In this thesis, the author introduces two strategies used to construct various types of N-heterocycles, based on the chemistry of zirconacycles and 2,6-diazasemibullvalenes. In the first part, the author presents the development of multi-component cyclization of a zirconacyclobutene-silacyclobutene fused compound, nitriles and unsaturated compounds. These reactions provide synthetically useful methodology for various N-heterocycles such as 3-acyl pyrrole, pyrrolo[3,2-d]pyridazine and dihydropyrroloazepine, which are all difficult to synthesize by other means. The isolation and characterization of the key three-fused-ring Zr/Si-containing intermediates are also described in detail. These results show that the zirconacyclobutene-silacyclobutene fused compound behaves as a "chemical transformer" upon treatment with various substrates via the "coordination-induced skeleton rearrangement" mechanism. In the second part, the author demonstrates the synthesis and isolation of a series of 2,6-diazasemibullvalenes (NSBVs) from the reaction of 1,4-dilithio-1,3-dienes and nitriles, highlighting the significant progress made for the first time in this work: (1) determination of X-ray crystal structure of a substituted 2,6-diazasemibullvalene; (2) measurement of the activation barrier of its rapid intramolecular aza-Cope rearrangement in solution; (3) exploration of several reaction types of NSBV with diverse ring-expansion products and "bowl-shape" or "cage-shape" N-containing polycyclic skeletons; (4) demonstration of the localized structure as the predominant form and the homoaromatic delocalized structure as a minor component in the equilibrium using theoretical analysis. Based on well-founded results, this work sheds new light on this controversial topic.

This fourth volume in the series opens some new arenas in the realm of molten salts technology, with research reports on amides, amide mixtures, and their electrochemical properties; chromatography in liquid organic salts; thermal conductivity; magnetic, calorimetric, and ultra-high-pressure measure

Fine Particles Science and Technology deals with the preparation, characterization and technological applications of monodisperse particles in the micro to nano size range. A broad view of this frontier field is given, covering understanding the mechanisms by which uniform fine particles are formed and the search for new processes; the mechanism of the precipitation technique, requiring knowledge of the relationship between the complex solution chemistry and the products formed; the sequence of events leading to the formation of monodisperse colloids. The following topics are presented: microparticles, nanoparticles, applications in the preparation of materials, synthesis and properties, environmental applications, and many others.

Various metallic or non-metallic surfaces are frequently treated by elewctrochemical methods (e.g. electrodeposition, electroless deposition, anodization, passivation, etc.) in order to achieve a desirable property important for biomedical applications. Applications include orthopedic or dental implants, dressings for wound healing and different skin diseases, surfaces for the prevention of bio-film formation of corrosion inhibition in biological media.

The aim of this issue of Modern Aspects of Electrochemistry is to review the latest developments of the surface treatments for biomedical applications in relation to electrochemical science and technology.

This new volume of Modern Aspect of Electrochemistry brings to the scientists, engineers and students summarized results and new concepts of surface treatments for the biomedical applications which may have significant influence for the future practical applications.

The original properties of mesoporous molecular sieves are so unique that the design of most existing catalysts could be reconsidered. It might indeed be of interest to introduce MMS either as a support or as the active phase, merely on the basis of their high surface areas, narrow pore size distribution and flexibility in composition. The recent literature provides examples of MMS based catalysts of many types such as acid-base solids, supported metals and supported oxides, mixed oxides, anchored complexes and clusters, grafted organic functional groups and others. Examples of all these developments are documented in the present proceedings including some spectacular new proposals. The new metallic (Pt) mesophases are specially worth mentioning because they represent a new approach to producing non-supported highly dispersed metals.

In these proceedings the reader will find feature articles and regular papers from many worldwide groups, covering all aspects of synthesis, physical characterization and catalytic reactivity of MMS and their chemically modified forms. It is actually remarkable that this recent development brought together an even broader spectrum of scientists from traditionally unrelated fields such as those of liquid crystals, surfactants, sol-gels, amorphous oxides and mixed oxides, solid state, adsorbents and heterogeneous catalysts. Obviously, this is a fast-growing research area which triggers the imagination and creativity at the cross-road between material design, molecular surface tailoring and catalytic applications.

