水解法测定血液中的毒鼠强

建立了毒鼠强的血液样品水解方法并对相应的GC FPD定量、GC MS定性的分析条件进行了优化 ,同时考察了水解过程中的水解温度、水解强度等方面的影响因素 ,建立了一个提取效率高、灵敏度佳、干扰少的毒鼠强提取分析方法。毒鼠强工作曲线在 0 .0 1～ 0 .2 0 μg μL之间呈线性关系 ,相关系数r=0 .9999。与传统的液 液直接提取方法相比 ,血液样品毒鼠强的检出率提高 1 69% ,并可应用于生物样品的毒鼠强提取分析中。     

气相色谱-质谱法测定生物检材中毒鼠强的含量

采用气相色谱-质谱提取离子的方法测定了生物检材中毒鼠强的含量。毒鼠强的线性范围为0.05-50ng，检出限为0.01ng，以苯为溶剂，毒鼠强的提取回收率为93.5%，RSD为4.96%(n=5)。方法准确、快速，适用于生物检材中毒鼠强的测定。     

毒鼠强薄层色谱分析的检出限

建立薄层色谱法快速对毒鼠强进行简易分析的方法,利用薄层色谱进行层析分离,采用特殊显色方法,对毒鼠强进行显色,以能正常观察到斑点的色泽状态,辅助GC-MS方法确定检出极限。薄层色谱法分析毒鼠强检出限可达5~10μg。能用此方法对大多数中毒案件提取的检材进行定性分析。     

荧光光谱法研究分解后白术挥发油与β-环糊精和羟丙基-β-环糊精的包合作用

采用荧光光谱法研究了多组分分解后白术挥发油(DVOA)与β-环糊精(β-CD)和羟丙基-β-环糊精(HP-β-CD)的包合作用。固定挥发油质量,考察了β-CD和HP-β-CD的浓度及包合时间对挥发油荧光强度的影响,同时采用荧光双倒数法计算了挥发油与β-CD和HP-β-CD的包合比及包合常数,并进一步研究了挥发油/HP-β-CD包合物的热力学特性。实验结果表明,挥发油的荧光强度随β-CD和HP-β-CD浓度的增大而逐渐增加,表明包合物的形成,包合比均为1∶1;25℃下挥发油与β-CD和HP-β-CD的包合常数分别为110、172L/mol,表明包合稳定性为HP-β-CDβ-CD。温度25℃、35℃和45℃下,挥发油与HP-β-CD的包合常数分别为172、130、83L/mol,△G、△H和△S均为负值,且△H小于一般反应热,表明升高温度挥发油与HP-β-CD的包合稳定性降低;包合反应可自发进行,且为放热反应,包合过程是挥发油分子与HP-β-CD分子间氢键和范德华力作用的结果。     

离子阱GC-MS-MS检测鼠药中的毒鼠强

建立了离子阱气相色谱-串级质谱（MS—MS）检测鼠药中毒鼠强的方法。测定毒鼠强的线性范围为0．2～5．0mg／L,线性相关系数为0．9984,检出限为0．0013mg／kg,回收率为76．1％～116．7％,测定结果的相对标准偏差为6．1％（n=6）。同时利用二级质谱分析了毒鼠强裂解规律,该法对毒鼠强具有良好的确证性。     

血样和尿样中毒鼠强气相色谱测定方法的研究及其初步应用

〕本文报道一种血、尿样品里毒鼠强的分离与分析方法。血样加入10W/VNaCl用乙酸乙酯萃取,尿样以X5树脂小柱固相萃取,气相色谱测定。所建方法已用于1例中毒病人血、尿样品的测定,在中毒4天后血中、7天后尿中仍可测出毒鼠强。另外,本方法还用于对治疗该病人的人工炭肾内毒鼠强的测定,根据测定结果对人工炭肾的疗效进行了评价。     

肼类推进剂色谱分析方法的研究

采用HP-5毛细管柱和以Tenax-TA为担体的填充枉色谱法分析肼类推进剂的组分含量,并与国家军用标准中采用的GDX-403填充柱的方法进行对照试验,结果表明,用HP-5毛细管柱和以Tenax-TA为担体的填充柱的分析方法与国军标中采用的方法无显著性差异,精密度、准确度能满足分析检测的要求,在肼类推进剂检验分析中可与国军标法等同采用,且用HP-5毛细管柱的色谱法在检测无水肼时所得结果具有更高的精密度和准确度。     

