Convenient and robust one-pot synthesis of symmetrical and unsymmetrical benzyl thioethers from benzyl halides using thiourea

A series of symmetrical and unsymmetrical benzyl thioethers have been synthesised using a one-pot reaction from benzyl halides and thiourea. This procedure avoids the isolation or handling of malodorous thiols and generates high yields of benzyl thioethers in excellent purity

Sulfoxides: potent co-crystal formers

The design of co-crystals requires knowledge of robust supramol. synthons. The sulfoxide is a potent H bond acceptor and was used as a co-crystal former with a range of NH functional groups, via N-H···O=S H bonds. The NH functional group retains favorable H bond motifs from its own structure in all cases where this is possible, with the sulfoxide interacting in a discrete, capping fashion in four cases and in a bifurcated, bridging fashion in the three other cases presented here. Crystallog. data are given for 7 co-formers, dibenzyl sulfoxide and cyclohexanecarbothioamide

Extreme Precipitation Appears a Key Driver of Mercury Transport from the Watershed to Cottage Grove Reservoir, Oregon

An abandoned cinnabar mining and roasting site is in the major sub-basin of the watershed for Cottage Grove Reservoir, Oregon. Average surface sediment total mercury concentration in the river draining this sub-basin (0.61±0.52 μg /g) was about ten-fold higher than three smaller tributaries to the reservoir. Total mercury in reservoir surface sediments averaged 1.66 ± 0.70 μg /g. Stratigraphy for two sediment cores indicated generally decreased reservoir mercury loading from 1963-2002 but two pronounced peaks in mercury deposition. Years of extreme precipitation immediately prior to these peaks at least partially explained them. Epaxial muscle total mercury concentrations of largemouth bass increased with body weight up to 2.5 μg /g. A gradient of mercury concentrations in soils from a 3.3 km diameter grid indicated condensation of mercury vapors from the mine site polluted the sub-basin.Keywords: Fish mercury contamination, Mercury transport, Pollutio

Unzipping the dimer in primary amides by cocrystallization with sulfoxides

A systematic crystal engineering study was undertaken to investigate how different electronic substituents on the aromatic ring of primary aromatic amides impact on the ability of the amide to cocrystallize with dibenzyl sulfoxide. Amides which cocrystallize with dibenzyl sulfoxide form 1:1 cocrystals containing a discrete N-H•••O=S supramolecular synthon as well as the well-known C(4) amide chain. The combination of these two synthons give rise to linear chains of amide molecules, with each amide molecule capped by one sulfoxide molecule. Thus, the R 2(over)2 (8) dimer typically seen for primary amides is no longer present in these cocrystals. The influence of the amide due to electronic effects is similar to that observed for acids in cocrystals

Evidence for the association of the DAOA (G72) gene with schizophrenia and bipolar disorder but not for the association of the DAO gene with schizophrenia

Background: Previous linkage and association studies have implicated the D-amino acid oxidase activator gene (DAOA)/G30 locus or neighbouring region of chromosome 13q33.2 in the genetic susceptibility to both schizophrenia and bipolar disorder. Four single nucleotide polymorphisms (SNPs) within the D-amino acid oxidase (DAO) gene located at 12q24.11 have also been found to show allelic association with schizophrenia.Methods: We used the case control method to test for genetic association with variants at these loci in a sample of 431 patients with schizophrenia, 303 patients with bipolar disorder and 442 ancestrally matched supernormal controls all selected from the UK population.Results: Ten SNPs spanning the DAOA locus were genotyped in these samples. In addition three SNPs were genotyped at the DAO locus in the schizophrenia sample. Allelic association was detected between the marker rs3918342 (M23), 3' to the DAOA gene and both schizophrenia (chi(2) = 5.824 p = 0.016) and bipolar disorder (chi(2) = 4.293 p = 0.038). A trend towards association with schizophrenia was observed for two other DAOA markers rs3916967 (M14, chi(2) = 3.675 p = 0.055) and rs1421292 (M24; chi(2) = 3.499 p = 0.062). A test of association between a three marker haplotype comprising of the SNPs rs778293 (M22), rs3918342 (M23) and rs1421292 (M24) and schizophrenia gave a global empirical significance of p = 0.015. No evidence was found to confirm the association of genetic markers at the DAO gene with schizophrenia.Conclusion: Our results provide some support for a role for DAOA in susceptibility to schizophrenia and bipolar disorder

