Nuclear magnetic resonance studies of molecular interactions and structures

This thesis is concerned with the investigation, by nuclear magnetic resonance spectroscopy, of the molecular interactions occurring in mixtures of benzene and cyclohexane to which either chloroform or deutero-chloroform has been added. The effect of the added polar molecule on the liquid structure has been studied using spin-lattice relaxation time, 1H chemical shift, and nuclear Overhauser effect measurements. The main purpose of the work has been to validate a model for molecular interaction involving local ordering of benzene around chloroform. A chemical method for removing dissolved oxygen from samples has been developed to encompass a number of types of sample, including quantitative mixtures, and its supremacy over conventional deoxygenation technique is shown. A set of spectrometer conditions, the use of which produces the minimal variation in peak height in the steady state, is presented. To separate the general diluting effects of deutero-chloroform from its effects due to the production of local order a series of mixtures involving carbon tetrachloride, instead of deutero-chloroform, have been used as non-interacting references. The effect of molecular interaction is shown to be explainable using a solvation model, whilst an approach involving 1:1 complex formation is shown not to account for the observations. It is calculated that each solvation shell, based on deutero-chloroform, contains about twelve molecules of benzene or cyclohexane. The equations produced to account for the T1 variations have been adapted to account for the 1H chemical shift variations in the same system. The shift measurements are shown to substantiate the solvent cage model with a cage capacity of twelve molecules around each chloroform molecule. Nuclear Overhauser effect data have been analysed quantitatively in a manner consistent with the solvation model. The results show that discrete shells only exist when the mole fraction of deutero-chloroform is below about 0.08.

Green innovation management in the automotive industry

Online case studies. Managing Innovation is an established, bestselling text for MBA, MSc and advanced undergraduate courses on management of technology, innovation management and entrepreneurship. It is also used widely by managers in both the service and manufacturing sectors. Now in its fourth edition, Managing Innovation has been fully revised and updated based on extensive user feedback to incorporate the latest findings and techniques in innovation management. The authors have included a new and more explicit innovation model, which is used throughout the book and have introduced two new features – Research Notes and Views from the Front Line – to incorporate more real life case material into the book. The strong evidence–based and practical approach makes this a must–read for anyone studying or working within innovation. An extensive website accompanies this text at www.managing–innovation.com. Readers can browse an online database of audio and video clips, as well as case study material, interactive exercises and tools for innovation, whilst lecturers can find additional support material including instructor slides and teaching guides and tips. "Tidd and Bessant's text has become a standard for students and practitioners of innovation. They offer a lively account on innovation management full of interesting and new examples, but one that at the same is rigorously anchored in what we have learned over the last thirty years on how to manage that ultimate business challenge of renewing products, processes, and business models. Those who want to innovate must read this book." — Professor Arnoud De Meyer, Director, Judge Business School, University of Cambridge, UK "Innovation matters and this book by two leaders in the field which is clear and practical as well as rigorous should be essential reading for all seeking to study or to become involved in innovation." — Chris Voss, Professor of Operations and Technology Management, London Business School "...comprehensive and comprehensible compendium on the management of innovation. It is very well organized and very well presented. A pedagogic tool that will work at multiple levels for those wishing to gain deeper insights into some of the most challenging and important management issues of the day." — David J. Teece, Thomas W. Tusher Professor in Global Business, Haas School of Business, University of California, Berkeley, USA "Those of us who teach in the field of Innovation Management were delighted when the first edition of this book appeared 11 years ago. The field had long been in need of such a comprehensive and integrated empirically–based work. The fact that this is now the 4th edition is clear testimony to the value of its contribution. We are deeply indebted to the authors for their dedication and diligence in providing us with this updated and expanded volume." — Thomas J. Allen,Howard W. Johnson Professor of Management, MIT Sloan School of Management, USA.

Solvable model for distribution networks on random graphs

We propose a simple model that captures the salient properties of distribution networks, and study the possible occurrence of blackouts, i.e., sudden failings of large portions of such networks. The model is defined on a random graph of finite connectivity. The nodes of the graph represent hubs of the network, while the edges of the graph represent the links of the distribution network. Both, the nodes and the edges carry dynamical two state variables representing the functioning or dysfunctional state of the node or link in question. We describe a dynamical process in which the breakdown of a link or node is triggered when the level of maintenance it receives falls below a given threshold. This form of dynamics can lead to situations of catastrophic breakdown, if levels of maintenance are themselves dependent on the functioning of the net, once maintenance levels locally fall below a critical threshold due to fluctuations. We formulate conditions under which such systems can be analyzed in terms of thermodynamic equilibrium techniques, and under these conditions derive a phase diagram characterizing the collective behavior of the system, given its model parameters. The phase diagram is confirmed qualitatively and quantitatively by simulations on explicit realizations of the graph, thus confirming the validity of our approach. © 2007 The American Physical Society.

