超高效液相色谱-三重四极杆质谱法测定饮料中的γ-羟基丁酸和γ-丁内酯
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摘要
目的建立超高效液相色谱-三重四极杆质谱法(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)检测饮料中γ-羟基丁酸(4-hydroxybutanoic acid,GHB)和γ-丁内酯(gamma-butyrolactone,GBL)的含量。方法样品经稀释后,采用C18色谱柱(100 mm×2.1 mm,1.7μm)进行分离,用甲醇和0.02%甲酸水作为流动相进行梯度洗脱后上机检测。结果在50~1000μg/L内GHB和GBL的浓度与峰面积的线性关系良好,相关系数均大于0.998。γ-羟基丁酸在饮料中的检出限为0.045 mg/kg,定量限为0.15 mg/kg,γ-丁内酯在饮料中的检出限为0.033 mg/kg,定量限为0.11 mg/kg。该方法在检测4种不同类型的饮料时,加标回收率为70%~130%,相对标准偏差(relative standard deviation,RSD)均小于5.0%(n=6)。结论该方法操作简单,灵敏度高,准确可靠,适用于饮料中γ-羟基丁酸和γ-丁内酯的测定。
Objective To establish a method for the determination of γ-hydroxybutyric acid(GHB) and γ-butyrolactone(GBL) in beverages by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). Methods The sample was separated by C18(100 mm×2.1 mm, 1.7 μm) column after dilution, and methanol and 0.02% formic acid water were used as mobile phase for gradient elution and then detected by UPLC-MS/MS. Results The concentrations of GHB and GBL had a good linearity with the areas of peak in the range of 50-1000 μg/m L and the correlation coefficients were greater than 0.998. The limit of detection of GHB was 0.045 mg/kg and the limit of quantization was 0.15 mg/kg. The limit of detection of GBL was 0.033 mg/kg and the limit of quantitation was 0.11 mg/kg. The spiked recoveries were 70%-130%, and the relative standard deviations(RSDs) were less than 5.0%(n=6). Conclusion The established method is reliable, accurate and sensitive, which is suitable for detecting GHB and GBL in beverages.
Objective To establish a method for the determination of γ-hydroxybutyric acid(GHB) and γ-butyrolactone(GBL) in beverages by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). Methods The sample was separated by C18(100 mm×2.1 mm, 1.7 μm) column after dilution, and methanol and 0.02% formic acid water were used as mobile phase for gradient elution and then detected by UPLC-MS/MS. Results The concentrations of GHB and GBL had a good linearity with the areas of peak in the range of 50-1000 μg/m L and the correlation coefficients were greater than 0.998. The limit of detection of GHB was 0.045 mg/kg and the limit of quantization was 0.15 mg/kg. The limit of detection of GBL was 0.033 mg/kg and the limit of quantitation was 0.11 mg/kg. The spiked recoveries were 70%-130%, and the relative standard deviations(RSDs) were less than 5.0%(n=6). Conclusion The established method is reliable, accurate and sensitive, which is suitable for detecting GHB and GBL in beverages.
引文
[1]陈学国,马生祥,马玄中,等.γ-羟基丁酸的分析研究进展[J].现代生物医学进展,2013,13(36):7182-7185.Chen XG,Ma SX,Ma XZ,et al.Research advancement on the analysis of GHB[J].Prog Mod Biomed,2013,13(36):7182-7185.
[2]张绍雨,林云珠,柯洪伟,等.GC-MS法测定尿中γ-羟基丁酸[J].分析仪器,2005,(2):24-27.Zhang SY,Lin YZ,Ke HW,et al.Determination of gammahydroxybutyric acid in urine by GC-MS[J].Anal Instrum,2005,(2):24-27.
[3]沈敏,刘晓茜,刘伟,等.毛发中GHB的检测及评价[J].法医学杂志,2006,(1):48-51.Shen M,Liu XQ,Liu W,et al.Detection and evaluation of GHB in hair[J].J Forensic Med,2006,(1):48-51.
[4]Kankaanpaa A,Liukkonen R,Ariniemi K.Determination of gamma-hydroxybutyrate(GHB)and its precursors in blood and urine samples:A salting-out approach[J].Forensic Sci Int,2007,170:133-138.
[5]张绍雨,黄增萍.化学显色法快速筛选饮料及尿液中γ-羟基丁酸和γ-丁内酯[J].法医学杂志,2006,(6):424-427,439.Zhang XY,Huang ZP.A color test for rapid screening of gamma-hydroxybutyric acid and gamma-butyrolactone in drink and urin[J].J Forensic Med,2006,(6):424-427,439.
