This thesis identifies the turning point in chain length, after which alkanes self-solvate into a folded structure instead of an extended stretched conformation. After this turning point, London dispersion forces rearrange isolated n-alkanes into a particular hairpin-structure, while for shorter chain lengths, a simple stretched conformation is energetically preferred. This thesis can locate the experimental turning point for the first time in an interaction-free manner from measurements of unbranched alkanes at low temperatures in supersonic jet expansions. It contains a detailed analysis of the vibrational Raman spectra of the chain molecules, which is supported by comprehensive quantum chemical simulations. In this way, the detailed balance between inter-chain attraction and conformational flexibility can be quantified. The investigations are complemented by measurements of perfluoroalkanes and similarities and differences between the compounds are discussed. Furthermore, Nils Luttschwager determines the stiffnesses (elastic moduli) of two of the most common industrial polymers: polyethylene and polytetrafluorethylene. He uses in this thesis a sophisticated extrapolation to calculate this value from quantities of their building blocks, showing that the single polymer molecules can be as stiff as a rod of steel.

This book describes the fabrication of a frequency-based electronic tongue using a modified glassy carbon electrode (GCE), opening a new field of applying organic precursors to achieve nanostructure growth. It also presents a new approach to optimizing nanostructures by means of statistical analysis. The chemical vapor deposition (CVD) method was utilized to grow vertically aligned carbon nanotubes (CNTs) with various aspect ratios. To increase the graphitic ratio of synthesized CNTs, sequential experimental strategies based on response surface methodology were employed to investigate the crystallinity of CNTs. In the next step, glucose oxidase (GOx) was immobilized on the optimized multiwall carbon nanotubes/gelatin (MWCNTs/Gl) composite using the entrapment technique to achieve enzyme-catalyzed oxidation of glucose at anodic potentials, which was drop-casted onto the GCE. The modified GCE's performance indicates that a GOx/MWCNTs/Gl/GC electrode can be utilized as a glucose biosensor with a high direct electron transfer rate between GOx and MWCNTs/Gl. It was possible to use the fabricated biosensor as an electronic tongue thanks to a frequency-based circuit attached to the electrochemical cell. The results indicate that the modified GCE (with GOx/MWCNTs/Gl) holds promising potential for application in voltammetric electronic tongues.

Structure, Bonding, and Reactivity of Reactant Complexes and Key Intermediates, by Elena Soriano and Jose Marco-Contelles.-

Cycloisomerization of 1, "n"-Enynes Via Carbophilic Activation, by Patrick Yves Toullec and Veronique Michelet.-

DFT-Based Mechanistic Insights into Noble Metal-Catalyzed Rearrangement of Propargylic Derivatives: Chirality Transfer Processes, by Olalla Nieto Faza and Angel R. de Lera.-

"N"-Heterocyclic Carbene Complexes of Au, Pd, and Pt as Effective Catalysts in Organic Synthesis, by Andrea Correa, Steven P. Nolan and Luigi Cavallo.-

Activation of Allenes by Gold Complexes: A Theoretical Standpoint, by Max Malacria, Louis Fensterbank and Vincent Gandon.-

Heterocyclization of Allenes Catalyzed by Late Transition Metals: Mechanisms and Regioselectivity, by Benito Alcaide, Pedro Almendros, Teresa Martinez del Campo, Elena Soriano and Jose Marco-Contelles.-

Gold-Catalyzed Cycloadditions Involving Allenes: Mechanistic Insights from Theoretical Studies, by Sergi Montserrat, Gregori Ujaque, Fernando Lopez, Jose L. Mascarenas and Agusti Lledos.-

"

