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Materials based on biodegradable polyesters, such as poly(butylene terephthalate) (PBT) or poly(butylene terephthalate-co-poly(alkylene glycol) terephthalate) (PBTAT), have potential application as pro-regenerative scaffolds for bone tissue engineering. Herein, the preparation of films composed of PBT or PBTAT and an engineered spider silk protein, (eADF4(C16)), that displays multiple carboxylic acid moieties capable of binding calcium ions and facilitating their biomineralization with calcium carbonate or calcium phosphate is reported. Human mesenchymal stem cells cultured on films mineralized with calcium phosphate show enhanced levels of alkaline phosphatase activity suggesting that such composites have potential use for bone tissue engineering.
The effect of cellulose-based polyelectrolytes on biomimetic calcium phosphate mineralization is described. Three cellulose derivatives, a polyanion, a polycation, and a polyzwitterion were used as additives. Scanning electron microscopy, X-ray diffraction, IR and Raman spectroscopy show that, depending on the composition of the starting solution, hydroxyapatite or brushite precipitates form. Infrared and Raman spectroscopy also show that significant amounts of nitrate ions are incorporated in the precipitates. Energy dispersive X-ray spectroscopy shows that the Ca/P ratio varies throughout the samples and resembles that of other bioinspired calcium phosphate hybrid materials. Elemental analysis shows that the carbon (i.e., polymer) contents reach 10% in some samples, clearly illustrating the formation of a true hybrid material. Overall, the data indicate that a higher polymer concentration in the reaction mixture favors the formation of polymer-enriched materials, while lower polymer concentrations or high precursor concentrations favor the formation of products that are closely related to the control samples precipitated in the absence of polymer. The results thus highlight the potential of (water-soluble) cellulose derivatives for the synthesis and design of bioinspired and bio-based hybrid materials.
Herstellung anisotroper Kolloide mittels templatgesteuerter Assemblierung und Kontaktdruckverfahren
(2017)
Diese Arbeit befasste sich mit neuen Konzepten zur Darstellung anisotroper Partikelsysteme durch Anordnung von funktionalisierten Partikeln unter Zuhilfenahme etablierter Methoden wie der templatgestützten Assemblierung von Partikeln und dem Mikrokontaktdruck.
Das erste Teilprojekt beschäftigte sich mit der kontrollierten Herstellung von Faltenstrukturen im Mikro- bis Nanometerbereich. Die Faltenstrukturen entstehen durch die Relaxation eines Systems bestehend aus zwei übereinander liegender Schichten unterschiedlicher Elastizität. In diesem Fall wurden Falten auf einem elastischen PDMS-Substrat durch Generierung einer Oxidschicht auf der Substratoberfläche mittels Plasmabehandlung erzeugt. Die Dicke der Oxidschicht, die über verschiedene Parameter wie Behandlungszeit, Prozessleistung, Partialdruck des plasmaaktiven Gases, Vernetzungsgrad, Deformation sowie Substratdicke einstellbar war, bestimmte Wellenlänge und Amplitude der Falten.
Das zweite Teilprojekt hatte die Darstellung komplexer, kolloidaler Strukturen auf Basis supramolekularer Wechselwirkungen zum Ziel. Dazu sollte vor allem die templatgestützte Assemblierung von Partikeln sowohl an fest-flüssig als auch flüssig-flüssig Grenzflächen genutzt werden. Für Erstere sollten die in Teilprojekt 1 hergestellten Faltenstrukturen als Templat, für Letztere Pickering-Emulsionen zur Anwendung kommen. Im ersten Fall wurden verschiedene, modifizierte Silicapartikel und Magnetitnanopartikel, deren Größe und Oberflächenfunktionalität (Cyclodextrin-, Azobenzol- und Arylazopyrazolgruppen) variierte, in Faltenstrukturen angeordnet. Die Anordnung hing dabei nicht nur vom gewählten Verfahren, sondern auch von Faktoren wie der Partikelkonzentration, der Oberflächenladung oder dem Größenverhältnis der Partikel zur Faltengeometrie ab.
Die Kombination von Cyclodextrin (CD)- und Arylazopyrazol-modifizierten Partikeln ermöglichte, auf Basis einer Wirt-Gast-Wechselwirkung zwischen den Partikeltypen und einer templatgesteuerten Anordnung, die Bildung komplexer und strukturierter Formen in der Größenordnung mehrerer Mikrometer. Dieses System kann einerseits als Grundlage für die Herstellung verschiedener Janus-Partikel herangezogen werden, andererseits stellt die gerichtete Vernetzung zweier Partikelsysteme zu größeren Aggregaten den Grundstein für neuartige, funktionale Materialien dar. Neben der Anordnung an fest-flüssig Grenzflächen konnte außerdem nachgewiesen werden, dass Azobenzol-funktionalisierte Silicapartikel in der Lage sind, Pickering-Emulsionen über mehrere Monate zu stabilisieren. Die Stabilität und Größe der Emulsionsphase kann über Parameter, wie das Volumenverhältnis und die Konzentration, gesteuert werden. CD-funktionalisierte Silicapartikel besaßen dagegen keine Grenzflächenaktivität, während es CD-basierten Polymeren wiederum möglich war, durch die Ausbildung von Einschlusskomplexen mit den hydrophoben Molekülen der Ölphase stabile Emulsionen zu bilden. Dagegen zeigte die Kombination zwei verschiedener Partikelsysteme keinen oder einen destabilisierenden Effekt bezüglich der Ausbildung von Emulsionen.
Im letzten Teilprojekt wurde die Herstellung multivalenter Silicapartikel mittels Mikrokontaktdruck untersucht. Die Faltenstrukturen wurden dabei als Stempel verwendet, wodurch es möglich war, die Patch-Geometrie über die Wellenlänge der Faltenstrukturen zu steuern. Als Tinte diente das positiv geladene Polyelektrolyt Polyethylenimin (PEI), welches über elektrostatische Wechselwirkungen auf unmodifizierten Silicapartikeln haftet. Im Gegensatz zum Drucken mit flachen Stempeln fiel dabei zunächst auf, dass sich die Tinte bei den Faltenstrukturen nicht gleichmäßig über die gesamte Substratfläche verteilt, sondern hauptsächlich in den Faltentälern vorlag. Dadurch handelte es sich bei dem Druckprozess letztlich nicht mehr um ein klassisches Mikrokontaktdruckverfahren, sondern um ein Tiefdruckverfahren. Über das Tiefdruckverfahren war es dann aber möglich, sowohl eine als auch beide Partikelhemisphären gleichzeitig und mit verschiedenen Funktionalitäten zu modifizieren und somit multivalente Silicapartikel zu generieren. In Abhängigkeit der Wellenlänge der Falten konnten auf einer Partikelhemisphäre zwei bis acht Patches abgebildet werden. Für die Patch-Geometrie, sprich Größe und Form der Patches, spielten zudem die Konzentration der Tinte auf dem Stempel, das Lösungsmittel zum Ablösen der Partikel nach dem Drucken sowie die Stempelhärte eine wichtige Rolle. Da die Stempelhärte aufgrund der variierenden Dicke der Oxidschicht bei verschiedenen Wellenlängen nicht kontant ist, wurden für den Druckprozess meist Abgüsse der Faltensubstrate verwendet. Auf diese Weise war auch die Vergleichbarkeit bei variierender Wellenlänge gewährleistet. Neben dem erfolgreichen Nachweis der Modifikation mittels Tiefdruckverfahren konnte auch gezeigt werden, dass über die Komplexierung mit PEI negativ geladene Nanopartikel auf die Partikeloberfläche aufgebracht werden können.
Among modern functional materials, the class of nitrogen-containing carbons combines non-toxicity and sustainability with outstanding properties. The versatility of this materials class is based on the opportunity to tune electronic and catalytic properties via the nitrogen content and –motifs: This ranges from the electronically conducting N-doped carbon, where few carbon atoms in the graphitic lattice are substituted by nitrogen, to the organic semiconductor graphitic carbon nitride (g-C₃N₄), with a structure based on tri-s-triazine units.
In general, composites can reveal outstanding catalytic properties due to synergistic behavior, e.g. the formation of electronic heterojunctions. In this thesis, the formation of an “all-carbon” heterojunction was targeted, i.e. differences in the electronic properties of the single components were achieved by the introduction of different nitrogen motives into the carbon lattice. Such composites are promising as metal-free catalysts for the photocatalytic water splitting. Here, hydrogen can be generated from water by light irradiation with the use of a photocatalyst. As first part of the heterojunction, the organic semiconductor g-C₃N₄ was employed, because of its suitable band structure for photocatalytic water splitting, high stability and non-toxicity. The second part was chosen as C₂N, a recently discovered semiconductor. Compared to g-C₃N₄, the less nitrogen containing C₂N has a smaller band gap and a higher absorption coefficient in the visible light range, which is expected to increase the optical absorption in the composite eventually leading to an enhanced charge carrier separation due to the formation of an electronic heterojunction.
The aim of preparing an “all-carbon” composite included the research on appropriate precursors for the respective components g-C₃N₄ and C₂N, as well as strategies for appropriate structuring. This was targeted by applying precursors which can form supramolecular pre-organized structures. This allows for more control over morphology and atom patterns during the carbonization process.
In the first part of this thesis, it was demonstrated how the photocatalytic activity of g-C₃N₄ can be increased by the targeted introduction of defects or surface terminations. This was achieved by using caffeine as a “growth stopping” additive during the formation of the hydrogen-bonded supramolecular precursor complexes. The increased photocatalytic activity of the obtained materials was demonstrated with dye degradation experiments.
The second part of this thesis was focused on the synthesis of the second component C₂N. Here, a deep eutectic mixture from hexaketocyclohexane and urea was structured using the biopolymer chitosan. This scaffolding resulted in mesoporous nitrogen-doped carbon monoliths and beads. CO₂- and dye-adsorption experiments with the obtained monolith material revealed a high isosteric heat of CO₂-adsorption and showed the accessibility of the monolithic pore system to larger dye molecules. Furthermore, a novel precursor system for C₂N was explored, based on organic crystals from squaric acid and urea. The respective C₂N carbon with an unusual sheet-like morphology could be synthesized by carbonization of the crystals at 550 °C. With this precursor system, also microporous C₂N carbon with a BET surface area of 865 m²/g was obtained by “salt-templating” with ZnCl₂.
Finally, the preparation of a g-C₃N₄/C₂N “all carbon” composite heterojunction was attempted by the self-assembly of g-C₃N₄ and C₂N nanosheets and tested for photocatalytic water splitting. Indeed, the composites revealed high rates of hydrogen evolution when compared to bulk g-C₃N₄. However, the increased catalytic activity was mainly attributed to the high surface area of the nanocomposites rather than to the composition. With regard to alternative composite synthesis ways, first experiments indicated N-Methyl-2-pyrrolidon to be suitable for higher concentrated dispersion of C₂N nanosheets. Eventually, the results obtained in this thesis provide precious synthetic contributions towards the preparation and processing of carbon/nitrogen compounds for energy applications.
In the present work side-chain polystyrenes were synthesized and characterized, in order to be applied in multilayer OLEDs fabricated by solution process techniques. Manufacture of optoelectronic devices by solution process techniques is meant to decrease significantly fabrication cost and allow large scale production of such devices.
This dissertation focusses in three series, enveloped in two material classes. The two classes differ to each other in the type of charge transport exhibited, either ambipolar transport or electron transport. All materials were applied in all-organic solution processed green Ir-based devices.
In the first part, a series of ambipolar host materials were developed to transport both charge types, holes and electrons, and be applied especially as matrix for green Ir-based emitters. It was possible to increase devices efficacy by modulating the predominant charge transport type. This was achieved by modification of molecules electron transport part with more electron-deficient heterocycles or by extending the delocalization of the LUMO. Efficiencies up to 28.9 cd/A were observed for all-organic solution-process three layer devices.
In the second part, suitability of triarylboranes and tetraphenylsilanes as electron transport materials was studied. High triplet energies were obtained, up to 2.95 eV, by rational combination of both molecular structures. Although the combination of both elements had a low effect in materials electron transport properties, high efficiencies around 24 cd/A were obtained for the series in all-organic solution-processed two layer devices.
In the last part, benzene and pyridine were chosen as the series electron-transport motif. By controlling the relative pyridine content (RPC) solubility into methanol was induced for polystyrenes with bulky side-chains. Materials with RPC ≥ 0.5 could be deposited orthogonally from solution without harming underlying layers. From the best of our knowledge, this is the first time such materials are applied in this architecture showing moderate efficiencies around 10 cd/A in all-organic solution processed OLEDs.
Overall, the outcome of these studies will actively contribute to the current research on materials for all-solution processed OLEDs.
In this work, a sensor system based on thermoresponsive materials is developed by utilizing a modular approach. By synthesizing three different key monomers containing either a carboxyl, alkene or alkyne end group connected with a spacer to the methacrylic polymerizable unit, a flexible copolymerization strategy has been set up with oligo ethylene glycol methacrylates. This allows to tune the lower critical solution temperature (LCST) of the polymers in aqueous media. The molar masses are variable thanks to the excurse taken in polymerization in ionic liquids thus stretching molar masses from 25 to over 1000 kDa. The systems that were shown shown to be effective in aqueous solution could be immobilized on surfaces by copolymerizing photo crosslinkable units. The immobilized systems were formulated to give different layer thicknesses, swelling ratios and mesh sizes depending on the demand of the coupling reaction.
The coupling of detector units or model molecules is approached via reactions of the click chemistry pool, and the reactions are evaluated on their efficiency under those aspects, too. These coupling reactions are followed by surface plasmon resonance spectroscopy (SPR) to judge efficiency. With these tools at hand, Salmonella saccharides could be selectively detected by SPR. Influenza viruses were detected in solution by turbidimetry in solution as well as by a copolymerized solvatochromic dye to track binding via the changes of the polymers’ fluorescence by said binding event. This effect could also be achieved by utilizing the thermoresponsive behavior. Another demonstrator consists of the detection system bound to a quartz surface, thus allowing the virus detection on a solid carrier.
The experiments show the great potential of combining the concepts of thermoresponsive materials and click chemistry to develop technically simple sensors for large biomolecules and viruses.
In der vorliegenden Arbeit konnte gezeigt werden, dass die beiden verwendeten Amphiphile mit Cholesterol als hydrophoben Block, gute Template für die Mineralisation von Calciumphosphat an der Wasser/Luft-Grenzfläche sind. Mittels Infrarot-Reflexions-Absorptions-Spektroskopie (IRRAS), Röntgenphotoelektronenspektroskopie (XPS), Energie dispersiver Röntgenspektroskopie (EDXS), Elektronenbeugung (SAED) und hochauflösende Transmissionselektronenmikroskopie (HRTEM) konnte die erfolgreiche Mineralisation von Calciumphosphat für beide Amphiphile an der Wasser/Luft-Grenzfläche nachgewiesen werden. Es konnte auch gezeigt werden, dass das Phasenverhalten der beiden Amphiphile und die bei der Mineralisation von Calciumphosphat gebildeten Kristallphasen nicht identisch sind. Beide Amphiphile üben demnach einen unterschiedlichen Einfluss auf den Mineralisationsverlauf aus.
