Catalytic, Enantioselective Sulfenylation of Ketone-Derived Enoxysilanes

A catalytic, enantioselective, Lewis base-catalyzed \u3b1-sulfenylation of silyl enol ethers has been developed. To avoid acidic hydrolysis of the silyl enol ether substrates, a sulfenylating agent that did not require additional Br\uf8nsted acid activation, namely N-phenylthiosaccharin, was developed. Three classes of Lewis bases-tertiary amines, sulfides, and selenophosphoramides-were identified as active catalysts for the \u3b1-sulfenylation reaction. Among a wide variety of chiral Lewis bases in all three classes, only chiral selenophosphoramides afforded \u3b1-phenylthio ketones in generally high yield and with good enantioselectivity. The selectivity of the reaction does not depend on the size of the silyl group but is highly sensitive to the double bond geometry and the bulk of the substituents on the double bond. The most selective substrates are those containing a geminal bulky substituent on the enoxysilane. Computational analysis revealed that the enantioselectivity arises from an intriguing interplay among sterically guided approach, distortion energy, and orbital interactions

A new liver perfusion and preservation system for transplantation Research in large animals

A kidney perfusion machine, model MOX-100 (Waters Instruments, Ltd, Rochester, MN) was modified to allow continuous perfusion of the portal vein and pulsatile perfusion of the hepatic artery of the liver. Additional apparatus consists of a cooling system, a membrane oxygenator, a filter for foreign bodies, and bubble traps. This system not only allows hypothermic perfusion preservation of the liver graft, but furthermore enables investigation of ex vivo simulation of various circulatory circumstances in which physiological perfusion of the liver is studied. We have used this system to evaluate the viability of liver allografts preserved by cold storage. The liver was placed on the perfusion system and perfused with blood with a hematocrit of approximately 20% and maintained at 37°C for 3 h. The flows of the hepatic artery and portal vein were adjusted to 0.33 mL and 0.67 mL/g of liver tissue, respectively. Parameters of viability consisted of hourly bile output, oxygen consumption, liver enzymes, electrolytes, vascular resistance, and liver histology. This method of liver assessment in large animals will allow the objective evaluation of organ viability for transplantation and thereby improve the outcome of organ transplantation. Furthermore, this pump enables investigation into the pathophysiology of liver ischemia and preservation. © 1990 Informa UK Ltd All rights reserved: reproduction in whole or part not permitted

A methodology for precision manufacture of a nozzle using hybrid laser powder-bed fusion: a case study

This paper presents a methodology for precision manufacture of a nozzle using the hybrid laser powder-bed fusion (L-PBF) technology. A new distortion predictive model for hybrid L-PBF was developed using finite element techniques. The model was validated against experimentally measured distortion using optical scanning. The validated model was utilised to mitigate distortion by applying additional stiffeners to the nozzle geometry where the distortion was reduced by 60% to acceptable tolerance of ±200 µm. Micro-milling trials were conducted to identify optimum cutting parameters delivering high material removal rates while maintaining the average surface roughness of less than 1 µm. Finally, a nozzle with reduced distortion and desirable surface finish was manufactured, which has been used in industrial research context for process and product development of food products

A Cross-Sectional Survey on Knowledge and Perceptions of Health Risks Associated with Arsenic and Mercury Contamination from Artisanal Gold mining in Tanzania.

An estimated 0.5 to 1.5 million informal miners, of whom 30-50% are women, rely on artisanal mining for their livelihood in Tanzania. Mercury, used in the processing gold ore, and arsenic, which is a constituent of some ores, are common occupational exposures that frequently result in widespread environmental contamination. Frequently, the mining activities are conducted haphazardly without regard for environmental, occupational, or community exposure. The primary objective of this study was to assess community risk knowledge and perception of potential mercury and arsenic toxicity and/or exposure from artisanal gold mining in Rwamagasa in northwestern Tanzania. A cross-sectional survey of respondents in five sub-villages in the Rwamagasa Village located in Geita District in northwestern Tanzania near Lake Victoria was conducted. This area has a history of artisanal gold mining and many of the population continue to work as miners. Using a clustered random selection approach for recruitment, a total of 160 individuals over 18 years of age completed a structured interview. The interviews revealed wide variations in knowledge and risk perceptions concerning mercury and arsenic exposure, with 40.6% (n=65) and 89.4% (n=143) not aware of the health effects of mercury and arsenic exposure respectively. Males were significantly more knowledgeable (n=59, 36.9%) than females (n=36, 22.5%) with regard to mercury (x²=3.99, p<0.05). An individual's occupation category was associated with level of knowledge (x²=22.82, p=<0.001). Individuals involved in mining (n=63, 73.2%) were more knowledgeable about the negative health effects of mercury than individuals in other occupations. Of the few individuals (n=17, 10.6%) who knew about arsenic toxicity, the majority (n=10, 58.8%) were miners. The knowledge of individuals living in Rwamagasa, Tanzania, an area with a history of artisanal gold mining, varied widely with regard to the health hazards of mercury and arsenic. In these communities there was limited awareness of the threats to health associated with exposure to mercury and arsenic. This lack of knowledge, combined with minimal environmental monitoring and controlled waste management practices, highlights the need for health education, surveillance, and policy changes

