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The increasing development of antibiotic resistance in bacteria has been a major problem for years, both in human and veterinary medicine. Prophylactic measures, such as the use of vaccines, are of great importance in reducing the use of antibiotics in livestock. These vaccines are mainly produced based on formaldehyde inactivation. However, the latter damages the recognition elements of the bacterial proteins and thus could reduce the immune response in the animal. An alternative inactivation method developed in this work is based on gentle photodynamic inactivation using carbon nanodots (CNDs) at excitation wavelengths λex > 290 nm. The photodynamic inactivation was characterized on the nonvirulent laboratory strain Escherichia coli K12 using synthesized CNDs. For a gentle inactivation, the CNDs must be absorbed into the cytoplasm of the E. coli cell. Thus, the inactivation through photoinduced formation of reactive oxygen species only takes place inside the bacterium, which means that the outer membrane is neither damaged nor altered. The loading of the CNDs into E. coli was examined using fluorescence microscopy. Complete loading of the bacterial cells could be achieved in less than 10 min. These studies revealed a reversible uptake process allowing the recovery and reuse of the CNDs after irradiation and before the administration of the vaccine. The success of photodynamic inactivation was verified by viability assays on agar. In a homemade flow photoreactor, the fastest successful irradiation of the bacteria could be carried out in 34 s. Therefore, the photodynamic inactivation based on CNDs is very effective. The membrane integrity of the bacteria after irradiation was verified by slide agglutination and atomic force microscopy. The method developed for the laboratory strain E. coli K12 could then be successfully applied to the important avian pathogens Bordetella avium and Ornithobacterium rhinotracheale to aid the development of novel vaccines.
This thesis focuses on the synthesis of novel functional materials based on plasmonic nanoparticles. Three systems with targeted surface modification and functionalization have been designed and synthesized, involving modified perylenediimide doped silica-coated silver nanowires, polydopamine or TiO2 coated gold-palladium nanorods and thiolated poly(ethylene glycol) (PEG-SH)/dodecanethiol (DDT) modified silver nanospheres. Their possible applications as plasmonic resonators, chiral sensors as well as photo-catalysts have been studied. In addition, the interaction between silver nanospheres and 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) molecules has also been investigated in detail.
In the first part of the thesis, surface modification on Ag nanowires (NWs) with optimized silica coating through a modified Stöber method has been firstly conducted, employing sodium hydroxide (NaOH) to replace ammonia solution (NH4OH). The coated silver nanowires with a smooth silica shell have been investigated by single-particle dark-field scattering spectroscopy, transmission electron microscopy and electron-energy loss spectroscopy to characterize the morphologies and structural components. The silica-coated silver nanowires can be further functionalized with fluorescent molecules in the silica shell via a facile one-step coating method. The as-synthesized nanowire is further coupled with a gold nanosphere by spin-coating for the application of the sub-diffractional chiral sensor for the first time. The exciton-plasmon-photon interconversion in the system eases the signal detection in the perfectly matched 1D nanostructure and contributes to the high contrast of the subwavelength chiral sensing for the polarized light.
In the second part of the thesis, dumbbell-shaped Au-Pd nanorods coated with a layer of polydopamine (PDA) or titanium dioxide (TiO2) have been constructed. The PDA- and TiO2- coated Au-Pd nanorods show a strong photothermal conversion performance under NIR illumination. Moreover, the catalytic performance of the particles has been investigated using the reduction of 4-nitrophenol (4-NP) as the model reaction. Under light irradiation, the PDA-coated Au-Pd nanorods exhibit a superior catalytic activity by increasing the reaction rate constant of 3 times. The Arrhenius-like behavior of the reaction with similar activation energies in the presence and absence of light irradiation indicates the photoheating effect to be the dominant mechanism of the reaction acceleration. Thus, we attribute the enhanced performance of the catalysis to the strong photothermal effect that is driven by the optical excitation of the gold surface plasmon as well as the synergy with the PDA layer.
In the third part, the kinetic study on the adsorption of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquino-dimethane (F4TCNQ) on the surface of Ag nanoparticles (Ag NPs) in chloroform has been reported in detail. Based on the results obtained from the UV-vis-NIR absorption spectroscopy, cryogenic transmission electron microscopy (cryo-TEM), scanning nano-beam electron diffraction (NBED) and electron energy loss spectroscopy (EELS), a two-step interaction kinetics has been proposed for the Ag NPs and F4TCNQ molecules. It includes the first step of electron transfer from Ag NPs to F4TCNQ indicated by the ionization of F4TCNQ, and the second step of the formation of Ag-F4TCNQ complex. The whole process has been followed via UV-vis-NIR absorption spectroscopy, which reveals distinct kinetics at two stages: the instantaneous ionization and the long-term complex formation. The kinetics and the influence of the molar ratio of Ag NPs/F4TCNQ molecules on the interaction between Ag NPs and F4TCNQ molecules in the organic solution are reported herein for the first time. Furthermore, the control experiment with silica-coated Ag NPs indicates that the charge transfer at the surface between Ag NPs and F4TCNQ molecules has been prohibited by a silica layer of 18 nm.
The need for multifunctional materials is driven by emerging technologies and innovations, such as in the field of soft robotics and tactile or haptic systems, where minimizing the number of operational components is not only desirable, but can also be essential for realizing such devices. This study report on designing a multifunctional soft polymer material that can address a number of operating requirements such as solvent resistance, reshaping ability, self-healing capability, fluorescence stimuli-responsivity, and anisotropic structural functions. The numerous functional abilities are associated to rhodium(I)-phosphine coordination bonds, which in a polymer network act with their dynamic and non-covalently bonded nature as multifunctional crosslinks. Reversible aggregation of coordination bonds leads to changes in fluorescence emission intensity that responds to chemical or mechanical stimuli. The fast dynamics and diffusion of rhodium-phosphine ions across and through contacting areas of the material provide for reshaping and self-healing abilities that can be further exploited for assembly of multiple pieces into complex forms, all without any loss to material-sensing capabilities.
Shape-Memory effects of thermoplatic multiblock copolymers with overlapping thermal transitions
(2021)
Toll-like receptor (TLR) can trigger an immune response against virus including SARS-CoV-2. TLR expression/distribution is varying in mesenchymal stromal cells (MSCs) depending on their culture environments. Here, to explore the effect of periodic thermomechanical cues on TLRs, thermally controlled shape-memory polymer sheets with programmable actuation capacity were created. The proportion of MSCs expressing SARS-CoV-2-associated TLRs was increased upon stimulation. The TLR4/7 colocalization was promoted and retained in the endoplasmic reticula. The TLR redistribution was driven by myosin-mediated F-actin assembly. These results highlight the potential of boosting the immunity for combating COVID-19 via thermomechanical preconditioning of MSCs.
Numerous nanostructured materials have been reported as efficient sulfur hosts to suppress the problematic "shuttling" of lithium polysulfides (LiPSs) in lithium-sulfur (Li-S) batteries. However, direct comparison of these materials in their efficiency of suppressing LiPSs shuttling is challenging, owing to the structural and morphological differences between individual materials. This study introduces a simple route to synthesize a series of sulfur host materials with the same yolk-shell nanospindle morphology but tunable compositions (Fe3O4, FeS, or FeS2), which allows for a systematic investigation into the specific effect of chemical composition on the electrochemical performances of Li-S batteries. Among them, the S/FeS2-C electrode exhibits the best performance and delivers an initial capacity of 877.6 mAh g(-1) at 0.5 C with a retention ratio of 86.7 % after 350 cycles. This approach can also be extended to the optimization of materials for other functionalities and applications.
The use of acidic ionic liquids and solids as electrolytes in fuel cells is an emerging field due to their efficient proton conductivity and good thermal stability. Despite multiple reports describing conducting properties of acidic ILs, little is known on the charge-transport mechanism in the vicinity of liquid-glass transition and the structural factors governing the proton hopping. To address these issues, we studied two acidic imidazolium-based ILs with the same cation, however, different anions-bulk tosylate vs small methanesulfonate. High-pressure dielectric studies of anhydrous and water-saturated materials performed in the close vicinity of T-g have revealed significant differences in the charge-transport mechanism in these two systems being undetectable at ambient conditions. Thereby, we demonstrated the effect of molecular architecture on proton hopping, being crucial in the potential electrochemical applications of acidic ILs.
The response of the hydrogen molecular ion, H-2(+), to few-cycle laser pulses of different intensities is simulated. To treat the coupled electron-nuclear motion, we use adiabatic potentials computed with Gaussian-type basis sets together with a heuristic ionization model for the electron and a grid representation for the nuclei. Using this mixed-basis approach, the time-dependent Schrodinger equation is solved, either within the Born-Oppenheimer approximation or with nonadiabatic couplings included. The dipole response spectra are compared to all-grid-based solutions for the three-body problem, which we take as a reference to benchmark the Gaussian-type basis set approaches. Also, calculations employing the fixed-nuclei approximation are performed, to quantify effects due to nuclear motion. For low intensities and small ionization probabilities, we get excellent agreement of the dynamics using Gaussian-type basis sets with the all-grid solutions. Our investigations suggest that high harmonic generation (HHG) and high-frequency response, in general, can be reliably modeled using Gaussian-type basis sets for the electrons for not too high harmonics. Further, nuclear motion destroys electronic coherences in the response spectra even on the time scale of about 30 fs and affects HHG intensities, which reflect the electron dynamics occurring on the attosecond time scale. For the present system, non-Born-Oppenheimer effects are small. The Gaussian-based, nonadiabatically coupled, time-dependent multisurface approach to treat quantum electron-nuclear motion beyond the non-Born-Oppenheimer approximation can be easily extended to approximate wavefunction methods, such as time-dependent configuration interaction singles (TD-CIS), for systems where no benchmarks are available.
The photochemical fragmentation of N-aroylsulfonamides 9 (ASAP) is a powerful method for the preparation of various biaryls. Compounds 9 are easily accessible in two steps from amines by treatment with arenesulfonyl chlorides and aroyl chlorides. Many of these compounds were prepared for the first time. The irradiation takes place in a previously developed continuous-flow reactor using inexpensive UVB or UVC fluorescent lamps. Isocyanates and sulphur dioxide are formed as the only by-products. The ASAP tolerates a variety of functional groups and is even suited for the preparation of phenylnaphthalenes and terphenyls. The ASAP mechanism was elucidated by interaction of photophysical and quantum chemical (DFT) methods and revealed a spirocyclic biradical as key intermediate.
Elucidation of the reaction mechanism for the synthesis of ZnGeN2 through Zn2GeO4 ammonolysis
(2021)
Ternary II-IV-N-2 materials have been considered as a promising class of materials that combine photovoltaic performance with earth-abundance and low toxicity. When switching from binary III-V materials to ternary II-IV-N-2 materials, further structural complexity is added to the system that may influence its optoelectronic properties. Herein, we present a systematic study of the reaction of Zn2GeO4 with NH3 that produces zinc germanium oxide nitrides, and ultimately approach stoichiometric ZnGeN2, using a combination of chemical analyses, X-ray powder diffraction and DFT calculations. Elucidating the reaction mechanism as being dominated by Zn and O extrusion at the later reaction stages, we give an insight into studying structure-property relationships in this emerging class of materials.
Eine mit digitalen Informationen angereicherte Realität spielt eine zunehmend wichtigere Rolle in unserem Alltag, aber auch im Chemieunterricht. So werden Lehr-Lernszenarien mit Augmented Reality (AR) positive Effekte auf den Wissenserwerb, Motivation und andere Faktoren des Lernens zugeschrieben. Dieser Beitrag gibt einerseits einen Überblick über medienfachdidaktische Gestaltungsparameter und andererseits werden Werkzeuge vorgestellt, um diese Technologie AR-gestütztes Unterrichtsmaterial zu erstellen.
In diesem Artikel werden die Synthese von Thymolblau als Schülerexperiment und passende Augmented-Reality (AR)-gestützte Lernmaterialien vorgestellt. Zudem wird der Kenntnisstand zur Synthese von Thymolblau sowie dessen pH-abhängige Struktur-Eigenschafts-Beziehung vor dem Hintergrund neuerer Erkenntnisse diskutiert und es wird über Erfahrungen mit dem Einsatz des Experimentes in der schulischen und universitären Praxis und im Rahmen von Fortbildungen berichtet.
Photosensitive azobenzene-containing surfactants have attracted great attention in past years because they offer a means to control soft-matter transformations with light. At concentrations higher than the critical micelle concentration (CMC), the surfactant molecules aggregate and form micelles, which leads to a slowdown of the photoinduced trans -> cis azobenzene isomerization. Here, we combine nonadiabatic dynamics simulations for the surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the reaction slowdown. Our simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles. We also observe a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans -> cis switching in micelles of the azobenzene-containing surfactants.
Azobenzene-containing molecules may associate with each other in systems such as self-assembled monolayers or micelles. The interaction between azobenzene units leads to a formation of exciton states in these molecular assemblies. Apart from local excitations of monomers, the electronic transitions to the exciton states may involve charge transfer excitations. Here, we perform quantum chemical calculations and apply transition density matrix analysis to quantify local and charge transfer contributions to the lowest electronic transitions in azobenzene dimers of various arrangements. We find that the transitions to the lowest exciton states of the considered dimers are dominated by local excitations, but charge transfer contributions become sizable for some of the lowest pi pi* electronic transitions in stacked and slip-stacked dimers at short intermolecular distances. In addition, we assess different ways to partition the transition density matrix between fragments. In particular, we find that the inclusion of the atomic orbital overlap has a pronounced effect on quantifying charge transfer contributions if a large basis set is used.
An easy-to-do synthesis for the hexanuclear niobium cluster compound [Nb6Cl12(CH3OH)(4)(OCH3)(2)] . DABCO . 1.66 CH2Cl2 has been developed. An one-pot reaction between the cluster precursor [Nb6Cl14(H2O)(4)] . 4H(2)O and methanol with the addition of DABCO leads to the crystallization of the title compound in high yield within a few minutes. The single-crystal X-ray structure of this cluster compound has been determined. Very strong, nearly symmetric intercluster hydrogen bonds Nb-6-MeO...H...OMe-Nb-6 are present between the cluster units. A bridging co-crystalline DABCO molecule is also involved in a three-dimensional hydrogen-bonding network.
Four new hexanuclear niobium cluster compounds of the general formula [Nb6Cl12(HIm)(6)](A)(n) . x(solvent molecule) (HIm=1H-imidazole, A=mineral acid anion, Cl- (n=2) (1), (SO4)(2-) (n=1) (2), (CrO4)(2-) (n=1) (3), and (HAsO4)(2-) (n=1) (4)) were prepared. Their synthesis can be done in basic ionic liquids, which form on the addition of a mineral acid, which also delivers the counter anion for the final cluster compound, to an excess of the 1H-imidazole. Some addition of an auxiliary solvent, like methanol, improves the speed of crystallisation. The cluster unit comprises a hexanuclear Nb-6 unit of octahedral shape with the edges bridged by Cl atoms and the exo sites being occupied by N-bonded 1H-imidazole ligands. The cluster cation carries sixteen cluster-based electrons. Between the NH groups of the ligands of the cluster unit, the anions and the co-crystallised water (1), or 1H-imidazole and methanol molecules (2, 3, and 4) a network of hydrogen bonds exists.