This book provides comprehensive coverage of Lithium (Li) metal anodes for rechargeable batteries. Li is an ideal anode material for rechargeable batteries due to its extremely high theoretical specific capacity (3860 mAh g-1), low density (0.59 g cm-3), and the lowest negative electrochemical potential ( 3.040 V vs. standard hydrogenelectrodes). Unfortunately, uncontrollable dendritic Li growth and limited Coulombic efficiency during Li deposition/stripping inherent in these batteries have prevented their practical applications over the past 40 years. With the emergence of post Liion batteries, safe and efficient operation of Li metal anodes has become an enabling technology which may determine the fate of several promising candidates for the next generation energy storage systems, including rechargeable Li-air batteries, Li-S batteries, and Li metal batteries which utilize intercalation compounds as cathodes. In this work, various factors that affect the morphology and Coulombic efficiency of Li anodes are analyzed. The authors also present the technologies utilized to characterize the morphology of Li deposition and the results obtained by modeling of Li dendrite growth. Finally, recent developments, especially the new approaches that enable safe and efficient operation of Li metal anodes at high current densities are reviewed. The urgent need and perspectives in this field are also discussed. The fundamental understanding and approaches presented in this work will be critical for the applicationof Li metal anodes. The general principles and approaches can also be used in other metal electrodes and general electrochemical deposition of metal films.

Thisbookistalkingabouthowtousesupercriticalwater(SCW)torapidlyproduce micro- and nano-particles of metal oxides, inorganic salts, metals and organics. Itcoversbasicprinciples,experimentalmethodologiesandreactors,particlep- duction,characterizationsandapplicationsaswellastherecentadvancement. Fine particlescanbeproducedbybothchemicalandphysicalprecipitationofproducts from SCW. They can be used as catalysts, materials in ceramics and electronic devices andcompositematerials. Particlesareeasilyproduced continuouslyina owreactorinshortreactiontimes(0. 4s?2min)butcanalsobesynthesizedin batchreactorsforlongreactiontimes(e. g. ,12h). Theycanbeeasilystudiedin-situ microscopically(optical/IR/Raman/SR-XRD)inanopticalmicro-reactor,diamond anvilcell. Thesize,sizedistribution,crystalgrowth&structure,andmorphologyof particlescanbecontrolledbychangingtheconcentrationsofstatingmaterials,pH, pressures,temperatures,heating&coolingrates,organicmodi cations,reducingor oxidizingatmospheres, owratesandreactiontimes. Thisisthe rstbooktosystematicallyintroduceusingSCWforproductionof neparticles. Itisanidealreferencebookforengineers,researchersandgraduate studentsinmaterialscienceandengineering. vii Acknowledgments I would like to thank Drs. T. Ogi & T. Minowa (Biomass Technology Research Center,NationalInstituteofAdvancedIndustrialScienceandTechnology,Japan), and Profs. K. Arai, H. Inomata, R. L. Smith Jr. and T. Adschiri (Chemical Engineering,TohokuUniversity,Japan),whoinitiallyintroducedthehydrothermal andsupercritical uidsareastomewhenIworkedinJapanfrom1996to1999. Thanks are also due to Profs. J. A. Kozinski, R. I. L. Guthrie (Materials Engineering,McGillUniversity,Canada)andI. S. Butler(Chemistry,McGill)for theirguidanceinmyworkonhydrothermalprocessduringmyworkinCanadafrom 1999to2007. Profs. W. Bassett (Geological Sciences, Cornell University) and D. Baker (Earth&PlanetarySciences,McGill)forinstructionsregardingDAC,Dr. I-Ming Chou(U. S. GeologicalSurvey)forusefuldiscussionsofthepressurecalculation procedure. Drs. M. Watanabe and T. Sato (Research Center of Supercritical Fluid Technology, Tohoku University, Japan) for discussions about the experimental set-upofthebatchand owreactors. Drs. S. Xu,H. Assaaoudi,R. HashaikehandA. Sobhy,whoworkedwithmeat McGillinCanada. ix Contents 1 Introduction...1 1. 1 Background ...1 1. 2 RapidExpansionofSupercriticalSolution(RESS)Process ...4 1. 3 SupercriticalAntisolvent(SAS)Process ...4 1. 4 OtherPhysicalProcesses ...5 1. 5 SupercriticalWaterProcess ...5 References...8 2 Supercritical Water Process...11 2. 1 Introduction ...11 2. 2 BatchReactor ...15 2. 3 FlowReactor...18 2. 4 DiamondAnvilCell(DAC)...20 References...25 3 Metal Oxides Synthesis...29 3. 1 Introduction ...29 3. 2 Boehmite(AlOOH) ...30 3. 3 Ferrites...31 3. 4 Phosphor(YAG) ...32 3. 5 LiCoO /LiMn O ...33 2 2 4 3. 6 Ce Zr O (x =0?1)...33 1?x x 2 3. 7 PotassiumHexatitanate,PotassiumNiobateandTitania ...35 3. 8 ZincOxide...38 3. 9 Nickel,Nickel/CobaltOxide...

