Cyclic voltammetry and spectroelectrochemical study of nickel and cobalt diphenyltetraazaannulene complexes

The absorption spectra. cyclic voltammetry and spectroelectrochemistry of [Ni(II)DPTAA] and [Co(II)DPTAA] (DPTAA = 6,13-diphenyldibenzo[b,i][1,4,8,11] tetraaza[14]annulene) complexes in DMF are reported in detail. The ligand oxidation is observed for [Ni(II)DPTAA] at +0.70 V vs. SCE whereas Ni2(+/+) occurs at - 1.60 V. For [Co(II)DPTAA], a ligand oxidation redox couple is seen at +0.56 V while the Co2+/+ and Co2+/3+ redox couples appear at -1.21 and +0.24 V, respectively. All observed redox couples are assigned to reversible one-electron processes on account of peak separations and scan-rate dependency. These processes were further investigated by spectroelectrochemistry for [Co(II)DPTAA]. For [Co(II)DPTAA], axial ligation of pyridine was found to shift the Co2+/3+ redox couple more negative. while the ligand oxidation was shifted to more positive potentials. From a spectrophotometric titration of [Co(II)DPTAA] with pyridine an equilibrium constant, K-f, was determined for the binding of pyridine to [Co(II)DPTAA]. This was found to be 10.2 dm(3) mol(-1), slightly lower than that of [Co(II)TAA], indicating the influence of the phenyl groups. From this value and shifts in the Co2+/3+ redox couple upon ligation, an equilibrium constant for the binding of pyridine to [Co(III)DPTAA], K'(f), was found to be 5.06 x 10(6) dm(3) mol(-1). (c) 2007 Elsevier B.V. All rights reserved.

A FUNCTIONAL, COMPARATIVE AND CLINICAL ANALYSIS OF SPERM-BORNE OOCYTE ACTIVATING FACTOR, PAWP

Successful fertilization depends upon the activation of metaphase II arrested oocytes by sperm-borne oocyte activating factor (SOAF). Failure of oocyte activation is considered as the cause of treatment failure in a proportion of infertile couples. SOAF induces the release of intracellular calcium in oocyte which leads to meiotic resumption and pronuclear formation. Calcium release is either in the form of single calcium transient in echinoderm and amphibian oocytes or several calcium oscillations in ascidian and mammalian oocytes. Although the SOAF attributes are established, it is not clear which sperm protein(s) play such role. Sperm postacrosomal WW binding protein (PAWP) satisfies a developmental criteria set for a candidate SOAF. This study shows that recombinant human PAWP protein or its transcript acts upstream of calcium release and fully activates the amphibian and mammalian oocytes. Interference trials provided evidence for the first time that PAWP mediates sperm-induced intracellular calcium release through a PPXY/WWI domain module in Xenopus, mouse and human oocytes. Clinical applications of PAWP were further investigated by prospective study on the sperm samples from patients undergoing intracytoplasmic sperm injection (ICSI). PAWP expression level, analyzed by flow cytometry, was correlated to ICSI success rate and embryonic development. This study also explored the developmental expression of the other SOAF candidate, PLCζ in male reproductive system and its function during fertilization. Our findings showed for the first time that PLCζ most likely binds to the sperm head surface during epididymal passage and is expressed in epididymis. We demonstrated that PLCζ is also compartmentalized early in spermiogenesis and thus could play an important role during spermiogenesis. Detailed analysis of in vitro fertilization revealed that PLCζ disappears from sperm head during acrosome reaction and is not detectable during sperm incorporation into the oocyte cytoplasm. In conclusion, this dissertation provides evidence for the essential non-redundant role of sperm PAWP in amphibian and mammalian fertilization; recommends PAWP as a biomarker for prediction of ICSI outcomes in infertile couples; and proposes that sperm PLCζ may have functions other than inducing oocyte activation during fertilization.

Ferroelectricity and isotope effects in hydrogen-bonded KDP crystals

Based on an accurate first principles description of the energetics in H-bonded potassium-dihydrogen-phosphate crystals, we conduct a first study of nuclear quantum effects and of the changes brought about by deuteration. Tunneling is allowed only for clusters involving correlated protons and heavy ion displacements, the main effect of deuteration being a depletion of the proton probability density at the O-H-O bridge center, which in turn weakens its proton-mediated covalent bonding. The ensuing lattice expansion couples self-consistently with the proton off-centering, thus explaining both the giant isotope effect and its close connection with geometrical effects.