Somewhat surprisingly, inverted ("O-down") CO adsorbates on NaCl(100) were recently observed experimentally after infrared vibrational excitation (Lau et al., Science, 2020, 367, 175-178). Here we characterize these species using periodic density functional theory and a quantum mechanical description of vibrations. We determine stationary points and minimum energy paths for CO inversion, for low (1/8 and 1/4 monolayers (ML)) and high (1 ML) coverages. Transition state theory is applied to estimate thermal rates for "C-down" to "O-down" isomerization and the reverse process. For the 1/4 ML p(1 x 1) structure, two-dimensional and three-dimensional potential energy surfaces and corresponding anharmonic vibrational eigenstates obtained from the time-independent nuclear Schrodinger equation are presented. We find (i) rather coverage-independent CO inversion energies (of about 0.08 eV or 8 kJ mol(-1) per CO) and corresponding classical activation energies for "C-down" to "O-down" isomerization (of about 0.15 eV or 14 kJ mol(-1) per CO); (ii) thermal isomerization rates at 22 K which are vanishingly small for the "C-down" to "O-down" isomerization but non-negligible for the back reaction; (iii) several "accidentally degenerate" pairs of eigenstates well below the barrier, each pair describing "C-down" to "O-down" localized states.
Combining high hydrophilicity with charge neutrality, polyzwitterions are intensely explored for their high biocompatibility and low-fouling properties. Recent reports indicated that in addition to charge neutrality, the zwitterion's segmental dipole orientation is an important factor for interacting with the environment. Accordingly, a series of polysulfobetaines with a novel architecture was designed, in which the cationic and anionic groups of the zwitterionic moiety are placed at equal distances from the backbone. They were investigated by in vitro biofouling assays, covering proteins of different charges and model marine organisms. All polyzwitterion coatings reduced the fouling effectively compared to model polymer surfaces of poly(butyl methacrylate), with a nearly equally good performance as the reference polybetaine poly(3-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonio)propanesulfonate). The specific fouling resistance depended on the detailed chemical structure of the polyzwitterions. Still, while clearly affecting the performance, the precise dipole orientation of the sulfobetaine group in the polyzwitterions seems overall to be only of secondary importance for their antifouling behavior.
In this article, we report on the synthesis of acyclic bis(monoalkylamino)maleonitriles and on the intended synthesis of macrocyclic bis(dialkylamino)maleonitriles to get fluorescent probes for cations. During our efforts to synthesize macrocyclic bis(dialkylamino)maleonitriles, we were only able to isolate macrocyclic bis(dialkylamino)-fumaronitriles. The synthesis of macrocyclic bis(dialkylamino)maleonitriles is challenging, due to the fact that bis-(dialkylamino)fumaronitriles are thermodynamically more stable than the corresponding bis(dialkylamino)-maleonitriles. Further, it turned out that the acyclic bis(monoalkylamino)maleonitriles and macrocyclic bis-(dialkylamino)fumaronitriles are no suitable tools to detect cations by a strong fluorescence enhancement. Further, only the bis(monoalkylamino)maleonitriles, which are bearing a 2-pyridyl unit as an additional complexing unit, are able to selectively recognize copper(II) by a color change from yellow to red.
In this paper, we report on the fluorescence behaviour of three regioisomers which consist of two 9-anthracenyl fluorophores and of differently substituted dithiodicyanoethene moieties. These isomeric fluorescent probes show different quantum yields (phi(f)). In these probes, an oxidative photoinduced electron transfer (PET) from the excited 9-anthracenyl fluorophore to the dithiodicyanoethene unit quenches the fluorescence. This quenching process is accelerated by an intramolecular charge transfer (ICT) of the push-pull pi-electron system of the dithiodicyanoethene group. The acceleration of the PET depends on the strength of the ICT unit. The higher the dipole moment of the ICT unit, the stronger the observed fluorescence quenching. To the best of our knowledge, this is the first report of a regioisomeric influence on an oxidative PET by an ICT.
In this paper, we introduce a fluorescent dye 1, which is able to detect selectively Pd2+ by a clear fluorescence enhancement (FE) in THF. In the presence of eight Pd2+ equivalents, we observed a fluorescence enhancement factor (FEF) of 28.3. The high Pd2+ induced FEF can be explained by an off switching of multiple quenching processes within 1 by Pd2+. In the free dye 1 a photoinduced electron transfer (PET) and energy transfer (ET) takes place and quenches the anthracenic fluorescence. The coordination of eight Pd2+ units by the alkylthio-substituted porphyrazine receptor suppresses the PET and ET quenching process and the anthracenic fluorescence is switched on.
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.
The high solids semicontinuous emulsion polymerization of polyvinyl acetate using poly (vinyl alcohol-co-vinyl acetate) as protective colloid is investigated by optical spectroscopy. The suitability of Photon Density Wave (PDW) spectroscopy as inline Process Analytical Technology (PAT) for emulsion polymerization processes at high solid contents (>40% (w/w)) is studied and evaluated. Inline data on absorption and scattering in the dispersion is obtained in real-time. The radical polymerization of vinyl acetate to polyvinyl acetate using ascorbic acid and sodium persulfate as redox initiator system and poly (vinyl alcohol-co-vinyl acetate) as protective colloid is investigated. Starved-feed radical emulsion polymerization yielded particle sizes in the nanometer size regime. PDW spectroscopy is used to monitor the progress of polymerization by studying the absorption and scattering properties during the synthesis of dispersions with increasing monomer amount and correspondingly decreasing feed rate of protective colloid. Results are compared to particle sizes determined with offline dynamic light scattering (DLS) and static light scattering (SLS) during the synthesis.
Fibrous shape-memory polymer (SMP) scaffolds were investigated considering the fiber as basic microstructural feature. By reduction of the fiber diameter in randomly oriented electrospun polyetherurethane (PEU) meshes from the micro-to the nano-scale, we observed changes in the molecular orientation within the fibers and its impact on the structural and shape-memory performance. It was assumed that a spatial restriction by reduction of the fiber diameter increases molecular orientation along the orientation of the fiber. The stress-strain relation of random PEU scaffolds is initially determined by the 3D arrangement of the fibers and thus is independent of the molecular orientation. Increasing the molecular orientation with decreasing single fiber diameter in scaffolds composed of randomly arranged fibers did not alter the initial stiffness and peak stress but strongly influenced the elongation at break and the stress increase above the Yield point. Reduction of the single fiber diameter also distinctly improved the shape-memory performance of the scaffolds. Fibers with nanoscale diameters (< 100 nm) possessed an almost complete shape recovery, high recovery stresses and fast relaxation kinetics, while the shape fixity was found to decrease with decreasing fiber diameter. Hence, the fiber diameter is a relevant design parameter for SMP.
The potential of using crystallinity as morphological parameter to control polyester degradation in acidic environments is explored in ultrathin films by Langmuir technique. Films of hydroxy or methacrylate end-capped oligo(epsilon-caprolactone) (OCL) are prepared at the air-water interface as a function of mean molecular area (MMA). The obtained amorphous, partially crystalline or highly crystalline ultrathin films of OCL are hydrolytically degraded at pH similar to 1.2 on water surface or on silicon surface as-transferred films. A high crystallinity reduces the hydrolytic degradation rate of the films on both water and solid surfaces. Different acceleration rates of hydrolytic degradation of semi-crystalline films are achieved either by crystals complete melting, partially melting, or by heating them below their melting temperatures. Semi-crystalline OCL films transferred via water onto a solid surface retain their crystalline morphology, degrade in a controlled manner, and are of interest as thermoswitchable coatings for cell substrates and medical devices.
Polymeric films and coatings derived from semi-crystalline oligomers are of relevance for medical and pharmaceutical applications. In this context, the material surface is of particular importance, as it mediates the interaction with the biological system. Two dimensional (2D) systems and ultrathin films are used to model this interface. However, conventional techniques for their preparation, such as spin coating or dip coating, have disadvantages, since the morphology and chain packing of the generated films can only be controlled to a limited extent and adsorption on the substrate used affects the behavior of the films. Detaching and transferring the films prepared by such techniques requires additional sacrificial or supporting layers, and free-standing or self supporting domains are usually of very limited lateral extension. The aim of this thesis is to study and modulate crystallization, melting, degradation and chemical reactions in ultrathin films of oligo(ε-caprolactone)s (OCL)s with different end-groups under ambient conditions. Here, oligomeric ultrathin films are assembled at the air-water interface using the Langmuir technique. The water surface allows lateral movement and aggregation of the oligomers, which, unlike solid substrates, enables dynamic physical and chemical interaction of the molecules. Parameters like surface pressure (π), temperature and mean molecular area (MMA) allow controlled assembly and manipulation of oligomer molecules when using the Langmuir technique. The π-MMA isotherms, Brewster angle microscopy (BAM), and interfacial infrared spectroscopy assist in detecting morphological and physicochemical changes in the film. Ultrathin films can be easily transferred to the solid silicon surface via Langmuir Schaefer (LS) method (horizontal substrate dipping). Here, the films transferred on silicon are investigated using atomic force microscopy (AFM) and optical microscopy and are compared to the films on the water surface.
The semi-crystalline morphology (lamellar thicknesses, crystal number densities, and lateral crystal dimensions) is tuned by the chemical structure of the OCL end-groups (hydroxy or methacrylate) and by the crystallization temperature (Tc; 12 or 21 °C) or MMAs. Compression to lower MMA of ~2 Å2, results in the formation of a highly crystalline film, which consists of tightly packed single crystals. Preparation of tightly packed single crystals on a cm2 scale is not possible by conventional techniques. Upon transfer to a solid surface, these films retain their crystalline morphology whereas amorphous films undergo dewetting.
The melting temperature (Tm) of OCL single crystals at the water and the solid surface is found proportional to the inverse crystal thickness and is generally lower than the Tm of bulk PCL. The impact of OCL end-groups on melting behavior is most noticeable at the air-solid interface, where the methacrylate end-capped OCL (OCDME) melted at lower temperatures than the hydroxy end-capped OCL (OCDOL). When comparing the underlying substrate, melting/recrystallization of OCL ultrathin films is possible at lower temperatures at the air water interface than at the air-solid interface, where recrystallization is not visible. Recrystallization at the air-water interface usually occurs at a higher temperature than the initial Tc.
Controlled degradation is crucial for the predictable performance of degradable polymeric biomaterials. Degradation of ultrathin films is carried out under acidic (pH ~ 1) or enzymatic catalysis (lipase from Pseudomonas cepcia) on the water surface or on a silicon surface as transferred films. A high crystallinity strongly reduces the hydrolytic but not the enzymatic degradation rate. As an influence of end-groups, the methacrylate end-capped linear oligomer, OCDME (~85 ± 2 % end-group functionalization) hydrolytically degrades faster than the hydroxy end capped linear oligomer, OCDOL (~95 ± 3 % end-group functionalization) at different temperatures. Differences in the acceleration of hydrolytic degradation of semi-crystalline films were observed upon complete melting, partial melting of the crystals, or by heating to temperatures close to Tm. Therefore, films of densely packed single crystals are suitable as barrier layers with thermally switchable degradation rates.
Chemical modification in ultrathin films is an intricate process applicable to connect functionalized molecules, impart stability or create stimuli-sensitive cross-links. The reaction of end-groups is explored for transferred single crystals on a solid surface or amorphous monolayer at the air-water interface. Bulky methacrylate end-groups are expelled to the crystal surface during chain-folded crystallization. The density of end-groups is inversely proportional to molecular weight and hence very pronounced for oligomers. The methacrylate end-groups at the crystal surface, which are present at high concentration, can be used for further chemical functionalization. This is demonstrated by fluorescence microscopy after reaction with fluorescein dimethacrylate. The thermoswitching behavior (melting and recrystallization) of fluorescein functionalized single crystals shows the temperature-dependent distribution of the chemically linked fluorescein moieties, which are accumulated on the surfaces of crystals, and homogeneously dispersed when the crystals are molten. In amorphous monolayers at the air-water interface, reversible cross-linking of hydroxy-terminated oligo(ε-caprolactone) monolayers using dialdehyde (glyoxal) lead to the formation of 2D networks. Pronounced contraction in the area occurred for 2D OCL films in dependence of surface pressure and time indicating the reaction progress. Cross linking inhibited crystallization and retarded enzymatic degradation of the OCL film. Altering the subphase pH to ~2 led to cleavage of the covalent acetal cross-links. Besides as model systems, these reversibly cross-linked films are applicable for drug delivery systems or cell substrates modulating adhesion at biointerfaces.
The palladium-catalyzed oxidative Heck-reaction, also referred to as Fujiwara-Moritani-reaction, has been investigated for the synthesis of styrenylsulfonyl compounds. Acetanilides and vinylsulfonyl compounds undergo dehydrogenative coupling reactions in moderate to quantitative yields, using benzoquinone as the oxidant of choice. Potassium peroxodisulfate, which had previously been identified as a superior oxidant for the coupling with acrylates, did not provide any coupling products with these olefins. Traceless removal of the catalyst directing group through a deacetylation-diazotation-coupling (DDC) sequence was demonstrated for 2-arylethene sulfones.
Ruthenium-catalyzed sulfoalkenylation of acetanilides and dual-use of the catalyst directing group
(2021)
In contrast to vinylsulfonates and vinylsulfones, vinylsulfonamides are unreactive in Pd-catalyzed oxidative Heck-coupling reactions with acetanilides. This limitation has been resolved by using a C-H-activation protocol based on Ru-Cu-Ag-catalysis. Overall, the Ru-Cu-Ag-catalyzed conditions turned out to be more reliable and showed better reproducibility than the Pd-catalyzed C-H-activation. The coupling products thus obtained are functionalized styrenyl sulfones and -sulfonamides which can be used as starting materials for the synthesis of sulfonyl pyrroles and sulfonyl pyrrolo[2,3-c]quinolines.
Innerhalb dieser Arbeit erfolgte die erstmalige systematische Untersuchung von Vinylsulfonsäureethylester (1a), Phenylvinylsulfon (1b), N-Benzyl-N-methylethensulfonamid (1c) in der FUJIWARA-MORITANI Reaktion (alternativ als DHR bezeichnet). Bei dieser übergangsmetallkatalysierten Reaktion erfolgt der Aufbau einer neuen C-C-Bindung unter der doppelten Aktivierung einer C-H-Bindung. Somit kann ein atomökonomischer Aufbau von Molekülen realisiert werden, da keine Beiprodukte in Form von Salzen entstehen. Als aromatischer Reaktant wurden Acetanilide (2) verwendet, damit eine regiospezifische Kupplung durch die katalysatordirigierende Acetamid-Gruppe (CDG) erfolgt. Für die Pd-katalysierte DHR wurde eine umfangreiche Optimierung durchgeführt und anschließend konnten neun verschieden, substituierte 2 mit 1a und sieben verschieden, substituierte 2 mit 1b funktionalisiert werden. Da eine Reaktion mit 1c ausblieb, erfolgte ein Wechsel auf eine Ru-katalysierte Methode für die DHR. Mit dieser Methode konnte 1c mit Acetaniliden funktionalisiert werden und das Spektrum der verwendeten 2, in Form von deaktivierenden Substituenten erweitert werden.
