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931.
932.
喜树碱类抗肿瘤药物作用模式的柔性分子对接研究 总被引:3,自引:0,他引:3
研究采用柔性分子对接技术,将15个喜树碱类化合物对接到拓扑异构酶I (Topo I)-DNA切割复合物中,从原子水平和分子力场角度阐明了喜树碱类抗肿瘤药 物与DNA,Topo I的相互作用机制。研究发现,喜树碱分子插入Topp I-DNA复合物 的切割位点,并与Asn722,Asp533,Lys532和Lys720形成氢键作用网络。定量构效 关系研究进一步表明喜树碱分子可以与Topo I-DNA切割复合物形成电荷迁移作用。 该对接模型系统解释了喜树碱类化合物的构效关系、定点突变等诸多实验事实,为 下一步设计、合成新型高效的喜树碱类衍生物打下了坚实基础。 相似文献
933.
Makoto Karakawa Yuji Mikawa Hiroshi Kamitakahara Fumiaki Nakatsubo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(23):4167-4179
Seven possible regioselectively methylated cellulose acetates (RS‐MCAs)—2,3,6‐tri‐O‐methyl cellulose acetate, 3,6‐di‐O‐methyl cellulose acetate, 2,6‐di‐O‐methyl cellulose acetate, 2,3‐di‐O‐methyl cellulose acetate, 6‐O‐methyl cellulose acetate, 3‐O‐methyl cellulose acetate, and 2‐O‐methyl cellulose acetate—were prepared for the first time from chemically synthesized cellulose derivatives obtained by cationic ring‐opening polymerization and then were analyzed by 1H and 13C NMR spectroscopy. The chemical shifts of ring protons and carbons were influenced by substituent groups (methyl or acetyl) and clearly reflected the pattern of substituent distribution in anhydroglucose units. These data may conveniently be used for the determination of the substituent distribution of methyl cellulose. The synthesized RS‐MCAs also may be used for the elucidation of the structure–property relationship. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4167–4179, 2002 相似文献
934.
Elenise Bannwart de Moraes Patricia Fazzio Martins César Benedito Batistella Mario Eusebio Torres Alvarez Rubens Maciel Filho Maria Regina Wolf Maciel 《Applied biochemistry and biotechnology》2006,132(1-3):1066-1076
Molecular distillation was studied for the separation of tocopherols from soya sludge, both experimentally and by simulation,
under different operating conditions, with good agreement. Evaporator temperatures varied from 100°C to 160°C and feed flow
rates ranged from 0.1 to 0.8 kg/h. The process pressure was maintained at 10−6 bar, the feed temperature at 50°C, the condenser temperature at 60°C, and the stirring at 350 rpm. For each process condition,
samples of both streams (distillate and residue) were collected and stored at −18°C before tocopherols analyses. Owing to
the differences between molecular weights and vapor pressures of free fatty acids and tocopherols, tocopherols preferentially
remained in the residue at evaporator temperatures of 100°C and 120°C, whereas for higher temperatures (140°C and 160°C) and
lower feed flow rate, tocopherols tended to migrate to the distillate stream. 相似文献
935.
Y. Sun T.J.A. Ewing A.G. Skillman I.D. Kuntz 《Journal of computer-aided molecular design》1998,12(6):597-604
We have developed a strategy for efficiently docking a large combinatorial library into a target receptor. For each scaffold orientation, all potential fragments are attached to the scaffold, their interactions with the receptor are individually scored and factorial combinations of fragments are constructed. To test its effectiveness, this approach is compared to two simple control algorithms. Our method is more efficient than the controls at selecting best scoring molecules and at selecting fragments for the construction of an exhaustive combinatorial library. We also carried out a retrospective analysis of the experimental results of a 10×10×10 exhaustive combinatorial library. An enrichment factor of approximately 4 was found for identifying the compounds in the library that are active at 330 nM. 相似文献
936.
Three-dimensional quantum mechanical calculations for vibrational predissociation of HeI2(B) van der Waals molecules are presented using the time-dependent wave packet technique within the golden rule approxima tion.The total and partial decay widths,lifetimes,rates and their dependence on initial vibrational states were obtained for HeI2 at low initial vibrational excited levels.Our calculations show that the calculated tota decay widths,lifetimes and rates agree well with those extrapolated from experimental data available The predicted total decay widths as a function of initial vibrational states exhibit highly nonlinear behavior.The very short propagation time (less.than 1 ps) required in the golden rule wave packet calculation is determined by the duration time of the final state inter-action between the fragments on the vibrationally deexcited adiabatic potential surface.The final state interaction between the fragments is shown to play an important role in determining the final rotational distri 相似文献
937.
