In recent years,benzodiazepines and benzodiazepine-like drugs are the most common substances associated with drug-facilitated sexual assaults(DFSA);however,barbiturates are also detected occasionally.Segmental hair an...In recent years,benzodiazepines and benzodiazepine-like drugs are the most common substances associated with drug-facilitated sexual assaults(DFSA);however,barbiturates are also detected occasionally.Segmental hair analysis provides useful information on the historic pattern of drug use,enabling differentiation between single exposure in DFSA cases and chronic use.However,sensitive and specific methods for barbiturate analysis in hair samples are needed.Herein,we present an ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry(UHPLC-HRMS)method for qualitative and quantitative determination of seven barbiturates in hair samples.Firstly,a hair strand was decontaminated and then freeze-milled in liquid nitrogen.Next,50mg of powdered hair was extracted with methanol in an ultrasonic bath for 10 min in the presence of 10 ng phenobarbital-d5.The supernatant was dried under nitrogen gas,and the pellet was dissolved in 100 μL mobile phase.Afterwards,10 μL of the suspension was injected into the UHPLC-HRMS system.The present method involved two UHPLC conditions for determination of barbiturates(I)and identification of the structural isomers amobarbital and pentobarbital(II).This method showed satisfactory linearity in a range of 0.02–20.00 ng/mg for UHPLC conditions I and II,both with a high determination coefficient(0.9991–0.9999).The selectivity,intra-and interday precision,accuracy and matrix effect of the method were acceptable.Next,the validated method was applied to investigate an authentic DFSA case.Hair samples(black,approximate 25cm long)were collected 3 months after the assault,and the proximal segments(0–5 cm from the root;each segment was 1 cm long)were analysed.Amobarbital was detected at a concentration of<LOQ(limit of quantification)and 0.09 ng/mg in the second and third 1-cm hair segment but not in the other segments.Thus,our method was successful in determining barbiturate concentration in human hair after a single-dose exposure,showing its potential for application in the investigation of DFSA cases.展开更多
食品中潜在风险因子筛查对保障食品安全至关重要。该研究基于超高效液相色谱-高分辨质谱(UHPLC-HRMS)技术,提出了一种非靶向快速筛查果蔬中农药残留的策略。建立了包括样品快速前处理、UHPLC准确分离和HRMS检测在内的复杂基质中农药残...食品中潜在风险因子筛查对保障食品安全至关重要。该研究基于超高效液相色谱-高分辨质谱(UHPLC-HRMS)技术,提出了一种非靶向快速筛查果蔬中农药残留的策略。建立了包括样品快速前处理、UHPLC准确分离和HRMS检测在内的复杂基质中农药残留分析方法,引入保留时间校正策略,拓宽外部数据库适用度,提高定性筛查准确性。经1%乙酸乙腈提取,分散固相萃取净化后,以Accucore aQ C_(18)色谱柱进行分离,通过静电场轨道阱质谱Full Scan/dd-MS^(2)进行高通量定性筛查和定量检测。结果显示,不同农药在5~500μg/L浓度范围内线性关系良好(相关系数r^(2)>0.99),果蔬基质添加108种代表性农药,除了矮壮素和灭蝇胺,其余农药的回收率均为61.2%~120%,相对标准偏差(RSD,n=5)为0.1%~9.9%。该方法快速、准确、灵敏,适用于农产品中未知农药残留的快速筛查与定量分析。展开更多
基金This study was financially supported in part by the National Key R&D Program of China[grant number 2016YFC0800704]the Natural Science Foundation of China[grant number 81501633].
文摘In recent years,benzodiazepines and benzodiazepine-like drugs are the most common substances associated with drug-facilitated sexual assaults(DFSA);however,barbiturates are also detected occasionally.Segmental hair analysis provides useful information on the historic pattern of drug use,enabling differentiation between single exposure in DFSA cases and chronic use.However,sensitive and specific methods for barbiturate analysis in hair samples are needed.Herein,we present an ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry(UHPLC-HRMS)method for qualitative and quantitative determination of seven barbiturates in hair samples.Firstly,a hair strand was decontaminated and then freeze-milled in liquid nitrogen.Next,50mg of powdered hair was extracted with methanol in an ultrasonic bath for 10 min in the presence of 10 ng phenobarbital-d5.The supernatant was dried under nitrogen gas,and the pellet was dissolved in 100 μL mobile phase.Afterwards,10 μL of the suspension was injected into the UHPLC-HRMS system.The present method involved two UHPLC conditions for determination of barbiturates(I)and identification of the structural isomers amobarbital and pentobarbital(II).This method showed satisfactory linearity in a range of 0.02–20.00 ng/mg for UHPLC conditions I and II,both with a high determination coefficient(0.9991–0.9999).The selectivity,intra-and interday precision,accuracy and matrix effect of the method were acceptable.Next,the validated method was applied to investigate an authentic DFSA case.Hair samples(black,approximate 25cm long)were collected 3 months after the assault,and the proximal segments(0–5 cm from the root;each segment was 1 cm long)were analysed.Amobarbital was detected at a concentration of<LOQ(limit of quantification)and 0.09 ng/mg in the second and third 1-cm hair segment but not in the other segments.Thus,our method was successful in determining barbiturate concentration in human hair after a single-dose exposure,showing its potential for application in the investigation of DFSA cases.
文摘食品中潜在风险因子筛查对保障食品安全至关重要。该研究基于超高效液相色谱-高分辨质谱(UHPLC-HRMS)技术,提出了一种非靶向快速筛查果蔬中农药残留的策略。建立了包括样品快速前处理、UHPLC准确分离和HRMS检测在内的复杂基质中农药残留分析方法,引入保留时间校正策略,拓宽外部数据库适用度,提高定性筛查准确性。经1%乙酸乙腈提取,分散固相萃取净化后,以Accucore aQ C_(18)色谱柱进行分离,通过静电场轨道阱质谱Full Scan/dd-MS^(2)进行高通量定性筛查和定量检测。结果显示,不同农药在5~500μg/L浓度范围内线性关系良好(相关系数r^(2)>0.99),果蔬基质添加108种代表性农药,除了矮壮素和灭蝇胺,其余农药的回收率均为61.2%~120%,相对标准偏差(RSD,n=5)为0.1%~9.9%。该方法快速、准确、灵敏,适用于农产品中未知农药残留的快速筛查与定量分析。