Organic semiconductors are a central topic of advanced materials research. The book is aiming at bridging the gap between the development and production of devices and basic research on thin film characterisation using cutting-edge techniques in surface and interface science. Topics involve organic molecular-based sensors; interfaces in organic diodes and transistors; mobility in organic field effect transistors and space charge problems; integration of optoelectronic nanostructures; nonlinear optical properties of organic nanostructures; the wetting layer problem; how to get from functionalized molecules to nanoaggregates; optical, electrical and mechanical properties of organic nanofibers as well; as near field investigations of organic thin films.

This is the ?fth volume in the Reviews in Fluorescence series. To date, four previous volumes have been both published and well received by the scienti?c community. Several book reviews in the last few years have also favorably remarked on the series. In this ?fth volume we continue the tradition of publishing leading edge and timely articles from authors around the world. With the recent Nobel Prize in Chemistry for 2008 being awarded for the discovery and development of the Green Fluorescent Protein (GFP) to Shimomura, Chal?e, and Tsien, we have subsequently included several timely reviews on GFP in this volume. We thank the authors for their timely and exciting contributions. We hope you ?nd this volume as useful as past volumes, which promises to be just as diverse with regard to ?uorescence-based content. Finally, in closing, I would like to thank Caroleann Aitken for helping coordin- ing content with authors and Michael Weston at Springer for help in publishing this current volume. Baltimore, MD, USA Chris D. Geddes v . Contents Fluorescence Anisotropy to Study the Preferential Orientation of Fluorophores in Ordered Bi-Dimensional Systems: Rhodamine 6G/Laponite Layered Films ...1 F. Lopez Arbeloa, V. Martinez, T. Arbeloa, and I. Lopez Arbeloa Room Temperature Tryptophan Phosphorescence of Proteins in the Composition of Biological Membranes and Solutions ...37 Vladimir M. Mazhul', Alexander V. Timoshenko, Ekaterina M.

The breadth of scientific and technological interests in the general topic of photochemistry is truly enormous and includes, for example, such diverse areas as microelectronics, atmospheric chemistry, organic synthesis, non-conventional photoimaging, photosynthesis, solar energy conversion, polymer technologies, and spectroscopy. This Specialist Periodical Report on Photochemistry aims to provide an annual review of photo-induced processes that have relevance to the above wide-ranging academic and commercial disciplines, and interests in chemistry, physics, biology and technology. In order to provide easy access to this vast and varied literature, each volume of Photochemistry comprises sections concerned with photophysical processes in condensed phases, organic aspects which are sub-divided by chromophore type, polymer photochemistry, and photochemical aspects of solar energy conversion. Volume 34 covers literature published from July 2001 to June 2002. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading authorities in the relevant subject areas, the series creates a unique service for the active research chemist, with regular, in-depth accounts of progress in particular fields of chemistry. Subject coverage within different volumes of a given title is similar and publication is on an annual or biennial basis.

We present here the second issue devoted entirely to the spin-labeling technique as part of Biological Magnetic Resonance. Volume 14 commemorates a modifi- tion in our editorial policy with the retirement of my esteemed coeditor, Jacques Reuben. From thisjuncture into the future, each issue will focus on some special topic in magnetic resonance. Each volume will be organized in most cases by guest editors, for example forthcoming issues will address the following topics: in vivo magnetic resonance (P. Robitaille and L. J. Berliner, eds. ) Modern techniques in proton NMR ofproteins (R. Krishna and L. J. Berliner, eds. ) Instrumental techniques of EPR (C. Bender and L. J. Berliner, eds. ) Thecurrent volume, Spin Labeling: The NextMillennium, presents an excellent collection of techniques and applications that evolved during the past decade since the last volume, volume 8 (1989). Someobvious omissions, such as multiquantum EPR and very high-frequency FT-ESR were unfortunately not possible for this volume. Perhaps they will appear in Spin Labeling: 2001. Lastly it is a pleasure to honor two scientists whose contributions were both pioneering and pivotal to the spin label technique: Professor Eduard G. Rozantsev (Moscow), whose synthetic feats in nitroxyl chemistry set the broad stage for a versatile catalog of labels; and Professor Harden M. McConnell, last year's Int- national ESR (EPR) Society Gold Medalist, who conceived and developed the spin label technique to address many biological problems (proteins, enzymes, m- branes, cells, immune response, etc. ). Lawrence J.

