水产品中己烷雌酚、己烯雌酚与双烯雌酚残留的毛细管电泳测定

建立了毛细管电泳-紫外检测法测定水产品中己烷雌酚(HXS)、己烯雌酚(DES)及双烯雌酚(DIES)残留的新方法。研究了缓冲体系的酸度、浓度、添加剂、分离电压、进样时间及温度等对组分分离的影响。在检测波长为200 nm,分离电压为20 kV,运行缓冲液为50 mmol/L硼砂-25 mmol/L氢氧化纳(pH12.3,含30%的N,N-二甲基甲酰胺)的条件下,3种目标组分在14 min内达到基线分离。HXS、DES与DIES的质量浓度与峰面积分别在2.0~120、1.0~100、1.0~100 mg/L范围内呈良好线性,相关系数(r2)分别为0.9998、0.9992、0.9994,检出限为0.3~0.9 mg/L。将该方法用于鲫鱼中3种雌酚类激素的检测,结果令人满意。     

流动注射阻抑化学发光法测定己烯雌酚

基于在碱性介质中,己烯雌酚对N-溴代丁二酰亚胺-鲁米诺化学发光体系的阻抑作用,建立了测定己烯雌酚的流动注射化学发光分析新方法,探讨并优化了流动注射化学发光的分析条件。该方法测定己烯雌酚的线性范围为1.5×10-8~2.6×10-7g/mL,检出限为5.0×10-9g/mL,对1.0×10-7g/mL的己烯雌酚标准溶液进行11次测定,相对标准偏差为2.6%。并应用于饲料、己烯雌酚片剂中的己烯雌酚的测定。     

混合胶束毛细管电动色谱法测定片仔癀中有效成分

采用混合胶束毛细管电动色谱法(mixMs-MEKC)同时分离检测片仔癀中的三七皂苷R1、人参皂苷Rg1、麝香草酚、人参皂苷Rb1及牛磺胆酸钠5种有效成分。实验发现,采用单一胶束5种目标化合物不能完全分离,当采用胆酸钠-十二烷基硫酸钠(SC-SDS)二元混合胶束时5种化合物达到完全分离。实验优化了混合表面活性剂的浓度、缓冲溶液pH值、分离电压和进样时间等条件对分离效果的影响。在最优化的电泳条件下,5种化合物在16min内得到基线分离,且线性关系良好,检测限(S/N=3)分别为0.2μg/mL、0.08μg/mL、0.01μg/mL、0.2μg/mL、0.2μg/mL。将该方法应用于片仔癀中上述化合物含量的测定,获得较为满意的结果     

双胶束电动毛细管色谱测定复方化学消毒剂中聚六亚甲基单胍、聚六亚甲基双胍、醋酸洗必泰和苄索氯铵

建立了双胶束电动毛细管色谱(MEKC)分离测定复方化学消毒剂中有效成分聚六亚甲基单胍(PHMG)、聚六亚甲基双胍(PHMB)、醋酸洗必泰(CHA)及苄索氯铵(BTC)的新方法。以50.2 cm(有效长度:40 cm)×50 μm i.d.未涂层熔融石英毛细管为分离柱,20 mmol/L硼砂+30 mmol/L十二烷基硫酸钠(SDS)+5 mmol/L脱氧胆酸钠(SD)+0.8 g/L聚乙二醇 20000为分离缓冲溶液。详细研究了分离缓冲溶液中各组分浓度、样品提取液对分离的影响。4种物质的检出限和定量限均分别为1 mg/L和3 mg/L。4种物质的校正峰面积与相应质量浓度在3~140 mg/L范围内,均具有良好的线性关系,相关系数均大于0.999。回收率在84.1%~109.6%间,相对标准偏差(RSD)均低于6%。用该法测定了11件复方化学消毒剂样品中PHMG、PHMB、CHA和BTC,与产品标识值基本吻合。该法可成功区分单胍与双胍,且操作简单,适用于消毒产品的质量监督。     

离子液体修饰毛细管胶束电动色谱法分离测定槲皮素、绿原酸和异槲皮甙

建立了一种离子液体(1-乙基-3-甲基咪唑四氟硼酸盐,1E-3M I-TFB)修饰毛细管胶束电动色谱法分离测定异槲皮甙、绿原酸和槲皮素的方法。研究了缓冲溶液的酸度和浓度、牛磺胆酸纳的浓度以及1E-3M I-TFB对分离的影响。分离的最佳条件为:25 mmol/L硼砂-磷酸二氢钾(pH 9.0)-40 mmol/L牛磺胆酸钠-1‰(V/V)1E-3M I-TFB,电压16 kV。在优化条件下,3种分析物在11 m in内可以得到良好的分离。异槲皮甙、绿原酸和槲皮素的峰面积和浓度分别在0.02~0.40、0.02~0.20和0.08~0.60 g/L浓度范围内呈良好的线性;线性相关系数分别为0.9998、0.9988和0.9991;3种物质基于峰面积的相对标准偏差分别为:2.48%,2.56%和3.03%;基于迁移时间的相对标准偏差分别为1.12%、1.46%和1.59%;检出限(S/N=3)分别为:异槲皮甙,0.0050 g/L;绿原酸,0.0045 g/L;槲皮素,0.0040 g/L。将此方法应用于分离测定欧亚旋覆花中的异槲皮甙、绿原酸和槲皮素,取得良好结果。     

