Crystallographic studies of magnetite and titanomaghemite

The crystal structure of natural magnetite has been investigated on the basis of previously published X-ray intensity data and a newly acquired, more extensive data base. Both investigations show that the structure does not conform to the centrosymmetrical space group Fd3m, as is normally assumed, but the non-centrosymmetrical space group F43m. The structure refinement provides values for the atom positions, anisotropic thermal parameters and bond lengths. A study of Friedel related pairs of X-ray intensities shows that Friedel's law is violated in magnetite, further confirming that the space group is non-centrosymmetrical. It was found that the octahedral site cations in magnetite do not occupy special positions at the centres of the octahedral interstices as they should under the space group Fd3m, but are displaced along <111 > directions leading to F43m symmetry. A mechanism is known for the origin of these displacements and the likelihood of similar displacements occurring in other natural and synthetic spinels is discussed. The crystal structure of a natural titanomaghemite was determined by a combination of X-ray diffraction and Mõssbauer spectroscopy. This was confirmed as possessing a primitive cubic Bravais lattice with the space group P4332 and the structural formula: Fe3+.0.96 0 0.04 [Fe2+0.23 Fe3+0.99 Ti4+0.42 0 0.37 ] 042 - where 0 represents a cation vacancy. As the above formula shows, there are cation vacancies on both tetrahedral arrl octahedral sites, the majority being restricted to octahedral sltes. No tetrahedral site Fe2+ or Ti4+ was observed. Values for the atom positions, anisotropic thermal parameters and bond lengths have been determined for this particular specimen.

Which is the best solar thermal collection technology for electricity generation in north-west India? Evaluation of options using the analytical hierarchy process

This study of concentrating solar thermal power generation sets out to evaluate the main existing collection technologies using the framework of the Analytical Hierarchy Process (AHP). It encompasses parabolic troughs, heliostat fields, linear Fresnel reflectors, parabolic dishes, compound parabolic concentrators and linear Fresnel lenses. These technologies are compared based on technical, economic and environmental criteria. Within these three categories, numerous sub-criteria are identified; similarly sub-alternatives are considered for each technology. A literature review, thermodynamic calculations and an expert workshop have been used to arrive at quantitative and qualitative assessments. The methodology is applied principally to a case study in Gujarat in north-west India, though case studies based on the Sahara Desert, Southern Spain and California are included for comparison. A sensitivity analysis is carried out for Gujarat. The study concludes that the linear Fresnel lens with a secondary compound parabolic collector, or the parabolic dish reflector, is the preferred technology for north-west India.

Solar thermal collectors for use in hybrid solar-biomass power plants in India

This thesis examined solar thermal collectors for use in alternative hybrid solar-biomass power plant applications in Gujarat, India. Following a preliminary review, the cost-effective selection and design of the solar thermal field were identified as critical factors underlying the success of hybrid plants. Consequently, the existing solar thermal technologies were reviewed and ranked for use in India by means of a multi-criteria decision-making method, the Analytical Hierarchy Process (AHP). Informed by the outcome of the AHP, the thesis went on to pursue the Linear Fresnel Reflector (LFR), the design of which was optimised with the help of ray-tracing. To further enhance collector performance, LFR concepts incorporating novel mirror spacing and drive mechanisms were evaluated. Subsequently, a new variant, termed the Elevation Linear Fresnel Reflector (ELFR) was designed, constructed and tested at Aston University, UK, therefore allowing theoretical models for the performance of a solar thermal field to be verified. Based on the resulting characteristics of the LFR, and data gathered for the other hybrid system components, models of hybrid LFR- and ELFR-biomass power plants were developed and analysed in TRNSYS®. The techno-economic and environmental consequences of varying the size of the solar field in relation to the total plant capacity were modelled for a series of case studies to evaluate different applications: tri-generation (electricity, ice and heat), electricity-only generation, and process heat. The case studies also encompassed varying site locations, capacities, operational conditions and financial situations. In the case of a hybrid tri-generation plant in Gujarat, it was recommended to use an LFR solar thermal field of 14,000 m2 aperture with a 3 tonne biomass boiler, generating 815 MWh per annum of electricity for nearby villages and 12,450 tonnes of ice per annum for local fisheries and food industries. However, at the expense of a 0.3 ¢/kWh increase in levelised energy costs, the ELFR increased saving of biomass (100 t/a) and land (9 ha/a). For solar thermal applications in areas with high land cost, the ELFR reduced levelised energy costs. It was determined that off-grid hybrid plants for tri-generation were the most feasible application in India. Whereas biomass-only plants were found to be more economically viable, it was concluded that hybrid systems will soon become cost competitive and can considerably improve current energy security and biomass supply chain issues in India.

