微流控芯片非接触电导法分离检测5种阳离子

建立了微流控芯片非接触电导法快速分离检测5种常见阳离子的分析方法。考察了缓冲溶液的种类、浓度和pH、添加剂、检测器的激发电压和激发频率等因素对离子分离及检测的影响。根据离子的峰高和信噪比(S/N),研究了非接触电导检测器的激发电压和激发频率对不同阳离子检测的影响规律。以pH 3.8的15 mmol/L精氨酸(Arg)+15 mmol/L酒石酸+2 mmol/L18-冠醚-6+10%(V/V)甲醇作为运行缓冲液,检测器激发电压100 Vp-p、激发频率40 k Hz,可在70 s内实现NH~+_4,K~+,Na~+,Mg~(2+)和Ca~(2+)的分离检测,5种离子的迁移时间重现性RSD均在1.5%以内。结果还表明,非接触电导检测器激发电压和激发频率对5种阳离子检测的影响规律和最佳检测条件基本相同。     

几种无机阳离子的毛细管电泳-电容耦合非接触电导分离检测

研制出电容耦合非接触电导检测器,检测器使用两个5 mm长的管状电极套在分离毛细管的外面,电极相距2 mm并与函数信号发生器连接。对影响检测器检测限和线性范围的激发频率、峰峰电压(V p-p )等因素进行了考察,结果发现频率为25～35 kHz、V p-p 在30 V时检测器有最佳的信号噪声比;以2-N-吗啡啉乙磺酸(MES)-组氨酸(His)为缓冲体系,用自制的检测器对Li+,Na+,K+,Mg 2+ ,Ca 2+ 和Ba 2+ 等几种常见的无机离子进行了毛细管电泳分离检测,优化了缓冲溶液     

一种以发光二极管为激发光源的荧光检测器

利用高亮度发光二极管作为激发光源组装了一荧光检测器并应用于毛细管电泳检测 ;激发光斑与毛细管检测池的耦合通过透镜加光阑组合方式实现 ;光纤用于收集并传输荧光信号 ,增加了光学系统的灵活性和紧凑性 ;光阑、检测池和光纤之间的校准简单、方便 ;用荧光素和异硫氰酸荧光素衍生的氨基酸考察了体系性能 ,最小检测浓度为0.18μmol/L(S/N=5) ,在2×10-7～4×10-5 mol/L范围内表现出较好的线性关系(r=0.993) ,结果表明该系统灵敏度达到了普通荧光检测器的指标     

毛细管电泳-电容耦合非接触电导检测法对运动员营养补剂中人体必需支链氨基酸的检测

建立了运动员营养补剂中3种人体必需支链氨基酸(缬氨酸、亮氨酸、异亮氨酸)的毛细管电泳-电容耦合非接触电导检测(CE-C4D)测定方法。通过研究电泳时背景电解质种类、浓度以及电导检测器的激发电压,激发频率等参数的影响,确定最佳的实验条件为采用未涂层熔融石英毛细管(60 cm×75μm,有效长度50 cm),以5.0 mol/L的乙酸为背景电解质;C4D检测器激发电压为40 V,激发频率为600 kHz;运行电压为+15 kV,温度为25℃。3种氨基酸在50.0~1000.0μmol/L范围内线性关系良好,线性相关系数(R2)均大于0.9994,加标回收率在98.6%~105.4%之间,方法的检出限为14.88μmol/L。方法已应用于运动员蛋白营养补剂中的支链氨基酸的测定。     

高效液相色谱-化学发光法检测牛奶中磺胺类药物残留

以4种磺胺类药物(Sulfonamides, SAs), 即磺胺脒(Sulfaguanidine, SGD)、磺胺嘧啶(sulfadiazine, SDZ)、磺胺噻唑(sulfathiazole, STZ)和磺胺二甲嘧啶(Sulfamethazine,SMZ)为分析物,基于其在碱性介质中对Ag配合物-鲁米诺(Luminol)与Ni配合物鲁米诺两化学发光体系发光强度均具有抑制作用的性质,建立了高效液相色谱-化学发光法检测牛奶中4种磺胺类药物的方法.将化学发光体系作为高效液相色谱的新型检测器,并对两种化学发光体系的检测器性能进行了比较.4种磺胺药物经高效液相色谱分离后,分别与Ag-Luminol及Ni-Luminol化学发光体系作用.色谱条件为:反相C18分离柱(250 mm × 4.6 mm,5 μm);0.1%甲酸-甲醇为流动相(V/V);梯度洗脱;流速1 mL/min.化学发光条件:Ag、Ni-Luminol两体系中,Ag配合物浓度1.4×10.-4 mol/L(含0.12 mol/L NaOH);Ni配合物浓度1.5×10.-5 mol/L(含0.12 mol/L NaOH);Luminol浓度均为1.2×10.-7 mol/L;试剂流速均为1.0 mL/min.在最佳的分离检测条件下,Ag-Luminol体系检测4种磺胺类药物的检出限分别为0.15、0.96、1.10和1.50 μg/mL,加标回收率为81.0%~101.5%;Ni-Luminol体系检测SGD、SDZ、STZ 3种磺胺类药物的检出限分别为1.5、17.2和16.8 μg/mL,加标回收率为83.9%~110.8%.相比之下,Ag-Luminol体系作为高效液相色谱检测器更佳.应用本方法对牛奶中4种磺胺类药物残留量进行检测,结果令人满意.     

