Time-resolved fluorescence studies on covalently linked porphyrin�nitroarene complexes. Conformational control of photoinduced electron transfer reactions

Time-resolved fluorescence studies were carried out on a series of free-base and zinc(II) derivatives of meso-tetraphenylporphyrins covalently linked to either 1,3-dinitrobenzene (DNB) or 1,3,5-trinitrobenzene (TNB) acceptor units. These acceptor units were linked at different sites (at the ortho, meta or para positions of one of the phenyl groups of meso-tetraphenylporphyrin) to the donor porphyrins such that the resulting isomeric intramolecular donor-acceptor complexes exhibit different centre-to-centre (ctc) distances and relative orientations. Biexponential fluorescence decay profiles observed for several of these covalently linked complexes were rationalized in terms of the presence of ''closed'' and ''extended'' conformers. Detailed analyses of the fluorescence decay data have provided a comprehensive understanding of the photoinduced electron transfer (PET) reactions occurring in systems containing zinc(II) porphyrin donors. It is observed that although DNB-linked zinc(II) complexes follow the trends predicted for the efficiency of PET with respect to donor-acceptor distance, the TNB-linked zinc(II) porphyrins exhibit a behaviour which is dictated by steric effects. Similarly, although the thermodynamic criteria predict a greater efficiency of charge separation in TNB-linked complexes compared with DNB-linked complexes, the reverse trend observed has been attributed to orientational effects. In the complexes containing free-base porphyrin donors, PET is expected to be less efficient from a thermodynamic viewpoint. In a few of these cases, fluorescence quenching seems to occur by parallel mechanisms other than PET.

Model track studies on fouled ballast using ground penetrating radar and multichannel analysis of surface wave

Ballast fouling is created by the breakdown of aggregates or outside contamination by coal dust from coal trains, or from soil intrusion beneath rail track. Due to ballast fouling, the conditions of rail track can be deteriorated considerably depending on the type of fouling material and the degree of fouling. So far there is no comprehensive guideline available to identify the critical degree of fouling for different types of fouling materials. This paper presents the identification of degree of fouling and types of fouling using non-destructive testing, namely seismic surface-wave and ground penetrating radar (GPR) survey. To understand this, a model rail track with different degree of fouling has been constructed in Civil engineering laboratory, University of Wollongong, Australia. Shear wave velocity obtained from seismic survey has been employed to identify the degree of fouling and types of fouling material. It is found that shear wave velocity of fouled ballast increases initially, reaches optimum fouling point (OFP), and decreases when the fouling increases. The degree of fouling corresponding after which the shear wave velocity of fouled ballast will be smaller than that of clean ballast is called the critical fouling point (CFP). Ground penetrating radar with four different ground coupled antennas (500 MHz, 800 MHz, 1.6 GHz and 2.3 GHz) was also used to identify the ballast fouling condition. It is found that the 800 MHz ground coupled antenna gives a better signal in assessing the ballast fouling condition. Seismic survey is relatively slow when compared to GPR survey however it gives quantifiable results. In contrast, GPR survey is faster and better in estimating the depth of fouling. (C) 2011 Elsevier B.V. All rights reserved.

Experimental studies on the influence of intermediate principal stress and inclination on the mechanical behaviour of angular sands

A comprehensive experimental study has been made on angular sand to investigate various aspects of mechanical behavior. A hollow cylinder torsion testing apparatus is used in this program to apply a range of stress conditions on this angular quartzitic fine sand under monotonic drained shear. The effect of the magnitude and inclination of the principal stresses on an element of sand is studied through these experiments. This magnitude and inclination of the principal stresses are presented as an ``ensemble measure of fabric in sands''. This ensemble measure of fabric in the sands evolves through the shearing process, and reaches the final state, which indeed has a unique fabric. The sand shows significant variation in strength with changing inclination of the principal stresses. The locus of the final stress state in principal stress space is also mapped from these series of experiments. Additional aspects of non-coaxiality, a benchmarking exercise with a few constitutive models is presented here. This experimental approach albeit indirect shows that a unique state which is dependent on the fabric, density and confining stress exists. This suite of experiments provides a well-controlled data set for a clear understanding on the mechanical behavior of sands.