Intermediate pyrolysis studies of aquatic biomass and potential applications in the BtVB-process

Aquatic biomass is seen as one of the major feedstocks to overcome difficulties associated with 1st generation biofuels, such as competition with food production, change of land use and further environmental issues. Although, this finding is widely accepted only little work has been carried out to investigate thermo-chemical conversion of algal specimen to produce biofuels, power and heat. This work aims at contributing fundamental knowledge for thermo-chemical processing of aquatic biomass via intermediate pyrolysis. Therefore, it was necessary to install and commission an analytical pyrolysis apparatus which facilitates intermediate pyrolysis process conditions as well as subsequent separation and detection of pyrolysates (Py- GC/MS). In addition, a methodology was established to analyse aquatic biomass under intermediate conditions by Thermo-Gravimetric Analysis (TGA). Several microalgae (e.g. Chlamydomonas reinhardtii, Chlorella vulgaris) and macroalgae specimen (e.g. Fucus vesiculosus) from main algal divisions and various natural habitats (fresh and saline water, temperate and polar climates) were chosen and their thermal degradation under intermediate pyrolysis conditions was studied. In addition, it was of interest to examine the contribution of biochemical constituents of algal biomass onto the chemical compounds contained in pyrolysates. Therefore, lipid and protein fractions were extracted from microalgae biomass and analysed separately. Furthermore, investigations of residual algal materials obtained by extraction of high valuable compounds (e.g. lipids, proteins, enzymes) were included to evaluate their potential for intermediate pyrolysis processing. On basis of these thermal degradation studies, possible applications of algal biomass and from there derived materials in the Bio-thermal Valorisation of Biomass-process (BtVB-process) are presented. It was of interest to evaluate the combination of the production of high valuable products and bioenergy generation derived by micro- and macro algal biomass.

Investigating the role of cholesterol in the formation of non-ionic surfactant based bilayer vesicles:thermal analysis and molecular dynamics

The aim of this research was to investigate the molecular interactions occurring in the formulation of non-ionic surfactant based vesicles composed monopalmitoyl glycerol (MPG), cholesterol (Chol) and dicetyl phosphate (DCP). In the formulation of these vesicles, the thermodynamic attributes and surfactant interactions based on molecular dynamics, Langmuir monolayer studies, differential scanning calorimetry (DSC), hot stage microscopy and thermogravimetric analysis (TGA) were investigated. Initially the melting points of the components individually, and combined at a 5:4:1 MPG:Chol:DCP weight ratio, were investigated; the results show that lower (90 C) than previously reported (120-140 C) temperatures could be adopted to produce molten surfactants for the production of niosomes. This was advantageous for surfactant stability; whilst TGA studies show that the individual components were stable to above 200 C, the 5:4:1 MPG:Chol:DCP mixture show ∼2% surfactant degradation at 140 C, compared to 0.01% was measured at 90 C. Niosomes formed at this lower temperature offered comparable characteristics to vesicles prepared using higher temperatures commonly reported in literature. In the formation of niosome vesicles, cholesterol also played a key role. Langmuir monolayer studies demonstrated that intercalation of cholesterol in the monolayer did not occur in the MPG:Chol:DCP (5:4:1 weight ratio) mixture. This suggests cholesterol may support bilayer assembly, with molecular simulation studies also demonstrating that vesicles cannot be built without the addition of cholesterol, with higher concentrations of cholesterol (5:4:1 vs 5:2:1, MPG:Chol:DCP) decreasing the time required for niosome assembly. © 2013 Elsevier B.V.

