(1/318) A community outbreak of Campylobacter jejuni infection from a chlorinated public water supply.
An outbreak of Campylobacter jejuni infection occurred in a South Wales Valleys housing estate. Illness in estate residents was associated with tap water consumption [population attributable risk (PAR) 50%, relative risk (RR) 2.53, 95% confidence interval (CI) 1.9-3.37] and residence in the upper estate (PAR 49%, RR 2.44, 95% CI 1.83-3.24). Amongst upper estate residents, rates of diarrhoeal illness increased with rates of water consumption (OR 18, 95% CI 3.5-92.4 for heaviest consumers, chi2 trend P<0.0001). The upper estate received mains water via a covered holding reservoir. A crack in the wall of the holding reservoir was identified. Contamination with surface water from nearby pasture land was the likely cause of this outbreak. Service reservoirs are common in rural communities and need regular maintenance and inspection. The role of water in sporadic cases of campylobacter enteritis may be underestimated. (+info)
(2/318) Thermodynamic calculations for molecules with asymmetric internal rotors. II. Application to the 1,2-dihaloethanes.
The thermodynamic properties of three halocarbon molecules relevant in atmospheric and public health applications are presented from ab initio calculations. Our technique makes use of a reaction path-like Hamiltonian to couple all the vibrational modes to a large-amplitude torsion for 1,2-difluoroethane, 1,2-dichloroethane, and 1,2-dibromoethane, each of which possesses a heavy asymmetric rotor. Optimized ab initio energies and Hessians were calculated at the CCSD(T) and MP2 levels of theory, respectively. In addition, to investigate the contribution of electronically excited states to thermodynamic properties, several excited singlet and triplet states for each of the halocarbons were computed at the CASSCF/MRCI level. Using the resulting potentials and projected frequencies, the couplings of all the vibrational modes to the large-amplitude torsion are calculated using the new STAR-P 2.4.0 software platform that automatically parallelizes our codes with distributed memory via a familiar MATLAB interface. Utilizing the efficient parallelization scheme of STAR-P, we obtain thermodynamic properties for each of the halocarbons, with temperatures ranging from 298.15 to 1000 K. We propose that the free energies, entropies, and heat capacities obtained from our methods be used to supplement theoretical and experimental values found in current thermodynamic tables. (+info)
(3/318) What's new in enzymatic halogenations.
The halogenation of thousands of natural products occurs during biosynthesis and often confers important functional properties. While haloperoxidases had been the default paradigm for enzymatic incorporation of halogens, via X+ equivalents into organic scaffolds, a combination of microbial genome sequencing, enzymatic studies and structural biology have provided deep new insights into enzymatic transfer of halide equivalents in three oxidation states. These are (1) the halide ions (X-) abundant in nature, (2) halogen atoms (X*), and (3) the X+ equivalents. The mechanism of halogen incorporation is tailored to the electronic demands of specific substrates and involves enzymes with distinct redox coenzyme requirements. (+info)
(4/318) CD and MCD of CytC3 and taurine dioxygenase: role of the facial triad in alpha-KG-dependent oxygenases.
The alpha-ketoglutarate (alpha-KG)-dependent oxygenases are a large and diverse class of mononuclear non-heme iron enzymes that require FeII, alpha-KG, and dioxygen for catalysis with the alpha-KG cosubstrate supplying the additional reducing equivalents for oxygen activation. While these systems exhibit a diverse array of reactivities (i.e., hydroxylation, desaturation, ring closure, etc.), they all share a common structural motif at the FeII active site, termed the 2-His-1-carboxylate facial triad. Recently, a new subclass of alpha-KG-dependent oxygenases has been identified that exhibits novel reactivity, the oxidative halogenation of unactivated carbon centers. These enzymes are also structurally unique in that they do not contain the standard facial triad, as a Cl- ligand is coordinated in place of the carboxylate. An FeII methodology involving CD, MCD, and VTVH MCD spectroscopies was applied to CytC3 to elucidate the active-site structural effects of this perturbation of the coordination sphere. A significant decrease in the affinity of FeII for apo-CytC3 was observed, supporting the necessity of the facial triad for iron coordination to form the resting site. In addition, interesting differences observed in the FeII/alpha-KG complex relative to the cognate complex in other alpha-KG-dependent oxygenases indicate the presence of a distorted 6C site with a weak water ligand. Combined with parallel studies of taurine dioxygenase and past studies of clavaminate synthase, these results define a role of the carboxylate ligand of the facial triad in stabilizing water coordination via a H-bonding interaction between the noncoordinating oxygen of the carboxylate and the coordinated water. These studies provide initial insight into the active-site features that favor chlorination by CytC3 over the hydroxylation reactions occurring in related enzymes. (+info)
(5/318) An aromatic iodination method, with iodic acid used as the only iodinating reagent.
Benzene, halobenzenes, and a number of more or less deactivated arenes,including nitrobenzene, readily reacted in anhydrous HIO3/AcOH/Ac2O/conc. H2SO4 mixtures to probably give ArIO2 intermediates or other hypervalent species (not isolated). The final reaction mixtures were poured into excess aq. Na2SO3 solution (a reductant) to give the purified iodinated products in 39-83% yields. (+info)
(6/318) A comparison of microwave-accelerated and conventionally heated iodination reactions of some arenes and heteroarenes, using ortho-periodic acid as the oxidant.
A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method. (+info)
(7/318) Chemical Manganese Dioxide (CMD): its application to the oxidative iodination of benzene, halobenzenes and some deactivated arenes.
After comparing our previous and newer results for numerous oxidative aromatic iodination experiments using various brands of active MnO2 as the oxidants,we recommend the use of a Chemical Manganese Dioxide (Aldrich CMD; 90 +% MnO2) as the oxidant of choice, since it is satisfactorily pure and chemically active, and is notably less costly than other options. (+info)
(8/318) Microwave-accelerated or conventionally heated iodination reactions of some aromatic amines, using ortho-periodic acid as the oxidant.
A fast and simple method for the oxidative iodination of some aromatic amines, either under microwave irradiation or conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in boiling CH2Cl2 solutions under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were usually less influenced as compared with the conventional method. (+info)