A comprehensive method for the elastic calculation of the two-point wheel-rail contact

This work shows the method developed to solve the wheel-rail contact problem via a look-up table with a three-dimensional elastic model. This method enables introduction of the two contact point effect on vehicle movement using three-dimensional analysis of surfaces including the influence of the angle of attack. This work presents several dynamic simulations and studies the impact that the introduction of the two contact points on three dimensions has on wear indexes and derailment risk against traditional bidimensional analysis. Furthermore, it studies advantages and disadvantages of using a look-up table against an on-line resolution of the problem.

Studies of the equation of state and elasticity of mantle minerals

Because the Earth’s upper mantle is inaccessible to us, in order to understand the chemical and physical processes that occur in the Earth’s interior we must rely on both experimental work and computational modeling. This thesis addresses both of these geochemical methods. In the first chapter, I develop an internally consistent comprehensive molar volume model for spinels in the oxide system FeO-MgO-Fe₂O₃-Cr₂O₃-Al₂O₃-TiO₂. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure. In the second chapter, I calibrate a molar volume model for cubic garnets in the system SiO₂-Al₂O₃-TiO₂-Fe₂O₃-Cr₂O₃-FeO-MnO-MgO-CaO-Na₂O. I use the method of singular value analysis to calibrate excess volume of mixing parameters for the garnet model. The implications the model has for the density of the lithospheric mantle are explored. In the third chapter, I discuss the nuclear inelastic X-ray scattering (NRIXS) method, and present analysis of three orthopyroxene samples with different Fe contents. Longitudinal and shear wave velocities, elastic parameters, and other thermodynamic information are extracted from the raw NRIXS data.

Experimental, Numerical and Analytical Studies of the MHD-driven plasma jet, instabilities and waves

This thesis describes a series of experimental, numerical, and analytical studies involving the Caltech magnetohydrodynamically (MHD)-driven plasma jet experiment. The plasma jet is created via a capacitor discharge that powers a magnetized coaxial planar electrodes system. The jet is collimated and accelerated by the MHD forces.

We present three-dimensional ideal MHD finite-volume simulations of the plasma jet experiment using an astrophysical magnetic tower as the baseline model. A compact magnetic energy/helicity injection is exploited in the simulation analogous to both the experiment and to astrophysical situations. Detailed analysis provides a comprehensive description of the interplay of magnetic force, pressure, and flow effects. We delineate both the jet structure and the transition process that converts the injected magnetic energy to other forms.

When the experimental jet is sufficiently long, it undergoes a global kink instability and then a secondary local Rayleigh-Taylor instability caused by lateral acceleration of the kink instability. We present an MHD theory of the Rayleigh-Taylor instability on the cylindrical surface of a plasma flux rope in the presence of a lateral external gravity. The Rayleigh-Taylor instability is found to couple to the classic current-driven instability, resulting in a new type of hybrid instability. The coupled instability, produced by combination of helical magnetic field, curvature of the cylindrical geometry, and lateral gravity, is fundamentally different from the classic magnetic Rayleigh-Taylor instability occurring at a two-dimensional planar interface.

In the experiment, this instability cascade from macro-scale to micro-scale eventually leads to the failure of MHD. When the Rayleigh-Taylor instability becomes nonlinear, it compresses and pinches the plasma jet to a scale smaller than the ion skin depth and triggers a fast magnetic reconnection. We built a specially designed high-speed 3D magnetic probe and successfully detected the high frequency magnetic fluctuations of broadband whistler waves associated with the fast reconnection. The magnetic fluctuations exhibit power-law spectra. The magnetic components of single-frequency whistler waves are found to be circularly polarized regardless of the angle between the wave propagation direction and the background magnetic field.

