The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C(2)mim][NTf2]; the latter behaves as a 'melt' rather than an 'organic solvent'

The electrochemical oxidation of 1-butyl-3-methylimidazolium nitrate [C(4)mim][NO3] was studied by cyclic voltammetry in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C(2)mim][NTf2]. A sharp peak was observed on a Pt microelectrode (d = 10 mu m), and a diffusion coefficient at infinite dilution of ca. 2.0 x 10(-11) m(2) s(-1) was obtained. Next, the cyclic voltammetry of sodium nitrate (NaNO3) and potassium nitrate (KNO3) was studied, by dissolving small amounts of solid into the RTIL [ C2mim][ NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 8.8 and 9.0 x 10(-12) m(2) s(-1) and solubilities of 11.9 and 10.8 mM for NaNO3 and KNO3, respectively. The smaller diffusion coefficients for NaNO3 and KNO3 (compared to [C(4)mim][NO3]) may indicate that NO3- is ion-paired with Na+ or K+. This work may have applications in the electroanalytical determination of nitrate in RTIL solutions. Furthermore, a reduction feature was observed for both NaNO3 and KNO3, with additional anodic peaks indicating the formation of oxides, peroxides, superoxides and nitrites. This behaviour is surprisingly similar to that obtained from melts of NaNO3 and KNO3 at high temperatures ( ca. 350 - 500 degrees C), and this observation could significantly simplify experimental conditions required to investigate these compounds. We then used X-ray photoelectron spectroscopy (XPS) to suggest that disodium( I) oxide (Na2O), which has found use as a storage compound for hydrogen, was deposited on a Pt electrode surface following the reduction of NaNO3.

Extended electrochemical windows made accessible by room temperature ionic liquid/organic solvent electrolyte systems

The electrochemical windows of acetonitrile solutions doped with 0.1 m concentrations of several ionic liquids were examined by cyclic voltammetry at gold and platinum microelectrodes. These results were compared with those observed in the commonly used 0.1 m tetrabutylammonium perchlorate/acetonitrile system as well as with neat ionic liquids. The use of a trifluorotris(pentofluoroethyl)phosphate-based ionic liquid, specifically, as supporting electrolyte in acetonitrile solutions affords a wider anodic window, which is attributed to the high stability of the anionic component of these intrinsically conductive and thermally robust compounds.

Properties of Super-Hydrophobic Copper and Stainless Steel Meshes: Applications in Controllable Water Permeation and Organic Solvents/Water Separation

The wettability and hydrophobicity of super-hydrophobic (SH) meshes is greatly influenced by their topographic structures, chemical composition and coating process. In this study, the properties of copper and stainless steel meshes, coated with super-hydrophobic electrolessly deposited silver were investigated. A new method to test the pressure resistance of super-hydrophobic mesh was applied to avoid any deformation of mesh. Results showed that SH copper mesh and SH stainless steel meshes with the same pore size have almost the same contact angle and the same hydrophobicity. SH copper mesh with a pore size of 122 μm can resist water pressure of 4900 Pa and a decrease of pore size of mesh can increase the pressure resistance of SH copper mesh. The SH copper mesh modified with 0.1 M HS(CH2)10COOH solution in ethanol has a controllable water permeation property by simply adjusting the pH of water solution. SH copper mesh shows super-oleophilicity with organic solvents and so with a water contact angle of 0° and it can be an effective tool for organic solvents/water separation. The separation efficiency of SH copper mesh for separating mixtures of organic solvent and water can be as high as 99.8%.

Identification of the region of non-A beta component (NAC) of alzheimer's disease amyloid responsible for its aggregation and toxicity

