Multiple superoxide dismutase 1/splicing factor serine alanine 15 variants are associated with the development and progression of diabetic nephropathy:the Diabetes Control and Complications Trial/Epidemiology of Diabetes Interventions and Complications Genetics study

Despite familial clustering of nephropathy and retinopathy severity in type 1 diabetes, few gene variants have been consistently associated with these outcomes.

Triply-bridged diphos disilver helical complexes [Ag-2(mu(2)-dppa-P,P')(3)(anion)(2)] [dppa = bis(diphenylphosphino)acetylene]

Triply-bridged disilver complexes [Ag-2(mu(2)-dppa-P,P')(3)(anion)(2)] form selectively and are stabilised by many aromatic interactions.

Anion-templated formation of a unique inorganic 'super-adamantoid' cage [Ag-6(triphos)(4)(O3SCF3)(4)](2+) [triphos = (PPh2CH2)(3)CMe]

In the presence of templating anions, 2:3 molar mixtures of triphos and silver(I) cations unexpectedly give novel hexanuclear cages, which result from an unusual 'endo-methyl' geometry of the triphos ligands.

Transport properties of protic ionic liquids, pure and in aqueous solutions: Effects of the anion and cation structure

Ionic conductivities of twelve protic ionic liquids (PILs) and their mixtures with water over the whole composition range are reported at 298.15 K and atmospheric pressure. The selected PILs are the pyrrolidinium-based PILs containing nitrate, acetate or formate anions; the formate-based PILs containing diisopropylethylammonium, amilaminium, quinolinium, lutidinium or collidinium cations; and the pyrrolidinium alkylcarboxylates, [Pyrr][CnH2n+1COO] with n = 5–8. This study was performed in order to investigate the influence of molecular structures of the ions on the ionic conductivities in aqueous solutions. The ionic conductivities of the aqueous solutions are 2–30 times higher than the conductivities of pure PILs. The maximum in conductivity varies from ww=0.41???to???0.74 and is related to the nature of cations and anions. The molar conductance and the molar conductance at infinite dilution for (PIL + water) solutions are then determined. Self-diffusion coefficients of the twelve protic ionic liquids in water at infinite dilution and at 298.15 K are calculated by using the Nernst–Haskell, the original and the modified Wilke–Chang equations. These calculations show that similar values are obtained using the modified Wilke–Chang and the Nernst–Haskell equations. Finally, the effective hydrodynamic (or Stokes) radius of the PILs was determined by using the Stokes–Einstein equation. A linear relationship was established in order to predict this radius as a function of the anion alkyl chain length in the case of the pyrrolidinium alkylcarboxylates PILs.

Influence of the anion on the electrical conductivity and glass formation of 1-butyl-3-methylimidazolium ionic liquids

Six ionic liquids based on the 1-butyl-3-methylimidazolium cation have been studied. As anions Cl-, Br-, I-, [NCS](-), [N(CN)(2)](-), and [BF4](-) were selected. The electrical conductivities were determined between 173 and 393 K based on impedance measurements in the frequency range from 0.1 to 10(7) Hz. The electrical conductivity increases, whereas the glass transition temperature, the fragility, and the low temperature activation energy decrease with increasing anion size. The results can be understood from the changing anion-cation interaction strength with changing anion size and from the energy landscape interpretation of the glass transition dynamics. (C) 2010 American Institute of Physics. [doi:10.1063/1.3455892]

Characterization of SodC, a periplasmic superoxide dismutase from Burkholderia cenocepacia

Burkholderia cenocepacia is a gram-negative, non-spore-forming bacillus and a member of the Burkholderia cepacia complex. B. cenocepacia can survive intracellularly in phagocytic cells and can produce at least one superoxide dismutase (SOD). The inability of O2- to cross the cytoplasmic membrane, coupled with the periplasmic location of Cu,ZnSODs, suggests that periplasmic SODs protect bacteria from superoxide that has an exogenous origin (for example, when cells are faced with reactive oxygen intermediates generated by host cells in response to infection). In this study, we identified the sodC gene encoding a Cu,ZnSOD in B. cenocepacia and demonstrated that a sodC null mutant was not sensitive to a H2O2, 3-morpholinosydnonimine, or paraquat challenge but was killed by exogenous superoxide generated by the xanthine/xanthine oxidase method. The sodC mutant also exhibited a growth defect in liquid medium compared to the parental strain, which could be complemented in trans. The mutant was killed more rapidly than the parental strain was killed in murine macrophage-like cell line RAW 264.7, but killing was eliminated when macrophages were treated with an NADPH oxidase inhibitor. We also confirmed that SodC is periplasmic and identified the metal cofactor. B. cenocepacia SodC was resistant to inhibition by H2O2 and was unusually resistant to KCN for a Cu,ZnSOD. Together, these observations establish that B. cenocepacia produces a periplasmic Cu,ZnSOD that protects this bacterium from exogenously generated O2- and contributes to intracellular survival of this bacterium in macrophages.

