Synthetic, EPR spectroscopic, magnetic and X-ray crystallographic structural studies on copper(II) complexes of the tridentate N2S donor ligand formed from 6-methyl-2-formylpyridine and S-methyldithiocarbazate (Hmpsme)

New copper(II) complexes of general empirical formula, Cu(mpsme)X center dot xCH(3)COCH(3) (mpsme = anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate; X = Cl, N-3, NCS, NO3; x = 0, 0.5) have been synthesized and characterized by IR, electronic, EPR and susceptibility measurements. Room temperature mu(eff) values for the complexes are in the range 1.75-2.1 mu(beta) typical of uncoupled or weakly coupled Cu(II) centres. The EPR spectra of the [Cu(mpsme)X] (X = Cl, N-3, NO3, NCS) complexes reveal a tetragonally distorted coordination sphere around the mononuclear Cu(II) centre. We have exploited second derivative EPR spectra in conjunction with Fourier filtering (sine bell and Hamming functions) to extract all of the nitrogen hyperfine coupling matrices. While the X-ray crystallography of [Cu(mpsme)NCS] reveals a linear polymer in which the thiocyanate anion bridges the two copper(II) ions, the EPR spectra in solution are typical of a magnetically isolated monomeric Cu(II) centres indicating dissociation of the polymeric chain in solution. The structures of the free ligand, Hmpsme and the {[Cu(mpsme)NO3] center dot 0.5CH(3)COCH(3)}(2) and [Cu(mpsme)NCS](n) complexes have been determined by X-ray diffraction. The {[Cu(mpsme)NO3]0.5CH(3)COCH(3)}(2) complex is a centrosymmetric dimer in which each copper atom adopts a five-coordinate distorted square-pyramidal geometry with an N2OS2 coordination environment, the Schiff base coordinating as a uninegatively charged tridentate ligand chelating through the pyridine and azomethine nitrogen atoms and the thiolate, an oxygen atom of a unidentate nitrato ligand and a bridging sulfur atom from the second ligand completing the coordination sphere. The [Cu(mpsme)(NCS)](n) complex has a novel staircase-like one dimensional polymeric structure in which the NCS- ligands bridge two adjacent copper(II) ions asymmetrically in an end-to-end fashion providing its nitrogen atom to one copper and the sulfur atom to the other. (c) 2005 Elsevier B.V. All rights reserved.

Disorders of breathing and continence have a stronger association with back pain than obesity and physical activity

Although obesity and physical activity have been argued to predict back pain, these factors are also related to incontinence and breathing difficulties. Breathing and continence mechanisms may interfere with the physiology of spinal control, and may provide a link to back pain. The aim of this study was to establish the association between back pain and disorders of continence and respiration in women. We conducted a cross-sectional analysis of self-report, postal survey data from the Australian Longitudinal Study on Women's Health. We used multinomial logistic regression to model four levels of back pain in relation to both the traditional risk factors of body mass index and activity level, and the potential risk factors of incontinence, breathing difficulties, and allergy. A total of 38 050 women were included from three age-cohorts. When incontinence and breathing difficulties were considered, obesity and physical activity were not consistently associated with back pain. In contrast, odds ratios (OR) for often having back pain were higher for women often having incontinence compared to women without incontinence (OR were 2.5, 2.3 and 2.3 for young, mid-age! and older women, respectively). Similarly, mid-aged and older women had higher odds of having back pain often when they experienced breathing difficulties often compared to women with no breathing problems (OR of 2.0 and 1.9, respectively). Unlike obesity and physical activity, disorders of continence and respiration were strongly related to frequent back pain. This relationship may be explained by physiological limitations of co-ordination of postural, respiratory and continence functions of trunk muscles.

