Studies of molecular interactions using physical techniques

The investigations described in this thesis concern the molecular interactions between polar solute molecules and various aromatic compounds in solution. Three different physical methods were employed. Nuclear magnetic resonance (n.m.r.) spectroscopy was used to determine the nature and strength of the interactions and the geometry of the transient complexes formed. Cryoscopic studies were used to provide information on the stoichiometry of the complexes. Dielectric constant studies were conducted in an attempt to confirm and supplement the spectroscopic investigations. The systems studied were those between nitromethane, chloroform, acetonitrile (solutes) and various methyl substituted benzenes. In the n.m.r. work the dependence of the solute chemical shift upon the compositions of the solutions was determined. From this the equilibrium quotients (K) for the formation of each complex and the shift induced in the solute proton by the aromatic in the complex were evaluated. The thermodynamic parameters for the interactions were obtained from the determination of K at several temperatures. The stoichiometries of the complexes obtained from cryoscopic studies were found to agree with those deduced from spectroscopic investigations. For most systems it is suggested that only one type of complex, of 1:1 stiochiometry, predominates except that for the acetonitrile-benzene system a 1:2 complex is formed. Two sets of dielectric studies were conducted, the first to show that the nature of the interaction is dipole-induced dipole and the second to calculate K. The equilibrium quotients obtained from spectroscopic and dielectric studies are compared. Time-averaged geometries of the complexes are proposed. The orientation of solute, with respect to the aromatic for the 1:1 complexes, appears to be the one in which the solute lies symmetrically about the aromatic six-fold axis whereas for the 1:2 complex, a sandwich structure is proposed. It is suggested that the complexes are formed through a dipole-induced dipole interaction and steric factors play some part in the complex formation.

A systems and cybernetic perspective on complex problem solving

This thesis is concerned with Organisational Problem Solving. The work reflects the complexities of organisational problem situations and the eclectic approach that has been necessary to gain an understanding of the processes involved. The thesis is structured into three main parts. Part I describes the author's understanding of problems and suitable approaches. Chapter 2 identifies the Transcendental Realist (TR) view of science (Harre 1970, Bhaskar 1975) as the best general framework for identifying suitable approaches to complex organisational problems. Chapter 3 discusses the relationship between Checkland's methodology (1972) and TR. The need to generate iconic (explanatory) models of the problem situation is identified and the ability of viable system modelling to supplement the modelling stage of the methodology is explored in Chapter 4. Chapter 5 builds further on the methodology to produce an original iconic model of the methodological process. The model characterises the mechanisms of organisational problem situations as well as desirable procedural steps. The Weltanschauungen (W's) or "world views" of key actors is recognised as central to the mechanisms involved. Part II describes the experience which prompted the theoretical investigation. Chapter 6 describes the first year of the project. The success of this stage is attributed to the predominance of a single W. Chapter 7 describes the changes in the organisation which made the remaining phase of the project difficult. These difficulties are attributed to a failure to recognise the importance of differing W's. Part III revisits the theoretical and organisational issues. Chapter 8 identifies a range of techniques embodying W's which are compatible with .the framework of Part I and which might usefully supplement it. Chapter 9 characterises possible W's in the sponsoring organisation. Throughout the work, an attempt 1s made to reflect the process as well as the product of the author's leaving.

Strategic development of transport systems: a study of the physical constraints on planning processes

Investment in transport infrastructure can be highly sensitive to uncertainty. The scale and lead time of strategic transport programmes are such that they require continuing policy support and accurate forecasting. Delay, cost escalation and abandonment of projects often result if these conditions are not present. In Part One the physical characteristics of infrastructure are identified as a major constraint on planning processes. The extent to which strategies and techniques acknowledge these constraints is examined. A simple simulation model is developed to evaluate the effects on system development of variations in the scale and lead time of investments. In Part Two, two case studies of strategic infrastructure investment are analysed. The absence of a policy consensus for airport location was an important factor in the delayed resolution of the Third London Airport issue. In London itself, the traffic and environmental effects of major highway investment ultimately resulted in the abandonment of plans to construct urban motorways. In both cases, the infrastructure implications of alternative strategies are reviewed with reference to the problems of uncertainty. In conclusion, the scale of infrastructure investment is considered the most important of the constraints on the processes of transport planning. Adequate appraisal of such constraints may best be achieved by evaluation more closely aligned to policy objectives.

