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Biomakromoleküle sind in der Natur für viele Abläufe in lebenden Organismen verantwortlich. Dies reicht vom Aufbau der extrazellulären Matrix und dem Cytoskelett über die Erkennung von Botenstoffen durch Rezeptoren bis hin zur Katalyse der verschiedensten Reaktionen in den Zellen selbst. Diese Aufgaben werden zum größten Teil von Proteinen übernommen, und besonders das spezifische Erkennen der Interaktionspartner ist für alle diese Moleküle äußerst wichtig, um eine fehlerfreie Funktion zu gewährleisten. Als Alternative zur evolutiven Erzeugung von optimalen Bindern und Katalysatoren auf der Basis von Aminosäuren und Nukleotiden wurden von Wulff, Shea und Mosbach synthetische molekular geprägte Polymere (molecularly imprinted polymers, MIPs) konzipiert. Das Prinzip dieser künstlichen Erkennungselemente beruht auf der Tatsache, dass sich funktionelle Monomere spezifisch um eine Schablone (Templat) anordnen. Werden diese Monomere dann vernetzend polymerisiert, entsteht ein Polymer mit molekularen Kavitäten, in denen die Funktionalitäten komplementär zum Templat fixiert sind. Dadurch ist die selektive Bindung des Templats in diese Kavitäten möglich. Aufgrund ihrer hohen chemischen und thermischen Stabilität und ihrer geringen Kosten haben “bio-inspirierte” molekular geprägte Polymere das Potential, biologische Erkennungselemente in der Affinitätschromatographie sowie in Biosensoren und Biochips zu ersetzen. Trotz einiger publizierter Sensorkonfigurationen steht der große Durchbruch noch aus. Ein Hindernis für Routineanwendungen ist die Signalgenerierung bei Bindung des Analyten an das Polymer. Eine Möglichkeit für die markerfreie Detektion ist die Benutzung von Kalorimetern, die Bindungs- oder Reaktionswärmen direkt messen können. In der Enzymtechnologie wird der Enzym-Thermistor für diesen Zweck eingesetzt, da enzymatische Reaktionen eine Enthalpie in einer Größenordnung von 5 – 100 kJ/mol besitzen. In dieser Arbeit wird die Herstellung von katalytisch geprägten Polymeren nach dem Verfahren des Oberflächenprägens erstmalig beschrieben. Die Methode zur Immobilisierung des Templats auf der Oberfläche von porösem Kieselgel sowie die Polymerzusammensetzung wurden optimiert. Weiter wird die Evaluation der katalytischen Eigenschaften über einen optischen Test, sowie das erste Mal die Kombination eines kalorimetrischen Transduktors – des Thermistors – mit der Analyterkennung durch ein katalytisch aktives MIP gezeigt. Bei diesen Messungen konnte zum ersten Mal gleichzeitig die Bindung/Desorption, sowie die katalytische Umwandlung des Substrats durch konzentrationsabhängige Wärmesignale nachgewiesen werden.
