Theoretical studies of systems of biochemical interest containing Fe and Cu transition metals

La presència de la química teòrica i computacional està augmentant en quasi tots els camps de la recerca en química. Els càlculs teòrics poden ajudar a entendre millor l'estructura, les propietats i la reactivitat de compostos metàl·lics d'àrees tan diferents com la química inorgànica, organometàl·lica i bioinorgànica. No obstant això, és imprescindible utilitzar la metodologia adequada per obtenir resultats teòrics fiables. Els estudis d'aquesta tesi es poden dividir en dos grups diferents. El primer grup inclou l'estudi teòric del mecanisme de reacció de diversos sistemes que contenen coure i tenen diferents estructures Cun-O2. Aquests estudies s'han dut a terme amb l'objectiu de profunditzar en la natura dels processos oxidants químics i biològics promoguts per sistemes que contenen coure. En la segona part de la tesi, s'estudia la fiabilitat de diferents tècniques utilitzades per estudiar l'estructura electrònica i la reactivitat de sistemes que contenen coure, ferro i altres metalls de transició.

Cuidar dos cuidadores : o (des)envolvimento da espiritualidade na prevenção de quadros de stress e burnout

A Humanidade anda cansada, esgotado. Um cansaço que é a soma do fardo de cada um e também parte do fardo de outros. E a Humanidade busca explicações para este cansaço. E quer aliviá-lo. E quer minimizá-lo. Mas busca muito mais que isso. Trata-se, enfim, de buscar não o remédio mas o sentido da própria existência, as respostas adedentro, ou seja, bem no interior do ser humano. O presente trabalho pretende ser uma reflexão – compreender para agir - sobre a busca da dimensão da espiritualidade como possível resposta na prevenção de quadros de stress e burnout. Quem trabalho na área da assistência e na relação de ajuda contínua com pessoas em situação de extrema fragilidade sabe que se não houver um cuidado na reposição de energias, com muita facilidade a pessoa chega a um estado de cansaço e a qualquer momento o turboadrenalina pode queimar. No âmbito da gestão de unidades sociais e bem-estar, cuidar dos cuidadores é a maior e mais nobre missão de qualquer Instituição. Pois, que serviços seriam vivenciados sem as pessoas que formam o corpo e, por isso, a vida de uma Instituição? O caminho da nossa reflexão é orientado para a Comunidade Vida e Paz, como espaço relacional que quer e procura ser um espaço de renovação de vidas – das pessoas sem abrigo – onde, amparadas por um conjunto de Cuidadores, cujo olhar se orienta num trabalho de unificação da pessoa, são imbuídos por uma espiritualidade que se quer colaborante na missão de dignificar cada pessoa e devolvê-la à sua condição original. A pessoa, cada pessoa, é a soma de si, da relação com outros e da relação com o transcendente. Na missão de cuidar, pode a espiritualidade ser ausente? Desta, retiramos um sentido coerente da existência, a verdade do dom e da dádiva e, por isso, uma vida feliz.

The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes

Four new antimony sulphides, [T(dien)(2)]Sb6S10 center dot xH(2)O [T = Ni (1), Co (2) x approximate to 0.45], [Co(en)(3)]SbsSI(3) (3) and [Ni(en)(3)]Sb12S19 (4), have been synthesised under solvothermal conditions. In compounds (1) - (3), Sb12S228- secondary building units are connected to form layered structures. In (1) and (2), Sb-6 S-2- layers containing Sb16S16 heterorings are separated by [T(dien]2](2+) cations, whilst in (3), Sb8 S2- layers 10 13 contain [Co(en)3]2+ cations within large Sb22S22 pores. Compound (4) adopts a three-dimensional structure in which [Ni(en)3 12 cations lie within ca. 5 A wide channels. (c) 2007 Elsevier Ltd. All rights reserved.

Responsiveness to change by standard-form contract drafters: A case study of the FIDIC White Book

Purpose – The purpose of this paper is to focus on the Fédération Internationale des Ingénieurs-Conseils (FIDIC) White Book standard form of building contract. It tracks the changes to this contract over its four editions, and seeks to identify their underlying causes. Design/methodology/approach – The changes made to the White Book are quantified using a specific type of quantitative content analysis. The amended clauses are then examined to understand the nature of the changes made. Findings – The length of the contract increased by 34 per cent between 1990 and 2006. A large proportion of the overall increase can be attributed to the clauses dealing with “conflict of interest/corruption” and “dispute resolution”. In both instances, the FIDIC drafting committees have responded to international developments to discourage corruption, and to encourage the use of alternative dispute resolution. Between 1998 and 2006, the average length of the sentences increased slightly, raising the question of whether long sentences are easily understood by users of contracts. Research limitations/implications – Quantification of text appears to be particularly useful for the analysis of documents which are regularly updated because changes can be clearly identified and the length of sentences can be determined, leading to conclusions about the readability of the text. However, caution is needed because changes of great relevance can be made to contract clauses without actually affecting their length. Practical implications – The paper will be instructive for contract drafters and informative for users of FIDIC's White Book. Originality/value – Quantifying text has been rarely used regarding standard-form contracts in the field of construction.