Cloning and characterization of natriuretic peptides from the venom glands of Australian elapids

The venom from Australian elapid snakes contains a complex mixture of polypeptide toxins that adversely affect multiple homeostatic systems within their prey in a highly specific and targeted manner. Included in these toxin families are the recently described venom natriuretic peptides, which display similar structure and vasoactive functions to mammalian natriuretic peptides. This paper describes the identification and detailed comparative analysis of the cDNA transcripts coding for the mature natriuretic peptide from a total of nine Australian elapid snake species. Multiple isoforms were identified in a number of species and represent the first description of a natriuretic peptide from the venom gland for most of these snakes. Two distinct natriuretic peptide isoforms were selected from the common brown snake (Pseudonaja textilis), PtNP-a, and the mulga (Pseudechis australis), PaNP-c, for recombinant protein expression and functional analysis. Only one of these peptides, PtNP-a, displayed cGMP stimulation indicative of normal natriuretic peptide activity. Interestingly, both recombinant peptides demonstrated a dose-dependent inhibition of angiotensin converting enzyme (ACE) activity, which is predictive of the vasoactive effects of the toxin. The natriuretic peptides, however, did not possess any coagulopathic activity, nor did they inhibit or potentiate thrombin, adenosine diphosphate or arachidonic acid induced platelet aggregation. The data presented in this study represent a significant resource for understanding the role of various natriuretic peptides isoforms during the envenomation process by Australian elapid snakes. (c) 2006 Published by Elsevier Masson SAS.

Electrolyte transport in the mammalian colon: mechanisms and implications for disease Kunzelmann and Marcus Mall

Electrolyte Transport in the Mammalian Colon: Mechanisms and Implications for Disease. Physiol. Rev. 82: 245-289, 2002.The colonic epithelium has both absorptive and secretory functions. The transport is characterized by a net absorption of NaCl, short-chain fatty acids (SCFA), and water, allowing extrusion of a feces with very little water and salt content. In addition, the epithelium does secret mucus, bicarbonate, and KCl. Polarized distribution of transport proteins in both luminal and basolateral membranes enables efficient salt transport in both directions, probably even within an individual cell. Meanwhile, most of the participating transport proteins have been identified, and their function has been studied in detail. Absorption of NaCl is a rather steady process that is controlled by steroid hormones regulating the expression of epithelial Na+ channels (ENaC), the Na+-K+-ATPase, and additional modulating factors such as the serum- and glucocorticoid-regulated kinase SGK. Acute regulation of absorption may occur by a Na+ feedback mechanism and the cystic fibrosis transmembrane conductance regulator (CFTR). Cl- secretion in the adult colon relies on luminal CFTR, which is a cAMP-regulated Cl- channel and a regulator of other transport proteins. As a consequence, mutations in CFTR result in both impaired Cl- secretion and enhanced Na+ absorption in the colon of cystic fibrosis (CF) patients. Ca2+- and cAMP-activated basolateral K+ channels support both secretion and absorption of electrolytes and work in concert with additional regulatory proteins, which determine their functional and pharmacological profile. Knowledge of the mechanisms of electrolyte transport in the colon enables the development of new strategies for the treatment of CF and secretory diarrhea. It will also lead to a better understanding of the pathophysiological events during inflammatory bowel disease and development of colonic carcinoma.

Practicing social e-atmospherics:French and Turkish web designers' perspectives

E-atmospherics have motivated an emerging body of research which reports that both virtual layouts and atmospherics encourage consumers to modify their shopping habits. While the literature has analyzed mainly the functional aspect of e-atmospherics, little has been done in terms of linking its characteristics’ to social (co-) creation. This paper focuses on the anatomy of social dimension in relation to e-atmospherics, which includes factors such as the aesthetic design of space, the influence of visual cues, interpretation of shopping as a social activity and meaning of appropriate interactivity. We argue that web designers are social agents who interact within intangible social reference sets, restricted by social standards, value, beliefs, status and duties embedded within their local geographies. We aim to review the current understanding of the importance and voluntary integration of social cues displayed by web designers from a mature market and an emerging market, and provides an analysis based recommendation towards the development of an integrated e-social atmospheric framework. Results report the findings from telephone interviews with an exploratory set of 10 web designers in each country. This allows us to re-interpret the web designers’ reality regarding social E-atmospherics. We contend that by comprehending (before any consumer input) social capital, daily micro practices, habits and routine, deeper understanding of social e-atmospherics preparatory, initial stages and expected functions will be acquired.