Beim CHOL-HEM konnte sowohl nach 3 h als auch nach 5 h Octacalciumphosphat (OCP) als einzige Kristallphase mittels XPS, SAED, HRTEM und EDXS nachgewiesen werden. Das A-CHOL hingegen zeigte bei der Mineralisation von Calciumphosphat nach 1 h zunächst eine nicht eindeutig identifizierbare Vorläuferphase aus amorphen Calciumphosphat, Brushit (DCPD) oder OCP. Diese wandelte sich dann nach 3 h und 5 h in ein Gemisch, bestehend aus OCP und ein wenig Hydroxylapatit (HAP) um.
Die Schlussfolgerung daraus ist, dass das CHOL-HEM in der Lage ist, dass während der Mineralisation entstandene OCP zu stabilisieren. Dies geschieht vermutlich durch die Adsorption des Amphiphils bevorzugt an der OCP Oberfläche in [100] Orientierung. Dadurch wird die Spaltung entlang der c-Achse unterdrückt und die Hydrolyse zum HAP verhindert.
Das A-CHOL ist hingegen sterisch anspruchsvoller und kann wahrscheinlich aufgrund seiner Größe nicht so gut an der OCP Kristalloberfläche adsorbieren verglichen zum CHOL HEM. Das CHOL-HEM kann also die Hydrolyse von OCP zu HAP besser unterdrücken als das A-CHOL. Da jedoch auch beim A-CHOL nach einer Mineralisationszeit von 5 h nur wenig HAP zu finden ist, wäre auch hier ein Stabilisierungseffekt der OCP Kristalle möglich. Um eine genaue Aussage darüber treffen zu können, sind jedoch zusätzliche Kontrollexperimente notwendig. Es wäre zum einen denkbar, die Mineralisationsexperimente über einen längeren Zeitraum durchzuführen. Diese könnten zeigen, ob das CHOL-HEM die Hydrolyse vom OCP zum HAP komplett unterdrückt. Außerdem könnte nachgewiesen werden, ob beim A-CHOL das OCP weiter zum HAP umgesetzt wird oder ob ein Gemisch beider Kristallphasen erhalten bleibt.
Um die Mineralisation an der Wasser/Luft-Grenzfläche mit der Mineralisation in Bulklösung zu vergleichen, wurden zusätzlich Mineralisationsexperimente in Bulklösung durchgeführt. Dazu wurden Nitrilotriessigsäure (NTA) und Ethylendiamintetraessigsäure (EDTA) als Mineralisationsadditive verwendet, da NTA unter anderem der Struktur der hydrophilen Kopfgruppe des A-CHOLs ähnelt. Es konnte gezeigt werden, dass ein Vergleich der Mineralisation an der Grenzfläche mit der Mineralisation in Bulklösung nicht ohne weiteres möglich ist. Bei der Mineralisation in Bulklösung wird bei tiefen pH-Werten DCPD und bei höheren pH-Werten HAP gebildet. Diese wurde mittels Röntgenpulverdiffraktometrie Messungen nachgewiesen und durch Infrarotspektroskopie bekräftigt. Die Bildung von OCP wie an der Wasser/Luft-Grenzfläche konnte nicht beobachtet werden.
Es konnte auch gezeigt werden, dass beide Additive NTA und EDTA einen unterschiedlichen Einfluss auf den Verlauf der Mineralisation nehmen. So unterscheiden sich zum einen die Morphologien des gebildeten DCPDs und zum anderen wurde beispielsweise in Anwesenheit von 10 und 15 mM NTA neben DCPD auch HAP bei einem Ausgangs-pH-Wert von 7 nachgewiesen.
Da unser Augenmerk speziell auf der Mineralisation von Calciumphosphat an der Wasser/Luft-Grenzfläche liegt, könnten Folgeexperimente wie beispielsweise GIXD Messungen durchgeführt werden. Dadurch wäre es möglich, einen Überblick über die gebildeten Kristallphasen nach unterschiedlichen Reaktionszeiten direkt auf dem Trog zu erhalten.
Es konnte weiterhin gezeigt werden, dass auch einfache Amphiphile in der Lage sind, die Mineralisation von Calciumphosphat zu steuern. Amphiphile mit Cholesterol als hydrophoben Block bilden offensichtlich besonders stabile Monolagen an der Wasser/Luft-Grenzfläche. Eine Untersuchung des Einflusses ähnlicher Amphiphile mit unterschiedlichen hydrophilen Kopfgruppen auf das Mineralisationsverhalten von Calciumphosphat wäre durchaus interessant.
I. Ceric ammonium nitrate (CAN) mediated thiocyanate radical additions to glycals
In this dissertation, a facile entry was developed for the synthesis of 2-thiocarbohydrates and their transformations. Initially, CAN mediated thiocyanation of carbohydrates was carried out to obtain the basic building blocks (2-thiocyanates) for the entire studies. Subsequently, 2-thiocyanates were reduced to the corresponding thiols using appropriate reagents and reaction conditions. The screening of substrates, stereochemical outcome and the reaction mechanism are discussed briefly (Scheme I).
Scheme I. Synthesis of the 2-thiocyanates II and reductions to 2-thiols III & IV.
An interesting mechanism was proposed for the reduction of 2-thiocyanates II to 2-thiols III via formation of a disulfide intermediate. The water soluble free thiols IV were obtained by cleaving the thiocyanate and benzyl groups in a single step. In the subsequent part of studies, the synthetic potential of the 2-thiols was successfully expanded by simple synthetic transformations.
II. Transformations of the 2-thiocarbohydrates
The 2-thiols were utilized for convenient transformations including sulfa-Michael additions, nucleophilic substitutions, oxidation to disulfides and functionalization at the anomeric position. The diverse functionalizations of the carbohydrates at the C-2 position by means of the sulfur linkage are the highlighting feature of these studies. Thus, it creates an opportunity to expand the utility of 2-thiocarbohydrates for biological studies.
Reagents and conditions: a) I2, pyridine, THF, rt, 15 min; b) K2CO3, MeCN, rt, 1 h; c) MeI, K2CO3, DMF, 0 °C, 5 min; d) Ac2O, H2SO4 (1 drop), rt, 10 min; e) CAN, MeCN/H2O, NH4SCN, rt, 1 h; f) NaN3, ZnBr2, iPrOH/H2O, reflux, 15 h; g) NaOH (1 M), TBAI, benzene, rt, 2 h; h) ZnCl2, CHCl3, reflux, 3 h.
Scheme II. Functionalization of 2-thiocarbohydrates.
These transformations have enhanced the synthetic value of 2-thiocarbohydrates for the preparative scale. Worth to mention is the Lewis acid catalyzed replacement of the methoxy group by other nucleophiles and the synthesis of the (2→1) thiodisaccharides, which were obtained with complete β-selectivity. Additionally, for the first time, the carbohydrate linked thiotetrazole was synthesized by a (3 + 2) cycloaddition approach at the C-2 position.
III. Synthesis of thiodisaccharides by thiol-ene coupling.
In the final part of studies, the synthesis of thiodisaccharides by a classical photoinduced thiol-ene coupling was successfully achieved.
Reagents and conditions: 2,2-Dimethoxy-2-phenylacetophenone (DPAP), CH2Cl2/EtOH, hv, rt.
Scheme III. Thiol-ene coupling between 2-thiols and exo-glycals.
During the course of investigations, it was found that the steric hindrance plays an important role in the addition of bulky thiols to endo-glycals. Thus, we successfully screened the suitable substrates for addition of various thiols to sterically less hindered alkenes (Scheme III). The photochemical addition of 2-thiols to three different exo-glycals delivered excellent regio- and diastereoselectivities as well as yields, which underlines the synthetic potential of this convenient methodology.
The field of nanophotonics focuses on the interaction between electromagnetic radiation and matter on the nanometer scale. The elements of nanoscale photonic devices can transfer excitation energy non-radiatively from an excited donor molecule to an acceptor molecule by Förster resonance energy transfer (FRET). The efficiency of this energy transfer is highly dependent on the donor-acceptor distance. Hence, in these nanoscale photonic devices it is of high importance to have a good control over the spatial assembly of used fluorophores. Based on molecular self-assembly processes, various nanostructures can be produced. Here, DNA nanotechnology and especially the DNA origami technique are auspicious self-assembling methods. By using DNA origami nanostructures different fluorophores can be introduced with a high local control to create a variety of nanoscale photonic objects. The applications of such nanostructures range from photonic wires and logic gates for molecular computing to artificial light harvesting systems for artificial photosynthesis.
In the present cumulative doctoral thesis, different FRET systems on DNA origami structures have been designed and thoroughly analyzed. Firstly, the formation of guanine (G) quadruplex structures from G rich DNA sequences has been studied based on a two-color FRET system (Fluorescein (FAM)/Cyanine3 (Cy3)). Here, the influences of different cations (Na+ and K+), of the DNA origami structure and of the DNA sequence on the G-quadruplex formation have been analyzed. In this study, an ion-selective K+ sensing scheme based on the G-quadruplex formation on DNA origami structures has been developed. Subsequently, the reversibility of the G-quadruplex formation on DNA origami structures has been evaluated. This has been done for the simple two-color FRET system which has then been advanced to a switchable photonic wire by introducing additional fluorophores (FAM/Cy3/Cyanine5 (Cy5)/IRDye®700). In the last part, the emission intensity of the acceptor molecule (Cy5) in a three-color FRET cascade has been tuned by arranging multiple donor (FAM) and transmitter (Cy3) molecules around the central acceptor molecule. In such artificial light harvesting systems, the excitation energy is absorbed by several donor and transmitter molecules followed by an energy transfer to the acceptor leading to a brighter Cy5 emission. Furthermore, the range of possible excitation wavelengths is extended by using several different fluorophores (FAM/Cy3/Cy5). In this part of the thesis, the light harvesting efficiency (antenna effect) and the FRET efficiency of different donor/transmitter/acceptor assemblies have been analyzed and the artificial light harvesting complex has been optimized in this respect.
Proteins are natural polypeptides produced by cells; they can be found in both animals and plants, and possess a variety of functions. One of these functions is to provide structural support to the surrounding cells and tissues. For example, collagen (which is found in skin, cartilage, tendons and bones) and keratin (which is found in hair and nails) are structural proteins. When a tissue is damaged, however, the supporting matrix formed by structural proteins cannot always spontaneously regenerate. Tailor-made synthetic polypeptides can be used to help heal and restore tissue formation.
Synthetic polypeptides are typically synthesized by the so-called ring opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA). Such synthetic polypeptides are generally non-sequence-controlled and thus less complex than proteins. As such, synthetic polypeptides are rarely as efficient as proteins in their ability to self-assemble and form hierarchical or structural supramolecular assemblies in water, and thus, often require rational designing. In this doctoral work, two types of amino acids, γ-benzyl-L/D-glutamate (BLG / BDG) and allylglycine (AG), were selected to synthesize a series of (co)polypeptides of different compositions and molar masses.
A new and versatile synthetic route to prepare polypeptides was developed, and its mechanism and kinetics were investigated. The polypeptide properties were thoroughly studied and new materials were developed from them. In particular, these polypeptides were able to aggregate (or self-assemble) in solution into microscopic fibres, very similar to those formed by collagen. By doing so, they formed robust physical networks and organogels which could be processed into high water-content, pH-responsive hydrogels. Particles with highly regular and chiral spiral morphologies were also obtained by emulsifying these polypeptides. Such polypeptides and the materials derived from them are, therefore, promising candidates for biomedical applications.
Diese Arbeit befasst sich mit der Herstellung und Charakterisierung von thermoresponsiven Filmen auf Goldelektroden durch Fixierung eines bereits synthetisierten thermoresponsiven Polymers. Als Basis für die Entwicklung der responsiven Grenzfläche dienten drei unterschiedliche Copolymere (Polymere I, II und III) aus der Gruppe der thermisch schaltbaren Poly(oligo(ethylenglykol)methacrylate).
Die turbidimetrischen Messungen der Copolymere in Lösungen haben gezeigt, dass der Trübungspunkt vom pH-Wert, der Gegenwart von Salzen sowie von der Ionenstärke der Lösung abhängig ist. Nach der Charakterisierung der Polymere in Lösung wurden Experimente der kovalenten Kopplung der Polymere I bis III an die Oberfläche der Gold-Elektroden durchgeführt. Während bei Polymeren I und II die Ankopplung auf einer Amidverbrückung basierte, wurde bei Polymer III als alternative Methode zur Immobilisierung eine photoinduzierte Anbindung unter gleichzeitiger Vernetzung gewählt. Der Nachweis der erfolgreichen Ankopplung erfolgte bei allen Polymeren elektrochemisch mittels Cyclovoltammetrie und Impedanzspektroskopie in K3/4[Fe(CN)6]-Lösungen. Wie die Ellipsometrie-Messungen zeigten, waren die erhaltenen Polymer-Filme unterschiedlich dick. Die Ankopplung über Amidverbrückung lieferte dünne Filme (10 – 15 nm), während der photovernetzte Film deutlich dicker war (70-80 nm) und die darunter liegende Oberfläche relativ gut isolierte.
Elektrochemische Temperaturexperimente an Polymer-modifizierten Oberflächen in Lösungen in Gegenwart von K3/4[Fe(CN)6] zeigten, dass auch die immobilisierten Polymere I bis III responsives Temperaturverhalten zeigen. Bei Elektroden mit den immobilisierten Polymeren I und II ist der Temperaturverlauf der Parameterwerte diskontinuierlich – ab einem kritischen Punkt (37 °C für Polymer I und 45 °C für Polymer II) wird zunächst langsame Zunahme der Peakströme wird deutlich schneller. Das Temperaturverhalten von Polymer III ist dagegen bis 50 °C kontinuierlich, der Peakstrom sinkt hier durchgehend.
Weiterhin wurde mit den auf Polymeren II und III basierten Elektroden deren Anwendung als responsive Matrix für Bioerkennungsreaktionen untersucht. Es wurde die Ankopplung von kleinen Biorezeptoren, TAG-Peptiden, an Polymer II- und Polymer III-modifizierten Elektroden durchgeführt. Das hydrophile FLAG-TAG-Peptid verändert das Temperaturverhalten des Polymer II-Films unwesentlich, da es die Hydrophilie des Netzwerkes nicht beeinflusst. Weiterhin wurde der Effekt der Ankopplung der ANTI-FLAG-TAG-Antikörper an FLAG-TAG-modifizierte Polymer II-Filme untersucht. Es konnte gezeigt werden, dass die Antikörper spezifisch an FLAG-TAG-modifiziertes Polymer II binden. Es wurde keine unspezifische Anbindung von ANTI-FLAG-TAG an Polymer II beobachtet. Die Temperaturexperimente haben gezeigt, dass die thermische Restrukturierung des Polymer II-FLAG-TAG-Filmes auch nach der Antikörper-Ankopplung noch stattfindet. Der Einfluss der ANTI-FLAG-TAG-Ankopplung ist gering, da der Unterschied in der Hydrophilie zwischen Polymer II und FLAG-TAG bzw. ANTI-FLAG-TAG zu gering ist.