High resolution electron microscope studies of chromosomal fibers

Techniques are described for mounting and visualizing biological macromolecules for high resolution electron microscopy. Standard techniques are included in a discussion of new methods designed to provide the highest structural resolution. Methods are also discussed for handling samples on the grid, for making accurate size measurements at the 20 Å level, and for photographically enhancing image contrast.

The application of these techniques to the study of the binding of DNA polymerase to DNA is described. It is shown that the electron micrographs of this material are in agreement with the model proposed by Dr. Arthur Kornberg. A model is described which locates several active sites on the enzyme.

The chromosomal material of the protozoan tetrahymena has been isolated and characterized by biochemical techniques and by electron microscopy. This material is shown to be typical of chromatin of higher creatures.

Comparison with other chromatins discloses that the genome of tetrahymena is highly template active and has a relatively simple genetic construction.

High resolution electron microscope procedures developed in this work have been combined with standard biochemical techniques to give a comprehensive picture of the structure of interphase chromosome fibers. The distribution of the chromosomal proteins along its DNA is discussed.

Structural role of fluoride in aluminophosphate sol-gel glasses: High-resolution double-resonance NMR studies

The local structure of Na-Al-P-O-F glasses, prepared by a novel sol-gel route, was extensively investigated by advanced solid-state NMR techniques. Al-21{F-19} rotational echo double resonance (REDOR) results indicate that the F incorporated into aluminophosphate glass is preferentially bonded to octahedral Al units and results in a significant increase in the concentration of six-coordinated aluminum. The extent of Al-F and Al-O-P connectivities are quantified consistently by analyzing Al-27{P-31} and Al-21{F-19} REDOR NMR data. Two distinct types of fluorine species were identified and characterized by various F-19{Al-27}, F-19{Na-23}, and F-19{P-31} double resonance experiments, which were able to support peak assignments to bridging (Al-F-Al, -140 ppm) and terminal (Al-F, -170 ppm) units. On the basis of the detailed quantitative dipole-dipole coupling information obtained, a comprehensive structural model for these glasses is presented, detailing the structural speciation as a function of composition.

Evaluation of NRA tracking studies. Future projects and technical development

Fish tracking is a valuable technique for the provision of detailed information on the behaviour patterns of individual fish especially during estuarine and riverine migration. 2. Tracking studies help in the provision of a comprehensive description of the variety offish behaviour patterns in response to factors such as water flow, obstructions and water quality. 3. There are advantages to be gained by complementing fish tracking studies with data collected from fish counters and vice versa. 4. An overall evaluation of NRA fish tracking projects is presented in the wider context of NRA strategic research objectives. 5. The requirement for future development of tracking equipment, improved data analysis techniques, better communication and more immediate report preparation is identified. 6. Individual project evaluation is given for NRA (or the appropriate Water Authority predecessor) tracking studies conducted on the Ribble estuary, the River Tamar, River Torridge, Rivers Test and Itchen, River Lodden, the Welsh River Dee, River Glaslyn, River Taff, River Tawe, River Tywi, River Usk, Rivers Avon and Stour and the River Frome. 7. An outline for future strategic research is provided which identifies particular areas for study:- i) Identification of environmental factors which control the entry of fish into rivers. ii) Improvement of the understanding of the relationship between water flow and upstream movement of salmonids. iii) Examination of the detailed movements and behaviour of fish in relation to obstructions. iv) Closer definition of water quality requirements for salmonid fish. v) Definition of habitat preferences of salmonids in rivers. vi) Subsidiary topics such as the movements of non-salmonid fish and the downstream migration of kelts and juvenile salmonids.

