反相高效液相色谱-脉冲电化学检测法测定重组人生长激素中异丙基-β-D-硫代半乳糖苷（英文）

采用反相高效液相色谱(RP-HPLC)-脉冲电化学检测(PED)法测定了重组人生长激素(rhGH)中的诱导剂异丙基-β-D-硫代半乳糖苷(IPTG)。rhGH样品经超滤离心后,用超纯水提取,经C18色谱柱分离,用脉冲电化学器检测。结果表明,样品中添加0.02~0.10 mg/L的IPTG,其回收率为100%~102%,相对标准偏差(n=3)小于10%。在优化的条件下,IPTG的检出限可达1μg/L(0.1 pmol,25μL)。该方法简便高效,具有良好的灵敏度、回收率和重复性。     

高效液相色谱-串联质谱法测定葡萄中的吡效隆和赤霉素

采用高效液相色谱-串联质谱法（HPLC-MS/MS）建立了葡萄果实中吡效隆（CPPU）和赤霉素（GA3）两种植物生长调节剂残留量的定性定量分析方法。样品用0.5%甲酸水溶液和乙腈（体积比4:1）混合溶剂提取,经Strata-X固相萃取净化,使用Agilent SB-C18 色谱柱（50mm×2.1mm,1.8μm）,以0.5%甲酸水溶液-乙腈为流动相,流量0.3mL/min,采用电喷雾离子化源（ESI）多反应监测（MRM）模式下HPLC-MS/MS检测。在最佳检测条件下,得到吡效隆和赤霉素在2.0～100.0μg/L检测范围内线性关系良好,相关系数大于0.999;检出限(LOD)分别为0.3μg/L、0.5μg/L,定量限(LOQ)分别为1.0μg/L、2.0μg/L,回收率和精密度均能达到要求,表明该法准确,可用于葡萄中吡效隆和赤霉素残留量测定。     

超高效亲水作用色谱-串联质谱法检测水中的苦味酸及苦氨酸

建立了一种超高效亲水作用色谱-串联质谱检测水中苦味酸及其降解产物苦氨酸的方法。采用Acquity UPLC BEH HILIC亲水作用色谱柱（100 mm×2.1 mm,1.7 μm,Waters）分离,用电喷雾电离串联质谱检测。地表水样品经过0.2 μm滤膜过滤之后即可直接进样,加标回收率达89%~107%;废水样品通过固相萃取（SPE）净化后进样分析,加标回收率达72%~101%。方法重复性的相对标准偏差为4.9%~14.7%。本方法对苦味酸和苦氨酸的检出限分别为0.1 μg/L和0.3 μg/L。此方法快速、准确,特异性强,灵敏度高,样品前处理方法简便易行,适用于地表水、废水样品的检测。     

超高效液相色谱-串联质谱法测定稻田水产品中毒死蜱残留

以QuEChERS作为样品前处理手段，采用超高效液相色谱-串联质谱（UPLC-MS/MS）检测技术，建立了稻田水产品中毒死蜱残留的检测方法。样品经乙腈提取，由0.2 g乙二胺-N-丙基硅烷（PSA）和1.2 g无水硫酸镁分散萃取净化，采用Hypersil GOLD C₁₈色谱柱（100 mm×2.1 mm，5 μm）进行分离，用加热大气压电喷雾电离源、正离子模式进行扫描，在选择反应监测模式下检测，基质匹配标准曲线外标法定量。结果表明，毒死蜱在0.5~100.0 μg/L范围内线性关系良好，相关系数大于0.999；毒死蜱的加标回收率为86.2%~103.6%，相对标准偏差为3.5%~7.6%（n=6），检出限为0.25 μg/kg，定量限为0.5 μg/kg。该方法简单、快速、灵敏，能够满足稻田水产品中毒死蜱残留的检测需求。     

