富马酸比索洛尔与茜素的荷移反应研究

研究了富马酸比索洛尔与茜素的电荷转移反应条件,建立了快速测定富马酸比索洛尔的可见分光光度法。富马酸比索洛尔与茜素反应生成的电荷转移络合物的最大吸收波长是542nm,表观摩尔吸光系数为4.67×103L·mol-1·cm-1。富马酸比索洛尔质量浓度在12～160mg·L-1范围内服从比耳定律,相关系数为0.9993。当富马酸比索洛尔浓度为80mg·L-1时,六次测定结果的相对标准偏差为1.42%。测得荷移络合物的组成比和稳定常数分别为1∶1和1.53×104。本方法用于测定胶囊中富马酸比索洛尔的含量结果与文献方法相符,平均回收率在99.0%以上。     

荷移反应-分光光度法测定富马酸比索洛尔

在醇-酮(3+7)介质中,富马酸比索洛尔与7,7,8,8-四氰基对二次甲基苯醌于35℃反应30min,形成1比1的络合物。络合物的稳定常数为4.8×103,最大吸收波长为845nm,表观摩尔吸光率为5.37×104L·mol-1·cm-1。富马酸比索洛尔的质量浓度在2.0~14mg·L-1范围内与吸光度呈线性关系,测定值的相对标准偏差(n=6)为1.5%。采用此方法对片剂和胶囊样品中富马酸比索洛尔的含量进行测定,结果与药典法一致,加标回收率在99.0%以上。     

毛细管电泳-激光诱导荧光法测定人血浆中的富马酸比索洛尔

建立了毛细管电泳-激光诱导荧光检测(CE-LIFD)技术测定人血浆中富马酸比索洛尔含量的新方法。选用荧光素异硫氰酸酯(FITC)为衍生化试剂,当缓冲溶液为25mmol/LNa2B4O7(pH9.2)、分离电压25kV、柱温20℃、电动进样(10kV×8s)、以峰面积内标法定量、于激发波长/发射波长=488/520nm柱上检测时,富马酸比索洛尔得到较好分离。在选定的电泳条件下,对其线性范围(20～1000μg/L)、检出限(10μg/L)、重现性(日内和日间精密度分别小于4.44%和5.59%)和回收率(96.19%～101.80%)进行了测定。结果表明:迁移时间的重现性<1.58%;峰面积之比的重现性<6%。     

硫胺素-亚硝酸根体系的荧光性质研究及应用

研究了在碱性溶液中硫胺素（VB1）与亚硝酸根的荧光反应,建立了荧光光度法测定硫胺素的新方法。方法线性范围为1．28－324ng/mL,检出限0．52ng/mL,对15个浓度为100ng/mL的硫胺素溶液进行测定,相对标准偏差为1．4％。应用于药物中硫胺素的测定,回收率在96．5％－101．8％之间。     

固定化酶流动注射化学发光法测定尿酸

本文制备了高活性和长寿命固定化尿酸酶,并用流动注射化学发光分析在线测定了人血清和尿中尿酸含量。线性范围为40～1000ng/mL,检测下限为16ng/mL,对200ng/mL尿酸测定,相对标准偏差为2.6％。尿和血清中其它物质均无干扰,血清取样量只需50μL,每次测定时间少于1min。     

流动注射-化学发光法测定富马酸依美斯汀

在酸性条件下,KMnO4与甲醛能够产生微弱的化学发光,而富马酸依美斯汀的存在能够大大增强该化学发光强度;结合流动注射技术,建立了测定富马酸依美斯汀的流动注射-化学发光新方法。该方法的线性范围分别为3.0×10-8～2.0×10-7g/mL,2.0×10-7～1.0×10-6g/mL和1.0×10-6～8.0×10-6g/mL。检出限为1.0×10-8g/mL,对2.0×10-6g/mL富马酸依美斯汀滴眼液平行测定11次,其相对标准偏差为1.3%。该方法已成功应用于滴眼液中富马酸依美斯汀的含量测定。     

糕点中富马酸二甲酯的毛细管气相色谱快速测定

建立了糕点中富马酸二甲酯的毛细管气相色谱快速检测方法.富马酸二甲酯易溶于三氯甲烷,通过超声波提取,用三氯甲烷提取糕点中的富马酸二甲酯,用毛细管气相色谱测定.方法的最低检出限为2.00mg/kg,标准曲线的线性范围:10～500μg/mL,相关系数r为0.999 99,样品加标回收率为93.0%～109.0%,相对标准偏差RSD为1.30%～1.90%.结果表明方法操作简便、快速、回收率高、精密度好,可用于糕点中富马酸二甲酯含量的快速测定.     