An ecological characterization of the marine resources of Vieques, Puerto Rico Part II: Field studies of habitats, nutrients, contaminants, fish, and benthic communities

Since the 1940s, portions of the Island of Vieques, Puerto Rico have been used by the United States Navy (USN) as an ammunition support detachment and bombing and maneuver training range. In April 2001, the USN began phasing out military activities on the island and transferring military property to the U.S. Department of the Interior, the Municipality of Vieques, and the Puerto Rico Conservation Trust. A small number of studies have been commissioned by the USN in the past few decades to assess selected components of the coral reef ecosystem surrounding the island; however, these studies were generally of limited geographic scope and short duration. The National Oceanic and Atmospheric Administration’s (NOAA) National Centers for Coastal Ocean Science (NCCOS), in consultation with NOAA’s Office of Response and Restoration (OR&R) and other local and regional experts, conducted a more comprehensive characterization of coral reef ecosystems, contaminants, and nutrient distribution patterns around Vieques. This work was conducted using many of the same protocols as ongoing monitoring work underway elsewhere in the U.S. Caribbean and has enabled comparisons among coral reef ecosystems in Vieques and other locations in the region. This characterization of Vieques’ marine ecosystems consists of a two part series. First, available information on reefs, fish, birds, seagrasses, turtles, mangroves, climate, geology, currents, and human uses from previous studies was gathered and integrated into a single document comprising Part I of this two part series (Bauer et al. 2008). For Part II of the series, presented in this document, new field studies were conducted to fill data gaps identified in previous studies, to provide an island-wide characterization, and to establish baseline values for the distribution of habitats, nutrients, contaminants, fish, and benthic communities. An important objective underlying this suite of studies was to quantify any differences in the marine areas adjacent to the former and current land-use zoning around Vieques. Specifically of interest was the possibility that either Naval (e.g., practice bombing, munitions storage) or civilian activities (e.g., sewage pollutants, overfishing) could have a negative impact on adjacent marine resources. Measuring conditions at this time and so recently after the land transfer was essential because present conditions are likely to be reflective of past land-use practices. In addition, the assessment will establish benchmark conditions that can be influenced by the potentially dramatic future changes in land-use practices as Vieques considers its development. This report is organized into seven chapters that represent a suite of interrelated studies. Chapter 1 provides a short introduction to the island setting, the former and current land-use zoning, and how the land zoning was used to spatially stratify much of the sampling. Chapter 2 is focused on benthic mapping and provides the methods, accuracy assessment, and results of newly created benthic maps for Vieques. Chapter 3 presents the results of new surveys of fish, marine debris, and reef communities on hardbottom habitats around the island. Chapter 4 presents results of flora and fauna surveys in selected bays and lagoons. Chapter 5 examines the distribution of nutrients in lagoons, inshore, and offshore waters around the island. Chapter 6 is focused on the distribution of chemical contaminants in sediments and corals. Chapter 7 is a brief summary discussion that highlights key findings of the entire suite of studies.

Future-proofed energy design for dwellings: Case studies from England and application to the Code for Sustainable Homes

This paper investigates 'future-proofing' as an unexplored yet all-important aspect in the design of low-energy dwellings. It refers particularly to adopting lifecycle thinking and accommodating risks and uncertainties in the selection of fabric energy efficiency measures and low or zero-carbon technologies. Based on a conceptual framework for future-proofed design, the paper first presents results from the analysis of two 'best practice' housing developments in England; i.e., North West Cambridge in Cambridge and West Carclaze and Baal in St. Austell, Cornwall. Second, it examines the 'Energy and CO2 Emissions' part of the Code for Sustainable Homes to reveal which design criteria and assessment methods can be practically integrated into this established building certification scheme so that it can become more dynamic and future-oriented.Practical application: Future-proofed construction is promoted implicitly within the increasingly stringent building regulations; however, there is no comprehensive method to readily incorporate futures thinking into the energy design of buildings. This study has a three-fold objective of relevance to the building industry:Illuminating the two key categories of long-term impacts in buildings, which are often erroneously treated interchangeably:- The environmental impact of buildings due to their long lifecycles.- The environment's impacts on buildings due to risks and uncertainties affecting the energy consumption by at least 2050. This refers to social, technological, economic, environmental and regulatory (predictable or unknown) trends and drivers of change, such as climate uncertainty, home-working, technology readiness etc.Encouraging future-proofing from an early planning stage to reduce the likelihood of a prematurely obsolete building design.Enhancing established building energy assessment methods (certification, modelling or audit tools) by integrating a set of future-oriented criteria into their methodologies. © 2012 The Chartered Institution of Building Services Engineers.

