Thermodynamics of binding of regulatory ligands to tissue transglutaminase

The transamidating activity of tissue transglutaminase is regulated by the ligands calcium and GTP, via conformational changes which facilitate or interfere with interaction with the peptidyl-glutamine substrate. We have analysed binding of these ligands by calorimetric and computational approaches. In the case of GTP we have detected a single high affinity site (K (D) approximately 1 muM), with moderate thermal effects suggestive that binding GTP involves replacement of GDP, normally bound to the protein. On line with this possibility no significant binding was observed during titration with GDP and computational studies support this view. Titration with calcium at a high cation molar excess yielded a complex binding isotherm with a number of "apparent binding sites" in large excess over those detectable by equilibrium dialysis (6 sites). This binding pattern is ascribed to occurrence of additional thermal contributions, beyond those of binding, due to the occurrence of conformational changes and to catalysis itself (with protein self-crosslinking). In contrast only one site for binding calcium with high affinity (K (D) approximately 0.15 muM) is observed with samples of enzyme inactivated by alkylation at the active site (to prevent enzyme crosslinkage and thermal effects of catalysis). These results indicate an intrinsic ability of tissue transglutaminase to bind calcium with high affinity and the necessity of careful reassessment of the enzyme regulatory pattern in relation to the concentrations of ligands in living cells, taking also in account effects of ligands on protein subcellular compartimentation.

Random graph coloring:Statistical physics approach

The problem of vertex coloring in random graphs is studied using methods of statistical physics and probability. Our analytical results are compared to those obtained by exact enumeration and Monte Carlo simulations. We critically discuss the merits and shortcomings of the various methods, and interpret the results obtained. We present an exact analytical expression for the two-coloring problem as well as general replica symmetric approximated solutions for the thermodynamics of the graph coloring problem with p colors and K-body edges. ©2002 The American Physical Society.

A study in the application of domestic solar assisted heat pumps for heating and cooling

In the present work, the more important parameters of the heat pump system and of solar assisted heat pump systems were analysed in a quantitative way. Ideal and real Rankine cycles applied to the heat pump, with and without subcooling and superheating were studied using practical recommended values for their thermodynamics parameters. Comparative characteristics of refrigerants here analysed looking for their applicability in heat pumps for domestic heating and their effect in the performance of the system. Curves for the variation of the coefficient of performance as a function of condensing and evaporating temperatures were prepared for R12. Air, water and earth as low-grade heat sources and basic heat pump design factors for integrated heat pumps and thermal stores and for solar assisted heat pump-series, parallel and dual-systems were studied. The analysis of the relative performance of these systems demonstrated that the dual system presents advantages in domestic applications. An account of energy requirements for space and hater heating in the domestic sector in the O.K. is presented. The expected primary energy savings by using heat pumps to provide for the heating demand of the domestic sector was found to be of the order of 7%. The availability of solar energy in the U.K. climatic conditions and the characteristics of the solar radiation here studied. Tables and graphical representations in order to calculate the incident solar radiation over a tilted roof were prepared and are given in this study in section IV. In order to analyse and calculate the heating load for the system, new mathematical and graphical relations were developed in section V. A domestic space and water heating system is described and studied. It comprises three main components: a solar radiation absorber, the normal roof of a house, a split heat pump and a thermal store. A mathematical study of the heat exchange characteristics in the roof structure was done. This permits to evaluate the energy collected by the roof acting as a radiation absorber and its efficiency. An indication of the relative contributions from the three low-grade sources: ambient air, solar boost and heat loss from the house to the roof space during operation is given in section VI, together with the average seasonal performance and the energy saving for a prototype system tested at the University of Aston. The seasonal performance as found to be 2.6 and the energy savings by using the system studied 61%. A new store configuration to reduce wasted heat losses is also discussed in section VI.

A detailed design study of leaching and ancillary processes in the hydrometallurgical extraction of iron from iron bearing feedstocks

