顶空液相微萃取在环境水样中邻硝基苯酚的萃取机制研究

目的 探讨顶空液相微萃取在挥发性组分邻硝基苯酚萃取中的萃取机制,建立水样中邻硝基苯酚的顶空液相微萃取-高效液相色谱测定方法。方法 将密封玻璃瓶中的样品溶液置于恒温磁力搅拌器上搅拌加热,以甲醇为萃取溶剂将其悬于样品溶液的上部空间,萃取40s,连续萃取5次,合并萃取液进行高效液相色谱紫外检测。结果 实验考察了萃取条件对萃取效率的影响;讨论了顶空液相微萃取理论富集倍数、表观富集倍数和萃取率的公式;阐明了醇类有机溶剂的理化性质与萃取效率之间的相关关系,并对同类醇溶剂的萃取效率进行了预测;在优化的实验条件下,建立了水样中邻硝基苯酚含量测定方法,线性范围为0.00004～25μg/m(lr=0.9993,n=15),检测限为10pg/ml,方法的相对标准偏差为4.0%～10.1%,平均回收率97.2%～113.3%,富集倍数为20倍。结论 该方法操作简单、快捷、灵敏度高,对环境样品中挥发性或半挥发性痕量成分的分析具有重要意义。     

中空纤维液相微萃取结合高效液相色谱法测定比索洛尔血浆蛋白结合率

目的将中空纤维液相微萃取技术与高效液相色谱法结合,建立测定比索洛尔血浆蛋白结合率的新方法。方法优化比索洛尔血浆样本的液相微萃取条件;利用高效液相色谱法测定比索洛尔在接受相中的浓度,色谱条件为水-甲醇-乙腈-0.1%磷酸(50∶34∶6∶10),检测波长Ex:232 nm,Em:300 nm,分别代入当日标准曲线计算出比索洛尔血浆游离药物浓度及总药物浓度,进而计算比索洛尔血浆蛋白结合率。结果在低、中、高3种浓度下测得比索洛尔的血浆蛋白结合率分别为31.2%,32.0%,31.8%。结论所建立的方法简便快速,重复性好,适用于药物游离浓度及血浆蛋白结合率的测定。比索洛尔与人血浆蛋白有中等程度结合,且不存在浓度依赖性。     

分散液相微萃取-HPLC法用于大鼠血浆中对香豆酸测定

目的建立了分散液相微萃取与高效液相色谱联用技术测定大鼠血浆中对香豆酸浓度。方法微萃取条件为:20μL 1-己基-3-甲基咪唑六氟磷酸盐离子液体(1-hextyl-3-methylimidazoliumhexafluorophosphate,[C6MIM][PF6])作萃取剂,80μL乙腈作分散剂,0.5 mol.L-1硫酸作酸化剂,萃取时间为1 min。结果在优化的萃取条件下,血浆中对香豆酸质量浓度在0.012～2.400 mg.L-1内,线性关系良好(相关系数r=0.997 5),日内和日间精密度(RSD%)<9%(n=6),相对回收率为96.7%～101.6%,提取回收率为59.0%～70.4%。结论该方法适于血浆中对香豆酸浓度的测定。     

液相微萃取／后萃取-高效液相色谱法测定厚朴及其制剂中厚朴酚与和厚朴酚的含量

本文采用液相微萃取／后萃取（LPME／BE）与高效液相色谱联用法萃取并测定了中药厚朴及其制剂-藿香正气口服液和香砂养胃丸中厚朴酚与和厚朴酚的含量。优化了萃取效率影响因素，萃取溶剂、供相与接受相、转速及萃取时间。厚朴酚与和厚朴酚的线性范围分别为1．56—156μg/mL和1．10—110μg／mL；检测限（S／N=3）分别为0．10ug/mL和0.07μg/mL，回收率范围为98.3％-105．1％，RSD〈2．5％。     

液相微萃取技术及其在生物样品预处理中的应用进展

液相微萃取是在液相萃取技术基础上发展起来的新型生物样品前处理技术,具有简便、快速、经济、环保等特点,已在血液、尿液、唾液等生物基质样品分析中广泛应用。本文通过查阅近5年文献,对液相微萃取技术的主要模式,即单液滴微萃取、分散液-液微萃取和中空纤维液相微萃取的基本原理,以及其在生物样品预处理中的应用进展进行综述,以期为体内药物分析、药代动力学研究以及新药研发等领域样品前处理提供技术支撑和参考。     

液相微萃取结合气相色谱测定复方可待因口服溶液中可待因的含量

目的:建立中空纤维膜液相微萃取结合气相色谱(HF-LPME)测定止咳糖浆中磷酸可待因含量的方法.方法:制作中空纤维膜液相微萃取装置,对萃取条件进行优化,结合气相色谱方法,测定复方可待因口服溶液中磷酸可待因的含量.结果:可待因及内标在设定色谱条件下得到了很好的分离,磷酸可待因在1.0～50.0 μg/mL浓度范围内具有良好的线性关系,线性方程为Y=0.0397X+0.1309,r=0.9891,平均回收率为102.5%,RSD=3.78%.结论:HF-LPME测定磷酸可待因含量,方法简单、灵敏,可用于复方可待因口服溶液中可待因的含量测定.     