MEG and complex systems

MEG beamformer algorithms work by making the assumption that correlated and spatially distinct local field potentials do not develop in the human brain. Despite this assumption, images produced by such algorithms concur with those from other non-invasive and invasive estimates of brain function. In this paper we set out to develop a method that could be applied to raw MEG data to explicitly test his assumption. We show that a promax rotation of MEG channel data can be used as an approximate estimator of the number of spatially distinct correlated sources in any frequency band.

Complex Protection System of Metadata-based Distributed Information Systems

A description of architecture and approaches to the implementation of a protection system of metadatabased adaptable information systems is suggested. Various protection means are examined. The system described is a multilevel complex based on a multiagent system combining IDS functional abilities with structure and logics protection means.

Evolutionary Clustering of Complex Systems and Processes

In a paper the method of complex systems and processes clustering based use of genetic algorithm is offered. The aspects of its realization and shaping of fitness-function are considered. The solution of clustering task of Ukraine areas on socio-economic indexes is represented and comparative analysis with outcomes of classical methods is realized.

CEPBen:a benchmark for complex event processing systems

Complex Event processing (CEP) has emerged over the last ten years. CEP systems are outstanding in processing large amount of data and responding in a timely fashion. While CEP applications are fast growing, performance management in this area has not gain much attention. It is critical to meet the promised level of service for both system designers and users. In this paper, we present a benchmark for complex event processing systems: CEPBen. The CEPBen benchmark is designed to evaluate CEP functional behaviours, i.e., filtering, transformation and event pattern detection and provides a novel methodology of evaluating the performance of CEP systems. A performance study by running the CEPBen on Esper CEP engine is described and discussed. The results obtained from performance tests demonstrate the influences of CEP functional behaviours on the system performance. © 2014 Springer International Publishing Switzerland.

A Solver for Complex-Valued Parametric Linear Systems

This work reports on a new software for solving linear systems involving affine-linear dependencies between complex-valued interval parameters. We discuss the implementation of a parametric residual iteration for linear interval systems by advanced communication between the system Mathematica and the library C-XSC supporting rigorous complex interval arithmetic. An example of AC electrical circuit illustrates the use of the presented software.

Diagonalizable Complex Systems, Reduced Dimension and Hermitian Systems II

2002 Mathematics Subject Classification: 35L40

Complex Oscillations and Limit Cycles in Autonomous Two-Component Incommensurate Fractional Dynamical Systems

MSC 2010: 26A33, 34D05, 37C25

Hydro-physical characterization of media used in agricultural systems to develop the best management practices for operation of an environmentally sustainable agricultural enterprise

Florida is the second leading horticulture state in the United States with a total annual industry sale of over $12 Billion. Due to its competitive nature, agricultural plant production represents an extremely intensive practice with large amounts of water and fertilizer usage. Agrochemical and water management are vital for efficient functioning of any agricultural enterprise, and the subsequent nutrient loading from such agricultural practices has been a concern for environmentalists. A thorough understanding of the agrochemical and the soil amendments used in these agricultural systems is of special interest as contamination of soils can cause surface and groundwater pollution leading to ecosystem toxicity. The presence of fragile ecosystems such as the Everglades, Biscayne Bay and Big Cypress near enterprises that use such agricultural systems makes the whole issue even more imminent. Although significant research has been conducted with soils and soil mix, there is no acceptable method for determining the hydraulic properties of mixtures that have been subjected to organic and inorganic soil amendments. Hydro-physical characterization of such mixtures can facilitate the understanding of water retention and permeation characteristics of the commonly used mix which can further allow modeling of soil water interactions. The objective of this study was to characterize some of the locally and commercially available plant growth mixtures for their hydro-physical properties and develop mathematical models to correlate these acquired basic properties to the hydraulic conductivity of the mixture. The objective was also to model the response patterns of soil amendments present in those mixtures to different water and fertilizer use scenarios using the characterized hydro-physical properties with the help of Everglades-Agro-Hydrology Model. The presence of organic amendments helps the mixtures retain more water while the inorganic amendments tend to adsorb more nutrients due to their high surface area. The results of these types of characterization can provide a scientific basis for understanding the non-point source water pollution from horticulture production systems and assist in the development of the best management practices for the operation of environmentally sustainable agricultural enterprise