The non-beta-amyloid (Aß) component of Alzheimer's disease amyloid (NAC) and its precursor a-synuclein have been linked to amyloidogenesis in several neurodegenerative diseases. NAC and a-synuclein both form ß-sheet structures upon ageing, aggregate to form fibrils, and are neurotoxic. We recently established that a peptide comprising residues 3±18 of NAC retains these properties. To pinpoint the exact region responsible we have carried out assays of toxicity and physicochemical properties on smaller fragments of NAC. Toxicity was measured by the ability of fresh and aged peptides to inhibit the reduction of the redox dye 3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide (MTT) by rat pheochromocytoma PC12 cells and human neuroblastoma SHSY-5Y cells. On immediate dissolution, or after ageing, the fragments NAC(8±18) and NAC(8±16) are toxic, whereas NAC(12±18), NAC(9±16) and NAC(8±15) are not. Circular dichroism indicates that none of the peptides displays ß-sheet structure; rather all remain random coil throughout 24 h. However, in acetonitrile, an organic solvent known to induce ß sheet, fragments NAC(8±18) and NAC(8±16) both form ß-sheet structure. Only NAC(8±18) aggregates, as indicated by concentration of peptide remaining in solution after 3 days, and forms fibrils, as determined by electron microscopy. These findings indicate that residues 8±16 of NAC, equivalent to residues 68±76 in a-synuclein, comprise the region crucial for toxicity.

Comparison of mass transfer effects in the heterogeneously catalysed hydrogenation of phenyl acetylene in heptane and an ionic liquid

The selective heterogeneous catalytic reduction of phenyl acetylene to styrene over palladium supported on calcium carbonate is reported in both an ionic liquid and a molecular solvent. By using a rotating disc reactor in conjunction with results from a stirred tank reactor it is possible, for the first time, to disentangle the mass transfer contributions in the ionic liquid system. For both heptane and 1-butyl-3-methyl imidazolium bis{(trifluoromethyl)sulfonyl}imide, the reaction in the rotating disc reactor is dominated by reaction in the entrained film on the disc compared with very limited reaction in the bulk liquid. The lower reaction rate obtained in the ionic liquid compared with the organic solvent is shown to be due to the slow transport of the hydrogen dissolved in the liquid. It is clear from the results presented herein that, although the hydrodynamics of similar reactors used for biological treatment of wastewater are well understood, on using a more viscous fluid and higher rotation speeds necessary for fine chemical catalysis these simple relationships breakdown.

Identical extraction behavior and coordination of trivalent or hexavalent f-element cations using ionic liquid and molecular solvents

The extraction of both UO22+ and trivalent lanthanide and actinide ions (Am3+, Nd3+, Eu3+) by dialkylphosphoric or dialkylphosphinic acids from aqueous solutions into the ionic liquid, 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide has been studied and compared to extractions into dodecane. Radiotracer partitioning measurements show comparable patterns of distribution ratios for both the ionic liquid/aqueous and dodecane/aqueous systems, and the limiting slopes at low acidity indicate the partitioning of neutral complexes in both solvent systems. The metal ion coordination environment, elucidated from EXAFS and UV-visible spectroscopy measurements, is equivalent in the ionic liquid and dodecane solutions with coordination of the uranyl cation by two hydrogen-bonded extractant dimers, and of the trivalent cations by three extractant dimers. This is the first definitive report of a system where both the biphasic extraction equilibria and metal coordination environment are the same in an ionic liquid and a molecular organic solvent.

Lewis acid platinum complexes of conformationally flexible NUPHOS diphosphines: Highly efficient catalysts for the carbonyl-ene reaction

Enantiopure Lewis acid complexes of conformationally flexible acyclic and monocyclic NUPHOS diphosphines, delta- and lambda-[(NUPHOS)Pt(OTf)(2)], are efficient catalysts for the carbonyl-ene reaction between various unsymmetrical 1,1'-disubstituted alkenes and phenylglyoxal or ethyl glyoxylate. While catalyst performance was substrate dependent, ee values as high as 95% and yields up to 90% have been obtained. In a number of cases catalysts generated from delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] showed marked enhancements in enantioselectivity in ionic liquids compared with organic media. Although an enhancement in enantioselectivity was not obtained for all substrate combinations in such cases, the enantioselectivities were comparable to those obtained in dichloromethane. Furthermore, although the ee's are initially comparable in both the ionic liquid and dichloromethane, a gradual erosion of ee with time was found in the organic solvent, whereas the ee remained constant in the ionic liquid. Preliminary kinetic investigations suggest that the decrease in ee may be due to a faster racemization of the catalyst in dichloromethane compared with the ionic liquid.