Für die Untersuchungen mit Polymer III-Elektroden wurde neben dem hydrophilen FLAG-TAG-Peptid das deutlich hydrophobere HA-TAG-Peptid ausgewählt. Wie im Falle der Polymer II Elektrode beeinflusst das gekoppelte FLAG-TAG-Peptid das Temperaturverhalten des Polymer III-Netzwerkes nur geringfügig. Die gemessenen Stromwerte sind geringer als bei der Polymer III-Elektrode. Das Temperaturverhalten der FLAG-TAG-Elektrode ähnelt dem der reinen Polymer III-Elektrode – die Stromwerte sinken kontinuierlich bis die Temperatur von ca. 40 °C erreicht ist, bei der ein Plateau beobachtet wird. Offensichtlich verändert FLAG-TAG auch in diesem Fall nicht wesentlich die Hydrophilie des Polymer III-Netzwerkes. Das an Polymer III-Elektroden gekoppelte hydrophobe HA-TAG-Peptid beeinflusst dagegen im starken Maße den Quellzustand des Netzwerkes. Die Ströme für die HA-TAG-Elektroden sind deutlich geringer als die für die FLAG-TAG-Polymer III-Elektroden, was auf geringeren Wassergehalt und dickeren Film zurückzuführen ist. Bereits ab 30 °C erfolgt der Anstieg von Stromwerten, der bei Polymer III- bzw. bei Polymer III-FLAG-TAG-Elektroden nicht beobachtet werden kann. Das gekoppelte hydrophobe HA-TAG-Peptid verdrängt Wasser aus dem Polymer III-Netzwerk, was in der Stauchung des Films bereits bei Raumtemperatur resultiert. Dies führt dazu, dass der Film im Laufe des Temperaturanstieges kaum noch komprimiert. Die Stromwerte steigen in diesem Fall entsprechend des Anstiegs der temperaturabhängigen Diffusion des Redoxpaares. Diese Untersuchungen zeigen, dass das HA-TAG-Peptid als Ankermolekül deutlich besser für eine potentielle Verwendung der Polymer III-Filme für sensorische Zwecke geeignet ist, da es sich deutlich in der Hydrophilie von Polymer III unterscheidet.
The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which – together with alloyed CdxHg1−xTe – are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1−xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.
The excitation of localized surface plasmons in noble metal nanoparticles (NPs) results in different nanoscale effects such as electric field enhancement, the generation of hot electrons and a temperature increase close to the NP surface. These effects are typically exploited in diverse fields such as surface-enhanced Raman scattering (SERS), NP catalysis and photothermal therapy (PTT). Halogenated nucleobases are applied as radiosensitizers in conventional radiation cancer therapy due to their high reactivity towards secondary electrons. Here, we use SERS to study the transformation of 8-bromoadenine (8BrA) into adenine on the surface of Au and AgNPs upon irradiation with a low-power continuous wave laser at 532, 633 and 785 nm, respectively. The dissociation of 8BrA is ascribed to a hot-electron transfer reaction and the underlying kinetics are carefully explored. The reaction proceeds within seconds or even milliseconds. Similar dissociation reactions might also occur with other electrophilic molecules, which must be considered in the interpretation of respective SERS spectra. Furthermore, we suggest that hot-electron transfer induced dissociation of radiosensitizers such as 8BrA can be applied in the future in PTT to enhance the damage of tumor tissue upon irradiation.
Macrocycles based on L-cystine were synthesized by ring-closing metathesis (RCM) and subsequently polymerized by entropy-driven ring-opening metathesis polymerization (ED-ROMP). Monomer conversion reached ∼80% in equilibrium and the produced poly(ester-amine-disulfide-alkene)s exhibited apparent molar masses (Mappw) of up to 80 kDa and dispersities (Đ) of ∼2. The polymers can be further functionalized with acid anhydrides and degraded by reductive cleavage of the main-chain disulfide.
This cumulative doctoral dissertation, based on three publications, is devoted to the investigation of several aspects of azobenzene molecular switches, with the aid of computational chemistry.
In the first paper, the isomerization rates of a thermal cis → trans isomerization of azobenzenes for species formed upon an integer electron transfer, i.e., with added or removed electron, are calculated from Eyring’s transition state theory and activation energy barriers, computed by means of density functional theory. The obtained results are discussed in connection with an experimental study of the thermal cis → trans isomerization of azobenzene derivatives in the presence of gold nanoparticles, which is demonstrated to be greatly accelerated in comparison to the same isomerization reaction in the absence of nanoparticles.
The second paper is concerned with electronically excited states of (i) dimers, composed of two photoswitchable units placed closely side-by-side, as well as (ii) monomers and dimers adsorbed on a silicon cluster. A variety of quantum chemistry methods, capable of calculating molecular electronic absorption spectra, based on density functional and wave function theories, is employed to quantify changes in optical absorption upon dimerization and covalent grafting to a surface. Specifically, the exciton (Davydov) splitting between states of interest is determined from first-principles calculations with the help of natural transition orbital analysis, allowing for insight into the nature of excited states.
In the third paper, nonadiabatic molecular dynamics with trajectory surface hopping is applied to model the photoisomerization of azobenzene dimers, (i) for the isolated case (exhibiting the exciton coupling between two molecules) as well as (ii) for the constrained case (providing the van der Waals interaction with environment in addition to the exciton coupling between two monomers). For the latter, the additional azobenzene molecules, surrounding the dimer, are introduced, mimicking a densely packed self-assembled monolayer. From obtained results it is concluded that the isolated dimer is capable of isomerization likewise the monomer, whereas the steric hindrance considerably suppresses trans → cis photoisomerization.
Furthermore, the present dissertation comprises the general introduction describing the main features of the azobenzene photoswitch and objectives of this work, theoretical basis of the employed methods, and discussion of gained findings in the light of existing literature. Also, additional results on (i) activation parameters of the thermal cis → trans isomerization of azobenzenes, (ii) an approximate scheme to account for anharmonicity of molecular vibrations in calculation of the activation entropy, as well as (iii) absorption spectra of photoswitch–silicon composites obtained from time-demanding wave function-based methods are presented.
In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F0 and F2+ defects but not at F1+ sites, (2) electron redistribution from the F0 vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F0 type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F0, and (5) the moderate adsorption energy of the gold atom on the F0 defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step.
Information about the strength of donor–acceptor interactions in push–pull alkenes is valuable, as this so-called “push–pull effect” influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C double bond to quantify the push–pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in 13C NMR chemical shifts of the two carbons constituting the C[double bond, length as m-dash]C double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor–acceptor interactions in the push–pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters (apparent activation energy Ea and frequency factor A) and activation parameters (ΔS‡, ΔH‡ and ΔG‡), were determined from the data of the experimentally studied configurational isomerization of (E)-9a. These results were compared to previously published related data for other two compounds, (Z)-1b and (2E,5Z)-7, showing that experimentally determined ΔG‡ values are a good indicator of the strength of push–pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated C[double bond, length as m-dash]C bond lengths and corroborate the applicability of ΔG‡ for estimation of the strength of the push–pull effect in these and related systems.
The interaction of water with α-alumina (i.e. α-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with α-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined α-Al2O3(1[1 with combining macron]02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1–4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schrödinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm−1. Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.
In this work, three ligands produced from amino acids were synthesized and used to produce five bis- and PEPPSI-type palladium–NHC complexes using a novel synthesis route from sustainable starting materials. Three of these complexes were used as precatalysts in the aqueous-phase Suzuki–Miyaura coupling of various substrates displaying high activity. TEM and mercury poisoning experiments provide evidence for Pd-nanoparticle formation stabilized in water.
The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.
The aim of this study was to develop a one-step synthesis of gold nanotriangles (NTs) in the presence of mixed phospholipid vesicles followed by a separation process to isolate purified NTs. Negatively charged vesicles containing AOT and phospholipids, in the absence and presence of additional reducing agents (polyampholytes, polyanions or low molecular weight compounds), were used as a template phase to form anisotropic gold nanoparticles. Upon addition of the gold chloride solution, the nucleation process is initiated and both types of particles, i.e., isotropic spherical and anisotropic gold nanotriangles, are formed simultaneously. As it was not possible to produce monodisperse nanotriangles with such a one-step procedure, the anisotropic nanoparticles needed to be separated from the spherical ones. Therefore, a new type of separation procedure using combined polyelectrolyte/micelle depletion flocculation was successfully applied. As a result of the different purification steps, a green colored aqueous dispersion was obtained containing highly purified, well-defined negatively charged flat nanocrystals with a platelet thickness of 10 nm and an edge length of about 175 nm. The NTs produce promising results in surface-enhanced Raman scattering.
Optical biosensors based on porous silicon were fabricated by metal assisted chemical etching. Thereby double layered porous silicon structures were obtained consisting of porous pillars with large pores on top of a porous silicon layer with smaller pores. These structures showed a similar sensing performance in comparison to electrochemically produced porous silicon interferometric sensors.
In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([CnC1im]+[NTf2]- and [C4C1im]+[I]-). A combination of measurements and quantum chemical calculations of C K and N K NEXAFS resonances is presented. The simulations, based on the transition potential density functional theory method (TP-DFT), reproduce all characteristic features observed by the experiment. Furthermore, a detailed assignment of resonance features to excitation centers (carbon or nitrogen atoms) leads to a consistent interpretation of the spectra.
Die vorgelegte Dissertation präsentiert wissenschaftliche Ergebnisse, die in der Zeit vom Dezember 2012 bis August 2016, erarbeitet wurden. Der zentrale Inhalt der Arbeit ist die Simulation von Röntgenabsorptionsprozessen von verschiedenen Systemen in kondensierter Phase. Genauer gesagt, werden Nahkantenabsorptions- (NEXAFS) sowie Röntgenphotoelektronenspektren (XPS) berechnet. In beiden Fällen wird ein Röntgenphoton von einem molekularen System absorbiert. Aufgrund der hohen Photonenenergie wird ein stark gebundenes kernnahes Elektron angeregt. Bei der XPS gelangt dieses mit einer zu messenden kinetischen Energie in Kontinuumszustände. In Abhängigkeit der eingestrahlten Photonenenergie und der kinetischen Energie des austreten Elektrons, kann die Bindungsenergie berechnet werden, welche die zentrale Größe der XPS ist. Im Falle der NEXAFS-Spektroskopie wird das kernnahe Elektron in unbesetzte gebundene Zustände angeregt. Die zentrale Größe ist die Absorption als Funktion der eingestrahlten Photonenenergie. Das erste Kapitel meiner Arbeit erörtert detailliert die experimentellen Methoden sowie die daraus gewonnenen charakteristischen Größen.
Die experimentellen Spektren zeigen oft viele Resonanzen, deren Interpretation aufgrund fehlender Referenzmaterialien schwierig ist. In solchen Fällen bietet es sich an, die Spektren mittels quantenchemischer Methoden zu simulieren. Der dafür erforderliche mathematisch-physikalische Methodenkatalog wird im zweiten Kapitel der Arbeit erörtert.
Das erste von mir untersuchte System ist Graphen. In experimentellen Arbeiten wurde die Oberfläche mittels Bromplasma modifiziert. Die im Anschluss gemessenen NEXAFS-Spektren unterscheiden sich maßgeblich von den Spektren der unbehandelten Oberfläche. Mithilfe periodischer DFT-Rechnungen wurden verschiedene Gitterdefekte sowie bromierte Systeme untersucht und die NEXAFS-Spektren simuliert. Mittels der Simulationen können die Beiträge verschiedener Anregungszentren analysiert werden. Die Berechnungen erlauben den Schluss, dass Gitterdefekte maßgeblich für die entstandenen Veränderungen verantwortlich sind.
Polyvinylalkohol (PVA) wurde als zweites System behandelt. Hierbei sollte untersucht werden, wie groß der Einfluss der Molekularbewegung auf die Verbreiterung der Peaks im XP-Spektrum ist. Des Weiteren wurde untersucht, wie groß der Einfluss von intermolekularen Wechselwirkungen auf die Peakpositionen und Peakverbreiterung ist. Für die Berechnung dieses Systems wurde eine Kombination aus molekulardynamischen und quantenchemischen Methoden verwendet. Als Strukturen dienten Oligomermodelle, die unter dem Einfluss eines (ab initio) Potentials propagiert wurden. Entlang der erstellten Trajektorie wurden Schnappschüsse der Geometrien extrahiert und für die Berechnung der XP-Spektren verwendet. Die Spektren werden bereits mithilfe klassischer Molekulardynamik sehr gut reproduziert. Die erhaltenen Peakbreiten sind verglichen mit dem Experiment allerdings zu klein. Die Hauptursache der Peakverbreiterung ist die Molekularbewegung. Intermolekulare Wechselwirkungen verschieben die Peakpositionen um 0.6 eV zu kleineren Anregungsenergien.
Im dritten Teil der Arbeit stehen die NEXAFS-Spektren von ionischen Flüssigkeiten (ILs) im Fokus. Die experimentell gefundenen Spektren zeigen eine komplexe Struktur mit vielen Resonanzen. In der Arbeit wurden zwei ILs untersucht. Als Geometrien verwenden wir Clustermodelle, die aus experimentellen Kristallstrukturen extrahiert wurden. Die berechneten Spektren erlauben es, die Resonanzen den Anregungszentren zuzuordnen. Außerdem kann eine erstmals gemessene Doppelresonanz simuliert und erklärt werden. Insgesamt kann die Interpretation der Spektren mithilfe der Simulation signifikant erweitert werden.
In allen Systemen wurde zur Berechnung des NEXAFS-Spektrums eine auf Dichtefunktionaltheorie basierende Methode verwendet (die sogenannte Transition-Potential Methode). Gängige wellenfunktionsbasierte Methoden, wie die Konfigurationswechselwirkung mit Einfachanregungen (CIS), zeigen eine starke Blauverschiebung, wenn als Referenz eine Hartree-Fock Slaterdeterminante verwendet wird. Wir zeigen, dass die Verwendung von kernnah-angeregten Determinanten sowohl das resultierende Spektrum als auch die Anregungsenergien deutlich verbessert. Des Weiteren werden auch Referenzen aus Dichtefunktionalrechnungen getestet. Zusätzlich werden auch Referenzen mit gebrochenen Besetzungszahlen für kernnahe Elektronen verwendet. In der Arbeit werden die Resultate der verschiedenen Referenzen miteinander verglichen. Es zeigt sich, dass Referenzen mit gebrochenen Besetzungszahlen das Spektrum nicht weiter verbessern. Der Einfluss der verwendeten Elektronenstrukturmethode ist eher gering.
Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called “hot spots”, have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information.
Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA
(dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules.
In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that
single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami
substrates very well, which enables the monitoring of structural alterations by AFM imaging.
In this way, it is shown that graphene encapsulation significantly increases the structural
stability of bare DNA origami substrates towards mechanical force and prolonged exposure
to deionized water.
Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a
40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits
several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice.
Although SLG can significantly influence the SERS substrate in the aforementioned ways, all
those effects are strongly related to the extent of contact with the underlying AuNP dimer.
Lignin valorization
(2017)
The topic of this project is the use of lignin as alternative source of aromatic building blocks and oligomers to fossil feedstocks. Lignin is known as the most abundant aromatic polymer in nature and is isolated from the lignocellulosic component of plants by different possible extraction treatments. Both the biomass source and the extraction method affect the structure of the isolated lignin, therefore influencing its further application. Lignin was extracted from beech wood by two different hydrothermal alkaline treatments, which use NaOH and Ba(OH)2 as base and by an acid-catalyzed organosolv process. Moreover, lignin was isolated from bamboo, beech wood and coconut by soda treatment of the biomasses. A comparison of the structural features of such isolated lignins was performed through the use of a wide range of analytical methods. Alkaline lignins resulted in a better candidate as carbon precursor and macromonomers for the synthesis of polymer than organosolv lignin. In fact, alkaline lignins showed higher residual mass after carbonization and higher content of the reactive hydroxy functionalities. In contrast, the lignin source turned out to slightly affect the lignin hydroxyl content.