Ivan Bernal D. C. Levendis Richard Fuchs G. M. Reisner Juanita M. Cassidy 《Structural chemistry》1997,8(4):275-285
The crystal structure of 4-cyclopropylacetanilide was investigated at room temperature (21C) and at –100C in order to determine the orientation of the phenyl ring with respect to the cyclopropane moiety and the effect of this substituent on the stereochemistry of the three-membered ring. The compound was chosen because it is one of the few species containing a simple phenyl ring as the sole cyclopropane ring substituent and whose crystals are suitable for X-ray diffraction at room temperature. The substance crystallizes in space groupP2l/c at either temperature (no phase transitions) with cell constants: (at 21C)a=9.725(2),b=10.934(3), andc=9.636(2) å,=106.13(1);V=984.21 å3 andd(calc;z=4)=1.182 g cm–3. The relevant parameters for the –100C structure area=9.557(4),b=10.980(2), andc=9.641(2) å,=106.34(3);V=970.76 å3 and d(calc;z=4)=1.199 g cm–3. Final values wereR(F)=0.042, Rw=0.035, using unit weights, and its nonhydrogen atoms were used to phase the low-temperature data, whose final discrepancy indices wereR(F)=0.051,R
w
=0.061. The phenyl substituent is almost exactly in the bisecting conformation with respect to the C-C-C angle at the point of attachment to cyclopropane and conjugative effects are clearly evident in the lengths of the cyclopropane ring [1.494(3), 1.498(3), and 1.474(4) å, the later being the distal bond]. If one omits the terminal methylene fragments at C10 and C11, the atoms comprising the acetanilide fragment and the substituted carbon of the cyclopropane ring lie in a nearly perfect plane. Molecular mechanics as well as semiempirical (AM1) calculations were carried out in order to determine the structure of the energy-minimized configurations in the two computational environments. The molecular conformations thus obtained are close to that experimentally observed from the X-ray diffraction experiment. In both theoretical models, the lowest energy conformation is that in which the plane of the phenyl ring bisects the cyclopropane C-C-C angle as was experimentally observed. Finally, the shape of the conformational barrier as a function of the orientation of the plane of the phenyl ring was computed, giving a maximum barrier to rotation of 2.2 kcal/mol. Similar calculations were carried out for two other aryl cyclopropanes, whose rings (naphthalene and anthracene) cannot adopt the bisecting position. Comparisons of experimental geometrical parameters as well as of the barriers to rotation are presented.on leave at the University of Houston, 1995–1996. 相似文献
938.
以脉冲激光在高真空中溅射钒粉和硫粉的混合物,产生了一系列钒硫原子簇正负离子。根据对其实验记录的激光等离子体质谱进行分析,发现钒硫原子簇的化学键基本上是共价型的,对应于相同钒原子数目的正负离子的相对丰度分别符合于不同形式的对数正态分布。正离子的相对丰度随硫原子数的增加呈对数衰减,由此可以确定各种大小簇合物的簇骼与几何构型;负离子的相对丰度则基本上呈正常的正态分布,说明在簇骼上结合了不同数量硫原子的负离子之结构稳定性大致相近。在实验中还观察到一类硫原子含量较高的簇离子,其中的部分硫原子可能在本身成键形成环状的硫集团后,又与原来的簇骼结合,因而在硫原子数较多时它们的相对丰度符合另一条对数正态分布曲线。 相似文献
939.
The metal ion distribution on the two metal sites of monoclinic Mn1?xCux(HCOO)2 · 2(H,D)2O mixed crystals are studied by infrared and Raman spectroscopic methods. The spectral regions 3 200–3 400 cm?1 (vOH), 2 875–2 990 cm?1 (vCH), 2 330–2 500 cm?1 (vOD of matrix isolated HDO molecules), 1 350–1 400 cm?1 (symmetric CO2 stretching modes), 570–950 cm?1 (H2O librations), and 490 cm?1 (M? O lattice modes) are mostly sensitive to the metal ions present. The frequency shifts of these bands with increasing content of copper show that Cu2+ prefers the M(1) site, coordinated by HCOO? only. The strengths of the hydrogen bonds increase on going from manganese to copper formate, due to the increased synergetic effect of Cu2+. Solubility and X-ray data of the mixed crystals are included. Irrespective of the same crystal structure, two series of mixed crystals are formed: eutonic area at 0.65 ≥ x ≥ 0.5. 相似文献
940.
Gutiérrez-Dabán A Fernández-Espinosa AJ Ternero-Rodríguez M Fernández-Alvarez F 《Analytical and bioanalytical chemistry》2005,381(3):721-736
The size distribution of polycyclic aromatic hydrocarbons (PAH) was determined for airborne particles from a large city with high vehicular traffic. The analytical method was optimised and validated using NIST standard reference material (SRM 1649a Urban Dust). The 16 priority PAH listed in the US-EPA were Soxhlet-extracted from filtered particulate matter and then fractionated using on-column chromatography. The aromatic fraction was quantified by gas chromatography-mass spectrometry. Real samples of particles collected in Seville (Spain) were analysed using the validated method. Values for the total concentration of PAH in the air, as well as the concentrations of each PAH in six particle-size ranges were obtained. Values of the PAH in TSP, PM10, PM2.5 and PM1 were assessed. 相似文献