A stereocontrolled method for the synthesis of D- and L-2-deoxy-C-nucleosides using an intramolecular Sakurai-type cyclisation reaction

A novel synthetic procedure has been developed that provides access to D/L-2-deoxy-C-nucleosides from 3,4-epoxytetrahydrofuran in seven steps and in moderate to good yields. The key chemical transformation was the Lewis acid catalysed intramolecular cyclisation reaction of an acetal for which the stereochemical outcome was dependent of the reagents' ratio.

Gendered Spaces and Intimate Citizenship: The Case of Breastfeeding

This article situates breastfeeding politics in the context of intimate citizenship, where women’s capability to care in a range of social spaces is at stake. Drawing on the work of Lefebvre and Fenster, the article considers the extent to which recent breastfeeding promotion work by the Health Promotion Agency in Northern Ireland has sought to reconceive of social spaces in ways that have the potential to improve intimate citizenship for breastfeeding women.

The electrochemical oxidation of hydrogen at activated platinum electrodes in room temperature ionic liquids as solvents

The oxidation of hydrogen was studied at an activated platinum micro-electrode by cyclic voltammetry in the following ionic liquids: [C(2)mim][NTf2], [C(4)mim][NTf2], [N-6.2.2.2][NTf2], [P-14.6.6.6][NTf2], [C(4)mim][OTf], [C(4)mim][BF4] [C(4)mim][PF6], [C(4)mim][NO3], [C(6)mim]Cl and [C(6)mim][FAP] (where [C(n)mim](+) = 1-alkyl-3-methylimidazolium, [N-6,N-2,N-2,N-2](+) = n-hexyltriethylammonium, [P-14,P-6,P-6,P-6](+) = tris(n-hexyltetradecyl) phosphonium, [NTf2](-) = bis(trifluoromethylsulfonyl)amide, [OTf] = trifluoromethlysulfonate and [FAP](-) = tris(perfluoroethyl)trifluorophosphate). Activation of the Pt electrode was necessary to obtain reliable and reproducible voltammetry. After activation of the electrode, the H-2 oxidation waves were nearly electrochemically and chemically reversible in [C(n)mim][NTf2] ionic liquids, chemically irreversible in [C(6)mim]Cl and [C(4)mim][NO3], and showed intermediate characteristics in OTf-, [BF4](-), [PF6](-), [FAP](-) and other [NTf2](-)-based ionic liquids. These differences reflect the contrasting interactions of protons with the respective RTIL anions. The oxidation peaks are reported relative to the half-wave potential of the cobaltocenium/cobaltocene redox couple in all ionic liquids studied, giving an indication of the relative proton interactions of each ionic liquid. A preliminary temperature study (ca. 298-333 K) has also been carried out in some of the ionic liquids. Diffusion coefficients and solubilities of hydrogen at 298 K were obtained from potential-step chronoamperometry, and there was no relationship found between the diffusion coefficients and solvent viscosity. RTILs possessing [NTf2](-) and [FAP](-) anions showed the highest micro-electrode peak currents for the oxidation in H-2 saturated solutions, with[C(4)mim][NTf2] toeing the most sensitive. The large number of available RTIL anion/cation pairs allows scope for the possible electrochemical detection of hydrogen gas for use in gas sensor technology. (c) 2008 Elsevier B.V. All rights reserved.