A systematic survey of the possible methods of chemical extraction of iron by chloride formation has been presented and supported by a comparable study of :feedstocks, products and markets. The generation and evaluation of alternative processes was carried out by the technique of morphological analysis vihich was exploited by way of a computer program. The final choice was related to technical feasibility and economic viability, particularly capital cost requirements and developments were made in an estimating procedure for hydrometallurgjcal processes which have general applications. The systematic exploration included the compilation of relevant data, and this indicated a need.to investigate precipitative hydrolysis or aqueous ferric chloride. Arising from this study, two novel hydrometallurgical processes for manufacturing iron powder are proposed and experimental work was undertaken in the following .areas to demonstrate feasibility and obtain basic data for design purposes: (1) Precipitative hydrolysis of aqueous ferric chloride. (2) Gaseous chloridation of metallic iron, and oxidation of resultant ferrous chloride. (3) Reduction of gaseous ferric chloride with hydrogen. (4) Aqueous acid leaching of low grade iron ore. (5) Aqueous acid leaching of metallic iron. The experimentation was supported by theoretical analyses dealing with: (1) Thermodynamics of hydrolysis. (2) Kinetics of ore leaching. (3) Kinetics of metallic iron leaching. (4) Crystallisation of ferrous chloride. (5) Oxidation of anhydrous ferrous chloride. (6) Reduction of ferric chloride. Conceptual designs are suggested fbr both the processes mentioned. These draw attention to areas where further work is necessary, which are listed. Economic analyses have been performed which isolate significant cost areas, und indicate total production costs. Comparisons are mode with previous and analogous proposals for the production of iron powder.

The steam reforming of hydrocarbons with special reference to methane

From an examination of the literature relating to the catalytic steam reforming of hydrocarbons, it is concluded that the kinetics of high pressure reforming, particularly steam-methane reforming, has received relatively little attention. Therefore because of the increasing availability of natural gas in the U.K., this system was considered worthy of investigation. An examination of the thermodynamics relating to the equilibria of steam-hydrocarbon reforming is described. The reactions most likely to have influence over the process are established and from these a computer program was written to calculate equilibrium compositions. A means of presenting such data in a graphica1 form for ranges of the operating variables is given, and also an operating chart which may be used to quickly check feed ratios employed on a working naphtha reforming plant is presented. For the experimental kinetic study of the steam-methane system, cylindrical pellets of ICI 46-1 nickel catalyst were used in the form of a rod catalyst. The reactor was of the integral type and a description is given with the operating procedures and analytical method used. The experimental work was divided into two parts, qualitative and quantitative. In the qualitative study the various reaction steps are examined in order to establish which one is rate controlling. It is concluded that the effects of film diffusion resistance within the conditions employed are negligible. In the quantitative study it was found that at 250 psig and 6500C the steam-methane reaction is much slower than the CO shift reaction and is rate controlling. Two rate mechanisms and accompanying kinetic rate equations are derived, both of which represent 'chemical' steps in the reaction and are considered of equal merit. However the possibility of a dual control involving 'chemical' and pore diffusion resistances is also expressed.

Transition metal ion coordination in hydrophilic polymer membranes

The research described within this thesis is concerned with the investigation of transition metal ion complexation within hydrophilic copolymer membranes. The membranes are copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine, the 2-hydroxyethyl ester of 4,4'- dicarboxy-2,2'-bipyridine & bis-(5-vinylsalicylidene)ethylenediamine with 2-hydroxyethyl methacrylate. The effect of the polymer matrix on the formation and properties of transition metal iron complexes has been studied, specifically Cr(III) & Fe(II) salts for the bipyridyl- based copolymer membranes and Co(II), Ni(II) & Cu(II) salts for the salenH2- based copolymer membranes. The concomitant effect of complex formation on the properties of the polymer matrix have also been studied, e.g. on mechanical strength. A detailed body of work into the kinetics and thermodynamics for the formation of Cu(II) complexes in the salenH2- based copolymer membranes has been performed. The rate of complex formation is found to be very slow while the value of K for the equilibrium of complex formation is found to be unexpectedly small and shows a slight anion dependence. These phenomena are explained in terms of the effects of the heterogeneous phase provided by the polymer matrix. The transport of Cr(III) ions across uncomplexed and Cr(III)-pre-complexed bipyridyl-based membranes has been studied. In both cases, no Cr(III) coordination occurs within the time-scale of an experiment. Pre-complexation of the membrane does not lead to a change in the rate of permeation of Cr(III) ions. The transport of Co(II), Ni(II) & Cu(II) ions across salenH2- based membranes shows that there is no detectable lag-time in transport of the ions, despite independent evidence that complex formation within the membranes does occur. Finally, the synthesis of a number of functionalised ligands is described. Although they were found to be non-polymerisable by the methods employed in this research, they remain interesting ligands which provide a startmg pomt for further functionalisation.