Effects of vasectomy on spermatogenesis and fertility outcomes after assisted conception

Abstract BACKGROUND: Each year 40,000 men have a vasectomy in the UK whilst another 2400 request a reversal to begin a second family. Sperm can now be obtained by testicular biopsy and subsequently used in assisted conception with intracytoplasmic sperm injection (ICSI). The study aims were to compare sperm yields of men post-vasectomy or with obstructive azoospermia (OA) of unknown aetiology with fertile men and to assess any alteration in the clinical pregnancy rates after ICSI. METHODS: Testicular tissue was obtained by Trucut needle from men who had undergone a vasectomy >5yrs previously, had OA from other causes and from fertile men during vasectomy. Seminiferous tubules were milked to measure sperm yields. Numbers of Sertoli cells, spermatids and thickness of the seminiferous tubule walls were assessed using quantitative computerized analysis. RESULTS and CONCLUSIONS: Sperm yields/g testis were significantly decreased in men post-vasectomy and in men with OA, relative to fertile men. Significant reductions were also observed in early (40%) and mature (29%) spermatid numbers and an increase of 31% was seen in the seminiferous tubule wall (basal membrane and collagen thickness) of vasectomised men compared to fertile men. Clinical pregnancy rates in couples who had had a vasectomy were also significantly reduced.

La incidencia de los valores culturales en el voluntariado: el caso de Europa

La realidad del voluntariado es sumamente compleja hasta el punto de que resulta complicado definir y caracterizar el trabajo voluntario, dada la gran variedad de interpretaciones, motivaciones, variables sociodemográficas y aspectos culturales que configuran el perfil de los voluntarios. El objetivo de este trabajo es analizar la influencia conjunta de algunas variables sociodemográficas, así como de los valores culturales de índole secular o tradicional, sobre el perfil de los voluntarios en Europa. Además, se investiga qué variables orientan a los voluntarios hacia un determinado tipo de voluntariado u otro. Para ello se ha aplicado principalmente una metodología de regresión logística a partir de la información disponible en la European Value Study. Los resultados obtenidos ayudan a establecer una caracterización del voluntariado en Europa, y confirman la influencia de los valores culturales, en primer lugar, en la realización o no de trabajos de voluntariado, y en segundo lugar, en la elección que hacen estas personas del tipo de actividad con la que están comprometidos. Al analizar dos tipos de voluntariado de motivación supuestamente muy diferente, se concluye que existe un grupo de valores que influyen en ambos, aunque el sentido y la intensidad en la que lo hacen sea diferente; por otra parte, algunos valores tienen influencia o no en la realización de trabajos de voluntariado, dependiendo del tipo específico al que nos refiramos.

The role of Y chromosome deletions in male infertility.

Male infertility affects approximately 2-7% of couples around the world. Over one in ten men who seek help at infertility clinics are diagnosed as severely oligospermic or azoospermic. Recent extensive molecular studies have revealed that deletions in the azoospermia factor region of the long arm of the Y chromosome are associated with severe spermatogenic impairment (absent or severely reduced germ cell development). Genetic research into male infertility, in the last 7 years, has resulted in the isolation of a great number of genes or gene families on the Y chromosome, some of which are believed to influence spermatogenesis.

Coupled consolidation of a solid, infinite cylinder using a Terzaghi formulation

Axisymmetric consolidation is a classical boundary value problem for geotechnical engineers. Under some circumstances an analysis in which the changes in pore pressure, effective stress and displacement can be uncoupled from each other is sufficient, leading to a Terzaghi formulation of the axisymmetric consolidation equation in terms of the pore pressure. However, representation of the Mandel-Cryer effect usually requires more complex, coupled, Biot formulations. A new coupled formulation for the plane strain, axisymmetric consolidation problem is presented for small, linear elastic deformations. A single, easily evaluated parameter couples changes in pore pressure to changes in effective stress, and the resulting differential equation for pore pressure dissipation is very similar to Terzaghi’s classic formulation. The governing equations are then solved using finite differences and the consolidation of a solid infinite cylinder analysed, calculating the variation with time and with radius of the excess pore pressure and the radial displacement. Comparison with a previously published semi-analytical solution indicates that the formulation successfully embodies the Mandel-Cryer effect.