Im Anschluss wurden die sulfalkenylierten Acetanilide in weiterführenden Reaktionen untersucht. Hierfür wurde eine Reaktionssequenz bestehend aus einer DeacetylierungDiazotierung-Kupplungsreaktion verwendet, um die Acetamid-Gruppe in eine Abgangsgruppe zu überführen und danach in einer MATSUDA-HECK Reaktion zu kuppeln. Mit dieser Methode konnten mehrere 1,2-Dialkenylbenzole erhalten werden und die CDG ein weiteres Mal genutzt werden. Neben der Überführung der CDG in eine Abgangsgruppe konnte diese auch in die Synthese verschiedener Heterozyklen integriert werden. Dafür erfolgte zunächst eine 1,3-Zykloaddition durch deprotonierten Tosylmethylisocanid an der elektronenarmen Sulfalkenylgruppe zur Synthese von Pyrrolen. Anschließend erfolgte eine Kupplung der PyrrolFunktion und der CDG durch Zyklokondensation, wodurch Quinoline dargestellt wurden. Durch diese Synthesen konnten Schwefelanaloga des Naturstoffes Marinoquionolin A erhalten werden.
Ein weitere übergangsmetallkatalysierte C-H-Aktivierungsreaktion, die MATSUDA-HECK Reaktion, wurde genutzt, um 1b zu mit verschieden, subtituierten Diazoniumsalzen zu arylieren. Hier konnten zahlreichen Styrenylsulfone erhalten werden. Der erfolgreiche Einsatz der Vinylsulfonylverbindungen in der Kreuzmetathese konnte innerhalb dieser Arbeit nicht erreicht werden. Daher erfolgte die Synthese verschiedener dialkenylierter Sulfonamide. Hierfür wurde die Kettenlänge der Alkenyl-Gruppe am Schwefel zwischen 2-3 und am Stickstoff zwischen 3-4 variiert. Der Einsatz der dialkenylierten Sulfonamide erfolgte in den zuvor untersuchten C-H-Aktivierungsmethoden.
N-Allyl-N-phenylethensulfonamid (3) konnte erfolgreich in der DHR und HECK Reaktion funktionalisiert werden. Hierbei erfolgte eine methodenspezifische Kupplung in Abhängigkeit von der Elektronendichte der entsprechenden Alkenyl-Gruppe. Die DHR führte zur selektiven Arylierung der Vinyl-Gruppe und die HECK Reaktion zur Arylierung an der Allyl-Gruppe. Gemischte Produkte wurden nicht erhalten. Für die weiteren Diolefine wurde komplexe Produktgemische erhalten. Des Weiteren wurden die Diolefine in der Ringschlussmetathese untersucht und die entsprechenden Sultame in sehr guten Ausbeuten erhalten. Die Verwendung der Sultame in der C-H-Aktivierung war erfolglos. Es wird vermutet, dass für diese zweifachsubstituierten Sulfonamide die vorhandenen Reaktionsbedingungen optimiert werden müssen.
Abschließend wurden verschiedene, enantiomerenreine Olefine ausgehend von Levoglucosenon dargestellt. Hierfür wurde Levoglucosenon zunächst mit einem Allyl- und 3-Butenylgrignard Reagenz umgesetzt. Die entsprechenden Produkte wurden in moderaten Ausbeuten erhalten. Eine weitere Methode begann mit der Reduktion von Levoglucosenon zum Levoglucosenol. Dieser Alkohol wurde mit Allylbromid erfolgreich verethert. Neben der Untersuchungen zur Ethersynthese, erfolgte die Veresterung von Levoglucosenol mit verschiedenen Sulfonylchloriden zu den entsprechenden Sulfonsäureestern. Diese Olefine wurden in einer Dominometathesereaktion untersucht. Ausgehend vom Allyllevoglucosenylether erfolgte die Darstellung eines Dihydrofurans.
The present work focuses on minimising the usage of toxic chemicals by integration of the biobased monomers, derived from fatty acid esters, to photopolymerization processes, which are known to be nature friendly. Internal double bond present in the oleic acid was converted to more reactive (meth)acrylate or epoxy group. Biobased starting materials, functionalized by different pendant groups, were used for photopolymerizing formulations to design of new polymeric structures by using ultraviolet light emitting diode (UV-LED) (395 nm) via free radical polymerization or cationic polymerization.
New (meth)acrylates (2,3 and 4) consisting of two isomers, methyl 9-((meth)acryloyloxy)-10-hydroxyoctadecanoate / methyl 9-hydroxy-10-((meth)acryloyloxy)octadecanoate (2 and 3) and methyl 9-(1H-imidazol-1-yl)-10-(methacryloyloxy)octadecanoate / methyl 9-(methacryloyloxy)-10-(1H-imidazol-1-yl)octadecanoate (4), modified from oleic acid mix, and ionic liquid monomers (1a and 1b) bearing long alkyl chain were polymerized photochemically. New (meth)acrylates are based on vegetable oil, and ionic liquids (ILs) have nonvolatile behaviour. Therefore, both monomer types have green approach. Photoinitiated polymerization of new (meth)acrylates and ionic liquids was investigated in the presence of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate (Irgacure® TPO−L) or di(4-methoxybenzoyl)diethylgermane (Ivocerin®) as photoinitiator (PI). Additionally, the results were discussed in comparison with those obtained from commercial 1,6-hexanediol di(meth)acrylate (5 and 6) for deeper investigation of biobased monomer’s potential to substitute petroleum derived materials with renewable resources for possible coating applications. Kinetic study shows that methyl 9-(1H-imidazol-1-yl)-10-(methacryloyloxy)octadecanoate / methyl 9-(methacryloyloxy)-10-(1H-imidazol-1-yl)octadecanoate (4) and ionic liquids (1a and 1b) have quantitative conversion after irradiation process which is important for practical applications. On the other hand, heat generation occurs in a longer time during the polymerization of biobased systems or ILs.
The poly(meth)acrylates modified from (meth)acrylated fatty acid methyl ester monomers generally show a low glass transition temperature because of the presence of long aliphatic chain in the polymer structure. However, poly(meth)acrylates containing aromatic group have higher glass transition temperature. Therefore, new 4-(4-methacryloyloxyphenyl)-butan-2-one (7) was synthesized which can be a promising candidate for the green techniques, such as light induced polymerization. Photokinetic investigation of the new monomer, 4-(4-methacryloyloxyphenyl)-butan-2-one (7), was discussed using Irgacure® TPO−L or Ivocerin® as photoinitiator. The reactivity of that monomer was compared to commercial 2-phenoxyethyl methacrylate (8) and phenyl methacrylate (9) basis of the differences on monomer structures. The photopolymer of 4-(4-methacryloyloxyphenyl)-butan-2-one (7) might be an interesting candidate for the coating application with the properties of quantitative conversion and high molecular weight. It also shows higher glass transition temperature.
In addition to the linear systems based on renewable materials, new crosslinked polymers were also designed in this thesis. Therefore, isomer mixture consisting of ethane-1,2-diyl bis(9-methacryloyloxy-10-hydroxy octadecanoate), ethane-1,2-diyl 9-hydroxy-10-methacryloyloxy-9’-methacryloyloxy10’-hydroxy octadecanoate and ethane-1,2-diyl bis(9-hydroxy-10-methacryloyloxy octadecanoate) (10) was synthesized by derivation of the oleic acid which has not been previously described in the literature. Crosslinked material based on this biobased monomer was produced by photoinitiated free radical polymerization using Irgacure® TPO−L or Ivocerin® as photoinitiator. Furthermore, material properties were diversified by copolymerization of 10 with 4-(4-methacryloyloxyphenyl)-butan-2-one (7) or methyl 9-(1H-imidazol-1-yl)-10-(methacryloyloxy)octadecanoate / methyl 9-(methacryloyloxy)-10-(1H-imidazol-1-yl)octadecanoate (4). In addition to this, influence of comonomer with different chemical structure on the network system was investigated by analysis of thermo-mechanical properties, crosslink density and molecular weight between two crosslink junctions. An increase in the glass transition temperature caused by copolymerization of biobased monomer 10 with the excess amount of 4-(4-methacryloyloxyphenyl)-butan-2-one (7) was confirmed by both techniques, differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). On the other hand, crosslink density decreased as a result of copolymerization reactions due to the reduction in the mean functionality of the system. Furthermore, surface characterization has been tested by contact angle measurements using solvents with different polarity.
This work also contributes to the limited data reported about cationic photopolymerization of the epoxidized vegetable oils in the literature in contrast to the widely investigation of thermal curing of the biorenewable epoxy monomers. In addition to the 9,10-epoxystearic acid methyl ester (11), a new monomer of bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) has been synthesized from oleic acid. These two biobased epoxies have been polymerized via cationic photoinitiated polymerization in the presence of bis(t-butyl)-iodonium-tetrakis(perfluoro-t-butoxy)aluminate ([Al(O-t-C4F9)4]-) and isopropylthioxanthone (ITX) as photinitiating system. Polymerization kinetic of 9,10-epoxystearic acid methyl ester (11) and bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) was investigated and compared with the kinetic of commercial monomers being 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexane carboxylate (13), 1,4-butanediol diglycidyl ether (14), and diglycidylether of bisphenol-A (15). Both biobased epoxies (11 and 12) showed higher conversion than cycloaliphatic epoxy (13), and lower reactivity than 1,4-butanediol diglycidyl ether (14). Additional network systems were designed by copolymerization of bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) and diglycidylether of bisphenol-A (15) in different molar ratios (1:1; 1:5; 1:9). It addresses that, final conversion is dependent on polymerization rate as well as physical processes such as vitrification during polymerization. Moreover, low glass transition temperature of homopolymer derived from bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) was successfully increased by copolymerization with diglycidylether bisphenol-A (15). On the other hand, the surface produced from bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) shows hydrophobic character. Higher concentration of biobased diepoxy (12) in the copolymerizing mixture decreases surface free energy. Network systems were also investigated according to the rubber elasticity theory. Crosslinked polymer derived from the mixture of bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) and diglycidylether of bisphenol-A (15) (molar ratio=1:5) exhibits almost ideal polymer network.
This study deals with the facile synthesis of Fe1-xS nanoparticle-containing nitrogen-doped porous carbon membranes (denoted as Fe1-xS/N-PCMs) via vacuum carbonization of hybrid porous poly(ionic liquid) (PIL) membranes, and their successful use as a sulfur host material to mitigate the shuttle effect in lithium-sulfur (Li-S) batteries. The hybrid porous PIL membranes as the sacrificial template were prepared via ionic crosslinking of a cationic PIL with base-neutralized 1,1 '-ferrocenedicarboxylic acid, so that the iron source was molecularly incorporated into the template. The carbonization process was investigated in detail at different temperatures, and the chemical and porous structures of the carbon products were comprehensively analyzed. The Fe1-xS/N-PCMs prepared at 900 degrees C have a multimodal pore size distribution with a satisfactorily high surface area and well-dispersed iron sulfide nanoparticles to physically and chemically confine the LiPSs. The sulfur/Fe1-xS/N-PCM composites were then tested as electrodes in Li-S batteries, showing much improved capacity, rate performance and cycle stability, in comparison to iron sulfide-free, nitrogen-doped porous carbon membranes.
exo-Methylene-beta-lactams were synthesized in two steps from commercially available 3-bromo-2-(bromomethyl)-propionic acid and reacted with arene diazonium salts in a Heck-type arylation in the presence of catalytic amounts of Pd(OAc)(2) under ligand-free conditions. The products, arylidene-beta-lactams, were obtained in high yields as single isomers. The beta-hydride elimination step of the Pd-catalyzed coupling reaction proceeds with high exo-regioselectivity and E-stereoselectivity. With aryl iodides, triflates, or bromides, the coupling products were isolated only in low yields, due to extensive decomposition of the starting material at elevated temperatures. This underlines that arene diazonium salts can be superior arylating reagents in Heck-type reactions and yield coupling products in synthetically useful yields and selectivities when conventional conditions fail.
The numerous applications of rare earth elements (REE) has lead to a growing global demand and to the search for new REE deposits. One promising technique for exploration of these deposits is laser-induced breakdown spectroscopy (LIBS). Among a number of advantages of the technique is the possibility to perform on-site measurements without sample preparation. Since the exploration of a deposit is based on the analysis of various geological compartments of the surrounding area, REE-bearing rock and soil samples were analyzed in this work. The field samples are from three European REE deposits in Sweden and Norway. The focus is on the REE cerium, lanthanum, neodymium and yttrium. Two different approaches of data analysis were used for the evaluation. The first approach is univariate regression (UVR). While this approach was successful for the analysis of synthetic REE samples, the quantitative analysis of field samples from different sites was influenced by matrix effects. Principal component analysis (PCA) can be used to determine the origin of the samples from the three deposits. The second approach is based on multivariate regression methods, in particular interval PLS (iPLS) regression. In comparison to UVR, this method is better suited for the determination of REE contents in heterogeneous field samples. View Full-Text
The numerous applications of rare earth elements (REE) has lead to a growing global demand and to the search for new REE deposits. One promising technique for exploration of these deposits is laser-induced breakdown spectroscopy (LIBS). Among a number of advantages of the technique is the possibility to perform on-site measurements without sample preparation. Since the exploration of a deposit is based on the analysis of various geological compartments of the surrounding area, REE-bearing rock and soil samples were analyzed in this work. The field samples are from three European REE deposits in Sweden and Norway. The focus is on the REE cerium, lanthanum, neodymium and yttrium. Two different approaches of data analysis were used for the evaluation. The first approach is univariate regression (UVR). While this approach was successful for the analysis of synthetic REE samples, the quantitative analysis of field samples from different sites was influenced by matrix effects. Principal component analysis (PCA) can be used to determine the origin of the samples from the three deposits. The second approach is based on multivariate regression methods, in particular interval PLS (iPLS) regression. In comparison to UVR, this method is better suited for the determination of REE contents in heterogeneous field samples. View Full-Text
Mycotoxins and pesticides regularly co-occur in agricultural products worldwide. Thus, humans can be exposed to both toxic contaminants and pesticides simultaneously, and multi-methods assessing the occurrence of various food contaminants and residues in a single method are necessary. A two-dimensional high performance liquid chromatography tandem mass spectrometry method for the analysis of 40 (modified) mycotoxins, two plant growth regulators, two tropane alkaloids, and 334 pesticides in cereals was developed. After an acetonitrile/water/formic acid (79:20:1, v/v/v) multi-analyte extraction procedure, extracts were injected into the two-dimensional setup, and an online clean-up was performed. The method was validated according to Commission Decision (EC) no. 657/2002 and document N° SANTE/12682/2019. Good linearity (R2 > 0.96), recovery data between 70-120%, repeatability and reproducibility values < 20%, and expanded measurement uncertainties < 50% were obtained for a wide range of analytes, including very polar substances like deoxynivalenol-3-glucoside and methamidophos. However, results for fumonisins, zearalenone-14,16-disulfate, acid-labile pesticides, and carbamates were unsatisfying. Limits of quantification meeting maximum (residue) limits were achieved for most analytes. Matrix effects varied highly (−85 to +1574%) and were mainly observed for analytes eluting in the first dimension and early-eluting analytes in the second dimension. The application of the method demonstrated the co-occurrence of different types of cereals with 28 toxins and pesticides. Overall, 86% of the samples showed positive findings with at least one mycotoxin, plant growth regulator, or pesticide.