微波消解-氢化物发生原子荧光光谱法同时测定化肥中砷、汞含量

采用微波消解样品前处理手段以及双道原子荧光光度计,建立了微波消解一氢化物发生原子荧光光谱法同时测定化肥中砷、汞含量的方法。通过试验确定了样品前处理方法,对负高压、灯电流,载气、屏蔽气、原子化器高度、酸度等测试条件进行了优化。在优化的工作条件下,砷、汞含量分别在0-50ng／mL和0—1．0ng／mL范围内与荧光强度呈良好的线性关系,线性相关系数分别为0．9996,0．9996,检出限分别为0．085,0．008ng／mL,回收率分别为88．8％～107．4％,90．0％～120％,测定结果的相对标准偏差均小于7％（n=6）。     

塞曼石墨炉原子吸收法直接测定血清中的硒

采用硝酸钯为硒的基体改进剂，用塞曼效应扣除背景，对消化后的血样直接进行测定。该法的检出限为6．0ng/mL，线性范围10ng/mL－136ng/mL，回收率为94．8％－102．5％。     

生物样品中Se的荧光测定方法

运用微波消化系统处理生物样品，以2，3-二氨基萘为荧光试剂建立了一种测定生物样品中Se的荧光分光光度法。方法的最低检出限为1．6ng／mL，线性范围0～0．600μg／mL，回收率92．22％～99．78％，连续10次测定样品变异系数（CV）为0．4％（n=10），隔213重复实验变异系数为1．54％。该法具有灵敏、稳定、可靠等优点，适用于生物样品中Se含量的测定。     

An HPLC method for the determination of bisoprolol in human plasma and its application to a pharmacokinetic study

A new high-performance liquid chromatographic method is described for the determination of bisoprolol in human plasma. The proposed method was based on the derivatization of bisoprolol with 4-chloro-7-nitro-2,1,3-benzoxadiazole in borate buffer at pH 9.5 to yield a fluorescent product. Chromatographic separation of bisoprolol was achieved by using isocratic elution at a flow rate of 1.2 mL/min on a C18 reversed-phase column (Inertsil, 4 μm, 150 4.6 mm) at 40°C. The mobile phase used for the analysis was methanol-water (70:30, % v/v). Fluorescence detector was used at the excitation and emission wavelengths of 458 and 525 nm, respectively. The method was validated for linearity, limit of detection, limit of quantification, precision, accuracy, recovery and system suitability. The assay was linear over the concentration range of 10-2000 ng/mL. This method was applied in pharmacokinetic studies of bisoprolol preparations in healthy volunteers.     

Development,validation and analytical error function of two chromatographic methods with fluorimetric detection for the determination of bisoprolol and metoprolol in human plasma

This work describes two high-performance liquid chromatographic methods for the individual determination of bisoprolol and metoprolol in human plasma. Analytical methods involve two different liquid-liquid extractions of human plasma, with diethyl ether for bisoprolol and with dichloromethane for metoprolol, coupled with a similar Nucleosil C(18) reversed-phase HPLC column. Fluorimetric detection was used to identify both beta-blockers. Retention times for bisoprolol and metoprolol were 8.7 and 3.2 min, respectively. Linear regressions for the calibration curves were linear at a concentration range of 6.25-200 ng/mL. Intra- and inter-day precision coefficients of variations and accuracy bias were acceptable (within 15%) over the entire range for both drugs. Average recovery was 89% for metoprolol and 98% for bisoprolol. Once the methods had been validated, analytical error functions were established as standard deviation (SD; ng/mL) = 2.216 + 3.608 x 10(-4)C(2) (C = theoretical concentration value) and SD-(ng/mL) = 0.408 + 0.378 x 10(-1)C for bisoprolol and metoprolol, respectively. The methods developed and their associated analytical error functions will be suitable for pharmacokinetic studies and for determination of plasma concentration if posology individualization of these drugs is needed.     

