of aminated PEPE in the composition, the Tgel of the system could be tailored to 27-36 °C. The physical mixtures of HA with di-amino PEPE (HA·di-PEPE) showed higher elastic moduli G′ and stability towards dissolution compared to the physical mixtures of HA with mono-amino PEPE (HA·mono-PEPE). This indicates a strong influence of electrostatic interaction between –COOH groups of HA and –NH2 groups of PEPE. The physical properties of HA with di-amino PEPE (HA·di-PEPE) compare beneficially with the physical properties of the human vitreous body, the systems are highly transparent, and have a comparable refractive index and viscosity. Therefore,this material was tested for a potential biological application and was shown to be non-cytotoxic in eluate and direct contact tests. The materials will in the future be investigated in further studies as vitreous body substitutes. In addition, enzymatic degradation of these hydrogels was performed using hyaluronidase to specifically degrade the HA. During the degradation of these hydrogels, increase in the Tgel was observed along with decrease in the mechanical properties. The aminated PEPE were further utilised in the covalent coupling to Pectin and chondroitin sulphate by using EDC as a coupling agent. Here, it was possible to adjust the Tgel (28-33 °C) by varying the grafting density of PEPE to the biopolymer. The grafting of PEPE to Pectin enhanced the thermal stability of the hydrogel. The Pec-g-PEPE hydrogels were degradable by enzymes with slight increase in Tgel and decrease in G′ during the degradation time. The covalent coupling of aminated PEPE to HA was performed by DMTMM as a coupling agent. This method of coupling was observed to be more efficient compared to EDC mediated coupling. Moreover, the purification of the final product was performed by ultrafiltration technique, which efficiently removed the unreacted PEPE from the final product, which was not sufficiently achieved by dialysis. Interestingly, the final products of these reaction were in a gel state and showed enhancement in the mechanical properties at very low concentrations (2.5 wt%) near body temperature. In these hydrogels the resulting increase in mechanical properties was due to the combined effect of micelle packing (physical interactions) by PEPE and covalent netpoints between PEPE and HA. PEPE alone or the physical mixtures of the same components were not able to show thermosensitive behavior at concentrations below 16 wt%. These thermosensitive hydrogels also showed on demand solubilisation by enzymatic degradation. The concept of thermosensitivity was introduced to 3D architectured porous hydrogels, by covalently grafting the PEPE to gelatin and crosslinking with LDI as a crosslinker. Here, the grafted PEPE resulted in a decrease in the helix formation in gelatin chains and after fixing the gelatin chains by crosslinking, the system showed an enhancement in the mechanical properties upon heating (34-42 °C) which was reversible upon cooling. A possible explanation of the reversible changes in mechanical properties is the strong physical interactions between micelles formed by PEPE being covalently linked to gelatin. Above the transition temperature, the local properties were evaluated by AFM indentation of pore walls in which an increase in elastic modulus (E) at higher temperature (37 °C) was observed. The water uptake of these thermosensitive architectured porous hydrogels was also influenced by PEPE and temperature (25 °C and 37 °C), showing lower water up take at higher temperature and vice versa. In addition, due to the lower water uptake at high temperature, the rate of hydrolytic degradation of these systems was found to be decreased when compared to pure gelatin architectured porous hydrogels. Such temperature sensitive architectured porous hydrogels could be important for e.g. stem cell culturing, cell differentiation and guided cell migration, etc. Altogether, it was possible to demonstrate that the crosslinking of micelles by a macromolecular crosslinker increased the shear moduli, viscosity, and stability towards dissolution of CMC-based gels. This effect could be likewise be realized by covalent or non-covalent mechanisms such as, micelle interactions, physical interactions of gelatin chains and physical interactions between gelatin chains and micelles. Moreover, the covalent grafting of PEPE will create additional net-points which also influence the mechanical properties of thermosensitive architectured porous hydrogels. Overall, the physical and chemical interactions and reversible physical interactions in such thermosensitive architectured porous hydrogels gave a control over the mechanical properties of such complex system. The hydrogels showing change of mechanical properties without a sol-gel transition or volume change are especially interesting for further study with cell proliferation and differentiation.
