A class of novel nickel cobalt oxide hollow nanosponges were synthesized through a sodium borohydride reduction strategy. Due to their porous and hollow nanostructures, and synergetic effects between their components, the optimized nickel cobalt oxide nanosponges exhibited excellent catalytic activity towards oxygen evolution reaction.

The mechanisms of interaction between inorganic matter and biomolecules, as well as properties of resulting hybrids, are receiving growing interest due to the rapidly developing field of bionanotechnology. The majority of potential applications for metal-biohybrid structures require stability of these systems under vacuum conditions, where their chemistry is elusive, and may differ dramatically from the interaction between biomolecules and metal ions in vivo. Here we report for the first time a photoemission and X-ray absorption study of the formation of a hybrid metal-protein system, tracing step-by-step the chemical interactions between the protein and metals (Cu and Fe) in vacuo. Our experiments reveal stabilization of the enol form of peptide bonds as the result of protein-metal interactions for both metals. The resulting complex with copper appears to be rather stable. In contrast, the system with iron decomposes to form inorganic species like oxide, carbide, nitride, and cyanide.

The mechanisms of interaction between inorganic matter and biomolecules, as well as properties of resulting hybrids, are receiving growing interest due to the rapidly developing field of bionanotechnology. The majority of potential applications for metal-biohybrid structures require stability of these systems under vacuum conditions, where their chemistry is elusive, and may differ dramatically from the interaction between biomolecules and metal ions in vivo. Here we report for the first time a photoemission and X-ray absorption study of the formation of a hybrid metal-protein system, tracing step-by-step the chemical interactions between the protein and metals (Cu and Fe) in vacuo. Our experiments reveal stabilization of the enol form of peptide bonds as the result of protein-metal interactions for both metals. The resulting complex with copper appears to be rather stable. In contrast, the system with iron decomposes to form inorganic species like oxide, carbide, nitride, and cyanide.

Capillary stamping is a versatile patterning platform to create micron/sub-micron features on surfaces. When used in combination with mesoporous silica stamps, dot arrays with length scale characteristics matching those of various biomolecular organizations on living cells can be printed. Therefore, different types of ink with functional molecules were printed onto a glass surface and assessed toward their capability to enable an analysis of cellular interactions. Among the evaluated patterned surfaces were dot arrays generated with heterocyclic silanes, which react in a ring-opening reaction upon contact with hydroxyl-terminated surfaces and allow post-modifications of the stamped dot array. Similarly, functionalized proteins were stamped from an aqueous solution, analyzed in regards to specific geometric descriptors and overall contrast between dot and background. After the establishment of a robust patterning system, the stamped substrates were used to spatially manipulate protein-protein interactions in live cells. With the introduction of optogenetics, namely the photoactivatable iLID-system into HeLa cells, protein recruitment from the cytosol to the membrane-bound domains upon irradiation with light was investigated. The technique was also utilized to explore the determinants of Wnt signalosome formation. Wnt co-receptor Lrp6 expressed at the surface of living cells was successfully assembled into nanodot arrays. Strikingly, the co-receptor Fzd8 and the cytosolic scaffold proteins Axin1 and Disheveled2 were spontaneously recruited into the nanodot array to form spatially defined signalosomes in the absence of ligand pointing toward Liquid-Liquid Phase Separation driven signalosome assembly. Immunofluorescence staining confirmed ligand-independent Wnt/β-catenin signaling activated the nanodot arrays.

