肌肽类生物活性肽的毛细管电泳在线富集技术

建立了毛细管区带电泳(CZE)在线富集3种肌肽类活性肽(肌肽、鹅肌肽和高肌肽)的两种简便有效的方法。一种是大体积进样反向压力排除基体富集（LVSRP）技术,即通过流体动力学进样,在不改变电源极性的条件下,利用反向压力排除样品基体,电堆积富集后进行CZE分离;另一种是大体积进样电渗流排除基体富集（LVSEP）技术,即通过流体动力学进样,于运行缓冲液中加入溴化十六烷基三甲基铵(CTAB)动态修饰毛细管表面,通过电渗流排除样品基体,改变电源极性后进行CZE分离。与常规CZE相比,LVSRP技术和LVSEP技术使检测灵敏度提高了40~60倍。对影响两种富集过程的一些因素进行了研究,在最优富集条件下考察本方法的线性范围为0.080~5.0 μmol/L。对3种生物活性肽的检测限(S/N=3)分别为LVSRP 41~58 nmol/L,LVSEP 35~43 nmol/L。     

Fast Determination of Clenbuterol and Salbutamol in Feed and Meat Products Based on Miniaturized Capillary Electrophoresis with Amperometric Detection

The fast separation capability of a novel miniaturized capillary electrophoresis with an amperometric detection (μCE‐AD) system was demonstrated by determining clenbuterol and salbutamol in real samples. The effects of several factors such as the acidity and concentration of the running buffer, the separation voltage, the applied potential and the injection time on CE‐AD were examined and optimized. Under the optimum conditions, the two β‐agonists could be baseline separated within 60 s at a separation voltage of 2 kV in a 90 mmol/L H₃BO₃‐Na₂B₄O₇ running buffer (pH 7.4), which was not interfered by ascorbic acid and uric acid. Highly linear response was obtained for above compounds over three orders of magnitude with detection limits ranging from 1.20×10^?7 to 6.50×10^?8 mol/L (S/N=3). This method was successfully used in the analysis of feed and meat products with relatively simple extraction procedures.     

Metal‐binding Sites of N‐Acetylneuraminic Acid

Sialic acid represents a group of thirty derivates of neuraminic acid with various substituents at the amino residue and the alcoholic hydroxy groups. We analysed the behaviour of the tetracoordinated metal ions palladium(II) and silicon(IV) against the most important derivative N‐acetylneuraminic acid (NANA). The molecular structures were assigned by a combined ¹H, ¹³C and ²⁹Si NMR‐spectroscopic approach. Despite the presence of many different functional groups, the coordination chemistry of NANA with Pd^II follows established rules. Coordination via the N‐acetyl‐group – sterically impossible with Pd^II – was realised with Si^IV.     

场增强样品堆积-毛细管电泳法测定山楂粉中的氨基酸

采用场增强样品堆积-毛细管电泳法建立了在线富集氨基酸的分析方法,用于中药山楂中水解氨基酸的检测,并进行了回收率实验. 采用富集电压为-20 kV,进样压力为3 psi,进样时间为50 s,紫外检测波长为214 nm,运行缓冲溶液为270 mmol/L乙酸-270 mmol/L乙酸钠（pH=4.15）-6%（V/V）乙腈溶液,分离电压为17 kV,组氨酸、精氨酸、色氨酸、酪氨酸、缬氨酸、苯丙氨酸、亮氨酸、苏氨酸、丙氨酸、甘氨酸、谷氨酸和门冬氨酸等12种氨基酸在50 min内达到分离,检出限在0.000 3~0.08 μg/mL之间.     