A rare example of in situ linker generation with the formation of soft porous Zn- and Co-MOFs (IFP-9 and -10, respectively) is reported. The flexible ethoxy groups of IFP-9 and -10 protrude into the 1D hexagonal channels. The gas-sorption behavior of both materials for H2, CO2 and CH4 showed wide hysteretic isotherms, typical for MOFs having a flexible substituent which can give rise to a gate effect.
In den vergangenen Jahren wurden stetig wachsende Produktionskapazitäten von Biokunststoffen aus nachwachsenden Rohstoffe nverzeichnet. Trotz großer Produktionskapazitäten und einem geeigneten Eigenschaftsprofil findet Stärke nur als hydrophile, mit Weichmachern verarbeitete thermoplastische Stärke (TPS) in Form von Blends mit z. B. Polyestern Anwendung. Gleiches gilt für Kunststoffe auf Proteinbasis. Die vorliegende Arbeit hat die Entwicklung von Biokunststoffen auf Stärkebasis zum Ziel, welche ohne externe Weichmacher thermoplastisch verarbeitbar und hydrophob sind sowie ein mechanisches Eigenschaftsprofil aufweisen, welches ein Potenzial zur Herstellung von Materialien für eine Anwendung als Verpackungsmittel bietet. Um die Rohstoffbasis für Biokunststoffe zu erweitern, soll das erarbeitete Konzept auf zwei industriell verfügbare Proteintypen, Zein und Molkenproteinisolat (WPI), übertragen werden. Als geeignete Materialklasse wurden Fettsäureester der Stärke herausgearbeitet. Zunächst fand ein Vergleich der Säurechlorid-Veresterung und der Umesterung von Fettsäurevinylestern statt, woraus letztere als geeignetere Methode hervorging. Durch Variation der Reaktionsparameter konnte diese optimiert und auf eine Serie der Fettsäurevinylester von Butanoat bis Stearat für DS-Werte bis zu 2,2-2,6 angewandt werden. Möglich war somit eine systematische Studie unter Variation der veresterten Fettsäure sowie des Substitutionsgrades (DS). Sämtliche Produkte mit einem DS ab 1,5 wiesen eine ausgprägte Löslichkeit in organischen Lösungsmitteln auf wodurch sowohl die Aufnahme von NMR-Spektren als auch Molmassenbestimmung mittels Größenausschlusschromatographie mit gekoppelter Mehrwinkel-Laserlichtstreuung (GPC-MALLS) möglich waren. Durch dynamische Lichtstreuung (DLS) wurde das Löslichkeitsverhalten veranschaulicht. Sämtliche Produkte konnten zu Filmen verarbeitet werden, wobei Materialien mit DS 1,5-1,7 hohe Zugfestigkeiten (bis zu 42 MPa) und Elastizitätsmodule (bis 1390 MPa) aufwiesen. Insbesondere Stärkehexanoat mit DS <2 sowie Stärkebutanoat mit DS >2 hatten ein mechanisches Eigenschaftsprofil, welches insbesondere in Bezug auf die Festigkeit/Steifigkeit vergleichbar mit Verpackungsmaterialien wie Polyethylen war (Zugfestigkeit: 15-32 MPa, E-Modul: 300-1300 MPa). Zugfestigkeit und Elastizitätsmodul nahmen mit steigender Kettenlänge der veresterten Fettsäure ab. Ester längerkettiger Fettsäuren (C16-C18) waren spröde. Über Weitwinkel-Röntgenstreuung (WAXS) und Infrarotspektroskopie (ATR-FTIR) konnte der Verlauf der Festigkeiten mit einer zunehmenden Distanz der Stärke im Material begründet werden. Es konnten von DS und Kettenlänge abhängige Glasübergänge detektiert werden, die kristallinen Strukturen der langkettigen Fettsäuren zeigten einen Schmelzpeak. Die Hydrophobie der Filme wurde anhand von Kontaktwinkeln >95° gegen Wasser dargestellt. Blends mit biobasierten Polyterpenen sowie den in der Arbeit hergestellten Zein-Acylderivaten ermöglichten eine weitere Verbesserung der Zugfestigkeit bzw. des Elastizitätsmoduls hochsubstituierter Produkte. Eine thermoplastische Verarbeitung mittels Spritzgießen war sowohl für Produkte mit hohem als auch mittlerem DS-Wert ohne jeglichen Zusatz von Weichmachern möglich. Es entstanden homogene, transparente Prüfstäbe. Untersuchungen der Härte ergaben auch hier für Stärkehexanoat und –butanoat mit Polyethylen vergleichbare Werte. Ausgewählte Produkte wurden zu Fasern nach dem Schmelzspinnverfahren verarbeitet. Hierbei wurden insbesondere für hochsubstituierte Derivate homogenen Fasern erstellt, welche im Vergleich zur Gießfolie signifikant höhere Zugfestigkeiten aufwiesen. Stärkeester mit mittlerem DS ließen sich ebenfalls verarbeiten. Zunächst wurden für eine Übertragung des Konzeptes auf die Proteine Zein und WPI verschiedene Synthesemethoden verglichen. Die Veresterung mit Säurechloriden ergab hierbei die höchsten Werte. Im Hinblick auf eine gute Löslichkeit in