This dissertation is concerned with design, fabrication, and mathematical modeling of three different microactuators driven by light. Compared to electricity, electromagnetic wave is a wireless source of power. A distant light source can be delivered, absorbed, and converted to generate a driving force for a microactuator. The study of light-driven microsystems, still at its early stage, is already expanding the horizon for the research of microsystems. The microactuators of this dissertation include micro-cantilevers driven by pulsed laser, photo-deformable microshells coated with gold nanospheres, and a nano-particles coated micro-turbine driven by visible light. Experimental investigation and theoretical analysis of these microactuators showed interesting results. These microactuators were functioned based on cross-linked, multiple physics phenomenon, such as photo-heating, thermal expansion, photo-chemistry effect, plasomonics enhancement, and thermal convection in rarefied gas. These multiple physics effects dominate the function of a mechanical system, when the system size becomes small. The modeling results of the microactuators suggest that, to simulate a microscale mechanical system accurately, one has to take account the minimum dimension of the system and to consider the validity of a theoretical model. Examples of the building of different microstructures were shown to demonstrate the capacity of a digital-micromirror-device (DMD) based apparatus for three-dimensional, heterogeneous fabrication of polymeric microstructures. / text

The work described in this thesis is inspired by natural-occurring molecules that are used throughout biology to perform specific, highly-selective tasks. This thesis illustrates the design, synthesis and investigation of novel molecular devices based on acyl hydrazones for the synthesis of a small molecule walker and light-driven molecular shuttles. Chapter One outlines a general overview of the design and synthesis of molecular devices, including molecular walkers and molecular shuttles. Some of the most important examples of walking molecules (both natural and synthetic) are described in detail, along with a comprehensive introduction of molecular shuttles and their synthetic mimics. Examples of stimuli-responsive molecular shuttles that have been developed are highlighted throughout the chapter. Chapter Two describes the design and synthetic progress towards a molecular walker, as well as detailing the optimisation of the synthetic steps achieved thus far. In this chapter, most of the work presented is based on the design and optimisation of the synthesis of an acyl hydrazone-based molecular walker, which will be able to walk directionally and repetitively along its conjugate track when the conditions are changed. A novel acyl hydrazone pyridine moiety is introduced to the system to achieve a high directional bias during the walking process. First, the concept and basis of the design is explained and further, the synthesis of the walker system is discussed in detail. Chapter Three illustrates the synthesis and operation of 1- and 2- station [2]-rotaxanes which exhibit all the requirements for a light-driven molecular shuttle. The effect of a new photo switchable binding station, an acyl pyridyl hydrazone, on the shuttling process is investigated by comparing the positional distribution of the macrocycle between the acyl hydrazone station and the succinamide-ester station, while the acyl hydrazone undergoes photo- and thermal isomerisation. The successful synthesis of this molecular architecture is described along with its operation, demonstrating high positional integrity and efficiency during the shuttling process.

Visible light-driven photocatalysis has shown considerable potential in the area of clean and renewable energy, as well as in wastewater treatment. This thesis describes the synthesis, characterization and applicability of a visible-light active photocatalyst, bismuth oxybromide (BiOBr). The photocatalytic activity of BiOBr was investigated through its preparation via hydrothermal and solvothermal synthesis routes under various conditions. Hydrothermal catalyst was prepared using non template based method while for solvothermal synthesis CTAB was used as a template. Parameters of temperature and time of thermal treatment were optimized for each synthesis method and overall tests for catalyst dosage and recyclability were performed. An overall optimal route leading to high photocatalytic performance was also proposed based on the obtained results. Studies were also conducted to examine the applicability of optimally synthesized BiOBr in drinking water applications by studying catalyst-mediated disinfection of E. coli and degradation of phenol. Favourable results were obtained, confirming the prospective application of BiOBr as a viable photocatalyst for disinfection. Furthermore, the potential of enhancing BiOBr to further improve its performance is described through synthesis of a novel PdCl2/BiOBr based photocatalyst. Overall, the performance of BiOBr under various conditions in this study establishes its potential as a holistic photocatalyst and merits further development.