GC-FPD、GC-MS法分析血液样品中的毒鼠强

采用液-液提取方法及GC—FPD定量、GC—MS定性检测手段，对血液样品中毒鼠强的提取和检测方法进行了研究。时提取毒鼠强的溶剂类型、溶剂用量及质谱分析参数等因素进行了考察，建立了一种回收率高、重现性好、灵敏度佳、干扰少的毒鼠强分析方法。毒鼠强工作曲线的线性范围为0．01-0．2μg／μL，相关系数r=0．9999，空白血液的加标平均回收率为93．6％，测定结果的相对标准偏差为5．27％。该方法满足司法鉴定中生物样品的定性、定量检验要求。     

HP-β-环糊精对盐酸舍曲林异构体手性选择包合和色谱保留行为影响的研究

研究了不同色谱条件下HP-β-环糊精(HP-β-CD)作为反相高效液相色谱(RP-HPLC)手性添加剂对盐酸舍曲林异构体的手性选择性和色谱保留行为的影响。通过保留因子(k)的倒数1/k对［HP-β-CD］的良好线性关系证明HP-β-CD与盐酸舍曲林异构体形成了包合比为1∶1的包合物,并通过1/k对［HP-β-CD］的直线求得其结合常数。同时系统研究了pH值、缓冲液浓度(离子强度)、乙腈溶剂强度及温度对结合常数的影响,对结合常数与它们的关系做出了定量的描述;计算了手性分离过程中的热力学参数,并结合所计算的结     

虎杖甙/HP-β-CD包合物的制备及光稳定性研究

以羟丙基-β-环糊精(HP-β-CD)为主体,采用冷冻干燥法制备了虎杖甙的包合物,通过相溶解度法、粉末X射线衍射谱图(XRD)、热重分析(TG)、差示扫描量热法(DSC)、扫描电子显微镜(SEM)研究了HP-β-CD与虎杖甙的主客体作用,并考察了包合作用对虎杖甙光稳定性的影响。结果表明,HP-β-CD与虎杖甙形成了包合比为1∶1的包合物,缔合常数为1308mol-1·L;包合后虎杖甙在水中的溶解度提高10倍以上,热稳定性提高,分解温度从270℃提高至298℃;光稳定性实验表明包合后虎杖甙的光稳定性得到了有效提高。这为虎杖甙在食品、化妆品等领域的使用提供了新的方法和信息。     

生物检材中毒鼠强的GC-MS选择离子分析

采用二氢甲烷萃取GC－MS及选择离子定性的方法,检测了血液、尸体脏器中的灭鼠药毒鼠强（四次甲基二砜四胺）,毒氧强分子量为240,其质谱图中有明显的分子离子峰240m/z、基峰42m/z及212、185、132、121、92、76m/z的碎片离子峰。对212、240m/z碎片离子进行扫描,可提高检测灵敏度。本法适用于中毒血液和脏器中低含量毒鼠强的定性检测。     

多壁碳纳米管固相萃取净化气相色谱法分析蔬菜中有机氯和拟除虫菊酯农药残留

建立了多壁碳纳米管为吸附剂的固相萃取(SPE)净化、气相色谱-电子捕获检测(GC-ECD)测定蔬菜中6种有机氯和7种拟除虫菊酯农药的方法。采用双柱(HP-50和HP-1色谱柱)双检测器进行定性和定量分析。蔬菜样品采用乙腈提取,多壁碳纳米管SPE柱净化,正己烷溶解上样,丙酮-正己烷(7:3, v/v)洗脱,13种农药中有11种农药的添加回收率高于70%。将该净化方法用于荷兰黄瓜、卷心菜、红圣女果、奶油生菜、紫甘蓝、韭菜、大葱和洋葱等样品的净化,与弗罗里硅土SPE柱相比较,净化效果更好,表明多壁碳纳米管具有较强的吸附去除色素的能力,可以避免色素对测定的干扰。     