In vitro resistance of Burkholderia cepacia complex isolates to reactive oxygen species in relation to catalase and superoxide dismutase production

The Burkholderia cepacia complex comprises groups of genomovars (genotypically distinct strains with very similar phenotypes) that have emerged as important opportunistic pathogens in cystic fibrosis (CF) patients. The inflammatory response against bacteria in the airways of CF individuals is dominated by polymorphonuclear cells and involves the generation of oxidative stress, which leads to further inflammation and tissue damage. Bacterial catalase, catalase-peroxidase and superoxide dismutase activities may contribute to the survival of B. cepacia following exposure to reactive oxygen metabolites generated by host cells in response to infection. In the present study the authors investigated the production of catalase, peroxidase and SOD by isolates belonging to various genomovars of the B. cepacia complex. Production of both catalase and SOD was maximal during late stationary phase in almost all isolates examined. Native PAGE identified 13 catalase electrophoretotypes and two SOD electrophoretotypes (corresponding to an Fe-SOD class) in strains belonging to the six genomovars of the B. cepacia complex. Seven out of 11 strains displaying high-level survival after H(2)O(2) treatment in vitro had a bifunctional catalase/peroxidase, and included all the genomovar III strains examined. These isolates represent most of the epidemic isolates that are often associated with the cepacia syndrome. The majority of the isolates from all the genomovars were resistant to extracellular O(-)(2), while resistance to intracellularly generated O(-)(2)was highly variable and could not be correlated with the detected levels of SOD activity. Altogether the results suggest that resistance to toxic oxygen metabolites from extracellular sources may be a factor involved in the persistence of B. cepacia in the airways of CF individuals.

Influence of the cation on the solubility of CO2 and H 2 in ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion

Experimental values for the solubility of carbon dioxide and hydrogen in three room temperature ionic liquids based on the same anion- (bistrifluoromethylsulfonyl)imide [Ntf2]-and three different cations-1-butyl-3-methylimidazolium, [C4mim], 1-ethyl-3- methylimidazolium, [C2mim] and trimethyl-butylammonium, [N 4111]-are reported between 283 and 343 K and close to atmospheric pressure. Carbon dioxide, with a mole-fraction solubility of the order of 10-2, is two orders of magnitude more soluble than hydrogen. The solubility of CO2 is very similar in the three ionic liquids although slightly lower in the presence of the [C2mim] cation. In the case of H2, noticeable differences were observed with larger mole fraction solubilities in the presence of [N4111] followed by [C 4mim]. All of the mole-fraction solubilities decrease with increasing temperature. From the variation of Henry's law constants with temperature, the thermodynamic functions of solvation were calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is always better than ±1%. © Springer Science+Business Media, LLC 2007.

Solubility of carbon dioxide and ethane in three ionic liquids based on the bis{(trifluoromethyl)sulfonyl}imide anion

The objective of this work was to study the influence of changing the cation of the ionic liquid (IL) on gas solubility. For this purpose, the low-pressure solubility of carbon dioxide and of ethane in three ILs based on the bis{(trifluoromethyl)sulfonyl}imide anion ([NTf2](-)) was determined experimentally. Solubility data is reported for 1-ethyl-3-methylimidazolium ([C(1)C(2)Im](+)), 1-butyl-1-methylpyrrolidinium ([C(1)C(4)pyrr](+)) and propylcholinium ([N1132-OH](+)) bis{(trifluoromethyl)sulfonyl}imide ILs between 300 and 345 K. These data are precise to within +/- 1% and accurate to within +/- 5%. In these ILs, carbon dioxide (mole fraction solubility between 1 and 3 x 10(-2), molarity between 0.03 and 0.1 mol L-1) is one order of magnitude more soluble than ethane. The effect of changing the cation is small but significant. Changing the cation has a similar effect on both gases even if the differences are more pronounced in the case of ethane with the order of solubility [C(1)C(4)pyrr][NTf2] > [C(1)C(2)Im][NTf2] > [N1132-OH][NTf2]. For all the systems, the solubility decreases with temperature corresponding to exothermic processes of solvation and negative enthalpies and entropies of solvation were calculated. The properties of solvation of the two gases in [C(1)C(4)pyrr][NTf2] do not vary significantly with temperature while important variations are depicted for both gases in [C(1)C(2)Im][NTf2]. (c) 2007 Elsevier B.V. All rights reserved.