This thesis describes the host-guest chemistry between Cucurbit[7]uril (CB[7]) and CB[8] and a series of guests including bispyridinium cations, phenols and  napthalenes. These guests are bound to ruthenium polypyridine complexes or ruthenium based water oxidation catalysts (WOCs). The investigations are based upon utilizing the covalently linked photosensitizer and the electronic effects and chemical processes are investigated. / QC 20100927

Biocatalysis is becoming an increasingly attractive alternative to more traditional chemical transformations for use in pharmaceutical and industrial applications. This interest is primarily a consequence of the high regio-, stereo- and enantioselectivity that is associated with enzyme catalysed reactions. However, the proliferation of such techniques has been limited due to the dependence of enzyme activity upon the presence of redox cofactors, which are typically expensive and must be used in conjunction with efficient regeneration systems. Whilst numerous methods have been described, of particular potential are those that employ exogenous photosensitisers as a means of generating reducing equivalents to promote catalytic turnover. In this study the potential of transition metal complexes as photosensitisers towards the development of light-driven biocatalytic systems is evaluated. Use of such compounds gives great scope towards fine-tuning the spectral and redox properties of the sensitisers with the aim of optimising catalytic efficiency. Detailed herein is an extensive study towards the synthesis and characterisation of a range of ruthenium(II) and iridium(III) coordination compounds. Using NMR, UV-vis, and electrochemical techniques, all complexes were fully characterised and the origins of the photophysical properties further investigated using time-dependent density functional theory (TD-DFT) calculations. A series of ruthenium compounds were synthesised containing the bis(2,2′-bipyrazyl)ruthenium(II) moiety, investigating the impact of changes made to the functionality of the ancillary ligand upon the overall properties of the complex. New synthetic procedures have been developed towards the preparation of both 2,2′-bipyrazine and the related complexes, exhibiting significant benefits over previously established methods. Through manipulating the electron density of the ancillary ligand it is shown that the redox properties may be effectively tuned upon inducing changes in the energy of the metal-based HOMO. The utilisation of cyclometalated iridium(III) complexes in aqueous systems has been limited due to a poor water solubility that is typically associated with these compounds. Herein it is demonstrated that this issue may be effectively circumvented on inclusion of the positively charged pyridinium moiety. Upon incorporation of this functional group into either the cyclometalating or ancillary ligands, two distinct series of compounds were successfully prepared. Complexes of the substituted quaterpyridinium ligands possess complicated UV-vis spectra that exhibit low intensity absorbance up to 650 nm. A number of monoquaternised bipyridinium compounds were also utilised as pyridine derived N-heterocyclic carbene cyclometalating ligands, to afford a range of complexes with unique redox properties. The prepared photosensitisers were subsequently used to induce catalytic turnover in light-driven biocatalytic systems utilising the flavin dependent oxidoreductase enzymes, pentaerythritol tetranitrate reductase (PETNR) and the thermophilic old yellow enzyme (TOYE). Through an extensive investigation, optimal reaction conditions have been identified and a mechanism of electron transfer proposed. These systems were successfully implemented in the reduction of a broad range of substrates under both aqueous and biphasic conditions, delivering yields and enantiomeric excesses comparable to those obtained utilising an enzyme coupled regeneration system. This study clearly demonstrates that transition metal complexes are excellent candidates in developing practical light-driven biocatalytic systems. It is expected that, with further investigation, this approach can be readily expanded to incorporate a variety of applications and provide an effective alternative to the use of costly redox cofactors and a reliance upon complex regeneration techniques.

Visible light-driven photocatalysis has shown considerable potential in the area of clean and renewable energy, as well as in wastewater treatment. This thesis describes the synthesis, characterization and applicability of a visible-light active photocatalyst, bismuth oxybromide (BiOBr). The photocatalytic activity of BiOBr was investigated through its preparation via hydrothermal and solvothermal synthesis routes under various conditions. Hydrothermal catalyst was prepared using non template based method while for solvothermal synthesis CTAB was used as a template. Parameters of temperature and time of thermal treatment were optimized for each synthesis method and overall tests for catalyst dosage and recyclability were performed. An overall optimal route leading to high photocatalytic performance was also proposed based on the obtained results. Studies were also conducted to examine the applicability of optimally synthesized BiOBr in drinking water applications by studying catalyst-mediated disinfection of E. coli and degradation of phenol. Favourable results were obtained, confirming the prospective application of BiOBr as a viable photocatalyst for disinfection. Furthermore, the potential of enhancing BiOBr to further improve its performance is described through synthesis of a novel PdCl2/BiOBr based photocatalyst. Overall, the performance of BiOBr under various conditions in this study establishes its potential as a holistic photocatalyst and merits further development.