Elucidation of the electrochemical oxidation pathway of ammonia in dimethylformamide and the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The direct electrochemical oxidation of ammonia has been examined in both the organic solvent dimethylformamide (DMF) and the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][N(Tf)(2)]. The corresponding voltammetric responses have been shown to be similar in each solvent with a broad oxidative wave occurring upon the introduction of ammonia to the solution and the appearance of a new reductive wave following the oxidation. The oxidative reaction process has been examined and a suitable reaction pathway has been deduced, corresponding to the formation of ammonium cations after oxidation of the ammonia. A linear response of limiting current against vol% ammonia was observed in both DMF and [EMIM][N(Tf)(2)], suggesting potential application for analytical methods.

Chemical etching of optical fibre tips - experiment and model

The formation of chemically etched fibre tips for use in optical scanning probe microscopy is addressed. For tips formed at a cleaved fibre end in the bulk of a buffered HF acid solution the morphological features (tip height, cone angle) are found to depend strongly on the temperature and etchant composition. The tip formation process is analysed and explained in terms of a simple model in which the only pertinent physical parameters are the fibre core diameter and etch rates of the fibre core and cladding. The etch rates are determined in separate experiments as a function of temperature (in the range 24-50 degreesC) for etchant solutions of de ionised water: 50% HF acid: 40% NH4F in the volume ratio 1 : 1 : X for X=2, 4 and 6, and used in the model to yield a correct description of the experimental tip cone angles. The model is successfully extended to the intriguing case of negative tip formation which initiates in a normal, positive tip structure. By contrast, tip formation in the meniscus region of a bare fibre/etchant/organic solvent system is found to be independent of etchant composition and temperature. (C) 2000 Elsevier Science B.V. All rights reserved.

A short synthesis of (+) and (−)-falcarinol

A short, practical synthesis of the bis-acetylenic natural product falcarinol 1 is reported. This method relies on the alternate functionalisation of bis-trimethylsilylbutadiyne 10. This may be achieved in one-pot, however, better yields were obtained more conventionally. Lipase mediated enzymatic kinetic resolution of the racemic adduct in an organic solvent afforded (+)-1 in 97% enantiomeric excess. The analogous process performed with racemic 3-acetoxy falcarinol 11 under aqueous conditions gave (-)-1. Oxidation of 1 with Dess–Martin periodinane gave falcarinone 2.

Physicochemical and drug diffusion analysis of rifampicin containing polyethylene glycol-poly(epsilon-caprolactone) networks designed for medical device applications

This study reports the physicochemical and drug diffusion properties of rifampicin containing poly(epsilon-caprolactone) (PCL)/polyethylene glycol (PEG) networks, designed as bioactive biomaterials. Uniquely, the effects of the states of both rifampicin and PEG and the interplay between these components on these properties are described. PCL matrices containing rifampicin (1-5%, w/w) and PEG 200 (0-15%, w/w) were prepared by casting from an organic solvent (dichloromethane). The films were subsequently characterized in terms of their thermal/thermorheological, surface and tensile properties, biodegradation and drug diffusion/release properties. Incorporation of PEG and/or rifampicin significantly affected the tensile and surface properties of PCL, lowering the ultimate tensile strength, % elongation at break, Young modulus and storage and loss moduli. Both in the absence and presence of PEG, solubilisation of rifampicin within the crystalline domains of PCL was observed. PEG was present as a dispersed liquid phase. The release of rifampicin (3% loading) was unaffected by the presence of PEG. Similarly the release of rifampicin (5%) was unaffected by low concentrations of PEG (5-10%) however, at higher loadings, the release rate of rifampicin was enhanced by the presence of PEG. Rifampicin release (10% loading) was enhanced by the presence of PEG in a concentration dependent fashion. These observations were accredited to enhanced porosity of the matrix. In all cases, diffusion-controlled release of rifampicin occurred which was unaffected by polymer degradation. This study has uniquely illustrated the effect of hydrophilic pore formers on the physicochemical properties of PCL. Interestingly, enhanced diffusion controlled release was only observed from biomaterials containing high loadings of PEG and rifampicin (5, 10%), concentrations that were shown to affect the mechanical properties of the biomaterials. Care should therefore be shown when adopting this strategy to enhance release of bioactive agents from biomaterials. (C) 2011 Elsevier B.V. All rights reserved.