在线样品浓缩毛细管区带电泳分析毛发中的苯丙胺类毒品

建立了毛细管区带电泳(CZE)的在线场放大样品堆积(FASS)方法。采用含有40%乙烯乙二醇的100 mmol/L磷酸盐二元缓冲液(pH 2.5),80%异丙醇的0.1 mmol/L磷酸样品溶液,利用缓冲体系与样品溶液体系电导率的差异,在毛细管中浓缩样品组分,对苯丙胺、甲基苯丙胺、亚甲基二氧基苯丙胺(MDA)、亚甲基二氧基甲基苯丙胺(MDMA)4种毒品进行了分离和定量测定,检测的灵敏度提高约1000倍。对于标准品的检出限可达到0.06μg/L。当样品浓度高于5μg/L时,分析的相对标准偏差在10%范围之内;用该方法对添加毒品的毛发进行了提取和测定,可检测到的添加浓度为1μg/g毛发。该方法可用于生物检材中苯丙胺类毒品的检测。     

毛细管电泳-场强放大堆积技术对制剂中磺胺嘧啶和磺胺甲噁唑的测定研究

利用高效毛细管电泳-场强放大柱内堆积技术分离测定磺胺嘧啶(SD)和磺胺甲噁唑(SMZ)。采用未涂层熔融石英毛细管柱(60.2 cm×75μm,有效长度50 cm),以50 mmol/L NaH2PO4(pH6.0)为运行缓冲液,分离电压27.5 kV,柱温25℃,检测波长214 nm进行测定。进样前压力进水3.42 kPa×12 s;电动进样-10kV×9 s。SD和SMZ的线性范围分别是0.05~10.00 mg/L(r=0.999 9),0.025~5.00 mg/L(r=0.999 4),检出限分别为1.74、1.39μg/L;将此方法应用于实际样品测定,SD回收率为98%~103%,SMZ回收率为97%~103%。     

非水介质毛细管电泳法测定野菊花中蒙花苷的含量

使用自行设计的毛细管电泳柱端安培检测系统,采用非水介质毛细管电泳法对野菊花中蒙花苷的含量进行测定.考察了缓冲溶液浓度及其pH值、非水介质的浓度、检测电位对测定的影响.在优化实验条件下,蒙花苷的质量浓度在2.0 ～80 mg/L范围内与峰高呈良好的线性关系,线性系数为0.999 6,检出限为0.20 mg/L,平均加标回...     

采用毛细管电泳电堆集富集技术分离与测定雪样中的痕量阳离子

以咪唑为背景电解质,以α－羟基异丁酸和１８－冠醚－６为络合剂,采用毛细管离子电泳间接紫外法,研究了发样中痕量ＮＨ４＾＋、Ｋ＾＋、Ｃａ＾＋、Ｍｇ＾２＋分离与测定的方法。通过向缓冲液中加入甲醇,使Ｃａ＾２＋、Ｎａ＾＋迁移顺序发生反转,有利于在Ｃａ＾２＋的浓度较高时少量Ｎａ＾＋的测定。采用电堆集富集技术,各离子的检测限达１×１０＾－７ｍｏｌ／Ｌ。以Ｌｉ＾＋作为内标,采用标准加入法对地样中的痕量阳离子进行     

Comparison of Pulsed Electrochemical Detection Modes Coupled with Microchip Capillary Electrophoresis

There is a need to develop analytical methods that are capable of rapidly measuring small biological markers in the field of metabolomics. Among others, carbohydrates play an important role biologically yet are traditionally hard to detect since they have no chromophore or fluorophore. In the present report, the first application of integrated pulsed amperometric detection (iPAD) coupled with microchip electrophoresis to the analysis of glucose, mannose, sucrose, maltose, glucosamine, lactose, maltotriose and galactose is demonstrated. iPAD is an electrochemical detection mode that can be used for direct detection of carbohydrates, amines and sulfur containing compounds. The effect of different solution parameters, including the buffer concentration, pH and the concentration of SDS on both separation and detection response was analyzed. In addition, a comparison study between PAD and iPAD was performed using glucose, glucosamine, sucrose and maltose as model carbohydrates.     