organischen Lösungsmitteln wurde für WPI die Veresterung mit carbonyldiimidazol (CDI)-aktivierten Fettsäuren in DMSO und für Zein die Veresterung mit Säu-rechloriden in Pyridin bevorzugt. Es stellte sich heraus, dass acyliertes WPI zwar hydrophob, jedoch ohne Weichmacher nicht thermoplastisch verarbeitet werden konnte. Die Erstellung von Gießfolien führte zu Sprödbruchverhalten. Unter Zugabe der biobasierten Ölsäure wurde die Anwendung von acyliertem WPI als thermoplastischer Filler z. B. in Blends mit Stärkeestern dargestellt. Im Gegensatz hierzu zeigte acyliertes Zein Glasübergänge <100 °C bei ausreichender Stabilität (150-200 °C). Zeinoleat konnte ohne Weichmacher zu einer transparenten Gießfolie verarbeitet werden. Sämtliche Derivate erwiesen sich als ausgeprägt hydrophob. Zeinoleat konnte über das Schmelzspinnverfahren zu thermoplastischen Fasern verarbeitet werden.
We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.
4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4’-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.
We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.
We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
Various 1,6- and 1,8-naphthalenophanes were synthesized by using the Photo-Dehydro-Diels-Alder (PDDA) reaction of bis-ynones. These compounds are easily accessible from omega-(3-iodophenyl)carboxylic acids in three steps. The obtained naphthalenophanes are axially chiral and the activation barrier for the atropisomerization could be determined in some cases by means of dynamic NMR (DNMR) and/or dynamic HPLC (DHPLC) experiments.
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
Various synthetic approaches were explored towards the preparation of poly(N-substituted glycine) homo/co-polymers (a.k.a. polypeptoids). In particular, monomers that would facilitate in the preparation of bio-relevant polymers via either chain- or step-growth polymerization were targeted. A 3-step synthetic approach towards N-substituted glycine N-carboxyanhydrides (NNCA) was implemented, or developed, and optimized allowing for an efficient gram scale preparation of the aforementioned monomer (chain-growth). After exploring several solvents and various conditions, a reproducible and efficient ring-opening polymerization (ROP) of NNCAs was developed in benzonitrile (PhCN). However, achieving molecular weights greater than 7 kDa required longer reaction times (>4 weeks) and sub-sequentially allowed for undesirable competing side reactions to occur (eg. zwitterion monomer mechanisms). A bulk-polymerization strategy provided molecular weights up to 11 kDa within 24 hours but suffered from low monomer conversions (ca. 25%). Likewise, a preliminary study towards alcohol promoted ROP of NNCAs suffered from impurities and a suspected alternative activated monomer mechanism (AAMM) providing poor inclusion of the initiator and leading to multi-modal dispersed polymeric systems. The post-modification of poly(N-allyl glycine) via thiol-ene photo-addition was observed to be quantitative, with the utilization of photo-initiators, and facilitated in the first glyco-peptoid prepared under environmentally benign conditions. Furthermore, poly(N-allyl glycine) demonstrated thermo-responsive behavior and could be prepared as a semi-crystalline bio-relevant polymer from solution (ie. annealing). Initial efforts in preparing these polymers via standard poly-condensation protocols were insufficient (step-growth). However, a thermally induced side-product, diallyl diketopiperazine (DKP), afforded the opportunity to explore photo-induced thiol-ene and acyclic diene metathesis (ADMET) polymerizations. Thiol-ene polymerization readily led to low molecular weight polymers (<2.5 kDa), that were insoluble in most solvents except heated amide solvents (ie. DMF), whereas ADMET polymerization, with diallyl DKP, was unsuccessful due to a suspected 6 member complexation/deactivation state of the catalyst. This understanding prompted the preparation of elongated DKPs most notably dibutenyl DKP. SEC data supports the aforementioned understanding but requires further optimization studies in both the preparation of the DKP monomers and following ADMET polymerization. This work was supported by NMR, GC-MS, FT-IR, SEC-IR, and MALDI-Tof MS characterization. Polymer properties were measured by UV-Vis, TGA, and DSC.