Many lithographic methods to pattern surfaces both by a mechanical manipulation of the surface or by printing functionalities in the form of particles or molecules have been developed and used in research. Examples for contact-lithographic methods are soft lithography and polymer-pen lithography. One of the main drawbacks of the these methods is the lateral dimension of the obtained pattern. Due to limitations of stamps, materials and the methods themselves, feature sizes of arrays consisting of discrete spots in the sub-micrometer range remain challenging. Another factor in the state-of-the-art contact-lithographic methods is the ex situ adsorption of ink prior to the stamping procedure and thus, an uninterrupted flow of ink cannot be guaranteed. As the variety of imaginable inks is wide and the appropriate solvent often appears to be of organic nature, state-of-the-art contact-lithographic methods are unable to print these inks. The elastomeric polymer stamps used within contact-lithographic methods swell or dissolve in contact with organic solvents. Often, contact-lithographic methods require expensive equipment or defined conditions, e.g. high vacuum or a solvent-enriched humidity, and cannot be carried out in a simple and efficient way under ambient conditions. In this work, a new approach to generate patterned structures with feature sizes in the sub-micrometer range and spot-to-spot distances in the one-micron range is presented. Stamps with an integrated, continuous pore system generate the patterns while the ink is supplied through the capillaries of the stamp. The method of capillary nanostamping provides a simple and low-cost stamping procedure by the synthesis of spongy mesoporous silica stamps. Due to a continuous pore system within the stamp, the ink can be supplied continuously and even without a refilling system, the stamp itself serves as ink reservoir. This provides a continuous or intermittently ink supply for a stamping process with several stamping cycles without the need to refill the stamp. A new stamp or re-inking after one stamping cycle is not necessary. The stamping process is carried out manually by hand under ambient conditions. Due to the silica network, the stamps can be infiltrated with organic solvents. The development of spongy mesoporous silica stamps for capillary nanostamping is presented in this work by demonstrating the progress from pure silica stamps in a typical well-known sol-gel synthesis to spongy and flexible silica stamps with a reduced network bonding and hydrophobic internal residues. For the proof of concept of capillary nanostamping with spongy mesoporous silica stamps, several different inks are stamped. All inks are chosen with respect to a potential application and consist of a volatile organic solvent to proof the stability of the stamps against these solvents, and a non-volatile component, which remains on the substrate surface after precipitation and drying of the solvent. As ink, a dispersion of C60 fullerenes in toluene is stamped onto perfluorinated glass slides. A solution of 1-dodecanethiol in ethanol is stamped onto a gold-coated glass with the outcome of a heterogeneous surface. As a model for nanoparticles, nanodiamonds dispersed in isopropanol are stamped and subsequently functionalized with a fluorescent dye in a click-reaction. A polymer and two different block copolymers dissolved in toluene/chloroform are stamped onto differently functionalized substrate surfaces to analyze the dependency of the nature of the substrate on the stamping results. In a final experiment, a solution of 17α-ethinylestradiol in acetonitrile is stamped as a model for an active pharmaceutical ingredient and subsequently detached from the substrate surface to obtain a defined nanodispersion.

This thesis focuses on the surface patterning by using nanoporous block copolymer (BCP) stamps. Polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) was used as model BCP. Nanoporous BCP stamps were fabricated by replication of lithographically patterned silicon molds. Nanopores inside of BCP stamps were generated by swelling‐induced pore formation. A method for scanner-based capillary stamping (SCS) with spongy nanoporous BCP stamps was developed. First, in the course of stamps design using replication molding of PS-b-P2VP against surface-modified macroporous silicon molds, PS-b-P2VP fiber rings remaining on the macroporous silicon molds were obtained that allow immobilization of water drops on the hydrophobically modified surfaces of the macroporous silicon molds. Water drops immobilized by these rings can be prevented from dewetting within the PS‐b‐P2VP fiber rings. Second, after spongy nanoporous PS-b-P2VP stamps had been obtained, preliminary experiments with non-inked PS-b-P2VP stamps revealed that parts of the stamps’ contact elements can be lithographically transferred onto counterpart surfaces. As a result, arrays of nanostructured submicron PS‐b‐P2VP dots with heights of ∼100 nm onto silicon wafers and glass slides were produced. Lastly, the SCS technique was developed, which overcomes the limitation of time-consuming re-inking procedures associated with classical soft lithography including microcontact printing (µCP) and polymer pen lithography (PPL) with solid stamps, as well as the limitations regarding throughput of scanning probe‐based serial writing approaches such as nanoscale dispensing (NADIS) and other micropipetting techniques. In addition, sizes of stamped droplets can be controlled by adjusting surface wettability and dwell time.