[6]孟品佳.γ-羟基丁酸的五氟卞基溴衍生化气相色谱/质谱分析[J].分析化学,2008,(1):61-65.Meng PJ.Analysis of gamma-hydroxybutyric acid by five fluorinated bromide derivatization by gas chromatography-mass spectrometry[J].Chin J Anal Chem,2008,(1):61-65.
[7]王蔚昕,张瑞瑛,黄星.液体检材中γ-羟基丁酸衍生化GC-MS定性分析方法的优化[J].化学工程师,2015,29(5):35-38,49.Wang WX,Zhang RY,Huang X.Optimization of GC-MS qualitative analysis method for gamma hydroxybutyric acid derivatization in liquid material[J].Chem Eng,2015,29(5):35-38,49.
[8]张绍雨.尿和血中γ-羟基丁酸(GHB)的GC-MS-SIM测定[C].全国第七次法医学术交流会,2004.Zhang SY.Determination of gamma-hydroxybutyric acid(GHB)in urine and blood by GC-MS-SIM[C].The 7th Forensic Medicine Association in China,2004.
[9]Frison G,Tedeschi L,Maietti S,et al.Determination of gamma-hydroxybutyric acid(GHB)in plasma and urine by headspace solid-phase microextraction and gas chromatography/positive ion chemical ionization mass spectrometry[J].Rapid Commun Mass Spectrom,2000,14(24):2401-2407.
[10]陈学国,马生祥,马玄中,等.衍生化-液相色谱-紫外检测联用测定尿中γ-羟基丁酸[J].福建分析测试,2014,23(2):20-22.Chen XG,Ma SX,Ma XZ,et al.Determination of gamma-hydroxybutyric acid in urine by derivatization-liquid chromatography-UV detection[J].Fujian Anal Testing,2014,23(2):20-22.
[11]张雪华,王静静,王猛,等.分子氧氧化四氢呋喃产物中γ-丁内酯、4-羟基丁酸与1,4-丁二酸的反相高效液相色谱法测定[J].分析测试学报,2013,32(10):1232-1236.Zhang XH,Wang JJ,Wang M,et al.RP-HPLC determination of ester and organic acids in the oxidative products of tetahydrofuran with molecular oxygen[J].J Instrum Anal,2013,32(10):1232-1236.
[12]张浩杰,王蔚昕,夏学明,等.超高效液相色谱-质谱联用法测定饮料中γ-羟基丁酸及其前体物质γ-丁内酯和1,4-丁二醇[J].分析试验室,2015,34(1):72-76.Zhang HJ,Wang WX,Xia XM,et al.Determination of gamma-hydroxybutyric acid and its precursors gamma-butylacyl and1,4-butanediol in beverages by ultra performance liquid chromatographymass spectrometry[J].Chin J Anal Lab,2015,34(1):72-76.
[13]Michelle W,Marleen L,Nele S,et al.Simultaneous analysis of gamma-hydroxybutyric acid and its precursors in urine using liquid chromatography-tandem mass spectrometry[J].J Chromatogr A,2004,1056:83-90.
[14]陈学国,马生祥,马玄中,等.液相色谱-电喷雾离子阱质谱联用测定尿中γ-羟基丁酸[J].广东化工,2013,40(5):17-18.Chen XG,Ma SX,Ma XZ,et al.Determination of gamma-hydroxybutyric acid in urine by liquid chromatography-mass spectrometry[J].Guangdong Chem Ind,2013,40(5):17-18.
[15]施妍,崔小培,向平,等.尿液中γ-羟基丁酸及其前体物质的检测和应用[J].法医学杂志,2015,31(3):200-203.Shi Y,Cui XP,Xiang P,et al.Analysis of GHB and its precursors in urine and their forensic application[J].J Forensic Med,2015,31(3):200-203.
[2]张绍雨,林云珠,柯洪伟,等.GC-MS法测定尿中γ-羟基丁酸[J].分析仪器,2005,(2):24-27.Zhang SY,Lin YZ,Ke HW,et al.Determination of gammahydroxybutyric acid in urine by GC-MS[J].Anal Instrum,2005,(2):24-27.
[3]沈敏,刘晓茜,刘伟,等.毛发中GHB的检测及评价[J].法医学杂志,2006,(1):48-51.Shen M,Liu XQ,Liu W,et al.Detection and evaluation of GHB in hair[J].J Forensic Med,2006,(1):48-51.