电堆积-非水毛细管电泳法同时分离测定虎杖中的有效成分

建立了电堆积富集-非水毛细管电泳同时分离测定中药虎杖中的大黄素、白藜芦醇和虎杖苷的新方法.对各种影响因素做了系统的研究,确立了中药虎杖中3种有效成分的最佳电堆积和分离条件,以甲醇为非水介质,30mmol/L NaAc-4 mmol/L NaOH-2 mmol/L CTAB溶液为背景电解质,运行电压为-25 kV,在220 nm波长下紫外检测.该法已应用于中药虎杖中大黄素、白藜芦醇和虎杖苷同时分离测定.     

环糊精修饰毛细管胶束电动色谱同时分离检测橙皮苷和柚皮苷对映体

本文利用环糊精修饰毛细管胶束电动色谱法(CD-MEKC)同时分离检测橙皮苷和柚皮苷对映体。实验优化的条件为:以60mmol/L胆酸钠(SC)+30mmol/L羟丙基-β-环糊精(HP-β-CD)+20 mmol/L NaH2PO4-100 mmol/L NaOH(pH=9.0,97%(V/V))+3%(V/V)甲醇为运行缓冲液,分离电压25kV,紫外检测波长214nm。在上述最佳条件下,橙皮苷和柚皮苷对映体在9min内得到完全分离,橙皮苷对映体的检测限(S/N=3)分别为0.13μg/mL和0.25μg/mL;柚皮苷对映体的检测限(S/N=3)分别为0.14μg/mL和0.07μg/mL。将所建立的方法用于胃苏颗粒制剂中橙皮苷和柚皮苷的对映体测定,回收率在86.0%~113.2%之间。     

核苷酸与β-环糊精及硼酸盐的络合作用在高效毛细管电泳分离核苷酸中的应用

核苷酸和β-环糊精(β-CD)及硼酸盐之间存在络合作用，可应用于核苷酸的高效毛细管电泳分离，在10mmol/L β-CD和20mmol/L硼酸盐存在时，实现了8种单磷酸核苷酸的分离测定；讨论了pH值、β-CD浓度、硼酸盐浓度及分离电压对分离和络合作用的影响。     

毛细管区带电泳技术快速分离检测爆炸残留物中的无机离子

利用间接紫外毛细管区带电泳方法完成了对爆炸残留物中7种无机离子(K+,NH+4,NO-2,NO-3,SO2-4,ClO-3,ClO-4)的分离检测。阳离子测定采用的缓冲体系为10 mmol/L吡啶（pH 4.5）-3 mmol/L冠醚,K+和NH+4在2.6 min内达到基线分离,检出限分别为0.25 mg/L和0.10 mg/L(S/N=3)。阴离子测定采用的缓冲体系为40 mmol/L硼酸-1.8 mmol/L重铬酸钾-2 mmol/L硼酸钠（pH 8.6）,氢氧化四甲铵为电渗流改性剂,5种阴离子在4.6 min内达到基线分离,检出限为0.10～1.85 mg/L。该方法已成功地应用于实际爆炸物样品种类的判定分析,取得了很好的结果。     

毛细管区带电泳技术快速分离检测爆炸残留物中的无机离子

利用间接紫外毛细管区带电泳方法完成了对爆炸残留物中7种无机离子(K+,NH+4,NO-2,NO-3,SO2-4,ClO-3,ClO-4)的分离检测。阳离子测定采用的缓冲体系为10 mmol/L吡啶（pH 4.5）-3 mmol/L冠醚,K+和NH+4在2.6 min内达到基线分离,检出限分别为0.25 mg/L和0.10 mg/L(S/N=3)。阴离子测定采用的缓冲体系为40 mmol/L硼酸-1.8 mmol/L重铬酸钾-2 mmol/L硼酸钠（pH 8.6）,氢氧化四甲铵为电渗流改性剂,5种阴离子在4.6 min内达到基线分离,检出限为0.10～1.85 mg/L。该方法已成功地应用于实际爆炸物样品种类的判定分析,取得了很好的结果。     

大体积进样-乙腈盐堆积-胶束扫集毛细管电动色谱法对马来酸氯苯那敏的测定

建立了大体积进样-乙腈盐堆积-胶束扫集毛细管电动色谱法测定马来酸氯苯那敏片中马来酸氯苯那敏的新方法,并考察了样品中乙腈和NaCl浓度对分离效果的影响.结果表明,以12 mmol/L四硼酸钠-50 mmol/L硼酸- 50 mmol/L十二烷基硫酸钠(SDS)为缓冲液(含10%甲醇,pH9.1),以70%乙腈- 200m...     