Semantic and organization considerations in database conceptual modelling : the Semantic Conceptual Organizational Model (SECOM)

This thesis presents a new approach to designing large organizational databases. The approach emphasizes the need for a holistic approach to the design process. The development of the proposed approach was based on a comprehensive examination of the issues of relevance to the design and utilization of databases. Such issues include conceptual modelling, organization theory, and semantic theory. The conceptual modelling approach presented in this thesis is developed over three design stages, or model perspectives. In the semantic perspective, concept definitions were developed based on established semantic principles. Such definitions rely on meaning - provided by intension and extension - to determine intrinsic conceptual definitions. A tool, called meaning-based classification (MBC), is devised to classify concepts based on meaning. Concept classes are then integrated using concept definitions and a set of semantic relations which rely on concept content and form. In the application perspective, relationships are semantically defined according to the application environment. Relationship definitions include explicit relationship properties and constraints. The organization perspective introduces a new set of relations specifically developed to maintain conformity of conceptual abstractions with the nature of information abstractions implied by user requirements throughout the organization. Such relations are based on the stratification of work hierarchies, defined elsewhere in the thesis. Finally, an example of an application of the proposed approach is presented to illustrate the applicability and practicality of the modelling approach.

A molecular dynamics model of the atomic structure of dysprosium alumino-phosphate glass

Molecular dynamics (MD) has been used to identify the relative distribution of dysprosium in the phosphate glass DyAl0.30P3.05O9.62. The MD model has been compared directly with experimental data obtained from neutron diffraction to enable a detailed comparison beyond the total structure factor level. The MD simulation gives Dy ... Dy correlations at 3.80(5) and 6.40(5) angstrom with relative coordination numbers of 0.8(1) and 7.3(5), thus providing evidence of minority rare-earth clustering within these glasses. The nearest neighbour Dy-O peak occurs at 2.30 angstrom with each Dy atom having on average 5.8 nearest neighbour oxygen atoms. The MD simulation is consistent with the phosphate network model based on interlinked PO4 tetrahedra where the addition of network modifiers Dy3+ depolymerizes the phosphate network through the breakage of P-(O)-P bonds whilst leaving the tetrahedral units intact. The role of aluminium within the network has been taken into explicit account, and A1 is found to be predominantly (78 tetrahedrally coordinated. In fact all four A1 bonds are found to be to P (via an oxygen atom) with negligible amounts of Al-O-Dy bonds present. This provides an important insight into the role of Al additives in improving the mechanical properties of these glasses.

Concentration polarization model of spiral-wound membrane modules with application to batch-mode RO desalination of brackish water

Batch-mode reverse osmosis (batch-RO) operation is considered a promising desalination method due to its low energy requirement compared to other RO system arrangements. To improve and predict batch-RO performance, studies on concentration polarization (CP) are carried out. The Kimura-Sourirajan mass-transfer model is applied and validated by experimentation with two different spiral-wound RO elements. Explicit analytical Sherwood correlations are derived based on experimental results. For batch-RO operation, a new genetic algorithm method is developed to estimate the Sherwood correlation parameters, taking into account the effects of variation in operating parameters. Analytical procedures are presented, then the mass transfer coefficient models are developed for different operation processes, i.e., batch-RO and continuous RO. The CP related energy loss in batch-RO operation is quantified based on the resulting relationship between feed flow rates and mass transfer coefficients. It is found that CP increases energy consumption in batch-RO by about 25% compared to the ideal case in which CP is absent. For continuous RO process, the derived Sherwood correlation predicted CP accurately. In addition, we determined the optimum feed flow rate of our batch-RO system.

Non-Markov state model of peptide dynamics

A hidden Markov state model has been applied to classical molecular dynamics simulated small peptide in explicit water. The methodology allows increasing the time resolution of the model and describe the dynamics with the precision of 0.3 ps (comparing to 6 ps for the standard methodology). It also permits the investigation of the mechanisms of transitions between the conformational states of the peptide. The detailed description of one of such transitions for the studied molecule is presented. © 2012 Elsevier B.V. All rights reserved.

Quantization of the Inhomogeneous Bianchi I model:quasi-Heisenberg picture

The quantization scheme is suggested for a spatially inhomogeneous 1+1 Bianchi I model. The scheme consists in quantization of the equations of motion and gives the operator (so called quasi-Heisenberg) equations describing explicit evolution of a system. Some particular gauge suitable for quantization is proposed. The Wheeler-DeWitt equation is considered in the vicinity of zero scale factor and it is used to construct a space where the quasi-Heisenberg operators act. Spatial discretization as a UV regularization procedure is suggested for the equations of motion.