Therapists’ and non-therapists’ constructions of heterosex: A qualitative story completion study

© 2018 The British Psychological Society Objectives: Little research has examined the discourses that shape therapists’ sense-making around heterosex. This paper explores the discourses of sexuality and gender underpinning therapists’ and non-therapists’ responses to a sexual experimentation scenario in a heterosexual relationship. It also considers the value of the novel technique of story completion (SC), in which participants are asked to write a story in response to a hypothetical scenario, for qualitative psychology and psychotherapy research. Design: This research used a comparative SC design (Kitzinger & Powell,). Participants were sequentially presented with and invited to complete two story stems: one in which a male character suggested ‘trying something new’ to his female partner and one in which the female character made the suggestion. The stems were otherwise identical. Methods: A total of 100 SCs were written by 49 (28 female; 21 male) therapists and 51 (29 female; 22 male) non-therapists. Participants were recruited mainly via UK-based email lists and Facebook groups, and therapeutic training organizations, and the data were analysed using a feminist post-structuralist thematic analysis (Braun & Clarke,). Results: Both groups of participants drew on heteronormative discourses of sexuality and gender to make sense of the stem. Engaging in sexual experimentation was often depicted as a demonstration of being normal. In some stories written by women, sex was framed as a site for negotiating ‘equality’ and reciprocity in relationships. Therapists were more likely than non-therapists to frame ‘difficulties’ within relationships as opportunities for personal growth and increased emotional depth, and their stories included greater emotional complexity. Conclusion: These findings raise questions about practitioner training and whether it results in therapists drawing on narrow and restrictive discourses of heterosex in clinical practice. Practitioner points: Training on sexual issues is largely absent from non-specialist practitioner training courses, which potentially means therapists are ill-equipped to respond to clients’ anxiety about sexual issues. Evidence from this and other research indicates that therapists’ sense-making around heterosexual sexual relationships is underpinned by narrow and restrictive discourses that entrench traditional gender relations and limit sexual agency. Psychologists are increasingly taking up positions of clinical leadership and are looked to for models of best practice. Drawing on theorizations of sexual difficulties, and of anxieties about sexual practice, that challenge traditional gender and heteronorms, and the commodification and medicalization of sex, is important for effective psychological leadership relating to the treatment of sexual issues and the furthering of social justice agendas

Feasibility and Coverage of Implementing Intermittent Preventive Treatment of Malaria in Pregnant women Contacting Private or Public Clinics in Tanzania: Experience-based Viewpoints of Health Managers in Mkuranga and Mufindi districts.

