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991.
The distribution of urocanic acid (UCA) isomers between aqueous solutions and n-octanol, egg yolk phosphatidylcholine (eggPC) liposomes or bovine serum albumin (BSA) has been evaluated. Regarding its partitioning between water and n-octanol, the behaviour of both isomers is very similar, and the amount incorporated to the organic solvent is mostly determined by the fraction of the compound that, in the aqueous phase, is present as uncharged species. This implies that the highest hydrophobicity occurs near the isoelectric point. cis- and trans-UCA are readily incorporated into eggPC unilamellar liposomes. A simple pseudophase treatment of ultrafiltration data renders a binding constant of 0.20+/-0.04mL/mg for the trans isomer at pH 7.4. The binding constant decreases, by a factor two, at pH 5.0, suggesting that the negatively charged species is more favourably bound to the liposomes than the neutral species, which is mostly present as zwitterions. The cis-isomer, at both pHs, is less incorporated to the bilayers. trans-UCA and cis-UCA readily bind to BSA at pH 7.4, with binding constants of 3400M(-1) and 6900M(-1), respectively. This result suggests that, as in the octanol/water partitioning, hydrophobic interactions predominate and the degree of binding is determined by the fraction present as uncharged species. A smaller binding constant at pH 5.0 indicates that the charge of the protein is also plying a relevant role.  相似文献   
992.
Let μ be a finite positive Borel measure with compact support consisting of an interval plus a set of isolated points in , such that μ>0 almost everywhere on [c,d]. Let , be a sequence of polynomials, , with real coefficients whose zeros lie outside the smallest interval containing the support of μ. We prove ratio and relative asymptotics of sequences of orthogonal polynomials with respect to varying measures of the form dμ/w2n. In particular, we obtain an analogue for varying measures of Denisov's extension of Rakhmanov's theorem on ratio asymptotics. These results on varying measures are applied to obtain ratio asymptotics for orthogonal polynomials with respect to fixed measures on the unit circle and for multi-orthogonal polynomials in which the measures involved are of the type described above.  相似文献   
993.
The hydrolysis of β-propiolactone and β-butyrolactone in binary water + dioxane mixtures was investigated by kinetic studies. The following conclusions were reached: First, β-propiolactone is more reactive than β-butyrolactone across the range of water + dioxane compositions. This observation was rationalized in terms of the electric charge flow caused by the β-butyrolactone’s methyl substituent. Second, hydrolysis of these lactones is essentially enthalpy controlled. Third, an increase in the dioxane percentage, which relaxes the intermolecular hydrogen bonds in the ordered structure of water, reduces the enthalpy of activation ΔH # and simultaneously increases the entropy of activation ΔS #(absolute value) for solvent compositions up to 60% dioxane. Fourth, plotting ΔH #S # against the solvent composition yields an N-shaped curve. This results is a consequence of the quadratic and cubic terms appearing in the expressions of ΔH # and ΔS # as functions of the solvent media composition. Fifth, an ABC classification was set up to characterize the behavior of ΔH #S # for the solvolysis of these lactones.  相似文献   
994.
Factors governing hydration, regioselectivity and conformational choice in hydrated carbohydrates have been examined by determining and reviewing the structures of a systematically varied set of singly and multiply hydrated monosaccharide complexes in the gas phase. This has been achieved through a combination of experiments, including infrared ion-depletion spectroscopy conducted in a supersonic jet expansion, and computation through molecular mechanics, density functional theory (DFT) and ab initio calculations. New spectroscopic and/or computational results obtained for the singly hydrated complexes of phenyl beta-D-mannopyranoside (beta-D-PhMan), methyl alpha-D-gluco- and alpha-D-galactopyranoside (alpha-D-MeGlc and alpha-D-MeGal), when coupled with those reported earlier for the singly hydrated complexes of alpha-D-PhMan, beta-D-PhGlc and beta-D-PhGal, have created a comprehensive data set, which reveals a systematic pattern of conformational preference and binding site selectivity, driven by the provision of optimal, co-operative hydrogen-bonded networks in the hydrated sugars. Their control of conformational choice and structure has been further revealed through spectroscopic and/or computational investigations of a series of multiply hydrated complexes; they include beta-D-PhMan.(H2O)2,3, which has an exocyclic hydroxymethyl group, and the doubly hydrated complex of phenyl alpha-L-fucopyranoside, alpha-L-PhFuc.(H2O)2, which does not. Despite the very large number of potential structures and binding sites, the choice is highly selective with binding invariably "focussed" around the hydroxymethyl group (when present). In beta-D-PhMan.(H2O)2,3, the bound water molecules are located exclusively on its polar face and their orientation is dictated by the (perturbed) conformation of the carbohydrate to which they are attached. The possible operation of similar rules governing the structures of hydrogen-bonded protein-carbohydrate complexes is proposed.  相似文献   
995.
996.
New members of the RuSr2(RE2?x, Cex)Cu2O10 family of magnetically ordered phases have been synthesized under high pressure / high temperature conditions for RE = Y (x = 0.5, 0.7) and Dy (x = 0.5). All compounds show tetragonal symmetry with cell parameters a ≈ 3.82 Å and c ≈ 28.4 Å. Magnetic susceptibility vs temperature measurements show ferromagnetic behaviour of these compounds with TM = 120–140 K, depending on Ce content. These compounds are semiconducting and tend to transform into insulator, by increasing Ce content, as observed by the temperature dependence of the resistance.  相似文献   
997.
Stereospecifity of the neuroleptic activity and chirality of (+)-3-{2-[4-(8-fluoro-2-methyl-10, 11-dihydrodibenzo[b,f]thiepin-10-yl)-1-piperazinyl]ethyl}-2-oxazolidinone (16). The synthesis and stereospecific neuroleptic action in animals of the (+)-enantiomer of 3-{2-[4-(8-fluoro-2-methyl-10,11-dihydrodibenzo [b,f]thiepin-10-yl)-1-piperazinyl]ethyl}-2-oxazolidinone ( 16 ) are briefly described. The (10S)-configuration of this compound was determined by X-ray diffraction.  相似文献   
998.
999.
Abstract

Several parameters governing the extraction of metals from iron oxide rich sediments, using sequential extraction schemes were optimized. The mode of shaking, soil/extractant ratio and concentrations of MgCl2 and NH2OH·HCl, for samples collected in the Odiel Marshes Natural Park (SW Spain), were considered. The concentration of NH2OH·HCl deserved particular attention due to the nature of the studied sediments. A 0.4 M concentration of this extractant was needed to avoid readsorption of Cu and As in the samples. In addition, readsorption processes were studied using a candidate to reference material with a high organic matter content that was previously analyzed in an interlaboratory study.  相似文献   
1000.
To study the composition of sodium cholate solutions, an investigation was carried out at 25 degrees C and in N(CH3)4Cl, as a constant ionic medium, at three different concentrations (W = 0.100; 0.500 and 0.800 mol dm(-3)). Electromotive force measurements of three different galvanic cells, the first involving a glass electrode for hydrogen ions, the second an electrode for sodium ions and the third a lead amalgam electrode, were performed. Independently, lead (II) cholate solubility measurements in the presence of sodium ions were performed, as well. The experimental results obtained from both approaches were explained by assuming the formation of aggregates in cholate and sodium of different composition depending on W and on the cholate concentration. The maximum aggregation found number for cholate was 24 and even aggregation numbers were markedly predominant. Only two species with odd aggregation number were found, but at a low percentage. The assumed species and the relative constants were compared with those found for the other sodium salt of cholanic acids.  相似文献   
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