It was the goal of this work to explore two different synthesis pathways using green chemistry. The first part of this thesis is focusing on the use of the urea-glass route towards single phase manganese nitride and manganese nitride/oxide nano-composites embedded in carbon, while the second part of the thesis is focusing on the use of the “saccharide route” (namely cellulose, sucrose, glucose and lignin) towards metal (Ni0), metal alloy (Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5, Cu0.5Ni0.5 and W0.15Ni0.85) and ternary carbide (Mn0.75Fe2.25C) nanoparticles embedded in carbon. In the interest of battery application, MnN0.43 nanoparticles surrounded by a graphitic shell and embedded in carbon with a high surface area (79 m^2/g) were synthesized, following a previously set route.The comparison of the material characteristics before and after the discharge showed no remarkable difference in terms of composition and just slight differences in the morphological point of view, meaning the particles are stable but agglomerate. The graphitic shell is contributing to the resistance of the material and leads to a fine cyclic stability over 140 cycles of 230 mAh/g after the first charge/discharge and coulombic efficiencies close to 100%. Due to the low voltage towards Li/Li+ and the low polarization, it might be an attractive anode material for lithium ion batteries. However, the capacity is still noticeably lower than the theoretical value for MnN0.43. A mixture of MnN0.43 and MnO nanoparticles embedded in carbon (surface area 93 m^2/g) was able to improve the cyclic stability to over 160 cycles giving a capacity of 811 mAh/g, which is considerably higher than the capacity of the conventional material graphite (372 mAh/g). This nano-composite seems to agglomerate less during the process of discharge. Interestingly, although the capacity is much higher than of the single phase manganese nitride, the nano-composite seems to only contain MnN0.43 nanoparticles after the process of discharge with no oxide phase to be found. Concerning catalysis application, different metal, metal alloy, and metal carbide nanoparticles were synthesized using the saccharide route. At first, systems that were already investigated before, being Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5 and Mn0.75Fe2.25C using cellulose as the carbon source were prepared and tested in an alkylation reaction of toluene with benzylchloride. Unexpectedly, the metal alloys did not show any catalytic activity, but the ternary carbide Mn0.75Fe2.25C showed fine catalytic activity of 98% conversion after 9 hour reaction time (110 °C). In a second step, the saccharide route was modified towards other carbon sources and carbon to metal ratios in order to improve the homogeneity of the samples and accessibility of the particle surfaces. The used carbon sources sucrose and glucose are similar in their basic structure of carbohydrates, but reducing the (polymeric) chain length. Indeed, the cellulose could be successfully replaced by sucrose and glucose. A lower carbon to metal ratio was found to influence the size, homogeneity and accessibility (as evidenced by TEM) of the samples. Since sucrose is an aliment, glucose is the better choice as a carbon source. Using glucose, the synthesis of Cu0.5Ni0.5 and W0.15Ni0.85 nano-composites was also possible, although the later was never obtained as pure phase. These alloy nano-composites were tested, along with nickel0 nanoparticles also prepared with glucose and on their catalytic activity towards the reduction of phenylacetylene. The results obtained let believe that any (poly) saccharide, including lignin, could be used as carbon source. The nickel0 nano-composites prepared with lignin as a carbon source were tested along with those prepared with cellulose and sucrose for their catalytic activity in the transfer hydrogenation of nitrobenzene (results compared with exposed nickel nanoparticles and nickel supported on carbon) leading to very promising results. Based on the urea-glass route and the saccharide route, simple equipment and transition metals, it was possible to have a one-pot synthesize with scale-up possibilities towards new material that can be applied in catalysis and battery systems.
Due to a challenging population growth and environmental changes, a need for new routes to provide required chemicals for human necessities arises. An effective solution discussed in this thesis is industrial heterogeneous catalysis. The development of an advanced industrial heterogeneous catalyst is investigated herein by considering porous carbon nano-material as supports and modifying their surface chemistry structure with heteroatoms. Such modifications showed a significant influence on the performance of the catalyst and provided a deeper insight regarding the interaction between the surface structure of the catalyst and the surrounding phase. This thesis contributes to the few present studies about heteroatoms effect on the catalyst performance and emphasizes on the importance of understanding surface structure functionalization in a catalyst in different phases (liquid and gaseous) and for different