Mechanism of the hydropyrolysis of Manvers coal

Manvers coal has been pyrolysed to 500ºC in a stirred autoclave under various pressures of nitrogen (pyrolysis) and hydrogen (hydropyrolysis). All products were investigated. Pyrolysis of coals involves the transfer of hydrogen atoms from one part of their structure to another. In the above experiments there was no way of labelling the hydrogen or of distinguishing between hydrogen which was initially part of the coal and hydrogen originating in the external atmosphere. Consequently, Manvers coal has been pyrolysed in an atmosphere of deuterium in order to obtain greater insight into the mechanism of hydropyrolysis. In particular it was hoped to distinguish between direct hydrogenation (deuteration!) of the coal and the products of pyrolysis and the 'shuttling' of hydrogen atoms between different parts of the pyrolysing coal. The addition to the coal of 5% (wt.% of coal) of either tetralin or pyrite was also studied. A variety of techniques were used to analyse the products of pyrolysis: gas chromatography - mass spectrometry and high performance liquid chromatography for tars; thermal conductivity gas chromatography and high resolution mass spectrometry for gases; methanol densities, microporosities and diffuse reflectance infra red spectroscopy for the cokes (chars); refractive index to determine deuterium in the liquor. An attempt has been made to apply basic thermodynamics to reactions which are likely to occur in the hydropyrolysis of coals. Diffusion and effusion rates for hydrogen and tar molecules have also been estimated.

Development of multiphase and multiscale mathematical models for thermal spray process

High velocity oxyfuel (HVOF) thermal spraying is one of the most significant developments in the thermal spray industry since the development of the original plasma spray technique. The first investigation deals with the combustion and discrete particle models within the general purpose commercial CFD code FLUENT to solve the combustion of kerosene and couple the motion of fuel droplets with the gas flow dynamics in a Lagrangian fashion. The effects of liquid fuel droplets on the thermodynamics of the combusting gas flow are examined thoroughly showing that combustion process of kerosene is independent on the initial fuel droplet sizes. The second analysis copes with the full water cooling numerical model, which can assist on thermal performance optimisation or to determine the best method for heat removal without the cost of building physical prototypes. The numerical results indicate that the water flow rate and direction has noticeable influence on the cooling efficiency but no noticeable effect on the gas flow dynamics within the thermal spraying gun. The third investigation deals with the development and implementation of discrete phase particle models. The results indicate that most powder particles are not melted upon hitting the substrate to be coated. The oxidation model confirms that HVOF guns can produce metallic coating with low oxidation within the typical standing-off distance about 30cm. Physical properties such as porosity, microstructure, surface roughness and adhesion strength of coatings produced by droplet deposition in a thermal spray process are determined to a large extent by the dynamics of deformation and solidification of the particles impinging on the substrate. Therefore, is one of the objectives of this study to present a complete numerical model of droplet impact and solidification. The modelling results show that solidification of droplets is significantly affected by the thermal contact resistance/substrate surface roughness.

The development and stability analysis of a nonlinear growth model for microorganisms

A nonlinear dynamic model of microbial growth is established based on the theories of the diffusion response of thermodynamics and the chemotactic response of biology. Except for the two traditional variables, i.e. the density of bacteria and the concentration of attractant, the pH value, a crucial influencing factor to the microbial growth, is also considered in this model. The pH effect on the microbial growth is taken as a Gaussian function G0e-(f- fc)2/G1, where G0, G1 and fc are constants, f represents the pH value and fc represents the critical pH value that best fits for microbial growth. To study the effects of the reproduction rate of the bacteria and the pH value on the stability of the system, three parameters a, G0 and G1 are studied in detail, where a denotes the reproduction rate of the bacteria, G0 denotes the impacting intensity of the pH value to microbial growth and G1 denotes the bacterial adaptability to the pH value. When the effect of the pH value of the solution which microorganisms live in is ignored in the governing equations of the model, the microbial system is more stable with larger a. When the effect of the bacterial chemotaxis is ignored, the microbial system is more stable with the larger G1 and more unstable with the larger G0 for f0 > fc. However, the stability of the microbial system is almost unaffected by the variation G0 and G1 and it is always stable for f0 < fc under the assumed conditions in this paper. In the whole system model, it is more unstable with larger G1 and more stable with larger G0 for f0 < fc. The system is more stable with larger G1 and more unstable with larger G0 for f0 > fc. However, the system is more unstable with larger a for f0 < fc and the stability of the system is almost unaffected by a for f0 > fc. The results obtained in this study provide a biophysical insight into the understanding of the growth and stability behavior of microorganisms.