Mixed configuration-interaction and many-body perturbation theory calculations of energies and oscillator strengths of J=1 odd states of neon

Ab-initio theory is developed for energies of J=1 particle-hole states of neutral neon and for oscillator strengths of transitions from such states to the J=0 ground state. Hole energies of low-Z neonlike ions are evaluated.Comment: 5 pages, 1 figure, 4 table

An Electrochemical Study of Frustrated Lewis Pairs: A Metal-free Route to Hydrogen Oxidation

[Image: see text] Frustrated Lewis pairs have found many applications in the heterolytic activation of H(2) and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H(2) can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H(2) oxidation by 610 mV (117.7 kJ mol(–1)). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology

The First Extrasolar Planet Discovered with a New Generation High Throughput Doppler Instrument

We report the detection of the first extrasolar planet, ET-1 (HD 102195b), using the Exoplanet Tracker (ET), a new generation Doppler instrument. The planet orbits HD 102195, a young star with solar metallicity that may be part of the local association. The planet imparts radial velocity variability to the star with a semiamplitude of $63.4\pm2.0$ m s$^{-1}$ and a period of 4.11 days. The planetary minimum mass ($m \sin i$) is $0.488\pm0.015$ $M_J$.Comment: 42 pages, 11 figures and 5 tables, Accepted for publication in Ap

Reduced cytochrome P4501A activity and recovery from oxidative stress during subchronic benzo[a]pyrene and benzo[e]pyrene treatment of rainbow trout

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Toxicology and Applied Pharmacology 254 (2011): 1-7, doi:10.1016/j.taap.2011.04.015.This study assessed the role of aryl hydrocarbon receptor (AHR) affinity, and cytochrome P4501A (CYP1A) protein and activity in polyaromatic hydrocarbon (PAH)-­‐induced oxidative stress. In the 1-­‐100 nM concentration range benzo[a]pyrene (BaP) but not benzo[e]pyrene (BeP) competitively displaced 2 nM [3H]2, 3, 7, 8-­‐tetrachloro-­‐dibenzo-­‐p-­‐dioxin from rainbow trout AHR2α. Based on appearance of fluorescent aromatic compounds in bile over 3, 7, 14, 28 or 50 days of feeding 3 μg of BaP or BeP/g fish/day, rainbow trout liver readily excreted these polyaromatic hydrocarbons (PAHs) and their metabolites at near steady state rates. CYP1A proteins catalyzed more than 98% of ethoxyresorufin-­‐O-­‐deethylase (EROD) activity in rainbow trout hepatic microsomes. EROD activity of hepatic microsomes initially increased and then decreased to control activities after 50 days of feeding both PAHs. Immunohistochemistry of liver confirmed CYP1A protein increased in fish fed both PAHs after 3 days and remained elevated for up to 28 days. Neither BaP nor BeP increased hepatic DNA adduct concentrations at any time up to 50 days of feeding these PAHs. Comet assays of blood cells demonstrated marked DNA damage after 14 days of feeding both PAHs that was not significant after 50 days. There was a strong positive correlation between hepatic EROD activity and DNA damage in blood cells over time for both PAHs. Neither CYP1A protein nor 3-­‐ nitrotyrosine (a biomarker for oxidative stress) immunostaining in trunk kidney were significantly altered by BaP or BeP after 3, 7, 14, or 28 days. There was no clear association between AHR2α affinity and BaP and BeP-­‐induced oxidative stress.The Oregon Agricultural Experiment Station, Northwest Fisheries Science Center, and RO1ES006272 from the National Institute of Health supported this work