This thesis addresses two fundamental areas in contemporary organic chemistry: synthesis of natural products and catalytic asymmetric synthesis. Firstly, a new methodology, developed by our research group, which allows the asymmetric synthesis of lactones, a structural unit ubiquitous in natural products, was utilised in the synthesis of a number of natural product analogues that showed significant biological activity. Secondly, the development of a catalytic asymmetric synthesis of a key structural motif present in a number of natural products and pharmaceuticals was accomplished. During the course of this work we discovered dual stereo control, which is significant because it allows the configuration of a new stereo centre to be controlled by a simple change of proton source.

Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic, and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles, and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science - as an introduction to a neighboring field, or as a compilation of detailed information for the specialist.

Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic, and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles, and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science - as an introduction to a neighboring field, or as a compilation of detailed information for the specialist.

Direct Alcohol Fuel Cells: Materials, Performance, Durability and Applications begins with an introductory overview of direct alcohol fuel cells (DAFC); it focuses on the main goals and challenges in the areas of materials development, performance, and commercialization. The preparation and the properties of the anodic catalysts used for the oxidation of methanol, higher alcohols, and alcohol tolerant cathodes are then described. The membranes used as proton conductors in DAFC are examined, as well as alkaline membranes, focusing on the electrical conductivity and alcohol permeability. The use of different kinds of carbon materials as catalyst supports, gas diffusion layers, and current collectors in DAFC is also discussed. State of the art of the modeling is used to estimate performance and durability. The closing chapter reviews the use of DAFC in portable equipment and mobile devices and features a detailed discussion on the mechanisms of component degradation which limits their durability. This book is written to facilitate the understanding of DAFC technology, applications, and future challenges. It is an excellent introduction for electrochemical and material engineers interested in small fuel cells as portable energy sources, scientists focused on materials science for energy production and storage, as well as policy-makers in the area of renewable energies.

This book is devoted to the new development of zeolitic catalysts with an emphasis on new strategies for the preparation of zeolites, novel techniques for their characterization and emerging applications of zeolites as catalysts for sustainable chemistry, especially in the fields of energy, biomass conversion and environmental protection. Over the years, energy and the environment have become the most important global issues, while zeolitic catalysts play important roles in addressing them. With individual chapters written by leading experts, this book offers an essential reference work for researchers and professionals in both academia and industry. Feng-Shou Xiao is a Professor at the Department of Chemistry, Zhejiang University, China. Xiangju Meng is an Associate Professor at the Department of Chemistry, Zhejiang University, China.

This book describes the fundamental concepts, the latest developments and the outlook of the field of nanozymes (i.e., the catalytic nanomaterials with enzymatic characteristics). As one of today's most exciting fields, nanozyme research lies at the interface of chemistry, biology, materials science and nanotechnology. Each of the book's six chapters explores advances in nanozymes. Following an introduction to the rise of nanozymes research in the course of research on natural enzymes and artificial enzymes in Chapter 1, Chapters 2 through 5 discuss different nanomaterials used to mimic various natural enzymes, from carbon-based and metal-based nanomaterials to metal oxide-based nanomaterials and other nanomaterials. In each of these chapters, the nanomaterials' enzyme mimetic activities, catalytic mechanisms and key applications are covered. In closing, Chapter 6 addresses the current challenges and outlines further directions for nanozymes. Presenting extensive information on nanozymes and supplemented with a wealth of color illustrations and tables, the book offers an ideal guide for readers from disparate areas, including analytical chemistry, materials science, nanoscience and nanotechnology, biomedical and clinical engineering, environmental science and engineering, green chemistry, and novel catalysis.