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

2-Phosphanylethylcyclopentadienyl lithium compounds, Li[C5R'(4)(CH2)(2)PR2] (R = Et, R' = H or Me, R = Ph, R' = Me), have been prepared from the reaction of spirohydrocarbons C5R'(4)(C2H4) with LiPR2. C5Et4HSiMe2CH2PMe2, was prepared from reaction of Li[C5Et4] with Me2SiCl2 followed by Me2PCH2Li. The lithium salts were reacted with [RhCl(CO)2]2,[IrCl(CO)3] or [Co-2(CO)(8)] to give [M(C5R'(4)(CH2) 2PR2)(CO)] (M = Rh, R = Et, R' = H or Me, R= Ph, R' = Me; M = Ir or Co, R = Et, R' = Me), which have been fully characterised, in many cases crystallographically as monomers with coordination of the phosphorus atom and the cyclopentadienyl ring. The values of nu(CO) for these complexes are usually lower than those for the analogous complexes without the bridge between the cyclopentadienyl ring and the phosphine, the exception being [Rh(Cp'(CH2)(2)PEt2)(CO)] (Cp' = C5Me4), the most electron rich of the complexes. [Rh(C5Et4SiMe2CH2PMe2)(CO)] may be a dimer. [Co-2(CO)(8)] reacts with C5H5(CH2)(2)PEt2 or C5Et4HSiMe2CH2PMe2 (L) to give binuclear complexes of the form [Co-2(CO)(6)L-2] with almost linear PCoCoP skeletons. [Rh(Cp'(CH2)(2)PEt2)(CO)] and [Rh(Cp'(CH2)(2)PPh2)(CO)] are active for methanol carbonylation at 150 degrees C and 27 bar CO, with the rate using [Rh(Cp'(CH2)(2)PPh2)(CO)] (0.81 mol dm(-3) h(-1)) being higher than that for [RhI2(CO)(2)](-) (0.64 mol dm(-3) h(-1)). The most electron rich complex, [Rh(Cp'(CH2)(2)PEt2)(CO)] (0.38 mol dm(-3) h(-1)) gave a comparable rate to [Cp*Rh(PEt3)(CO)] (0.30 mol dm(-3) h(-1)), which was unstable towards oxidation of the phosphine. [Rh(Cp'(CH2)(2)PEt2)I-2], which is inactive for methanol carbonylation, was isolated after the methanol carbonylation reaction using [Rh(Cp'(CH2)(2)PEt2)(CO)].

Phosphoenolpyruvate phosphomutase activity in an L-phosphonoalanine-mineralizing strain of Burkholderia cepacia

A strain of Burkholderia cepacia isolated by enrichment culture utilized L-2-amino-3-phosphonopropionic acid (phosphonoalanine) at concentrations up to 20 mM as a carbon, nitrogen, and phosphorus source in a phosphate-insensitive manner. Cells contained phosphoenolpyruvate phosphomutase activity, presumed to be responsible for cleavage of the C-P bond of phosphonopyruvate, the transamination product of L-phosphonoalanine; this was inducible in the presence of phosphonoalanine.

A new approach for the detection of ethylene using silica-supported palladium complexes

The coordination of olefins to square-planar Pd(II) and Pt(II) complexes containing 2,9-dimethylphenanthroline (L1) often involves a change of color associated with a change of geometry at the metal center. In order to obtain suitable colorimetric detectors for ethylene gas, a series of new Pd(II) and Pt(II) compounds with a range of 2,9-disubstituted phenanthroline ligands [2,9-di-n-butyl-1,10-phenanthroline (L-2), 2,9-di-s-butyl-1,10-phenanthroline (L3), 2,9-diphenyl-1,10-phenanthroline (L4), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, L5)] have been prepared and their reactivity toward ethylene investigated both in solution and after depositing the detector compounds on a variety of solid supports. The Pd(II) complex [PdCl2(L2)] supported on silica undergoes a clear color change upon exposure to ethylene, while remaining stable toward air and water, and forms the basis for new simple colorimetric detectors with potential applications in ethylene pipe-leak detection and the monitoring of fruit ripening. Encouragingly, the detector is able to discriminate between fruit at different stages of ripening. The response of the detector to other volatiles was also examined, and specific color changes were also observed upon exposure to aromatic acetylenes. The crystal structures of four new derivatives, including the ethylene-Pt(II) complex [PtCl2(C2H4)(L2)], are also described.

Resonance Raman probing of the interaction between dipyridophenazine complexes of Ru(II) and DNA

Resonance Raman (RR) spectroscopy has been used to probe the interaction between dipyridophenazine (dppz) complexes of ruthenium(II), [Ru(L)(2)(dppz)](2+) (L = 1,10-phenanthroline (1) and 2,2-bipyridyl (2)), and calf-thymus DNA. Ground electronic state RR spectra at selected probe wavelengths reveal enhancement patterns which reflect perturbation of the dppz-centered electronic transitions in the UV-vis spectra in the presence of DNA. Comparison of the RR spectra recorded of the short-lived MLCT excited states of both complexes in aqueous solution with those of the longer-lived states of the complexes in the DNA environment reveals changes to excited state modes, suggesting perturbation of electronic transitions of the dppz ligand in the excited state as a result of intercalation. The most prominent feature, at 1526 cm(-1), appears in the spectra of both 1 and 2 and is a convenient marker band for intercalation. For 1, the excited state studies have been extended to the A and A enantiomers. The marker band appears at the same frequency for both but with different relative intensities. This is interpreted as reflecting the distinctive response of the enantiomers to the chiral environment of the DNA binding sites. The results, together with some analogous data for other potentially intercalating complexes, are considered in relation to the more general application of time-resolved RR spectroscopy for investigation of intercalative interactions of photoexcited metal complexes with DNA.