毛细管电泳样品电堆积富集过程影响因素的数值分析

毛细管电泳样品电堆积富集是一种通过缓冲溶液浓度的差异在毛细管中形成电场强度梯度,从而对样品进行浓缩的富集技术。本文在已有数学模型的基础上,对影响毛细管电堆积富集过程的因素进行了分析。计算结果发现,样品粒子表面所带的电荷电性以及带电量会影响粒子的电泳速度,进而影响富集过程;外加电势的大小会影响样品粒子到达检测窗口的迁移时间;而样品塞的初始长度则会影响样品所能达到的最大富集浓度以及达到最佳的富集效果所需要的时间。所得到的结果对样品电堆积富集技术的进一步完善具有一定的理论指导意义。     

Monitoring Homovanillic Acid and Vanillylmandelic Acid in Human Urine by Capillary Electrophoresis with Electrochemical Detection

A simple,rapid and low-cost method of separation and determination of homovanillic acid and vanillylmandelic acid in human urine was developed based on capillary zone electrophoresis/amperometric detection with high sensitivity and good resolution.     

高效毛细管电泳-安培法同时检测感冒药中的扑尔敏、扑热息痛和维生素C

以碳糊电极作工作电极,采用高效毛细管电泳 安培法对感冒药中的扑尔敏、扑热息痛和维生素Ｃ的同时检测进行了研究。重点探讨了检测电位、缓冲溶液添加剂对分离检测的影响。结果表明,方法简便、灵敏,适合于常规分析。     

高效毛细管电泳安培法测定肉苁蓉中松果菊苷的含量

采用毛细管电泳安培法建立了肉苁蓉中松果菊苷含量的检测方法,探讨了缓冲溶液种类、工作电位、分离电压、进样时间等对分离和检测的影响.在15 mmol/L硼砂缓冲溶液(pH 9.5),25 kV电压,0.6 V工作电位的条件下,松果菊苷的质量浓度在0.5～50.0 mg/L范围内与峰面积呈良好线性,相关系数为0.9994,检...     

基于毛细管电泳-安培检测的新生儿苯丙酮尿症早期无创诊断

首次采用毛细管电泳-安培检测法(CE-AD)同时测定了苯丙酮尿症(Phenylketonuria,PKU)患者尿液中的两种标志物:具有电活性的苯丙酮酸及非电活性的苯乙酸。考察了运行液添加剂、SDS浓度、工作电极电位等因素对分离和检测的影响。在优化实验条件下,两种标志物在15 m in内可实现基线分离。苯丙酮酸和苯乙酸的检出限(S/N=3)分别为0.50、0.92 mg/L。苯丙酮酸、苯乙酸浓度与峰高分别在3.0～1.0×103mg/L、2.0～5.0×103mg/L范围内呈良好线性,峰高与迁移时间的相对标准偏差分别为4.4%、3.2%(苯丙酮酸)和2.2%、4.3%(苯乙酸)。该方法已成功用于PKU患儿尿液中两种标志物的测定,且完全避免了尿液中尿酸对标志物测定的干扰,有望用于PKU患儿的早期无创诊断。     

毛细管电泳安培法分离测定安痛定注射液中安替比林和氨基比林的含量

毛细管电泳法;安痛定注射液;安替比林;氨基比林;安培检测     

Determination of Active Ingredients of Hawthorn by Capillary Electrophoresis with Electrochemical Detection

A method based on capillary electrophoresis with electrochemical detection has been developed for the separa-tion and determination of epicatechin,kaempferol,chlorogenic acid,4-hydroxybenzoic acid,quercetin and proto-catechuic acid in hawthorn for the first time.The effects of working electrode potential,pH and concentration ofrunning buffer,separation voltage and injection time on CE-ED were investigated.Under the optimum conditions,the analytes could be separated in a 60 mmol·L~(-1) borate buffer(pH 8.7)within 21 min.A 300 μm diameter carbondisk electrode has a good response at 0.95 V(vs.SCE)for all analytes.The response was linear over three ordersof magnitude with detection limits(S/N=3)ranging from 3×10~(-8) to 2×10~(-7) g·mL~(-1) for the analytes.The methodhas been successfully applied to the analysis of real sample,with satisfactory results.     