High-pressure volumetric properties of imidazolium-based ionic liquids: Effect of the anion

The densities of five imidazolium-based ionic liquids (ILs) (1-butyl-3-methylimidazolium tetrafluoroborate, [CiC4-Im][BF 4]; 1-butyl-3-methylimidazolium hexafluorophosphate, [CiC 4Im][PF6]; 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [C1C4Im][Tf 2N]; 1-ethyl-3-methylimidazoliumbis{(trifluoromethyl)sulfonyl}-imide, [C1C2Im][Tf2N]; l-ethyl-3-methylimidazolium ethylsulfate, [C1C2Im][EtSO4]) were measured as a function of temperature from (293 to 415) K and over an extended pressure range from (0.1 to 40) MPa using a vibratingtube densimeter. Knowledge of the variation of the density with temperature and pressure allows access to the mechanical coefficients: thermal expansion coefficient and isothermal compressibility. The effects of the anion and of the length of the alkyl chain on the imidazolium ring on the volumetric properties were particularly examined. The mechanical coefficients were compared with those of common organic solvents, water and liquid NaCl. Finally, a prediction model, based on an "ideal" volumetric behavior of the ILs, is proposed to allow calculation of the molar volume of imidazolium-based ionic liquids as a function of temperature. ©2007 American Chemical Society.

Thermophysical properties, low pressure solubilities and thermodynamics of solvation of carbon dioxide and hydrogen in two ionic liquids based on the alkylsulfate anion

Densities and viscosities of the ionic liquid 1-butyl-3-methylimidazolium octylsulfate, [C4C1Im][C8SO4] were measured as a function of temperature between 313 K and 395 K. Solubilities of hydrogen and carbon dioxide were determined, between 283 K and 343 K, and at pressures close to atmospheric in [C4C1Im][C 8SO4] and in another ionic liquid based on the alkylsulfate anion-1-ethyl-3-methylimidazolium ethylsulfate, [C 2C1Im][C2SO4]. Density and viscosity were measured using a vibrating tube densimeter from Anton Paar and a rheometer from Rheometrics Scientific with accuracies of 10-3 g cm -3 and 1%, respectively. Solubilities were obtained using an isochoric saturation technique and, from the variation of solubility with temperature, the partial molar thermodynamic functions of solvation, such as the standard Gibbs energy, the enthalpy, and the entropy, are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is better than ±1%. © The Royal Society of Chemistry.

The Use of Electrospray Mass Spectrometry to Determine Speciation in a Dynamic Combinatorial Library for Anion Recognition

The composition of a dynamic mixture of similar 2,2'-bipyridine complexes of iron(II) bearing either an amide (5-benzylamido-2,2'-bipyridine and 5-(2-methoxyethane)amido-2,2'-bipyridine) or an ester (2,2'-bipyridine-5-carboxylic acid benzylester and 2,2'-bipyridine-5-carboxylic acid 2-methoxyethane ester) side chain have been evaluated by electrospray mass spectroscopy in acetonitrile. The time taken for the complexes to come to equilibrium appears to be dependent on the counteranion, with chloride causing a rapid redistribution of two preformed heteroleptic complexes (of the order of 1 hour), whereas the time it takes in the presence of tetrafluoroborate salts is in excess of 24^^h. Similarly the final distribution of products is dependent on the anion present, with the presence of chloride, and to a lesser extent bromide, preferring three amide-functionalized ligands, and a slight preference for an appended benzyl over a methoxyethyl group. Furthermore, for the first time, this study shows that the distribution of a dynamic library of metal complexes monitored by ESI-MS can adapt following the introduction of a different anion, in this case tetrabutylammonium chloride to give the most favoured heteroleptic complex despite the increasing ionic strength of the solution.