TRANSIENT RESONANCE RAMAN AND RAMAN SPECTROELECTROCHEMICAL STUDIES OF CUI COMPLEXES WITH POLYPYRIDYL LIGANDS

Studies by laser flash photolysis, transient Raman spectroscopy, and Raman and UV-vis spectroelectrochemistry are described in which the techniques have been used in parallel to compare the lowest energy charge-transfer excited states of Cu (1) complexes ([Cu(L)2]+ and [ (PPh3)2Cu(L)]+ [L = 2,2'-biquinoline (BIQ) or 6,7-dihydro-5,8-dimethyldibenzo[b,j] [1,10]-phenanthroline (DMCH)) with the species produced by electrochemical reduction in the same group of complexes. Transient resonance Raman spectra for the metal-to-ligand charge-transfer (MLCT) states of [Cu(DMCH)2]+ (1), [Cu(BIQ)2]+ (2), [Cu(DMCH)(PPh3)2]+ (3), and [Cu(BIQ)(PPh3)2]+ (4) are compared with the resonance Raman spectra of the same group of complexes following one-electron electrochemical reduction of the DMCH and BIQ ligands. The UV-vis and resonance Raman evidence suggests that the electrochemical reduction of the [Cu(I)L2]+ species proceeds according to the sequence [LCu(I)L]+ -->e- [LCu0L] -->e- [L.-Cu(I)L.-]-. Several features assignable to modes of the electrochemically generated DMCH.-and BIQ'- radical anions exhibit a close correspondence in both frequency and relative intensity with counterparts in the spectra of the MLCT states of 1 and 2. A notable exception is a band near 1590 cm-1 in the spectra of the electrochemically reduced species which occurs some 15 cm-1 lower in the corresponding spectra of the excited-state species. It is suggested that the shift may reflect the change in oxidation state of the metal center from Cu(I) to Cu(II) which occurs as a result of charge-transfer excitation.

Formation of nickel-thiolate aggregates via reaction with CH2Cl2

Reaction of the mononuclear nickel-thiolate complex [Ni(L-1)(dppe)] with CH2Cl2 affords the novel pentanuclear complex Ni5Cl2(L-1)(4)(dppe)(2)], while [Ni(L-1)(dcpe)] reacts with CH2Cl2 to give the binuclear species [Ni2Cl2(L-2)(dcpe)(2)] in which two L-1 units are linked by a methylene group derived from CH2Cl2.

Non-radial pulsation, rotation and outburst in the Be star omega Orionis from the MuSiCoS 1998 campaign

omega Ori (HD37490, HR1934) is a Be star known to have presented variations. In order to investigate the nature and origin of its short-term and mid-term variability, a study is performed of several spectral lines (Halpha, Hdelta, HeI 4471, 4713, 4921, 5876, 6678, CII 4267, 6578, 6583, Mg II 4481, Si III 4553 and Si II 6347), based on 249 high signal-to-noise high-resolution spectra taken with 8 telescopes over 22 consecutive nights during the MuSiCoS (Multi SIte COntinuous Spectroscopy) campaign in November-December 1998. The stellar parameters are revisited and the projected rotational velocity (v sin i = 179 km s(-1)) is redetermined using several methods. With the MuSiCoS 98 dataset, a time series analysis of line-profile variations (LPVs) is performed using the Restricted Local Cleanest (RLC) algorithm and a least squares method. The behaviour of the velocity of the centroid of the lines, the equivalent widths and the apparent vsini for several lines, as well as Violet and Red components of photospheric lines affected by emission (red He i lines, Si II 6347, CII 6578, 6583) are analyzed. The non-radial pulsation (NRP) model is examined using phase diagrams and the Fourier-Doppler Imaging (FDI) method. The LPVs are consistent with a NRP mode with l = 2 or 3, \m\ = 2 with frequency 1.03 cd(-1). It is shown that an emission line outburst occurred in the middle of the campaign. Two scenarios are proposed to explain the behaviour of a dense cloud, temporarily orbiting around the star with a frequency 0.46 c d(-1), in relation to the outburst.