Minoxidil–2-hydroxypropyl-β-cyclodextrin inclusion complexes: characterization and in vivo evaluation of an aqueous solution for hair growth in rats

Minoxidil dissolved in organic solvents is commonly used in the treatment of androgenic alopecia because it is hydrophobic and poorly soluble in water. The aim of this investigation was to develop an aqueous minoxidil solution without addition of organic solvents. To this end, minoxidil was encapsulated in 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) to form a minoxidil–HP-β-CD inclusion complex with aqueous solubility higher than that of pure minoxidil. Minoxidil–HP-β-CD inclusion complexes were prepared using a freeze-drying method from minoxidil and HP-β-CD at a molar ratio of 1:1. Complex formation was confirmed by nuclear magnetic resonance, thermogravimetric analysis, and thin layer chromatography. The structure of the complex was determined using two-dimensional rotating frame overhauser effect spectroscopy. Minoxidil–HP-β-CD inclusion complexes were dissolved in water to form a homogeneous aqueous solution, and its effect on the hair cycle of mice was evaluated in vivo. The results support the feasibility of using HP-β-CD to prepare an aqueous minoxidil solution to replace organic solvent-based solutions.     

羟丙基-β-环糊精对华法林的荧光增强作用及其分析应用

研究了羟丙基-β-环糊精(HP-β-CD)对抗凝药物华法林的荧光增强作用,探讨了华法林与HP-β-CD的包合特性.并与β-环糊精(β-CD)对华法林的荧光增强作用和包合特性进行了比较,结果表明,HP-β-CD的荧光增强作用强于β-CD.基于HP-β-CD的荧光增强作用,研究建立了一种荧光光谱测定华法林的新方法.华法林在10.3～2266μg/L范围内与荧光强度呈良好的线性关系,检出限为2.92μg/L.此法已应用于华法林钠药物的测定.     

液化石油气在模拟毛细管色谱柱内壁石英玻璃表面的吸附研究

用石英玻璃微珠模拟了ＨＰ－１，ＨＰ－２０Ｍ，ＨＰ－１７毛细管色谱柱内壁，用真空重量法测定了丙烷、丁烷、丙烯、液化石油气样品在３种模拟毛细管内壁表面的吸附等温线，并计算了等量吸附热随吸附量的变化关系。结果表明改性石英玻璃表面固定相的化学性质是吸附等温线类型的决定因素。本文所得结果对毛细管色谱动力学过程的理解，样品在毛细管柱上的活度系数及液化石油气组成准确测定等方面有重要意义。     

Complexation of triptolide and its succinate derivative with cyclodextrins: affinity capillary electrophoresis, isothermal titration calorimetry and 1H NMR studies

The complexation of the triptolide PG490 and its succinate derivative PG490-88Na with various cyclodextrins was studied using three complementary techniques: affinity capillary electrophoresis (ACE), isothermal titration calorimetry (ITC) and nuclear magnetic resonance (NMR). The apparent binding constants of the complexes formed between the drugs and 8 CDs (α-CD, β-CD, γ-CD, HP-α-CD, HP-β-CD, HP-γ-CD, CM-β-CD and amino-β-CD) were determined by ACE through linear Scott's plots. The apparent and averaged binding constants of the complexes formed between PG490-88 and β-CD, γ-CD, HP-α-CD, HP-β-CD or HP-γ-CD are contained in the narrow range 135-167 M(-1). For the anionic CM-β-CD and cationic amino-β-CD, these constants are 38 and 278 M(-1), respectively, which is in accordance with electrostatic repulsions or attractions with the succinate moiety. ITC and NMR investigations for the binding constants determinations were performed for 2 CDs allowing high complexation: HP-β-CD and amino-β-CD. The three techniques provided similar results. ITC and NMR, in contrast to ACE, allowed to study the complexes formed between the neutral compound PG490 and neutral cyclodextrins. A more advanced characterization of the PG 490-88Na/amino-β-CD complex, which displays the highest apparent binding constant, was undertaken using NMR spectroscopy. The 1:1 stoichiometry of the complex was established by (1)H NMR 1D and selective 1D TOCSY experiments using the continuous variation method. Moreover, the 1D and 2D ROESY experiments revealed the inclusion of the isopropyl moiety of the triptolide derivative in the hydrophobic CD cavity. Altogether, the data provide strong evidences that the two triptolide compounds can be efficiently complexed with CD.     