"Adhesion of Cells, Viruses and Nanoparticles" describes the adhesion of cells, viruses and nanoparticles starting from the basic principles of adhesion science, familiar to postgraduates, and leading on to recent research results. The underlying theory is that of van der Waals forces acting between cells and substrates, embodied in the molecules lying at the surfaces, together with the geometry and elasticity of the materials involved. The first part describes the fundamental background to adhesion principles, including the phenomenology, the important equations and the modeling ideas. Then the mechanisms of adhesion are explored in the second part, including the elastic deformations of spheres and the importance of the energy of adhesion as measured in various tests. It is demonstrated that adhesion of cells is statistical and depends on Brownian movement and on the complex multiple contacts that can form as cells move around. Then, detailed chapters on cell adhesion, contact of viruses and aggregation of nanoparticles follow in Part 3. Finally, the last chapter looks to the future understanding of cell adhesion and points out some interesting directions of research, development and treatment of diseases related to these phenomena. This book is an ideal resource for researchers on adhesion molecules, receptors, cell and tissue culturing, virus infection, toxicity of nanoparticles and bioreactor fouling. It can also be used to support undergraduate and Masters level teaching courses. "This is a fascinating book and it is an invaluable resource for understanding particle-particle/surface adhesion at micro- and nano- scales. I intend to keep one for my future reference and highly recommend it to my students." (Prof. Zhibing Zhang, School of Chemical Engineering, University of Birmingham, UK)

Fifty years ago, a new approach to reaction kinetics began to emerge: one based on mathematical models of reaction kinetics, or formal reaction kinetics. Since then, there has been a rapid and accelerated development in both deterministic and stochastic kinetics, primarily because mathematicians studying differential equations and algebraic geometry have taken an interest in the nonlinear differential equations of kinetics, which are relatively simple, yet capable of depicting complex behavior such as oscillation, chaos, and pattern formation. The development of stochastic models was triggered by the fact that novel methods made it possible to measure molecules individually. Now it is high time to make the results of the last half-century available to a larger audience: students of chemistry, chemical engineering and biochemistry, not to mention applied mathematics. Based on recent papers, this book presents the most important concepts and results, together with a wealth of solved exercises. The book is accompanied by the authors' Mathematica package, ReactionKinetics, which helps both students and scholars in their everyday work, and which can be downloaded from http://extras.springer.com/ and also from the authors' websites. Further, the large set of unsolved problems provided may serve as a springboard for individual research.

"Photoelectrochemical Hydrogen Production" describes the principles and materials challenges for the conversion of sunlight into hydrogen through water splitting at a semiconducting electrode. Readers will find an analysis of the solid state properties and materials requirements for semiconducting photo-electrodes, a detailed description of the semiconductor/electrolyte interface, in addition to the photo-electrochemical (PEC) cell. Experimental techniques to investigate both materials and PEC device performance are outlined, followed by an overview of the current state-of-the-art in PEC materials and devices, and combinatorial approaches towards the development of new materials. Finally, the economic and business perspectives of PEC devices are discussed, and promising future directions indicated.

Photoelectrochemical Hydrogen Production is a one-stop resource for scientists, students and R&D practitioners starting in this field, providing both the theoretical background as well as useful practical information on photoelectrochemical measurement techniques. Experts in the field benefit from the chapters on current state-of-the-art materials/devices and future directions.