The Role of Metals and Ligands in Organic Hydroformylation, by Luca Gonsalvi, Antonella Guerriero, Eric Monflier, Frédéric Hapiot, Maurizio Peruzzini. Hydroformylation in Aqueous Biphasic Media Assisted by Molecular Receptors, by Frédéric Hapiot, Hervé Bricout, Sébastien Tilloy, Eric Monflier. Asymmetric Hydroformylation, by Bernabé F. Perandones, Cyril Godard, Carmen Claver. Domino Reactions Triggered by Hydroformylation, by Elena Petricci, Elena Cini. Rhodium-Catalyzed Hydroformylation in Fused Azapolycycles Synthesis, by Roberta Settambolo. Hydroformylation in Natural Product Synthesis, by Roderick W. Bates, Sivarajan Kasinathan.

Ana Escribano Cuesta's thesis presents a detailed study of the inter- and intramolecular reactions of carbonyl compounds with 1,6-enynes using gold (I) complexes. An important part of the work involved streamlining the variables that allow the selective synthesis of different products such as tricyclic compounds, dihydropyrans, 1,3-dienes or cyclobutenes. The second chapter highlights the importance and difficulties in synthesising a cyclobutene subunit and the author includes a detailed description of how the products were prepared. The final chapter outlines the synthesis of lundurines using methodology developed by the author's research group for intramolecular gold-catalyzed cyclization of indoles with alkynes. The lundurine products developed in this work show significant in vitro cytoxicity toward B16 melanoma cells. The work in this thesis has led to a number of publications in high-profile chemistry journals.

Transition Metal Catalyzed Carbonylation Reactions is a comprehensive monograph focusing on carbon monoxide usage. This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. The authors have structured the book around the types of reactions, based on the different nucleophiles involved. Scientists working in carbonylation or with carbon monoxide, as well as teachers of organic synthesis can use this book to become familiar with this important area of organic chemistry.

Christopher M. Cheatum and Amnon Kohen, Relationship of Femtosecond-Picosecond Dynamics to Enzyme-Catalyzed H-Transfer. Cindy Schulenburg and Donald Hilvert, Protein Conformational Disorder and Enzyme Catalysis. A. Joshua Wand, Veronica R. Moorman and Kyle W. Harpole, A Surprising Role for Conformational Entropy in Protein Function. Travis P. Schrank, James O. Wrabl and Vincent J. Hilser, Conformational Heterogeneity Within the LID Domain Mediates Substrate Binding to Escherichia coli Adenylate Kinase: Function Follows Fluctuations. Buyong Ma and Ruth Nussinov, Structured Crowding and Its Effects on Enzyme Catalysis. Michael D. Daily, Haibo Yu, George N. Phillips Jr and Qiang Cui, Allosteric Activation Transitions in Enzymes and Biomolecular Motors: Insights from Atomistic and Coarse-Grained Simulations. Karunesh Arora and Charles L. Brooks III, Multiple Intermediates, Diverse Conformations, and Cooperative Conformational Changes Underlie the Catalytic Hydride Transfer Reaction of Dihydrofolate Reductase. Steven D. Schwartz, Protein Dynamics and the Enzymatic Reaction Coordinate.

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Carboamination or Carboalkoxylation Reactions, by John P. Wolfe Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Diamination, Aminoalkoxylation, or Dialkoxylation Reactions, by Sherry R. Chemler Synthesis of Heterocycles via Metal-Catalyzed Wacker-Type Oxidative Cyclization Reactions of Alkoxy- or Amino-Alkenes, by Wanbin Zhang Synthesis of Saturated Heterocycles via Metal-Catalyzed Hydroamination or Hydroalkoxylation Reactions, by Lisa D. Julian Synthesis of Saturated Heterocycles via Metal-Catalyzed Allylic Alkylation Reactions, by Aaron Aponick Synthesis of Heterocycles via Metal-Catalyzed Cascade/Domino Reactions that Generate a C-N or C-O Bond, by Mark Lautens Synthesis of Saturated Heterocycles via Metal-Catalyzed Formal Cycloaddition Reactions that Generate a C-N or C-O Bond, by Jerome Waser