离子色谱电导-紫外检测器串联法测定海洋沉积物孔隙水中的4种阴离子EI北大核心CSCD

建立了电导-紫外检测器串联离子色谱法测定海洋沉积物孔隙水中的NO_2^-,NO-3,PO_4^(3-)和SO2-4,选用高通量色谱柱和保护柱,以1.9 mmol/L Na HCO3-3.2 mmol/L Na2CO3为淋洗液,采用电导和紫外检测器同时检测4种离子,抑制电导检测器检测PO_4^(3-)和SO2-4,紫外检测器检测NO_2^-和NO-3以消除高含量Cl-的影响。在优化的色谱条件下,单个样品测试时间为6 min,NO_2^-,NO-3,PO_4^(3-)和SO2-4的方法检出限分别为17.2,32.0,144和22.7μg/L。对2个真实样品进行检测,各离子的相对标准偏差(RSD,n=6)为1.5%~5.3%,对样品进行加标回收实验,加标回收率为95.6%~105.6%。     

毛细管电泳非接触式电导检测快速分离和测定氨基糖苷类抗生素

用带非接触式电导检测器的毛细管电泳法(CE)分离并测定了3种氨基糖苷类抗生素,即缺少较强紫外吸收发色团或荧光发射基团的庆大霉素(GE)、卡那霉素(KA)和链霉素(ST)。对影响CE分析的因素进行了研究,并确定以下几项优化的参数:①电泳介质:选用35mmol·L-12-(N-吗啉)乙磺酸溶液和15mmol·L-1组氨酸溶液组成的缓冲体系;②分离电压:17kV;③激发电压:60V;④激发频率:600kHz;⑤进样时间:5s。在所选最佳条件下,上述3种抗生素可在10min内达到完全分离。上述3种抗生素的质量浓度在一定范围内与其相应的峰面积呈线性关系,其检出限(3S/N)依次为0.2,0.4,0.2mg·L-1。     

离子色谱电导-紫外检测器串联法测定海洋沉积物孔隙水中的4种阴离子

建立了电导-紫外检测器串联离子色谱法测定海洋沉积物孔隙水中的NO_2~-,NO-3,PO_4~(3-)和SO2-4,选用高通量色谱柱和保护柱,以1.9 mmol/L Na HCO3-3.2 mmol/L Na2CO3为淋洗液,采用电导和紫外检测器同时检测4种离子,抑制电导检测器检测PO_4~(3-)和SO2-4,紫外检测器检测NO_2~-和NO-3以消除高含量Cl-的影响。在优化的色谱条件下,单个样品测试时间为6 min,NO_2~-,NO-3,PO_4~(3-)和SO2-4的方法检出限分别为17.2,32.0,144和22.7μg/L。对2个真实样品进行检测,各离子的相对标准偏差(RSD,n=6)为1.5%~5.3%,对样品进行加标回收实验,加标回收率为95.6%~105.6%。     

高效液相色谱-荧光-紫外串联测定土壤中16种多环芳烃

采用高效液相色谱-荧光-紫外检测器串联测定土壤中16种多环芳烃。通过液相色谱柱、荧光激发和发射波长等条件的优化,实现16种多环芳烃组分基线完全分离来和15种多环芳烃荧光高灵敏度检测,并通过荧光-紫外串联检测来提高定性的准确度等。在优化的实验条件下,荧光检测器的检出限为0.015~0.8μg/L;紫外检测器检出限为0.4~30μg/L;方法精密度为0.58%~1.36%(荧光)、1.13%~5.48%(紫外);样品加标回收率为76.4%~111%。     