Superhydrophobic surfaces (water contact angles higher than 150A ) can only be achieved by a combination of hydrophobicity (low surface energy materials) with appropriate surface texture. In nature one can find an array of impressive and elegant examples of superhydrophobic surfaces. For example, on a lotus leaf rain drops bounce off after impact, then entirely roll off the lotus leaf and drag along any dirt particles, without leaving residues. The artificial design of superhydrophobic and self-cleaning surfaces has become an extremely active area of fundamental and applied research. This book presents both fundamental and applied aspects of superhydrophobic surfaces. It describes also different strategies for making superhydrophobic surfaces from a large diversity of materials (polymers, metals and other inorganic materials, composites) and processes (lithographic techniques, electrochemical processes, self-assembly processes, colloidal particles, sol-gel processes, nanofilaments, or simple scraping). A bountiful of information is covered in this book which represents cumulative wisdom of many world-renowned researchers in the fascinating and burgeoning area of superhydrophobic surfaces.

Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued.

The field of atomic clusters continues to attract great interest amongst physicists and chemists alike. This is in part due to their intrinsic properties and potential industrial applications. The first part of Binary Clusters is devoted to recent developments in experimental techniques, the second part covers a variety of theoretical approaches. Different theoretical methods based on group/graph theories and quantum chemical computational methods as well as various spectroscopy techniques (such as mass, laser, infrared, photoelectron etc.) are applied to the determination of the existence of geometrical and electronic structures, chemical bonding phenomena, and the thermodynamic stabilities of several classes of binary clusters. All chapters within this review volume have been contributed by experts in chemistry, physics, and material sciences based at the University of Leuven, Belgium. This book is aimed at professionals and students working in cluster science.

In this thesis, applications of aminoacylation ribozymes named flexizymes are described. Flexizymes have the following unique characteristics: (i) substrate RNA is recognized by two consecutive base pairs between the 3'-end of substrate RNA and the 3'-end of the flexizyme; (ii) these base pairs can be substituted with other base pairs; and (iii) various activated amino acids can be used as substrates including both canonical and noncanonical amino acids. This flexible aminoacylation of RNAs by flexizymes was used to label endogenous tRNAs to be removed, and in vitro selection using the tRNA-depleted library enabled the discovery of the novel interaction between the microRNA precursor and metabolites. Flexizymes are also used to prepare various aminoacyl-tRNAs bearing mutations at the 3'-end to engineer the translation machinery and to develop the orthogonal translation machinery. The first part of the research demonstrated that SELEX is appropriate for discovering the interaction between small RNA and ligands, and suggested that more RNA motif binding to small molecules exists in small RNAs. The second part opened a door to new opportunities for in vitro synthetic biology involving the engineering of the genetic codes and translation machineries. This research also indicated the great potential of aminoacylation by flexizymes to be applied in various fields of RNA research, which is beneficial for RNA researchers.

This thesis discusses the use of asymmetric organic catalysis for the direct enantioselective synthesis of complex chiral molecules, and by addressing the many aspects of both vinylogy and atropisomerism, it appeals to researchers and scholars interested in both areas. Organocatalysis is a relatively modern and "hot" topic in the chemical community; it is constantly expanding and its use has been extended to interesting areas like vinylogous reactivity and atropisomerism. Vinylogous systems are very important for their synthetic applications but also pose a number of challenges, the most notable of which are their reduced reactivity and the reduced stereocontrol at these positions. On the other hand, atropisomeric systems are even more important because of the huge potential they have as drugs, ligands and catalysts. Chemists have only recently "recognized" the importance of these two areas and are focusing their efforts on studying them and the challenges they pose. This thesis offers an extensive introduction on the general aspects of chirality and organocatalysis and an equally extensive experimental section that allow nonexperts to understand the discussion section and reproduce the experiments.

There is an increasing challenge for chemical industry and research institutions to find cost-efficient and environmentally sound methods of converting natural resources into fuels chemicals and energy. Catalysts are essential to these processes and the Catalysis Specialist Periodical Report series serves to highlight major developments in this area. This series provides systematic and detailed reviews of topics of interest to scientists and engineers in the catalysis field. The coverage includes all major areas of heterogeneous and homogeneous catalysis and also specific applications of catalysis such as NOx control kinetics and experimental techniques such as microcalorimetry. Each chapter is compiled by recognised experts within their specialist fields and provides a summary of the current literature. This series will be of interest to all those in academia and industry who need an up-to-date critical analysis and summary of catalysis research and applications. Catalysis will be of interest to anyone working in academia and industry that needs an up-to-date critical analysis and summary of catalysis research and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr

The composition of the most remote objects brought into view by the Hubble telescope can no longer be reconciled with the nucleogenesis of standard cosmology and the alternative explanation, in terms of the Λ-Cold-Dark-Matter model, has no recognizable chemical basis. A more rational scheme, based on the chemistry and periodicity of atomic matter, opens up an exciting new interpretation of the cosmos in terms of projective geometry and general relativity.