[4]Kankaanpaa A,Liukkonen R,Ariniemi K.Determination of gamma-hydroxybutyrate(GHB)and its precursors in blood and urine samples:A salting-out approach[J].Forensic Sci Int,2007,170:133-138.
[5]张绍雨,黄增萍.化学显色法快速筛选饮料及尿液中γ-羟基丁酸和γ-丁内酯[J].法医学杂志,2006,(6):424-427,439.Zhang XY,Huang ZP.A color test for rapid screening of gamma-hydroxybutyric acid and gamma-butyrolactone in drink and urin[J].J Forensic Med,2006,(6):424-427,439.
[6]孟品佳.γ-羟基丁酸的五氟卞基溴衍生化气相色谱/质谱分析[J].分析化学,2008,(1):61-65.Meng PJ.Analysis of gamma-hydroxybutyric acid by five fluorinated bromide derivatization by gas chromatography-mass spectrometry[J].Chin J Anal Chem,2008,(1):61-65.
[7]王蔚昕,张瑞瑛,黄星.液体检材中γ-羟基丁酸衍生化GC-MS定性分析方法的优化[J].化学工程师,2015,29(5):35-38,49.Wang WX,Zhang RY,Huang X.Optimization of GC-MS qualitative analysis method for gamma hydroxybutyric acid derivatization in liquid material[J].Chem Eng,2015,29(5):35-38,49.
[8]张绍雨.尿和血中γ-羟基丁酸(GHB)的GC-MS-SIM测定[C].全国第七次法医学术交流会,2004.Zhang SY.Determination of gamma-hydroxybutyric acid(GHB)in urine and blood by GC-MS-SIM[C].The 7th Forensic Medicine Association in China,2004.
[9]Frison G,Tedeschi L,Maietti S,et al.Determination of gamma-hydroxybutyric acid(GHB)in plasma and urine by headspace solid-phase microextraction and gas chromatography/positive ion chemical ionization mass spectrometry[J].Rapid Commun Mass Spectrom,2000,14(24):2401-2407.
[10]陈学国,马生祥,马玄中,等.衍生化-液相色谱-紫外检测联用测定尿中γ-羟基丁酸[J].福建分析测试,2014,23(2):20-22.Chen XG,Ma SX,Ma XZ,et al.Determination of gamma-hydroxybutyric acid in urine by derivatization-liquid chromatography-UV detection[J].Fujian Anal Testing,2014,23(2):20-22.
[11]张雪华,王静静,王猛,等.分子氧氧化四氢呋喃产物中γ-丁内酯、4-羟基丁酸与1,4-丁二酸的反相高效液相色谱法测定[J].分析测试学报,2013,32(10):1232-1236.Zhang XH,Wang JJ,Wang M,et al.RP-HPLC determination of ester and organic acids in the oxidative products of tetahydrofuran with molecular oxygen[J].J Instrum Anal,2013,32(10):1232-1236.
[12]张浩杰,王蔚昕,夏学明,等.超高效液相色谱-质谱联用法测定饮料中γ-羟基丁酸及其前体物质γ-丁内酯和1,4-丁二醇[J].分析试验室,2015,34(1):72-76.Zhang HJ,Wang WX,Xia XM,et al.Determination of gamma-hydroxybutyric acid and its precursors gamma-butylacyl and1,4-butanediol in beverages by ultra performance liquid chromatographymass spectrometry[J].Chin J Anal Lab,2015,34(1):72-76.
[13]Michelle W,Marleen L,Nele S,et al.Simultaneous analysis of gamma-hydroxybutyric acid and its precursors in urine using liquid chromatography-tandem mass spectrometry[J].J Chromatogr A,2004,1056:83-90.
[14]陈学国,马生祥,马玄中,等.液相色谱-电喷雾离子阱质谱联用测定尿中γ-羟基丁酸[J].广东化工,2013,40(5):17-18.Chen XG,Ma SX,Ma XZ,et al.Determination of gamma-hydroxybutyric acid in urine by liquid chromatography-mass spectrometry[J].Guangdong Chem Ind,2013,40(5):17-18.
[15]施妍,崔小培,向平,等.尿液中γ-羟基丁酸及其前体物质的检测和应用[J].法医学杂志,2015,31(3):200-203.Shi Y,Cui XP,Xiang P,et al.Analysis of GHB and its precursors in urine and their forensic application[J].J Forensic Med,2015,31(3):200-203.