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

Frustrated Lewis Pairs: From Dihydrogen Activation to Asymmetric Catalysis, by Dianjun Chen, Jurgen Klankermayer Coexistence of Lewis Acid and Base Functions: A Generalized View of the Frustrated Lewis Pair Concept with Novel Implications for Reactivity, by Heinz Berke, Yanfeng Jiang, Xianghua Yang, Chunfang Jiang, Subrata Chakraborty, Anne Landwehr New Organoboranes in "Frustrated Lewis Pair" Chemistry, by Zhenpin Lu, Hongyan Ye, Huadong Wang Paracyclophane Derivatives in Frustrated Lewis Pair Chemistry, by Lutz Greb, Jan Paradies Novel Al-Based FLP Systems, by Werner Uhl, Ernst-Ulrich Wurthwein N-Heterocyclic Carbenes in FLP Chemistry, by Eugene L. Kolychev, Eileen Theuergarten, Matthias Tamm Carbon-Based Frustrated Lewis Pairs, by Shabana Khan, Manuel Alcarazo Selective C-H Activations Using Frustrated Lewis Pairs. Applications in Organic Synthesis, by Paul Knochel, Konstantin Karaghiosoff, Sophia Manolikakes FLP-Mediated Activations and Reductions of CO2 and CO, by Andrew E. Ashley, Dermot O'Hare Radical Frustrated Lewis Pairs, by Timothy H. Warren and Gerhard Erker Polymerization by Classical and Frustrated Lewis Pairs, by Eugene Y.-X. Chen Frustrated Lewis Pairs Beyond the Main Group: Transition Metal-Containing Systems, by D. Wass Reactions of Phosphine-Boranes and Related Frustrated Lewis Pairs with Transition Metal Complexes, by Abderrahmane Amgoune, Ghenwa Bouhadir, Didier Bourissou

Discovery of Frustrated Lewis Pairs: Intermolecular FLPs for Activation of Small Molecules, by Douglas W. Stephan Intramolecular Frustrated Lewis Pairs: Formation and Chemical Features, by Gerald Kehr, Sina Schwendemann, Gerhard Erker Frustrated Lewis Pair Mediated Hydrogenations, by Douglas W. Stephan, Gerhard Erker Amine-Borane Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation, by Victor Sumerin, Konstantin Chernichenko, Felix Schulz, Markku Leskela, Bernhard Rieger, Timo Repo Hydrogen Activation by Frustrated Lewis Pairs: Insights from Computational Studies, by Tibor Andras Rokob, Imre Papai Quantum Chemistry of FLPs and Their Activation of Small Molecules: Methodological Aspects, by Birgitta Schirmer, Stefan Grimme Computational Design of Metal-Free Molecules for Activation of Small Molecules, Hydrogenation, and Hydroamination, by Zhi-Xiang Wang, Lili Zhao, Gang Lu, Haixia Li, Fang Huang Computational Studies of Lewis Acidity and Basicity in Frustrated Lewis Pairs, by Thomas M. Gilbert Solid-State NMR as a Spectroscopic Tool for Characterizing Phosphane - Borane Frustrated Lewis Pairs, by Thomas Wiegand, Hellmut Eckert, Stefan Grimme

This work describes novel, effective hydrogen-bond (HB) donor catalysts based on a known bifunctional tertiary amine-thiourea, a privileged structure, which has been proven to be one of the most widely used organocatalysts. These HB donor catalysts derived from quinazoline and benzothiadiazine were initially synthesized as novel HB donors with their HB-donating abilities being measured by analytical methods. They were found to be effective for a variety of asymmetric transformations including Michael reactions of a, b-unsaturated imides and hydrazination reactions of 1,3-dicarbonyl compounds. Thiourea catalysts that have an additional functional group are also described. Specifically, thioureas that bear a hydroxyl group were synthesized and subsequently used as novel bifunctional organocatalysts for catalytic, asymmetric Petasis-type reactions involving organoboronic acids as nucleophiles. These addition reactions were difficult to achieve using existing organocatalysts. One of the developed catalytic methods can be applied to the synthesis of biologically interesting peptide-derived compounds possessing unnatural vinyl glycine moieties. These findings introduce new criteria required for the development of organocatalysts for asymmetric reactions, thus making a significant contribution to the field of organocatalysis.

