气动毛细管微滴进样-化学发光法测定酚磺乙胺

传统的化学发光(CL)分析有分立式取样和流动注射式两种方式,各有优缺点,目前国内外的仪器都采用手动进样或电动进样方法,速度和进样量均很难精确控制,对微升级的样品尤为困难,另外也无法实现在线分析。本文提出的气动毛细管微滴进样化学发光(AFCM-CL)检测法是以气体压力作为     

毛细管电泳芯片的电特性研究

摘要芯片毛细管电泳技术是20世纪末发展起来的一项新兴分析技术.本文研究了毛细管电泳芯片的电特性.在一定的电压范围内,玻璃和有机玻璃芯片的伏安特性都有线性段区域,因此在此线性段内研究芯片的电特性可以将其简化为电阻模型.根据基尔霍夫电流定律建立了毛细管电泳芯片的等效电阻模型,研究了分离电压以及分离焦耳热的影响因素,为毛细管电泳芯片的优化设计提供了理论依据.     

腐蚀接头毛细管电泳电化学发光系统用于临床药物的快速检测

毛细管电泳作为近年来发展起来的分离分析技术,以其分辨率高、分离时间短及样品试剂用量小等特点而被广泛用于环境、生物以及临床分析^[1].基于三联吡啶钌的电化学发光检测技术结合了电化学检测的微型、原位和化学发光的高灵敏,可用于胺类、醇类、DNA以及免疫分析^[2].毛细管电泳和电化学发光检测技术的结合可以成为一种低费用、低成本及简便快速的分离分析技术.     

A procedure to determine the viscosity function from experimental data of capillary flow

The accurate calculation of the viscosity η as function of the shear rate &γdot; from capillary viscometry is still a matter of debate in the literature. In fact, this problem involves the inversion of an integral equation, which leads to multiple solutions due to the unavoidable noise present in the experimental data. The purpose of this work is to develop an efficient procedure to determine the viscosity function from experimental data of capillary flow without presenting the difficulties inherent in other methods discussed previously in the literature. The system identification procedure is used here to estimate the parameters of a viscosity model, which is appropriately selected for the fluid under study through preliminary calculations involving the apparent shear rate – shear stress data. Once the model is chosen by satisfying criteria for the fit goodness and its parameters are evaluated, a smooth and continuous function η(γdot;) is obtained in the range of experimental shear rates. The procedure proposed is also applicable to fluids in shear flow that present two Newtonian plateaus, as it is typically found in macromolecular dilute solutions. The mean value theorem of continuous functions is used to reduce significantly the computational time. Received: 15 November 1999 Accepted: 7 November 2000     

Concurrent solvent recondensation large sample volume splitless injection

Concurrent Solvent Recondensation Large Sample Volume (CRS‐LV) splitless injection overcomes the limitation of the maximum sample volume to 1–2 μL valid for classical splitless injection. It is based on control of the evaporation rate in the vaporizing chamber, utilization of a strong pressure increase in the injector resulting from solvent evaporation, and greatly accelerated transfer of the sample vapors from the injector into the inlet of an uncoated precolumn by recondensation of the solvent. The sample vapors are transferred into the column as rapidly as they are formed in the injector (concurrent transfer). 20–50 μL of liquid sample is injected with liquid band formation. The sample liquid is received by a small packing of deactivated glass wool positioned slightly above the column entrance at the bottom of the vaporizing chamber. Solvent evaporation strongly increases the pressure in the injector (auto pressure surge), provided the septum purge outlet is closed and the accessible volumes around the vaporizing chamber are small, driving the first vapors into the precolumn. Transfer continues to be fast because of recondensation of the solvent, obtained by keeping the oven temperature below the pressure‐corrected solvent boiling point. The uncoated precolumn must have sufficient capacity to retain most of the sample as a liquid. The experimental data show virtually complete absence of discrimination of volatile or high boiling components as well as high reproducibility.     

Analysis of polynuclear aromatic hydrocarbons by glass capillary gas chromatography using simultaneous flame ionization and electron capture detection

The possibility of simultaneous application of an electron capture (ECD) and a flame ionization detector (FID) connected to a glass capillary column for analyzing polynuclear aromatic hydrocarbons (PNA) has been investigated. The ECD/FID ratio is determined for 46 PNA compounds. The ratios vary from 0.02 to 117 with relative standard deviations better than 20 percent determined from 10 replicate analyses. The results suggest that the method may be used for obtaining additional evidence in identifying PNA in environmental samples. Impurities and transformation products in the standard were identified by computerized glass capillary gas chromatography/mass spectrometry. Quinones and diones are responsible for the high EC-response determined in some trace components in the standard. An application of the method is shown for PNA from particulates in urban atmospheres.     