Extraction of electrode kinetic parameters from microdisc voltammetric data measured under transport conditions intermediate between steady-state convergent and transient linear diffusion as typically applies to room temperature ionic liquids

The extraction of electrode kinetic parameters for electrochemical couples in room-temperature ionic liquids (RTILs) is currently an area of considerable interest. Electrochemists typically measure electrode kinetics in the limits of either transient planar or steady-state convergent diffusion for which the voltammetic response is well understood. In this paper we develop a general method allowing the extraction of this kinetic data in the region where the diffusion is intermediate between the planar and convergent limits, such as is often encountered in RTILs using microelectrode voltammetry. A general working surface is derived, allowing the inference of Butler-Volmer standard electrochemical rate constants for the peak-to-peak potential separation in a cyclic voltammogram as a function of voltage scan rate. The method is applied to the case of the ferrocene/ferrocenium couple in [C(2)mim][N(Tf)(2)] and [C(4)mim][N(Tf)(2)].

Salt-bridge dynamics control substrate-induced conformational change in the membrane transporter GlpT.

Active transport of substrates across cytoplasmic membranes is of great physiological, medical and pharmaceutical importance. The glycerol-3-phosphate (G3P) transporter (GlpT) of the E. coli inner membrane is a secondary active antiporter from the ubiquitous major facilitator superfamily that couples the import of G3P to the efflux of inorganic phosphate (Pi) down its concentration gradient. Integrating information from a novel combination of structural, molecular dynamics simulations and biochemical studies, we identify the residues involved directly in binding of substrate to the inward-facing conformation of GlpT, thus defining the structural basis for the substrate-specificity of this transporter. The substrate binding mechanism involves protonation of a histidine residue at the binding site. Furthermore, our data suggest that the formation and breaking of inter- and intradomain salt bridges control the conformational change of the transporter that accompanies substrate translocation across the membrane. The mechanism we propose may be a paradigm for organophosphate:phosphate antiporters.

'Leaving Nothing to Chance'?: Joint Tenancies, The 'Right' of Survivorship and Unilateral Severance

The joint tenancy with its inherent right of survivorship is the most prevalent form of co-ownership in the common law world today. Most couples will be joint tenants of a family home, while relations (such as siblings) who purchase property together may opt for this arrangement. Inter vivos acquisitions aside, the huge intergenerational transfer of wealth within families on death can result in a joint tenancy, and it may also be a convenient estate planning device. The fact that property automatically vests in the surviving joint tenants on death is the reason why many people choose this form of co-ownership. However, there is one serious disadvantage. A joint tenancy is an inflexible form of landholding where relationships sour or family circumstances change over time, and co-owners want their respective `shares' of the property to pass to someone else on death. Where consensual severance is not possible, one joint tenant can sever unilaterally. The latter mechanism is vital in terms of giving effect to the wishes of the severing joint tenant, especially in situations of discord or a breakdown in relations with their fellow co-owners. However, unilateral severance also has serious implications for the non-severing joint tenant(s) who expected to inherit property through survivorship, and can impact significantly on ownership of the home and other family property. This article looks at unilateral severance as a means of subverting the right of survivorship. The focus is on personal and inter-family relationships, and the various legal issues and policy considerations associated with unilateral severance across the common law jurisdictions of Britain, Ireland, Australia, Canada, and New Zealand. It assesses the various methods of effecting unilateral severance and proposes specific measures, as well as considering novel arguments for preventing unilateral severance based on contractual agreements to the contrary and proprietary estoppel.

It's Better to Stick to your own Kind: Teenagers' Views on Cross-community marriages in Northern Ireland

This article presents the attitudes of 80 teenagers-growing up in one of the most contested localities in Northern Ireland-to cross-community marriages, i.e. those between Catholics and Protestants. Research suggests that adults in interface areas continue to exhibit ethno-sectarian prejudices despite wider political developments such as the Good Friday Agreement. The teenagers perceived that their families would be largely unsupportive of cross-community unions but felt that their own views were much less prejudiced than those of their parents. However, while the majority of teenagers had no objections in principle to marrying outside their religious group, they outlined a number of practical difficulties which couples from cross-community unions would face. These included deciding where to live, in which religion, if any, to bring children up and where to send children to school. Most of the teenagers suggested that these potential problems would work against them marrying outside their own religious group. These practical dilemmas provide a more nuanced set of reasons for marrying within one's own community than dilemmas based on traditional prejudices and stereotypes and suggest that teenagers living in sectarian enclaves are more receptive to cross-community marriages than their parents.