柱后加碱-高效阴离子交换色谱-脉冲安培检测法测定农田土中草铵膦、氨甲基膦酸和草甘膦残留

应用柱后加碱-高效阴离子交换色谱-脉冲安培检测法同时测定了农田土中草铵膦、氨甲基膦酸和草甘膦的残留。土壤样品用2 mmol/L氢氧化钠振荡提取，混匀后依次用0.22 μm滤膜、IC-C₁₈和IC-Na柱处理。滤液中的3种目标物和共存离子经IonPacAS11-HC离子色谱柱分离，柱后加碱-脉冲安培检测器检测。结果表明，草铵膦和草甘膦质量浓度在20.0~1000 μg/L、氨甲基膦酸质量浓度在5.0~400 μg/L范围内线性关系良好，相关系数均大于0.999。草铵膦、氨甲基膦酸和草甘膦的检出限分别为0.08、0.02和0.04 mg/kg，回收率为80.2%~106%，相对标准偏差为0.7%~5.0%（n=6）。该方法抗干扰性强、灵敏度和准确度高，操作简便快捷，适用于农田土中草铵膦，氨甲基膦酸和草甘膦残留量的检测。     

超高效液相色谱-三重四极杆质谱法测定血浆和尿液中马桑亭和马桑宁

建立了超高效液相色谱-三重四极杆质谱联用技术测定血浆和尿液中马桑中毒标志物马桑亭和马桑宁的方法。血浆和尿液样品经固相支持液液萃取法提取净化后，溶于15%（v/v）甲醇水溶液中，以Cortecs C₁₈色谱柱（100 mm×2.1 mm，1.6 μm）作为分析柱进行分离，电喷雾负离子多反应监测（MRM）模式下检测，以氟苯尼考作为内标物，基质工作曲线内标法定量。血浆和尿液中马桑亭和马桑宁的平均加标回收率为86.2%~110%，相对标准偏差为5.1%~14.6%（n=6），血浆中马桑亭和马桑宁的检出限（S/N=3）分别为0.01 μg/L和0.1 μg/L，尿液中马桑亭和马桑宁的检出限分别为0.03 μg/L和0.3 μg/L。本法简单、灵敏、准确，可用于血浆和尿液中马桑亭和马桑宁的中毒检测。     

超高效液相色谱法测定婴幼儿配方奶粉中的叶黄素

建立了采用超高效液相色谱测定婴幼儿配方奶粉中叶黄素的检测方法。样品经丙酮溶液提取,离心分层,冷冻离心去脂,YMC Carotenoid C30色谱柱（150 mm×4.6 mm,3 μm）分离。以甲醇-甲基叔丁基醚（70：30,v/v）为流动相等度洗脱,流速为0.5 mL/min,进样量5 μL,柱温25 ℃,二极管阵列检测器检测,检测波长445 nm。方法在20~500 μg/L范围内线性关系良好;相关系数为0.999 9;定量限为20 μg/L。添加量在50、250、2000 μg/kg时,叶黄素的回收率为97.9%~104.4%。本方法操作简便,结果准确,灵敏度高,适用于婴幼儿奶粉中叶黄素的测定。     

气相色谱法测定苹果和土壤中的高效氯氟氰菊酯

建立了改进的QuEChERS-气相色谱检测苹果和土壤中高效氯氟氰菊酯残留的分析方法,考察和评价了苹果和土壤两种基质对高效氯氟氰菊酯的基质效应。苹果和土壤样品均用乙腈提取,经石墨化碳黑（GCB）净化后直接进样分析。结果表明：在优化后的QuEChERS条件下,高效氯氟氰菊酯在0.05~10 mg/L范围内线性关系良好,相关系数（R²）大于0.999,检出限为0.12~0.15 μg/kg,定量限为0.38~0.50 μg/kg。用基质标准曲线定量时,高效氯氟氰菊酯在土壤和苹果中的回收率分别为88.29%~97.65%和80.70%~98.69%。苹果和土壤样品对高效氯氟氰菊酯都表现出基质增强效应。该方法的回收率均能达到残留分析要求,用基质配制标准溶液能够有效、方便地校正气相色谱-电子捕获检测器测定高效氯氟氰菊酯残留时的基质效应,且能应用于苹果和土壤实际样品的检测。     

