人尿中合成麻醉镇痛剂的系统分析

采用液－液萃取结合ＧＣ／ＭＳ选择离子的方法，建立了人尿中８种合成麻醉镇痛剂的分析方法，讨论了回收率和检测限问题，并成功地用于实际尿样检测。     

甲基睾酮人体代谢物的选择反应监控检测法

采用ＧＣ／ＭＳ／ＭＳ的选择反应监控（ＳＲＭ）法检测尿中甲基睾酮的人体代谢物，与ＧＣ／ＭＳ的选择离子检测（ＳＩＭ）法比较，ＳＲＭ法有更高的选择性和确证能力。该种检测方法的建立，可以更有效地判定阳性尿。     

β－阻断剂及其代谢产物的气相色谱分析研究（Ⅲ）──用固相提取及GC／MS法分析大鼠尿中5种β－阻断剂及其代谢物

用Ｓｅｐ－ｐａｋ柱固相提取、酶解、液－液萃取、衍生化及ＧＣ／ＭＳ分析等步骤，研究了大鼠尿中５种β－阻断剂，初步推断了多种代谢物的结构，建立了此类药物的分析方法。     

β—阻断剂及其代谢产物的气相色谱分析研究（Ⅲ）—用固相提取…

用Ｓｅｐ－ｐａｋ柱固相提取、酶解、液－液萃取、衍生化及ＧＣ／ＭＳ分析等步骤，研究了大鼠尿中５种β－阻断剂，初步推断了多种代谢物的结构，建立了此类药物的分析方法。     

用GC—MS法测定尿中可待因及其代谢物的浓度

建立了用ＧＣ－ＭＳ（ＳＩＭ）内标定量法快速测定人尿中可待因及其代谢物浓度的方法，样品经酸水解、乙醚／异丙醇提取，用ＭＳＴＦＡ－ＭＢＴＦＡ衍生化后进样于ＧＣ－ＭＳＤ，方法灵敏、准确，可用于监测吸毒者尿中可待因，吗啡类药物的浓度。本法已经受ＩＯＣ的１９９２年水平考试的考验。     

用GC－MS法测定尿中可待因及其代谢物的浓度

建立了用ＧＣ－ＭＳ（ＳＩＭ）内标定量法快速测定人尿中可待因及其代谢物浓度的方法。样品经酸水解、乙醚／异丙醇提取，用ＭＳＴＦＡ－ＭＢＴＦＡ衍生化后进样于ＧＣ－ＭＳＤ，方法灵敏、准确，可用于监测吸毒者尿中可待因、吗啡类药物的浓度。本法已经受ＩＯＣ的１９９２年水平考试的考验。     

β—阻断剂及其代谢产物的气相色谱分析研究：Ⅱ.GC／MS分析卡替洛尔…

本文用ＧＣ／ＭＳ法研究了国际奥委会药物禁用表中新增药卡替洛尔，吲哚洛尔及噻吗洛尔，从人尿中检出了药物原型及数种代谢产物，讨论了衍生化方法及代谢情况并给出了回收率及检测限数据。     

β－阻断剂及其代谢产物的气相色谱分析研究 Ⅱ．GC／MS分析卡替洛尔、吲哚洛尔、噻吗洛尔及其代谢产物

本文用ＧＣ／ＭＳ法研究了国际奥委会药物禁用表中新增药卡替洛尔、吲哚洛尔及噻吗洛尔，从人尿中检出了药物原型及数种代谢产物，讨论了衍生化方法及代谢情况并给出了回收率及检测限数据。     

高效液相色谱法紫外检测人尿中美托洛尔和α－羟基美托洛尔

用高效液相色谱法紫外检测人尿中美托洛尔（Ｍ）和α－羟基美托洛尔（ＨＭ）浓度，采用ＳｐｈｅｒｉｓｏｒｂＯＤＳ１２５ｍｍ×４ｍｍｉ．ｄ．（５μｍ）色谱柱，甲醇：水：冰乙酸：三乙胺（７０：３０：０：１２：０：０３）为流动相，紫外检测波长为２１５ｎｍ。Ｍ和ＨＭ的平均回收率分别为９８．５／和９９．８％，日内和日间变异系数均小于４．５％。方法快速、简便、灵敏，可用于药物氧化分型研究。     