Half-precessional dynamics of monsoon rainfall near the East African Equator

External climate forcings-such as long-term changes in solar insolation-generate different climate responses in tropical and high latitude regions(1). Documenting the spatial and temporal variability of past climates is therefore critical for understanding how such forcings are translated into regional climate variability. In contrast to the data-richmiddle and high latitudes, high-quality climate-proxy records from equatorial regions are relatively few(2-4), especially from regions experiencing the bimodal seasonal rainfall distribution associated with twice-annual passage of the Intertropical Convergence Zone. Here we present a continuous and well-resolved climate-proxy record of hydrological variability during the past 25,000 years from equatorial East Africa. Our results, based on complementary evidence from seismic-reflection stratigraphy and organic biomarker molecules in the sediment record of Lake Challa near Mount Kilimanjaro, reveal that monsoon rainfall in this region varied at half-precessional (similar to 11,500-year) intervals in phase with orbitally controlled insolation forcing. The southeasterly and northeasterly monsoons that advect moisture from the western Indian Ocean were strengthened in alternation when the inter-hemispheric insolation gradient was at a maximum; dry conditions prevailed when neither monsoon was intensified and modest local March or September insolation weakened the rain season that followed. On sub-millennial timescales, the temporal pattern of hydrological change on the East African Equator bears clear high-northern-latitude signatures, but on the orbital timescale it mainly responded to low-latitude insolation forcing. Predominance of low-latitude climate processes in this monsoon region can be attributed to the low-latitude position of its continental regions of surface air flow convergence, and its relative isolation from the Atlantic Ocean, where prominent meridional overturning circulation more tightly couples low-latitude climate regimes to high-latitude boundary conditions.

Clinical significance of sperm DNA damage in assisted reproduction outcome

Background: Sperm DNA damage shows great promise as a biomarker of infertility. The study aim is to determine the usefulness of DNA fragmentation (DF), including modified bases (MB), to predict assisted reproduction treatment (ART) outcomes. Methods: DF in 360 couples (230 IVF and 130 ICSI) was measured by the alkaline Comet assay in semen and in sperm following density gradient centrifugation (DGC) and compared with fertilization rate (FR), embryo cumulative scores (ECS1) for the total number of embryos/treatment, embryos transferred (ECS2), clinical pregnancy (CP) and spontaneous pregnancy loss. MB were also measured using formamidopyrimidine DNA glycosylase to convert them into strand breaks. Results: In IVF, FR and ECS decreased as DF increased in both semen and DGC sperm, and couples who failed to achieve a CP had higher DF than successful couples (+12.2 semen, P = 0.004; +9.9 DGC sperm, P = 0.010). When MB were added to existing strand breaks, total DF was markedly higher (+17.1 semen, P = 0.009 and +13.8 DGC sperm, P = 0.045). DF was not associated with FR, ECS or CP in either semen or DGC sperm following ISCI. In contrast, by including MB, there was significantly more DNA damage (+16.8 semen, P = 0.008 and +15.5 DGC sperm, P = 0.024) in the group who did not achieve CP. Conclusion: SDF can predict ART outcome for IVF. Converting MB into further DNA strand breaks increased the test sensitivity, giving negative correlations between DF and CP for ICSI as well as IVF. © 2010 The Author.

Intimate Mixing - Bridging the Gap? Catholic-Protestant Relationships in Northern Ireland

For many years Northern Ireland has been a divided society where members of the two main religious groups, Catholics and Protestants, have limited opportunities to interact due to segregation in their social lives. Attempts have been made to encourage religious mixing through integration in schools, housing and workplaces predicated on the theory that bringing people together can improve community relations and remove prejudices – known as the ‘contact hypothesis’. However, little is known about those who enter into mixed-religion partnerships often against the wishes of their families and communities. This paper examines the characteristics and attitudes of mixed-religion couples and suggests that they differ in their socio-demographic characteristics and in their attitudes from those who marry within their own religion. These findings add to the weight of evidence from other countries in conflict suggesting that intermarriage has a role to play in contributing to less sectarian views and improved community relations.