用中空纤维液相微萃取-HPLC法测定人血浆中酒石酸美托洛尔的浓度

目的:建立中空纤维液相微萃取-HPLC法测定人血浆中酒石酸美托洛尔的浓度.方法:优化酒石酸美托洛尔液相微萃取法供给相和接受相的浓度、萃取时间、萃取温度、萃取转速和离子强度,血浆样品经中空纤维液相微萃取法萃取后,用HPLC法测定酒石酸美托洛尔的浓度.色谱柱:Agilent Zorbax Eclipse XDB-C18柱,流动相:甲醇-0.1％磷酸(40∶60),流速:1 ml/min,激发波长:227 nm,发射波长:305 nm,柱温:30℃.结果:酒石酸美托洛尔在2～ 125 ng/ml线性关系良好,低、中、高三种浓度(5、20、100 ng/ml)的日内、日间精密度均＜10％,回收率分别为(87.1±7.3)％、(92.6±5.8)％和(89.1±2.5)％.结论:中空纤维液相微萃取-HPLC法适用于测定血浆样品中酒石酸美托洛尔的浓度.     

中空膜液相微萃取-HPLC法用于人血浆中水杨酸的测定

建立灵敏、准确地测定人血浆中水杨酸浓度的HPLC法。样品经过酸化处理后,以甲苯-正辛醇(4:6,V/V)为萃取溶剂、NaOH水溶液(pH=10)为接收相进行中空纤维膜微萃取。在该条件下,血浆中水杨酸浓度在2~250 ng.mL-1范围内,线性关系良好(r=0.9994);检测限为0.7ng.mL-1(S/N=3);精密度(RSD)<8%(n=5);回收率为87.6%~102.0%。该方法灵敏、有效、所需有机溶剂少、富集效率高,适于血浆中水杨酸浓度的测定。     

中空纤维液相微萃取技术的应用研究

近年来,随着人们对食品和环境安全的重视度不断提高,单纯的检测分析不能对复杂样品中痕量组分进行定量分析,也使传统的样品前处理面临新的挑战,因此,寻求一种高富集、绿色环保、快速净化的样品前处理新技术,已成为目前检测分析研究的热点之一.基于这一问题,提出了中空纤维的液相微萃取(HF-LPME),其具有高浓缩、快速友好的样品前处理功能.本文重点对HF-LPME的模式及原理、仪器装置、影响因素、应用领域以及发展前景作了综述.     

液相微萃取-后萃取光化学荧光高效液相色谱法测定生物样品中甲氨蝶呤的含量

目的:采用液相微萃取-后萃取光化学荧光高效液相色谱法测定生物样品中甲氨蝶呤的含量。方法:应用自制的液相微萃取装置,在0.05mol.L-1盐酸酸性介质中,甲氨蝶呤以分子状态首先被聚醚砜中空纤维孔壁中的正丁醇萃取,继而被25μL0.05mol.L-1氨水溶液后萃取。后萃取液用等体积的0.2mol.L-1盐酸酸化后,经紫外光照射45min,发生光化学反应,取样20μL进行高效液相色谱分析,在λex=275nm,λem=370nm荧光检测,建立了液相微萃取-后萃取-光化学荧光高效液相色谱法测定生物样品中甲氨蝶呤含量的方法。结果:该方法在血浆和尿液中的浓缩倍数可达20~24倍,线性范围分别为0.05~50mg.L-1和0.01~50mg.L-1,检出限分别为10μg.L-1和5μg.L-1,RSD<11%。通过液相微萃取-后萃取,能有效地去除生物样品中干扰甲氨蝶呤测定的内源性杂质,提高了选择性。结论:该方法将液相微萃取和光化学荧光-高效液相色谱法相结合,为生物样品中甲氨蝶呤的检测提供了一种有效的分离分析方法。     

高效液相色谱法检测七味都气丸中活性成分五味子醇甲、马钱苷和23-乙酰泽泻醇B的含量

目的 研究建立采用高效液相色谱法检测七味都气丸中活性成分五味子醇甲、马钱苷和23-乙酰泽泻醇B含量的分析方法。方法 研究起止时间为2019年3月至2022年5月。七味都气丸样品经粉碎,90%甲醇水溶液超声提取后,采用Waters X-bridge C18色谱柱分离,柱温27℃,检测波长228 nm,进样体积25μL,流动包括流动相A（乙腈）,流动相B(0.3%磷酸水溶液),梯度洗脱,洗脱程序为0～7 min 8%A,7～18 min 8%～60%A,18～28 min 60%～91%A,28～30 min 91%～8%A,30～35min 8%A,外标法定量检测。结果 马钱苷、五味子醇甲和23-乙酰泽泻醇B在质量浓度0.1～20.0 mg/L范围内具有良好的线性关系,相关系数（r）均大于0.995;重复性RSD(n=6)分别为2.7%、3.1%和3.4%;加样回收率分别为99.67%、100.11%和100.49%。结论该方法具有简便、快速、准确度好等优点,适用于七味都气丸品种的质量控制。     

