The study of fluctuations in statistical physics has a long history, and a general theory is well established, connecting fluctuations to response properties of equilibrium systems. Remarkably, this framework fails as soon as some current is flowing across the system, driving it out of equilibrium. The presence of currents is quite common in nature and produces rich phenomena which are far from being included in a general framework. This thesis focuses on this general problem by studying different models such as granular materials and systems exhibiting anomalous diffusion and shows how the generalized response techniques can be successfully used to catch the relevant degrees of freedom that drive the systems out of equilibrium. This study paves the way to the use of the generalized fluctuation relations in an operative way, in order to extract information from a non-equilibrium system and to build the corresponding phenomenological theory.

This thesis focuses on the bottom-up design, construction and operation of supramolecular systems capable of behaving as devices and machines on the molecular scale, which is a topic of great interest in nanoscience and a fascinating challenge in nanotechnology. In particular, the systems investigated here include: polyviologen dendrimers capable of behaving as hosts and chargestoring devices; molecular machines based on pseudorotaxanes/rotaxanes and operated by photoinduced proton transfer, or photoisomerization reactions; and a simple unimolecular multiplexer/demultiplexer. The systems have been characterized using a variety of techniques including absorption and emission spectra, laser flash photolysis, NMR spectroscopy, electrochemical experiments, stopped flow measurements. This research addresses a large number of open problems in the nanosciences, dealing with a wide range of the most advanced applications of supramolecular systems.

"Fundamental Aspects of Plasma Chemical Physics - Thermodynamics" develops basic and advanced concepts of plasma thermodynamics from both classical and statistical points of view.

After a refreshment of classical thermodynamics applied to the dissociation and ionization regimes, the book invites the reader to discover the role of electronic excitation in affecting the properties of plasmas, a topic often overlooked by the thermal plasma community.

Particular attention is devoted to the problem of the divergence of the partition function of atomic species and the state-to-state approach for calculating the partition function of diatomic and polyatomic molecules. The limit of ideal gas approximation is also discussed, by introducing Debye-Huckel and virial corrections.

Throughout the book, worked examples are given in order to clarify concepts and mathematical approaches.

This book is a first of a series of three books to be published by the authors on fundamental aspects of plasma chemical physics. The next books will discuss transport and kinetics.

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How can we obtain tools able to process and exchange information at the molecular scale? In order to do this, it is necessary to activate and detect single molecules under controlled conditions. This book focuses on the generation of biologically-inspired molecular devices. These devices are based on the developments of new photonic tools able to activate and stimulate single molecule machines. Additionally, new light sensitive molecules can be selectively activated by photonic tools. These technological innovations will provide a way to control activation of single light-sensitive molecules, allowing the investigation of molecular computation in a biological environment.

This book presents an overview of fundamental aspects of surface-based biosensors and techniques for enhancing their detection sensitivity and speed. It focuses on rapid detection using miniaturized sensors and describes the physical principles of nanoscale transducers, surface modifications, microfluidics and reaction engineering, diffusion and kinetics. A key challenge in the field of bioanalytical sensors is the rapid delivery of target biomolecules to the sensing surface. While various nanostructures have shown great promise in sensitive detection, diffusion-limited binding of analyte molecules remains a fundamental problem. Recently, many researchers have put forward novel schemes to overcome this challenge, such as nanopore channels, electrokinetics, and dielectrophoresis, to name but a few. This book provides the readers an up-to-date account on these technological advances.

This book shows the availability and potential of the coupled acoustic-gravitational (CAG) field for trace-level biosensing. The proposed detection scheme also allows the evaluation of the kinetics and thermodynamics of the reaction occurring on a single microparticle (MP). This method has wide applicability in important fields, involving not only chemistry but also life, environmental, and medical sciences. The author proposes novel trace-level biosensing based on measurements of the levitation coordinate shift of an MP in the CAG field. The levitation coordinate of the MP in the CAG field is determined by its density and compressibility. The levitation coordinate shift is induced by the binding of gold nanoparticles (AuNPs) to the MP through interparticle reactions. Therefore, the quantity of molecules involved in the reaction can be determined from the levitation coordinate shift. The author demonstrates the zmol level detection for biotin, DNA/RNA, and organic molecules. In addition, the kinetics and thermodynamics are evaluated for various reactions occurring between the MP and AuNP, such as the avidin-biotin reaction, direct hybridization, sandwich hybridization, and aptamer-target complexation. This book provides a new concept based on the CAG field, in which the extent of a reaction is converted into the levitation coordinate shift, that is, "length." The proposed method has many advantages over other methods, e.g., high biocompatibility, high applicability, and short analysis time. In addition, because the apparatus used in this study is inexpensive and easy to miniaturize, this method is useful in important practical fields, such as forensic and environmental science and diagnosis. Thus, this book inspires many researchers to apply the present method to their own fields of interest.