COMPARATIVE-STUDIES ON PERIODATOCUPRATE(II, III) AND TELLURATOCUPRATE(II, III)

The crystal structures, electronic spectra, and Cu2p XPS of Cu(III) complexes Na4H[Cu(H2TeO6)(2)]. 17H(2)O and Na4K[Cu(HlO(6))(2)]. 12H(2)O have been described. The characterizations of a Cu(III) atom in a complex are as follows: (i) In a square-planar coordination, the average bond length of Cu-O is 0.183 nm, shorter than the 0.190-0.200 nm found for a Cu(II) complex. (2) The ''blue shift'' occurs for d-d transitions in the electronic spectrum of the Cu(III) complex compared to those of its related Cu(II) complex, resulting from the higher valence state. (3) Cu(III) compounds with CuO4 square-planar coordination are expected to be diamagnetic whereas Cu(II) compounds to be paramagnetic. (4) Comprehensive investigations on Cu2p XPS show that the binding energy of Cu2p(3/2) of a pure Cu(III) compound is about 2.0 eV higher than that of its corresponding Cu(II) compound: the shake-up satellites do not appear in the Cu2p XPS for a pure diamagnetic Cu(III) compound, the same as found for a diamagnetic Ni(II) compound: the FWHM of the signal of Cu2p XPS may become broader for Cu(III) compound because its core hole's lifetime shortens due to the higher valence state of copper. (C) 1995 Academic Press, Inc.

Changes in innovation styles - comprehensive study of the changes in innovation styles to identify the causes and effects of different influencing factors and capabilities to create a general innovation pattern.

An investigation in innovation management and entrepreneurial management is conducted in this thesis. The aim of the research is to explore changes of innovation styles in the transformation process from a start-up company to a more mature phase of business, to predict in a second step future sustainability and the probability of success. As businesses grow in revenue, corporate size and functional complexity, various triggers, supporters and drivers affect innovation and company's success. In a comprehensive study more than 200 innovative and technology driven companies have been examined and compared to identify patterns in different performance levels. All of them have been founded under the same formal requirements of the Munich Business Plan Competition -a research approach which allowed a unique snapshot that only long-term studies would be able to provide. The general objective was to identify the correlation between different factors, as well as different dimensions, to incremental and radical innovations realised. The 12 hypothesis were formed to prove have been derived from a comprehensive literature review. The relevant academic and practitioner literature on entrepreneurial, innovation, and knowledge management as well as social network theory revealed that the concept of innovation has evolved significantly over the last decade. A review of over 15 innovation models/frameworks contributed to understand what innovation in context means and what the dimensions are. It appears that the complex theories of innovation can be described by the increasing extent of social ingredients in the explanation of innovativeness. Originally based on tangible forms of capital, and on the necessity of pull and technology push, innovation management is today integrated in a larger system. Therefore, two research instruments have been developed to explore the changes in innovations styles. The Innovation Management Audits (IMA Start-up and IMA Mature) provided statements related to product/service development, innovativeness in various typologies, resources for innovations, innovation capabilities in conjunction to knowledge and management, social networks as well as the measurement of outcomes to generate high-quality data for further exploration. In obtaining results the mature companies have been clustered in the performance level low, average and high, while the start-up companies have been kept as one cluster. Firstly, the analysis exposed that knowledge, the process of acquiring knowledge, interorganisational networks and resources for innovations are the most important driving factors for innovation and success. Secondly, the actual change of the innovation style provides new insights about the importance of focusing on sustaining success and innovation ii 16 key areas. Thirdly, a detailed overview of triggers, supporters and drivers for innovation and success for each dimension support decision makers in putting their company in the right direction. Fourthly, a critical review of contemporary strategic management in conjunction to the findings provides recommendation of how to apply well-known management tools. Last but not least, the Munich cluster is analysed providing an estimation of the success probability of the different performance cluster and start-up companies. For the analysis of the probability of success of the newly developed as well as statistically and qualitative validated ICP Model (Innovativeness, Capabilities & Potential) has been developed and applied. While the model was primarily developed to evaluate the probability of success of companies; it has equal application in the situation to measure innovativeness to identify the impact of various strategic initiatives within small or large enterprises. The main findings of the model are that competitor, and customer orientation and acquiring knowledge important for incremental and radical innovation. Formal and interorganisation networks are important to foster innovation but informal networks appear to be detrimental to innovation. The testing of the ICP model h the long term is recommended as one subject of further research. Another is to investigate some of the more intangible aspects of innovation management such as attitude and motivation of mangers. IV