Determinants of entry and exit in the foreign owned sector of UK manufacturing

This paper examines the extent to which foreign entry and exit in the UK is related to domestic industry characteristics. The units of analysis are firm numbers, and thus entry and exit at the industry level are treated as being generated by Poisson processes. This therefore uses quasimaximum likelihood estimation, to estimate entry and exit functions simultaneously. The results demonstrate that foreign entry is attracted by industry level profitability and performance, but that firm specific 'ownership' advantages are also important. The results also demonstrate that inward investors that are motivated by the desire to exploit firm-specific assets, are unlikely to be more transient than domestic firms. This however, cannot be said of those foreign entrants who are attracted to the UK by location advantage or investment incentives.

Empirical analysis of human capital development and economic growth in Europe

Recent discussion of the knowledge-based economy draws increasingly attention to the role that the creation and management of knowledge plays in economic development. Development of human capital, the principal mechanism for knowledge creation and management, becomes a central issue for policy-makers and practitioners at the regional, as well as national, level. Facing competition both within and across nations, regional policy-makers view human capital development as a key to strengthening the positions of their economies in the global market. Against this background, the aim of this study is to go some way towards answering the question of whether, and how, investment in education and vocational training at regional level provides these territorial units with comparative advantages. The study reviews literature in economics and economic geography on economic growth (Chapter 2). In growth model literature, human capital has gained increased recognition as a key production factor along with physical capital and labour. Although leaving technical progress as an exogenous factor, neoclassical Solow-Swan models have improved their estimates through the inclusion of human capital. In contrast, endogenous growth models place investment in research at centre stage in accounting for technical progress. As a result, they often focus upon research workers, who embody high-order human capital, as a key variable in their framework. An issue of discussion is how human capital facilitates economic growth: is it the level of its stock or its accumulation that influences the rate of growth? In addition, these economic models are criticised in economic geography literature for their failure to consider spatial aspects of economic development, and particularly for their lack of attention to tacit knowledge and urban environments that facilitate the exchange of such knowledge. Our empirical analysis of European regions (Chapter 3) shows that investment by individuals in human capital formation has distinct patterns. Those regions with a higher level of investment in tertiary education tend to have a larger concentration of information and communication technology (ICT) sectors (including provision of ICT services and manufacture of ICT devices and equipment) and research functions. Not surprisingly, regions with major metropolitan areas where higher education institutions are located show a high enrolment rate for tertiary education, suggesting a possible link to the demand from high-order corporate functions located there. Furthermore, the rate of human capital development (at the level of vocational type of upper secondary education) appears to have significant association with the level of entrepreneurship in emerging industries such as ICT-related services and ICT manufacturing, whereas such association is not found with traditional manufacturing industries. In general, a high level of investment by individuals in tertiary education is found in those regions that accommodate high-tech industries and high-order corporate functions such as research and development (R&D). These functions are supported through the urban infrastructure and public science base, facilitating exchange of tacit knowledge. They also enjoy a low unemployment rate. However, the existing stock of human and physical capital in those regions with a high level of urban infrastructure does not lead to a high rate of economic growth. Our empirical analysis demonstrates that the rate of economic growth is determined by the accumulation of human and physical capital, not by level of their existing stocks. We found no significant effects of scale that would favour those regions with a larger stock of human capital. The primary policy implication of our study is that, in order to facilitate economic growth, education and training need to supply human capital at a faster pace than simply replenishing it as it disappears from the labour market. Given the significant impact of high-order human capital (such as business R&D staff in our case study) as well as the increasingly fast pace of technological change that makes human capital obsolete, a concerted effort needs to be made to facilitate its continuous development.

Learning and teaching through context: a data-driven approach

A word may have many potential meanings, but its actual meaning in any authentic written or spoken text is determined by its context: its collocations, structural patterns, and pragmatic functions. Large language corpora offer access to words in a wide range of natural contexts, which can improve and enrich both language learning and teaching.