Study of thermal spin crossover in [Fe(II)(isoxazole)6](BF4)2 with Mössbauer spectroscopy

57Fe Mössbauer spectroscopy of the mononuclear [Fe(II)(isoxazole)6](BF4) 2compound has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states. A temperature-dependent spin transition curve has been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures in the 240-60K range during the cooling and heating cycle. The compound exhibits a temperature-dependent two-step spin transition phenomenon with Tsco (step 1) = 92 and Tsco (step2) = 191K. The compound has three high-spin Fe(II) sites at the highest temperature of study; among them, two have slightly different coordination environments. These two Fe(II) sites are found to undergo a spin transition, while the third Fe(II) site retains the high-spin state over the whole temperature range. Possible reasons for the formation of the two steps in the spin transition curve are discussed. The observations made from the present study are in complete agreement with those envisaged from earlier magnetic and structural studies made on [Fe(II)(isoxazole)6](BF4)2, but highlights the nature of the spin crossover mechanism.

In situ studies of titania-supported Au shell-Pd core nanoparticles for the selective aerobic oxidation of crotyl alcohol

The thermal evolution of titania-supported Au shell–Pd core bimetallic nanoparticles, prepared via colloidal routes, has been investigated by in situ XPS, DRIFTS, EXAFS and XRD and ex situ HRTEM. As-prepared nanoparticles are terminated by a thin (∼5 layer) Au shell, encapsulating approximately 20 nm diameter cuboctahedral palladium cores, with the ensemble stabilised by citrate ligands. The net gold composition was 40 atom%. Annealing in vacuo or under inert atmosphere rapidly pyrolyses the citrate ligands, but induces only limited Au/Pd intermixing and particle growth <300 °C. Higher temperatures promote more dramatic alloying, accompanied by significant sintering and surface roughening. These changes are mirrored by the nanoparticle catalysed liquid phase selective aerobic oxidation of crotyl alcohol to crotonaldehyde; palladium surface segregation enhances both activity and selectivity, with the most active surface alloy attainable containing ∼40 atom% Au.

In situ X-ray studies of crotyl alcohol selective oxidation over Au/Pd(1 1 1) surface alloys

The selective oxidation of crotyl alcohol to crotonaldehyde over ultrathin Au overlayers on Pd(1 1 1) and Au/Pd(1 1 1) surface alloys has been investigated by time-resolved X-ray photoelectron spectroscopy (XPS) and mass spectrometry. Pure gold is catalytically inert towards crotyl alcohol which undergoes reversible adsorption. In contrast, thermal processing of a 3.9 monolayer (ML) gold overlayer allows access to a range of AuPd surface alloy compositions, which are extremely selective towards crotonaldehyde production, and greatly reduce the extent of hydrocarbon decomposition and eventual carbon laydown compared with base Pd(1 1 1). XPS and CO titrations suggest that palladium-rich surface alloys offer the optimal balance between alcohol oxidative dehydrogenation activity while minimising competitive decomposition pathways, and that Pd monomers are not the active surface ensemble for such selox chemistry over AuPd alloys. Crown Copyright © 2008.

Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Preformulation studies on grewia gum as a formulation excipient

Grewia gum is a naturally occurring polysaccharide which has potential as a pharmaceutical excipient. Differential scanning calorimetry and Fourier transform infrared (FT-IR) spectroscopy techniques were used to examine the thermal and molecular behaviours, respectively, of mixtures of grewia gum with cimetidine, ibuprofen or standard excipients, to assess potential interactions. No disappearance or broadening of the melting endotherm was seen with cimetidine or ibuprofen. Similarly, there was no interaction between grewia gum and the standard excipients tested. The results obtained using thermal analyses were supported by FT-IR analysis of the material mixtures. Grewia gum is an inert natural polymer which can be used alone or in combination with other excipients in the formulation of pharmaceutical dosage forms. © 2011 Akadémiai Kiadó, Budapest, Hungary.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Understanding the Effect of Protein Tyrosine Phosphatase Receptor Type 0 on Mammalian Sensory Development: Behavioral Studies on PTPRO Knockout Mice

Nerve development, which includes axon outgrowth and guidance, is regulated by many protein families, including receptor protein tyrosine phosphatases (RPTP's).Protein tyrosine phosphatase receptor type 0 (PTPRO) is a type III RPTP that is important for axon growth and guidance, as observed in chicks and flies. In order to examine the effects ofPTPRO on mammalian development, standard behavioral tests were used to compare mice lacking the gene for PTPRO (ROKO mice) to wild-type (WT) mice. The ROKO mice showed a significant delay in reacting to a thermal noxious stimulus, hotplate analgesia, when compared to the WT mice suggesting deficient nociceptive function. In a rotarod test for proprioceptive function the ROKO mice exhibited a significant decrease in the amount of time spent on the rotating rod than did the WT mice. Additional proprioception tests were performed including the climb, step reflex, beam, and mesh walk tests. In the climb and step (place) test, the ROKO group had a significantly lower accuracy in performing the tests than did the WT mice. Thus, mice lacking the PTPRO gene showed behavioral deficiencies that reflect impairment in sensory function, specifically for nociception and proprioception.

Advanced thermal analysis of microelectronics using spreading resistance models

Thermal analysis of electronic devices is one of the most important steps for designing of modern devices. Precise thermal analysis is essential for designing an effective thermal management system of modern electronic devices such as batteries, LEDs, microelectronics, ICs, circuit boards, semiconductors and heat spreaders. For having a precise thermal analysis, the temperature profile and thermal spreading resistance of the device should be calculated by considering the geometry, property and boundary conditions. Thermal spreading resistance occurs when heat enters through a portion of a surface and flows by conduction. It is the primary source of thermal resistance when heat flows from a tiny heat source to a thin and wide heat spreader. In this thesis, analytical models for modeling the temperature behavior and thermal resistance in some common geometries of microelectronic devices such as heat channels and heat tubes are investigated. Different boundary conditions for the system are considered. Along the source plane, a combination of discretely specified heat flux, specified temperatures and adiabatic condition are studied. Along the walls of the system, adiabatic or convective cooling boundary conditions are assumed. Along the sink plane, convective cooling with constant or variable heat transfer coefficient are considered. Also, the effect of orthotropic properties is discussed. This thesis contains nine chapters. Chapter one is the introduction and shows the concepts of thermal spreading resistance besides the originality and importance of the work. Chapter two reviews the literatures on the thermal spreading resistance in the past fifty years with a focus on the recent advances. In chapters three and four, thermal resistance of a twodimensional flux channel with non-uniform convection coefficient in the heat sink plane is studied. The non-uniform convection is modeled by using two functions than can simulate a wide variety of different heat sink configurations. In chapter five, a non-symmetrical flux channel with different heat transfer coefficient along the right and left edges and sink plane is analytically modeled. Due to the edge cooling and non-symmetry, the eigenvalues of the system are defined using the heat transfer coefficient on both edges and for satisfying the orthogonality condition, a normalized function is calculated. In chapter six, thermal behavior of two-dimensional rectangular flux channel with arbitrary boundary conditions on the source plane is presented. The boundary condition along the source plane can be a combination of the first kind boundary condition (Dirichlet or prescribed temperature) and the second kind boundary condition (Neumann or prescribed heat flux). The proposed solution can be used for modeling the flux channels with numerous different source plane boundary conditions without any limitations in the number and position of heat sources. In chapter seven, temperature profile of a circular flux tube with discretely specified boundary conditions along the source plane is presented. Also, the effect of orthotropic properties are discussed. In chapter 8, a three-dimensional rectangular flux channel with a non-uniform heat convection along the heat sink plane is analytically modeled. In chapter nine, a summary of the achievements is presented and some systems are proposed for the future studies. It is worth mentioning that all the models and case studies in the thesis are compared with the Finite Element Method (FEM).