场放大进样-胶束扫集法测定升麻中3种有机酸

利用两种在线富集技术,对阿魏酸、异阿魏酸、咖啡酸同时测定的方法进行了研究.在胶束扫集的基础上,联用场放大进样,使富集倍数提高了约100倍;检出限降至4 μg/L,线性范围向下延伸到10 μg/L.胶束扫集电动色谱缓冲体系为90 mmol/L SDS 20 mmol/L Na2PO4(pH=2.20) 10%甲醇,分离电压20 kV.进样电压10 kV,进样时间21 s,进水时间210 s(H=20.0 cm),测量波长214 nm.讨论了SDS浓度、进样长度、进样电压等对分离效果的影响.在优化条件下,3种有机酸在14 min内出峰,峰面积RSD≤3.8%.方法检出限(μg/L)、线性范围(μg/L)、相关系数分别为:阿魏酸4.0、10～400、0.9982;异阿魏酸4.0、10～400、0.9970;咖啡酸5.0、10～400、0.9980.回收率为83.9%～114.3%.     

Separation of Organomercury Species Using Nonaqueous Capillary Electrophoresis Coupled with Sample Stacking and Electrokinetic Injection Techniques

A nonaqueous capillary electrophoresis (NACE) method, 30 mM ammonium acetate in methanol as background electrolyte (BGE), was developed for separation of the organomercury species without complexing reagents. The effects of different solutes and solvents in BGE were studied. Three species of organomercury, methylmercury, ethylmercury and phenylmercury, were separated well and all the number of theoretical plates were over 10⁶. The present NACE method was also coupled with sample stacking and electrokinetic injection techniques to enhance the detection sensitivity. Under the optimum conditions, the limit of detection (S/N = 3) is 18 ng mL⁻¹ and the linear relation range from 40 to 750 ng mL⁻¹ were obtained for methylmercury.     

Determination of Four Active Ingredients in Vc Yinqiao Tablets by Capillary Zone Electrophoresis with Amperometric Detection†

A simple, reliable and reproducible method, based on capillary zone electrophoresis with amperometric detection （CZE-AD）, has been developed for simultaneous determination of four active ingredients in Vc Yinqiao tablets including paracetamol, vitamin C, caffeic acid and chlorogenic acid. A carbon-disk electrode was used as working electrode and 0.95 V （versus SCE） was selected as detection potential. The optimal conditions of CZE experiment were 30 mmol·L^-1 borate solution （pH 9.5） as running buffer, 14 kV as separation voltage and 8 s （14 kV） as electro-kinetic sampling time. Under the selected optimum conditions, paracetamol, vitamin C, caffeic acid and chlorogenic acid could be perfectly separated within 22 min, and their detection limits （S/N=3） ranged from 5×10^-7 to 1 ×10^-6 mol·L^-1. This proposed method demonstrated good reproducibility with relative standard deviations of less than 3% for both migration time and peak current （n=7）. The utility of this method was demonstrated by monitoring a kind of compound medicine named Vc Yinqiao tablets and the assay results were satisfactory.     

毛细管电泳中移动反应界面法富集和检测尿样中的氧化苦参碱

采用建立在移动反应界面理论上的体系进行尿样中氧化苦参碱的富集与定量检测。与传统的毛细管电泳相比,体系中引入了富集缓冲溶液(富集相)和分离缓冲溶液(分离相)。优化的条件如下:样品缓冲溶液为20 mmol/L 甲酸钠(用氨水调节pH至10.70),富集缓冲溶液为40 mmol/L 甲酸-甲酸钠(pH 2.60),分离缓冲溶液为100 mmol/L 甲酸-甲酸钠(pH 4.80);样品相压力进样1.4 kPa×3 min,富集相压力进样1.4 kPa×7 min,紫外检测波长210 nm,电压21 kV。氧化苦参碱在2.2~65 mg/L的质量浓度范围内呈良好的线性关系(r=0.9991),检出限为0.74 mg/L,灵敏度比常规毛细管电泳方法提高约70倍,重现性良好。该方法已经成功地应用于尿样中氧化苦参碱的检测。