柱前衍生-超高效液相色谱-串联四极杆质谱法测定茶叶中乙撑硫脲的残留

建立了茶叶中乙撑硫脲残留的柱前衍生-超高效液相色谱-串联四极杆质谱检测方法。样品采用乙腈提取,提取液经QuEChERS基质分散固相萃取净化后采用9-芴基甲基氯甲酸酯（FMOC-CL）柱前衍生;衍生溶液经BEH-C18色谱柱（100 mm×2.0 mm,1.7 μm）分离后进入串联四极杆质谱仪检测,采用同位素内标法定量;流动相为0.1%（v/v）甲酸-乙腈。该方法对茶叶样品检出限为1.3 μg/kg,定量限为4.2 μg/kg;加标回收率在97.7%~107.5%之间,相对标准偏差（RSD,n=6）在2.1%~10.0%之间;在1.0~203.4 μg/L范围内线性回归系数r为0.9993。该方法灵敏度高,重现性好,定性定量准确,可有效满足对茶叶中乙撑硫脲残留检测的要求。     

阴离子交换色谱-脉冲安培法检测味精中的硫化物

建立了阴离子交换色谱柱分离、脉冲安培检测器测定味精中微量硫化物的方法。味精样品经2 g/L氢氧化钠溶液直接溶解并过滤后直接进样,硫离子与高浓度谷氨酸等阴离子在IonPac AS7阴离子色谱柱(250 mm×4 mm)上可实现较好的分离。以100 mmol/L氢氧化钠-500 mmol/L醋酸钠-0.5%乙二胺为淋洗液等度淋洗,6 min内可完成一次样品测定。脉冲安培检测器检测硫离子的检出限(25 μL进样,信噪比为3)为0.3 μg/L,并具有较宽的线性范围(0.001～1 mg/L),样品加标回收率为94.2%～99.0%。应用该方法检测99%味精、增鲜味精和加盐味精样品中的硫化物,结果表明该方法具有简便快捷、高选择性、高灵敏度等优点。     

Determination of ethyl glucuronide in urine using reversed-phase HPLC and pulsed electrochemical detection (Part II)

A direct, versatile method for the determination of ethyl glucuronide (EtG), a biomarker of ethanol consumption, in urine has been developed using reversed-phase liquid chromatography with pulsed electrochemical detection (PED). EtG and methyl glucuronide (MetG), which serves as an internal standard, are readily separated using a mobile phase consisting of 1% acetic acid/acetonitrile (98/2, v/v). Post-column addition of NaOH allows for the detection of all glucuronides using PED at a gold working electrode. Upon optimization, EtG was found to have a limit of detection of 0.03 μg/mL (7 pmol; 50 μL injection volume) and repeatability at the limit of quantitation of 1.7%R.S.D. (relative standard deviation). Solid-phase extraction (SPE) using an aminopropyl phase was used to remove interferents in urine samples prior to their analysis. Compound recovery following SPE was approximately 50 ± 2%. The forensic utility of this method was further validated by the analysis of 29 post-mortem urine specimens, whose results agreed strongly with certified determinations.     

Coupling Capillary Electrophoresis and Pulsed Electrochemical Detection

Pulsed electrochemical detection (PED) is an excellent method for detection of analytes that normally foul electrodes. In PED, the detection electrode is first cleaned at a high positive potential, then reactivated at a negative potential dissolving the surface oxide, and finally used to oxidize the analyte at a moderate positive potential. Due to the advantages and versatility of PED, many different variations of the detection waveform can be found in literature. This review focuses on application of PED to CE and in particular, the most commonly used modes: pulsed amperometric detection (PAD) and integrated pulsed amperometric detection (iPAD).     