The theme of this thesis is the development of mononuclear Ru-based complexes that are capable of catalyzing the water oxidation (or O2-evolving) reaction, e.g. 2 H2O → O2 + 4 H+ + 4 e−. Several families of mononuclear Ru water oxidation catalysts were designed and prepared. They feature with anionic ancillary ligands that contain carboxylate or phenolate donors. The properties of the catalysts were investigated in various aspects including coordination geometry, electrochemical behavior, and ligand exchange. All catalysts showed outstanding catalytic activity towards water oxidation in the presence of cerium(IV) ammonium nitrate as a sacrificial oxidant. High-valent Ru intermediates involved in the reactions were characterized both experimentally and theoretically. The kinetics of catalytic water oxidation was examined based on one catalyst and a prevailing catalytic pathway was proposed. The catalytic cycle involved a sequence of oxidation steps from RuII−OH2 to RuV=O species and O−O bond formation via water-nucleophilic-attack to the RuV=O intermediate. By comparing properties and catalytic performance of Ru catalysts herein with that of previously reported examples, the effect of anionic ancillary ligands was clearly elucidated in the context of catalytic water oxidation. Aiming to further application in an envisaged artificial photosynthesis device, visible light-driven water oxidation was conducted and achieved primarily in a homogeneous three-component system containing catalyst, photosensitizer, and sacrificial electron acceptor. Moreover, one model Ru catalyst was successfully immobilized on ordinary glass carbon surface through a facile and widely applicable method. / <p>QC 20121112</p>

Our group has developed a family of single molecules termed nanocars, which are aimed at performing controllable motion on surfaces. In this work, a series of light-activated motorized nanomachines incorporated with a MHz frequency light-activated unidirectional rotary motor were designed and synthesized. We hope the light-activated motor can serve as the powering unit for the nanomachines, and perform controllable translational motion on surfaces or in solution. A series of motorized nanovehicles intended for scanning tunneling microscopy (STM) imaging were designed and synthesized. A p-carborane-wheeled motorized nanocar was synthesized and monitored by STM. Single-molecule imaging was accomplished on a Cu(111) surface. However, further manipulations did lead to motor induced lateral motion. We attributed this result to the strong molecule-surface interactions between the p-carborane-wheeled nanocar and the Cu(111) surface. To fine-tune the molecule-surface interactions, an adamantane-wheeled motorized nanocar and a three-wheel nanoroadster were designed and synthesized. In addition, the STM substrates will be varied and different combinations of molecule-surface interactions will be studied. As a complimentary imaging method to STM, single-molecule fluorescence microscopy (SMFM) also provides single-molecule level resolution. Unlike STM experiment requires ultra-high vacuum and conductive substrate, SMFM experiment is conducted at ambient conditions and uses non-conductive substrate. This imaging method allows us to study another category of molecule-surface interactions. We plan to design a fluorescent motorized nanocar that is suitable for SMFM studies. However, both the motor and fluorophore are photochemically active molecules. In proximity, some undesired energy transfer or interference could occur. A cyanine 5- (cy5-) tagged motorized nanocar incorporated with the MHz motor was designed and synthesized in order to minimize the potential energy transfer or interference between the motor and the fluorophore. The SMFM study of this cy5-tagged motorized nanocar is currently undergoing. The design of light-activated motorized nanocar inspired the design of nanosubmarines. We used fluorescence quenching and fluorescence correlation spectroscopy (FCS) to study the diffusion of single molecules. The fluorescence quenching experiments of Ru(bpy)3+2 by a quenching nanosubmarine was conducted, but no motor induced acceleration of the molecule were observed. Another fluorescent nanosubmarine was monitored by FCS, and no increase of diffusion coefficient was found. Finally, a 1-D channel approach was adopted for decreasing the effects of Brownian motion, and acceleration of nanosubmarine was observed.