Bruce Yoder's thesis outlines his investigation of the dissociative chemisorption of methane (CH4) on a nickel single crystal. In this work Bruce uses a molecular beam and infrared laser techniques to prepare methane in excited rovibrational states. The excited methane molecules are aligned relative to the target nickel surface. Bruce describes the discovery and exploration of a previously unknown steric effect in the dissociation reaction between a vibrationally excited methane molecule and a nickel crystal. From these studies we see that methane molecules are up to twice as reactive when the vibration is aligned parallel rather than perpendicular to the surface. This discovery will help guide the development of detailed predictive models of methane chemisorption, which in turn may lead to better catalysts for the synthesis of several industrially relevant chemicals, including hydrogen fuel from natural gas.

This book introduces various types of reactions to produce chemicals by the direct conversion of methane from the point of view of mechanistic and functional aspects. The chemicals produced from methane are aliphatic and aromatic hydrocarbons such as propylene and benzene, and methanol. These chemicals are created by using homogeneous catalysts, heterogeneous catalysts such as zeolites, and biocatalysts such as enzymes. Various examples of methane conversion reactions that are discussed have been chosen to illustrate how heterogeneous and homogenous catalysts and biocatalysts and/or their reaction environments control the formation of highly energetic species from methane contributing to C-C and C-O bond formation.

In the 1980s, capillary electrophoresis (CE) joined high-performance liquid chromatography (HPLC) as the most powerful separation technique available to analytical chemists and biochemists. Published research using CE grew from 48 papers in the year of commercial introduction (1988) to 1200 in 1997. While only a dozen major pharmaceutical and biotech companies have reduced CE to routine practice, the applications market is showing real or potential growth in key areas, particularly in the DNA marketplace for genomic mapping and forensic identification. For drug development involving small molecules (including chiral separations), one CE instrument can replace 10 liquid chromatographs in terms of speed of analysis. CE also uses aqueous rather than organic solvents and is thus environmentally friendlier than HPLC. The second edition of Practical Capillary Electrophoresis has been extensively reorganized and rewritten to reflect modern usage in the field, with an emphasis on commercially available apparatus and reagents. This authoritative and very comprehensible treatment builds on the author's extensive experience as an instructor of short courses for the American Chemical Society and for industry.
Key Features
* Illustrated with detailed diagrams of electrophoretic phenomena
* Offers step-by-step methods development schemes
* Presents techniques for developing quantitative, robust, and precise methods
* Includes an extensive troubleshooting guide
* Updates and greatly expands on the first edition-more than 50% of the text is new
* Written by an internationally recognized scientist who is an instructor for American Chemical Society short courses on HPCE

Volume 15 in this series continues the voyage of discovery started almost a decade ago. Chapter 98 adds significantly to an evaluation of systematic, experimental low-temperature studies of the ambivalent behaviours of cerium (ferromagnetism, antiferromagnetism, spin glass, superconductivity etc.) which depend upon its environment in materials. The conclusions arrived at should provide new data against which the theory can be advanced. The next chapter provides a review of rare earth carbides, emphasizing the thermodynamics, phase diagrams, crystal structures and physical properties. The binary rare earth carbides present an exceptionally wide range of compositions and structures both as solids and gas-phase molecules. Complex carbides with additional metal and non-metal components also receive attention. Metal-rich halides (i.e. compounds with an X/R ratio <2) are the subject of the next chapter. The compounds are classified according to their structure and chemical bonding characteristics and their electrical and magnetic properties are also reviewed. Chapter 101 deals with the preparation, structure, chemical and physical properties of heavy-metal fluoride glasses. Large amounts of rare earths can be added into these, and they possess a great potential for optical applications in the mid-infrared range as fiber optic glasses for communication and transmission of information, optical wave guides, fiber lasers and sensors. The following chapter explores the chemical kinetics of solvent and ligand exchange in aqueous lanthanide solutions. A wealth of tabulated information on rate and equilibrium constants is provided in textual and tabular form. Chapter 103 considers the fundamentally important reactions of the lanthanide ions with water. These interactions are discussed for both solids and solutions. The hydrated species are considered in detail for the aqueous solution, revealing the consequences of the lanthanide series sequence. The concluding chapter reviews macrocyclic complexes formed by rare earth and dioxouranium ions as templates. Synthetic trends and reactivity are considered as well as potential uses of these intriguing wrap-around structures.