Characterization of heparin-binding site of tissue transglutaminase:its importance in cell surface targeting, matrix deposition, and cell signaling

Tissue transglutaminase (TG2) is a multifunctional Ca2+ activated protein crosslinking enzyme secreted into the extracellular matrix (ECM), where it is involved in wound healing and scarring, tissue fibrosis, celiac disease and metastatic cancer. Extracellular TG2 can also facilitate cell adhesion important in wound healing through a non-transamidating mechanism via its association with fibronectin (FN), heparan sulphates (HS) and integrins. Regulating the mechanism how TG2 is translocated into the ECM therefore provides a strategy for modulating these physiological and pathological functions of the enzyme. Here, through molecular modelling and mutagenesis we have identified the HS binding site of TG2 202KFLKNAGRDCSRRSSPVYVGR222. We demonstrate the requirement of this binding site for translocation of TG2 into the ECM through a mechanism involving cell surface shedding of HS. By synthesizing a peptide NPKFLKNAGRDCSRRSS corresponding to the HS binding site within TG2, we also demonstrate how this mimicking peptide can in isolation compensate the RGD-induced loss of cell adhesion on FN via binding to syndecan-4, leading to activation of PKCa, pFAK-397 and ERK1/2 and the subsequent formation of focal adhesions and actin cytoskeleton organization. A novel regulatory mechanism for TG2 translocation into the extracellular compartment that depends upon TG2 conformation and the binding of HS is proposed.

The European Union and the racialization of immigration, 1985-2006

Over the past two decades, the European Union (EU) has played an increasingly influential role in the construction of a de facto common immigration and asylum policy, providing a forum for policy-formulation beyond the scrutiny of national parliaments. The guiding principles of this policy include linking the immigration portfolio to security rather than justice; reaffirming the importance of political, conceptual and organizational borders; and attempting to transfer policing and processing functions to non-EU countries. The most important element, I argue, is the structural racialization of immigration that occurs across the various processes and which escapes the focus of much academic scrutiny. Exploring this phenomenon through the concept of the “racial state,” I examine ways to understand the operations of immigration policy-making at the inter-governmental level, giving particular attention to the ways in which asylum-seekers emerge as a newly racialized group who are both stripped of their rights in the global context and deployed as Others in the construction of national narratives.

Recent advances in fibre grating devices and their sensing applications

Over the last twenty years, we have been continuously seeing R&D efforts and activities in developing optical fibre grating devices and technologies and exploring their applications for telecommunications, optical signal processing and smart sensing, and recently for medical care and biophotonics. In addition, we have also witnessed successful commercialisation of these R&Ds, especially in the area of fibre Bragg grating (FBG) based distributed sensor network systems and technologies for engineering structure monitoring in industrial sectors such as oil, energy and civil engineering. Despite countless published reports and papers and commercial realisation, we are still seeing significant and novel research activities in this area. This invited paper will give an overview on recent advances in fibre grating devices and their sensing applications with a focus on novel fibre gratings and their functions and grating structures in speciality fibres. The most recent developments in (i) femtosecond inscription for microfluidic/grating devices, (2) tilted grating based novel polarisation devices and (3) dual-peak long-period grating based DNA hybridisation sensors will be discussed.

Teenage mothers' experiences of stigma and formal support services

This research has two focal points: experiences of stigma and experiences of formal support services among teenage mothers. Twenty teenage mothers were interviewed in depth, ten from a one-to-one support service, and ten from a group based support service. Contributions to knowledge consisted of the following. First, regarding experiences of stigma, this research integrated concepts from the social psychology literature and established the effects of stigma which are experienced by teenage mothers, offering reasons for the same. Additionally, further coping mechanisms in response to being stigmatized were discovered and grouped into two new headings: active and passive coping mechanisms. It is acknowledged that for a minority of participants, stigma does have negative effects, however, the majority experiences no such serious negative effects. Secondly, regarding experiences of support services, this research was able to directly compare one-to-one with group based support for teenage mothers. Knowledge was unearthed as to influential factors in the selection of a mode of support and the functions of each of the modes of support, which were categorised under headings for ease of comparison. It was established that there is indeed a link between these two research foci in that both the one-to-one and group based support services fulfil a stigma management function, in which teenage mothers discuss the phenomenon, share experiences and offer advice to others. However, it was also established that this function is of minor importance compared to the other functions fulfilled by the support services.