Liquid chromatographic-electrospray tandem mass spectrometric determination of bisoprolol in human plasma

An analytical method for the determination of bisoprolol in human plasma has been developed based on liquid chromatography-tandem mass spectrometry (LC-MS/MS). The analyte and internal standard (IS) diphenhydramine were cleaned up by protein precipitation with acetonitrile, reconstituted in mobile phase and separated by reversed-phase high-performance liquid chromatography (HPLC) using methanol:10 mm ammonium acetate:formic acid (70:30:0.1 v/v/v) as mobile phase. Detection was carried out by multiple reaction monitoring (MRM) on an LC-MS/MS system and was completed within 2.5 min. The assay was linear over the range 0.5-100 ng/mL with a limit of quantitation (LOQ) of 0.5 ng/mL. The intra- and inter-day precision levels were within 5.54 and 9.95%, respectively, while the accuracy was in the range 89.4-113%. This method has been utilized in a pharmacokinetic study, where healthy volunteers were treated with an oral dose of 5 mg bisoprolol.     

Liquid chromatography tandem mass spectrometry method for determination of bisoprolol in human plasma using d5‐bisoprolol as the internal standard

A simple, reliable and sensitive liquid chromatography tandem mass spectrometry (LC‐MS/MS) protocol was developed and validated for quantification of bisoprolol in human plasma. The sample was pretreated with a simple procedure of protein precipitation and an isotope‐labeled d5‐bisoprolol was used as internal standard. The chromatographic separation was performed on a Capcell Pak C₁₈ MG III column (100 mm × 2.0 mm, 5 µm). The protonated ion of the analyte was detected in positive ionization by multiple reaction monitoring mode. The mass transition pairs of m/z 326.3 → 116.3 and m/z 331.3 → 121.3 were used to detect bisoprolol and the internal standard, respectively. Linearity, accuracy, precision, recovery, matrix effect, dilution test and stability were evaluated during method validation over the range of 0.5–100 ng/mL. The validated method was successfully applied to analyze human plasma samples in a bisoprolol bioavailability study. Copyright © 2009 John Wiley & Sons, Ltd.     

直链淀粉手性固定相高效液相色谱法拆分比索洛尔对映体

采用直链淀粉手性固定相高效液相色谱法在正相条件下直接拆分了比索洛尔对映异构体。分别以异丙醇、乙醇为有机改性剂,考察了流动相的组成与配比、流速及柱温等因素对比索洛尔对映体分离的影响。确定了比索洛尔对映体的最佳拆分条件:流动相正己烷-乙醇-二乙胺(体积比为88∶12∶0.1),流速0.6 mL/min,检测波长270 nm,柱温20 ℃。该方法可快捷、简便地拆分比索洛尔对映体。     

Study on the determination of polyphenols in tobacco by HPLC coupled with ESI-MS after solid-phase extraction

A high-performance liquid chromatography method coupled with electrospray ionization-mass spectrometry for the determination of polyphenols in tobacco is studied. The polyphenols are extracted from a tobacco sample by being refluxed in a boiling water bath with 80% methanol and purified by solid-phase extraction with a C18 cartridge. The chlorogenic acid, rutin, scopoletin, caffeic acid, scopolin, and other polyphenols are satisfactorily separated on a Nova-Pak C18 chromatographic column (3.9 x 150 mm) with methanol and 0.05 mol/L potassium dihydrogen phosphate buffer solution gradient elution as mobile phase at a flow rate of 0.5 mL/min. Each of the polyphenols is monitored by photodiode array detector at its maximum wavelength: chlorogenic acid, 326.1 nm; rutin, 354.8 nm; scopoletin, 344.0 nm; caffeic acid, 323.7 nm; and scopolin, 365.2 nm. The limits of detection are: 100 ng/mL for chlorogenic acid, 125 ng/mL for rutin, 60 ng/mL for scopoletin, 50 ng/mL for caffeic acid, and 100 ng/mL for scopolin. The key polyphenols in tobacco are identified by comparing the retention time, the UV-spectrum, and the mass spectra with those of the standards. The recovery of tobacco polyphenols is 94-105%, and the relative standard deviations are 1.28-1.49%. This method is successfully applied to qualitatively and quantitatively analyze the polyphenols in tobacco with good results.     