On-line coupling of pressurized capillary electrochromatography with end-column amperometric detection for analysis of estrogens

An improved technique, pressurized capillary electrochromatography (pCEC) coupling with end-column amperometric detection (AD), was developed and used for the separation and determination of estrogens. The effects of pH value, composition of mobile phase, concentration of the surfactant sodium dodecyl sulfate (SDS) and applied voltage on separation were investigated. The electrochemical oxidation of diethylstilbestrol (DES), dienestrol (DE), and hexestrol (HEX) could be reliably monitored with a carbon electrode at 0.9 V (vs. Ag/AgCl). The pCEC analyses were performed on a capillary separation column packed with 3 microm C18 particles with an acetonitrile/water (31%: 69%) mobile phase containing Tris buffer (5 mmol/L, pH 4.5) and 4 mmol/L SDS. High voltage up to 12 kV reduced the retention time dramatically and still provided a baseline resolution. In addition, supplementary pressure prevented bubble formation and provided reliability and reproducibility of the pCEC performance. The detection limits for the three estrogens ranged from 1.2 to 2.2x10(-7) mol/L, about 10 20-fold lower than those obtained with pCEC-UV detection. To evaluate the feasibility and reliability of this system, the proposed pCEC-AD method was further demonstrated with fish muscle samples spiked with estrogens.     

在线扫集-胶束毛细管电动色谱法测定复方氨酚烷胺胶囊中的3种有效成分

以在线扫集-胶束毛细管电动色谱法(Sweeping-MEKC)测定了复方氨酚烷胺胶囊中的马来酸氯苯那敏、咖啡因和对乙酰氨基酚3种有效成分。考察了缓冲溶液pH值、SDS浓度、分离电压及进样时间等对分离效果的影响。优化条件:以未涂层熔融石英毛细管(55 cm×50μm,有效柱长35 cm)为分离柱;环境温度25℃;80 mmol/L十二烷基磺酸钠+20 mmol/L NaH2PO4(pH 2.2)+15%乙腈为缓冲体系,分离电压-20kV,进样时间60 s(H=20.0 cm),测量波长210 nm。在该条件下氯苯那敏、咖啡因和对乙酰氨基酚在25min内出峰,峰面积RSD均小于4%;线性范围分别为2.45～39.17、1.61～25.76、1.58～25.28 mg/L;检出限(S/N=3)分别达139、34、24μg/L,回收率分别为96%～101%、98%～102%、96%～102%。     

Determination of hydrocortisone,polymyxin B and Zn-bacitracin in pharmaceutical preparations by micellar electrokinetic chromatography

A new, simple and accurate micellar electrokinetic chromatography (MEKC) method is established for quantification of hydrocortisone, polymyxin B and Zn-bacitracin in local pharmaceutical preparations. The separation was carried out at 25 degrees C and 25 kV, using a 15 mmol L(-1) phosphate-15 mmol L(-1) borate buffer (pH 8.2), 60 mmol L(-1) sodium dodecylsulfate (SDS), and 10% methanol-water (v/v) as background electrolyte. Under these conditions the analysis takes about 23 min. The method has been applied for quantifying these compounds in two different commercial pharmaceutical products and the method gave good results when compared with a reference spectrophotometric multivariate calibration method.     

Separation of structurally related estrogens using isocratic elution pressurized capillary electrochromatography

In this paper, the pressurized capillary electrochromatography (pCEC) with UV detection was utilized for the separation and determination of three structurally related estrogens, such as diethylstilbestrol (DES), hexestrol (HEX) and dienestrol (DE), which were difficult to be separated by capillary electrophoresis (CE) and HPLC due to their similarity in the structure and charge-to-mass ratios. Experiments were carried out in a commercially available pCEC instrument using a capillary column packed with 3 microm octadecyl silica (ODS). Surfactant sodium dodecyl sulfate (SDS) was introduced in the mobile phase to enhance the speed of analysis. The effective factors on the retention time and separation resolution, such as the applied voltage, supplementary pressure, the pH and the concentration of the buffer solution, the concentration of SDS, and the content of acetonitrile in the mobile phase, were evaluated. Based on the investigation, 31% (v/v) acetonitrile and 69% (v/v) of 10 mmol/L phosphate buffer (pH 6.5) containing 1.0 mmol/L SDS at an applied voltage of -12 kV and a supplementary pressure of 1000 psi were found to be the optimal conditions for pCEC to separate the three estrogens. The method also had been applied to the analysis of fish muscle samples spiked with estrogens.     