Comprehensive assessment of alcohol-related brain damage (ARBD): gap or chasm in the evidence?

Alcohol-related brain damage (ARBD) is primarily caused by chronic alcohol misuse and thiamine deficiency, and results in a broad range of impairments. Despite the increasing incidence of ARBD in the UK in recent decades, it is currently underdiagnosed, managed inappropriately and treated inadequately. Moreover, information about assessments for individuals with ARBD is currently absent from clinical guidelines and policy documents. The aim of this paper was to review the evidence relating to the neurological, neuropsychological, psychosocial, physical and nutritional assessment of individuals with ARBD to identify appropriate assessment tools that could be used to measure and monitor the impact of ARBD over time. A systematic online database search revealed a total of 160 separate references, 133 of which were rejected and two of which could not be accessed. Twenty-five papers were included in the review, including six neuroimaging studies, 17 neuropsychological studies and two studies using psychosocial methods of assessment. A lack of evidence for nutritional and physical assessment of individuals with ARBD was found. The review findings are inconclusive; most instruments currently used in ARBD research have not specifically been validated for use within an ARBD context. Further research is required to identify comprehensive methods of ARBD assessment.

Studies on equine milk and comparative studies on equine and bovine milk systems

The composition of equine milk differs considerably from that of the milk of the principal dairying species, i.e., the cow, buffalo, goat and sheep. Because equine milk resembles human milk in many respects and is claimed to have special therapeutic properties, it is becoming increasingly popular in Western Europe, where it is produced on large farms in several countries. Equine milk is considered to be highly digestible, rich in essential nutrients and to possess an optimum whey protein:casein ratio, making it very suitable as a substitute for bovine milk in paediatric dietetics. There is some scientific basis for the special nutritional and health-giving properties of equine milk but this study provides a comprehensive analysis of the composition and physico-chemical properties of equine milk which is required to fully exploit its potential in human nutrition. Quantification and distribution of the nitrogenous components and principal salts of equine milk are reported. The effects of the high concentration of ionic calcium, large casein micelles (~ 260 nm), low protein, lack of a sulphydryl group in equine β-lactoglobulin and a very low level of κ-casein on the physico-chemical properties of equine milk are reported. This thesis provides an insight into the stability of equine casein micelles to heat, ethanol, high pressure, rennet or acid. Differences in rennet- and acid-induced coagulation between equine and bovine milk are attributed not only to the low casein content of equine milk but also to differences in the mechanism by which the respective micelles are stabilized. It has been reported that β-casein plays a role in the stabilization of equine casein micelles and proteomic techniques support this view. In this study, equine κ-casein appeared to be resistant to hydrolysis by calf chymosin but equine β-casein was readily hydrolysed. Resolution of equine milk proteins by urea-PAGE showed the multi-phosphorylated isoforms of equine αs- and β-caseins and capillary zone electrophoresis showed 3 to 7 phosphorylated residues in equine β-casein. In vitro digestion of equine β-casein by pepsin and Corolase PP™ did not produce casomorphins BCM-5 or BCM-7, believed to be harmful to human health. Electron microscopy provided very clear, detailed images of equine casein micelles in their native state and when renneted or acidified. Equine milk formed flocs rather then a gel when renneted or acidified which is supported by dynamic oscillatory analysis. The results presented in this thesis will assist in the development of new products from equine milk for human consumption which will retain some of its unique compositional and health-giving properties.