One of the most common lignin modifications is its deconstruction to obtain aromatic molecules, which can be used as starting materials for the synthesis of fine chemicals. Lignin deconstruction leads to a complex mixture of aromatic molecules. A gas chromatographic analytical method was developed to characterize the mixture of products obtained by lignin deconstruction via heterogeneous catalytic hydrogenolysis. The analytical protocol allowed the quantification of three main groups of molecules by means of calibration curves, internal standard and a preliminary silylation step of the sample. The analytical method was used to study the influence of the hydrogenolysis catalyst, temperature and system (flow and batch reactor) on the yield and selectivity of the aromatic compounds.
Lignin extracted from beech wood by a hydrothermal process using Ba(OH)2 as base, was functionalized by aromatic nitration in order to add nitrogen functionalities. The final goal was the synthesis of a nitrogen doped carbon. Nitrated lignin was reduced to the amino form in order to compare the influence of different nitrogen functionalities on the porosity of the final carbon. The carbons were obtained by ionothermal treatment of the precursors in the presence of the eutectic salt mixture KCl/ZnCl2 Such synthesized carbons showed micro-, macro- and mesoporosity and were tested for their electrocatalytic activity towards the oxygen reduction reaction. Mesoporous carbon derived from nitro lignin displayed the highest electrocatalytic activity.
Lignins isolated from coconut, beech wood and bamboo were used as macromonomers for the synthesis of biobased polyesters. A condensation reaction was performed between lignin and a hyper branched poly(ester-amine), previously obtained by condensation of triethanolamine and adipic acid. The influence of the lignin source and content on the thermochemical and mechanical properties of the final material was investigated. The prepolymer showed adhesive properties towards aluminum and its shear strength was therefore measured. The gluing properties of such synthesized glues turned out to be independent from the lignin source but affected by the amount of lignin in the final material.
This work shows that, although still at a laboratory scale, the valorization of lignin can overcome the critical issues of lignin´s structure variability and complexity.
Physikalische Hydrogele gewinnen derzeit als Zellsubstrate zunehmend an Interesse, da Viskoelastizität oder Stressrelaxation ein bedeutender Parameter in der Mechanotransduktion ist, der bisher vernachlässigt wurde. In dieser Arbeit wurden multi-funktionelle Polyurethane entworfen, die über einen neuartigen Gelierungsmechanismus physikalische Hydrogele bilden. In Wasser bilden die anionischen Polyurethane spontan Aggregate, welche durch elektrostatische Abstoßung in Lösung gehalten werden. Eine schnelle Gelierung kann von hier aus durch Ladungsabschirmung erreicht werden, wodurch die Aggregation voranschreitet und ein Netzwerk ausgebildet wird. Dies kann durch die Zugabe von verschiedenen Säuren oder Salzen geschehen, sodass sowohl saure (pH 4 - 5) als auch pH-neutrale Hydrogele erhalten werden können. Während konventionelle Hydrogele auf Polyurethan-Basis in der Regel durch toxische isocyanat-haltige Präpolymere hergestellt werden, eignet sich der hier beschriebene physikalische Gelierungsmechanismus für in situ Anwendungen in sensitiven Umgebungen. Sowohl Härte als auch Stressrelaxation der Hydrogele können unabhängig voneinander über einen breiten Bereich eingestellt werden. Darüberhinaus zeichnen sich die Hydrogele durch exzellente Stressregeneration aus.
Diese Arbeit zu Grunde liegenden Forschung zielte darauf ab, neue schmelzbare Acrylnitril-Copolymere zu entwickeln. Diese sollten im Anschluss über ein Schmelzspinnverfahren zur Chemiefaser geformt und im letzten Schritt zur Carbonfaser konvertiert werden. Zu diesem Zweck wurden zunächst orientierende Untersuchungen an unterschiedlichen Copolymeren des Acrylnitril aus Lösungspolymerisation durchgeführt. Die Untersuchungen zeigten, dass elektrostatische Wechselwirkungen besser als sterische Abschirmung dazu geeignet sind, Schmelzbarkeit unterhalb der Zersetzungstemperatur von Polyacrylnitril zu bewirken. Aus der Vielzahl untersuchter Copolymere stellten sich jene mit Methoxyethylacrylat (MEA) als am effektivsten heraus. Für diese Copolymere wurden sowohl die Copolymerisationsparameter bestimmt als auch die grundlegende Kinetik der Lösungspolymerisation untersucht. Die Copolymere mit MEA wurden über Schmelzspinnen zur Faser umgeformt und diese dann untersucht. Hierbei wurden auch Einflüsse verschiedener Parameter, wie z.B. die der Molmasse, auf die Fasereigenschaften und -herstellung untersucht. Zuletzt wurde ein Heterophasenpolymerisationsverfahren zur Herstellung von Copolymeren aus AN/MEA entwickelt; dadurch konnten die Materialeigenschaften weiter verbessert werden. Zur Unterdrückung der thermoplastischen Eigenschaften der Fasern wurde ein geeignetes Verfahren entwickelt und anschließend die Konversion zu Carbonfasern durchgeführt.
Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition–fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.
New V-shaped non-centrosymmetric dyes, possessing a strongly electron-deficient azacyanine core, have been synthesized based on a straightforward two-step approach. The key step in this synthesis involves palladium-catalysed cross-coupling of dibromo-N,N′-methylene-2,2′-azapyridinocyanines with arylacetylenes. The resulting strongly polarized π-expanded heterocycles exhibit green to orange fluorescence and they strongly respond to changes in solvent polarity. We demonstrate that differently electron-donating peripheral groups have a significant influence on the internal charge transfer, hence on the solvent effect and fluorescence quantum yield. TD-DFT calculations confirm that, in contrast to the previously studied bis(styryl)azacyanines, the proximity of S1 and T2 states calculated for compounds bearing two 4-N,N-dimethylaminophenylethynyl moieties establishes good conditions for efficient intersystem crossing and is responsible for its low fluorescence quantum yield. Non-linear properties have also been determined for new azacyanines and the results show that depending on peripheral groups, the synthesized dyes exhibit small to large two-photon absorption cross sections reaching 4000 GM.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
In complement to the well-established zwitterionic monomers 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (“SPE”) and 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (“SPP”), the closely related sulfobetaine monomers were synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar mass were characterized with respect to their solubility in water, deuterated water, and aqueous salt solutions. These poly(sulfobetaine)s show thermoresponsive behavior in water, exhibiting upper critical solution temperatures (UCST). Phase transition temperatures depend notably on the molar mass and polymer concentration, and are much higher in D2O than in H2O. Also, the phase transition temperatures are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed structure of the zwitterionic side chain, on the other hand. For the polymers with the same zwitterionic side chain, it is found that methacrylamide-based poly(sulfobetaine)s exhibit higher UCST-type transition temperatures than their methacrylate analogs. The extension of the distance between polymerizable unit and zwitterionic groups from 2 to 3 methylene units decreases the UCST-type transition temperatures. Poly(sulfobetaine)s derived from aliphatic esters show higher UCST-type transition temperatures than their analogs featuring cyclic ammonium cations. The UCST-type transition temperatures increase markedly with spacer length separating the cationic and anionic moieties from 3 to 4 methylene units. Thus, apparently small variations of their chemical structure strongly affect the phase behavior of the polyzwitterions in specific aqueous environments.
Water-soluble block copolymers were prepared from the zwitterionic monomers and the non-ionic monomer N-isopropylmethacrylamide (“NIPMAM”) by the RAFT polymerization. Such block copolymers with two hydrophilic blocks exhibit twofold thermoresponsive behavior in water. The poly(sulfobetaine) block shows an UCST, whereas the poly(NIPMAM) block exhibits a lower critical solution temperature (LCST). This constellation induces a structure inversion of the solvophobic aggregate, called “schizophrenic micelle”. Depending on the relative positions of the two different phase transitions, the block copolymer passes through a molecularly dissolved or an insoluble intermediate regime, which can be modulated by the polymer concentration or by the addition of salt. Whereas, at low temperature, the poly(sulfobetaine) block forms polar aggregates that are kept in solution by the poly(NIPMAM) block, at high temperature, the poly(NIPMAM) block forms hydrophobic aggregates that are kept in solution by the poly(sulfobetaine) block. Thus, aggregates can be prepared in water, which switch reversibly their “inside” to the “outside”, and vice versa.
In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes.
The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer.
The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts.
Ionothermal carbon materials
(2016)
Alternative concepts for energy storage and conversion have to be developed, optimized and employed to fulfill the dream of a fossil-independent energy economy. Porous carbon materials play a major role in many energy-related devices. Among different characteristics, distinct porosity features, e.g., specific surface area (SSA), total pore volume (TPV), and the pore size distribution (PSD), are important to maximize the performance in the final device. In order to approach the aim to synthesize carbon materials with tailor-made porosity in a sustainable fashion, the present thesis focused on biomass-derived precursors employing and developing the ionothermal carbonization.
During the ionothermal carbonization, a salt melt simultaneously serves as solvent and porogen. Typically, eutectic mixtures containing zinc chloride are employed as salt phase. The first topic of the present thesis addressed the possibility to precisely tailor the porosity of ionothermal carbon materials by an experimentally simple variation of the molar composition of the binary salt mixture. The developed pore tuning tool allowed the synthesis of glucose derived carbon materials with predictable SSAs in the range of ~ 900 to ~ 2100 m2 g-1. Moreover, the nucleobase adenine was employed as precursor introducing nitrogen functionalities in the final material. Thereby, the chemical properties of the carbon materials are varied leading to new application fields. Nitrogen doped carbons (NDCs) are able to catalyze the oxygen reduction reaction (ORR) which takes place on the cathodic site of a fuel cell. The herein developed porosity tailoring allowed the synthesis of adenine derived NDCs with outstanding SSAs of up to 2900 m2 g-1 and very large TPV of 5.19 cm3 g-1. Furthermore, the influence of the porosity on the ORR could be directly investigated enabling the precise optimization of the porosity characteristics of NDCs for this application. The second topic addressed the development of a new method to investigate the not-yet unraveled mechanism of the oxygen reduction reaction using a rotating disc electrode setup. The focus was put on noble-metal free catalysts. The results showed that the reaction pathway of the investigated catalysts is pH-dependent indicating different active species at different pH-values. The third topic addressed the expansion of the used salts for the ionothermal approach towards hydrated calcium and magnesium chloride. It was shown that hydrated salt phases allowed the introduction of a secondary templating effect which was connected to the coexistence of liquid and solid salt phases. The method enabled the synthesis of fibrous NDCs with SSAs of up to 2780 m2 g-1 and very large TPV of 3.86 cm3 g-1. Moreover, the concept of active site implementation by a facile low-temperature metalation employing the obtained NDCs as solid ligands could be shown for the first time in the context of ORR.
Overall, the thesis may pave the way towards highly porous carbon with tailor-made porosity materials prepared by an inexpensive and sustainable pathway, which can be applied in energy related field thereby supporting the needed expansion of the renewable energy sector.
Polypeptides having secondary structures often undergo self-assembly which can extend over multiple length scales. Poly(γ-benzyl-L-glutamate) (PBLG), for example, folds into α-helices and forms physical organogels, whereas poly(L-glutamic acid) (PLGA at acidic pH) or poly(L-glutamate) (PLG at neutral/basic pH) do not form hydrogels. We explored the gelation of modified PBLG and investigated the deprotection of the carboxylic acid moieties in such gels to yield unique hydrogels. This was accomplished through photo-crosslinking gelation of poly(γ-benzyl-L-glutamate-co-allylglycine) statistical copolymers in toluene, tetrahydrofuran, and 1,4-dioxane. Unlike most polymer-based chemical gels, our gels were prepared from dilute solutions (<20 g L−1, i.e., <2% w/v) of low molar mass polymers. Despite such low concentrations and molar masses, our dioxane gels showed high mechanical stability and little shrinkage; remarkably, they also exhibited a porous fibrillar network. Deprotection of the carboxylic acid moieties in dioxane gels yielded pH responsive and highly absorbent PLGA/PLG-based hydrogels (swelling ratio of up to 87), while preserving the network structure, which is an unprecedented feature in the context of crosslinked PLGA gels. These outstanding properties are highly attractive for biomedical materials.
A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers’ precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.
The title compounds, [(1R,3R,4R,5R,6S)-4,5-bis(acetyloxy)-7-oxo-2-oxabicyclo[4.2.0]octan-3-yl]methyl acetate, C14H18O8, (I), [(1S,4R,5S,6R)-5-acetyloxy-7-hydroxyimino-2-oxobicyclo[4.2.0]octan-4-yl acetate, C11H15NO6, (II), and [(3aR,5R,6R,7R,7aS)-6,7-bis(acetyloxy)-2-oxooctahydropyrano[3,2-b]pyrrol-5-yl]methyl acetate, C14H19NO8, (III), are stable bicyclic carbohydrate derivatives. They can easily be synthesized in a few steps from commercially available glycals. As a result of the ring strain from the four-membered rings in (I) and (II), the conformations of the carbohydrates deviate strongly from the ideal chair form. Compound (II) occurs in the boat form. In the five-membered lactam (III), on the other hand, the carbohydrate adopts an almost ideal chair conformation. As a result of the distortion of the sugar rings, the configurations of the three bicyclic carbohydrate derivatives could not be determined from their NMR coupling constants. From our three crystal structure determinations, we were able to establish for the first time the absolute configurations of all new stereocenters of the carbohydrate rings.
In this contribution, we provide a detailed dynamical analysis of the interfacial hydrogen migration mediated by scanning tunneling microscopy (STM). Contributions from the STM-current and from the non-adiabatic couplings are taken into account using only first principle models. The slight asymmetry of the tunnelling rates with respect to the potential bias sign inferred from experimental observations is reproduced by weighting the contributions of the metal acceptor–donor states for the propagation of the impinging electrons. The quasi-thermal inelastic collision mechanism is treated perturbatively. The influence of hydrogen pre-coverage is also investigated using new potential energy surfaces obtained from periodic density functional theory calculations. Fully quantum dynamical simulations of the system evolution are performed by solving the Pauli master equation, providing insight into the reaction mechanism of STM manipulation of subsurface hydrogens. It is observed that the hydrogen impurity favors resurfacing over occupation of the bulk and subsurface sites whenever possible. The present simulations give strong indication that the experimentally observed protuberances after STM-excitation are due to hydrogen accumulating in the vicinity of the surface.
Hemolysis, the rupturing of red blood cells, can result from numerous medical conditions (in vivo) or occur after collecting blood specimen or extracting plasma and serum out of whole blood (in vitro). In clinical laboratory practice, hemolysis can be a serious problem due to its potential to bias detection of various analytes or biomarkers. Here we present the first ‘‘mix-and-measure’’ method to assess the degree of hemolysis in biosamples using luminescence spectroscopy. Luminescent terbium complexes (LTC) were studied in the presence of free hemoglobin (Hb) as indicators for hemolysis in TRIS-buffer, and in fresh human plasma with absorption, excitation and emission measurements. Our findings indicate dynamic as well as resonance energy transfer (FRET) between the LTC and the porphyrin ligand of hemoglobin. This transfer leads to a decrease in luminescence intensity and decay time even at nanomolar hemoglobin concentrations either in buffer or plasma. Luminescent terbium complexes are very sensitive to free hemoglobin in buffer and blood plasma. Due to the instant change in luminescence properties of the LTC in presence of Hb it is possible to access the concentration of hemoglobin via spectroscopic methods without incubation time or further treatment of the sample thus enabling a rapid and sensitive detection of hemolysis in clinical diagnostics.