Separation of Biphenyl Nitrile Compounds by Microemulsion Electrokinetic Chromatography with Mixed Surfactants

A mixture of nine biphenyl nitrile compounds with high hydrophobicity and similar structures was successfully separated by microemulsion electrokinetic chromatography (MEEKC) within 30 rain. The buffer system contained 100 mmol/L sodium dodecyl sulfate (SDS), 80 mlnol/L sodium cholate (SC), 0.81% heptane, 7.5% n-butanol, 10% acetonitrile and 10 mmol/L borate. The addition of SC, organic modifiers, sample preparation and temperature all showedremarkable effect on the separation. Meanwhile, the MEEKC method was briefly compared with micellar electrokinetic chromatography (MEKC) method.     

磺胺类人工合成甜味剂的毛细管电泳/电导法分离检测

采用15 mmol/L Tris-10 mmol/L H3BO3-0.2 mmol/L EDTA为电泳运行液,0.2%四乙烯五胺为电渗流抑制剂,融硅石英毛细管(45 cm×50 μm),负高压分离(-15 kV),柱端接触式电导检测,建立了磺胺类人工合成甜味剂(糖精钠、安赛蜜、甜蜜素)的高效毛细管电泳/电导法分离检测方法.糖精钠、安赛蜜、甜蜜素的线性检测范围分别为0.8 ～120、1.1 ～120、1.5 ～120 μmol/L,检出限分别为0.3、0.4、0.6 μmol/L.详细讨论了电泳运行液的组成、浓度以及进样方式对灵敏度和分离度的影响.该法用于市售饮料中3种甜味剂的分离检测,结果满意.     

粒子群算法优化中药化学成分的毛细管电泳分离条件

建立了一种基于粒子群优化算法的毛细管电泳条件辅助优化方法。以丹参为研究对象,将改良的色谱指数方程用于评价酚酸类成分的电泳分离性能,用粒子群优化算法对分离条件进行全局寻优,获得最佳的区带电泳分离条件(5.0 mmol/L硼砂,18.5 mmol/L磷酸二氢钠,6.1%乙腈,运行电压18.2 kV)。为进一步改善分离,在所获优化条件下添加50.0 mmol/L SDS,在胶束电动毛细管色谱分离模式下使酚酸类成分(原儿茶醛、丹参素、丹酚酸B等)得到更好分离。本方法准确可靠,可推广应用于其他复杂化学体系的毛细管电泳分离条件优化。     

聚合离子液体为添加剂的毛细管电泳法用于快速高效分离饮料中7种有机酸

用一种聚合离子液体(聚1-乙烯基-3-丁基咪唑溴盐)为添加剂,以毛细管电泳法(CE)快速直接分离饮料中7种有机酸(丙二酸、酒石酸、抗坏血酸、反丁烯二酸、苯甲酸、山梨酸和柠檬酸)。详细考察了几种影响分离效果的条件,最佳背景电解质条件是125 mmol/L磷酸二氢钠缓冲液(pH 6.5)添加0.01 g/L聚合离子液体。7种分析物在4 min内能够快速高效分离(105000~636000 塔板/m),迁移时间的标准偏差(n=3)都不大于0.0213 min。7种分析物的检出限（以信噪比为3计）在0.001与0.05 g/L之间。这种方法被应用于一种美年达葡萄汁饮料中的有机酸检测。柠檬酸钠、苯甲酸和山梨酸被检测出,含量分别是2.64、0.10和0.08 g/L,其加标回收率分别为100.3%、100.7%和131.7%。该方法简单、快速、低廉,可以用作食品中有机酸添加剂的检测。     

Baseline separation of α and β‐acids homologues and isomers in hop (Humulus lupulus L.) by CD‐MEKC‐UV

An alternative method for simultaneous baseline separation of α and β‐acids homologues and isomers in hop by CD‐MEKC with UV detection was proposed. The optimized background electrolyte was composed of 30 mmol/L sodium tetraborate solution, 45 mmol/L sodium dodecyl sulfate, 20 mmol/L β‐cyclodextrin and 10% v/v acetonitrile. The instrumental conditions were evaluated by using a 3³ Box‐Benhken experimental design. In order to demonstrate the applicability of the method, 21 hop samples from different varieties were analyzed. The repeatability intra‐ and interday tests were performed and relative standard deviations lower than 7% for area and migration times were observed. The present method comprehended 8 min analysis time and revealed to be faster and more efficient when compared to previous reports from literature.