新型环氧水解酶手性拆分环氧氯丙烷的气相色谱法

建立了一种用于快速测定生物酶转化体系中手性环氧氯丙烷的气相色谱法。采用ZKAT-ChiralB毛细管柱,FID检测器检测,内标法计算含量。(R)-环氧氯丙烷和(S)-环氧氯丙烷在0.012～0.461g/mL呈良好的线性关系,RSD为1.3%、1.7%,回收率为97.6%、101.3%。     

Fundamental aspects of contactless conductivity detection for capillary electrophoresis. Part II: Signal-to-noise ratio and stray capacitance

The signal-to-noise ratio of a contactless conductivity detector for capillary electrophoresis was examined for different cell arrangements and operating parameters. The best signal-to-noise ratios, and hence the best detection limits, are obtained for frequencies which give highest sensitivity. Comparative experiments for three different excitation voltages (20, 100, and 200 V(pp)) showed that the best signal-to-noise ratios were achieved for the highest excitation voltage of 200 V(pp). Low conductivity of the background electrolyte solution is mandatory to obtain lowest noise levels, and also the improvement on applying high excitation voltages was best for the electrolyte solution with lowest conductivity. The diameter of the electrodes was found to have only a negligible effect, so that a tight fitting of the electrodes to the external diameter of the capillary is not necessary. A cell without shielding between the two electrodes showed significant direct coupling (stray capacitance) and lower signal-to-noise ratios for all experimental conditions used. A serious distortion of the peak shapes was also observed for this cell arrangement.     

Determination of pharmaceuticals classified as emerging pollutants using capillary electrophoresis with capacitively coupled contactless conductivity detection

A study on the simultaneous separation of 13 pharmaceutical products by capillary electrophoresis with capacitively coupled contactless conductivity detection was presented. The parameters of the background electrolyte, such as pH, organic additives as well as types and concentrations of cyclodextrins (CD) were studied. The optimal separation conditions were achieved with a background electrolyte consisting of 9 mM Tris/5 mM lactic acid at pH 8.0, containing 5% n-propanol, 0.025% gamma-CD, 0.075% hydroxyl-beta-CD and 0.15% dimethyl-beta-CD. Limits of detections ranged from 61 to 1676 microg/L (S/N=3) and the relative standard deviations for migration time and peak area were below 2 and 6%, respectively. This demonstrated the potential of the capillary electrophoresis-capacitively coupled contactless conductivity detection method for biomedical and environmental analysis, as shown in the determination of pharmaceuticals identified as emerging pollutants in water samples.     

常规离子色谱系统-电容耦合非接触式电导检测器的构建

通过考察电极长度及电极间距、检测管管径及材质、激励信号频率、电压和波形等参数对信噪比的影响,研制了一种适用于常规型离子色谱系统的电容耦合非接触式电导检测器（C⁴D）。在抑制模式下,该检测器对常见无机阴离子（F^-、Cl^-、NO₂^-、Br^-、NO₃^-和SO₄^2-）的检出限（信噪比=3）为0.02~0.08 μmol/L;峰面积的相对标准偏差<1.8%（n=6）;在0.1~10 μmol/L范围内上述6种无机阴离子线性关系良好,相关系数（R²）>0.999。自制C⁴D的主要性能参数与商品化接触式电导检测器相当。该检测器具有结构简单、成本低廉、无电极污染等优点,有利于拓展离子色谱的应用范围。     

Integration of a contactless conductivity detector into a commercial capillary cassette. Detection of inorganic cations and catecholamines

A contactless conductivity detector integrated into the capillary cassette of Agilent ^3DCE equipment is described. The detector is user-friendly, compact and easily modified. The UV detector of the ^3DCE equipment is available parallel with the contactless conductivity detector increasing the detection power. Two electrolyte solutions, 2-(N-morpholino)ethanesulfonic acid–histidine solution (20 mM, pH 6.0) and ammonium acetate (10 mM, pH 4.0), were used as the separation media for inorganic cations and organic catecholamines, respectively. The detection limit for all metal cations except barium was under 0.5 mg/l, and that for four catecholamines was ca. 10 mg/l. This last value was the same order of magnitude as achieved with parallel UV detection.     