Im Rahmen dieser Arbeit wurden verschiedene Teilchendetektoren zur Verwendung in einem gepulsten Überschallmolekularstrahlexperiment entworfen und hergestellt. In den hier durchgeführten Experimenten kollidiert ein Molekularstrahl mit einer sensitiven Detektoroberfläche, nämlich einer Polyvinylidenfluorid(PVDF)-Folie. Da PVDF sowohl pyroelektrisch wie auch piezoelektrisch ist, entstehen durch die Kollision der Molekularstrahlteilchen auf der Folie Oberflächenladungen. Vorteile von PVDF-Detektoren sind die hohe Effizient der Detektion, die Detektion von neutralen Atomen und Molekülen (eine Ionisierung der zu detektierenden Teilchen ist nicht notwendig), ein einfaches und leicht anzupassendes Detektordesign und außerdem eine schnelle Antwortzeit (im Mikrosekundenbereich). Da nur Ladungen im Bereich von wenigen Pikocoulomb generiert werden, sind verschiedene Verstärker getestet worden. Zur Analyse und Beschreibung des detektierten Signals wird der piezoelektrische Anteil durch ein Materialmodell in Verbindung mit einem schwingenden System, nämlich der erzwungenen Schwingung einer gedämpften Kreismembran, beschrieben. Der pyroelektrische Anteil wird durch einen Energieaustausch beschrieben. Durch die Ausnutzung des pyroelektrischen sowie des piezoelektrischen Effektes können zusätzliche wichtige Informationen wie zum Beispiel der Restitutionskoeffizient oder der Energieakkommodationkoeffizient experimentell erhalten werden. Zur Demonstration der Anwendungsmöglichkeiten sind Detektoren in verschiedenen Größen zur Messung von unterschiedlichen Strahleigenschaften verwendet worden. Untersucht wurde dabei die Strahlgeschwindigkeit von verschiedenen Edelgasen über einen großen Stagnationsdruck- und Stagnationstemperaturbereich. Außerdem wurden Strahlprofile zur Bestimmung der Strahldichte gemessen und mathematisch beschrieben. Zusätzlich wird eine Methode zur Bestimmung der Strahltemperatur mit Hilfe der Strahldichte und der Strahlgeschwindigkeit vorgestellt. / In this study, different particle detectors with a foil of polyvinylidene difluoride have been designed and built for use in a pulsed supersonic molecular jet experiment. Here, the molecular jet collides with the sensitive detector area and generates a charge. This generated charge is caused by the piezo- and the pyroelectric effect. Advantages of polyvinylidene difluoride detectors are a high detection efficiency, the detection of neutral atoms or molecules --- no ionization is required, a simple setup which can be easily incorporated in an existing experiment, an easy adjustment of the detector design because the shape and size can be changed easily, and a fast response-time in the sub-microsecond regime. Because the amount of charges generated is in the order of some picocoulomb, different amplifiers are used. In this analysis of the detected signal, the piezoelectric contribution is defined by the constitutive equations of piezoelectricity, which are used in combination with the concept of a driven damped circular membrane in order to obtain an analytic solution. The pyroelectric contribution is described via the exchanged energy. Because both the piezo- and the pyroelectric effects can be exploited, valuable additional information such as the coefficient of energy accommodation or the coefficient of restitution can be determined experimentally. In order to demonstrate the application possibilities of polyvinylidene difluoride detectors, detectors of different sizes are used as a local jet probe to determine different jet properties. The mean velocities of different rare gases for a wide range of source conditions are determined. Density profiles of various supersonic jets are measured and described mathematically in detail. In addition, both quantities, the velocity and the density, are used to determine the temperature of the supersonic jet.