Janus droplets were prepared by vortex mixing of three non-mixable liquids, i.e., olive oil, silicone oil and water, in the presence of gold nanoparticles (AuNPs) in the aqueous phase and magnetite nanoparticles (MNPs) in the olive oil. The resulting Pickering emulsions were stabilized by a red-colored AuNP layer at the olive oil/water interface and MNPs at the oil/oil interface. The core–shell droplets can be stimulated by an external magnetic field. Surprisingly, an inner rotation of the silicon droplet is observed when MNPs are fixed at the inner silicon droplet interface. This is the first example of a controlled movement of the inner parts of complex double emulsions by magnetic manipulation via interfacially confined magnetic nanoparticles.
Janus droplets were prepared by vortex mixing of three non-mixable liquids, i.e., olive oil, silicone oil and water, in the presence of gold nanoparticles (AuNPs) in the aqueous phase and magnetite nanoparticles (MNPs) in the olive oil. The resulting Pickering emulsions were stabilized by a red-colored AuNP layer at the olive oil/water interface and MNPs at the oil/oil interface. The core–shell droplets can be stimulated by an external magnetic field. Surprisingly, an inner rotation of the silicon droplet is observed when MNPs are fixed at the inner silicon droplet interface. This is the first example of a controlled movement of the inner parts of complex double emulsions by magnetic manipulation via interfacially confined magnetic nanoparticles.
‘Smart’ Janus emulsions
(2021)
Emulsions constitute one of the most prominent and continuously evolving research areas in Colloid Chemistry, which involves the preparation of mixtures or dispersions of immiscible components in a continuous medium. Besides conventional oil-in-water or water-in-oil emulsions, other emulsions of complex droplet morphologies have recently attracted significant research interests. Especially Janus emulsions, in which each droplet is comprised of two distinct sub-regions, have shown versatile potential applications. One of their advantages is the possibility of compartmentalization, which enables to play with two different chemistries in a single droplet. Though microfluidic methods are conventionally used to prepare Janus emulsions, their industrial applications are largely hindered by low throughput and extensive instrumentations. Recently, it has been discovered that simply one-pot moderate/high energy emulsification is also capable of developing Janus morphology, although their preparation and stabilization remain rather substantially challenging. This cumulative doctoral thesis focuses on the preparation and characterization of ‘smart’ Janus emulsions, i.e. Janus emulsions with special stimuli-responsive features. One-step moderate/high energy emulsification of olive and silicone oil in an aqueous medium was carried out. Special consideration was devoted to the interfacial tensions among the components to maintain the criteria of forming characteristic droplet architectures, in addition to avoiding multiple emulsion destabilization phenomena like imminent phase separation or even separated droplet formation. A series of investigations were conducted related to the formation of complexes of charged macromolecules and role of them as stabilizers to achieve stable Janus emulsions for a realistic timeframe (more than 3 months). The correlation between the size of the stabilizer particles and the droplet size of emulsion was established. Furthermore, it was observed that Janus emulsion gels with interesting rheological properties can be fabricated in the presence of suitable polyelectrolyte complexes. Janus emulsions that could be influenced by pH, temperature or magnetic field were successfully produced in presence of characteristic stimuli-responsive stabilizers. Afterwards, the effect of these changes was studied by different characterization techniques. The size and morphology could be tuned easily by changing the pH. The incorporation of iron oxide magnetic nanoparticles (synthesized separately by a co-precipitation method) to one component of the Janus emulsion was carried out so that the movement and orientation of the complex droplets in aqueous media could be controlled by an external magnetic field. Additionally, temperature-triggered instantaneous reversible breakdown of Janus droplets was also accomplished. The responses of the Janus droplets by the stimuli were well-documented and explained. Another goal of the present contribution was to exploit this special morphological feature of emulsions as a template for producing porous materials. This was demonstrated by the preparation of ultralight magnetic responsive aerogels, utilizing Janus emulsion gels. The produced aerogels also showed the capacity to separate toxic dye from water. To the best of our knowledge, this is the first example of investigation towards batch scale production of Janus emulsion with such special stimuli-responsive properties by a simple bulk emulsification method.
"Water-in-salt" (WIS) electrolytes have emerged as an excellent superconcentrated ionic medium for high-power energy storage systems such as supercapacitors due to their extended working potential compared to the conventional dilute aqueous electrolyte. In this work, we have investigated the performance of WIS supercapacitors using hollow carbon nanoplates as electrodes and compared it to that based on the conventional "salt-in-water" electrolytes. Moreover, the potentiostatic electrochemical impedance spectroscopy has been employed to provide an insightful look into the charge transport properties, which also, for the first time, reveals the formation of a solid-electrolyte interphase (SEI and their temperature-dependent impedance for charge transfer and adsorption. Furthermore, the effect of temperature on the electrochemical performance of the WIS supercapacitors in the temperature range from 15 to 60 degrees C has been studied, which presents a gravimetric capacitance of 128 F g(-1) and a volumetric capacitance of 197.12 F cm(-3) at 55 degrees C compared to 87.5 F g(-1) and 134.75 F cm(-3) at 15 degrees C. The in-depth understanding about the formation of SEI layer and the electrochemical performance at different temperatures for WIS supercapacitors will assist the efforts toward designing better aqueous electrolytes for supercapacitors.
Glyco-assemblies derived from amphiphilic sugar-decorated block copolymers (ASBCs) have emerged prominently due to their wide application, for example, in biomedicine and as drug carriers. However, to efficiently construct these glyco-assemblies is still a challenge. Herein, we report an efficient technology for the synthesis of glyco-inside nano-assemblies by utilizing RAFT polymerization of a galactose-decorated methacrylate for polymerization-induced self-assembly (PISA). Using this approach, a series of highly ordered glyco-inside nano-assemblies containing intermediate morphologies were fabricated by adjusting the length of the hydrophobic glycoblock and the polymerization solids content. A specific morphology of complex vesicles was captured during the PISA process and the formation mechanism is explained by the morphology of its precursor and intermediate. Thus, this method establishes a powerful route to fabricate glyco-assemblies with tunable morphologies and variable sizes, which is significant to enable the large-scale fabrication and wide application of glyco-assemblies.
The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest pi pi* excited states and a n pi* state, which has high energy in the Franck-Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10-15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time- resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1 pi pi* <- S-0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2 pi pi* <- S-0 excitation are instead nonadiabatic, and the n pi* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone. <br /> [GRAPHICS] <br /> .
Natural gas hydrate occurrences contain predominantly methane; however, there are increasing reports of complex mixed gas hydrates and coexisting hydrate phases. Changes in the feed gas composition due to the preferred incorporation of certain components into the hydrate phase and an inadequate gas supply is often assumed to be the cause of coexisting hydrate phases. This could also be the case for the gas hydrate system in Qilian Mountain permafrost (QMP), which is mainly controlled by pores and fractures with complex gas compositions. This study is dedicated to the experimental investigations on the formation process of mixed gas hydrates based on the reservoir conditions in QMP. Hydrates were synthesized from water and a gas mixture under different gas supply conditions to study the effects on the hydrate formation process. In situ Raman spectroscopic measurements and microscopic observations were applied to record changes in both gas and hydrate phase over the whole formation process. The results demonstrated the effects of gas flow on the composition of the resulting hydrate phase, indicating a competitive enclathration of guest molecules into the hydrate lattice depending on their properties. Another observation was that despite significant changes in the gas composition, no coexisting hydrate phases were formed.
Sorption measurements of water vapor on an isoreticular series of Imidazolate Frameworks Potsdam (IFP), based on penta-coordinated metal centers with secondary building units (SBUs) connected by multidentate amido-imidate-imidazolate linkers, have been carried out at 303.15 K. The isotherm shapes were analyzed in order to gain insight into material properties and compared to sorption experiments with nitrogen at 77.4 K and carbon dioxide at 273.15 K. Results show that water vapor sorption measurements are strongly influenced by the pore size distribution while having a distinct hysteresis loop between the adsorption and desorption branch in common. Thus, IFP-4 and -8, which solely contain micropores, exhibit H4 (type I) isotherm shapes, while those of IFP-1, -2 and -5, which also contain mesopores, are of H3 (type IV) shape with three inflection points. The choice of the used linker substituents and transition metals employed in the framework has a tremendous effect on the material properties and functionality. The water uptake capacities of the examined IFPs are ranging 0.48 mmol g(-1) (IFP-4) to 6.99 mmol g(-1) (IFP-5) and comparable to those documented for ZIFs. The water vapor stability of IFPs is high, with the exception of IFP-8.
Zanthoxylum leprieurii Guill. and Perr. (Rutaceae) stem bark is used locally in Uganda for treating tuberculosis (TB) and cough-related infections. Lupeol (1), sesamin (2), trans-fagaramide (3), arnottianamide (4), (S)-marmesinin (5), and hesperidin (6) were isolated from the chloroform/methanol (1:1) extract of Z. leprieurii stem bark. Their structures were elucidated using spectroscopic techniques and by comparison with literature data. Furthermore, the extract and isolated compounds were subjected to antimycobacterial activity. The extract exhibited moderate activity against the susceptible (H(37)Rv) TB strain, but weak activity against the multidrug resistant (MDR)-TB strain with minimum inhibitory concentrations (MICs) of 586.0 and 1172.0 mu g/mL, respectively. Compound 3 (trans-fagaramide) showed significant antimycobacterial activity against the susceptible (H(37)Rv) TB strain (MIC 6 mu g/mL), but moderate activity against the MDR-TB strain (MIC 12.2 mu g/mL). Compounds 2, 5, 6, and 1 showed moderate activities against the susceptible (H(37)Rv) strain (MIC 12.2-98.0 mu g/mL) and moderate to weak activities against the MDR-TB strain (MIC 24.4-195.0 mu g/mL). This study reports for the first time the isolation of compounds 1 to 6 from the stem bark of Z leprieurii. trans-Fagaramide (3) may present a vital template in pursuit of novel and highly effective TB drugs.
Effects of manganese on genomic integrity in the multicellular model organism Caenorhabditis elegans
(2021)
Although manganese (Mn) is an essential trace element, overexposure is associated with Mn-induced toxicity and neurological dysfunction. Even though Mn-induced oxidative stress is discussed extensively, neither the underlying mechanisms of the potential consequences of Mn-induced oxidative stress on DNA damage and DNA repair, nor the possibly resulting toxicity are characterized yet. In this study, we use the model organism Caenorhabditis elegans to investigate the mode of action of Mn toxicity, focusing on genomic integrity by means of DNA damage and DNA damage response. Experiments were conducted to analyze Mn bioavailability, lethality, and induction of DNA damage. Different deletion mutant strains were then used to investigate the role of base excision repair (BER) and dePARylation (DNA damage response) proteins in Mn-induced toxicity. The results indicate a dose- and time-dependent uptake of Mn, resulting in increased lethality. Excessive exposure to Mn decreases genomic integrity and activates BER. Altogether, this study characterizes the consequences of Mn exposure on genomic integrity and therefore broadens the molecular understanding of pathways underlying Mn-induced toxicity. Additionally, studying the basal poly(ADP-ribosylation) (PARylation) of worms lacking poly(ADP-ribose) glycohydrolase (PARG) parg-1 or parg-2 (two orthologue of PARG), indicates that parg-1 accounts for most of the glycohydrolase activity in worms.
Effects of manganese on genomic integrity in the multicellular model organism Caenorhabditis elegans
(2021)
Although manganese (Mn) is an essential trace element, overexposure is associated with Mn-induced toxicity and neurological dysfunction. Even though Mn-induced oxidative stress is discussed extensively, neither the underlying mechanisms of the potential consequences of Mn-induced oxidative stress on DNA damage and DNA repair, nor the possibly resulting toxicity are characterized yet. In this study, we use the model organism Caenorhabditis elegans to investigate the mode of action of Mn toxicity, focusing on genomic integrity by means of DNA damage and DNA damage response. Experiments were conducted to analyze Mn bioavailability, lethality, and induction of DNA damage. Different deletion mutant strains were then used to investigate the role of base excision repair (BER) and dePARylation (DNA damage response) proteins in Mn-induced toxicity. The results indicate a dose- and time-dependent uptake of Mn, resulting in increased lethality. Excessive exposure to Mn decreases genomic integrity and activates BER. Altogether, this study characterizes the consequences of Mn exposure on genomic integrity and therefore broadens the molecular understanding of pathways underlying Mn-induced toxicity. Additionally, studying the basal poly(ADP-ribosylation) (PARylation) of worms lacking poly(ADP-ribose) glycohydrolase (PARG) parg-1 or parg-2 (two orthologue of PARG), indicates that parg-1 accounts for most of the glycohydrolase activity in worms.
Ethylene oxide sterilization of electrospun poly(L-lactide)/poly(D-lactide) core/shell nanofibers
(2021)
The application of polymers in medicine requires sterilization while retaining material structure and properties. This demands detailed analysis, which we show exemplarily for the sterilization of PLLA/PDLA core-shell nanofibers with ethylene oxide (EtO). The electrospun patch was exposed to EtO gas (6 vol% in CO2, 1.7 bar) for 3 h at 45 degrees C and 75% rel. humidity, followed by degassing under pressure/vacuum cycles for 12 h. GC-MS analysis showed that no residual EtO was retained. Fiber diameters (similar to 520 +/- 130 nm) of the patches remained constant as observed by electron microscopy. Young's modulus slightly increased and the elongation at break slightly decreased, determined at 37 degrees C. No changes were detected in H-1-NMR spectra, in molar mass distribution (GPC) or in crystallinity measured for annealed samples with comparable thermal history (Wide Angle X-Ray Scattering). Altogether, EtO emerged as suitable sterilization method for polylactide nanofibers with core-shell morphology.
Functionalization of gelatin with glycidylmethacrylate (GMA-gelatin) enables network formation employing the double bond, so that the reaction is orthogonal to the inherent functional groups in the biomacromolecule. Here, network formation by crosslinking of GMA-gelatin with hexane 1,6-dithiol or nonane 1,9-dithiol to tailor properties and enable a shape-memory effect is shown by H-1 NMR and FT-IR spectroscopy. Hydrogel swelling (460-1900 vol%) and mechanical properties (Young's modulus E = 59-512 kPa, elongation at break epsilon(b) = 44-127%) depended on the molecular composition of the networks and temperature. Increased crosslinker length, thiol:methacrylate molar ratio, and precursor concentrations led to denser networks. Change of properties with temperature suggested adoption of triple helices by gelatin chains, forming physical netpoints at lower temperatures (< 20 degrees C). However, the limited freedom of the gelatin chains to move allowed only a minimal extent of triple helices formation, as it became apparent from the related signal in wide-angle X-ray scattering and the thermal transition associated to triple helices in some networks by DSC. The presented strategy is likely transferable to other biomacromolecules, and the results suggest that too short crosslinkers may result in a significant amount of grafting rather than network formation.
Shape-memory hydrogels (SMH) are multifunctional, actively-moving polymers of interest in biomedicine. In loosely crosslinked polymer networks, gelatin chains may form triple helices, which can act as temporary net points in SMH, depending on the presence of salts. Here, we show programming and initiation of the shape-memory effect of such networks based on a thermomechanical process compatible with the physiological environment. The SMH were synthesized by reaction of glycidylmethacrylated gelatin with oligo(ethylene glycol) (OEG) alpha,omega-dithiols of varying crosslinker length and amount. Triple helicalization of gelatin chains is shown directly by wide-angle X-ray scattering and indirectly via the mechanical behavior at different temperatures. The ability to form triple helices increased with the molar mass of the crosslinker. Hydrogels had storage moduli of 0.27-23 kPa and Young's moduli of 215-360 kPa at 4 degrees C. The hydrogels were hydrolytically degradable, with full degradation to water-soluble products within one week at 37 degrees C and pH = 7.4. A thermally-induced shape-memory effect is demonstrated in bending as well as in compression tests, in which shape recovery with excellent shape-recovery rates R-r close to 100% were observed. In the future, the material presented here could be applied, e.g., as self-anchoring devices mechanically resembling the extracellular matrix.