Surface modification with thermoresponsive polymer brushes for a switchable electrochemical sensor
(2014)
Elaboration of switchable surfaces represents an interesting way for the development of a new generation of electrochemical sensors. In this paper, a method for growing thermoresponsive polymer brushes from a gold surface pre-modified with polyethyleneimine (PEI), subsequent layer-by-layer polyelectrolyte assembly and adsorption of a charged macroinitiator is described. We propose an easy method for monitoring the coil-to-globule phase transition of the polymer brush using an electrochemical quartz crystal microbalance with dissipation (E-QCM-D). The surface of these polymer modified electrodes shows reversible switching from the swollen to the collapsed state with temperature. As demonstrated from E-QCM-D measurements using an original signal processing method, the switch is operating in three reversible steps related to different interfacial viscosities. Moreover, it is shown that the one electron oxidation of ferrocene carboxylic acid is dramatically affected by the change from the swollen to the collapsed state of the polymer brush, showing a spectacular 86% decrease of the charge transfer resistance between the two states.
Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo- and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials.
Polyglycolide (PGA) is a biodegradable polymer with multiple applications in the medical sector. Here the synthesis of high molecular weight polyglycolide by ring-opening polymerization of diglycolide is reported. For the first time stabilizer free supercritical carbon dioxide (scCO2) was used as a reaction medium. scCO2 allowed for a reduction in reaction temperature compared to conventional processes. Together with the lowering of monomer concentration and consequently reduced heat generation compared to bulk reactions thermal decomposition of the product occurring already during polymerization is strongly reduced. The reaction temperatures and pressures were varied between 120 and 150 °C and 145 to 1400 bar. Tin(II) ethyl hexanoate and 1-dodecanol were used as catalyst and initiator, respectively. The highest number average molecular weight of 31 200 g mol−1 was obtained in 5 hours from polymerization at 120 °C and 530 bar. In all cases the products were obtained as a dry white powder. Remarkably, independent of molecular weight the melting temperatures were always at (219 ± 2) °C.
The large-scale green synthesis of graphene-type two-dimensional materials is still challenging. Herein, we describe the ionothermal synthesis of carbon-based composites from fructose in the iron-containing ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III), [Bmim][FeCl4] serving as solvent, catalyst, and template for product formation. The resulting composites consist of oligo-layer graphite nanoflakes and iron carbide particles. The mesoporosity, strong magnetic moment, and high specific surface area of the composites make them attractive for water purification with facile magnetic separation. Moreover, Fe3Cfree graphite can be obtained via acid etching, providing access to fairly large amounts of graphite material. The current approach is versatile and scalable, and thus opens the door to ionothermal synthesis towards the larger-scale synthesis of materials that are, although not made via a sustainable process, useful for water treatment such as the removal of organic molecules.
The synthesis of two novel types of π-expanded coumarins has been developed. Modified Knoevenagel bis-condensation afforded 3,9-dioxa-perylene-2,8-diones. Subsequent oxidative aromatic coupling or light driven electrocyclization reaction led to dibenzo-1,7-dioxacoronene-2,8-dione. Unparalleled synthetic simplicity, straightforward purification and superb optical properties have the potential to bring these perylene and coronene analogs towards various applications.
Proteins are amphiphilic and adsorb at liquid interfaces. Therefore, they can be efficient stabilizers of foams and emulsions. β-lactoglobulin (BLG) is one of the most widely studied proteins due to its major industrial applications, in particular in food technology.
In the present work, the influence of different bulk concentration, solution pH and ionic strength on the dynamic and equilibrium pressures of BLG adsorbed layers at the solution/tetradecane (W/TD) interface has been investigated. Dynamic interfacial pressure (Π) and interfacial dilational elastic modulus (E’) of BLG solutions for various concentrations at three different pH values of 3, 5 and 7 at a fixed ionic strength of 10 mM and for a selected fixed concentration at three different ionic strengths of 1 mM, 10 mM and 100 mM are measured by Profile Analysis Tensiometer PAT-1 (SINTERFACE Technologies, Germany). A quantitative data analysis requires additional consideration of depletion due to BLG adsorption at the interface at low protein bulk concentrations. This fact makes experiments more efficient when oil drops are studied in the aqueous protein solutions rather than solution drops formed in oil. On the basis of obtained experimental data, concentration dependencies and the effect of solution pH on the protein surface activity was qualitatively analysed. In the presence of 10 mM buffer, we observed that generally the adsorbed amount is increasing with increasing BLG bulk concentration for all three pH values. The adsorption kinetics at pH 5 result in the highest Π values at any time of adsorption while it exhibits a less active behaviour at pH 3.
Since the experimental data have not been in a good agreement with the classical diffusion controlled model due to the conformational changes which occur when the protein molecules get in contact with the hydrophobic oil phase in order to adapt to the interfacial environment, a new theoretical model is proposed here. The adsorption kinetics data were analysed with the newly proposed model, which is the classical diffusion model but modified by assuming an additional change in the surface activity of BLG molecules when adsorbing at the interface. This effect can be expressed through the adsorption activity constant in the corresponding equation of state. The dilational visco-elasticity of the BLG adsorbed interfacial layers is determined from measured dynamic interfacial tensions during sinusoidal drop area variations. The interfacial tension responses to these harmonic drop oscillations are interpreted with the same thermodynamic model which is used for the corresponding adsorption isotherm.
At a selected BLG concentration of 2×10-6 mol/l, the influence of the ionic strength using different buffer concentration of 1, 10 and 100 mM on the interfacial pressure was studied. It is affected weakly at pH 5, whereas it has a strong impact by increasing buffer concentration at pH 3 and 7. In conclusion, the structure formation of BLG adsorbed layer in the early stage of adsorption at the W/TD interface is similar to those of the solution/air (W/A) surface. However, the equation of state at the W/TD interface provides an adsorption activity constant which is almost two orders of magnitude higher than that for the solution/air surface.
At the end of this work, a new experimental tool called Drop and Bubble Micro Manipulator DBMM (SINTERFACE Technologies, Germany) has been introduced to study the stability of protein covered bubbles against coalescence. Among the available protocols the lifetime between the moment of contact and coalescence of two contacting bubble is determined for different BLG concentrations. The adsorbed amount of BLG is determined as a function of time and concentration and correlates with the observed coalescence behaviour of the contacting bubbles.
In the context of an increasing population of aging people and a shift of medical paradigm towards an individualized medicine in health care, nanostructured lanthanides doped sodium yttrium fluoride (NaYF4) represents an exciting class of upconversion nanomaterials (UCNM) which are suitable to bring forward developments in biomedicine and -biodetection. Despite the fact that among various fluoride based upconversion (UC) phosphors lanthanide doped NaYF4 is one of the most studied upconversion nanomaterial, many open questions are still remaining concerning the interplay of the population routes of sensitizer and activator electronic states involved in different luminescence upconversion photophysics as well as the role of phonon coupling. The collective work aims to explore a detailed understanding of the upconversion mechanism in nanoscaled NaYF4 based materials co-doped with several lanthanides, e.g. Yb3+ and Er3+ as the "standard" type upconversion nanoparticles (UCNP) up to advanced UCNP with Gd3+ and Nd3+. Especially the impact of the crystal lattice structure as well as the resulting lattice phonons on the upconversion luminescence was investigated in detail based on different mixtures of cubic and hexagonal NaYF4 nanoscaled crystals. Three synthesis methods, depending on the attempt of the respective central spectroscopic questions, could be accomplished in the following work. NaYF4 based upconversion nanoparticles doped with several combination of lanthanides (Yb3+, Er3+, Gd3+ and Nd3+) were synthesized successfully using a hydrothermal synthesis method under mild conditions as well as a co-precipitation and a high temperature co-precipitation technique. Structural information were gathered by means of X-ray diffraction (XRD), electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy and inductively coupled plasma atomic emission spectrometry (ICP-OES). The results were discussed in detail with relation to the spectroscopic results. A variable spectroscopic setup was developed for multi parameter upconversion luminescence studies at various temperature 4 K to 328 K. Especially, the study of the thermal behavior of upconversion luminescence as well as time resolved area normalized emission spectra were a prerequisite for the detailed understanding of intramolecular deactivation processes, structural changes upon annealing or Gd3+ concentration, and the role of phonon coupling for the upconversion efficiency. Subsequently it became possible to synthesize UCNP with tailored upconversion luminescence properties. In the end, the potential of UCNP for life science application should be enunciated in context of current needs and improvements of a nanomaterial based optical sensors, whereas the "standard" UCNP design was attuned according to the special conditions in the biological matrix. In terms of a better biocompatibility due to a lower impact on biological tissue and higher penetrability for the excitation light. The first step into this direction was to use Nd3+ ions as a new sensitizer in tridoped NaYF4 based UCNP, whereas the achieved absolute and relative temperature sensitivity is comparable to other types of local temperature sensors in the literature.
Photoinduced excitation energy transfer and accompanying charge separation are elucidated for a supramolecular system of a single fullerene covalently linked to six pyropheophorbide-a dye molecules. Molecular dynamics simulations are performed to gain an atomistic picture of the architecture and the surrounding solvent. Excitation energy transfer among the dye molecules and electron transfer from the excited dyes to the fullerene are described by a mixed quantum–classical version of the Förster rate and the semiclassical Marcus rate, respectively. The mean characteristic time of energy redistribution lies in the range of 10 ps, while electron transfer proceeds within 150 ps. In between, on a 20 to 50 ps time-scale, conformational changes take place in the system. This temporal hierarchy of processes guarantees efficient charge separation, if the structure is exposed to a solvent. The fast energy transfer can adopt the dye excitation to the actual conformation. In this sense, the probability to achieve charge separation is large enough since any dominance of unfavorable conformations that exhibit a large dye–fullerene distance is circumvented. And the slow electron transfer may realize an averaging with respect to different conformations. To confirm the reliability of our computations, ensemble measurements on the charge separation dynamics are simulated and a very good agreement with the experimental data is obtained.
Formation of a Eu(III) borate solid species from a weak Eu(III) borate complex in aqueous solution
(2014)
In the presence of polyborates (detected by 11B-NMR) the formation of a weak Eu(III) borate complex (lg β11 ∼ 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid.
A feasible approach to construct multilayer films of sulfonated polyanilines – PMSA1 and PABMSA1 – containing different ratios of aniline, 2-methoxyaniline-5-sulfonic acid (MAS) and 3-aminobenzoic acid (AB), with the entrapped redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on Au and ITO electrode surfaces, is described. The formation of layers has been followed and confirmed by electrochemical impedance spectroscopy (EIS), which demonstrates that the multilayer assembly can be achieved in a progressive and uniform manner. The gold and ITO electrodes subsequently modified with PMSA1:PQQ-GDH and PABMSA1 films are studied by cyclic voltammetry (CV) and UV-Vis spectroscopy which show a significant direct bioelectrocatalytical response to the oxidation of the substrate glucose without any additional mediator. This response correlates linearly with the number of deposited layers. Furthermore, the constructed polymer/enzyme multilayer system exhibits a rather good long-term stability, since the catalytic current response is maintained for more than 60% of the initial value even after two weeks of storage. This verifies that a productive interaction of the enzyme embedded in the film of substituted polyaniline can be used as a basis for the construction of bioelectronic units, which are useful as indicators for processes liberating glucose and allowing optical and electrochemical transduction.
As an engineering material derived from renewable resources, wood possesses excellent mechanical properties in view of its light weight but also has some disadvantages such as low dimensional stability upon moisture changes and low durability against biological attack. Polymerization of hydrophobic monomers in the cell wall is one of the potential approaches to improve the dimensional stability of wood. A major challenge is to insert hydrophobic monomers into the hydrophilic environment of the cell walls, without increasing the bulk density of the material due to lumen filling. Here, we report on an innovative and simple method to insert styrene monomers into tosylated cell walls (i.e. –OH groups from natural wood polymers are reacted with tosyl chloride) and carry out free radical polymerization under relatively mild conditions, generating low wood weight gains. In-depth SEM and confocal Raman microscopy analysis are applied to reveal the distribution of the polystyrene in the cell walls and the lumen. The embedding of polystyrene in wood results in reduced water uptake by the wood cell walls, a significant increase in dimensional stability, as well as slightly improved mechanical properties measured by nanoindentation.
In this thesis, a route to temperature-, pH-, solvent-, 1,2-diol-, and protein-responsive sensors made of biocompatible and low-fouling materials is established. These sensor devices are based on the sensitivemodulation of the visual band gap of a photonic crystal (PhC), which is induced by the selective binding of analytes, triggering a volume phase transition.
The PhCs introduced by this work show a high sensitivity not only for small biomolecules, but also for large analytes, such as glycopolymers or proteins. This enables the PhC to act as a sensor that detects analytes without the need of complex equipment.
Due to their periodical dielectric structure, PhCs prevent the propagation of specific wavelengths. A change of the periodicity parameters is thus indicated by a change in the reflected wavelengths. In the case explored, the PhC sensors are implemented as periodically structured responsive hydrogels in formof an inverse opal.
The stimuli-sensitive inverse opal hydrogels (IOHs) were prepared using a sacrificial opal template of monodispersed silica particles. First, monodisperse silica particles were assembled with a hexagonally packed structure via vertical deposition onto glass slides. The obtained silica crystals, also named colloidal crystals (CCs), exhibit structural color. Subsequently, the CCs templates were embedded in polymer matrix with low-fouling properties. The polymer matrices were composed of oligo(ethylene glycol) methacrylate derivatives (OEGMAs) that render the hydrogels thermoresponsive. Finally, the silica particles were etched, to produce highly porous hydrogel replicas of the CC. Importantly, the inner structure and thus the ability for light diffraction of the IOHs formed was maintained.
The IOH membrane was shown to have interconnected pores with a diameter as well as interconnections between the pores of several hundred nanometers. This enables not only the detection of small analytes, but also, the detection of even large analytes that can diffuse into the nanostructured IOH membrane. Various recognition unit – analyte model systems, such as benzoboroxole – 1,2-diols, biotin – avidin and mannose – concanavalin A, were studied by incorporating functional
comonomers of benzoboroxole, biotin and mannose into the copolymers. The incorporated recognition units specifically bind to certain low and highmolar mass biomolecules, namely to certain saccharides, catechols, glycopolymers or proteins.
Their specific binding strongly changes the overall hydrophilicity, thus modulating the swelling of the IOH matrices, and in consequence, drastically changes their internal periodicity. This swelling is amplified by the thermoresponsive properties of the polymer matrix. The shift of the interference band gap due to the specific molecular recognition is easily visible by the naked eye (up to 150 nm shifts). Moreover, preliminary trial were attempted to detect even larger entities. Therefore anti-bodies were immobilized on hydrogel platforms via polymer-analogous esterification. These platforms incorporate comonomers made of tri(ethylene glycol) methacrylate end-functionalized with a carboxylic acid. In these model systems, the bacteria analytes are too big to penetrate into the IOH membranes, but can only interact with their surfaces. The selected model bacteria, as Escherichia coli, show a specific affinity to anti-body-functionalized hydrogels. Surprisingly in the case functionalized IOHs, this study produced weak color shifts, possibly opening a path to detect directly living organism, which will need further investigations.
This paper is focused on the temperature dependent synthesis of gold nanotriangles in a vesicular template phase, containing phosphatidylcholin and AOT, by adding the strongly alternating polyampholyte PalPhBisCarb.