Optical and infrared photometry of the Type IInSN1998S: days 11-146

We present contemporaneous optical and infrared (IR) photometric observations of the Type IIn SN 1998S covering the period between 11 and 146 d after discovery. The IR data constitute the first ever IR light curves of a Type IIn supernova. We use blackbody and spline fits to the photometry to examine the luminosity evolution. During the first 2-3 months, the luminosity is dominated by the release of shock-deposited energy in the ejecta. After similar to 100 d the luminosity is powered mostly by the deposition of radioactive decay energy from 0.15 +/-0.05 M-. of Ni-56 which was produced in the explosion. We also report the discovery of an astonishingly high IR excess, K-L'=2.5, that was present at day 130. We interpret this as being due to thermal emission from dust grains in the vicinity of the supernova. We argue that to produce such a high IR luminosity so soon after the explosion, the dust must be pre-existing and so is located in the circumstellar medium of the progenitor. The dust could be heated either by the UV/optical flash (IR echo) or by the X-rays from the interaction of the ejecta with the circumstellar material.

Asymptotic layer-type model of high pressure direct current glow discharge in electronegative gases

Here a self-consistent one-dimensional continuum model is presented for a narrow gap plane-parallel dc glow discharge. The governing equations consist of continuity and momentum equations for positive and negative ions and electrons coupled with Poisson's equation. A singular perturbation method is developed for the analysis of high pressure dc glow discharge. The kinetic processes of the ionization, electron attachment, and ion-ion recombination are included in the model. Explicit results are obtained for the asymptotic limits: delta=(r(D)/L)(2)--> 0, omega=(r(S)/L)(2)--> 0, where r(D) is the Debye radius, r(S) is recombination length, and L is the gap length. The discharge gap divides naturally into four layers with multiple space scales: anode fall region, positive column, transitional region, cathode fall region and diffusion layer adjacent to the cathode surface, its formation is discussed. The effects of the gas pressure, gap spacing and dc voltage on the electrical properties of the layers and its dimension are investigated. (C) 2000 American Institute of Physics. [S0021-8979(00)00813-6].

Asymptotic modeling of short plane-parallel high-pressure glow discharge

Here a self-consistent continuum model is presented for a narrow gap plane-parallel dc glow discharge. The set of governing equations consisting of continuity and momentum equations for positive ions, fast (emitted by the cathode) and slow electrons (generated by fast electron impact ionization) coupled with Poisson's equation is treated by the technique of matched asymptotic expansions. Explicit results are obtained in the asymptotic limit: (chi delta) much less than 1, where chi = e Phi(a)/kT, delta = (r(D)/L)(2) (Phi(a) is the applied voltage, r(D) is the Debye radius) and pL much greater than 1(Hg mm cm), where p is the gas pressure and L is the gap length. In the case of high pressure, the electron energy relaxation length is much smaller than the gap length, and so the local field approximation is valid. The discharge space divides naturally into a cathode fall sheath, a quasineutral plasma region, and an anode fall sheath. The electric potential distribution obtained for each region in a (semi)analytical form is asymptotically matched to the adjoining regions in the region of overlap. The effects of the gas pressure, gap length, and applied voltage on the length of each region are investigated. (C) 2000 American Institute of Physics. [S1070-664X(00)01302-1].

Predicting the need for insulin therapy in late onset (40-69 years) diabetes mellitus

A six-year prospective study of 144 newly diagnosed, symptomatic diabetic patients aged 40-69 years showed that 21 (15%) required insulin therapy, commencing 1-61 months after diagnosis. The plasma insulin response to oral glucose was assessed at the time of diagnosis. All 12 patients with very low peak insulin response (less than or equal to 6 mU/l) required insulin therapy. Thirty-six patients had an intermediate insulin response (greater than 6 less than or equal to 18 mU/l); of these, 7 with a mean weight 88% (range 73-96%) of average body weight required insulin, while 29 with a mean weight 117% (range 98-158%) of average body weight, did not. Ninety-six patients had a peak insulin response (greater than 18 mU/l); 2 patients whose weights were 96% and 100% of average body weight, required insulin, while the remainder did not. Consideration of initial body weight and peak insulin response provides a useful prediction of the eventual need for insulin.