Widespread range expansions shape latitudinal variation in insect thermal limits

I thank the authors of previous studies on global variation in insect thermal tolerances who have generously provided open access use of their data sets.

Biochemical and Structural Studies on PrfA, the Transcriptional Regulator of Virulence in Listeria monocytogenes

Abstract

Listeria monocytogenes is a gram-positive soil saprophytic bacterium that is capable of causing fatal infection in humans. The main virulence regulator PrfA, a member of the Crp/FNR family of transcriptional regulators, activates the expression of essential proteins required for host cell invasion and cell-to-cell spread. The mechanism of PrfA activation and the identity of its small molecule coactivator have remained a mystery for more than 20 years, but it is hypothesized that PrfA shares mechanistic similarity to the E. coli cAMP binding protein, Crp. Crp activates gene expression by binding cAMP, increasing the DNA binding affinity of the protein and causing a significant DNA bend that facilitates RNA polymerase binding and downstream gene activation. Our data suggests PrfA activates virulence protein expression through a mechanism distinct from the canonical Crp activation mechanism that involves a combination of cysteine residue reduction and glutathione (GSH) binding.

Listeria lacking glutathione synthase (ΔgshF) is avirulent in mice; however virulence is rescued when the bacterium expresses the constitutively active PrfA mutant G145S. Interestingly, Listeria expressing a PrfA mutant in which its four cysteines are mutated to alanine (Quad PrfA), demonstrate a 30-fold decrease in virulence. The Quad and ΔgshF double mutant strains are avirulent. DNA-binding affinity, measured through fluorescence polarization assays, indicate reduction of the cysteine side chains is sufficient to allow PrfA to binds its physiological promoters Phly and PactA with low nanomolar affinity. Oxidized PrfA binds the promoters poorly.

Unexpectedly, Quad also binds promoter DNA with nanomolar affinity, suggesting that the cysteines play a role in transcription efficiency in addition to DNA binding. Both PrfA and Quad bind GSH at physiologically relevant and comparable affinities, however GSH did not affect DNA binding in either case. Thermal denaturation assays suggest that Quad and wild-type PrfA differ structurally upon binding GSH, which supports the in vivo difference in infection between the regulator and its mutant.

Structures of PrfA in complex with cognate DNA, determined through X-ray crystallography, further support the disparity between PrfA and Crp activation mechanisms as two structures of reduced PrfA bound to Phly (PrfA-Phly30 and PrfA-Phly24) suggest the DNA adopts a less bent DNA conformation when compared to Crp-cAMP- DNA. The structure of Quad-Phly30 confirms the DNA-binding data as the protein-DNA complex adopts the same overall conformation as PrfA-Phly.

From these results, we hypothesize a two-step activation mechanism wherein PrfA, oxidized upon cell entry and unable to bind DNA, is reduced upon its intracellular release and binds DNA, causing a slight bend in the promoter and small increase in transcription of PrfA-regulated genes. The structures of PrfA-Phly30 and PrfA-Phly24 likely visualize this intermediate complex. Increasing concentrations of GSH shift the protein to a (PrfA-GSH)-DNA complex which is fully active transcriptionally and is hypothesized to resemble closely the transcriptionally active structure of the cAMP-(Crp)-DNA complex. Thermal denaturation results suggest Quad PrfA is deficient in this second step, which explains the decrease in virulence and implicates the cysteine residues as critical for transcription efficiency. Further structural and biochemical studies are on-going to clarify this mechanism of activation.