High crystallization rate and thermomechanical stability make polylactide stereocomplexes effective nanosized physical netpoints. Here, we address the need for soft, form-stable degradable elastomers for medical applications by designing such blends from (co)polyesters, whose mechanical properties are ruled by their nanodimensional architecture and which are applied as single components in implants. By careful controlling of the copolymer composition and sequence structure of poly[(L-lactide)-co-(epsilon-caprolactone)], it is possible to prepare hyperelastic polymer blends formed through stereocomplexation by adding poly(D-lactide) (PDLA). Low glass transition temperature T-g <= 0 degrees C of the mixed amorphous phase contributes to the low Young's modulus E. The formation of stereocomplexes is shown in DSC by melting transitions T-m > 190 degrees C and in WAXS by distinct scattering maxima at 2 theta = 12 degrees and 21 degrees. Tensile testing demonstrated that the blends are soft (E = 12-80 MPa) and show an excellent hyperelastic recovery R-rec = 66-85% while having high elongation at break epsilon(b) up to >1000%. These properties of the blends are attained only when the copolymer has 56-62 wt% lactide content, a weight average molar mass >140 kg center dot mol(-1), and number average lactide sequence length >= 4.8, while the blend is formed with a content of 5-10 wt% of PDLA. The devised strategy to identify a suitable copolymer for stereocomplexation and blend formation is transferable to further polymer systems and will support the development of thermoplastic elastomers suitable for medical applications.
Synthesis and Characterization of Upconversion Nanaparticles for Applications in Life Sciences
(2021)
Vibrational relaxation of adsorbates is a sensitive tool to probe energy transfer at gas/solid and liquid/solid interfaces. The most direct way to study relaxation dynamics uses time-resolved spectroscopy. Here we report on a non-equilibrium ab initio molecular dynamics (NE-AIMD) methodology to model vibrational relaxation of OH vibrations on a hydroxylated, water-covered alpha-Al2O3(0001) surface. In our NE-AIMD approach, after exciting selected O-H bonds their coupling to surface phonons and to the water adlayer is analyzed in detail, by following both the energy flow in time, as well as the time-evolution of Vibrational Density of States (VDOS) curves. The latter are obtained from Time-dependent Correlation Functions (TCFs) and serve as prototypical, generic representatives of time-resolved vibrational spectra. As most important results, (i) we find a few-picosecond lifetime of the excited modes and (ii) identify both hydrogen-bonded aluminols and water molecules in the adsorbed water layer as main dissipative channels, while the direct coupling to Al2O3 surface phonons is of minor importance on the timescales of interest. Our NE-AIMD/TCF methodology is powerful for complex adsorbate systems, in principle even reacting ones, and opens a way towards time-resolved vibrational spectroscopy.
The widespread use of antimicrobial agents to treat infectious diseases has led to the emergence of antibiotic resistant pathogens. Plants have played a central role in combating many ailments in humans, and Parinari curatellifolia has been used for medicinal purposes. Seven extracts from P. curatellifolia leaves were prepared using serial exhaustive extraction of nonpolar to polar solvents. The microbroth dilution method was used to evaluate antimicrobial bioactivities of extracts. Five of the extracts were significantly active against at least one test microbe. Mycobacterium smegmatis was the most susceptible to most extracts. The methanol and ethanol extracts were the most active against M. smegmatis with an MIC of 25 mu g/mL. The hexane extract was the most active against Candida krusei with an MIC of 25 mu g/mL. None of the extracts significantly inhibited growth of Klebsiella pneumoniae and Staphylococcus aureus. Active extracts were selected for fractionation and isolation of pure compounds using gradient elution column chromatography. TLC analyses was carried out for pooling fractions of similar profiles. A total of 43 pools were obtained from 428 fractions. Pools 7 and 10 were selected for further isolation of single compounds. Four compounds, Pc4963r, Pc4962w, Pc6978p, and Pc6978o, were isolated. Evaluation of antimicrobial activities of Pc4963r, Pc4962w, and Pc6978p showed that the compounds were most active against C. krusei with MFC values ranging from 50 to 100 mu g/mL. Only Pc6978p was shown to be pure. Using spectroscopic analyses, the structure of Pc6978p was determined to be beta-sitosterol. The antifungal effects of beta-sitosterol were evaluated against C. krusei in vitro and on fabrics. Results showed that beta-sitosterol reduced the growth of C. krusei attached to Mendy fabric by 83%. Therefore, P. curatellifolia can be a source of lead compounds for prospective development of novel antimicrobial agents. Further work needs to be done to improve the antifungal activity of the isolated compound using quantitative structure-activity relationships.
The incorporation of proteins in artificial materials such as membranes offers great opportunities to avail oneself the miscellaneous qualities of proteins and enzymes perfected by nature over millions of years. One possibility to leverage proteins is the modification with artificial polymers. To obtain such protein-polymer conjugates, either a polymer can be grown from the protein surface (grafting-from) or a pre-synthesized polymer attached to the protein (grafting-to). Both techniques were used to synthesize conjugates of different proteins with thermo-responsive polymers in this thesis.
First, conjugates were analyzed by protein NMR spectroscopy. Typical characterization techniques for conjugates can verify the successful conjugation and give hints on the secondary structure of the protein. However, the 3-dimensional structure, being highly important for the protein function, cannot be probed by standard techniques. NMR spectroscopy is a unique method allowing to follow even small alterations in the protein structure. A mutant of the carbohydrate binding module 3b (CBM3bN126W) was used as model protein and functionalized with poly(N-isopropylacrylamide). Analysis of conjugates prepared by grafting-to or grafting-from revealed a strong impact of conjugation type on protein folding. Whereas conjugates prepared by grafting a pre-formed polymer to the protein resulted in complete preservation of protein folding, grafting the polymer from the protein surface led to (partial) disruption of the protein structure.
Next, conjugates of bovine serum albumin (BSA) as cheap and easily accessible protein were synthesized with PNIPAm and different oligoethylene glycol (meth)acrylates. The obtained protein-polymer conjugates were analyzed by an in-line combination of size exclusion chromatography and multi-angle laser light scattering (SEC-MALS). This technique is particular advantageous to determine molar masses, as no external calibration of the system is needed. Different SEC column materials and operation conditions were tested to evaluate the applicability of this system to determine absolute molar masses and hydrodynamic properties of heterogeneous conjugates prepared by grafting-from and grafting-to. Hydrophobic and non-covalent interactions of conjugates lead to error-prone values not in accordance to expected molar masses based on conversions and extents of modifications.
As alternative to this method, conjugates were analyzed by sedimentation velocity analytical ultracentrifugation (SV-AUC) to gain insights in the hydrodynamic properties and how they change after conjugation. Within a centrifugal field, a sample moves and fractionates according to the mass, density, and shape of its individual components. Conjugates of BSA with PNIPAm were analyzed below and above the cloud point temperature of the thermo-responsive polymer component. It was identified that the polymer characteristics were transferred to the conjugate molecule which than showed a decreased ideality – defined as increased deviation from a perfect sphere model – below and increased ideality above the cloud point temperature. This effect can be attributed to an arrangement of the polymer chain pointing towards the solvent (expanded state) or snuggling around the protein surface depending on the applied temperature.
The last project dealt with the synthesis of ferric hydroxamate uptake protein component A (FhuA)-polymer conjugates as building blocks for novel membrane materials. The shape of FhuA can be described as barrel and removal of a cork domain inside the protein results in a passive channel aimed to be utilized as pores in the membrane system. The polymer matrix surrounding the membrane protein is composed of a thermo-responsive and a UV-crosslinkable part. Therefore, an external trigger for covalent immobilization of these building blocks in the membrane and switchability of the membrane between different states was incorporated. The overall performance of membranes prepared by a drying-mediated self-assembly approach was evaluated by permeability and size exclusion experiments. The obtained membranes displayed an insufficiency in interchain crosslinking and therefore a lack in performance. Furthermore, the aimed switch between a hydrophilic and hydrophobic state of the polymer matrix did not occur. Correspondingly, size exclusion experiments did not result in a retention of analytes larger than the pores defined by the dimension of the used FhuA variant.
Overall, different paths to generate protein-polymer conjugates by either grafting-from or grafting-to the protein surface were presented paving the way to the generation of new hybrid materials. Different analytical methods were utilized to describe the folding and hydrodynamic properties of conjugates providing a deeper insight in the overall characteristics of these seminal building blocks.
Copolyesterurethanes (PDLCLs) based on oligo(epsilon-caprolactone) (OCL) and oligo(omega-pentadecalactone) (OPDL) segments are biodegradable thermoplastic temperature-memory polymers. The temperature-memory capability in these polymers with crystallizable control units is implemented by a thermomechanical programming process causing alterations in the crystallite arrangement and chain organization. These morphological changes can potentially affect degradation. Initial observations on the macroscopic level inspire the hypothesis that switching of the controlling units causes an accelerated degradation of the material, resulting in programmable degradation by sequential coupling of functions. Hence, detailed degradation studies on Langmuir films of a PDLCL with 40 wt% OPDL content are carried out under enzymatic catalysis. The temperature-memory creation procedure is mimicked by compression at different temperatures. The evolution of the chain organization and mechanical properties during the degradation process is investigated by means of polarization-modulated infrared reflection absorption spectroscopy, interfacial rheology and to some extend by X-ray reflectivity. The experiments on PDLCL Langmuir films imply that degradability is not enhanced by thermal switching, as the former depends on the temperature during cold programming. Nevertheless, the thin film experiments show that the leaching of OCL segments does not induce further crystallization of the OPDL segments, which is beneficial for a controlled and predictable degradation.
Among the high-performance and engineering polymers, polyimides and the closely related polyetherimide (PEI) stand out by their capability to react with nucleophiles under relatively mild conditions. By targeting the phthalimide groups in the chain backbone, post-functionalization offers a pathway to adjust surface properties such as hydrophilicity, solvent resistance, and porosity. Here, we use ultrathin PEI films on a Langmuir trough as a model system to investigate the surface functionalization with ethylene diamine and tetrakis(4-aminophenyl)porphyrin as multivalent nucleophiles. By means of AFM, Raman spectroscopy, and interfacial rheology, we show that hydrolysis enhances the chemical and mechanical stability of ultrathin films and allows for the formation of EDC/NHS-activated esters. Direct amidation of PEI was achieved in the presence of a Lewis acid catalyst, resulting in free amine groups rather than cross-linking. When comparing amidation with hydrolysis, we find a greater influence of the latter on material properties.
Increasing the surface hydrophilicity of polyetherimide (PEI) through partial hydrolysis of the imide groups while maintaining the length of the main-chain was explored for adjusting its function in biomedical and membrane applications. The outcome of the polymer analogous reaction, i.e., the degree of ring opening and chain cleavage, is difficult to address in bulk and microstructured systems, as these changes only occur at the interface. Here, the reaction was studied at the air-water interface using the Langmuir technique, assisted by atomic force microscopy and vibrational spectroscopy. Slow PEI hydrolysis sets in at pH > 12. At pH = 14, the ring opening is nearly instantaneous. Reduction of the layer viscosity with time at pH = 14 suggested moderate chain cleavage. No hydrolysis was observed at pH = 1. Hydrolyzed PEI films had a much more cohesive structure, suggesting that the nanoporous morphology of PEI can be tuned via hydrolysis.
A set of new functionalized poly(2-oxazoline) homopolymers and copolymers carrying protected catecholic side chains were prepared by microwave-assisted cationic ring-opening (co)polymerization. The copolymerizations of 2-ethyl-2-oxazoline with either 2-(3,4-dimethoxyphenyl)-, 2-(3,4-dimethoxybenzyl)-, or 2-(3,4-dimethoxycinnamyl)-2-oxazoline (comonomer ratio 90 : 10) produced gradient or random copolymers with narrow molar mass distributions. During the copolymerization with the 2-(3,4-dimethoxycinnamyl)-2-oxazoline, however, chain coupling reactions occurred at monomer conversions of >50%, supposedly via Michael-type addition of intermediately formed ketene N,O-acetal end groups to 3,4-dimethoxycinnamyl amide side chains. A poly[(2-ethyl-2-oxazoline)-grad-(2-(3,4-dimethoxyphenyl)-2-oxazoline)] was examplarily subjected to partial demethylation and acidic hydrolysis to give a hydrophilic copolymer carrying both catecholic and cationic units, which is designed as a bioinspired adhesive copolymer mimicking mussel adhesive protein.
CxNy
(2021)
The search for metal-free and visible light-responsive materials for photocatalytic applications has attracted the interest of not only academics but also the industry in the last decades. Since graphitic carbon nitride (g-C3N4) was first reported as a metal-free photocatalyst, this has been widely investigated in different light-driven reactions. However, the high recombination rate, low electrical conductivity, and lack of photoresponse in most of the visible range have elicited the search for alternatives. In this regard, a broad family of carbon nitride (CxNy) materials was anticipated several decades ago. However, the attention of the researchers in these materials has just been awakened in the last years due to the recent success in the syntheses of some of these materials (i.e., C3N3, C2N, C3N, and C3N5, among others), together with theoretical simulations pointing at the excellent physico-chemical properties (i.e., crystalline structure and chemical morphology, electronic configuration and semiconducting nature, or high refractive index and hardness, among others) and optoelectronic applications of these materials. The performance of CxNy, beyond C3N4, has been barely evaluated in real applications, including energy conversion, storage, and adsorption technologies, and further work must be carried out, especially experimentally, in order to confirm the high expectations raised by simulations and theoretical calculations. Herein, we have summarized the scarce literature related to recent results reporting the synthetic routes, structures, and performance of these materials as photocatalysts. Moreover, the challenges and perspectives at the forefront of this field using CxNy materials are disclosed. We aim to stimulate the research of this new generation of CxNy-based photocatalysts, beyond C3N4, with improved photocatalytic efficiencies by harnessing the striking structural, electronic, and optical properties of this new family of materials.
Natural products have proved to be a major resource in the discovery and development of many pharmaceuticals that are in use today. There is a wide variety of biologically active natural products that contain conjugated polyenes or benzofuran structures. Therefore, new synthetic methods for the construction of such building blocks are of great interest to synthetic chemists. The recently developed one-pot tethered ring-closing metathesis approach allows for the formation of Z,E-dienoates in high stereoselectivity. The extension of this method with a Julia-Kocienski olefination protocol would allow for the formation of conjugated trienes in a stereoselective manner. This strategy was applied in the total synthesis of conjugated triene containing (+)-bretonin B. Additionally, investigations of cross metathesis using methyl substituted olefins were pursued. This methodology was applied, as a one-pot cross metathesis/ring-closing metathesis sequence, in the total synthesis of benzofuran containing 7-methoxywutaifuranal. Finally, the design and synthesis of a catalyst for stereoretentive metathesis in aqueous media was investigated.
