Highly fluorinated naphthalenes and bifurcated C–H⋯F–C hydrogen bonding

The synthesis and crystal structures of 1,2,4,5,6,8-hexafluoronaphthalene and 1,2,4,6,8-pentafluoronaphthalene are reported. Intermolecular interactions are dominated by offset stacking and by C–H⋯F–C hydrogen bonds. For hexafluoronaphthalene, molecules are linked in layers with (4,4) network topology via R12(6) C–H⋯(F–C)2 supramolecular synthons that are rationalised by consideration of the calculated electrostatic potential of the molecule. Such an arrangement is prevented by the additional hydrogen atom in pentafluoronaphthalene and molecules instead form tapes via an R12(8) (C–H⋯F)2 synthon. The geometric characteristics of C–H⋯(F–C)2 bifurcated hydrogen bonds have been analysed for crystal structures in the Cambridge Structural Database (6416 crystal structures; 9534 C–H⋯(F–C)2 bifurcated hydrogen bonds). A geometric analysis of these hydrogen bonds has enabled the extent of asymmetry of these hydrogen bonds to be assessed and indicates a preference for symmetrically bifurcated interactions

Singlet diradicals: from transition states to crystalline compounds

Scheschkewitz D, Amii H, Gornitzka H, Schoeller W, Bourissou D, Bertrand G. Singlet diradicals: from transition states to crystalline compounds. SCIENCE. 2002;295(5561):1880-1881.Singlet diradicals are usually not energy minima. As observed by femtosecond spectroscopy, they readily couple to form sigma bonds. Substituent effects allow lifetimes to increase into the microsecond range. Taking advantage of the properties of hetero-elements, a diradical has been prepared that is indefinitely stable at room temperature. The availability of diradicals that can be handled under standard laboratory conditions wilt lead to further insight into their chemical and physical properties, raising the likelihood of practical applications, especially in the field of molecular materials such as electrical conductors and ferromagnets

alpha-bond stretching: A static approach for dynamic process

Scheschkewitz D, Amii H, Gornitzka H, Schoeller W, Bourissou D, Bertrand G. alpha-bond stretching: A static approach for dynamic process. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 2004;43(5):585-587

Newborn screening for hepatorenal tyrosinemia-I by tandem mass spectrometry using pooled samples: a four-year summary by the New England newborn screening program

OBJECTIVE: The objective of this study is to develop an isotope dilution liquid chromatography tandem mass spectrometry assay to screen for hepatorenal tyrosinemia (HT) from newborn filter paper samples using pooled extracts to increase high throughput screening. DESIGN AND METHODS: Succinylacetone (SUAC), the marker for HT, was extracted from dried blood spots with the formation of the hydrazone derivative of SUAC; up to eight sample extracts were pooled and the SUAC-derivative was analyzed by mass spectrometry methods with an injection-to-injection time of one minute. If any pooled sample extract screened positive, then the samples comprising the pooled sample were assayed individually. RESULTS: Two newborn infants were identified with high levels of SUAC (7 and 23muM) and later confirmed to have HT. Three older children whose initial filter paper samples were taken at 195days to 614days of age with elevated SUAC (range 4.9-5muM) were identified; one of the three had clinical signs of HT and was placed on treatment (diagnosis of the other two are unavailable). CONCLUSION: MS/MS analysis of pooled dried blood sample extracts permits sensitive, reduced instrumental analytical time and increase high throughput screening for HT. Elsevier Inc. All rights reserved

Synthesis of aryl-substituted quinolines and tetrahydroquinolines through Suzuki–Miyaura coupling reactions