高效液相色谱法紫外检测人尿中美托洛尔和α－羟基美托洛尔

 用高效液相色谱法紫外检测人尿中美托洛尔（Ｍ）和α－羟基美托洛尔（ＨＭ）浓度，采用ＳｐｈｅｒｉｓｏｒｂＯＤＳ１２５ｍｍ×４ｍｍｉ．ｄ．（５μｍ）色谱柱，甲醇：水：冰乙酸：三乙胺（７０：３０：０：１２：０：０３）为流动相，紫外检测波长为２１５ｎｍ。Ｍ和ＨＭ的平均回收率分别为９８．５／和９９．８％，日内和日间变异系数均小于４．５％。方法快速、简便、灵敏，可用于药物氧化分型研究。     

Derivatization reaction of the mycotoxin moniliformin with 1,2-diamino-4,5-dichlorobenzene: structure elucidation of an unexpected reaction product by liquid chromatography/tandem mass spectrometry and liquid chromatography/nuclear magnetic resonance spectroscopy

The derivatization reaction of the mycotoxin moniliformin with 1,2-diamino-4,5-dichlorobenzene was previously introduced to improve distinctly the sensitivity of an assay applying high-performance liquid chromatography prior to fluorescence detection. In the course of the implementation of this derivatization approach into a liquid chromatographic/mass spectrometric method, an unexpected derivatization product has now been discovered by mass spectrometry. In order to elucidate its structure, detailed investigations with liquid chromatography/tandem mass spectrometry and liquid chromatography coupled on-line with NMR spectroscopy were performed. These studies give evidence for a heterocyclic structure that has been formed by the loss of one water and one carbon monoxide molecule. A reasonable mechanism for this derivatization reaction is proposed.     

A systematic approach toward comparing electrospray ionization efficiencies of derivatized and non‐derivatized amino acids and biogenic amines

Ionization efficiency (IE) in mass spectrometry (MS) has been studied for many different compounds, and different IE scales have been constructed in order to quantitatively characterize IE. In the case of MS, derivatization has been used to increase the sensitivity of the method and to lower the limits of detection. However, the influence of derivatization on IE across different compounds and different derivatization reagents has not been thoroughly researched, so that practitioners do not have information on the IE‐enhancing abilities of different derivatization reagents. Moreover, measuring IE via direct infusion of compounds cannot be considered fully adequate. Since derivatized compounds are in complex mixtures, a chromatographic method is needed to separate these compounds to minimize potential matrix effects. In this work, an IE measurement system with a chromatographic column was developed for mainly amino acids and some biogenic amines. IE measurements with liquid chromatography electrospray ionization mass spectrometry (LC/ESI/MS) were carried out, and IE scales were constructed with a calibration curve for compounds with and without derivatization reagent diethyl ethoxymethylenemalonate. Additionally, eluent composition effects on ionization were investigated. Results showed that derivatization increases IE for most of the compounds (by average 0.9 and up to 2‐2.5 logIE units) and derivatized compounds have more similar logIE values than without derivatization. Mobile phase composition effects on ionization efficiencies were negligible. It was also noted that the use of chromatographic separation instead of flow injection mode slightly increases IE. In this work, for the first time, IE enhancement of derivatization reagents was quantified under real LC/ESI/MS conditions and obtained logIE values of derivatized compounds were linked with the existing scale.     

Microextraction combined with derivatization

Microextraction is still finding its niche in the world of analytical sample-preparation techniques and several alternatives have been explored for their ability to cover a wide range of analytes. Derivatization has been another important tool for analysis, especially using chromatography, and great strides have been made in developing key reactions for several classes of compounds. Combining microextraction with derivatization not only enhances analyte recovery, but also improves separation, detectability and compound identification. This article highlights operational principles, advances, directions and key strategies of microextraction combined with derivatization in analytical chemistry. The subjects covered also include design of microextraction–derivatization systems, integration of detection systems, operational requirements, derivatization reactions, typical applications and future prospects.     

耐压多样品微量衍生反应装置在气相色谱-质谱联用法分析极性杂环胺中的应用

设计并制作了耐压多样品微量衍生反应装置。在该装置中采用N-(叔丁基二甲基硅烷基)-N-甲基三氟乙酰胺(MTBSTFA,含1%叔丁基二甲基氯硅烷)硅烷化试剂高温衍生极性杂环胺,衍生产物可以直接在气相色谱-质谱联用仪上分析。使用该装置,既可以在比试剂沸点高的温度下实现衍生反应,也可以实现多个微量样品的同时衍生。着重考察了衍生化过程中反应瓶的顶空体积、试剂蒸发面积、温度、时间等实验条件的影响。结果表明,在90 ℃衍生时,与普通衍生装置相比,使用耐压衍生装置可以有效地减小挥发损失,显著增大衍生产量;在150 ℃衍生时,由于试剂挥发损失严重导致普通衍生装置无法使用,而采用耐压衍生装置却可以实现定量衍生,但通过加温加压方式来加快衍生反应速率的效果并不十分明显。     