Complexes from catalysts and initiator can be used to insert a specific number of additional chemical functional groups in (co)polymers prepared by ring-opening polymerization (ROP) of lactones. We report on the synthesis of cooligomers from sec-butyl-morpholine-2,5-dione (SBMD) and para-dioxanone (PDX) by ROP with varied feed ratios in the bulk using the catalyst complex SnOct(2)/2-hydroxyethyl sulfide. M-n of the cooligomers (determined by GPC) decreased with decreasing SBMD feed ratio from 4200 +/- 420 to 800 +/- 80 g mol(-1). When the feed ratio was reduced from 80 to 50 mol% the molar ratio of SBMD of the cooligomers (determined by H-1-NMR) remained nearly unchanged between 81 and 86 mol% and was attributed to a higher reactivity of SBMD. This assumption was confirmed by fractionation of GPC, in which an increase of SBMD with increasing molecular weight was observed. The catalyst/initiator system provides a high potential to create orthogonal building blocks by cleavage of the sulfide bond.
Oligodepsipeptides (ODPs) attract increasing attention as degradable materials in controlled drug delivery or as building blocks for nano-carriers. Their strong intermolecular interactions provide high stability. Tailoring the side groups of the amino acid repeating units to achieve a strong affinity to particular drugs allows a high drug-loading capacity. Here we describe synthesis and characterization of dihydroxy terminated teroligodepsipeptides (ter-ODPs) by ring-opening copolymerization (ROP) of three different morpholine-2,5-diones (MDs) in bulk in order to provide a set of teroligomers with structural variation for drug release or transfection. Ter-ODPs with equivalent co-monomer feed ratios were prepared as well as ter-ODPs, in which the co-monomer feed ratio was varied between 9 mol% and 78 mol%. Ter-ODPs were synthesized by ROP using 1,1,10,10-tetra-n-butyl-1,10-distanna-2,9,11,18-tetraoxa-5,6,14,15-tetrasulfur-cyclodecane (tin(IV) alkoxide) that was obtained by the reaction of dibutyl tin(II) oxide with 2-hydroxyethyl disulfide. The number average molecular weight (M-n) of ter-ODPs, determined by H-1 NMR and gel permeation chromatography (GPC), ranged between 4000 g center dot mol(-1) and 8600 g center dot mol(-1). Co-monomer compositions in ter-ODPs could be controlled by changing the feed ratio of co-monomers as observed by H-1 NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The amount of remaining monomers as determined by H-1 NMR could be kept below 1 wt%. Macrocycles as main sources of byproducts as determined from MALDI-TOF-MS measurements were significantly lower as compared to polymerization by Sn(Oct)(2). Glass-transition temperature (T-g) of ter-ODPs ranged between 59 degrees C and 70 degrees C.
Shape-memory polymers designed in view of thermomechanical energy storage and conversion systems
(2021)
Effect of endothelial culture medium composition on platelet responses to polymeric biomaterials
(2021)
Near-physiological in vitro thrombogenicity test systems for the evaluation of blood-contacting endothelialized biomaterials requires co-cultivation with platelets (PLT). However, the addition of PLT has led to unphysiological endothelial cell (EC) detachment in such in vitro systems. A possible cause for this phenomenon may be PLT activation triggered by the applied endothelial cell medium, which typically consists of basal medium (BM) and nine different supplements. To verify this hypothesis, the influence of BM and its supplements was systematically analyzed regarding PLT responses. For this, human platelet rich plasma (PRP) was mixed with BM, BM containing one of nine supplements, or with BM containing all supplements together. PLT adherence analysis was carried out in six-channel slides with plasma-treated cyclic olefin copolymer (COC) and poly(tetrafluoro ethylene) (PTFE, as a positive control) substrates as part of the six-channel slides in the absence of EC and under static conditions. PLT activation and aggregation were analyzed using light transmission aggregometry and flow cytometry (CD62P). Medium supplements had no effect on PLT activation and aggregation. In contrast, supplements differentially affected PLT adherence, however, in a polymer- and donor-dependent manner. Thus, the use of standard endothelial growth medium (BM + all supplements) maintains functionality of PLT under EC compatible conditions without masking the differences of PLT adherence on different polymeric substrates. These findings are important prerequisites for the establishment of a near-physiological in vitro thrombogenicity test system assessing polymer-based cardiovascular implant materials in contact with EC and PLT.
Insufficient endothelialization of cardiovascular grafts is a major hurdle in vascular surgery and regenerative medicine, bearing a risk for early graft thrombosis. Neither of the numerous strategies pursued to solve these problems were conclusive. Endothelialization is regulated by the endothelial basement membrane (EBM), a highly specialized part of the vascular extracellular matrix. Thus, a detailed understanding of the structure-function interrelations of the EBM components is fundamental for designing biomimetic materials aiming to mimic EBM functions. In this review, a detailed description of the structure and functions of the EBM are provided, including the luminal and abluminal interactions with adjacent cell types, such as vascular smooth muscle cells. Moreover, in vivo as well as in vitro strategies to build or renew EBM are summarized and critically discussed. The spectrum of methods includes vessel decellularization and implant biofunctionalization strategies as well as tissue engineering-based approaches and bioprinting. Finally, the limitations of these methods are highlighted, and future directions are suggested to help improve future design strategies for EBM-inspired materials in the cardiovascular field.
The reaction of flavanones with hypervalent iodine reagents was investigated with a view to the synthesis of naturally occurring isoflavones. In contrast to several previous reports in the literature, we did not observe the formation of any benzofurans via a ring contraction pathway, but could isolate only isoflavones, resulting from an oxidative 2,3-aryl rearrangement, and flavones, resulting from an oxidation of the flavanones. Although the 2,3-oxidative rearrangement allows a synthetically useful approach toward some isoflavone natural products due to the convenient accessibility of the required starting materials, the overall synthetic utility and generality of the reaction appear to be more limited than previous literature reports suggest.
A convenient method for the synthesis of gamma-spirolactams in only three steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of chloroacetonitrile affords nitriles in moderate to good yields. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and anthroic acid. Subsequent catalytic hydrogenation proceeds smoothly with PtO2 or Raney Ni as catalysts and lactams are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation at different pressures, affording products with 0, 1, or 2 double bonds. Overall, more than 15 new gamma-spirolactams have been synthesized in analytically pure form.
A convenient method for the synthesis of γ-spirolactones in only 2–3 steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of ethylene oxide affords hydroxy acids, which undergo direct lactonization during work-up. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and dicarboxylic acids. Subsequent hydrogenation proceeds smoothly with Pd/C as catalyst and saturated γ-spirolactones are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation with Raney nickel or Wilkinson's catalyst to obtain products with 1 double bond. Overall, more than 30 new γ-spirolactones have been synthesized in analytically pure form.
The water vapor-induced swelling, as well as subsequent phase-transition kinetics, of thin films of a diblock copolymer (DBC) loaded with different amounts of the salt NaBr, is investigated in situ. In dilute aqueous solution, the DBC features an orthogonally thermoresponsive behavior. It consists of a zwitterionic poly(sulfobetaine) block, namely, poly(4-(N-(3'-methacrylamidopropyl)-N, N-dimethylammonio) butane-1-sulfonate) (PSBP), showing an upper critical solution temperature, and a nonionic block, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), exhibiting a lower critical solution temperature. The swelling kinetics in D2O vapor at 15 degrees C and the phase transition kinetics upon heating the swollen film to 60 degrees C and cooling back to 15 degrees C are followed with simultaneous time-of-flight neutron reflectometry and spectral reflectance measurements. These are complemented by Fourier transform infrared spectroscopy. The collapse temperature of PNIPMAM and the swelling temperature of PSBP are found at lower temperatures than in aqueous solution, which is attributed to the high polymer concentration in the thin-film geometry. Upon inclusion of sub-stoichiometric amounts (relative to the monomer units) of NaBr in the films, the water incorporation is significantly increased. This increase is mainly attributed to a salting-in effect on the zwitterionic PSBP block. Whereas the addition of NaBr notably shifts the swelling temperature of PSBP to lower temperatures, the collapse temperature of PNIPMAM remains unaffected by the presence of salt in the films.
The swelling and co-nonsolvency behaviors in pure H2O and in a mixed H2O/CH3OH vapor atmosphere of two different polar, water-soluble polymers in thin film geometry are studied in situ. Films of a zwitterionic poly(sulfobetaine), namely, poly[3-((2-(methacryloyloxy)ethyl)dimethylammonio) propane-1-sulfonate] (PSPE), and a polar nonionic polymer, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), are investigated in real time by spectral reflectance (SR) measurements and Fourier transform infrared (FTIR) spectroscopy. Whereas PSPE is insoluble in methanol, PNIPMAM is soluble but exhibits cononsolvency behavior in water/methanol mixtures. First, the swelling of PSPE and PNIPMAM thin films in H2O vapor is followed. Subsequently, CH3OH is added to the vapor atmosphere, and its contracting effect on the water-swollen films is monitored, revealing a co-nonsolvency-type behavior for PNIPMAM and PSPE. SR measurements indicate that PSPE and PNIPMAM behave significantly different during the H2O swelling and subsequent exposure to CH3OH, not only with respect to the amounts of absorbed water and CH3OH, but also to the cosolvent-induced contraction mechanisms. While PSPE thin films exhibit an abrupt one-step contraction, the contraction of PNIPMAM thin films occurs in two steps. FTIR studies corroborate these findings on a molecular scale and reveal the role of the specific functional groups, both during the swelling and the cosolvent-induced switching of the solvation state.
The development and optimization of carbonaceous materials is of great interest for several applications including gas sorption, electrochemical storage and conversion, or heterogeneous catalysis. In this thesis, the exploration and optimization of nitrogen containing carbonaceous materials by direct condensation of smart chosen, molecular precursors will be presented. As suggested with the concept of noble carbons, the choice of a stable, nitrogen-containing precursor will lead to an even more stable, nitrogen doped carbonaceous material with a controlled structure and electronic properties. Molecules fulfilling this requirement are for example nucleobases. The direct condensation of nucleobases leads to highly nitrogen containing carbonaceous materials without any further post or pretreatment. By using salt melt templating, pore structure adjustment is possible without the use of hazardous or toxic reagents and the template can be reused.
Using these simple tools, the synergetic effect of the pore structure and nitrogen content of the materials can be explored. Within this thesis, the influence of the condensation parameters will be correlated to the structure and performance of the materials. First, the influence of the condensation temperature to the porosity and nitrogen content of guanine will be discussed and the exploration of highly CO2 selective structural pores in C1N1 materials will be shown. Further tuning the pore structure of the materials by salt melt templating will be then explored, the potential of the prepared materials as heterogeneous catalysts and their basic catalytic strength will be correlated to their nitrogen content and pore morphology. A similar approach is used to explore the water sorption behavior of uric acid derived carbonaceous materials as potential sorbents for heat transformation applications. Changes in maximum water uptake and hydrophilicity of the prepared materials will be correlated to the nitrogen content and pore architecture. Due to the high thermal stability, porosity, and nitrogen content of ionic liquid derived nitrogen doped carbonaceous materials, a simple impregnation and calcination route can be conducted to obtain copper nano cluster decorated nitrogen-doped carbonaceous materials. The activity as catalyst for the oxygen reduction reaction of the obtained materials will be shown and structure performance relations are discussed.
In conclusion, the versatility of nitrogen doped carbonaceous materials with a nitrogen to carbon ratio of up to one will be shown. The possibility to tune the pore structure as well as the nitrogen content by using a simple procedure including salt melt templating as well as the use of molecular precursors and their effect on the performance will be discussed.
In this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3–9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound states mediate the transition into the valence states. What is also of high importance is that both compounds while undergoing DEA reactions generate highly reactive neutral species that can lead to severe cell damage in a biological environment.
In this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3–9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound states mediate the transition into the valence states. What is also of high importance is that both compounds while undergoing DEA reactions generate highly reactive neutral species that can lead to severe cell damage in a biological environment.
Surface-enhanced Raman scattering is a powerful approach to detect molecules at very low concentrations, even up to the single-molecule level. One important aspect of the materials used in such a technique is how much the signal is intensified, quantified by the enhancement factor (EF). Herein we obtained the EFs for gold nanoparticle dimers of 60 and 80 nm diameter, respectively, self-assembled using DNA origami nanotriangles. Cy5 and TAMRA were used as surface-enhanced Raman scattering (SERS) probes, which enable the observation of individual nanoparticles and dimers. EF distributions are determined at four distinct wavelengths based on the measurements of around 1000 individual dimer structures. The obtained results show that the EFs for the dimeric assemblies follow a log-normal distribution and are in the range of 10(6) at 633 nm and that the contribution of the molecular resonance effect to the EF is around 2, also showing that the plasmonic resonance is the main source of the observed signal. To support our studies, FDTD simulations of the nanoparticle's electromagnetic field enhancement has been carried out, as well as calculations of the resonance Raman spectra of the dyes using DFT. We observe a very close agreement between the experimental EF distribution and the simulated values.
Using hot charge carriers far from a plasmonic nanoparticle surface is very attractive for many applications in catalysis and nanomedicine and will lead to a better understanding of plasmon-induced processes, such as hot-charge-carrier- or heat-driven chemical reactions. Herein we show that DNA is able to transfer hot electrons generated by a silver nanoparticle over several nanometers to drive a chemical reaction in a molecule nonadsorbed on the surface. For this we use 8-bromo-adenosine introduced in different positions within a double-stranded DNA oligonucleotide. The DNA is also used to assemble the nanoparticles into nanoparticles ensembles enabling the use of surface-enhanced Raman scattering to track the decomposition reaction. To prove the DNA-mediated transfer, the probe molecule was insulated from the source of charge carriers, which hindered the reaction. The results indicate that DNA can be used to study the transfer of hot electrons and the mechanisms of advanced plasmonic catalysts.
In der vorliegenden Arbeit wird die Herstellung und Charakterisierung von Mixed-Matrix-Membranen (MMM) für die Gastrennung thematisiert. Dazu wurden verschiedene Füllstoffe genutzt, um in Verbindung mit dem Membranmaterial Polysulfon MMMs herzustellen. Als Füllstoffe wurden 3 aktive und 2 passive Füllstoffe verwendet. Die aktiven Füllstoffe besaßen Porenöffnungen, die in der Lage sind Gase in Abhängigkeit der Molekülgröße zu trennen. Daraus folgt ein höherer idealer Trennfaktor für bestimmte Gaspaare als in Polysulfon selbst. Aufgrund der durch die Poren gebildeten permanenten Kanäle in den aktiven Füllstoffen ergibt sich ein schnellerer Gastransport (Permeabilität) als in Polysulfon. Es handelte sich bei den aktiven Füllstoffen um den Zeolith SAPO-34 und 2 Chargen eines Zeolitic Imidazolate Framework (ZIF) ZIF-8. Die beiden Chargen ZIF-8 unterschieden sich in ihrer spezifischen Oberfläche, was diesen Einfluss speziell in die Untersuchungen zum Gastransport einbeziehen sollte. Bei den passiven Füllstoffen handelte es sich um ein aminofunktionalisiertes Kieselgel und unporöse (dichte) Glaskügelchen. Das Kieselgel besaß Poren, die zu groß waren, um Gase effektiv zu trennen. Die Glaskügelchen konnten keine Gastrennung ermöglichen, da sie keine Poren besaßen.
Aus der Literatur ist bekannt, dass die Einbettung von Füllstoffen oft zu Defekten in MMMs führt. Ein Ziel dieser Arbeit war es daher die Einbettung zu optimieren. Weiterhin sollte der Gastransport in MMMs dieser Arbeit mit dem in einer unbeladenen Polysulfonmembran verglichen werden. Aufgrund des selektiveren Trennverhaltens der aktiven Füllstoffe im Vergleich zum Membranmaterial, sollte mit der Einbettung aktiver Füllstoffe die Trennleistung der MMMs mit steigender Füllstoffbeladung immer weiter verbessert werden.