Simple, rapid, and sensitive determination of beta-blockers in environmental water using dispersive liquid-liquid microextraction followed by liquid chromatography with fluorescence detection

A novel method, dispersive liquid-liquid microextraction combined with liquid chromatography-fluorescence detection is proposed for the determination of three beta-blockers (metoprolol, bisoprolol, and betaxolol) in ground water, river water, and bottled mineral water. Some important parameters, such as the kind and volume of extraction and dispersive solvents, extraction time, pH, and salt effect were investigated and optimized. In the method, a suitable mixture of extraction solvent (60 μL carbon tetrachloride) and dispersive solvent (1 mL acetonitrile) were injected into the aqueous samples (5.00 mL) and the cloudy solution was observed. After centrifugation, the enriched analytes in the bottom CCl(4) phase were determined by liquid chromatography with fluorescence detection. Under the optimum conditions, the enrichment factors (EFs) for metoprolol, bisoprolol, and betaxolol were 180, 190, and 182, and the limits of detection (LODs) were 1.8, 1.4, and 1.0 ng L(-1) , respectively. A good linear relationship between the peak area and the concentration of analytes was obtained in the range of 3-150 ng L(-1) . The relative standard deviations (RSDs) for the extraction of 10 ng L(-1) of beta-blockers were in the range of 4.6-5.7% (n = 5). Compared with other methods, dispersive liquid-liquid microextraction is a very simple, rapid, sensitive (low limit of detection), and economical (only 1.06 mL volume of organic solvent) method, which is in compliance with the requirements of green analytical methodologies.     

High performance liquid chromatography determination of doxorubicin and daunorubicin in plasma using UV detection and column switching

A method for the determination of doxorubicin and daunorubicin in plasma is described. The plasma is injected directly into a loop column and then washed with water. After switching the injection valve, the sample is separated on a phenyl column using detection at 254 nm. The detection limit is 10 ng/mL, the coefficient of variation is 7% for 100 ng/mL of doxorubicin and 4% for 200 ng/mL of daunorubicin.     

硫化镉纳米微粒作探针共振瑞利散射测定某些蒽环类抗癌药物

在pH=5.0—9.0的水溶液中, 硫化镉纳米微粒[(CdS)n]与蒽环类抗生素米托蒽醌(MXT)、 表柔比星(EPI)和柔红霉素(DNR)凭借静电引力及疏水作用力结合, 形成粒径更大的聚集体, 导致共振瑞利散射(RRS)的增强并产生新的RRS光谱, 最大的RRS峰位于292 nm(MXT体系)、 285 nm(DNR体系)和315 nm(EPI体系). 与此同时还观察到二级散射(SOS)和倍频散射(FDS)强度明显提高. 其最大SOS峰位于540 nm(MXT体系)和560 nm(EPI及DNR体系), 而最大的FDS峰分别位于335 nm(MXT体系)、 320 nm(EPI体系)和330 nm(DNR体系). 在一定条件下, 3种散射强度(ΔI)均与药物的浓度成正比, 反应具有高灵敏度, 对于3种药物的检出限在3.6—9.1 ng/mL之间. 其中(CdS)n-MXT体系灵敏度最高, 对MXT的检出限分别为4.1 ng/mL(RRS)、 3.8 ng/mL(SOS)和3.6 ng/mL(FDS). 据此发展了一种用纳米硫化镉作探针, 灵敏、 简便并快速测定蒽环类抗癌药物的共振瑞利散射新方法.     

以L-酒石酸正己酯-硼酸配合物作为反相液相色谱手性流动相添加剂拆分5种β-受体阻滞剂

本文以L-酒石酸正己酯-硼酸配合物为手性流动相添加剂,建立了普萘洛尔、艾司洛尔、美托洛尔、比索洛尔、索他洛尔和阿替洛尔六种β-受体阻滞剂的反相高效液相色谱手性分离方法。对影响对映体分离的主要因素：L-酒石酸正己酯、硼酸浓度,缓冲溶液种类、浓度、pH值和有机改性剂-甲醇含量等进行了详细考察。最佳色谱条件为：Venusil MP-C18色谱柱（4.6 mm × 250 mm,5 μm）,流动相为15 mmol/L乙酸铵-甲醇（体积比为20: 80或30: 70,含60 mmol/L硼酸,70 mmol/L L-酒石酸正己酯,醋酸调节pH值6.00）,检测波长214 nm。在最佳分离条件下,五对对映体（普萘洛尔、艾司洛尔、美托洛尔、比索洛尔、索他洛尔）可以分别获得基线分离。