Observed adaptation to climate change: UK evidence of transition to a well-adapting society

This paper investigates whether and to what extent a wide range of actors in the UK are adapting to climate change, and whether this is evidence of a social transition. We document evidence of over 300 examples of early adopters of adaptation practice to climate change in the UK. These examples span a range of activities from small adjustments (or coping) to building adaptive capacity, implementing actions and creating deeper systemic change in public and private organisations in a range of sectors. We find that adaptation in the UK has been dominated by government initiatives and has principally occurred in the form of research into climate change impacts. These actions within government stimulate a further set of actions at other scales in public agencies, regulatory agencies and regional government (or in the devolved administrations), though with little real evidence of climate change adaptation initiatives trickling down to local government level. The water supply and flood defence sectors, requiring significant investment in large scale infrastructure such as reservoirs and coastal defences, have invested more heavily in identifying potential impacts and adaptations. Economic sectors that are not dependent on large scale infrastructure appear to be investing far less effort and resources in preparing for climate change. We conclude that while the government-driven top-down targeted adaptation approach has generated anticipatory action at low cost, it may also have created enough niche activities to allow for diffusion of new adaptation practices in response to real or perceived climate change. These results have significant implications for how climate policy can be developed to support autonomous adaptors in the UK and other countries.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Reversible sphere-to-lamellar wetting transition at the interface of a diblock copolymer system

We use ellipsometry to investigate a transition in the morphology of a sphere-forming diblock copolymer thin-film system. At an interface the diblock morphology may differ from the bulk when the interfacial tension favours wetting of the minority domain, thereby inducing a sphere-to-lamella transition. In a small, favourable window in energetics, one may observe this transition simply by adjusting the temperature. Ellipsometry is ideally suited to the study of the transition because the additional interface created by the wetting layer affects the polarisation of light reflected from the sample. Here we study thin films of poly(butadiene-ethylene oxide) (PB-PEO), which order to form PEO minority spheres in a PB matrix. As temperature is varied, the reversible transition from a partially wetting layer of PEO spheres to a full wetting layer at the substrate is investigated.

Observed adaptation to climate change as initiated transition

This paper investigates whether and to what extent a wide range of actors in the UK are adapting to climate change, and whether this is evidence of a social transition. We document evidence of over 300 examples of early adopters of adaptation practice to climate change in the UK. These examples span a range of activities from small adjustments (or coping), to building adaptive capacity, to implementing actions and to creating deeper systemic change in public and private organisations in a range of sectors. We find that adaptation in the UK has been dominated by government initiatives and has principally occurred in the form of research into climate change impacts. These government initiatives have stimulated a further set of actions at other scales in public agencies, regulatory agencies and regional government (and the devolved administrations), though with little real evidence of climate change adaptation initiatives trickling down to local government level. The sectors requiring significant investment in large scale infrastructure have invested more heavily than those that do not in identifying potential impacts and adaptations. Thus we find a higher level of adaptation activity by the water supply and flood defence sectors. Sectors that are not dependent on large scale infrastructure appear to be investing far less effort and resources in preparing for climate change. We conclude that the UK government-driven top-down targeted adaptation approach has generated anticipatory action at low cost in some areas. We also conclude that these actions may have created enough niche activities to allow for diffusion of new adaptation practices in response to real or perceived climate change. These results have significant implications for how climate policy can be developed to support autonomous adaptors in the UK and other countries.

Reversible helical unwinding transition of a self-assembling peptide amphiphile

A designed peptide amphiphile C16-KKFFVLK self-assembles into nanotubes and helical ribbons in aqueous solution at room temperature. A remarkable unwinding transition, leading to twisted tapes, is observed on heating. Nanotubes and ribbons re-form on cooling.

Dynamic simulation studies of structural formation and transition in electro-magneto-rheological fluids

The computer simulation method has been used to study the structural formation and transition of electro-magneto-rheological (EMR) fluids under compatible electric and magnetic fields. When the fields are applied simultaneously and perpendicularly to each other, the particles rapidly arrange into two-dimensional close-packed layer structures parallel to both fields. The layers then combine together to form thicker sheet-like structures, which finally relax into three-dimensional close-packed structures with the help of the thermal fluctuations. On the other hand, if the electric field is applied firstly to induce the body-centered tetragonal (BCT) columns in the system, and then the magnetic field is applied in the perpendicular direction. the BCT to face-centered cubic (FCC) structure transition is observed in very short time. Following that. the structure keeps on evolving due to the demagnetization effect and finally form the three-dimensional close-packed structures.