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.

"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.

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.

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

Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

This graduate textbook, written by a former lecturer, addresses industrial chemical reaction topics, focusing on the commercial-scale exploitation of chemical reactions. It introduces students to the concepts behind the successful design and operation of chemical reactors, with an emphasis on qualitative arguments, simple design methods, graphical procedures, and frequent comparison of capabilities of the major reactor types. It starts by discussing simple ideas before moving on to more advanced concepts with the support of numerous case studies. Many simple and advanced exercises are present in each chapter and the detailed MATLAB code for their solution is available to the reader as supplementary material on Springer website. It is written for MSc chemical engineering students and novice researchers working in industrial laboratories.

Particle models play an important role in many applications in physics, chemistry and biology. They can be studied on the computer with the help of molecular dynamics simulations. This book presents in detail both the necessary numerical methods and techniques (linked-cell method, SPME-method, tree codes, multipole technique) and the theoretical background and foundations. It illustrates the aspects modelling, discretization, algorithms and their parallel implementation with MPI on computer systems with distributed memory. Furthermore, detailed explanations are given to the different steps of numerical simulation, and code examples are provided. With the description of the algorithms and the presentation of the results of various simulations from the areas material science, nanotechnology, biochemistry and astrophysics, the reader of this book will be able to write his own programs for molecular dynamics step by step and to run successful experiments.

Contains details on the geological units of Nigeria and the associated mineral resources. The book is divided into three parts. Part 1 discusses the geology of the crystalline rocks and their regional distribution while the sedimentary basins constitute the subject of Part 2. Part 3 takes the mineral resources of Nigeria one on one, their geological environment, mode of occurrence, localities and where possible the reserves estimation. Thereafter, an account of the previous and current mining policies (including that of petroleum) of the Nigerian government is given and goes ahead to list some specific investment opportunities in the solid minerals sector.

Grain boundaries are a main feature of crystalline materials. They play a key role in determining the properties of materials, especially when grain size decreases and even more so with the current improvements of processing tools and methods that allow us to control various elements in a polycrystal.
This book presents the theoretical basis of the study of grain boundaries and aims to open up new lines of research in this area. The treatment is light on mathematical approaches while emphasizing practical examples; the issues they raise are discussed with reference to theories. The general approach of the book has two main goals: to lead the reader from the concept of 'ideal' to 'real' grain boundaries;
to depart from established knowledge and address the opportunities emerging through "grain boundary engineering," the control of morphological and crystallographic features that affect material properties.

The book is divided in three parts:
I 'From interganular order to disorder' deals with the concept of the perfect grain boundary, at equilibrium, and questions the maintenance of its crystalline state.
II 'From the ideal to the real grain boundary' deals with the concept of the faulted grain boundary. It attempts to reveal the influence of the grain boundary structure on its defects, their formation and their accommodation.
III 'From free to constrained grain boundaries' is devoted to grain boundary ensembles starting from the triple junction (the elemental configuration) to real grain boundary networks in polycrystals

This part covers a new and topical development in the field. It presents for the first time an avenue for researchers working on macroscopic aspects, to approach the scale of description of grain boundaries.

Audience: graduate students, researchers and engineers in Materials Science and all those scientists pursuing grain boundary engineering in order to improvematerials performance.

Familiar combinations of ingredients and processing make the structures that give food its properties. For example in ice cream, the emulsifiers and proteins stabilize partly crystalline milk fat as an emulsion, freezing (crystallization) of some of the water gives the product its hardness and polysaccharide stabilizers keep it smooth. Why different recipes work as they do is largely governed by the rules of physical chemistry. This textbook introduces the physical chemistry essential to understanding the behavior of foods. Starting with the simplest model of molecules attracting and repelling one another while being moved by the randomizing effect of heat, the laws of thermodynamics are used to derive important properties of foods such as flavor binding and water activity. Most foods contain multiple phases and the same molecular model is used to understand phase diagrams, phase separation and the properties of surfaces. The remaining chapters focus on the formation and properties of specific structures in foods - crystals, polymers, dispersions and gels. Only a basic understanding of food science is needed, and no mathematics or chemistry beyond the introductory college courses is required. At all stages, examples from the primary literature are used to illustrate the text and to highlight the practical applications of physical chemistry in food science.