Lysosomen spielen entscheidende Rolle bei der zellulären Homöostase. Die Überwachung von Lysosomen, die Lipide ansammeln, ist eine erhebliche Herausforderung. Diese Arbeit konzentriert sich auf die Entwicklung der oberflächenverstärkten Raman-Streuung (SERS) als Methode zur Überwachung intakter Lysosomen, insbesondere hinsichtlich des Einflusses von Arzneimitteln, die den Lipidstoffwechsel stören. Um das Potenzial von SERS zur Untersuchung von Lysosomen in lebenden Zellen zu bewerten, wurden die Wechselwirkungen zwischen trizyklischen Antidepressiva und saurer Sphingomyelinase untersucht. Zunächst wurden Modellsysteme untersucht. Die Wechselwirkungen zwischen den Antidepressiva und Goldnanopartikeln wurden durch SERS charakterisiert. Die Daten zeigten, dass Moleküle mit den Nanopartikeln interagieren. Als Modellsystem der lipidreichen Umgebung wurden Komposite aus Liposomen und Goldnanopartikeln von SERS und Cryo-EM untersucht. Die SERS-Spektren sind charakteristisch für die Lipidzusammensetzung der Vesikel. Die Wechselwirkungen zwischen den Antidepressiva und den Lysosomen wurden in der Fibroblastenzelllinie 3T3 durch SERS und komplementäre Methoden untersucht. In Übereinstimmung mit den SERS-Spektren von Modellsystemen zeigen die SERS-Spektren lebender Zellen Signaturen sowohl der Antidepressiva als auch der Lipide. Um die Unterschiede in den Lysosomen zwischen behandelten und nicht behandelten Zellen aufzudecken, wurde ein zufälliger Waldansatz verwendet. Darüber hinaus wurde SERS verwendet, um die Lipidverteilung in Leishmania-infizierten Makrophagen zu untersuchen, von denen bekannt ist, dass sie Lipide akkumulieren. Die Ergebnisse zeigen, dass SERS verwendet werden kann, um die Lipidzusammensetzung in lebenden Zellen verschiedener Zelltypen zu untersuchen. Als neue methodische Entwicklung zeigt die Random-Forest-Analyse von SERS-Daten, dass Ansätze des maschinellen Lernens für ein besseres Verständnis von Daten aus biologischen Systemen nützlich sein können. / Lysosomes play a crucial role in cellular homeostasis. Monitoring lysosomes that accumulate lipids represents a considerable challenge. This thesis focuses on the development of surface-enhanced Raman scattering (SERS) as a method to monitor intact lysosomes, in particular regarding the influence of drugs that interfere with lipid metabolism. To evaluate the potential of SERS for studying lysosomes in live cells, the interactions between tricyclic antidepressants and acid sphingomyelinase were studied. First, model systems were investigated. The interactions between the antidepressants and gold nanoparticles were characterized by SERS. The data showed that molecules interact with the nanoparticles. As a model system of the lipid-rich environment, composites of liposome and gold nanoparticles were studied by SERS and cryo-EM. The SERS spectra are characteristic of the vesicles’ lipid composition. The interactions between the antidepressants and the lysosomes were studied in the fibroblast cell line 3T3 by SERS and complementary methods. In agreement with the SERS spectra of model systems, the SERS spectra of live cells show signatures of both, the antidepressants and the lipids. To reveal the differences in the lysosomes between treated and non-treated cells, a random forest approach was used. Moreover, SERS was used to study the lipid distribution in Leishmania-infected macrophages known to accumulate lipids. The results show that SERS can be used to investigate lipid composition in live cells of different cell types. As a new methodological development, the random forest analysis of SERS data shows that machine learning approaches can be useful for a better understanding of data from biological systems.

