Study of the effect of Wuzhi tablet (Schisandra sphenanthera extract) on tacrolimus tissue distribution in rat by liquid chromatography tandem mass spectrometry method

A liquid chromatography/tandem mass spectrometry (LC‐MS/MS) method was developed and validated for determining tacrolimus (FK506) in rat tissues to study the effect of Schisandra sphenanthera extract on FK506 tissue distribution. After a liquid–liquid extraction with ethyl acetate, FK506 and ascomycin (IS) were subjected to LC‐MS/MS analysis using positive electrospray ionization under multiple reactions monitoring mode. Chromatographic separation of FK506 and ascomycin was achieved on a Hypersil BDS C₁₈ column with a mobile phase consisting of methanol‐water (containing 2 mM ammonium acetate, 95 : 5, v/v). The intra‐ and inter‐batch precision of the method were less than 8.8 and 9.8%, respectively. The intra‐ and inter‐batch accuracies ranged from 97.5 to 104.0%. The lowest limit of quantification for FK506 was 0.5 ng/mL. The method was applied to a FK506 tissue distribution study with or without a dose of Wuzhi (WZ) tablet. Most of the FK506 tissue concentrations were slightly increased after a concomitant WZ tablet dose, but the whole blood concentration of FK506 was dramatically increased 3‐fold after a concomitant WZ tablet dose. These results indicated that the LC‐MS/MS method was rapid and sensitive enough to quantify FK506 in different rat tissues, and strict drug monitoring is recommended when co‐administering WZ tablet in clinical use. Copyright © 2009 John Wiley & Sons, Ltd.     

Highly effective binding and inverse fluorescent behavior of palmatine and l-tetrahydropalmatine alkaloids by p-sulfonatocalixarenes

The effects of pressure and solvent were examined for the inclusion complexation of phenothiazine dyes and trans-4-[4-(dimethylamino)styryl]-1-methylpyridinium (St-4Me) with water-soluble p-sulfonatocalix[8]arene (Calix-S8). Depending on the bulkiness of the guest dyes, external pressures and solvent polarity increase the inclusion equilibrium constants of dyes with Calix-S8. From the pressure dependence of the inclusion equilibria, the reaction volumes for inclusion by Calix-S8 in the alcohol-water mixtures were estimated to be negative values (?19.8 to ?5.29 cm³ mol^?1 for the phenothiazine dyes and ?13.1 to ?9.85 cm³ mol^?1 for St-4Me). Analysis of the results of the high pressure indicated that the intrinsic volume change related to inclusion into the Calix-S8 cavity plays an important role in the inclusion of Calix-S8, depending on the bulkiness of the guest molecules. Based on ¹H NMR measurements, the structures of the inclusion complexes of Calix-S8 with phenothiazine dyes have been established and the differences in the inclusion behaviors of the phenothiazine dyes and St-4Me are discussed.     

Determination of senkirkine and senecionine in Tussilago farfara using microwave-assisted extraction and pressurized hot water extraction with liquid chromatography tandem mass spectrometry

Tussilago farfara (Kuan Donghua) is an important Chinese herbal medicine which has been shown to contain many bioactive compounds and widely used to relieve cough and resolve phlegm. However, besides therapeutic bioactive compounds, this herb has been found to contain toxic pyrrolizidine alkaloids (PAs), mainly senkirkine and traces of senecionine. In this report, conditions for microwave-assisted extraction (MAE) and pressurized hot water extraction (PHWE) were optimized for the extraction of the PAs. The results were compared against heating under reflux. It was found that the binary mixture of MeOH:H₂O (1:1) acidified using HCl to pH 2-3 was the optimal solvent for the extraction of the PAs in the plant materials. Liquid chromatography (LC) with ultra-violet (UV) detection and electrospray ionization mass spectrometry (ESI-MS) in the positive mode was used for the determination and quantitation of senkirkine and senecionine in the botanical extract. The proposed extraction methods with LC/MS allow for the rapid detection of the major and the minor alkaloids in T. farfara in the presence of co-eluting peaks. With LC/MS, the quantitative analysis of PAs in the extract was done using internal standard calibration and the precision was found to vary from 0.6% to 5.4% on different days. The limits of detection (LODs) and limits of quantitation (LOQs) for MAE and PHWE were found to vary from 0.26 μg/g to 1.04 μg/g and 1.32 μg/g to 5.29 μg/g, respectively. The method precision of MAE and PHWE were found to vary from 3.7% to 10.4% on different days. The results showed that major and minor alkaloids extracted using MAE and PHWE were comparable to that by heating under reflux. Our data also showed that significant ion suppression was not observed in the analysis of senkirkine and senecionine in the botanical extracts with co-eluting peaks.     

STUDIES ON SELF-VULCANIZING FLUOROELASTOMER/PHENOL HYDROXY SILICONE RUBBER BLENDS

Self-vulcanizing blends of phenol hydroxy silicone rubber(PHSR)and fluoroelastomer(FPM)were prepared. Vulcanized rubbers with lower glass transition temperature(T_g)were successfully obtained.The results of dynamic mechanical analysis(DMA)show that the vulcanized FPM/PHSR(10 phr)blend has only one T_g temperature,demonstrating the well compatibility between FPM and PHSR.The thermogravimetric analysis(TGA)demonstrates that the PHSR do little damage to the thermal stability of FPM.The vulcanization charact...     

柱前衍生高效液相色谱法测定NTCA的光学纯度

用1-萘胺对乙酰四氢噻唑-2-硫酮-4-羧酸进行柱前衍生,产生非对映体衍生物.以正己烷和乙醇或异丙醇为流动相,选择Chiralcel OD-H色谱柱上对NTCA衍生物进行了拆分,考察了流动相组成和柱温对其衍生物分离的影响,获得较好的分析条件,分离因子达到1.3.该结果进一步与旋光仪法相比较,相对偏差不超过1.9%.     

PH_3配体在团簇Au_(20)的顶点和面心配位的DFT理论研究

采用DFT方法研究了在团簇Au20的顶端位点和面心位点配位PH3分子时的几何结构、电子结构以及Au-P的成键机理和能量分析.在两种配位方式下,配体PH3对团簇的几何结构影响都表现为强烈的局域形变效应.不同的配位方式下PH3与团簇的轨道作用方式不同,所形成的团簇化合物电子组态不同.两种配位方式下Au-P成键能的区别主要是来自于配体与团簇之间的Pauli排斥的不同,在面心配位时配体与团簇之间更大的Pauli排斥作用导致了该配位方式的不稳定.