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61.
Basheer C Jayaraman A Kee MK Valiyaveettil S Lee HK 《Journal of chromatography. A》2005,1100(2):137-143
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. 相似文献
62.
Sinenxan A, a taxoid isolated from callus tissue cultures of Taxus yunnanensis was converted into 13-oxo-7,9-dideoxy-2-debenzoyl-2-acetyl-baccatin IV and 7,9-dideoxy-2-debenzoyl-4-deacetyl-baccatin IV, a key framework of 1,7,9-trideoxypaclitaxel. Several special steps in this transformation are worthy of note: (1) deoxygenation by treatment with hypophosphorous acid at C-14 position; (2) a highly regioselective O-deacetylation of taxanes at C-5 position; and (3) stereoselective reduction of the 13-carbonyl group by transannular assistance from the C-4-hydroxyl. 相似文献
63.
Sesquiterpene Lactone Glycosides from Carpesium macrocephalum 总被引:1,自引:0,他引:1
Two new sesquiterpene lactone glycosides were isolated from the seeds of Carpesium meacrocephalum. Their structures were elucidated as 2α-O-β-D-glucopyranosy-5α,11αH-eudesma-4(15)-en-12,8β-olide and 2α-O-β-D-glucopyranosy-5αH-eudesma-4(15),11(13)-dien-12,8β-olide by spectral methods (HRMS,1D and 2D NMR). 相似文献
64.
Jie Chen Rong Ji Dai Bin Tong Sheng Yuan Xiao Wei Wei Meng 《中国化学快报》2007,18(1):10-12
The reduction of 4-nitrophenol catalyzed by nitroreductase in the presence of NADH was investigated in this paper.4-Amino- phenol and 4-bydroxylamino-phenol were found in the reductive products.The relationship between reaction time and the reductive ratio were studied.The similar reducing ratios of 4-nitrophenol were obtained under aerobic and anaerobic conditions.The results indicated that an oxygen-insensitive reaction was proceeded in the reduction of 4-nitrophenol and nitroreductase was an oxygen- insensitive enzyme.The reductive products of 4-nitrophenol were determined by HPLC and MS. 相似文献
65.
Yoshikatsu Ito Meng Ji-Ben Shin Suzuki Yoshitaka Kusunaga Teruo Matsuura Keiichi Fukuyama 《Tetrahedron letters》1985,26(17):2093-2096
In contrast to simple imidazoles, 1-methy1–2,4,5-triphenylimidazole () produced stable oxetane photoadducts - with good efficiency upon irradiation in the presence of benzophenone derivatives - in acetonitrile solution. Irradiation in the solid-phase was also studied. The oxetanes - readily underwent cycloreversion by acid catalysis or by heating. 相似文献
66.
A capillary electrophoresis (CE) method was developed for the separation of heparin oligosaccharides compatible to study the interactions between the oligosaccharides and granulocyte-colony stimulating factor (G-CSF). Unfractionated heparin was eliminitively degraded to heparin oligosaccharides by an endolytic heparinase. The degraded smaller oligosaccharides (M(r) < 1000) were baseline-separated by CE under a 50 mM phosphate buffer (pH 9.0) in 10 min. Standard heparin disaccharides and larger oligosaccharides (1000 < M(r) < 8000) were all separated under optimized separation conditions. Compared with standard heparin disaccharides, smaller oligosaccharides contained one nonsulfated, two monosulfated, and two disulfated disaccharides, but trisulfated disaccharides were not found. The smaller oligosaccharides were also identified and molecular mass was deduced by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, interactions between G-CSF and the oligosaccharides were studied by using capillary zone electrophoresis (CZE) under the above separation conditions. It was found that larger oligosaccharides could interact with G-CSF while smaller oligosaccharides were not observed to bind to G-CSF under the experimental conditions. In conclusion, the purified heparinase could selectively degrade heparin into oligosaccharides and the interaction between G-CSF and heparin was correlated with the chain length of heparin. 相似文献
67.
Three ion-pair complexes, [RbzPy](+)[Ni(mnt)(2)](-) (mnt(2)(-) = maleonitriledithiolate; [RbzPy](+) = 4-R-benzylpyridinium; R = Br (1), Cl (2), and NO(2) (3)), with unusual magnetic properties have been synthesized and characterized. The crystal structures of 1 and 2 have been solved. The two complexes belong to the P2(1)/c space group with Z = 4 and C(20)H(11)BrN(5)NiS(4), a = 12.0744(17) A, b = 26.369(4) A, c = 7.440(3) A, and beta = 102.63(3) degrees for 1 and C(20)H(11)ClN(5)NiS(4), a = 12.105(2) A, b = 26.218(4) A, c = 7.374(2) A, and beta = 102.55(2) degrees for 2, respectively. The [Ni(mnt)(2)](-) anions in 1-3 form uniformly spaced one-dimensional (1-D) magnetic chains of s = 1/2 at room temperature. The temperature dependences of the susceptibility for 1-3 show that they undergo phase transitions. All three complexes are paramagnetic in their high-temperature (abbreviation HT) phase and diamagnetic in the low-temperature (abbreviation LT) phase because of strong dimerization along the stacking direction. The results of thermal analysis (DSC) further confirm that the phase transition for 1 and 2 is first-order but maybe second-order for 3. The phenomena observed in this study are similar to those of the 1-D radical systems. 相似文献
68.
69.
We have developed a coarse-grained multiscale molecular simulation method for soft matter systems that directly incorporates stereochemical information. We divide the material into disjoint groups of atoms or particles that move as separate rigid bodies; we call these groups "rigid blobs," hence the name coarse-grained rigid blob model. The method is enabled by the construction of transferable interblob potentials that approximate the net intermolecular interactions, as obtained from ab initio electronic structure calculations, other all-atom empirical potentials, experimental data, or any combination of the above. We utilize a multipolar expansion to obtain the interblob potential-energy functions. The series, which contains controllable approximations that allow us to estimate the errors, approaches the original intermolecular potential as the number of terms increases. Using a novel numerical algorithm, we can calculate the interblob potentials very efficiently in terms of a few interaction moment tensors. This reduces the labor well beyond what is required in standard molecular-dynamics calculations and allows large-scale simulations for temporal scales commensurate with characteristic times of nano- and mesoscale systems. A detailed derivation of the formulas is presented, followed by illustrative applications to several systems showing that the method can effectively capture realistic microscopic details and can easily extend to large-scale simulations. 相似文献
70.
GuoXiangCHENG GuangLingPEI LingGangZENG LiYongZHANG ChaoLIU 《中国化学快报》2004,15(2):242-245
In this paper, the surface imprinted cross-linked polystyrene beads were prepared via suspension polymerization with styrene (St), divinylbezene (DVB), polyvinyl alcohol (PVA1788),the mixture of Span 85 and xylene or the mixture of Span 85 and paraffin as monomer,cross-linking agent, dispersion stabilizer and templates, respectively. The results indicate that there are dense cavities on the surface of beads, and the diameter and density of cavity are related with the composition and amount of emulsion template. The forming mechanism of cavity from thermodynamics and dynamics was proposed. 相似文献