毛细管电泳-荧光/非接触电导组合型检测器的研制

报道了一种毛细管电泳-荧光／非接触电导组合型检测器。该检测器共用非接触电导检测池,实现了双检测器响应同步。优化了非接触电导检测系统中激发电压信号及其频率;荧光检测是用发光二极管作为激发光源,用光纤收集并传输荧光信号至光电倍增管。用无机金属离子和异硫氰酸荧光素评价该体系,结果表明,该检测器达到了任一单类型检测器性能指标。     

Optimization of the high-frequency contactless conductivity detector for capillary electrophoresis

Two constructions of the high-frequency contactless conductivity detector that are fitted to the specific demands of capillary zone electrophoresis are described. The axial arrangement of the electrodes of the conductivity cell with two cylindrical electrodes placed around the outer wall of the capillary column is used. We propose an equivalent electrical model of the axial contactless conductivity cell, which explains the features of its behavior including overshooting phenomena. We give the computer numerical solution of the model enabling simulation of real experimental runs. The role of many parameters can be evaluated in this way, such as the dimension of the separation channel, dimension of the electrodes, length of the gap between electrodes, influence of the shielding, etc. The conception of model allows its use for the optimization of the construction of the conductivity cell, either in the cylindrical format or in the microchip format. The ability of the high-frequency contactless conductivity detector is demonstrated on separation of inorganic ions.     

Significant parameters in the optimization of MALDI-TOF-MS for synthetic polymers

One of the most significant issues in any analytical practice is optimization. Optimization and calibration are key factors in quantitation. In matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), instrument optimization is a limitation restricting quantitation. An understanding of the parameters that are most influential and the effects of these parameters on the mass spectrum is required for optimization. This understanding is especially important when characterizing synthetic polymers by MALDI-TOF-MS, due to the breadth of the polymer molecular mass distribution (MMD). Two considerations are important in quantitation, additivity of signal and signal-to-noise (S/N). In this study, the effects of several instrument parameters were studied using an orthogonal experimental design to understand effects on the signal-to-noise (S/N) of a polystyrene distribution. The instrument parameters examined included detector voltage, laser energy, delay time, extraction voltage, and lens voltage. Other parameters considered were polymer concentration and matrix. The results showed detector voltage and delay time were the most influential of the instrument parameters for polystyrene using all trans-retinoic acid (RA) as the matrix. These parameters, as well as laser energy, were most influential for the polystyrene with dithranol as the matrix.     

A chip-based capillary electrophoresis-contactless conductivity microsystem for fast measurements of low-explosive ionic components

A miniaturized analytical system for separating and detecting inorganic explosive residues, based on the coupling of a micromachined capillary electrophoresis (CE) chip with a contactless conductivity detector is described. The low electroosmotic flow (EOF) of the poly(methylmethacrylate) (PMMA) chip material facilitates the rapid switching between analyses of cations and anions using the same microchannel and run buffer (and without an EOF modifier), and hence offers rapid (< 1 min) measurement of seven explosive-related cations and anions. Experimental parameters relevant to the separation and detection processes have been optimized. Addition of a 18-crown-6 ether modifier has been used for separating the peaks of co-migrating potassium and ammonium ions. The ionic-explosive microchip system combines the distinct advantages of contactless conductivity detection with the attractive features of plastic CE microchips. The new microsystem offers great promise for monitoring explosive-related ions at the sample source, with significant advantages of speed/warning, efficiency, cost, or sample size.     

High-performance liquid chromatography with contactless conductivity detection for the determination of peptides and proteins using a monolithic capillary column

Gradient programs were applied to the determination of peptides and proteins in HPLC with contactless conductivity detection. A monolithic capillary column was used for the fast and sensitive determination of the biochemical species in acidic mobile phases consisting of acetic acid or trifluoroacetic acid in various concentrations of acetonitrile in water. The drift in baseline, which is caused by conductivity changes during the elution program, was minimized by careful optimization of the composition of the mobile phase and remaining drift was removed by computational baseline normalization. The flow rate from a conventional HPLC pump was reduced to a flow rate suitable for capillary systems using a pre-column flow splitter and a final total flow rate of 1.65 microl/min was used for all capillary HPLC separations. The contactless conductivity detector was positioned directly on the outlet capillary of the separation column and positively charged peptides and proteins were determined as sharp and symmetrical peaks. Detection limits in a concentration range from 3.7 x 10(-8) to 5.1 x 10(-7)M and a reproducibility of peak areas and peak heights between 2.3% and 7.3% were achieved for all biochemical species tested.     

微流控芯片非接触电导法测定感冒药中盐酸伪麻黄碱和氢溴酸右美沙芬

研究了用微流控芯片非接触式电导法分离检测感冒药日夜百服咛片中的两种主要成分盐酸伪麻黄碱和氢溴酸右美沙芬的方法。优化条件为:缓冲液20 mmol/L Tris 20 mmol/L H3BO3(pH=8.0);进样电压300 V;进样时间10.0 s;分离电压3.0 kV。非接触电导检测器激发电压60 V(Vp-p),频率60 kHz。两种成分的线性范围分别为20~1000 mg/L和10~1000 mg/L;检出限分别为10和5.0 mg/L;样品回收率分别为99.3%和97.6%。