Um die Eigenschaften der MMMs zu untersuchen, wurden diese mittels Rasterelektronenmikroskop (REM), Gaspermeationsmessungen (GP) und Thermogravimetrischer Analyse gekoppelt mit Massenspektrometrie (TGA-MS) charakterisiert.
Untersuchungen am REM konnten eine Verbesserung der Einbettung zeigen, wenn ein polymerer Haftvermittler verwendet wurde. Verglichen wurde die optimierte Einbettung mit der Einbettung ohne Haftvermittler und Ergebnissen aus der Literatur, in der die Verwendung verschiedener Silane als Haftvermittler beschrieben wurde. Trotz der verbesserten Einbettung konnte lediglich bei geringen Beladungen an Füllstoff (10 und 20 Ma-% bezogen auf das Membranmaterial) eine geringe Steigerung des idealen Trennfaktors in den MMMs gegenüber der unbeladenen Polysulfonmembranen beobachtet werden. Bei höheren Füllstoffbeladungen (30, 40 und 50 Ma-%) war ein deutlicher Anstieg der Permeabilität bei stark sinkendem idealen Trennfaktor zu beobachten. Mit Hilfe von TGA-MS Messungen konnte darüber hinaus festgestellt werden, dass der verwendete Zeolith SAPO-34 durch Wassermoleküle blockierte Porenöffnungen besaß. Das verhinderte den Gastransport im Füllstoff, wodurch die Trennleistung des Füllstoffes nicht ausgenutzt werden konnte. Die Füllstoffe ZIF-8 (chargenunabhängig) und aminofunktionalisiertes Kieselgel wiesen keine blockierten Poren auf. Dennoch zeigte sich in diesen MMMs keine Verbesserung der Gastrenn- oder Gastransporteigenschaften. MMMs mit dichten Glaskügelchen als Füllstoff zeigten dasselbe Gastrenn- und Gastransportverhalten, wie alle MMMs mit den zuvor genannten Füllstoffen.
In dieser Arbeit konnte, trotz optimierter Einbettung anorganischer Füllstoffe, für MMMs keine Verbesserung der Gastrenn- oder Gastransporteigenschaften nachgewiesen werden. Vielmehr wurde ein Einfluss der Füllstoffmenge auf die Gastransporteigenschaften in MMMs festgestellt. Die Änderungen der MMMs gegenüber Polysulfon stammen von den Folgen der Einbettung von Füllstoffen in das Matrixpolymer. Durch die Einbettung werden die Eigenschaften des Matrixpolymers ändern, sodass auch der Gastransport beeinflusst wird. Des Weiteren wurde dokumentiert, dass in Abhängigkeit der Füllstoffbeladung die entstehende Membranstruktur beeinflusst wird. Die Beeinflussung war dabei unabhängig von der Füllstoffart. Es wurde eine Korrelation zwischen Füllstoffmenge und veränderter Membranstruktur gefunden.
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent cyclobutylcarbene 8, 1,2-diboretane-3-ylidene 9, and some carbene analogues of boron 14-18 as most intriguing examples of carbenes, which can be stabilized as homoaromatic systems with 3c,2e bonding, have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually, ring current effect/anisotropy effects as measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the degree of present 3c,2e-homoaromaticity. Results are confirmed by geometry (bond angles and bond lengths) and spectroscopic data, the delta(B-11)/ppm data and the C-13 chemical shifts of the carbene electron-deficient centre.
The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of isolated as well as B-C bond length varied model compounds (BR3 trapped NHCs) have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the present dative vs. coordinative bond character of the boron-carbon bond in the trapped NHCs. Results are confirmed by bond lengths and B-11/C-13 chemical shift variations in the BR3 trapped NHCs.
The low temperature (95 K) NMR study of 1-Ph-1-t-Bu-silacyclohexane (1) showed the conformational equilibrium to be extremely one-sided toward thePh(ax),t-Bueq conformer. The barrier to interconversion has been measured (4.2-4.6 kcal/mol) and the conformational equilibrium [Delta nu = 1990.64 ppm (Si-29), 618.9 ppm (C-13), 1-Ph-ax:1-Pheq = (95.6-96.6%):(3.4-4.4%), K = 25 +/- 3, Delta G degrees = -RT ln K = 0.58-0.63 kcal/mol] analyzed. The assignment and quantification of the NMR signals is supported by MP2 and DFT calculations.
Membrane contact sites are of particular interest in the field of synthetic biology and biophysics. They are involved in a great variety of cellular functions. They form in between two cellular organelles or an organelle and the plasma membrane in order to establish a communication path for molecule transport or signal transmission.
The development of an artificial membrane system which can mimic membrane contact sites using bottom up synthetic biology was the goal of this research study. For this, a multi - compartmentalised giant unilamellar vesicle (GUV) system was created with the membrane of the outer vesicle mimicking the plasma membrane and the inner GUVs posing as cellular organelles.
In the following steps, three different strategies were used to achieve an internal membrane - membrane adhesion.
Modular toolkit of multifunctional block copoly(2-oxazoline)s for the synthesis of nanoparticles
(2021)
Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties. This concept was adapted to well-defined block copolymers of the poly(2-oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water-soluble, alkyne- and alkene-containing segments were synthesized and orthogonally modified with various low-molecular weight functional molecules by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and thiol-ene (TE) click reactions, respectively. Representative toolkit polymers were used for the synthesis of gold, iron oxide and silica nanoparticles.
Die vorliegende Arbeit thematisiert die Synthese und Charakterisierung von neuen funktionalisierten ionischen Flüssigkeiten und deren Polymerisation. Die ionischen Flüssigkeiten wurden dabei sowohl mit polymerisierbaren Kationen als auch Anionen hergestellt. Zum einen wurden bei thermisch initiierten Polymerisationen Azobis(isobutyronitril) (AIBN) verwendet und zum anderen dienten bei photochemisch initiierten Polymerisationen Bis-4-(methoxybenzoyl)diethylgermanium (Ivocerin®) als Radikalstarter.
Mittels Gelpermeationschromatographie konnte das Homopolymer Polydimethylaminoethylmethacrylat untersucht werden, welches erst im Anschluss an die GPC-Messungen polymeranalog modifiziert wurde. Dabei wurden nach einer Quaternisierung und anschließender Anionenmetathese bei diesen Polymeren die Grenzviskositäten bestimmt und mit den Grenzviskositäten der direkt polymerisierten ionischen Flüssigkeiten verglichen. Bei der direkten Polymerisation von Poly(N-[2-(Methacryloyloxy)ethyl]-N-butyl-N,N-dimethyl-ammoniumbis(trifluormethylsulfonyl)imid) lag [η_Huggins] bei 100 mL/g und bei dem polymeranalog hergestellten Polymer betrug [η_Huggins] = 40 mL/g.
Die ionischen Flüssigkeiten mit polymerisierbaren funktionellen Gruppen wurden mittels Photo-DSC hinsichtlich der maximalen Polymerisationsgeschwindigkeit (Rpmax), der Zeit, in der dieses Maximum erreicht wurde, tmax, ihrer Glasüberganstemperatur (Tg) und des Umsatzes an Vinylprotonen untersucht. Bei diesen Messungen wurde zum einen der Einfluss der unterschiedlichen Alkylkettenlänge am Ammoniumion und der Einfluss von verschiedenen Anionen bei gleichbleibender Kationenstruktur analysiert. So polymerisierte das ethylsubstituierte Kation mit einer tmax von 21 Sekunden am langsamsten. Die maximale Polymerisationsgeschwindigkeit (Rpmax) betrug 3.3∙10-2 s-1. Die tmax Werte der übrigen alkylsubstituierten ionischen Flüssigkeiten mit einer polymerisierbaren funktionellen Gruppe hingegen lagen zwischen 10 und 15 Sekunden. Die Glasübergangstemperaturen der mittels photoinduzierter Polymerisation hergestellten Polymere lagen mit 44 bis 55 °C nahe beieinander. Alle Monomere zeigten einen hohen Umsatz der Vinylprotonen; er betrug zwischen 93 und 100%.
Mithilfe einer Bandanlage, ausgerüstet mit einer LED (λ = 395 nm), konnten Polymerfilme hergestellt werden. Der Umsatz an Doppelbindungsäquivalenten dieser Filme wurde anhand der 1H-NMR Spektroskopie bestimmt. Bei der dynamisch-mechanischen Analyse wurden die Polymerfilme mit einer konstanten Heizrate und Frequenz periodisch wechselnden Beanspruchungen ausgesetzt, um die Glasübergangstemperaturen zu bestimmen. Die niedrigste Tg mit 26 °C besaß das butylsubstituierte N-[2-(Methacryloyloxy)ethyl]-N-butyl-N,N-dimethyl-ammoniumbis(trifluormethylsulfonyl)imid, welches als Polymerfilm mit Ivocerin® als Initiator hergestellt wurde, wohingegen die höchste Tg bei dem gleichen Polymer, welches direkt durch freie radikalische Polymerisation der ionischen Flüssigkeit in Masse mit AIBN hergestellt wurde, 51 °C betrug. Zusätzlich wurden die Filme unter dem Aspekt der Topographie mit einem Rasterkraftmikroskop untersucht, welches eine Domänenstruktur des Polymers N-[2-(methacryloyloxy)ethyl]-N-butyl-N,N-dimethyl-ammonium tris(pentafluorethyl)trifluorphosphat offenbarte.
Zusammenfassung zur Dissertation „Neuartige DBD-Fluoreszenzfarbstoffe: Synthese, Untersuchungen und Anwendungen“ von Leonard John
In dieser Arbeit konnten auf Basis der etablierten [1,3]-Dioxolo[4,5-f][1,3]benzodioxol (DBD) Fluoreszenzfarbstoffe zwei neue Konzepte zur Darstellung unsymmetrisch funktionalisierter DBD-Fluorophore entwickelt werden. Die Variation der elektronenziehenden Reste führte zu einer Erweiterung des Farbspektrums an DBD-Fluorophoren, wobei alle weiteren spektroskopischen Parameter (Fluoreszenzlebenszeit, -quantenausbeute und STOKES-Verschiebung) unverändert hohe Werte aufweisen. Neben der Variation der elektronenziehenden Reste wurde das "pi"-System des DBD-Farbstoffs mit der Einführung von Stilben-, und Tolan-Derivaten vergrößert. Stilben-Derivate zeigten ähnlich gute spektroskopische Eigenschaften wie die bereits etablierten DBD-Farbstoffe.
Fluorophore mit langwelliger Emission sind auf Grund der großen Gewebe-Eindringtiefe besonders interessant für biologische Anwendungen. Da der langwelligste Vertreter der O4-DBD-Farbstoffe in polaren Medien nur schwer löslich ist, wurde ein Weg zur Einführung löslichkeitsvermittelnder Gruppen gesucht. Hierbei fiel die Wahl auf eine Carbonsäure-Gruppe zur Steigerung der Hydrophilie. Eine von vier untersuchten Methoden erwies sich als zielführend, sodass das gewünschte Molekül isoliert werden konnte. Eine erhöhte Wasserlöslichkeit wurde allerdings nicht beobachtet.
Zur Erforschung von Fettstoffwechselkrankheiten wie der ALZHEIMER-Krankheit werden fluoreszenzmarkierte Lipide benötigt. Um unterschiedliche Bereiche einer Membran zu untersuchen, war das Ziel, den Fluorophor an unterschiedlichen Stellen innerhalb der Fettsäure zu lokalisieren. Hierbei sollte die Gesamtkettenlänge des DBD-Lipids einer C18-Kette, analog der Stearinsäure, entsprechen. Durch die stufenweise Einführung der Reste gelang es, drei DBD-Lipide herzustellen, wobei sich der Fluorophor an unterschiedlichen Positionen innerhalb der Kette befindet. Die photophysikalischen Eigenschaften der Lipide weichen nur marginal von denen der reinen Fluorophore ab. Eine Einlagerung in giant unilamellar vesicles (GUVs) konnte für zwei Derivate beobachtet werden, wobei keine domänenspezifisch war.
Ein weiteres Ziel dieser Arbeit war es, die vier Sauerstoffatome im DBD-Grundkörper stufenweise durch Schwefelatome zu ersetzen und die Ringgrößen des DBD-Fluorophors zu variieren. Für die Ringgröße zeigte der 1,2-S2-DBD mit jeweils zwei Fünfringen die besten spektroskopischen Eigenschaften. Durch die Synthese von zwei weiteren schwefelhaltigen DBD-Grundkörpern (S1- und 1,4-S2-DBD) konnten insgesamt drei neue Farbstoffklassen zugänglich gemacht werden. Für alle neuen Chromophore wurden elektronenziehende Reste (Aldehyd, Acyl, Ester, Carboxy) eingeführt und die jeweiligen Derivate spektroskopisch untersucht. Mit steigender Anzahl an Schwefel-Atomen im Grundkörper zeigt sich eine bathochrome Verschiebung der Emission,
wobei die Werte für die Fluoreszenzlebenszeit- und -quantenausbeute abnehmen. Die optimalen spektroskopischen Eigenschaften aus langwelliger Emission, hoher Fluoreszenzlebenszeit und -quantenausbeute zeigt das 1,4-S2-Dialdehyd-Derivat. Für die S1- und 1,2-S2-Dialdehyd-
Derivate wurden Konzepte entwickelt, um bioreaktive Reste (Alkin, HOSu, Maleimid) einzuführen und die Fluorophore in biologischen Systemen anwenden zu können.
Crystallization and degradation behaviour of multiblock copolyester blends in Langmuir monolayers
(2021)
Supporting the wound healing of soft tissues requires fixation devices becoming more elastic while degrading. To address this unmet need, we designed a blend of degradable multiblock copolymers, which is cross-linked by PLA stereocomplexation combining two soft segments differing substantially in their hydrolytic degradation rate. The degradation path and concomitant structural changes are predicted by Langmuir monolayer technique. The fast hydrolysis of one soft segment leads to a decrease of the total polymer mass at constant physical cross-linking density. The corresponding increase of the average spacing between the network nodes suggests the targeted increase of the blend's flexibility.
The hierarchical design approach provides various opportunities to adjust the structural performance of polymer materials. Electrospinning processing techniques give access to molecular orientation as a design parameter, which we consider here in view of the shape-memory actuation performance. The aim of this work is to investigate how the reversible strain epsilon'(rev) can be affected by a morphology change from a bulk material to an electrospun mesh. epsilon'(rev) could be increased from 5.5 +/- 0.5% to 15 +/- 1.8% for a blend from a multiblock copolymer with poly(epsilon-caprolactone) (PCL) and poly(L-lactide) (PLLA) segments with oligo(D-lactide) (ODLA). This study demonstrates an effective design approach for enhancing soft actuator performance, which can be broadly applied in soft robotics and medicine.
Soft actuators have drawn significant attention due to their relevance for applications, such as artificial muscles in devices developed for medicine and robotics. Tuning their performance and expanding their functionality are frequently done by means of chemical modification. The introduction of structural elements rendering non-synthetic modification of the performance possible, as well as control over physical appearance and facilitating their recycling is a subject of a great interest in the field of smart materials. The primary aim of this thesis was to create a shape-memory polymeric actuator, where the capability for non-synthetic tuning of the actuation performance is combined with reprocessability. Physically cross-linked polymeric matrices provide a solid material platform, where the in situ processing methods can be employed for modification of the composition and morphology, resulting in the fine tuning of the related mechanical properties and shape-memory actuation capability.