Fulleranes are a special class of carbon molecules derived from fullerenes whose double bonds are partially or at least theoretically fully saturated by hydrogen. The hydrogenation changes the chemical properties of fullerenes which can become susceptible to substitution reactions as opposed to addition reactions to the double bonds (present in common fullerenes). One of the most intriguing aspects of fulleranes is the fact that they have been thought to exist in the interstellar medium or even in certain circumstellar media.

"Fulleranes: The Hydrogenated Fullerenes" presents the state of the art research, synthesis and properties of these molecules.This book also includes astrophysicists' and astrochemists' expectations regarding the presence of these molecules in space.

This and volume no. 47of "Modern Aspects of Electrochemistry" is composed of eight chapters covering topics having relevance both in corrosion science and materials engineering. In particular, the first seven chapters provide comprehensive coverage of recent advances in corrosion science."

This book explores how structure impacts the dynamics of organic molecules in an extensive and impressive range of femtosecond time-resolved experiments that are combined with state-of-the-art theoretical approaches. It explores an area of molecular dynamics that remains largely uncharted and provides an extraordinary overview, along with novel insights into the concept of the dynamophore - the functional group of ultrafast science. Divided into four parts, this book outlines both experimental and computational studies on the VUV photoinduced dynamics of four cyclic ketones and one linear ketone, the ring-opening and dissociative dynamics of cyclopropane, and the potential ultrafast intersystem crossing in three methylated benzene derivatives. Model systems for the disulfide bond and the peptide bond, both of which are related to the structure of proteins, are also investigated. This highly informative and carefully presented book offers a wealth of scientific insights for all scholars with an interest in molecular dynamics.

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.

The book comprises an assembly of benchmarks and examples for porous media mechanics collected over the last twenty years. Analysis of thermo-hydro-mechanical-chemical (THMC) processes is essential to many applications in environmental engineering, such as geological waste deposition, geothermal energy utilisation, carbon capture and storage, water resources management, hydrology, even climate chance. In order to assess the feasibility as well as the safety of geotechnical applications, process-based modelling is the only tool to put numbers, i.e. to quantify future scenarios. This charges a huge responsibility concerning the reliability of computational tools. Benchmarking is an appropriate methodology to verify the quality of modelling tools based on best practices. Moreover, benchmarking and code comparison foster community efforts. The benchmark book is part of the OpenGeoSys initiative - an open source project to share knowledge and experience in environmental analysis and scientific computation.

This book describes a robust, low-cost electrochemical sensing system that is able to detect hormones and phthalates - the most ubiquitous endocrine disruptor compounds - in beverages and is sufficiently flexible to be readily coupled with any existing chemical or biochemical sensing system. A novel type of silicon substrate-based smart interdigital transducer, developed using MEMS semiconductor fabrication technology, is employed in conjunction with electrochemical impedance spectroscopy to allow real-time detection and analysis. Furthermore, the presented interdigital capacitive sensor design offers a sufficient penetration depth of the fringing electric field to permit bulk sample testing. The authors address all aspects of the development of the system and fully explain its benefits. The book will be of wide interest to engineers, scientists, and researchers working in the fields of physical electrochemistry and biochemistry at the undergraduate, postgraduate, and research levels. It will also be highly relevant for practitioners and researchers involved in the development of electromagnetic sensors.

This book reviews the latest advances in the bioelectrochemical degradation of recalcitrant environmental contaminants. The first part introduces readers to the basic principles and methodologies of bioelectrochemical systems, electron-respiring microorganisms, the electron transfer mechanism and functional electrode materials. In turn, the second part addresses the bioelectrochemical remediation/treatment of various environmental pollutants (including highly toxic refractory organics, heavy metals, and nitrates) in wastewater, sediment and wetlands. Reactor configuration optimization, hybrid technology amplification and enhanced removal principles and techniques are also discussed. The book offers a valuable resource for all researchers and professionals working in environmental science and engineering, bioelectrochemistry, environmental microbiology and biotechnology.