UV-vis absorption spectra in combination with TEM micrographs show that flat gold nanoplatelets are formed predominantly in presence of the polyampholyte at 45 °C. The formation of triangular and hexagonal nanoplatelets can be directly influenced by the kinetic approach, i.e., by varying the polyampholyte dosage rate at 45 °C. Corresponding zeta potential measurements indicate that a temperature dependent adsorption of the polyampholyte on the {111} faces will induce the symmetry breaking effect, which is responsible for the kinetically controlled hindered vertical and preferred lateral growth of the nanoplatelets.
Materials derived from renewable resources are highly desirable in view of more sustainable manufacturing. Among the available natural materials, wood is one of the key candidates, because of its excellent mechanical properties. However, wood and wood-based materials in engineering applications suffer from various restraints, such as dimensional instability upon humidity changes. Several wood modification treatments increase water repellence, but the insertion of hydrophobic polymers can result in a composite material which cannot be considered as renewable anymore. In this study, we report on the grafting of the fully biodegradable poly(ε-caprolactone) (PCL) inside the wood cell walls by Sn(Oct)2 catalysed ring-opening polymerization (ROP). The presence of polyester chains within the wood cell wall structure is monitored by confocal Raman imaging and spectroscopy as well as scanning electron microscopy. Physical tests reveal that the modified wood is more hydrophobic due to the bulking of the cell wall structure with the polyester chains, which results in a novel fully biodegradable wood material with improved dimensional stability.
A new functional luminescent lanthanide complex (LLC) has been synthesized with terbium as a central lanthanide ion and biotin as a functional moiety. Unlike in typical lanthanide complexes assembled via carboxylic moieties, in the presented complex, four phosphate groups are chelating the central lanthanide ion. This special chemical assembly enhances the complex stability in phosphate buffers conventionally used in biochemistry. The complex synthesis strategy and photophysical properties are described as well as the performance in time-resolved Förster Resonance Energy Transfer (FRET) assays. In those assays, this biotin-LLC transferred energy either to acceptor organic dyes (Cy5 or AF680) labelled on streptavidin or to quantum dots (QD655 or QD705) surface-functionalised with streptavidins. The permanent spatial donor–acceptor proximity is assured through strong and stable biotin–streptavidin binding. The energy transfer is evidenced from the quenching observed in donor emission and from a decrease in donor luminescence decay, both associated with simultaneous increase in acceptor intensity and in the decay time. The dye-based assays are realised in TRIS and in PBS, whereas QD-based systems are studied in borate buffer. The delayed emission analysis allows for quantifying the recognition process and for auto-fluorescence-free detection, which is particularly relevant for application in bioanalysis. In accordance with Förster theory, Förster-radii (R0) were found to be around 60 Å for organic dyes and around 105 Å for QDs. The FRET efficiency (η) reached 80% and 25% for dye and QD acceptors, respectively. Physical donor–acceptor distances (r) have been determined in the range 45–60 Å for organic dye acceptors, while for acceptor QDs between 120 Å and 145 Å. This newly synthesised biotin-LLC extends the class of highly sensitive analytical tools to be applied in the bioanalytical methods such as time-resolved fluoroimmunoassays (TR-FIA), luminescent imaging and biosensing.
In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (>1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1% up to 28% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.
Neue Systeme für triphile, fluorkohlenstofffreie Blockcopolymere in Form von Acrylat-basierten thermoresponsiven Blockcopolymeren sowie Acrylat- bzw. Styrol-basierten Terblock-Polyelektrolyten mit unterschiedlich chaotropen Kationen des jeweiligen polyanionischen Blocks wurden entwickelt. Multikompartiment-Mizellen, mizellare Aggregate mit ultrastrukturiertem hydrophobem Mizellkern die biologischen Strukturen wie dem Humanalbumin nachempfunden sind, sollten bei der Selbstorganisation in wässriger Umgebung entstehen. Durch Verwendung apolarer und polarer Kohlenwasserstoff-Domänen anstelle von fluorophilen Fluorkohlenstoff-Domänen sollte erstmals anhand solcher triphilen Systeme nachgewiesen werden, ob diese in der Lage zur selektiven Aufnahme hydrophober Substanzen in unterschiedliche Domänen des Mizellkerns sind.
Mit Hilfe von sequentieller RAFT-Polymerisation wurden diese neuen triphilen Systeme hergestellt, die über einen permanent hydrophilen, eine permanent stark hydrophoben und einen dritten Block verfügen, der durch externe Einflüsse, speziell die Induzierung eines thermischen Coil-to-globule-Übergangs bzw. die Zugabe von organischen, hydrophoben Gegenionen von einem wasserlöslichen in einen polar-hydrophoben Block umgewandelt werden kann. Als RAFT-Agens wurde 4-(Trimethylsilyl)benzyl(3-(trimethylsilyl)-propyl)-trithiocarbonat mit zwei unterschiedlichen TMS-Endgruppen verwendet, das kontrollierte Reaktions-bedingungen sowie die molekulare Charakterisierung der komplexen Copolymere ermöglichte.
Die beiden Grundtypen der linearen ternären Blockcopolymere wurden jeweils in zwei 2 Modell-Systeme, die geringfügig in ihren chemischen Eigenschaften sowie in dem Blocklängenverhältnis von hydrophilen und hydrophoben Polymersegmenten variierten, realisiert und unterschiedliche Permutation der Blöcke aufwiesen.
Als ersten Polymertyp wurden amphiphile thermoresponsive Blockcopolymere verwendet. Modell-System 1 bestand aus dem permanent hydrophoben Block Poly(1,3-Bis(butylthio)-prop-2-yl-acrylat), permanent hydrophilen Block Poly(Oligo(ethylenglykol)monomethyletheracrylat) und den thermoresponsiven Block Poly(N,N‘-Diethylacrylamid), dessen Homopolymer eine LCST-Phasenübergang (LCST, engl.: lower critical solution temperature) bei ca. 36°C aufweist. Das Modell-System 2 bestand aus dem permanent hydrophilen Block Poly(2-(Methylsulfinyl)ethylacrylat), dem permanent hydrophoben Block Poly(2-Ethylhexylacrylat) und wiederum Poly(N,N‘-Diethylacrylamid). Im ternären Blockcopolymer erhöhte sich, je nach Blocksequenz und relativen Blocklängen, der LCST-Übergang auf 50 – 65°C. Bei der Untersuchung der Selbstorganisation für die Polymer-Systeme dieses Typs wurde die Temperatur variiert, um verschieden mizellare Überstrukturen in wässriger Umgebung zu erzeugen bzw. oberhalb des LCST-Übergangs Multikompartiment-Mizellen nachzuweisen. Die Unterschiede in der Hydrophilie bzw. den sterischen Ansprüche der gewählten hydrophilen Blöcke sowie die Variation der jeweiligen Blocksequenzen ermöglichte darüber hinaus die Bildung verschiedenster Morphologien mizellarer Aggregate.
Der zweite Typ basierte auf ein Terblock-Polyelektrolyt-System mit Polyacrylaten bzw. Polystyrolen als Polymerrückgrat. Polymere ionische Flüssigkeiten wurden als Vorlage der Entwicklung zweier Modell-Systeme genommen. Eines der beiden Systeme bestand aus dem permanent hydrophilen Block Poly(Oligo(ethylenglykol)monomethyletheracrylat, dem permanent hydrophoben Block Poly(2-Ethylhexylacrylat) sowie dem Polyanion-Block Poly(3-Sulfopropylacrylat). Die Hydrophobie des Polyanion-Blocks variierte durch Verwendung großer organischer Gegenionen, nämlich Tetrabutylammonium, Tetraphenylphosphonium und Tetraphenylstibonium.
Analog wurde in einem weiteren System aus dem permanent hydrophilen Block Poly(4-Vinylbenzyltetrakis(ethylenoxy)methylether), dem permanent hydrophoben Block Poly(para-Methylstyrol) und Poly(4-Styrolsulfonat) mit den entsprechenden Gegenionen gebildet. Aufgrund unterschiedlicher Kettensteifigkeit in beiden Modell-Systemen sollte es bei der Selbstorganisation der mizellarer Aggregate zu unterschiedlichen Überstrukturen kommen.
Mittels DSC-Messungen konnte nachgewiesen werden, dass für alle Modell-Systeme die Blöcke in Volumen-Phase miteinander inkompatibel waren, was eine Voraussetzung für Multikompartimentierung von mizellaren Aggregaten ist. Die Größe mizellarer Aggregate sowie der Einfluss externer Einflüsse wie der Veränderung der Temperatur bzw. der Hydrophobie und Größe von Gegenionen auf den hydrodynamischen Durchmesser mittels DLS-Untersuchungen wurden für alle Modell-Systeme untersucht. Die Ergebnisse zu den thermoresponsiven ternären Blockcopolymeren belegten , dass sich oberhalb der Phasenübergangstemperatur des thermoresponsiven Blocks die Struktur der mizellaren Aggregate änderte, indem der p(DEAm)-Block scheinbar kollabierte und so zusammen mit den permanent hydrophoben Block den jeweiligen Mizellkern bildete. Nach gewisser Equilibrierungszeit konnten bei Raumtemperatur dir ursprünglichen mizellaren Strukturen regeneriert werden. Hingegen konnte für die Terblock-Polyelektrolyt-Systeme bei Verwendung der unterschiedlich hydrophoben Gegenionen kein signifikanter Unterschied in der Größe der mizellaren Aggregate beobachtet werden.
Zur Abbildung der mizellaren Aggregate mittels kryogene Transmissionselektronenmikroskopie (cryo-TEM) der mizellaren Aggregate war mit Poly(1,3-Bis(butylthio)-prop-2-yl-acrylat) ein Modell-System so konzipiert, dass ein erhöhter Elektronendichtekontrast durch Schwefel-Atome die Visualisierung ultrastrukturierter hydrophober Mizellkerne ermöglichte. Dieser Effekt sollte in den Terblock-Polyelektrolyt-Systemen auch durch die Gegenionen Tetraphenylphosphonium und Tetraphenylstibonium nachgestellt werden. Während bei den thermoresponsiven Systemen auch oberhalb des Phasenübergangs kein Hinweis auf Ultrastrukturierung beobachtet wurde, waren für die Polyelektrolyt-Systeme, insbesondere im Fall von Tetraphenylstibonium als Gegenion Überstrukturen zu erkennen. Der Nachweis der Bildung von Multikompartiment-Mizellen war für beide Polymertypen mit dieser abbildenden Methode nicht möglich. Die Unterschiede in der Elektronendichte einzelner Blöcke müsste möglicherweise weiter erhöht werden um Aussagen diesbezüglich zu treffen.
Die Untersuchung von ortsspezifischen Solubilisierungsexperimenten mit solvatochromen Fluoreszenzfarbstoffen mittels „steady-state“-Fluoreszenzspektroskopie durch Vergleich der Solubilisierungsorte der Terblockcopolymere bzw. –Polyelektrolyte mit den jeweiligen Solubilisierungsorten von Homopolymer- und Diblock-Vorstufen sollten den qualitativen Nachweis der Multikompartimentierung erbringen. Aufgrund der geringen Mengen an Farbstoff, die für die Solubilisierungsexperimente eingesetzt wurden zeigten DLS-Untersuchungen keine störenden Effekte der Sonden auf die Größe der mizellaren Aggregate. Jedoch erschwerten Quench-Effekte im Falle der Polyelektrolyt Modell-Systeme eine klare Interpretation der Daten. Im Falle der Modell-Systeme der thermoresponsiven Blockcopolymere waren dagegen deutliche solvatochrome Effekte zwischen der Solubilisierung in den mizellaren Aggregaten unterhalb und oberhalb des Phasenübergangs zu erkennen. Dies könnte ein Hinweis auf Multikompartimentierung oberhalb des LCST-Übergangs sein. Ohne die Informationen einer Strukturanalyse wie z.B. der Röntgen- oder Neutronenkleinwinkelstreuung (SAXS oder SANS), kann nicht abschließend geklärt werden, ob die Solubilisierung in mizellaren hydrophoben Domänen des kollabierten Poly(N,N‘-Diethylacrylamid) erfolgt oder in einer Mischform von mizellaren Aggregaten mit gemittelter Polarität.
The aim of this thesis was the elucidation of different ionization methods (resonance-enhanced multiphoton ionization – REMPI, electrospray ionization – ESI, atmospheric pressure chemical ionization – APCI) in ion mobility (IM) spectrometry. In order to gain a better understanding of the ionization processes, several spectroscopic, mass spectrometric and theoretical methods were also used. Another focus was the development of experimental techniques, including a high resolution spectrograph and various combinations of IM and mass spectrometry.
The novel high resolution 2D spectrograph facilitates spectroscopic resolutions in the range of commercial echelle spectrographs. The lowest full width at half maximum of a peak achieved was 25 pm. The 2D spectrograph is based on the wavelength separation of light by the combination of a prism and a grating in one dimension, and an etalon in the second dimension. This instrument was successfully employed for the acquisition of Raman and laser-induced breakdown spectra.
Different spectroscopic methods (light scattering and fluorescence spectroscopy) permitting a spatial as well as spectral resolution, were used to investigate the release of ions in the electrospray. The investigation is based on the 50 nm shift of the fluorescence band of rhodamine 6G ions of during the transfer from the electrospray droplets to the gas phase.
A newly developed ionization chamber operating at reduced pressure (0.5 mbar) was coupled to a time-of-flight mass spectrometer. After REMPI of H2S, an ionization chemistry analogous to H2O was observed with this instrument. Besides H2S+ and its fragments, H3S+ and protonated analyte ions could be observed as a result of proton-transfer reactions.
For the elucidation of the peaks in IM spectra, a combination of IM spectrometer and linear quadrupole ion trap mass spectrometer was developed. The instrument can be equipped with various ionization sources (ESI, REMPI, APCI) and was used for the characterization of the peptide bradykinin and the neuroleptic promazine.
The ionization of explosive compounds in an APCI source based on soft x-radiation was investigated in a newly developed ionization chamber attached to the ion trap mass spectrometer. The major primary and secondary reactions could be characterized and explosive compound ions could be identified and assigned to the peaks in IM spectra. The assignment is based on the comparison of experimentally determined and calculated IM. The methods of calculation currently available exhibit large deviations, especially in the case of anions. Therefore, on the basis of an assessment of available methods, a novel hybrid method was developed and characterized.
Polysarcosine (Mn = 3650–20 000 g mol−1, Đ ∼ 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.
The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using Förster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.
In this paper, we show experimentally that inside a microfluidic device, where the reactants are segregated, the reaction rate of an autocatalytic clock reaction is accelerated in comparison to the case where all the reactants are well mixed. We also find that, when mixing is enhanced inside the microfluidic device by introducing obstacles into the flow, the clock reaction becomes slower in comparison to the device where mixing is less efficient. Based on numerical simulations, we show that this effect can be explained by the interplay of nonlinear reaction kinetics (cubic autocatalysis) and differential diffusion, where the autocatalytic species diffuses slower than the substrate.
We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.