离子色谱积分脉冲安培法同时测定血浆中阿仑膦酸钠、帕米膦酸钠、伊班膦酸钠和利塞膦酸钠

建立了离子色谱积分脉冲安培检测器(IPAD)同时检测血浆中阿仑膦酸钠、帕米膦酸钠、伊班膦酸钠和利塞膦酸钠的方法。采用Dionex AS18 (250 mm×2 mm)和AG18 (50 mm×2 mm)色谱柱在24 mmol/L NaOH溶液中进行分离;对多电位波形参数优化以达到最大信噪比;采用优化后的波形方法对4种双膦酸盐类药物进行检测,具有良好的线性(r2为0.9972～0.9995)和重现性(峰面积的相对标准偏差(RSD)为0.84%～1.37%)及较高的灵敏度(检出限为0.061～0.18 μg/mL)。4种双膦酸盐在该方法中有很好的保留且有较好的分离度,与之前报道的衍生后检测方法相比,该方法不用衍生,更简单而易于操作。将该方法成功地用于人体血浆中双膦酸盐类的检测,其回收率为80.81%～97.32%, RSD为1.46%～3.02%。     

以天青Ⅰ为介体的纳米金颗粒增强的葡萄糖传感器

采用层层自组装的方法和异种电荷互相吸引的原理,将Nafion修饰在金电极上固载带正电荷的天青Ⅰ,并利用天青Ⅰ中的氨基固载纳米金,再通过纳米金将酶固定在金电极表面,制成了葡萄糖传感器.采用循环伏安法和交流阻抗法,研究了金电极表面组装各层之后的电化学特征,以及电极对葡萄糖的电化学催化作用. 结果表明,天青Ⅰ不仅可以固定酶和纳米金,而且还可以在酶和电极之间有效地传递电子.在优化的实验条件下,该传感器对葡萄糖响应的线性范围为5.1×10-6 ~4.0×10-3 mol/L,检出限(S/N=3)为1.0 μmol/L.该生物传感器显示出较好的稳定性和抗干扰能力,将其用于人体血清中葡萄糖的测定,结果令人满意.     

A review of pulsed electrochemical detection following liquid chromatography and capillary electrophoresis

Pulsed electrochemical detection (PED) has progressed as a highly sensitive and selective detection technique following aqueous-based separation systems over the past three decades. The application of on-line pulsed potential cleaning to electrocatalytic noble metal electrodes has significantly increased the number of applications formerly achieved with conventional electrochemical (EC) detection. Electrochemical cells are easily miniaturized, providing the ability to apply detection by PED at microelectrodes and onto microchips utilizing electrophoretic separations. In addition, recent advances in PED waveforms and instrumentation have enabled the detection technique to be easily coupled with high pressure separation systems which require rapid detection to maintain separation integrity. As a result, advanced applications for the determination of carbohydrates as well as the expansion of PED for the detection of other organic aliphatic compounds have been recently accomplished. This review will focus on developments and methods utilizing PED following liquid chromatography (LC) and capillary electrophoresis (CE). Publications are reviewed in chronological order to emphasize the advancement of the detection method and the sustained relevance of its applications.     

2,5-巯基-1,3,4-硫代二氮唑自组装金电极测定银(I)

制备了2,5-巯基-1,3,4-硫代二氮唑(DMTD)自组装单分子层修饰金电极,用电化学阻抗谱进行了表征,研究了Ag(I)在该电极上的电化学行为并用差分脉冲阳极溶出伏安法对其进行了测定。结果表明,DMTD/Au电极能显著提高Ag(I)测定的灵敏度和选择性,Ag(I)浓度在9.4×10-7～8.0×10-6mol/L范围内,氧化峰电流与Ag(I)呈现良好的线性关系,检出限为2×10-7 mol/L。该自组装电极可用于水样的测定。     

Modification of gold electrode by self-assembled 2-mercapto benzothiazole for the determination of Hg2+

An electrochemical method was developed for the determination of mercury using polycrystalline gold electrode modified by self-assembled monolayers (SAMs) of 2-mercaptobenzothiazole (MBTH). Morphological and electrochemical characterisation of the self-assembled structure of MBTH was performed using atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS) measurements. The monolayer of MBTH has shown high affinity for Hg²⁺. The limit of detection for the determination of Hg²⁺ using the MBTH SAMs modified gold electrode was obtained as 0.421 μg L^?1. The pre-concentration of Hg²⁺ at open circuit potential is beneficial for the onsite monitoring of mercury concentration in water samples.     

