Agonist–PPARγ interactions: Molecular modeling study with docking approach

Docking simulation of 18 agonists with the ligand binding pocket (LBP) of PPARγ has been performed. The binding conformations and binding affinities of these agonists were obtained by use of the flexible docking protocol FlexX. Test compound calculations indicated that FlexX can reproduce the binding conformation of the crystal structure (root mean square deviation = 1.43 Å); moreover, the predicted binding affinities correlate well with the activities of these agonists. The interaction model and pharmacophore of PPARγ agonists were derived and the difference in biologic activities of these agonists can be well explained. The PPARγ agonists must have both polar head and the hydrophobic tail, which form hydrogen bonds and hydrophobic contacts with hydrophilic and hydrophobic regions of the LBP of PPARγ, respectively. In addition, a suitable linker is also necessary. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 405–410, 2003     

大型液相色谱分离过程FAD－SMT数学模型及其数值解

提出大型液相色谱分离过程ＦＡＤ－ＳＭＴ数学模型，把色谱分离连续性方程转变为对流扩散方程和常微分方程组，并提出模型的数值方法，分析了数值解的稳定条件和收敛条件以及空间和时间步长的选取。实验结果表明，ＦＡＤ－ＳＭＴ数学模型计算的液相色谱分离葡萄糖、果糖和分离甘露醇、山梨醇理论与实验流出曲线相吻合。灵敏度分析结果表明：相平衡常数比轴向扩散系数和总传质系数对色谱分离有较大的影响。     

利用差异衍生同步分析醛糖和酮糖

建立了一种可同时对醛、酮糖进行精确定性和定量分析的方法。以肌醇作为内标，用80％乙醇超声提取，利用醋酸酐和HMDS＋TMCS（1：3）进行差异衍生，在EI源下用SIM模式进行GC／MS分析。结果表明：11种标准单糖在1—4mg／L范围内线性良好；仪器检出限：醛糖在8．15—22．4μg／L之间；酮糖为2．32μg／L和3．47μg/L；高、中、低3个量的平均回收率在73．0％-95．7％，相对标准偏差在3．1％-10．0％。对枸杞游离单糖进行测定，各单糖含量分别在0．26—368．6mg／g。该方法弥补了以前单糖分析中的缺陷，对既含有醛糖又含有酮糖的样品可同时进行精确的定性定量分析。     

Solution-phase synthesis and electrochemical hydrogen storage of ultra-long single-crystal selenium submicrotubes

Ultra-long single-crystalline trigonal selenium submicrotubes were synthesized using a facile one-step solution-phase approach with the assistance of nonionic surfactant Polyoxyethylene(20)sorbitan monolaurate (Tween-20), which turned out to be significant for the formation of ultra-long Se submicrotubes. XRD, Raman, SEM, and TEM were adopted to characterize the morphology, structure and phase composition of the as-prepared Se products. It was found that the length of the obtained Se submicrotubes was over 100 microm. By variation of the experimental parameters, the t-Se spheres, nanowires, and broken microtubes can be prepared. The possible growth mechanism of the ultra-long selenium submicrotubes was explained. In addition, we have also demonstrated that the synthesized ultra-long t-Se submicrotubes using the Tween-20-assisted approach can electrochemically charge and discharge with the high capacity of 265 mAh/g (corresponding to 0.97 wt % hydrogen in SWNTs) under normal atmosphere at room temperature. Cyclic voltammetry was adopted to investigate the adsorption-oxidation behavior of ultra-long selenium submicrotubes. It was observed that the morphology of the synthesized selenium products had a remarkable influence on their capacity of electrochemical hydrogen storage. These differences in hydrogen storage capacity are likely due to the size and density of tubes as well as the microcosmic morphology of different Se samples. The as-obtained ultra-long Se submicrotubes are expected to find wide applications in hydrogen storage, high-energy batteries, and optoelectronic, biologic, and catalytic fields as well as in the studies of structure-property relationships. This simple Tween-assisted approach might be extended to the preparations of one-dimensional nanostructures of tellurium and other anisotropic materials.     

V2O5/TiO2催化剂活性组分与载体相互作用研究

制备了一系列负载型V-Ti-O催化剂, 运用现代分析测试手段如BET、TPD、NARP、XRD等进行表征. 研究发现负载于TiO_2上的V_2O_5由于相互作用而使其表面V=O物种选择外露, 载体TiO_2的晶体结构是决定它们之间相互作用的关键因素. 锐铁矿型TiO_2上获得最大V=O暴露的表面V_2O_5浓度显著低于金红石TiO_2载体上获得最大V=O暴露时的表面V_2O_5浓度. 而具有较大比表面及较强酸中心的TiO_2载体导致较强的相互作用. 即可获得较大的表面V=O暴露度.     