Simultaneous analysis of glycyrrhizin, paeoniflorin, quercetin, ferulic acid, liquiritin, formononetin, benzoic acid and isoliquiritigenin in the Chinese proprietary medicine Xiao Yao Wan by HPLC

A high performance liquid chromatography coupled with photodiode-array detection method was developed for simultaneous determination of glycyrrhizin, paeoniflorin, benzoic acid, quercetin, ferulic acid, formononetin, liquiritin and isoliquiritigenin in the Chinese proprietary medicine "Xiao Yao Wan" (XYW). The analysis was performed by reverse phase gradient elution, using an aqueous mobile phase (containing 0.1% phosphoric acid) modified by acetonitrile and detection made simultaneously at four wavelengths. The method was validated for accuracy, precision and limits of detection and quantification. Ten batches of XYW obtained from different pharmaceutical companies were analyzed and found to contain different amounts of the eight bioactive markers. This method could be used for quality assessment of this herbal medicine.     

Metabolomics study on the therapeutic effect of traditional Chinese medicine Xue-Fu-Zhu-Yu decoction in coronary heart disease based on LC-Q-TOF/MS and GC-MS analysis

The present study aims is to investigate the metabolic mechanism of Xue-Fu-Zhu-Yu decoction (XFZYD) in the treatment of blood-stasis syndrome in Coronary Heart Disease (CHD). To that end, 30 CHD patients with Blood-Stasis Syndrome (BSS) and 20 healthy subjects were enrolled. LC-Q-TOF/MS analysis determined that in comparison between CHD with BSS patients (Group A) and healthy subjects (Group C), 59 significantly differential metabolites in the positive mode and 18 significantly differential metabolites in the negative mode. The metabolite constituents in the plasma of 30 CHD with BSS patients before (group A) and after 30 days of treatment (Group B), and 20 healthy subjects (Group C) were analyzed using LC-Q-TOF/MS and GC-MS. Based on multivariate statistical analysis (PCA, PLS-DA and OPLS-DA), we determined 69 differential metabolites. The levels of hemorheology indexes were significantly down-regulated after treatment. Metabolic pathway attribution analysis showed that lipid metabolism, amino acid metabolism and bile acid metabolism pathways are involved. Our study identifies the metabolic networks of CHD and demonstrates the efficacy of this metabolomics approach to systematically study the therapeutic effect of XFZYC on CHD.     

Possible involvement of the transient receptor potential vanilloid type 1 channel in postoperative adhesive obstruction and its prevention by a kampo (traditional Japanese) medicine, daikenchuto

This study focused on the localization of transient receptor potential vanilloid type 1 (TRPV1) in the intestines in postoperative adhesion model rats and investigated the underlying mechanism for the anti-adhesion action of daikenchuto (DKT), especially in relation to TRPV1. Postoperative intestinal adhesion was induced by sprinkling talc in the small intestine. The expression of TRPV1 mRNA was examined by in situ hybridization and real-time RT-PCR. The effects of DKT and its major ingredient, hydroxy sanshool, with or without ruthenium red, a TRP-channel antagonist, on talc-induced intestinal adhesions were evaluated. The level of TRPV1 mRNA was higher in the adhesion regions of talc-treated rats than in normal small intestine of sham-operated rats. Localization of TRPV1 mRNA expression was identified in the submucosal plexus of both sham-operated and talc-treated rats; and in talc-treated rats, it was observed also in the myenteric plexus and regions of adhesion. Capsaicin, DKT, and hydroxy sanshool significantly prevented formation of intestinal adhesions. The effects of DKT and hydroxy sanshool were abrogated by subcutaneous injection of ruthenium red. These results suggest that pharmacological modulation of TRPV1 might be a possible therapeutic option in postoperative intestinal adhesion, which might be relevant to the prevention of postoperative adhesive obstruction by DKT.     

Identification of adulterants in a Chinese herbal medicine by LC–HRMS and LC–MS–SPE/NMR and comparative in vivo study with standards in a hypertensive rat model

Based on anecdotal evidence of anti-hypertensive effect of Gold Nine Soft Capsules, an in vivo study of this complex Chinese “herbal-based” medicine was initiated. Dosage of the content of Gold Nine capsules in spontaneous hypertensive rats showed a remarkably good effect. This led to further investigation of the components of the preparation and eventual identification of three known anti-hypertensive drugs; amlodipine, indapamide and valsartan, which were not declared on the label. Compounds were rapidly identified using LC–HRMS and LC–MS–SPE/NMR, quantified by HPLC, and the in vivo activity of a combination of commercially purchased standards was shown to be equivalent to that of the capsule content. Adulteration of herbal remedies and dietary supplements with synthetic drugs is an increasing problem that may lead to serious adverse effects. LC–MS–SPE/NMR as a method for the rapid identification of such adulterants is highlighted in this case study.