The morphological features, required for shape-memory polymeric actuators, namely two crystallisable domains and anchoring points for physical cross-links, were embedded into a multiblock copolymer with poly(ε-caprolactone) and poly(L-lactide) segments (PLLA-PCL). Here, the melting transition of PCL was bisected into the actuating and skeleton-forming units, while the cross-linking was introduced via PLA stereocomplexation in blends with oligomeric poly(D-lactide) (ODLA). PLLA segment number average length of 12-15 repeating units was experimentally defined to be capable of the PLA stereocomplexes formation, but not sufficient for the isotactic crystallisation. Multiblock structure and phase dilution broaden the PCL melting transition, facilitating its separation into two conditionally independent crystalline domains. Low molar mass of the PLA stereocomplex components and a multiblock structure enables processing and reprocessing of the PLLA-PCL / ODLA blends with common non-destructive techniques. The modularity of the PLLA-PCL structure and synthetic approach allows for independent tuning of the properties of its components. The designed material establishes a solid platform for non-synthetic tuning of thermomechanical and structural properties of thermoplastic elastomers.
To evaluate the thermomechanical stability of the formed physical network, three criteria were appraised. As physical cross-links, PLA stereocomplexes have to be evenly distributed within the material matrix, their melting temperature shall not overlap with the thermal transitions of the PCL domains and they have to maintain the structural integrity within the strain ε ranges further applied in the shape-memory actuation experiments. Assigning PCL the function of the skeleton-forming and actuating units, and PLA stereocomplexes the role of physical netpoints, shape-memory actuation was realised in the PLLA-PCL / ODLA blends. Reversible strain of shape-memory actuation was found to be a function of PLA stereocomplex crystallinity, i.e. physical cross-linking density, with a maximum of 13.4 ± 1.5% at PLA stereocomplex content of 3.1 ± 0.3 wt%. In this way, shape-memory actuation can be tuned via adjusting the composition of the PLLA-PCL / ODLA blend. This makes the developed material a valuable asset in the production of cost-effective tunable soft polymeric actuators for the applications in medicine and soft robotics.
Hydrogels with a hierarchical structure were prepared from a new highly water-soluble crosslinker N,N,N',N'-tetramethyl-N,N'-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and from the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The free radical polymerization of the two compounds is rapid and yields near-transparent hydrogels with sizes up to 5 cm in diameter. Rheology shows a clear correlation between the monomer-to-crosslinker ratio and the storage and loss moduli of the hydrogels. Cryo-scanning electron microscopy, low-field nuclear magnetic resonance (NMR) spectroscopy, and small-angle X-ray scattering show that the gels have a hierarchical structure with features spanning the nanometer to the sub-millimeter scale. The NMR study is challenged by the marked inhomogeneity of the gels and the complex chemical structure of the sulfobetaine monomer. NMR spectroscopy shows how these complications can be addressed via a novel fitting approach that considers the mobility gradient along the side chain of methacrylate-based monomers.
New cryogels for selective dye removal from aqueous solution were prepared by free radical polymerization from the highly water-soluble crosslinker N,N,N’,N’-tetramethyl-N,N’-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The resulting white and opaque cryogels have micrometer sized pores with a smaller substructure. They adsorb methyl orange (MO) but not methylene blue (MB) from aqueous solution. Mixtures of MO and MB can be separated through selective adsorption of the MO to the cryogels while the MB remains in solution. The resulting cryogels are thus candidates for the removal of hazardous organic substances, as exemplified by MO and MB, from water. Clearly, it is possible that the cryogels are also potentially interesting for removal of other compounds such as pharmaceuticals or pesticides, but this must be investigated further.
New cryogels for selective dye removal from aqueous solution were prepared by free radical polymerization from the highly water-soluble crosslinker N,N,N’,N’-tetramethyl-N,N’-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The resulting white and opaque cryogels have micrometer sized pores with a smaller substructure. They adsorb methyl orange (MO) but not methylene blue (MB) from aqueous solution. Mixtures of MO and MB can be separated through selective adsorption of the MO to the cryogels while the MB remains in solution. The resulting cryogels are thus candidates for the removal of hazardous organic substances, as exemplified by MO and MB, from water. Clearly, it is possible that the cryogels are also potentially interesting for removal of other compounds such as pharmaceuticals or pesticides, but this must be investigated further.
The nanoscale combination of a conductive carbon and a carbon-based material with abundant heteroatoms for battery electrodes is a method to overcome the limitation that the latter has high affinity to alkali metal ions but low electronic conductivity. The synthetic protocol and the individual ratios and structures are important aspects influencing the properties of such multifunctional compounds. Their interplay is, herein, investigated by infiltration of a porous ZnO-templated carbon (ZTC) with nitrogen-rich carbon obtained by condensation of hexaazatriphenylene-hexacarbonitrile (HAT-CN) at 550-1000 degrees C. The density of lithiophilic sites can be controlled by HAT-CN content and condensation temperature. Lithium storage properties are significantly improved in comparison with those of the individual compounds and their physical mixtures. Depending on the uniformity of the formed composite, loading ratio and condensation temperature have different influence. Most stable operation at high capacity per used monomer is achieved with a slowly dried composite with an HAT-CN:ZTC mass ratio of 4:1, condensed at 550 degrees C, providing more than 400 mAh g(-1) discharge capacity at 0.1 A g(-1) and a capacity retention of 72% after 100 cycles of operation at 0.5 A g(-1) due to the homogeneity of the composite and high content of lithiophilic sites.
Die vorliegende Arbeit beschäftigt sich mit der Synthese von Disulfiden, der Thiol-Disulfid Metathesereaktion als Möglichkeit, Polymere zu funktionalisieren, und der Synthese von Polydisulfiden. Im ersten Teil der Arbeit wird die Aminolyse von RAFT-Polymeren und die Abhängigkeit der Polymer-Polymer Disulfidbildung von der Molmasse untersucht. Dabei wurde durch die Aufnahme von Reaktionskinetiken mittels Gel-Permeations-Chromatographie (GPC) festgestellt, dass je länger die Polymerketten sind, desto weniger Disulfid Polymerkopplung tritt auf. RAFT-Polymere werden oft genutzt, um die RAFT-Polymer Endgruppe nach der Polymerisation zu modifizieren oder in einer chemischen Reaktion zu funktionalisieren. Hier kann die Aminolyse in Anwesenheit von kurzkettigen Disulfiden, wie zum Beispiel Cystin, durchgeführt werden, um die Bildung von Polymer-Polymer Disulfiden vollständig zu unterdrücken und ein endgruppenfunktionalisiertes Polymer zu erhalten. Bei dieser Reaktion greift das bei der Aminolyse entstehende Polymerthiolat die kurzkettigen Disulfide an, und es kommt zur Bildung von funktionalisierten Polymeren. Es wurde ein Polyethylenglykoldisulfid eingesetzt, um ein amphiphiles Blockcopolymer zu erhalten. Als RAFT-Polymer wurde Polystyrol (PS) verwendet, und es konnte die Bildung von Polystyrol-Polyethylenglykol Copolymeren nachgewiesen werden. Das amphiphile Polymer bildet im wässrigen Medium Vesikel. Die Oberfläche der Vesikel konnte mittels der Thiol-Disulfid Metathese umfunktionalisiert werden. Die Aminolyse von PS RAFT-Polymeren mit einem Polylaktiddisulfid oder einem Polybenzylglutamatdisulfid ergab Polystyrol-block-Polyester und Polystyrol-block-Polyaminosäuren Copolymere. Im zweiten Teil der Arbeit liegt der Fokus auf der Synthese von Polydisulfiden und ihren thermischen Eigenschaften. Es wurden verschiedene Alkyldithiole synthetisiert und mittels Wasserstoffperoxid und Triethylamin polymerisiert. Dabei konnte gezeigt werden, dass die Polymere teilkristallin sind und dass der Schmelzpunkt und die Kristallinität der Polymere mit steigender Alkylkettenlänge zwischen den Disulfidbindungen zunehmen. Die Möglichkeit einer Polymerkettenerweiterung nach der Polymerisation ist mit diesem System gegeben. Die Abbaubarkeit der Polydisulfide konnte durch den Einsatz von Thiolen im basischen Milieu gezeigt werden.
In this paper the development, use, and evaluation of tasks based on the construct of school-related content knowledge are described. The tasks were used in seminars on organic chemistry for bachelor and master preservice chemistry teachers at a German university. For the evaluation a questionnaire with open and closed items was used. The tasks were rated by the preservice chemistry teachers as relevant for their future profession as a chemistry teacher if the content of the tasks is part of the school curriculum. If the content does not belong to the school curriculum, they rated the nature of the tasks still as relevant; they seem to recognize the importance of conceptual knowledge for their future profession. However, the master's preservice teachers argued with this conceptual knowledge more often than the bachelor's preservice teachers. Although the study is cross-sectional, a certain shift from the focus on the content to conceptual knowledge from bachelor's to master's preservice teachers can be observed.
In this paper, we describe a study on tasks following the construct of school-related content knowledge. We know from previous studies that such tasks were rated by the preservice chemistry teachers as important for their future profession. Those studies were conducted in a traditional course on organic chemistry which was organized around chemical families. Therefore, we used and evaluated the tasks again in a new course on organic chemistry which is organized around basic concepts in organic chemistry. The results of this evaluation show that the students rate the tasks equally well but use other arguments for their rating. They do not focus only on the content of the tasks and whether this content belongs to the school curriculum or not. The students of the conceptual course rated the content more often (95%) as important for their future profession compared with the students in the traditional course (57%). Both groups of students rated the importance of the nature of the task the same way.
Educational Scaffolding was first mentioned in 1976 by Wood et al. Several examples for scaffolding in chemistry are also known from the literature. As written scaffolds, stepped supporting tools to support students while solving problems in organic chemistry were developed, applied, and evaluated. Although the students rated the tool as very helpful, a think-aloud study showed that the support given by this scaffold was not sufficient. As a further development of stepped supporting tools, task navigators were therefore developed, applied, and evaluated. This new scaffold gives tips on strategy, knowledge, and application of knowledge after the STRAKNAP concept. The evaluation of this tool shows that the students rated the tool as being very helpful. A think-aloud study showed that the scaffold supports the students while they solve a problem. Because of the stepwise construction of the task navigators and the providing of the knowledge needed for the application, the students can solve parts of the task successfully even if they do not solve all parts correctly; the students can always start from scratch. When students use the tool regularly, their knowledge of organic chemistry increases compared to students who did not use the tool at all. The task navigator is not only a scaffold for the content of the task but also for the development of methodological competences on the field of strategies and applying knowledge.
Training OC
(2021)
The course design "Training OC" for training the application of basic concepts consists of four topics: formula language, structure-property relations, reaction mechanisms, and complex tasks that the students should solve with the conceptual knowledge they acquired in the first three topics. A main goal of the course was to enable the students to solve reaction mechanisms. To achieve the goals of the course, several games were specially designed and used. The course was conducted at a German university with ca. 30 students who participated voluntarily. The course was evaluated by several tools: students' products were collected in the course, there were two pre/post-tests, and additionally, interviews on the strategy of designing reaction mechanisms were conducted. The performance of the teacher and the self-assessment of the students were also part of the evaluation. The results of the written exam were compared with the results of the bachelor chemistry major students. The course "Training OC" was rated very well by the students. They were of the opinion that they learned the application of basic concepts taught in this course. This is supported by the results of the evaluation and the written exams. The course concept of Training OC will therefore become a permanent part of the course "Organic Chemistry I" which will be redesigned for the next round in 2020-21.
The self-assembly of amphiphilic polymers in aqueous systems is important for a plethora of applications, in particular in the field of cosmetics and detergents. When introducing thermoresponsive blocks, the aggregation behavior of these polymers can be controlled by changing the temperature. While confined to simple diblock copolymer systems for long, the complexity - and thus the versatility - of such smart systems can be strongly enlarged, once designed monomers, specific block sizes, different architectures, or additional functional groups such as hydrophobic stickers are implemented. In this work, the structure-property relationship of such thermoresponsive amphiphilic block copolymers was investigated by varying their structure systematically. The block copolymers were generally composed of a permanently hydrophobic sticker group, a permanently hydrophilic block, and a thermoresponsive block exhibiting a Lower Critical Solution Temperature (LCST) behavior. While the hydrophilic block consisted of N,N dimethylacrylamide (DMAm), different monomers were used for the thermoresponsive block, such as N n propylacrylamide (NPAm), N iso propylacrylamide (NiPAm), N,N diethylacrylamide (DEAm), N,N bis(2 methoxyethyl)acrylamide (bMOEAm), or N acryloylpyrrolidine (NAP) with different reported LCSTs of 25, 32, 33, 42 and 56 °C, respectively. The block copolymers were synthesized by successive reversible addition fragmentation chain transfer (RAFT) polymerization. For the polymers with the basic linear, the twinned hydrophobic and the symmetrical quasi miktoarm architectures, the results were well defined block sizes and end groups as well as narrow molar mass distributions (Ɖ ≤ 1.3). More complex architectures, such as the twinned thermoresponsive and the non-symmetrical quasi miktoarm one, were achieved by combining RAFT polymerization with a second technique, namely atom transfer radical polymerization (ATRP) or single unit monomer insertion (SUMI), respectively. The obtained block copolymers showed well defined block sizes, but due to the complexity of these reaction paths, the dispersities were generally higher (Ɖ ≤ 1.8) and some end groups were lost.
The thermoresponsive behavior of the block copolymers was investigated by turbidimetry and dynamic light scattering (DLS). Below the phase transition temperature, the polymers were soluble in water and small micellar structures were visible. However, above the phase transition temperature, the aggregation behavior was strongly dependent on the architecture and the chemical structure of the thermoresponsive block. Thermoresponsive blocks comprising PNAP and PbMOEAm with DPn = 40 showed no cloud point (CP), since their already high LCSTs were further increased by the attached hydrophilic block. Depending on the architecture as well as on the block size, block copolymers with PNiPAm, PDEAm and PNPAm showed different CP’s. Large aggregates were visible for block copolymers with PNiPAm and PDEAm above their CP. For PNPAm containing block copolymers, the phase transition was very sensitive towards the architecture resulting in either small or large aggregates.
In addition, fluorescence studies were performed using PDMAm and PNiPAm homo and block copolymers with linear architecture, functionalized with complementary fluorescence dyes introduced at the opposite chain ends. The thermoresponsive behavior was studied in pure aqueous solution as well as in an oil in water (o/w) microemulsion. The findings indicate that the block copolymer behaves as polymeric surfactant at low temperatures, with one relatively small hydrophobic end group and an extended hydrophilic chain forming ‘hairy micelles’ similar as the other synthesized architectures. Above the phase transition temperature of the PNiPAm block, however, the copolymer behaves as associative telechelic polymer with two non-symmetrical hydrophobic end groups, which do not mix. Thus, instead of a network of bridged ‘flower micelles’, large dynamic aggregates are formed. These are connected alternatingly by the original micellar cores as well as by clusters of the collapsed PNiPAm blocks. This type of bridged micelles is even more favored in the o/w microemulsion than in pure aqueous solution.