以万古霉素为流动相添加剂的高效液相色谱法手性分析系统的建立

以丹酰化苯甘氨酸、丹酰化苯丙氨酸、丹酰化丝氨酸、丹酯化丙氨酸为模型化合物，通过对色谱柱类型、缓冲液类型、pH和盐浓度、万古霉素用量、甲醇用量、柱温等色谱参数进行考察，建立了以万古霉素为手性流动相添加剂在普通色谱柱上进行手性分析的色谱系统，并在该系统中成功地拆分了酮洛芬对映体。     

Analysis of bufadienolides in the Chinese drug ChanSu by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry

The qualitative analysis of bufadienolides in the Chinese drug ChanSu was performed using high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS). Bufadienolides are the major bioactive constituents of ChanSu, which is used to treat heart failure and cancer in traditional Chinese medicine. The APCI-MS fragmentation behavior of bufadienolides was studied. For bufadienolides with only hydroxyl substituents, the fragmentation was characterized by successive eliminations of H(2)O and CO molecules, and the profile of MS/MS product ions was correlated with the number of hydroxyl groups. If a C-16 acetoxyl group was present, the fragmentation of [M+H](+) ions was triggered by initial loss of 60 Da (HOAc). The elimination of CO was significant for bufadienolides with a 19-formyl group, and the 19-hydroxyl group could be characterized by the loss of 30 Da (HCHO). These fragmentation rules were applied to the identification of bufadienolides in a methanolic extract of ChanSu, which was separated on a C(18) column with gradient elution. A total of 35 bufadienolides were identified, including four new constituents. The method established here facilitated the convenient and rapid quality control of ChanSu crude drug and its pharmaceutical preparations.     

Determination and Differentiation of Two Seemingly Identical Medicinal Herbs by Capillary Electrophoresis with Electrochemical Detection

A high-performance capillary electrophoresis with electrochemical detection (CE-ED) method has been employed for the determination of six bioactive ingredients in traditional Chinese herbs, Herba cepbalanoplosis segeti and Herba cirsii japonici. The effects of several factors such as the acidity and concentration of running buffer, the separation voltage, the applied potential and the injection time on CE-ED were investigated. Under the optimum conditions, the six analytes could be well separated within 21 min in a 75 cm length capillary at the separation voltage of 15 kV in a 50 mmol L^–1 borax running buffer (pH 8.4). A 300 m diameter carbon disk electrode was used as the working electrode positioned carefully opposite the outlet of the capillary in a wall-jet configuration at potential of +950 mV (vs. SCE). Good linear relationship was established between peak current and concentration of analytes over two orders of magnitude with detection limits (S/N=3) ranged from 1.5×10^–7 to 6.0×10^–7 g mL^–1 for all six analytes. This proposed method has been successfully applied for the analysis of traditional Chinese herbs after a relatively simple extraction procedure, further on, for the differentiation of these above two seemingly identical herbs based on their electropherograms or characteristic electrochemical profiles.     

Structural Study on NMR and X-Ray of Lactucopicrin—A Guaianolide Ester

The guaianolide ester is a potent inhibitor of cancer cells. Lactucopicrin, a guaianolide, shows analgesic, antitussic, and sedative activities. In order to investigate its structure, ¹H and ¹³C NMR and 2D NMR have been carried out at a proton field strength of 400 MHz and a carbon field strength of 100 Mhz in DMSO-d ₆ at 20°C. Resonances for all protons and carbons have been assigned. The results of HMQC and HMBC experiments suggest that the structure of lactucopicrin is as shown in Fig. 1. Its stereostructure is verified by the X-ray experiment. ¹H and ¹³C NMR of lactucopicrin are reported. Its 2D NMR and X-ray are reported for the first time.     

Synthesis and characterization of second-order nonlinear optical polyurethane with high thermal stability

A second-order nonlinear optical polyurethane was formed with an X-type multi-dimensional charge-transfer (CT) chromophore (DNPIPDHPI) and 3,3^′-dimethoxy-4,4^′-diphenyl diisocyanate. Simultaneous poling and polymerization and in situ second harmonic generation (SHG) measurement technique was carried on to evaluate the thermal stability of the poling induced orientation. The SHG signal of the poled polymer film was not decay below 150 °C and remains 90% of relative d₃₃ value at 200 °C, which is better than the results reported in literature. Comparison of thermal stability indicates that the X-type chromophores possess better property in controlling the decay of the SHG activity than classic chromophores.