On-column liquid–liquid–liquid microextraction coupled with base stacking as a dual preconcentration method for capillary zone electrophoresis

A simple and efficient dual preconcentration method of on-column liquid–liquid–liquid microextraction (LLLME) coupled with base stacking was developed for capillary zone electrophoresis (CZE) in this paper. Four N-methyl carbamates were used as target compounds to evaluate the enrichment means. The carbamates in sample solutions (donor phase) were extracted into a dodecanol phase immobilized on a porous hollow fiber, hydrolyzed and back extracted into 0.20 μL running buffer (acceptor phase) of 30 mmol/L methylamine hydrochloride (pH 11.6) containing 0.5 mmol/L tetradecyltrimethylammonium bromide inside the hollow fiber, stacked further with 0.5 mol/L NaOH injected at −10 kV for 60 s, and separated by CZE. Analytical parameters affecting the LLLME, base stacking and CZE were investigated, including sample solution volume, pH and temperature, extraction time, stirring rate, buffer component, buffer pH, NaOH concentration, stacking time, etc. The enrichment factors of the carbamates were higher than 1100. The relative standard deviation (RSD) of peak height and limits of detection (LODs) were 4.5–5.5% (n = 6) and 2–4 ng/mL (S/N = 3) for standard solutions, respectively. The proposed method was applied to the analysis of vegetable and fruit samples with the RSD less than 6.0% (n = 3) and LODs of 6–10 ng/g (S/N = 3). The calibration solutions were prepared by diluting the stock solutions with blank sample solutions, and the calibration concentrations ranged from 0.012 to 1.0 μg/mL (r > 0.9951). The analytical results demonstrated that the LLLME coupled with base stacking was a simple, convenient and reliable on-column sample pretreatment method for the analysis of anionic analytes in CZE.     

微流蒸发光散射检测器的研制及评价

构建了适用于纳升级到微升级流量的毛细管分离体系的微流蒸发光散射检测器(μELSD),实现了其与毛细管液相色谱(eLC)的联用.对雾化器孔径和雾化毛细管内径、蒸发管内径和长度、光散射池尺寸、雾化毛细管位置和辅助载气流量等参数进行了优化.在最优条件下,微流蒸发光散射检测器检出限为直接进样葡萄糖1 ng(S/N＞ 10),线性范围0.01～1.0 μg,重复性好,峰面积RSD(n=6)为0.4％,峰高RSD(n=6)为0.3％.本检测器已成功应用cLC-μELSD平台,使用C18毛细管色谱柱(内径250 μm),0.1％甲酸铵溶液(pH 4.5)-甲醇(60∶40,V/V)为流动相,分离检测了3种常用甜味剂,表明本研究构建的系统可以应用于实际分离检测中,具有分析时间快、溶剂消耗量少、样品需求量小的优点.     

毛细管气相色谱法测定5种中草药中有机氯农药的残留量

建立了怀牛夕等 5种中草药中六六六及滴滴涕异构体含量的气相色谱分析方法。样品以石油醚 +丙酮在索氏提取器中提取 ,提取液以浓硫酸净化。采用SE 30弹性石英毛细管柱分离样品 ,GC ECD检测六六六、滴滴涕农药的残留量。方法的线性范围为 5 .7× 10 - 7～ 2 .8× 10 - 4μg ;最小检测量为 1.3× 10 - 1 4～ 2 .5×10 - 1 2 g ;加样平均回收率为 88.8%～ 99.1% ;RSD为 0 .9%～ 5 .3%。     

快速溶剂萃取-毛细管电泳法测定土壤和底泥中磺胺类药物残留

建立了一种快速溶剂萃取(ASE)-毛细管电泳检测土壤和底泥中磺胺类药物残留的新方法。通过优化ASE的萃取条件,选取甲醇为萃取剂,在70℃、10.3 MPa的条件下提取土壤和底泥样品中的磺胺类药物。毛细管电泳检测磺胺嘧啶,磺胺甲基嘧啶和磺胺间二甲氧基嘧啶的标准曲线具有良好的线性(r>0.999)。方法的定量限(LOQ,S/N=10)为0.056～0.070 mg/kg。日内相对标准偏差在0.4%～2.5%之间,日间相对标准偏差在1.2%～4.6%之间。3个加标水平0.100、0.625、2.50 mg/kg的平均回收率在82%～103%之间,RSD≦4.3%。方法已用于土壤和底泥样品前处理和磺胺类药物残留检测。