As a potential solution to the global energy and environmental pollution, design and synthesis of artificial photocatalysts with high activities have attracted increasing scientific interests worldwide. In recent years, the graphitic carbon nitride (g-C3N4) has shown new possible applications in the photocatalytic field due to its unique properties. However, the photocatalytic efficiency of the pristine g-C3N4 is greatly limited by the high recombination rate of the photo-induced electron-hole pairs. In this thesis, the aim is to design and fabricate efficient g-C3N4 based photocatalysts with enhanced photocatalytic activities under a visible light irradiation. In order to achieve this goal, two strategies have been employed in the present thesis. First, the as-obtained g-C3N4 was used as the host material to construct staggered-aligned composite photocatalysts by selecting semiconductors with suitable band positions. By this method, three kinds of g-C3N4-based composite photocatalysts such as g-C3N4/ZnS nanocage, g-C3N4/m-Ag2Mo2O7 and g-C3N4/MIL-88A were successfully fabricated. Second, the microstructure of the g-C3N4 was modified by the H2O2-treatment at an elevated temperature and ambient pressure. In this study, the g-C3N4 was prepared by a simple pyrolysis of urea. As for all the as-synthesized phtocatalysts, the structures, morphologies and the optical properties were carefully characterized by the following techniques: XRD, SEM, TEM, FT-IR and DRS. Also, the band edge positions of m-Ag2Mo2O7 and MIL-88A were studied by the Mott-Schottky methods. Thereafter, the photocatalytic activities were evaluated by using a solution of rhodamine B (RhB) as a target pollutant for the photodegradation experiments performed under a visible light irradiation. The results showed that all the aforementioned g-C3N4-based photocatalysts exhibited enhanced photocatalytic activities in comparison with the pristine g-C3N4. For the case of the g-C3N4-based composite photocatalysts, the enhancement factor over the pristine g-C3N4 can achieve values ranging from 2.6 to 3.4. As for the H2O2-treated g-C3N4, the degradation rate constant can be 4.6 times higher than that of the pristine g-C3N4. To understand the key factors in new materials design, we also devote a lot of efforts to elucidate the basic mechanisms during the photocatalytic degradation of organic pollutant. Based on the results of the active species trapping (AST) experiments, the main active species in each photocatalytic system were determined. In the g-C3N4/m-Ag2Mo2O7 and the g-C3N4/MIL-88A system, three kinds of active species of ·O2-, h+ and ·OH were found to be involved in the photocatalytic reaction. Among them, the ·O2- and h+ were the main active species. In the g-C3N4/ZnS and H2O2-treated g-C3N4 photocatalytic systems, the main active species was determined as the ·O2-. The reaction pathways of these active species were also demonstrated by comparing the band edge positions with the potentials of the redox couple. In addition, the relationship between the active species and the photocatalytic behaviors of N-de-ethylation and conjugated structure cleavage were studied. Finally, possible mechanisms to explain the enhanced photocatalytic activities were proposed for each photocatalytic system. The results in this thesis clearly confirm that the photocatalytic activity of the g-C3N4 based photocatalyst can efficiently be enhanced by constructions of staggered-aligned composites and by modification of the microstructure of the g-C3N4. The enhanced photocatalytic performance can mainly be ascribed to the efficient separation of the photo-induced electron-hole pairs and the increase of the active sites for the photocatalytic reaction. / <p>QC 20150909</p>