Simulation of field-induced structural formation and transition in electromagnetorheological suspensions

A computer simulation method has been used to study the three-dimensional structural formation and transition of eleetromagnetorheological (EMR) suspensions under compatible electric and magnetic fields. When the fields are applied simultaneously and perpendicularly to each other, the particles rapidly arrange into single layer structures parallel to both fields. In each layer, there is a two-dimensional hexagonal lattice. The single layers then combine together to form thicker sheetlike structures. With the help of the thermal fluctuations, the thicker structures relax into three-dimensional close-packed structures, which may be face-centered cubic (fcc), hexagonal close-packed (hup) lattices, or, more probably, the mixture of them, depending on the initial configurations and the thermal fluctuations. On the other hand, if the electric field is applied first to induce the body-centered tetragonal (bct) columns in the system, and then the magnetic field is applied in the perpendicular direction, the bet to fee structure transition is observed in a very short time. Following that, the structure keeps on evolving due to the demagnetization effect and finally forms close-packed structures with fee and hcp lattice character. The simulation results are in agreement with the theoretical and experimental results.

Poetry of social conscience, poetry of transition: Ann Hawkshaw's 'Introductory Stanzas' and 'The Mother to her Starving Child'

Through close readings of Ann Hawkshaw's poetry in the context of industrial Manchester in the 1840s, this article highlights the interaction of form and content in poetry that makes use of the idea of the past to question or complicate the politics of the present.

Narratives of grassroots innovations: a comparison of voluntary simplicity and the transition movement in Italy

Grassroots innovations (GI) are promising examples of deliberate transformation of socio-technical systems towards resilience and sustainability. However, evidence is needed on the factors that limit or enable their success. This paper set out to study how GI use narratives to empower innovation in the face of incumbent socio-technical regimes. Institutional documents were comparatively analyzed to assess how the narratives influence the structure, form of action and external interactions of two Italian grassroots networks, Bilanci di Giustizia and Transition Network Italy. The paper finds an internal consistency between narratives and strategies for each of the two networks. The paper also highlights core similarities, but also significant differences in the ethical basis of the two narratives, and in the organizations and strategies. Such differences determine different forms of innovation empowerment and expose the niche to different potentials to transform incumbent regimes, or to the risk of being co-opted by them.

Cathepsin X cleaves the beta 2 cytoplasmic tail of LFA-1 inducing the intermediate affinity form of LFA-1 and alpha-actinin-1 binding

The motility of T cells depends on the dynamic spatial regulation of integrin-mediated adhesion and de-adhesion. Cathepsin X, a cysteine protease, has been shown to regulate T-cell migration by interaction with lymphocyte function associated antigen-1 (LFA-1). LFA-1 adhesion to the ICAM-1 is controlled by the association of actin-binding proteins with the cytoplasmic tail of the beta(2) chain of LFA-1. Cleavage by cathepsin X of the amino acid residues S(769), E(768) and A(767) from the C-terminal of the beta(2) cytoplasmic tail of LFA-1 is shown to promote binding of the actin-binding protein alpha-actinin-1. Furthermore, cathepsin X overexpression reduced LFA-1 clustering and induced an intermediate affinity LFA-1 conformation that is known to associate with a-actinin-1. increased levels of intermediate affinity LFA-1 resulted in augmented cell spreading due to reduced attachment of T cells to the ICAM-1-coated surface. Gradual cleavage of LFA-1 by cathepsin X enables the transition between intermediate and high affinity LFA-1, an event that is crucial for effective T-cell migration.

Thermal stability of extracellular hemoglobin of Glossoscolex paulistus: Determination of activation parameters by optical spectroscopic and differential scanning calorimetric studies

Glossoscolex paulistus hemoglobin (HbGp) was studied by dynamic light scattering (DLS), optical absorption spectroscopy (UV-VIS) and differential scanning calorimetry (DSC). At pH 7.0, cyanomet-HbGp is very stable, no oligomeric dissociation is observed, while denaturation occurs at 56 degrees C, 4 degrees C higher as compared to oxy-HbGp. The oligomeric dissociation of HbGp occurs simultaneously with some protein aggregation. Kinetic studies for oxy-HbGp using UV-VIS and DES allowed to obtain activation energy (E(a)) values of 278-262 kJ/mol (DES) and 333 kJ/mol (UV-VIS). Complimentary DSC studies indicate that the denaturation is irreversible, giving endotherms strongly dependent upon the heating scan rates, suggesting a kinetically controlled process. Dependence on protein concentration suggests that the two components in the endotherms are due to oligomeric dissociation effect upon denaturation. Activation energies are in the range 200-560 kJ/mol. The mid-point transition temperatures were in the range 50-65 degrees C. Cyanomet-HbGp shows higher mid-point temperatures as well as activation energies, consistent with its higher stability. DSC data are reported for the first time for an extracellular hemoglobin. (C) 2010 Elsevier B.V. All rights reserved.