The response of atomic structure to environmental pressure predicts non-Doppler cosmical redshifts and equilibrium nucleogenesis by α--particle addition, in accord with observed periodic variation of nuclear abundance.

Inferred cosmic self similarity elucidates the Bode -Titius law, general commensurability in the solar system and the occurrence of quantum phenomena on a cosmic scale.

The generalized periodic function involves both matter and anti-matter in an involuted mapping to a closed projective plane. This topology ensures the same symmetrical balance in a chiral universe, wrapped around an achiral vacuum interface, without singularities.

A new cosmology emerges, based on the theory of projective relativ-ity, presented here as a translation of Veblen's original German text. Not only does it provide a unification of gravity, electromagnetism and quantum theory, through gauge invariance, but also supports the solution of the gravitational field equations, obtained by Godel for a rotating universe.

The appearance of an Einstein-Rosen bridge as outlet from a black hole, into conjugate anti-space, accounts for globular clusters, quasars, cosmic radiation, γ-ray bursters, pulsars, radio sources and other re-gions of plasma activity.

The effects of a multiply-connected space-time manifold on observa-tions in an Euclidean tangent space are unpredictable and a complete re-assessment of the size and structure of the universe is indicated.

The target readership includes scientists, as well as non-scientists - everybody with a scientific or philosophical interest in cosmology and, especially those cosmologists and mathematicians with the ability to recast the crude ideas presented here into appropriate mathematical models.

Manuela Mura's thesis is devoted to ab initio studies of self-assembled organic molecules on a gold surface. This area of research is particularly vibrant because of the various applications such studies have in nanoscience and surface chemistry and physics. In this thesis Manuela Mura uses theory to suggest atomistic models for the observed assembled and she proposes an assembly mechanism. The methods and results developed as part of this work will be of wide interest to physicists and chemists working on the assemblies of organic molecules on crystal surfaces.

No. 28 of this highly regarded series explores the fundamental and applied aspects of electrochemical science. This volume features two detailed studies on the rapidly developing field of electrochemical surface science.

Unlike previous volumes in the series for colloid and surface scientists, revolves generally around two topics: surfactants and polymers. The six papers discuss micelles of block and graft copolymers in solutions, surfactant association in nonaqueous media, a study of the boundary viscosity of organ

There is no doubt that in the development of the Physics and Chemistry of Solids during the last fifteen years, the very important place taken by low-dimensional compounds will be remembered as a major event. Dealing very widely at the beginning with two-dimensional structures and intercalation chemistry, this theme progressively evolved as the synthesis of one-dimensional conductors increased, along with the observation of their remarkable properties. Beyond the classical separation of the traditional disciplines, essential progress has stemmed each time from the concerted efforts of, and overlapping between, chemists, experimental physicists, and theoreticians. This book is a synthetic approach which aims to retrace these united efforts. The observation and characterization of charge density waves in their static or dynamic aspects have been the main points to attract the interest of researchers. Two broad categories of compounds have been the material basis of these observa tions: transition-metal polychalcogenides and either condensed-cluster phases or bronze-type compounds. These families are referred to throughout the various chapters of this book, thus illustrating the continuous progress of concepts in this domain and, at the same time, providing the first synthetic and exhaustive view of this group of materials."