In this work, the development of temperature- and protein-responsive sensor materials based on biocompatible, inverse hydrogel opals (IHOs) is presented. With these materials, large biomolecules can be specifically recognised and the binding event visualised. The preparation of the IHOs was performed with a template process, for which monodisperse silica particles were vertically deposited onto glass slides as the first step. The obtained colloidal crystals with a thickness of 5 μm displayed opalescent reflections because of the uniform alignment of the colloids. As a second step, the template was embedded in a matrix consisting of biocompatible, thermoresponsive hydrogels. The comonomers were selected from the family of oligo(ethylene glycol)methacrylates. The monomer solution was injected into a polymerisation mould, which contained the colloidal crystals as a template. The space in-between the template particles was filled with the monomer solution and the hydrogel was cured via UV-polymerisation. The particles were chemically etched, which resulted in a porous inner structure. The uniform alignment of the pores and therefore the opalescent reflection were maintained, so these system were denoted as inverse hydrogel opals. A pore diameter of several hundred nanometres as well as interconnections between the pores should facilitate a diffusion of bigger (bio)molecules, which was always a challenge in the presented systems until now. The copolymer composition was chosen to result in a hydrogel collapse over 35 °C. All hydrogels showed pronounced swelling in water below the critical temperature. The incorporation of a reactive monomer with hydroxyl groups ensured a potential coupling group for the introduction of recognition units for analytes, e.g. proteins. As a test system, biotin as a recognition unit for avidin was coupled to the IHO via polymer-analogous Steglich esterification. The amount of accessible biotin was quantified with a colorimetric binding assay. When avidin was added to the biotinylated IHO, the wavelength of the opalescent reflection was significantly shifted and therefore the binding event was visualised. This effect is based on the change in swelling behaviour of the hydrogel after binding of the hydrophilic avidin, which is amplified by the thermoresponsive nature of the hydrogel. A swelling or shrinking of the pores induces a change in distance of the crystal planes, which are responsible for the colour of the reflection. With these findings, the possibility of creating sensor materials or additional biomolecules in the size range of avidin is given.
Modifizierung von Silikonelastomeren mit organischen Dipolen für Dielektrische Elastomer Aktuatoren
(2013)
Ein Dielektrischer Elastomer Aktuator (DEA) ist ein dehnbarer Kondensator, der aus einem Elastomerfilm besteht, der sich zwischen zwei flexiblen Elektroden befindet. Bei Anlegen einer elektrischen Spannung, ziehen sich die Elektroden aufgrund elektrostatischer Wechselwirkungen an, wodurch das Elastomer in z-Richtung zusammengepresst wird und sich dementsprechend in der x-,y-Ebene ausdehnt. Hierdurch werden Aktuationsbewegungen erreicht, welche sehr präzise über die Spannung gesteuert werden können. Zusätzlich sind DEAs kostengünstig, leicht und aktuieren geräuschlos. DEAs können beispielsweise für Produkte im medizinischen Bereich oder für optischer Komponenten genutzt werden. Ebenso kann aus diesen Bauteilen Strom erzeugt werden. Das größte Hindernis für eine weite Implementierung dieser Materialien liegt in den erforderlichen hohen Spannungen zum Erzeugen der Aktuationsbewegung, welche sich tendenziell im Kilovolt-Bereich befinden. Dies macht die Elektronik teuer und die Bauteile unsicher für Anwender. Um geringere Betriebsspannungen für die DEAs zu erreichen, sind signifikante Materialverbesserungen - insbesondere des verwendeten Elastomers - erforderlich. Um dies zu erreichen, können die dielektrischen Eigenschaften (Permittivität) der Elastomere gesteigert und/oder deren Steifigkeit (Young-Modul) gesenkt werden. In der vorliegenden Arbeit konnte die Aktuationsleistung von Silikonfilmen durch die Addition organischer Dipole erheblich verbessert werden. Hierfür wurde ein Verfahren etabliert, um funktionalisierte Dipole kovalent an das Polymernetzwerk zu binden. Dieser als "One-Step-Verfahren" bezeichnete Ansatz ist einfach durchzuführen und es werden homogene Filme erhalten. Die Dipoladdition wurde anhand verschiedener Silikone erprobt, die sich hinsichtlich ihrer mechanischen Eigenschaften unterschieden. Bei maximalem Dipolgehalt verdoppelte sich die Permittivität aller untersuchten Silikone und die Filme wurden deutlich weicher. Hierbei war festzustellen, dass die Netzwerkstruktur der verwendeten Silikone einen erheblichen Einfluss auf die erreichte Aktuationsdehnung hat. Abhängig vom Netzwerk erfolgte eine enorme Steigerung der Aktuationsleistung im Bereich von 100 % bis zu 4000 %. Dadurch können die Betriebsspannungen in DEAs deutlich abgesenkt werden, so dass sie tendenziell bei Spannungen unterhalb von einem Kilovolt betrieben werden können.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as “activation agents” with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this “induced carbonization” and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