Die Verwendung von pharmazeutischen Wirkstoffen (API) hat die moderne medizinische Behandlung erneuert und die menschliche Gesundheit vor Infektionskrankheiten geschützt. Andererseits werden Wirkstoffe in der Regel über Krankenhausabwässer oder Industrieabwässer in verschiedene Gewässer eingeleitet. Ihr kontinuierlicher Eintrag in die Umwelt hat eine ausgeglichene Umwandlungs-/Eliminierungsrate zur Folge und macht API zu 'pseudo-persistenten' Schadstoffen. Antibiotika gehören zur Gruppe der Wirkstoffe und werden in großem Umfang in Rohwasserquellen für Trinkwasser nachgewiesen. Die Konzentration der im Abwasser nachgewiesenen pharmazeutischen Verunreinigungen reicht von ng/L bis µg/L. Ciprofloxacin (CIP) wurde in Abwasser in extrem hohen Konzentrationen (bis zu 31 mg/L) nachgewiesen, die tausendmal höher sind als die für einige Bakterien toxischen Konzentrationen und es zum häufigsten Arzneimittel in Abwasser machen. Die zunehmende Konzentration von Antibiotika ist der Hauptgrund für die Entwicklung antibiotikaresistenter Bakterien, die eine Vielzahl von antibiotikaresistenten bakteriellen Infektionen verursachen. Von vielen pharmazeutischen Instituten wurde erwartet, dass sie neue Antibiotika entwickeln, um die antibiotikaresistenten Bakterien zu bekämpfen. Viele Studien über neue Antibiotika werden jedoch aufgrund der hohen Kosten und des Mangels an Innovation aufgegeben. Somit sind Antibiotika und antibiotikaresistente Bakterien widerspenstige Schadstoffe, die Anlass zu großer Sorge geben. Verschiedene konventionelle und moderne Techniken wie Ozonierung, Nanofiltration und biologische Methoden wurden zur Beseitigung von Schadstoffen eingesetzt. Dennoch sind teure Infrastrukturen, komplexe Systeme und ein hoher Bedarf an Platz und Energie (Strom, Gas) für die Umsetzung dieser Techniken erforderlich, die zudem nicht in der Lage sind, die in Spuren vorhandenen Schadstoffe zu entfernen. Daher werden fortgeschrittene Oxidationsverfahren (AOP) als interessante Lösung angesehen. AOPs sind chemische Behandlungen, die stark oxidierende Spezies, wie z. B. Hydroxylradikale, erzeugen können, um Schadstoffe in Abwässern abzubauen. Viele Studien wurden über den Einsatz der Photokatalyse durchgeführt, die eine der wichtigsten Untergruppen der AOPs ist. Die populärsten Photokatalysatoren, wie z.B. Halbleiter, werden seit dem zwanzigsten Jahrhundert wegen ihrer hohen photokatalytischen Effizienz und ihrer geringen Kosten in der Abwasserbehandlung eingesetzt. Allerdings haben diese Photokatalysatoren auch ihre Grenzen. Titandioxid, der am häufigsten verwendete Photokatalysator und Halbleiter mit großer Bandlücke, hat eine Bandlücke von 3,0 eV in der Rutilphase und 3,2 eV in der Anatasphase. Daher kann er hauptsächlich unter UV-Bestrahlung - die nur 4-5 % des Sonnenlichts ausmacht - photoaktiviert werden und erfordert den Einsatz künstlicher UV-Lichtquellen, um einen effizienten Photoabbau zu erreichen. Der Bedarf an externen Lichtquellen ist immer mit einem hohen Energiebedarf verbunden. Die weltweite Verknappung von Erdöl und Erdgas hat zu einer weit verbreiteten Besorgnis über die Energieversorgung geführt, da ein kalter und dunkler Winter befürchtet wird, insbesondere in der kritischen Situation der zunehmenden globalen Energiekrise. Diese Sorgen haben die Entwicklung alternativer, nachhaltiger Energiequellen in den Mittelpunkt gerückt. Die Lösung für all diese Probleme ist die Nutzung der Sonnenenergie. Eine florierende Forschung hat sich mit der Entwicklung von photokatalytischen Systemen beschäftigt, die im sichtbaren Bereich arbeiten. Allerdings machen ultraviolettes (UV) und sichtbares Licht zusammen nur die Hälfte der Photonen des Sonnenspektrums aus. Die verbleibenden Photonen im nahen Infrarot (NIR) werden für die Energieumwandlung noch zu wenig genutzt. Die Entwicklung praktischer Strategien zur Nutzung des NIR-Lichtanteils der Sonne ist von entscheidender Bedeutung, um die photokatalytische Effizienz für künftige industrielle Anwendungen zu erhöhen. Die Rückgewinnung und Wiederverwendung der verwendeten partikelförmigen Materialien ist ein weiterer mühsamer Schritt. Wie in neueren Studien beschrieben, erfordern die Partikeltrennverfahren höhere Kosten und komplizierte Systeme. Die Immobilisierung der Partikel auf einer Oberfläche wurde untersucht, wobei sich die Nachteile einer begrenzten Adsorptionsfläche und eines unzureichenden Kontakts mit Verunreinigungen oder Sekundärverschmutzungen durch das Auslaugen der Partikel aus den Trägermaterialien gezeigt haben. Ziel dieser Arbeit ist es, einen neuen Ansatz zur Herstellung effizienter solarbetriebener Tm3+-Photokatalysatoren auf UCNP-Basis zu demonstrieren, die aus relativ kostengünstigen Ausgangsstoffen (Poly(vinylalkohol) (PVA), Poly(acrylsäure) (PAA), Poly(etheretherketon) (PEEK)) und Spurenmengen von Lanthanidionen bestehen. Die Nanokomposit-Matrix besteht aus PVA und hydroxyliertem sulfoniertem PEEK (SPOH), die mit PAA-dekorierten UCNPs durch eine einfache Erhitzung bei 170 °C vernetzt wurden, was zu einem nicht auslaugenden porösen UCNP-Material führte. Die in die PVA/SPOH-Matrix eingebetteten UCNPs waren in der Lage, NIR-Licht zu absorbieren und die nach oben konvertierende Anregungsenergie auf die Polymermatrix zu übertragen, was zur Produktion von H2O2 (7,0-10-8 mol-L-1*min-1) führte. Dieses Material erwies sich auch unter Sonneneinstrahlung als funktionsfähig. Der so hergestellte Photokatalysator zeigte eine ausgezeichnete Adsorption (89%) und einen photokatalytischen Abbau (50%) in 4 Stunden gegenüber CIP sowie eine vielversprechende photokatalytische bakterizide Wirkung (55% in 1 Stunde) gegenüber E. coli unter Sonneneinstrahlung. Insgesamt deuten diese Ergebnisse darauf hin, dass dieses Nanokomposit den Weg für ein solarbetriebenes Abwasserreinigungsverfahren auf der Grundlage von hochkonvertierenden Nanopartikeln ebnen kann.