Derivatization of fullerene (C60) with branched aliphatic chains softens C60-based materials and enables the formation of thermotropic liquid crystals and room temperature nonvolatile liquids. This work demonstrates that by carefully tuning parameters such as type, number and substituent position of the branched chains, liquid crystalline C60 materials with mesophase temperatures suited for photovoltaic cell fabrication and room temperature nonvolatile liquid fullerenes with tunable viscosity can be obtained. In particular, compound 1, with branched chains, exhibits a smectic liquid crystalline phase extending from 84 °C to room temperature. Analysis of bulk heterojunction (BHJ) organic solar cells with a ca. 100 nm active layer of compound 1 and poly(3-hexylthiophene) (P3HT) as an electron acceptor and an electron donor, respectively, reveals an improved performance (power conversion efficiency, PCE: 1.6 ± 0.1%) in comparison with another compound, 10 (PCE: 0.5 ± 0.1%). The latter, in contrast to 1, carries linear aliphatic chains and thus forms a highly ordered solid lamellar phase at room temperature. The solar cell performance of 1 blended with P3HT approaches that of PCBM/P3HT for the same active layer thickness. This indicates that C60 derivatives bearing branched tails are a promising class of electron acceptors in soft (flexible) photovoltaic devices.
A water soluble fluorescent polymer as a dual colour sensor for temperature and a specific protein
(2013)
We present two thermoresponsive water soluble copolymers prepared via free radical statistical copolymerization of N-isopropylacrylamide (NIPAm) and of oligo(ethylene glycol) methacrylates (OEGMAs), respectively, with a solvatochromic 7-(diethylamino)-3-carboxy-coumarin (DEAC)- functionalized monomer. In aqueous solutions, the NIPAm-based copolymer exhibits characteristic changes in its fluorescence profile in response to a change in solution temperature as well as to the presence of a specific protein, namely an anti-DEAC antibody. This polymer emits only weakly at low temperatures, but exhibits a marked fluorescence enhancement accompanied by a change in its emission colour when heated above its cloud point. Such drastic changes in the fluorescence and absorbance spectra are observed also upon injection of the anti-DEAC antibody, attributed to the specific binding of the antibody to DEAC moieties. Importantly, protein binding occurs exclusively when the polymer is in the well hydrated state below the cloud point, enabling a temperature control on the molecular recognition event. On the other hand, heating of the polymer–antibody complexes releases a fraction of the bound antibody. In the presence of the DEAC-functionalized monomer in this mixture, the released antibody competitively binds to the monomer and the antibody-free chains of the polymer undergo a more effective collapse and inter-aggregation. In contrast, the emission properties of the OEGMA-based analogous copolymer are rather insensitive to the thermally induced phase transition or to antibody binding. These opposite behaviours underline the need for a carefully tailored molecular design of responsive polymers aimed at specific applications, such as biosensing.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as “activation agents” with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this “induced carbonization” and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
Continuous synthesis of pyridocarbazoles and initial photophysical and bioprobe characterization
(2013)
Pyridocarbazoles when ligated to transition metals yield high affinity kinase inhibitors. While batch photocyclizations enable the synthesis of these heterocycles, the non-oxidative Mallory reaction only provides modest yields and difficult to purify mixtures. We demonstrate here that a flow-based Mallory cyclization provides superior results and enables observation of a clear isobestic point. The flow method allowed us to rapidly synthesize ten pyridocarbazoles and for the first time to document their interesting photophysical attributes. Preliminary characterization reveals that these molecules might be a new class of fluorescent bioprobe.
Calcium phosphate nanofibers with a diameter of only a few nanometers and a cotton-ball-like aggregate morphology have been reported several times in the literature. Although fiber formation seems reproducible in a variety of conditions, the crystal structure and chemical composition of the fibers have been elusive. Using scanning transmission electron microscopy, low dose electron (nano)diffraction, energy-dispersive X-ray spectroscopy, and energy-filtered transmission electron microscopy, we have assigned crystal structures and chemical compositions to the fibers. Moreover, we demonstrate that the mineralization process yields true polymer/calcium phosphate hybrid materials where the block copolymer template is closely associated with the calcium phosphate.
A polymer analogous reaction for the formation of imidazolium and NHC based porous polymer networks
(2013)
A polymer analogous reaction was carried out to generate a porous polymeric network with N-heterocyclic carbenes (NHC) in the polymer backbone. Using a stepwise approach, first a polyimine network is formed by polymerization of the tetrafunctional amine tetrakis(4-aminophenyl)methane. This polyimine network is converted in the second step into polyimidazolium chloride and finally to a polyNHC network. Furthermore a porous Cu(II)-coordinated polyNHC network can be generated. Supercritical drying generates polymer networks with high permanent surface areas and porosities which can be applied for different catalytic reactions. The catalytic properties were demonstrated for example in the activation of CO2 or in the deoxygenation of sulfoxides to the corresponding sulfides.
4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4’-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.
Under standard conditions the cross metathesis of allyl alcohols and methyl acrylate is accompanied by the formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross metathesis and by adding a base or silane as chemical triggers.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
Foam fractionation of surfactant and protein solutions is a process dedicated to separate surface active molecules from each other due to their differences in surface activities. The process is based on forming bubbles in a certain mixed solution followed by detachment and rising of bubbles through a certain volume of this solution, and consequently on the formation of a foam layer on top of the solution column. Therefore, systematic analysis of this whole process comprises of at first investigations dedicated to the formation and growth of single bubbles in solutions, which is equivalent to the main principles of the well-known bubble pressure tensiometry. The second stage of the fractionation process includes the detachment of a single bubble from a pore or capillary tip and its rising in a respective aqueous solution. The third and final stage of the process is the formation and stabilization of the foam created by these bubbles, which contains the adsorption layers formed at the growing bubble surface, carried up and gets modified during the bubble rising and finally ends up as part of the foam layer.
Bubble pressure tensiometry and bubble profile analysis tensiometry experiments were performed with protein solutions at different bulk concentrations, solution pH and ionic strength in order to describe the process of accumulation of protein and surfactant molecules at the bubble surface. The results obtained from the two complementary methods allow understanding the mechanism of adsorption, which is mainly governed by the diffusional transport of the adsorbing protein molecules to the bubble surface. This mechanism is the same as generally discussed for surfactant molecules. However, interesting peculiarities have been observed for protein adsorption kinetics at sufficiently short adsorption times. First of all, at short adsorption times the surface tension remains constant for a while before it decreases as expected due to the adsorption of proteins at the surface. This time interval is called induction time and it becomes shorter with increasing protein bulk concentration. Moreover, under special conditions, the surface tension does not stay constant but even increases over a certain period of time. This so-called negative surface pressure was observed for BCS and BLG and discussed for the first time in terms of changes in the surface conformation of the adsorbing protein molecules. Usually, a negative surface pressure would correspond to a negative adsorption, which is of course impossible for the studied protein solutions. The phenomenon, which amounts to some mN/m, was rather explained by simultaneous changes in the molar area required by the adsorbed proteins and the non-ideality of entropy of the interfacial layer. It is a transient phenomenon and exists only under dynamic conditions.
The experiments dedicated to the local velocity of rising air bubbles in solutions were performed in a broad range of BLG concentration, pH and ionic strength. Additionally, rising bubble experiments were done for surfactant solutions in order to validate the functionality of the instrument. It turns out that the velocity of a rising bubble is much more sensitive to adsorbing molecules than classical dynamic surface tension measurements. At very low BLG or surfactant concentrations, for example, the measured local velocity profile of an air bubble is changing dramatically in time scales of seconds while dynamic surface tensions still do not show any measurable changes at this time scale. The solution’s pH and ionic strength are important parameters that govern the measured rising velocity for protein solutions. A general theoretical description of rising bubbles in surfactant and protein solutions is not available at present due to the complex situation of the adsorption process at a bubble surface in a liquid flow field with simultaneous Marangoni effects. However, instead of modelling the complete velocity profile, new theoretical work has been started to evaluate the maximum values in the profile as characteristic parameter for dynamic adsorption layers at the bubble surface more quantitatively.
The studies with protein-surfactant mixtures demonstrate in an impressive way that the complexes formed by the two compounds change the surface activity as compared to the original native protein molecules and therefore lead to a completely different retardation behavior of rising bubbles. Changes in the velocity profile can be interpreted qualitatively in terms of increased or decreased surface activity of the formed protein-surfactant complexes. It was also observed that the pH and ionic strength of a protein solution have strong effects on the surface activity of the protein molecules, which however, could be different on the rising bubble velocity and the equilibrium adsorption isotherms. These differences are not fully understood yet but give rise to discussions about the structure of protein adsorption layer under dynamic conditions or in the equilibrium state.
The third main stage of the discussed process of fractionation is the formation and characterization of protein foams from BLG solutions at different pH and ionic strength. Of course a minimum BLG concentration is required to form foams. This minimum protein concentration is a function again of solution pH and ionic strength, i.e. of the surface activity of the protein molecules. Although at the isoelectric point, at about pH 5 for BLG, the hydrophobicity and hence the surface activity should be the highest, the concentration and ionic strength effects on the rising velocity profile as well as on the foamability and foam stability do not show a maximum. This is another remarkable argument for the fact that the interfacial structure and behavior of BLG layers under dynamic conditions and at equilibrium are rather different. These differences are probably caused by the time required for BLG molecules to adapt respective conformations once they are adsorbed at the surface.
All bubble studies described in this work refer to stages of the foam fractionation process. Experiments with different systems, mainly surfactant and protein solutions, were performed in order to form foams and finally recover a solution representing the foamed material. As foam consists to a large extent of foam lamella – two adsorption layers with a liquid core – the concentration in a foamate taken from foaming experiments should be enriched in the stabilizing molecules. For determining the concentration of the foamate, again the very sensitive bubble rising velocity profile method was applied, which works for any type of surface active materials. This also includes technical surfactants or protein isolates for which an accurate composition is unknown.
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
The time-dependent approach to electronic spectroscopy, as popularized by Heller and coworkers in the 1980's, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption, emission and resonance Raman spectra of several diamondoids. Two-state models, the harmonic and the Condon approximations, are used for the calculations, making them easily applicable to larger molecules. The method is applied to nine pristine lower and higher diamondoids: adamantane, diamantane, triamantane, and three isomers each of tetramantane and pentamantane. We also consider a hybrid species “Dia = Dia” – a shorthand notation for a recently synthesized molecule comprising two diamantane units connected by a C[double bond, length as m-dash]C double bond. We resolve and interpret trends in optical and vibrational properties of these molecules as a function of their size, shape, and symmetry, as well as effects of “blending” with sp2-hybridized C-atoms. Time-dependent correlation functions facilitate the computations and shed light on the vibrational dynamics following electronic transitions.
We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.
A Co(II)–imidazolate-4-amide-5-imidate based MOF, IFP-5, is synthesized by using an imidazolate anion-based novel ionic liquid as a linker precursor under solvothermal conditions. IFP-5 shows significant amounts of gas (N2, CO2, CH4 and H2) uptake capacities. IFP-5 exhibits an independent high spin Co(II) centre and antiferromagnetic coupling.
A rare example of in situ linker generation with the formation of soft porous Zn- and Co-MOFs (IFP-9 and -10, respectively) is reported. The flexible ethoxy groups of IFP-9 and -10 protrude into the 1D hexagonal channels. The gas-sorption behavior of both materials for H2, CO2 and CH4 showed wide hysteretic isotherms, typical for MOFs having a flexible substituent which can give rise to a gate effect.
En route towards advanced catalyst materials for the electrocatalytic water splitting reaction
(2016)
The thesis on hand deals with the development of new types of catalysts based on pristine metals and ceramic materials and their application as catalysts for the electrocatalytic water splitting reaction. In order to breathe life into this technology, cost-efficient, stable and efficient catalysts are imploringly desired. In this manner, the preparation of Mn-, N-, S-, P-, and C-containing nickel materials has been investigated together with the theoretical and electrochemical elucidation of their activity towards the hydrogen (and oxygen) evolution reaction. The Sabatier principle has been used as the principal guideline towards successful tuning of catalytic sites. Furthermore, two pathways have been chosen to ameliorate the electrocatalytic performance, namely, the direct improvement of intrinsic properties through appropriate material selection and secondly the increase of surface area of the catalytic material with an increased amount of active sites. In this manner, bringing materials with optimized hydrogen adsorption free energy onto high surface area support, catalytic performances approaching the golden standards of noble metals were feasible. Despite varying applied synthesis strategies (wet chemistry in organic solvents, ionothermal reaction, gas phase reaction), one goal has been systematically pursued: to understand the driving mechanism of the growth. Moreover, deeper understanding of inherent properties and kinetic parameters of the catalytic materials has been gained.
In this thesis we investigate the evaporation behaviour of sessile droplets of aqueous saline solutions on planar inert and metallic surfaces and characterise the corrosion phenomenon for iron surfaces. First we study the evaporation behaviour of sessile salty droplets on inert surfaces for a wide range of salt concentrations, relative humidities, droplet sizes and contact angles. Our study reveals the range of validity of the well-accepted diffusion-controlled evaporation model and highlights the impact of salt concentration (surface tension) gradients driven Marangoni flows on the evaporation behaviour and the subsequent salty deposit patterns. Furthermore we study the spatial-temporal evolution of sessile droplets from saline solutions on metallic surfaces. In contrast to the simple, generally accepted Evans droplet model, we show that the corrosion spreads ahead of the macroscopic contact line with a peripheral film. The three-phase contact line is destabilized by surface tension gradients induced by ionic composition changes during the course of the corrosion process and migration of cations towards the droplet perimeter. Finally we investigate the corrosion behaviour under drying salty sessile droplets on metallic surfaces. The corrosion process, in particular the location of anodic and cathodic activities over the footprint droplet area is correlated to the spatial distribution of the salt inside the drying droplet.
Z,E-Diene sind ein häufig auftretendes Strukturmerkmal in Naturstoffen. Aus diesem Grund ist die einfache Darstellung dieser Struktureinheit von großen Interesse in der organischen Chemie.
Das erste Ziel der vorliegenden Arbeit war daher die Weiterentwicklung der Ringschlussmetathese-/ baseninduzierten Ringöffnungs-/ Veresterungssequenz (RBRV-Sequenz) zur Synthese von (2Z,4E)-Diencarbonsäureethylestern ausgehend von Butenoaten. Dazu wurde zunächst die RBRV-Sequenz optimiert. Diese aus drei Schritten bestehende Sequenz konnte in einem Eintopf-Verfahren angewendet werden. Die Ringschlussmetathese gelang mit einer Katalysatorbeladung von 1 mol% des GRUBBS-Katalysators der zweiten Generation in Dichlormethan. Für die baseninduzierte Ringöffnung des β,γ-ungesättigten δ Valerolactons wurde NaHMDS verwendet. Die Alkylierung der Carboxylatspezies gelang mit dem MEERWEIN-Reagenz. Die Anwendbarkeit der Sequenz wurde für verschiedene Substrate demonstriert.
Die Erweiterung der Methode auf α-substituierte Butenoate unterlag starken Einschränkungen. So konnte der Zugang für α Hydroxyderivate realisiert werden. Bei der Anwendung der RBRV-Sequenz auf die α-substituierten Butenoate wurde festgestellt, dass diese sich nur in moderaten Ausbeuten umsetzen ließen und zudem nicht selektiv zu den (2E,4E)-konfigurierten α-substituierten-Dienestern reagierten.
Der Einsatz von Eninen unter den Standardbedingungen der RBRV-Sequenz gelang nicht. Erst nach Modifizierung der Sequenz (höhere Katalysatorbeladung, Wechsel des Lösungsmittels) konnten die [3]Dendralen-Produkte in geringen Ausbeuten erhalten werden.
Im zweiten Teil der Arbeit wurde der Einsatz von (2Z,4E)-Diencarbonsäureethylestern in der Totalsynthese von Naturstoffen untersucht. Dazu wurden zunächst die Transformationsmöglichkeiten der Ester geprüft. Es konnte gezeigt werden, dass sich (2Z,4E)-Diencarbonsäureethylester insbesondere zur Synthese von (2Z,4E)-Aldehyden sowie zum Aufbau der (3Z,5E)-Dien-1-in-Struktur eignen.