Okten, Salih/0000-0001-9656-1803WOS: 000484663600009The synthesis and characterization of substituted (trifluoromethoxy, thiomethyl, and methoxy) phenyl quinolines is described. Dichlorobis(triphenylphosphine)palladiunn(II)-catalyzed Suzuki-Miyaura cross-coupling of 6-bromo- and 6,8-dibronno-1,2,3,4-tetrahydroquinolines, 5-bromo-8-methoxyquinoline, and 5,7-dibromo-8-methoxyquinoline with substituted phenylboronic acids affords the corresponding 6-aryl- (13a-d), 6,8-diaryl- (14a-c), 5-aryl- (15), and 5,7-diaryl- (16b, c) tetrahydroquinolines and quinolines in high yields (68%-82%). The structures of all the products are characterized by H-1 NMR, C-13 NMR, F-1(9) NMR, and Fourier transform infrared spectroscopy and by elemental analysis.Scientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [112T394]The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This study was supported by grants from the Scientific and Technological Research Council of Turkey (TUBITAK; project number: 112T394)

Study protocol for the Integra Initiative to assess the benefits and costs of integrating sexual and reproductive health and HIV services in Kenya and Swaziland.

BACKGROUND: In sub-Saharan Africa (SSA) there are strong arguments for the provision of integrated sexual and reproductive health (SRH) and HIV services. Most HIV transmissions are sexually transmitted or associated with pregnancy, childbirth, and breastfeeding. Many of the behaviours that prevent HIV transmission also prevent sexually transmitted infections and unintended pregnancies. There is potential for integration to increase the coverage of HIV services, as individuals who use SRH services can benefit from HIV services and vice-versa, as well as increase cost-savings. However, there is a dearth of empirical evidence on effective models for integrating HIV/SRH services. The need for robust evidence led a consortium of three organizations - International Planned Parenthood Federation, Population Council and the London School of Hygiene & Tropical Medicine - to design/implement the Integra Initiative. Integra seeks to generate rigorous evidence on the feasibility, effectiveness, cost and impact of different models for delivering integrated HIV/SRH services in high and medium HIV prevalence settings in SSA. METHODS/DESIGN: A quasi-experimental study will be conducted in government clinics in Kenya and Swaziland - assigned into intervention/comparison groups. Two models of service delivery are investigated: integrating HIV care/treatment into 1) family planning and 2) postnatal care. A full economic-costing will be used to assess the costs of different components of service provision, and the determinants of variations in unit costs across facilities/service models. Health facility assessments will be conducted at four time-periods to track changes in quality of care and utilization over time. A two-year cohort study of family planning/postnatal clients will assess the effect of integration on individual outcomes, including use of SRH services, HIV status (known/unknown) and pregnancy (planned/unintended). Household surveys within some of the study facilities' catchment areas will be conducted to profile users/non-users of integrated services and demand/receipt of integrated services, before-and-after the intervention. Qualitative research will be conducted to complement the quantitative component at different time points. Integra takes an embedded 'programme science' approach to maximize the uptake of findings into policy/practice. DISCUSSION: Integra addresses existing evidence gaps in the integration evaluation literature, building on the limited evidence from SSA and the expertise of its research partners. TRIAL REGISTRATION: Current Controlled Trials NCT01694862

Framing volcanic risk communication within disaster risk reduction: finding ways for the social and physical sciences to work together

Sixteen years have passed since the last global volcanic event and more than 25 since a volcanic catastrophe that killed tens of thousands. In this time, volcanology has seen major advances in understanding, modelling and predicting volcanic hazards and, recently, an interest in techniques for reducing and mitigating volcanic risk. This paper provides a synthesis of literature relating to this last aspect, specifically the communication of volcanic risk, with a view to highlighting areas of future research into encouraging risk-reducing behaviour. Evidence suggests that the current ‘multidisciplinary’ approach within physical science needs a broader scope to include sociological knowledge and techniques. Key areas where this approach might be applied are: (1) the understanding of the incentives that make governments and communities act to reduce volcanic risk; (2) improving the communication of volcanic uncertainties in volcanic emergency management and long-term planning and development. To be successful, volcanic risk reduction programmes will need to be placed within the context of other other risk-related phenomena (e.g. other natural hazards, climate change) and aim to develop an all-risks reduction culture. We suggest that the greatest potential for achieving these two aims comes from deliberative inclusive processes and geographic information systems