Conceptualising global strategic sustainability and corporate transformational change

Purpose – The purpose of this paper is to present the concept of global “strategic sustainability”, represented by a conceptual framework, the “spheres of strategic sustainability”. The paper examines routes, solutions and a vision for corporate strategic sustainability in the macro context of the global physical environment and the planet. This builds on previous research identifying key drivers and strategies for corporate sustainability. Design/methodology/approach – The paper is conceptual in nature and underpinned by Gaia theory, ecosystems theory and the laws of thermodynamics. These three offer specific foci for sustainability research including holism, integration and synthesis: without which, sustainability research would be difficult to achieve. Findings – The paper identifies two major domains – “corporate” and “consumer” strategic sustainability. It examines the corporate domain in which routes are identified through responses to existing globalisation, corporate strategy and corporate culture. Research limitations/implications – The paper provides insight and preliminary conceptual development towards a full theoretical model of corporate and consumer strategic sustainability. The framework will guide future conceptual and empirical investigations and broaden and deepen our understanding of how firm's can construct strategic business models that incorporate sustainability. Originality/value – The paper offers a conceptual framework that develops the concept of “corporate strategic sustainability” and provides positive, practical solutions to incorporating sustainability into business models. It also challenges the current dominant socio-economic paradigm and sets the scene for a more positive eco-paradigm that serves the present and future needs of the planet, environment, businesses and human society.

Numerical simulation of corneal transport processes

This paper presents a numerical study on the transport of ions and ionic solution in human corneas and the corresponding influences on corneal hydration. The transport equations for each ionic species and ionic solution within the corneal stroma are derived based on the transport processes developed for electrolytic solutions, whereas the transport across epithelial and endothelial membranes is modelled by using phenomenological equations derived from the thermodynamics of irreversible processes. Numerical examples are provided for both human and rabbit corneas, from which some important features are highlighted.

Energy-based damage and fracture framework for viscoelastic asphalt concrete

A framework based on the continuum damage mechanics and thermodynamics of irreversible processes using internal state variables is used to characterize the distributed damage in viscoelastic asphalt materials in the form of micro-crack initiation and accumulation. At low temperatures and high deformation rates, micro-cracking is considered as the source of nonlinearity and thus the cause of deviation from linear viscoelastic response. Using a non-associated damage evolution law, the proposed model shows the ability to describe the temperature-dependent processes of micro-crack initiation, evolution and macro-crack formation with good comparison to the material response in the Superpave indirect tensile (IDT) strength test.

Biomass fast pyrolysis energy balance of a 1kg/h test rig

The present paper offers a methodological approach towards the estimation and definition of enthalpies constituting an energy balance around a fast pyrolysis experiment conducted in a laboratory scale fluid bed with a capacity of 1 kg/ h. Pure N2 was used as fluidization medium at atmospheric pressure and the operating temperature (∼500°C) was adjusted with electrical resistors. The biomass feedstock type that was used was beech wood. An effort was made to achieve a satisfying 92.5% retrieval of products (dry basis mass balance) with the differences mainly attributed to loss of some bio-oil constituents into the quenching medium, ISOPAR™. The chemical enthalpy recovery for bio-oil, char and permanent gases is calculated 64.6%, 14.5% and 7.1%, respectively. All the energy losses from the experimental unit into the environment, namely the pyrolyser, cooling unit etc. are discussed and compared to the heat of fast pyrolysis that was calculated at 1123.5 kJ per kg of beech wood. This only represents 2.4% of the biomass total enthalpy or 6.5% its HHV basis. For the estimation of some important thermo-physical properties such as heat capacity and density, it was found that using data based on the identified compounds from the GC/MS analysis is very close to the reference values despite the small fraction of the bio-oil components detected. The methodology and results can help as a starting point for the proper design of fast pyrolysis experiments, pilot and/or industrial scale plants.

Interpretation of the Superpave IDT strength test using a viscoelastic-damage constitutive model

This paper presents a new interpretation for the Superpave IDT strength test based on a viscoelastic-damage framework. The framework is based on continuum damage mechanics and the thermodynamics of irreversible processes with an anisotropic damage representation. The new approach introduces considerations for the viscoelastic effects and the damage accumulation that accompanies the fracture process in the interpretation of the Superpave IDT strength test for the identification of the Dissipated Creep Strain Energy (DCSE) limit from the test result. The viscoelastic model is implemented in a Finite Element Method (FEM) program for the simulation of the Superpave IDT strength test. The DCSE values obtained using the new approach is compared with the values obtained using the conventional approach to evaluate the validity of the assumptions made in the conventional interpretation of the test results. The result shows that the conventional approach over-estimates the DCSE value with increasing estimation error at higher deformation rates.