原位衍生化技术在液相色谱和液相色谱-质谱联用分析中的应用

衍生化是将待分析物转化为更适合的物质形式以便于分析的有效手段。原位衍生化技术作为一种常用的柱前衍生化方法,可以在样品基质中同时完成分析物的萃取和衍生化,具有高效、灵敏和选择性好的优点。原位衍生化结合其他前处理技术广泛用于胺类、醛酮类、醇类、酚类、羧酸和巯基化合物的分析中,在生物、药物、食品、环境、化妆品分析等领域有广泛的应用。该文概述了原位衍生化的反应类型和代表性衍生试剂,综述了原位衍生化技术在液相色谱和液相色谱-质谱联用分析中的应用,并展望其发展趋势。     

Improved determination of the bisphosphonate alendronate in human plasma and urine by automated precolumn derivatization and high-performance liquid chromatography with fluorescence and electrochemical detection.

An improved method for the determination of 4-amino-1-hydroxybutane-1,1-bisphosphonic acid (alendronate) in human urine and an assay in human plasma are described. The methods are based on co-precipitation of the bisphosphonate with calcium phosphates, automated pre-column derivatization of the primary amino group of the bisphosphonic acid with 2,3-naphthalene dicarboxyaldehyde (NDA)-N-acetyl-D-penicillamine (NAP) or cyanide (CN-) reagents, and high-performance liquid chromatography (HPLC) with electrochemical (ED) or fluorescence detection (FD). The feasibility of ED of the NDA-CN- derivative of aldendronate has been demonstrated, and a HPLC-ED assay in human urine has been validated in the concentration range 2.5-50.0 ng/ml. In order to eliminate the cyanide ion from the assay procedure, several other nucleophiles in the NDA derivatization reaction were evaluated. An NDA-NAP reagent was found to produce highly fluorescent derivatives of alendronate. The assay in urine based on NDA-NAP derivatization and HPLC-FD has been developed and fully validated in the concentration range 1-25 ng/ml. Based on the same NDA-NAP derivatization, an assay in human plasma with a limit of quantification of 5 ng/ml has also been developed. Both HPLC-FD assays were utilized to support various human pharmacokinetic studies with alendronate.     

微波辅助萃取-衍生气相色谱-电子捕获检测器法测定电子电气产品中的四溴双酚A

以N,O-双(三甲基硅烷基)三氟乙酰胺(BSTFA)作衍生化试剂,采用微波辅助萃取-衍生气相色谱-电子捕获检测器法(GC-ECD)测定电子电气产品中的四溴双酚A。使用V(甲苯)∶V(甲醇)=10∶1微波辅助萃取电子电气样品,用正己烷沉淀萃取液中的高聚物,净化后,将萃取液进行衍生化反应,采用ECD检测器进行定量测定。对衍生化时间、衍生化温度、衍生化试剂用量、沉淀试剂用量等前处理条件进行了优化,并进行了线性、回收率、精密度等试验。结果表明,方法线性范围为0.005~5 mg/L,相关系数为0.9985,方法的检测下限为0.02 mg/kg。采用样品加标的方式进行四溴双酚A的精密度及回收率实验,回收率在81.7%~110%之间,相对标准偏差RSD(n=7)小于7.2%。所建方法能很好的应用于电子电气产品中四溴双酚A的检测。     

Amino acid analysis using DABS-CL

Summary Pre-column derivatization followed by reversed-phase HPLC has become widely used as a sensitive and speedy method of amino acid analysis.The technique has been improved by the development of simple and reproducible strategies for derivatization of the amino acids with DABS and for the HPLC analysis. Results obtained indicate that the method has a high sensitivity is well and suited to generate precise amino acid composition information from peptides and proteins.     

柱前衍生法在氨基酸分析测定中的应用

介绍了目前柱前衍生法分析氨基酸常用的几类衍生试剂及相应的衍生方法,并且比较了各类柱前衍生试剂的优缺点,对近期氨基酸分离分析中的色谱检测方法做了系统综述。     

Alternative procedure for charged derivatization to enhance detection responses of steroids in electrospray ionization-MS

A derivatization procedure has been examined to enhance the electrospray ionization (ESI)-MS detectabilities of steroids that charged derivatization is not suitable for. The derivatization procedure with 2-hydrazinopyridine or isonicotinoyl azide was very effective for the sensitive detection of di-oxosteroids or di-hydroxysteroids, respectively, and the detection limits of the resulting derivatives were as low as about 2 fmol. The derivatives also provided intense characteristic product ions in the MS-MS, which are expected to be usable for the selected reaction monitoring mode.