The book explains the principles and fundamentals of photocatalysis and highlights the current developments and future potential of the green-chemistry-oriented applications of various inorganic, organic, and hybrid photocatalysts. The book consists of eleven chapters, including the principles and fundamentals of heterogeneous photocatalysis; the mechanisms and dynamics of surface photocatalysis; research on TiO2-based composites with unique nanostructures; the latest developments and advances in exploiting photocatalyst alternatives to TiO2; and photocatalytic materials for applications other than the traditional degradation of pollutants, such as carbon dioxide reduction, water oxidation, a complete spectrum of selective organic transformations and water splitting by photocatalytic reduction. In addition, heterogeneized polyoxometalate materials for photocatalytic purposes and the proper design of photocatalytic reactors and modeling of light are also discussed. This book appeals to a wide readership of the academic and industrial researchers and it can also be used in the classroom for undergraduate and graduate students focusing on heterogeneous photocatalysis, sustainable chemistry, energy conversion and storage, nanotechnology, chemical engineering, environmental protection, optoelectronics, sensors, and surface and interface science. Juan Carlos Colmenares is a Professor at the Institute of Physical Chemistry, Polish Academy of Sciences, Poland. Yi-Jun Xu is a Professor at the State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, China.

Femtochemistry VII presents the most recent developments in femtochemistry and highlights the significance of the field today. This book contains extracts from the proceedings, presentations and posters from the Femtochemistry VII conference, held in Washington D.C., on July 17-22, 2005. The stimulating conference was opened by Professor Ahmed Zewail (1999 Nobel Prize Winner), and as was evident by the attendees at the conference, had a very active program with the presentation of numerous talks and a large number of posters. This collection of papers reflects the remarkable progress that has been made in femtosecond spectroscopy, and especially to its emergence as a field of research devoted to chemistry and biology, giving rise to femtochemistry and femtobiology. Subjects covered include imaging, structural dynamics, and spectroscopies, fundamentals of reaction dynamics, salvation phenomenta, liquids and interfaces, aggregates/particles/surfaces, protein dynamics and photobiology, quantum control, and intense laser-matter interactions. Subjects covered by this book include imaging, structural dynamics, and spectroscopies; fundamentals of reaction dynamics; salvation phenomenta; liquids and interfaces; aggregates/particles/surfaces; protein dynamics and photobiology; quantum control; and intense laser-matter interactions. This book would appeal to chemists, physicists and biologists in the fields of atomic and molecular science.

This book is devoted to various aspects of self-assembly of gold nanoparticles at liquid-liquid interfaces and investigation of their properties. It covers primarily two large fields: (i) self-assembly of nanoparticles and optical properties of these assemblies; and (ii) the role of nanoparticles in redox electrocatalysis at liquid-liquid interfaces. The first part aroused from a long-lasting idea to manipulate adsorption of nanoparticles at liquid-liquid with an external electric field to form 'smart' mirrors and/or filters. Therefore, Chapters 3 to 5 are dedicated to explore fundamental aspects of charged nanoparticles self-assembly and to investigate optical properties (extinction and reflectance) in a through manner. Novel tetrathiafulvalene (TTF)-assisted method leads to self-assembly of nanoparticles into cm-scale nanofilms or, so-called, metal liquid-like droplets (MeLLDs) with remarkable optical properties. The second part (Chapters 6 to 8) clarifies the role of nanoparticles in interfacial electron transfer reactions. They demonstrate how nanoparticles are charged and discharged upon equilibration of Fermi levels with redox couples in solution and how it can be used to perform HER and ORR. Finally, Chapter 9 gives a perspective outlook, including applications of suggested methods in fast, one-step preparation of colloidosomes, SERS substrates as well as pioneer studies on so-called Marangony-type shutters drive by the electric field.

There is an increasing challenge for chemical industry and research institutions to find cost-efficient and environmentally sound methods of converting natural resources into fuels chemicals and energy. Catalysts are essential to these processes and the Catalysis Specialist Periodical Report series serves to highlight major developments in this area. This series provides systematic and detailed reviews of topics of interest to scientists and engineers in the catalysis field. The coverage includes all major areas of heterogeneous and homogeneous catalysis and also specific applications of catalysis such as NOx control kinetics and experimental techniques such as microcalorimetry. Each chapter is compiled by recognised experts within their specialist fields and provides a summary of the current literature. This series will be of interest to all those in academia and industry who need an up-to-date critical analysis and summary of catalysis research and applications. Catalysis will be of interest to anyone working in academia and industry that needs an up-to-date critical analysis and summary of catalysis research and applications. Specialist Periodical Reports provide systematic and detailed review coverage in major areas of chemical research. Compiled by teams of leading experts in their specialist fields, this series is designed to help the chemistry community keep current with the latest developments in their field. Each volume in the series is published either annually or biennially and is a superb reference point for researchers. www.rsc.org/spr