Rolling bearing vibrations: the effects of varying compliance, manufacturing tolerances and wear

In this study some common types of Rolling Bearing vibrations are analysed in depth both theoretically and experimentally. The study is restricted to vibrations in the radial direction of bearings having pure radial load and a positive radial clearance. The general vibrational behaviour of such bearings has been investigated with respect to the effects of varying compliance, manufacturing tolerances and the interaction between the bearing and the machine structure into which it is fitted. The equations of motion for a rotor supported by a bearing in which the stiffness varies with cage position has been set up and examples of solutions,obtained by digital simulation. is given. A method to calculate amplitudes and frequencies of vibration components due to out of roundness of the inner ring and varying roller diameters has been developed. The results from these investigations have been combined with a theory for bearing/machine frame interaction using mechanical impedance technique, thereby facilitating prediction of the vibrational behaviour of the whole set up. Finally. the effects of bearing fatigue and wear have been studied with particular emphasis on the use of vibration analysis for condition monitoring purposes. A number of monitoring methods have been tried and their effectiveness discussed. The experimental investigation was carried out using two purpose built rigs. For the purpose of analysis of the experimental measurements a digital mini computer was adapted for signal processing and a suite of programs was written. The program package performs several of the commonly used signal analysis processes and :include all necessary input and output functions.

A legal perspective of integrated surface mining, solid waste landfill reclamation and land conservation

In the area of international environmental law this thesis proposes the formulation of one-step planning and permitting regulation for the integrated utilisation of new surface mines as depositories for municipal solid waste. Additionally, the utilisation of abandoned and currently operated surface mines is proposed as solid waste landfills as an integral step in their reclamation. Existing laws, litigation and issues in the United Kingdom, the U.S. and Canada are discussed because of their common legal system, language and heritage. The critical shortage of approved space for disposal of solid waste has caused an urgent and growing problem for both the waste disposal industry and society. Surface mining can serve three important environmental and societal functions inuring to the health and welfare of the public: (1) providing basic minerals for goods and construction; (20 sequentially, to provide critically needed, safe burial sites for society's wastes, and (3) to conserve land by dual purpose use and to restore derelict land to beneficial surface use. Currently, the first two functions are treated environmentally, and in regulation, as two different siting problems, yet they both are earth-disturbing and excavating industries requiring surface restoration. The processes are largely duplicative and should be combined for better efficiency, less earth disturbance, conservation of land, and for fuller and better reclamation of completed surface mines returning the surfaces to greater utility than present mined land reclamation procedures. While both industries are viewed by a developed society and its communities as "bad neighbours", they remain essential and critical for mankind's existence and welfare. The study offers successful examples of the integrated process in each country. The study argues that most non-fuel surface mine openings, if not already safe, can economically, through present containment technology, be made environmentally safe for use as solid waste landfills. Simultaneously, the procedure safeguards and monitors protection of ground and surface waters from landfill contamination.

Translation strategies and cross-cultural contraints : a case study of the translation of advertising texts

Since the transfer of a message between two cultures very frequently takes place through the medium of a written text qua communicative event, it would seem useful to attempt to ascertain whether there is any kind of pattern in the use of strategies for the effective interlingual transfer of this message. Awareness of potentially successful strategies, within the constraints of context, text type, intended TL function and TL reader profile will enhance quality and cost-effectiveness (time, effort, financial costs) in the production of the target text. Through contrastive analysis of pairs of advertising texts, SL and TL, French and English, this study will attempt to identify the nature of some recurring choices made by different translators in the attempt to recreate ST information in the TL in such a manner as to reproduce as closely as possible the informative, persuasive and affective functions of the text as advertising material. Whilst recurrence may be seen to be significant in terms of illustrating tendencies with regard to the solution of problems of translation, this would not necessarily be taken as confirmation of the existence of pre-determined or prescriptive rules. These tendencies could, however, be taken as a guide to potential solutions to certain kinds of context-bound and text-type specific problem. Analysis of translated text-pairs taken from the field of advertising should produce examples of constraints posed by the need to select the content, tone and form of the Target Text, in order to ensure maximum efficacy of persuasive effect and to ensure the desired outcome, as determined by the Source Text function. When evaluating the success of a translated advertising text, constraints could be defined in terms of the culture-specific references or assumptions on which a Source Text may build in order to achieve its intended communicative function within the target community.