A cobalt(III)-salen complex with an axial substituent in the diamine backbone: stereoselective recognition of amino alcohols

A cobalt(III)-salen complex (3) with an axial substituent on the diamine backbone has been synthesized. Crystal structure reveals that the axial substituent (p-nitrophenyl group) is positioned in close proximity to the metal binding site. The stereoselectivity of the cobalt complex for binding amino alcohols increases with increasing steric bulk of the amino alcohol from alaninol (2.9) to valinol (6.2) and t-leucinol (36.0).     

Determination of Dextromethorphan and its Metabolite Dextrorphan in Human Hair by Gas Chromatography–Mass Spectrometry

An analytical method has been developed for determination of dextromethorphan (DMP) and dextrorphan (DRP) in human hair by gas chromatography–mass spectrometry (GC–MS). Hair samples (30 mg) were washed with distilled water and acetone and cut into small fragments (<1 mm) before extraction with methanol. The extracts were evaporated to dryness and then derivatized by use of BSTFA containing 1% TMCS, for preparation of the trimethylsilyl (TMS) derivative of DRP. The extract (1 μL) was then injected into the GC–MS. Recoveries of DMP and DRP at 7.0 and 22.5 ng mg^?1 were in the range 90.6–97.2% with intra-assay and inter-assay precision of less than 5.7% and 4.7%, respectively. LOD and LOQ were, respectively, 0.67 and 2.13 ng mg^?1 for DMP and 0.14 and 0.47 ng mg^?1 for DRP. The responses were linear with correlation coefficients (r > 0.9995) for the drugs studied. The applicability of the method was proven by analysis of authentic hair samples.     

Application of diaza-18-crown-6-capped beta-cyclodextrin bonded silica particles as chiral stationary phases for ultrahigh pressure capillary liquid chromatography

Two bonded chiral stationary phases (CSPs), 8-aminoquinoline-2-ylmethyl- and 8-aminoquinoline-7-ylmethyl-diaza-18-crown-6-capped [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl silica particles (non-porous, 1.5 microm), have been prepared and evaluated using capillary liquid chromatography at high pressures (> or = 8000 p.s.i.). High column efficiency (up to 400 000 plates m(-1)) was achieved for chiral separations. These CSPs with two recognition sites, i.e. substituted-diaza-18-crown-6 and beta-cyclodextrin combined with high chromatographic efficiency provide good resolution of a variety of enantiomers and positional isomers in relatively short times under reversed-phase conditions. After inclusion of a Ni (II) ion from the mobile phase, the positively charged crown ether-capped beta-cyclodextrin facilitates specific static, dipolar, and host-guest complexation interactions with solutes.     

Some asymptotic results useful in enumeration problems

Suppose one is given two related generating functionsa(x) = a _n x ⁿ andb(x) = b _n x ⁿ , often it is of interest to determine the limiting behaviour of the quantitiesa _n /b _n We survey some earlier results of this nature and give some new ones     

Sequence- and site-specific photodissociation at 266 nm of protonated synthetic polypeptides containing a tryptophanyl residue

Photodissociation at 266 nm of protonated synthetic polypeptides containing a tryptophanyl residue was investigated using a homebuilt tandem time-of-flight mass spectrometer equipped with a matrix-assisted laser desorption/ionization source. Efficient photodissociation of the protonated peptides was demonstrated. Most of the intense peaks in the laser-induced tandem mass spectra were sequence ions. Furthermore, sequence ions due to cleavages at all the peptide bonds were observed; this is a feature of the technique that is particularly useful for peptide sequencing. Fragmentations at both ends of the tryptophanyl residue were especially prevalent, which can be useful for location of the tryptophanyl chromophore in a peptide.     

Ultraviolet radiation, vitamin D and risk of prostate cancer and other diseases

Most common diseases appear to result from complex, poorly understood interactions between genetic and environmental factors. Relatively few factors have been unequivocally linked with disease risk or outcome. Evidence from various studies using different experimental approaches has been interpreted as showing that, apart from its harmful effects on the pathogenesis of the common skin cancers, ultraviolet radiation (UVR) may exert a beneficial effect on development of various internal cancers and other pathologies. This concept is supported by parallel studies showing that hypovitaminosis D is linked with increased risk of various diseases including insulin resistance and multiple sclerosis. These findings suggest that, first, host factors such as skin pigmentation that affect UVR-induced synthesis of vitamin D and, second, polymorphism in genes that mediate the effectiveness of vitamin D action are susceptibility candidates for a variety of diseases. Collectively, these data suggest the hypothesis that, via effects on vitamin D synthesis, UVR exposure has beneficial effects on susceptibility and outcome to a variety of complex diseases. We describe evidence from studies in various diseases, but mainly from prostate cancer patients, that supports this hypothesis, but we emphasize that, although supportive data are available, the concept is unproven. Indeed, other explanations are possible. However, given the potentially important public health implications of the hypothesis and the potential for the development of novel therapeutic modalities, we believe the concept is worthy of further investigation.     

Polymer-coated hollow-fiber microextraction of estrogens in water samples with analysis by gas chromatography-mass spectrometry

A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples.     

Removal of nickel from water and synthetic nuclear power plant coolant water by ion exchange resins

A method for the removal of nickel from waste water by adsorption process on ion exchange resin was studied. The percentage removal of nickel depends upon the contact time, pH and dose of adsorbent. Adsorption of nickel on ion exchange resins obeys Freundlich adsorption isotherm. The applicability of Lagergren kinetic model has also been investigated. In order to understand the adsorption behavior of nickel, a number of batch experiments were conducted at various pH values. The results show that the adsorption is maximum in the pH range 2 to 8. The studies showed that the ion exchange resins IRN77 and SKN1 can be used as an efficient adsorbent material for the removal of Ni(II) from water and coolant water.