Evidence on healthcare managers' experience on operational feasibility of malaria intermittent preventive treatment for malaria during pregnancy (IPTp) using sulphadoxine-pyrimethamine (SP) in Africa is systematically inadequate. This paper elucidates the perspectives of District Council Health Management Team (CHMT)s regarding the feasibility of IPTp with SP strategy, including its acceptability and ability of district health care systems to cope with the contemporary and potential challenges. The study was conducted in Mkuranga and Mufindi districts. Data were collected between November 2005 and December 2007, involving focus group discussion (FGD) with Mufindi CHMT and in-depth interviews were conducted with few CHMT members in Mkuranga where it was difficult to summon all members for FGD. Participants in both districts acknowledged the IPTp strategy, considering the seriousness of malaria in pregnancy problem; government allocation of funds to support healthcare staff training programmes in focused antenatal care (fANC) issues, procuring essential drugs distributed to districts, staff remuneration, distribution of fANC guidelines, and administrative activities performed by CHMTs. The identified weaknesses include late arrival of funds from central level weakening CHMT's performance in health supervision, organising outreach clinics, distributing essential supplies, and delivery of IPTp services. Participants anticipated the public losing confidence in SP for IPTp after government announced artemither-lumefantrine (ALu) as the new first-line drug for uncomplicated malaria replacing SP. Role of private healthcare staff in IPTp services was acknowledged cautiously because CHMTs rarely supplied private clinics with SP for free delivery in fear that clients would be required to pay for the SP contrary to government policy. In Mufindi, the District Council showed a strong political support by supplementing ANC clinics with bottled water; in Mkuranga such support was not experienced. A combination of health facility understaffing, water scarcity and staff non-adherence to directly observed therapy instructions forced healthcare staff to allow clients to take SP at home. Need for investigating in improving adherence to IPTp administration was emphasised. High acceptability of the IPTp strategy at district level is meaningless unless necessary support is assured in terms of number, skills and motivation of caregivers and availability of essential supplies

A registry-based follow-up study, comparing the incidence of cardiovascular disease in native Danes and immigrants born in Turkey, Pakistan and the former Yugoslavia: do social inequalities play a role?

<p>Abstract</p> <p>Background</p> <p>This study compared the incidence of cardiovascular disease (CVD) and acute myocardial infarction (AMI) between native Danes and immigrants born in Turkey, Pakistan and the former Yugoslavia. Furthermore, we examined whether different indicators of socioeconomic status (SES), such as employment, income and housing conditions influenced potential differences.</p> <p>Methods</p> <p>In this registry-based follow-up study individuals were identified in a large database that included individuals from two major regions in Denmark, corresponding to about 60% of the Danish population. Incident cases of CVD and AMI included fatal and non-fatal events and were taken from registries. Using Cox regression models, we estimated incidence rates at 5-year follow-up.</p> <p>Results</p> <p>Immigrant men and women from Turkey and Pakistan had an increased incidence of CVD, compared with native Danish men. In the case of AMI, a similar pattern was observed; however, differences were more pronounced. Pakistanis and Turks with a shorter duration of residence had a lower incidence, compared with those of a longer residence. Generally, no notable differences were observed between former Yugoslavians and native Danes. In men, differences in CVD and AMI were reduced after adjustment for SES, in particular, among Turks regarding CVD. In women, effects were particularly reduced among Yugoslavians in the case of CVD and in Turks in the case of CVD and AMI after adjustment for SES.</p> <p>Conclusions</p> <p>In conclusion, country of birth-related differences in the incidence of CVD and AMI were observed. At least some of the differences that we uncovered were results of a socioeconomic effect. Duration of residence also played a certain role. Future studies should collect and test different indicators of SES in studies of CVD among immigrants.</p

Tandem application of C-C bond-forming reactions with reductive ozonolysis

Several variants of reductive ozonolysis, defined here as the in situ generation of aldehydes or ketones during ozonolytic cleavage of alkenes, are demonstrated to work effectively in tandem with a number of C-C bond-forming reactions. For reactions involving basic nucleophiles (1,2- addition of Grignard reagents, Wittig or Horner-Emmons olefinations, and directed Aldol reactions of lithium enolates) the one-pot process offers a rapid and high-yielding alternative to traditional two-step protocols

Cascade oxime formation, cyclization to a nitrone, and intermolecular dipolar cycloaddition.

Simple haloaldehydes, including enolisable aldehydes, were found to be suitable for the formation of cyclic products by cascade (domino) condensation, cyclisation, dipolar cycloaddition chemistry. This multi-component reaction approach to heterocyclic compounds was explored by using hydroxylamine, a selection of aldehydes, and a selection of activated dipolarophiles. Initial condensation gives intermediate oximes that undergo cyclisation with displacement of halide to give intermediate nitrones; these nitrones undergo in situ intermolecular dipolar cycloaddition reactions to give isoxazolidines. The cycloadducts from using dimethyl fumarate were treated with zinc/acetic acid to give lactam products and this provides an easy way to prepare pyrrolizinones, indolizinones, and pyrrolo[2,1-a]isoquinolinones. The chemistry is illustrated with a very short synthesis of the pyrrolizidine alkaloid macronecine and a formal synthesis of petasinecine