Karl Striegler investigates novel materials for photocatalytic hydrogen evolution from water. Graphitic Carbon Nitrides are an interesting class of materials with a structure close to graphite. For overcoming certain limitations, the author used different approaches to functionalize the basic material. He deposited nanoparticles to enhance the catalytic activity and used copolymerization as well as sensitizing to increase the amount of harvested light.

Sandra Haschke presents a strategy to enhance the Fe2O3 electrode performance by controlled nanostructuring of the catalyst surface, based on anodized aluminum oxide coated by means of atomic layer deposition. Furthermore, she investigates the influence of underlying conductive layers and post-deposition annealing on the electrode performance and the associated changes in morphology and chemical composition. Exploiting all effects combined delivers an increase in steady-state water oxidation throughput by a factor of 2.5 with respect to planar electrodes.

Janusz Lewinski and Andrew E. H. Wheatley: Simple trivalent organoaluminum species: perspectives on structure, bonding and reactivity.- Stephan Schulz: Organoaluminum complexes with bonds to s-block, p-block, d-block, and f-block metal centers.- Samuel Dagorne and Christophe Fliedel: Low valent organoaluminium (+I, +II) species.- Rudolf Wehmschulte: Organoaluminum species in homogeneous polymerization catalysis.- Paul Knochel, Tobias Blumke, Klaus Groll and Yi-Hung Chen: Preparation of Organoalanes for Organic Synthesis.- Yuki Naganawa and Keiji Maruoka: Reactions Triggered by Lewis Acidic Organoaluminum Species.- Usein M. Dzhemilev and Vladimir A. D'yakonov: Hydro-, Carbo- and Cycloalumination of Unsaturated Compounds.- Andreas Kolb and Paultheo von Zezschwitz: Organoaluminum Couplings to Carbonyls, Imines and Halides.- Oscar Pamies and Montserrat Dieguez: Conjugate Addition of Organoaluminum Species to Michael Acceptors and Related Processes.

In his Master project Sven Herrmann for the first time carried out fundamental investigations into the development of polyoxometalate based ionic liquids (POM-ILs). The POM-ILs were obtained by charge balancing inorganic polyoxometalate (POM) anions with sterically demanding tetraalkylammonium or tetraalkylphosphonium cations. By functionalization of lacunary Keggin clusters with 3d-transition metals and charge balancing with tetraalkylammonium cations of differing chain length, a model system for the correlation of the molecular structure with macroscopic materials properties was obtained. In a systematic approach the syntheses via self-aggregation is presented. Analytic methods comprise UV-Vis, FTIR, NMR, EPR and Moessbauer spectroscopy. For determination of the materials properties TGA and DSC were carried out and rheological studies shed light onto the flow characteristics of the highly viscous materials.

Processes that meet the objectives of green chemistry and chemical engineering minimize waste and energy use, and eliminate toxic by-products. Given the ubiquitous nature of products from chemical processes in our lives, green chemistry and chemical engineering are vital components of any sustainable future. Gathering together ten peer-reviewed articles from the Encyclopedia of Sustainability Science and Technology, Innovations in Green Chemistry and Green Engineering provides a comprehensive introduction to the state-of-the-art in this key area of sustainability research. Worldwide experts present the latest developments on topics ranging from organic batteries and green catalytic transformations to green nanoscience and nanotoxicology. An essential, one-stop reference for professionals in research and industry, this book also fills the need for an authoritative course text in environmental and green chemistry and chemical engineering at the upper-division undergraduate and graduate levels.