reactions (hydrogenolysis, oxidation, and hydrogenation/ polymerization). Herein, the heteroatoms utilized for the modifications are hydrogen (H), oxygen (O), and nitrogen (N). The heteroatoms effect on the metal particle size, on the polarity of the support/ the catalyst, on the catalytic performance (activity, selectivity, and stability), and on the interaction with the surrounding phase has been explored. First hierarchical porous carbon nanomaterials functionalized with heteroatoms (N) is synthesized and applied as supports for nickel nanoparticles for hydrogenolysis process of kraft lignin in liquid phase. This reaction has been performed in batch and flow reactors for three different catalysts, two of comparable hierarchical porosity, yet one is modified with N and the other is not, and a third is a prepared catalyst from a commercial carbon support. The reaction production and analyses show that the catalysts with hierarchical porosity perform catalytically much better than in presence of a commercial carbon support with lower surface area. Moreover, the modification with N-heteroatoms enhanced the catalytic performance because the heteroatom modified porous carbon material with nickel nanoparticles catalyst (Ni-NDC) performed highest among the other catalysts. In the flow reactor, Ni-NDC selectively degraded the ether bonds (β-O-4) in kraft lignin with an activity of 2.2 x10^-4 mg lignin mg Ni-1 s-1 for 50 h at 350°C and 3.5 mL min-1 flow, providing ~99 % conversion to shorter chained chemicals (mainly guaiacol derivatives). Then, the functionalization of carbon surface was further studied in selective oxidation of glucose to gluconic acid using < 1 wt. % of gold (Au) deposited on the previously-mentioned synthesized carbon (C) supports with different functionalities (Au-CGlucose, Au-CGlucose-H, Au-CGlucose-O, Au-CGlucoseamine). Except for Au-CGlucose-O, the other catalysts achieved full glucose conversion within 40-120 min and 100% selectivity towards gluconic acid with a maximum activity of 1.5 molGlucose molAu-1 s-1 in an aqueous phase at 45 °C and pH 9. Each heteroatom influenced the polarity of the carbon differently, affecting by that the deposition of Au on the support and thus the activity of the catalyst and its selectivity. The heteroatom effect was further investigated in a gas phase. The Fischer-Tropsch reaction was applied to convert synthetic gas (CO and H2) to short olefins and paraffins using surface-functionalized carbon nanotubes (CNTs) with heteroatoms as supports for ion (Fe) deposition in presence and absence of promoters (Na and S). The results showed the promoted Fe-CNT doped with nitrogen catalyst to be stable up to 180 h and selective to the formation of olefins (~ 47 %) and paraffins (~6 %) with a conversion of CO ~ 92 % at a maximum activity of 94 *10^-5 mol CO g Fe-1 s-1. The more information given regarding this topic can open wide range of applications not only in catalysis, but in other approaches as well. In conclusion, incorporation of heteroatoms can be the next approach for an advanced industrial heterogeneous catalyst, but also for other applications (e.g. electrocatalysis, gas adsorption, or supercapacitors).
Various ways of preparing enantiomerically pure 2-amino[6]helicene derivatives were explored. Ni(0) mediated cyclotrimerization of enantiopure triynes provided (M)- and (P)-7,8-bis(p-tolyl)hexahelicene-2-amine in >99% ee as well as its benzoderivative in >99% ee. The stereocontrol was found to be inefficient for a 2- aminobenzo[6]helicene congener with an embedded five-membered ring. Helically chiral imidazolium salts bearing one or two helicene moieties have been synthesized and applied in enantioselective [2+2+2] cyclotrimerization catalyzed by an in situ formed Ni(0)-NHC complex. The synthesis of the first helically chiral Pd- and Ru-NHC complexes and their application in enantioselective catalysis was demonstrated. The latter shows promising results in enantioselective olefin metathesis reactions. A mechanistic proposal for asymmetric ring closing metathesis is provided.
The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol
(2018)
Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.
Electrochemical methods offer the simple characterization of the synthesis of molecularly imprinted polymers (MIPs) and the readouts of target binding. The binding of electroinactive analytes can be detected indirectly by their modulating effect on the diffusional permeability of a redox marker through thin MIP films. However, this process generates an overall signal, which may include nonspecific interactions with the nonimprinted surface and adsorption at the electrode surface in addition to (specific) binding to the cavities. Redox-active low-molecular-weight targets and metalloproteins enable a more specific direct quantification of their binding to MIPs by measuring the faradaic current. The in situ characterization of enzymes, MIP-based mimics of redox enzymes or enzyme-labeled targets, is based on the indication of an electroactive product. This approach allows the determination of both the activity of the bio(mimetic) catalyst and of the substrate concentration.