Anhand dieser Ergebnisse wurde im Anschluss die RBRV-Sequenz in der Totalsynthese eingesetzt. Dazu wurde zunächst der (2Z,4E)-Dienester Microsphaerodiolin in seiner ersten Totalsynthese auf drei verschiedene Routen hergestellt. Im Anschluss wurden sechs verschiedene Polyacetylene mit einer (3Z,5E)-Dien-1-in-Einheit hergestellt. Schlüsselschritte in ihrer Synthese waren immer die RBRV-Sequenz zum Aufbau der Z,E-Dien-Einheit, die Transformation des Esters in ein terminales Alkin sowie die CADIOT-CHODKIEWICZ-Kupplung zum Aufbau unsymmetrischer Polyine. Alle sechs Polyacetylene wurden zum ersten Mal in einer Totalsynthese synthetisiert. Drei Polyacetylene wurden ausgehend von (S)-Butantriol enantiomerenrein dargestellt. Anhand ihrer Drehwerte konnte eine Revision der von YAO und Mitarbeitern vorgenommen Zuordnung der Absolutkonfiguration der Naturstoffe vorgenommen werden.
Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several “onium” cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and gK) of the tensors could be determined and information on the structural changes in the [CuBr4]2- anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.
DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.
Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N′-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of −22 to −71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.
Catalytic amounts of a weak base are sufficient to induce the decomposition of anthracene endoperoxides to anthraquinone. The mechanism has been elucidated by isolation of intermediates in combination with DFT calculations. The whole process is suitable for the convenient generation of hydrogen peroxide under very mild conditions.
Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides
(2015)
The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.
NaYF4:Yb:Er nanoparticles (UCNP) were synthesized under mild experimental conditions to obtain a pure cubic lattice. Upon annealing at different temperatures up to Tan = 700 °C phase transitions to the hexagonal phase and back to the cubic phase were induced. The UCNP materials obtained for different Tan were characterized with respect to the lattice phase using standard XRD and Raman spectroscopy as well as steady state and time resolved upconversion luminescence. The standard techniques showed that for the annealing temperature range 300 °C < Tan < 600 °C the hexagonal lattice phase was dominant. For Tan < 300 °C hardly any change in the lattice phase could be deduced, whereas for Tan > 600 °C a back transfer to the α-phase was observed. Complementarily, the luminescence upconversion properties of the annealed UCNP materials were characterized in steady state and time resolved luminescence measurements. Distinct differences in the upconversion luminescence intensity, the spectral intensity distribution and the luminescence decay kinetics were found for the cubic and hexagonal lattice phases, respectively, corroborating the results of the standard analytical techniques used. In laser power dependent measurements of the upconversion luminescence intensity it was found that the green (G1, G2) and red (R) emission of Er3+ showed different effects of Tan on the number of required photons reflecting the differences in the population routes of different energy levels involved. Furthermore, the intensity ratio of Gfull/R is highly effected by the laser power only when the β-phase is present, whereas the G1/G2 intensity ratio is only slightly effected regardless of the crystal phase. Moreover, based on different upconversion luminescence kinetics characteristics of the cubic and hexagonal phase time-resolved area normalized emission spectra (TRANES) proved to be a very sensitive tool to monitor the phase transition between cubic and hexagonal phases. Based on the TRANES analysis it was possible to resolve the lattice phase transition in more detail for 200 °C < Tan < 300 °C, which was not possible with the standard techniques.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
A multi-reference study of the byproduct formation for a ring-closed dithienylethene photoswitch
(2015)
Photodriven molecular switches are sometimes hindered in their performance by forming byproducts which act as dead ends in sequences of switching cycles, leading to rapid fatigue effects. Understanding the reaction pathways to unwanted byproducts is a prerequisite for preventing them. This article presents a study of the photochemical reaction pathways for byproduct formation in the photochromic switch 1,2-bis-(3-thienyl)-ethene. Specifically, using single- and multi-reference methods the post-deexcitation reaction towards the byproduct in the electronic ground state S0 when starting from the S1–S0 conical intersection (CoIn), is considered in detail. We find an unusual low-energy pathway, which offers the possibility for the formation of a dyotropic byproduct. Several high-energy pathways can be excluded with high probability.
What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer–surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sc—defining the adsorption–desorption transition—are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sc for the concave interfaces versus the Debye screening length 1/k and the extent of confinement a for these three interfaces for small ka values. For large ka the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/k. We also rationalize how sc(k) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption—the effect often hard to tackle theoretically—putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids.
The phase behavior of an amphiphilic block copolymer based on a poly(aspartic acid) hydrophilic block and a poly(n-butyl acrylate) hydrophobic block was investigated at the air–water and air–buffer interface. The polymer forms stable monomolecular films on both subphases. At low pH, the isotherms exhibit a plateau. Compression–expansion experiments and infrared reflection absorption spectroscopy suggest that the plateau is likely due to the formation of polymer bi- or multilayers. At high pH the films remain intact upon compression and no multilayer formation is observed. Furthermore, the mineralization of calcium phosphate beneath the monolayer was studied at different pH. The pH of the subphase and thus the polymer charge strongly affects the phase behavior of the film and the mineral formation. After 4 h of mineralization at low pH, atomic force microscopy shows smooth mineral films with a low roughness. With increasing pH the mineral films become inhomogeneous and the roughness increases. Transmission electron microscopy confirms this: at low pH a few small but uniform particles form whereas particles grown at higher pH are larger and highly agglomerated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the formation of calcium phosphate. The levels of mineralization are higher in samples grown at high pH.
Im Verlauf dieser Arbeit sind Blockcopolymere verschiedener Ladung auf Basis von PEO mit hohen Molekulargewichten durch lebendende freie radikalische Polymerisation hergestellt worden. Die Polymere sind einfach im Grammmaßstab herstellbar. Sie zeigen sowohl einen großen Einfluss auf die Nukleation als auch auf die Auflösung von Calciumphosphat. Gleichwohl scheint das Vorhandensein von positiven Gruppen (Kationen, Ampholyten und Betainen) keinen dramatischen Einfluss auf die Nukleation zu haben.
So verursachen Polymere mit positiven Ladungen die gleiche Retentionwirkung wie solche, die ausschließlich anionische Gruppen enthalten. Aus der Verwendung der kationischen, ampholytischen und betainischen Copolymere resultiert allerdings eine andersartige Morphologie der Niederschläge, als aus der Verwendung der Anionischen hervorgeht. Bei der Stabilisierung einer HAP-Oberfläche setzt sich dieser Trend fort, das heißt, rein anionische Copolymere wirken stärker stabilisierend als solche, die positive Ladungen enthalten. Durch Inkubation von menschlichem Zahnschmelz mit anionischen Copolymeren konnte gezeigt werden, dass die Biofilmbildung verglichen mit einer unbehandelten Zahnoberfläche eingeschränkt abläuft. All dies macht die Polymere zu interessanten Additiven für Zahnpflegeprodukte.
Zusätzlich konnten auf Basis dieser rein anionischen Copolymere Polymerbürsten, ebenfalls über lebendende freie radikalische Polymerisation, hergestellt werden. Diese zeichnen sich durch einen großen Einfluss auf die Kristallphase aus und bilden mit dem CHAP des AB-Types das Material, welches auch in Knochen und Zähnen vorkommt. Erste Cytotoxizitätstests lassen auf das große Potential dieser Polymerbürsten für Beschichtungen in der Medizintechnik schließen.
The size and morphology control of precipitated solid particles is a major economic issue for numerous industries. For instance, it is interesting for the nuclear industry, concerning the recovery of radioactive species from used nuclear fuel.
The precipitates features, which are a key parameter from the post-precipitate processing, depend on the process local mixing conditions. So far, the relationship between precipitation features and hydrodynamic conditions have not been investigated.
In this study, a new experimental configuration consisting of coalescing drops is set to investigate the link between reactive crystallization and hydrodynamics. Two configurations of aqueous drops are examined. The first one corresponds to high contact angle drops (>90°) in oil, as a model system for flowing drops, the second one correspond to sessile drops in air with low contact angle (<25°). In both cases, one reactive is dissolved in each drop, namely oxalic acid and cerium nitrate. When both drops get into contact, they may coalesce; the dissolved species mix and react to produce insoluble cerium oxalate. The precipitates features and effect on hydrodynamics are investigated depending on the solvent. In the case of sessile drops in air, the surface tension difference between the drops generates a gradient which induces a Marangoni flow from the low surface tension drop over the high surface tension drop. By setting the surface tension difference between the two drops and thus the Marangoni flow, the hydrodynamics conditions during the drop coalescence could be modified. Diols/water mixtures are used as solvent, in order to fix the surface tension difference between the liquids of both drops regardless from the reactant concentration. More precisely, the used diols, 1,2-propanediol and 1,3-propanediol, are isomer with identical density and close viscosity. By keeping the water volume fraction constant and playing with the 1,2-propanediol and 1,3-propanediol volume fractions of the solvents, the mixtures surface tensions differ up to 10 mN/m for identical/constant reactant concentration, density and viscosity. 3 precipitation behaviors were identified for the coalescence of water/diols/recatants drops depending on the oxalic excess. The corresponding precipitates patterns are visualized by optical microscopy and the precipitates are characterized by confocal microscopy SEM, XRD and SAXS measurements. In the intermediate oxalic excess regime, formation of periodic patterns can be observed. These patterns consist in alternating cerium oxalate precipitates with distinct morphologies, namely needles and “microflowers”. Such periodic fringes can be explained by a feedback mechanism between convection, reaction and the diffusion.
Diese Arbeit befasst sich mit der ganzheitlichen Betrachtung der Fluideigenschaften eines unterpermischen Reservoirs am Geothermie Forschungsstandort Groß Schönebeck (GrSk) bei Reservoirbedingungen und im Betrieb der Geothermieanlage. Die Untersuchungen zur Fluidherkunft ergeben, dass es sich um ein konnates Wasser meteorischen Ursprungs ohne den Einfluss der darüberliegenden Zechsteinwässer handelt. Die Ionen und Isotopenverhältnisse im Formationswasser gelöster Komponenten in GrSk belegen einen gemeinsamen Genesepfad mit Wässern anderer Rotliegend-Reservoire des Nordostdeutschen Beckens (NEGB). Die Isotopenverhältnisse von ⁸⁷Sr/⁸⁶Sr ≈ 0,7158 und von δ³⁴SV CDT ≈ 4,1 ‰ des Sulfats weisen auf die Anreicherung des Fluids mit schweren Isotopen durch die Fluid Gestein-Wechselwirkung mit Vulkaniten und Rotliegend Sandsteinen des Unteren Perms hin.
Das im Formationswasser bei Reservoirbedingungen gelöste Gas (Gas/Wasser ≤ 2 bei STP) enthält Stickstoff (δ¹⁵NAir ≈ 0,6 ‰) und thermogenes Methan (δ¹³CV-PDB ≈ - 18 ‰) aus organischen Karbonablagerungen (Kerogen Typ - III Kohlen) hoher Reife. Die Isotopenverhältnisse der Edelgase belegen eine krustale Herkunft des Gasgemisches. Die berechnete Verweilzeit τ (⁴He) der Gase im Reservoir liegt zwischen 275 und 317 Ma und überschreitet damit bei gegebener Konzentration von Mutternukliden im Reservoirgestein das allgemein angenommene Zeitalter der Sedimentgruppe. Das lässt sich durch eine Zuwanderung von Gasen aus älteren Sedimentfolgen erklären.
Die Veränderungen der physikochemischen Fluidparameter während des Anlagenbetriebs sind hauptsächlich temperaturbedingt. Bei stabilen Produktionsbedingungen und einer Temperatur von ca. 100 °C stabilisieren sich auch die Fluideigenschaften. Bei In situ Bedingungen übertage beträgt die Dichte ρ = 1,1325 ± 0,0002 g ∙ mL⁻¹, das Redoxpotential Eh = -105,5 ± 1,3 mV und der pH = 6,61 ± 0,002. Die relative Zusammensetzung der Gasphase bei stabilen Produktionsbedingungen zeigt dagegen eine geringe Erhöhung des Stickstoffanteils sowie des Anteils der Kohlenwasserstoffe (Ethan, Propan, usw.) und Abnahme des relativen Methananteils im Laufe des Betriebs.
Die quantitative Untersuchung der sekundären mineralischen Ausfällungen im Fluid mittels sequentieller Extraktion zeigte, dass Schwermetalle als eine Hauptkomponente der Fluidfestphase größtenteils in Verbindung mit organischen Molekülen vorliegen. Experimente zum Einfluss organischer Verbindungen unterschiedlicher Substanzklassen auf eine Mobilisierung der Schwermetalle aus dem Reservoirgestein ergaben, dass die Verbindungen wie Fettsäuren und PAK (polyzyklische aromatische Kohlenwasserstoffe) die Freisetzung von Kupfer, Nickel, Chrom und Blei verhindern bzw. zu derer Immobilisierung beitragen. Im Gegensatz dazu wird die Mobilität von Zink in Anwesenheit von diesen Verbindungen erhöht. Niedermolekulare Monocarbonsäuren und stickstoffhaltige Heteroaromaten tragen, mit Ausnahme von Blei, zur Freisetzung bzw. Mobilisierung von Schwermetallen aus dem Reservoirgestein bei.
Die gewonnenen Erkenntnisse dieser Arbeit bestätigen das Risiko massiver Ausfällungen auf der kalten Seite der Geothermieanlage bei Inbetriebnahme des Kraftwerks, wenn keine an den Fluidchemismus angepassten Präventionsmethoden eingesetzt werden. Die Isotopenzusammensetzung der Fluidkomponenten sowie geringfügige Schwankungen der Gaszusammensetzung im kontinuierlichen Anlagenbetrieb lässt eine Kommunikation des unterpermischen Reservoirs mit dem darunter liegenden Oberkarbon vermuten, was eine nachträgliche Veränderung der Fluidzusammensetzung beim Dauerbetrieb der Anlage bedeuten kann.
Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp2/sp3 hybrid species with C[double bond, length as m-dash]C double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics.
Fluid force microscopy combines the positional accuracy and force sensitivity of an atomic
force microscope (AFM) with nanofluidics via a microchanneled cantilever. However, adequate loading and cleaning procedures for such AFM micropipettes are required for various application situations. Here, a new frontloading procedure is described for an AFM micropipette functioning as a force- and pressure-controlled microscale liquid dispenser. This frontloading
procedure seems especially attractive when using target substances featuring high
costs or low available amounts. Here, the AFM micropipette could be filled from the tip side with liquid from a previously applied droplet with a volume of only a few μL using a short low-pressure pulse. The liquid-loaded AFM micropipettes could be then applied for experiments in air or liquid environments. AFM micropipette frontloading was evaluated with the well-known organic fluorescent dye rhodamine 6G and the AlexaFluor647-labeled antibody goat anti-rat IgG as an example of a larger biological compound. After micropipette usage, specific cleaning procedures were tested. Furthermore, a storage method is described, at which the AFM micropipettes could be stored for a few hours up to several days without drying out or clogging of the microchannel. In summary, the rapid, versatile and cost-efficient
frontloading and cleaning procedure for the repeated usage of a single AFM micropipette is beneficial for various application situations from specific surface modifications through to local manipulation of living cells, and provides a simplified and faster handling for already known experiments with fluid force microscopy.