Development of a Liquid Chromatography/Amperometric Detection Method for the Determination of Multiresidue Sulfonamide Antibiotics in Meat‐Based Baby Foods

Sulfonamides were oxidized at a polycrystalline gold electrode in neutral buffered phosphate medium at pH 7 and the electrochemical behavior was investigated using cyclic voltammetry technique. A liquid chromatography methodology based on the C₁₈ reverse phase for the simultaneous separation of nine sulfamides, was studied and optimized. The amperometric detector using a polycrystalline gold substrate as working electrode and operating under pulsed amperometric detection mode (PAD) was tested for the determination of the selected molecules. Under optimal chromatographic and amperometric conditions, the limit of detection of the investigated sulfamides are comprised between 1 µM and 0.05 µM and the dynamic linear range spanned generally over three orders of magnitude. A liquid extraction procedure based on the use of acetonitrile solvent was tested and proposed for the quantitative extraction of sulfonamides from homogenized meat samples. The analytical method was successful tested for the determination of sulfonamides in homogenized meat‐based baby foods with reproducibility and recovery levels ranged between 5.0 % and 7.6 %. and 86 %–106 %, respectively.     

Determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with electrochemical detection.

The cyclic voltammetric behavior of acetaldehyde and the derivatized product with 2,4-dinitrophenylhydrazine (DNPHi) has been studied at a glassy carbon electrode. This study was used to optimize the best experimental conditions for its determination by high-performance liquid chromatographic (HPLC) separation coupled with electrochemical detection. The acetaldehyde-2,4-dinitrophenylhydrazone (ADNPH) was eluted and separated by a reversed-phase column, C18, under isocratic conditions with the mobile phase containing a binary mixture of methanol/LiCl(aq) at a concentration of 1.0 x 10(-3) M (80:20 v/v) and a flow rate of 1.0 mL min(-1). The optimum condition for the electrochemical detection of ADNPH was +1.0 V vs. Ag/AgCl as a reference electrode. The proposed method was simple, rapid (analysis time 7 min) and sensitive (detection limit 3.80 microg L(-1)) at a signal-to-noise ratio of 3:1. It was also highly selective and reproducible [standard deviation 8.2% +/- 0.36 (n = 5)]. The analytical curve of ADNPH was linear over the range of 3-300 mg L(-1) per injection (20 microL), and the analytical recovery was > 99%.     

固相萃取-高效液相色谱-蒸发光散射检测法同时检测食品中5种人工合成甜味剂

建立了高效液相色谱-蒸发光散射检测仪(HPLC-ELSD)同时检测食品中安赛蜜、糖精钠、甜蜜素、三氯蔗糖和阿斯巴甜5种甜味剂的方法。甜味剂经0.1%(v/v)甲酸缓冲液提取后,利用C18固相萃取小柱净化浓缩,以3 μm C18柱为分离柱,0.1%(v/v)甲酸(氨水调节pH=3.5)-甲醇(61:39, v/v)为流动相,经高效液相色谱法分离,蒸发光散射检测器进行检测。结果表明,5种甜味剂在30～1000 mg/L的范围内,具有良好的线性关系(相关系数大于0.997);在3个添加水平下,样品的平均回收率为85.6%～109.0%,相对标准偏差小于4.0%;方法检出限(LOD,信噪比(S/N)=3)分别为安赛蜜2.5 mg/L、糖精钠3 mg/L、甜蜜素10 mg/L、三氯蔗糖2.5 mg/L及阿斯巴甜5 mg/L。该方法简单、灵敏、操作成本低,可用于不同形态食品中多种甜味剂的同时检测。