Written by an interdisciplinary group of experts from both industry and academia, Acoustic Wave Sensors provides an in-depth look at the current state of acoustic wave devices and the scope of their use in chemical, biochemical, and physical measurements, as well as in engineering applications. Because of the inherent interdisciplinary applications of these devices, this book will be useful for the chemist and biochemist interested in the use and development ofthese sensors for specific applications; the electrical engineer involved in the design and improvement of these devices; the chemical engineer and the biotechnologist interested in using these devices for process monitoring and control; and the sensor community at large.
Key Features
* Provides in-depth comparison and analyses of different types of acoustic wave devices
* Discusses operating principles and design considerations
* Includes table of relevant material constants for quick reference
* Presents an extensive review of current uses of these devices for chemical, biochemical, and physical measurements, and engineering applications

"Fundamental Aspects of Plasma Chemical Physics: Transport "develops basic and advanced concepts of plasma transport to the modern treatment of the Chapman-Enskog method for the solution of the Boltzmann transport equation.

The book invites the reader to consider actual problems of the transport of thermal plasmas with particular attention to the derivation of diffusion- and viscosity-type transport cross sections, stressing the role of resonant charge-exchange processes in affecting the diffusion-type collision calculation of viscosity-type collision integrals.

A wide range of topics is then discussed including (1) the effect of non-equilibrium vibrational distributions on the transport of vibrational energy, (2) the role of electronically excited states in the transport properties of thermal plasmas, (3) the dependence of transport properties on the multitude of Saha equations for multi-temperature plasmas, and (4) the effect of the magnetic field on transport properties.

Throughout the book, worked examples are provided to clarify concepts and mathematical approaches.

This book is the second of a series of three published by the Bari group on fundamental aspects of plasma chemical physics. The first book, "Fundamental Aspects of Plasma Chemical Physics: Thermodynamics," is dedicated to plasma thermodynamics; and the third, "Fundamental Aspects of Plasma Chemical Physics: Kinetics," deals with plasma kinetics.

Rapid evolution of trade, cultural and human relations provides the qualitative and quantitative enhancement of international collaborations, linking the countries with different economical and technological level. Delocalization of High-Tech industry inevitably leads to development of the material science and engineering researches in emergent countries, requiring transfer of know-how, restructuration of basic research and educational networks. This book presents the contributions of participants of the Advanced Research Workshop "Smart Materials for Energy, Communications and Security" (ARW SMECS; www.smecs.ferroix.net), organized in December 2007 in Marrakech in frame of the "NATO - Science for Peace" program. The objective of this event was the attempt to overview several hot topics of material physics related with problems of modern society: transformation and storage of energy, treatment and transmission of information, environmental security issues etc., with the focus of their implementation in Mediterranean Dialogue (MD) countries: Algeria, Egypt, Mauritania, Morocco and Tunisia. The workshop is an important stage in developing of the research network "Mediterranean Electronic Materials" - MEM (www.reseau-MEM.org), that has an objective to encourage the inter-Maghreb and Europe-Maghreb collaborative studies in the area of electroactive materials. Participants of the Advanced Research Workshop "Smart Materials for Energy, Communications and Security" , Marrakech, Morocco, December 2007 v vi PREFACE

This book is a research monograph summarizing recent advances related to the molecular structure of water and ice, and it is based on the latest spectroscopic data available. A special focus is given to radio- and microwave frequency regions. Within the five interconnected chapters, the author reviews the electromagnetic waves interaction with water, ice, and moist substances, discussing the microscopic mechanisms behind the dielectric responses. Well-established classic views concerning the structure of water and ice are considered along with new approaches related to atomic and molecular dynamics. Particular attention is given to nanofluidics, atmospheric science, and electrochemistry. The mathematical apparatus, based on diverse approaches employed in condensed matter physics, is widely used and allows the reader to quantitatively describe the electrodynamic response of water and ice in both bulk and confined states. This book is intended for a wide audience covering physicists, electrochemists, geophysicists, engineers, biophysicists, and general scientists who work on the electromagnetic radiation interaction with water and moist substances.