Role of AcrR and ramA in fluoroquinolone resistance in clinical Klebsiella pneumoniae isolates from Singapore

The MICs of ciprofloxacin for 33 clinical isolates of K. pneumoniae resistant to extended-spectrum cephalosporins from three hospitals in Singapore ranged from 0.25 to >128 microg/ml. Nineteen of the isolates were fluoroquinolone resistant according to the NCCLS guidelines. Strains for which the ciprofloxacin MIC was >or=0.5 microg/ml harbored a mutation in DNA gyrase A (Ser83-->Tyr, Leu, or IIe), and some had a secondary Asp87-->Asn mutation. Isolates for which the MIC was 16 microg/ml possessed an additional alteration in ParC (Ser80-->IIe, Trp, or Arg). Tolerance of the organic solvent cyclohexane was observed in 10 of the 19 fluoroquinolone-resistant strains; 3 of these were also pentane tolerant. Five of the 10 organic solvent-tolerant isolates overexpressed AcrA and also showed deletions within the acrR gene. Complementation of the mutated acrR gene with the wild-type gene decreased AcrA levels and produced a two- to fourfold reduction in the fluoroquinolone MICs. None of the organic solvent-tolerant clinical isolates overexpressed another efflux-related gene, acrE. While marA and soxS were not overexpressed, another marA homologue, ramA, was overexpressed in 3 of 10 organic solvent-tolerant isolates. These findings indicate that multiple target and nontarget gene changes contribute to fluoroquinolone resistance in K. pneumoniae. Besides AcrR mutations, ramA overexpression (but not marA or soxS overexpression) was related to increased AcrAB efflux pump expression in this collection of isolates.

Degradation of 4-fluorobiphenyl in soil investigated by 19F NMR spectroscopy and 14C radiolabelling analysis

The incubation of the model pollutant [U-14C]'-4-fluorobiphenyl (4FBP) in soil, in the presence and absence of biphenyl (a co-substrate), was carried out in order to study the qualitative disposition and fate of the compound using 14C-HPLC and 19F NMR spectroscopy. Components accounted for using the radiolabel were volatilization, CO2 evolution, organic solvent extractable and bound residue. Quantitative analysis of these data gave a complete mass balance. After sample preparation. 14C-HPLC was used to establish the number of 4FBP related components present in the organic solvent extract. 19F NMR was also used to quantify the organic extracts and to identify the components of the extract. Both approaches showed that the composition of the solvent extractable fractions comprised only parent compound with no metabolites present. As the 14C radiolabel was found to be incorporated into the soil organic matter this indicates that metabolites were being generated, but were highly transitory as incorporation into the SOM was rapid. The inclusion of the co-substrate biphenyl was to increase the overall rate of degradation of 4FBP in soil. The kinetics of disappearance of parent from the soil using the data obtained were investigated from both techniques. This is the first report describing the degradation of a fluorinated biphenyl in soil.

Optimised extraction of heterocyclic aromatic amines from blood using hollow fibre membrane liquid-phase microextraction and triple quadrupole mass spectrometry

Heterocyclic aromatic amines (HCA) are carcinogenic mutagens formed during cooking of proteinaceous foods, particularly meat. To assist in the ongoing search for biomarkers of HCA exposure in blood, a method is described for the extraction from human plasma of the most abundant HCAs: 2-Amino-1-methyl-6-phenylimidazo(4,5-b)pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) (and its isomer 7,8-DiMeIQx), using Hollow Fibre Membrane Liquid-Phase Microextraction. This technique employs 2.5 cm lengths of porous polypropylene fibres impregnated with organic solvent to facilitate simultaneous extraction from an alkaline aqueous sample into a low volume acidic acceptor phase. This low cost protocol is extensively optimised for fibre length, extraction time, sample pH and volume. Detection is by UPLC-MS/MS using positive mode electrospray ionisation with a 3.4 min runtime, with optimum peak shape, sensitivity and baseline separation being achieved at pH 9.5. To our knowledge this is the first description of HCA chromatography under alkaline conditions. Application of fixed ion ratio tolerances for confirmation of analyte identity is discussed. Assay precision is between 4.5 and 8.8% while lower limits of detection between 2 and 5 pg/mL are below the concentrations postulated for acid-labile HCA-protein adducts in blood.