Die Ablagerung von Siliziumdioxid ist ein verbreitetes Phänomen, das mit der Toleranz von Pflanzen gegenüber Belastungen korreliert. Die Pflanzen akkumulieren das amorphe Siliziumdioxid in mikroskopischen Partikeln, den Phytolithen, jedoch ist der exakte Mechanismus nicht vollständig aufgeklärt. Um ein besseres Verständnis über die Ablagerung von Siliziumdioxid zu erlangen, wurden verschiedene spektroskopische Techniken an Sorghumblättern und molekularen Modellen angewandt. Festkörper Kernspinresonanz und thermogravimetrische Analysen zeigen, dass die Siliziumdioxidstruktur von der Phytolithe-Extraktion abhängt. Basierend auf Raman- und IR-Daten einzelner Phytolithe lassen sich die Änderungen dieser Strukturen ermitteln. Das deutet auf unterschiedliche biologische Prozesse der Ablagerung des Siliciumdioxids hin. Die Pflanzengewebe in denen Siliciumdioxid abgelagert ist, wurden mit einem multimodalen Ansatz charakterisiert, welcher Fluoreszenz-, Hellfeld- und Rasterelektronenmikroskopie beinhaltet. Die chemische Zusammensetzung der Pflanzengewebe wurden mit Raman- und FTIR-Mikrospektroskopie kartiert. Ein neuartiger Ansatz zur Untersuchung von Pflanzengeweben wurde verwendet, basierend auf der optischen Nahfeldmikroskopie im mittleren IR-Bereich. Dieser ermöglicht eine kombinierte Analyse von mechanischen Materialeigenschaften sowie der chemischen Zusammensetzung und Struktur. Um die Rolle der organischen Matrix zu verstehen, wurden Modellverbindungen betrachtet, die die Ablagerung von Kieselsäure in den Pflanzen induzieren können. In-vitro-Reaktionen konnten eine gleichzeitige Präzipitation von Lignin und Siliciumdioxid sowie eine Polymerisation zusammen mit Peptiden simulieren. Die Ergebnisse lassen starke Wechselwirkungen zwischen diesen Verbindungen vermuten. Neben einem besseren Verständnis verschiedener Aspekte der Silifizierung von Pflanzen werden in dieser Arbeit neue Methoden zur Charakterisierung von Pflanzenproben vorgeschlagen. / Silica deposition is a common phenomenon that correlates with plant tolerance to various stresses. Plants accumulate amorphous silica in microscopic particles termed phytoliths, through yet unclear mechanisms. With the aim to gain better understanding of the processes that govern silica deposition, different vibrational techniques were used on sorghum leaves and molecular models to obtain chemical and structural information addressing different length scales. Solid-state Nuclear Magnetic Resonance and thermogravimetric analysis showed that phytolith extraction methods affect silica structure. Nevertheless, Raman and IR analysis of individual phytoliths revealed differences in the structure and composition between phytolith types, suggesting the existence of different biological pathways for silica deposition. The environment of sorghum tissues where silica is deposited was assessed using a multimodal approach consisting of fluorescence, brightfield and scanning electron microscopies, while chemical composition was mapped using Raman and Fourier transformed Infrared microspectroscopy. Scattering-type near-field optical microscopy in the mid-infrared region was used to characterize the plant tissues, in both fixed and native plant samples. The nano-IR images and the mechanical phase image enabled a combined probing of mechanical material properties together with the chemical composition and structure of both the cell walls and the phytolith structures. In vitro reactions simulating lignin-silica co-precipitation and silica polymerization with peptides revealed strong interaction between these compounds and silica, and their possible involvement in silica deposition in the plant. This thesis provides a better understanding of the chemical process that control plant silicification, suggests new methodologies to characterize plant samples, and evaluates the current methods used in plant science.

Neutral cyclometalated platinum(II) N-heterocyclic carbene complexes [Pt(C^C*)(O^O)] with C^C* ligands based on 1-phenyl-1,2,4-triazol-5-ylidene and 4-phenyl-1,2,4-triazol-5-ylidene, as well as acetylacetonato (O^O = acac) and 1,3-bis(2,4,6-trimethylphenyl)propan-1,3-dionato (O^O = mesacac) ancillary ligands were synthesized and characterized. All complexes are emissive at room temperature in a poly(methyl methacrylate) (PMMA) matrix with emission maxima in the blue region of the spectrum. High quantum efficiencies and short decay times were observed for all complexes with mesacac ancillary ligands. The sterically demanding mesityl groups of the mesacac ligand effectively prevent molecular stacking. The emission behavior of these emitters is in general independent of the position of the nitrogen in the backbone of the N-heterocyclic carbene (NHC) unit and a variety of substituents in 4-position of the phenyl unit, meta to the cyclometalating bond.