中毒样品中灭鼠药的分析鉴定与人工炭肾治疗效果浅评

1991年7月某单位发生集体食物中毒,78人发病。当时迫切需要鉴定出毒物,以便对这起中毒病人进行抢救治疗。本文建立了未见文献报道的血样,炭肾中痕量“四二四”的分离提取方法和GC-MS分析鉴定方法,在中毒样品中鉴定出剧毒灭鼠药“四二四”。根据治疗用的人工炭肾及治疗后病人血样的鉴定结果,对用人工炭肾透析治疗“四二四”中毒的疗效进行了评价。     

Simultaneous analysis and retention behavior of major isoflavonoids in Radix Puerariae lobatae and Radix Puerariae thomsonii by high performance liquid chromatography with cyclodextrins as a mobile phase modifier

In order to differentiate two species of Radix Puerariae (Radix Puerariae lobatae and Radix Puerariae thomsonii) and to determine major isoflavonoids (puerarin, daidzin, daidzein and genistein) in the samples, a simple high performance liquid chromatography (HPLC) method with isocratic elution employing cyclodextrins (CDs) as mobile phase additives was developed. Various factors affecting the retention of isoflavonoids in the C₁₈ reversed-phase column, such as the nature of CDs, the concentration of hydroxypropyl-β-cyclodextrin (HP-β-CD) and the methanol percentage in the mobile phase, were studied. Experimental results confirmed that HP-β-CD, as a very effective mobile phase additive, could markedly reduce the retention of isoflavonoids, especially daidzein and genistein. The elution of four isoflavonoids could be achieved on a Kromasil^® C₁₈ column within 56 min by using the methanol–water contained 5 mM HP-β-CD (25/75, v/v) mixture as the mobile phase. The formation of the inclusion complexes between isoflavonoids and HP-β-CD explained the modification of the retention of analytes. The apparent formation constants determined by HPLC confirmed that the stoichiometry of HP-β-CD-isoflavonoid complexes was 1:1, and the stability of the complexes depended on the size and property of isoflavonoids. The optimized method was successfully applied for the simultaneous determination of major isoflavonoids in P. lobatae and P. thomsonii samples. This work provides a useful method for the analysis of traditional Chinese herbs.     

加压毛细管电色谱法分离1-甲基-3-苯基丙胺对映体

运用毛细管电色谱(pCEC)模式,以羟丙基-β-环糊精(HP-β-CD)作为手性选择剂,对1-甲基-3-苯基丙胺对映体进行手性分离。1-甲基-3-苯基丙胺对映体在最佳的条件下如:手性选择剂浓度10g/L、流动相配比:V(乙腈)∶V(磷酸盐体系)=60∶40溶液(5mmol/L)、背景电解质pH=7.6、柱温16℃和分离电压10kV达到了基线分离,该方法重现性好、简便、快捷。     

Effect of hydroxypropyl-β-cyclodextrin complexation on the aqueous solubility, structure, thermal stability, antioxidant activity, and tyrosinase inhibition of paeonol

The objective of this paper is to study the effect of hydroxypropyl-β-cyclodextrin (HP-β-CD) complexation on the aqueous solubility, structure, thermal stability, antioxidant activity, and tyrosinase inhibition of paeonol (PAE). The inclusion complex (PAE-HP-β-CD complex) of HP-β-CD and PAE was prepared by a freeze-drying method. Phase solubility tests showed that the stability constant of the inclusion complex was about 33.8?M^?1 at 25?°C. The experimental results of proton nuclear magnetic resonance (H-NMR) spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) suggested that PAE was included by HP-β-CD to form the PAE-HP-β-CD complex. Furthermore, the thermogravimetric analysis (TGA) results showed that the thermal stability of PAE was improved when it was complexed with HP-β-CD. Comparing the antioxidant activity of PAE with that of the PAE-HP-β-CD complex at the same concentration revealed that the complex of PAE with HP-β-CD was better able to eliminate radical. Furthermore, the experimental results revealed that the formation of a complex with HP-β-CD increased the water solubility of PAE, improving its apparent inhibitive activity of tyrosinase.