Representing the first text to cover this exciting new area of research, this book will describe synthesis techniques of CNWs, their characterization and various expected applications using CNWs. Carbon-nanowalls (CNWs) can be described as two-dimensional graphite nanostructures with edges comprised of stacks of plane graphene sheets standing almost vertically on the substrate. These sheets form a wall structure with a high aspect ratio. The thickness of CNWs ranges from a few nm to a few tens of nm. The large surface area and sharp edges of CNWs may prove useful for a number of applications such as electrochemical devices, field electron emitters, storage materials for hydrogen gas, catalyst support. In particular, vertically standing CNWs with a high surface-to-volume ratio, serve as an ideal material for catalyst support for fuel cells and in gas storage materials.

As the title suggests, Isotope Effects in the Chemical, Geological and Bio Sciences deals with differences in the properties of isotopically substituted molecules, such as differences in the chemical and physical properties of water and the heavy waters. Since the various fields in which isotope effects are applied do not only share fundamental principles but also experimental techniques, this book includes a discussion of experimental apparatus and experimental techniques. Isotope Effects in the Chemical, Geological and Bio Sciences is an educational monograph addressed to graduate students and others undertaking isotope effect research. The fundamental principles needed to understand isotope effects are presented in appropriate detail. While it is true that these principles are more familiar to students of physical chemistry and some background in physical chemistry is recommended, the text provides enough detail to make the book an asset to students in organic and biochemistry, and geochemistry.

This book looks at new ways of tackling the problem of separating reaction products from homogeneous catalytic solutions. The new processes involve low leaching supported catalysts, soluble supports such as polymers and dendrimers and unusual solvents such as water, fluorinated organics, ionic liquids and supercritical fluids. The advantages of the different possibilities are discussed alongside suggestions for further research that will be required for commercialisation. Unlike other books, in addition to the chemistry involved, the book looks at the process design that would be required to bring the new approaches to fruition. Comparisons are given with existing processes that have already been successfully applied and examples are given where these approaches are not suitable. The book includes: - New processes for the separation of products from solutions containing homogeneous catalysts - Catalysts on insoluble or soluble supports - fixed bed catalysts - continuous flow or ultrafiltration - Biphasic systems: water - organic, fluorous - organic, ionic liquid - organic, supercritical fluids (monophasic or biphasic with water, organic or ionic liquid) - Comparisons with current processes involving atmospheric or low temperature distillation - Consideration of Chemistry and Process Design - Advantages and disadvantages of each process exposed - Consideration of what else is need for commercialisation

This thesis focuses on porous monolithic materials that are not in the forms of particles, fibers, or films. In particular, the synthetic strategy of porous monolithic materials via the sol-gel method accompanied by phase separation, which is characterized as the non-templating method for tailoring well-defined macropores, is described from the basics to actual synthesis. Porous materials are attracting more and more attention in various fields such as electronics, energy storage, catalysis, sensing, adsorbents, biomedical science, and separation science. To date, many efforts have been made to synthesize porous materials in various chemical compositions-organics, inorganics including metals, glasses and ceramics, and organic-inorganic hybrids. Also demonstrated in this thesis are the potential applications of synthesized porous monolithic materials to separation media as well as to electrodes for electric double-layer capacitors (EDLCs) and Li-ion batteries (LIBs). This work is ideal for graduate students in materials science and is also useful to engineers or scientists seeking basic knowledge of porous monolithic materials.

This book gives a comprehensive overview of graphene oxides (GO) from atomic structures and fundamental properties to technological applications. Atomic structural models, electronic properties, mechanical properties, optical properties, and functionalizing and compositing of GO are illustrated. Moreover, the excellent physical and chemical properties offer GO promising applications in electronic nanodevices, chemical sensors and catalyst, energy storage, and biotechnology, which are also presented in this book. Therefore, this book is of interest to researchers in physics, chemistry, materials science, and nanoscience.