固相萃取-固相辅助衍生-气相色谱-串联质谱对水样和尿液中氰化物的分析检测

引用本文: 李晓森, 黄桂兰, 吴姬娜, 杨旸, 刘石磊. 固相萃取-固相辅助衍生-气相色谱-串联质谱对水样和尿液中氰化物的分析检测[J]. 分析化学, 2023, 51(4): 611-620. doi: 10.19756/j.issn.0253-3820.221455 shu

Citation: LI Xiao-Sen, HUANG Gui-Lan, WU Ji-Na, YANG Yang, LIU Shi-Lei. Determination of Cyanide in Water and Urine by Solid Phase Extraction-Solid Phase Assisted Derivatization-Gas Chromatography-Tandem Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2023, 51(4): 611-620. doi: 10.19756/j.issn.0253-3820.221455 shu

固相萃取-固相辅助衍生-气相色谱-串联质谱对水样和尿液中氰化物的分析检测

国民核生化灾害防护国家重点实验室, 北京 102205

通讯作者: 杨旸,E-mail:ricdyihui@163.com; 刘石磊,E-mail:liushilei402@263.net

基金项目:
国民核生化灾害防护国家重点实验室科研基金项目（No.SKLNBC2020-16）资助。

摘要: 建立了一种针对氰化物的固相萃取-固相辅助衍生方法，结合气相色谱-串联质谱方法，实现了环境样本以及生物样本中痕量氰化物的定性及定量检测。首先采用氯胺T将氰根衍生为氯化氰，然后通过C₈型固相萃取柱同时实现反应物的富集纯化和衍生化。对样品前处理条件进行优化，发现固相萃取柱的类型和衍生反应的溶剂环境是决定氰化物衍生效率的关键。分别采用气相色谱-电子轰击质谱（Gas chromatography-electron ionization/mass spectrometry，GC-EI/MS）及600 MHz核磁共振-氢谱（Proton nuclear magnetic resonance，¹H-NMR）对产物进行分析，结果表明，衍生产物为硫氰酸正丁酯。基于此，以异丙基二硫醚为内标物，建立了水样及尿液中氰化物衍生产物的气相色谱三重四极杆-选择反应监测模式的定性及定量检测方法。在最优反应条件下对健康成年人（非吸烟组）及幼儿的尿液进行检测，发现尿液中含有内源性氰化物（浓度范围120~200 ng/mL）。本方法检测灵敏度高、专属性好且样品前处理时间短。对于水样和尿液中氰化物检测的线性范围分别为10~1000及10~800 ng/mL，检出限分别为7.0和8.0 ng/mL（S/N=3），日内和日间精密度分别为4.2%~7.8%（n=3）及5.2%~7.9%（n=6）。将本方法应用于禁止化学武器公约组织（OPCW）第2次生物样品水平考试的尿样（原样品中不含外源性氰化物）中氰化物的定量检测，平均加标回收率为97.7%。进一步对天津港“ 8.12”爆炸后现场遗留的氰化物废水进行检测，测得的氰化物浓度约为1.9 mg/mL。本研究为生物样本中毒剂毒物鉴定、化学事故救援以及化学武器核查等领域中痕量氰化物的筛查鉴定提供了有效方法。

关键词:

English

Determination of Cyanide in Water and Urine by Solid Phase Extraction-Solid Phase Assisted Derivatization-Gas Chromatography-Tandem Mass Spectrometry

State Key Laboratory of NBC Protection for Civilian, Beijing 102205, China

Corresponding author: YANG Yang, ; LIU Shi-Lei,

Received Date: 15 September 2022
Revised Date: 13 December 2022
Fund Project:
Supported by the State Key Laboratory of NBC Protection for Civilian (No. SKLNBC 2020-16).

Abstract: A solid phase extraction-solid phase assisted derivatization (SPE-SPAD) method combined with gas chromatography-tandem mass spectrometry analysis was established for qualitative and quantitative detection of trace cyanide in environmental samples and biological samples. The cyanide ion was transformed to cyanogen chloride via chloramine T. Next, the process of enrichment, purification and derivatization for reactants were simultaneously archived on the C₈ solid phase extraction (SPE) column. The types of SPE column and the solvent of reaction were optimized for the derivatization. The structure of derivative was identified as n-butyl thiocyanate by gas chromatography-mass spectrometry and nuclear magnetic resonance. The qualitative and quantitative detection method for cyanide in water and urine samples was established by gas chromatography-selective reaction monitoring (SRM) mode via isopropyl disulfide as internal standard. The established method had high sensitivity, good specificity and shorter time of sample preparation. The linear ranges for detection of cyanide in water and urine samples were 10-1000 ng/mL and 10-800 ng/mL, with detection limits of 7.0 and 8.0 ng/mL (S/N=3), respectively. The intra- and inter-day precisions were 4.2%-7.8% (n=3) and 5.2%-7.9% (n=6), respectively. The method was successfully applied to determine the cyanide in urine samples from the 2^nd Biological Proficiency Test, which was organized by the Organization for the Prohibition of Chemical Weapons (OPCW), and the average recovery was 97.7%. The wastewater from the Tianjin port after the explosion was detected and the concentration of cyanide was about 1.9 mg/mL. The established method was effective for screening and identification of trace cyanide, and had great potential in chemical accident rescue and chemical weapons verification.

Key words:

Cyanide
/ Gas chromatography-selective reaction monitoring
/ Solid phase extraction-solid phase assisted derivatization
/ Urine

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沈阳化工大学材料科学与工程学院沈阳 110142

固相萃取-固相辅助衍生-气相色谱-串联质谱对水样和尿液中氰化物的分析检测

通讯作者: 杨旸,E-mail:ricdyihui@163.com; 刘石磊,E-mail:liushilei402@263.net

English

Determination of Cyanide in Water and Urine by Solid Phase Extraction-Solid Phase Assisted Derivatization-Gas Chromatography-Tandem Mass Spectrometry

Corresponding author: YANG Yang, ; LIU Shi-Lei,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

固相萃取-固相辅助衍生-气相色谱-串联质谱对水样和尿液中氰化物的分析检测

通讯作者: 杨旸,E-mail:ricdyihui@163.com; 刘石磊,E-mail:liushilei402@263.net

English

Determination of Cyanide in Water and Urine by Solid Phase Extraction-Solid Phase Assisted Derivatization-Gas Chromatography-Tandem Mass Spectrometry

Corresponding author: YANG Yang, ; LIU Shi-Lei,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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