Hydrothermal carbonisation
(2013)
The world’s appetite for energy is producing growing quantities of CO2, a pollutant that contributes to the warming of the planet and which currently cannot be removed or stored in any significant way. Other natural reserves are also being devoured at alarming rates and current assessments suggest that we will need to identify alternative sources in the near future. With the aid of materials chemistry it should be possible to create a world in which energy use needs not be limited and where usable energy can be produced and stored wherever it is needed, where we can minimize and remediate emissions as new consumer products are created, whilst healing the planet and preventing further disruptive and harmful depletion of valuable mineral assets. In achieving these aims, the creation of new and very importantly greener industries and new sustainable pathways are crucial. In all of the aforementioned applications, new materials based on carbon, ideally produced via inexpensive, low energy consumption methods, using renewable resources as precursors, with flexible morphologies, pore structures and functionalities, are increasingly viewed as ideal candidates to fulfill these goals. The resulting materials should be a feasible solution for the efficient storage of energy and gases. At the end of life, such materials ideally must act to improve soil quality and to act as potential CO2 storage sinks. This is exactly the subject of this habilitation thesis: an alternative technology to produce carbon materials from biomass in water using low carbonisation temperatures and self-generated pressures. This technology is called hydrothermal carbonisation. It has been developed during the past five years by a group of young and talented researchers working under the supervision of Dr. Titirici at the Max-Planck Institute of Colloids and Interfaces and it is now a well-recognised methodology to produce carbon materials with important application in our daily lives. These applications include electrodes for portable electronic devices, filters for water purification, catalysts for the production of important chemicals as well as drug delivery systems and sensors.
The supercapacitor is one of the most important energy storage devices as its construction allows for addressing many of the drawbacks related to batteries, but the low energy density of current systems is a major issue. In this doctoral dissertation, with a view to attaining high energy density supercapacitor systems that can be comparable to those for batteries, new heteroatom-containing carbons in the form of particles and three-dimensional films were investigated. A nitrogen-containing material, acrodam, was chosen as the carbon precursor due to the inexpensiveness, high carbonization yield, oligomerizability, etc. The carbon particles were prepared from acrodam together with caesium acetate as a meltable flux agent, and disclosed excellent properties in hydroquinone-loaded sulphuric acid electrolyte with high energy densities (up to 133.0 Wh kg–1) and sufficient cycle stabilities. These properties are already now comparable to those of batteries. Besides, conductive carbon three-dimensional films were fabricated using acrodam oligomer as the precursor by the inexpensive spin coating method. The films were found to be homogeneous, flat, void- and crack-free, and high conductivities (up to 334 S cm–1) could be obtained at the carbonization temperature of 1000 ºC. Furthermore, a porous carbon three-dimensional film could be formed using an organic template at the first attempt. This finding demonstrates the film’s potentiality for various applications such as supercapacitor electrode; the essential absence of contact resistance within the network should contribute to effective transportation of electron within the electrode. The progress made in this dissertation will open a new way to further enhancement of energy density for supercapacitor as well as other applications that exceeds the current properties.