Determination of 26 trace cathinones new psychoactive substances in sewage by HPLC-MS/MS
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摘要:
建立了污水中26种痕量卡西酮类新精神活性物质的前处理及同时定量检测的方法，并成功应用于实际污水样品的检测。污水样品经过滤和加入内标溶液的预处理，在Oasis PRiME HLB固相萃取柱上经超纯水淋洗和甲醇溶液洗脱，在40 ℃下氮气吹干，用0.1%甲酸-乙腈溶液（95∶5）复溶，利用高效液相色谱-串联质谱（high-performance liquid chromatography-tandem mass spectrometry，HPLC-MS/MS）技术，采用选择反应监测（selected reaction monitoring，SRM）模式，用UPLC BEH C18（100 mm×2.1 mm，1.7 μm）色谱柱，柱温35 ℃，流动相为乙腈-0.1%甲酸的水溶液，梯度洗脱进行检测。经方法学验证，26种卡西酮类新精神活性物质的定量下限可达1.50~3.00 ng/L，其中21种待测物在1.50~375.0 ng/L范围内，5种在3.00~750.0 ng/L范围内，所有26种物质均具有良好的线性关系，相关系数r为0.99，批内和批间精密度的相对标准偏差（relative standard deviation，RSD）分别小于7.71%和13.91%，提取回收率均高于92.64%。该方法简单、准确、灵敏，可作为卡西酮类物质检测和滥用情况监测的方法。
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关键词:
- 卡西酮 /
- 新精神活性物质 /
- 新型毒品分析 /
- 污水流行病学 /
- 超高效液相色谱-串联质谱
Abstract:A method for the pretreatment and qualitative detection of 26 trace cathinone new psychoactive substances in wastewater was established and applied in actual wastewater cases. The effluent samples were eluted on the Oasis PRiME HLB solid phase extraction column by ultra-pure water drenching and methanol solution, then dried with nitrogen at 40 ℃, and finally re-dissolved with 0.1% formic acid-acetonitrile solution (95∶5), and detected by liquid chromatography-tandem mass spectrometry, The effluent sample was determined by high-performance liquid chromatography-Tandem mass spectrometry (HPLC-MS/MS) using selected reaction monitoring (SRM) mode and separated on chromatographic column UPLC BEH C18(100 mm×2.1 mm, 1.7 μm） at 35 ℃ with a mobile phase consisting of acetonitrile-0.1% formic acid in aqueous solution gradient elution. After methodological validation, the lower quantification of 26 cathinone new psychoactive substances could reach 1.50−3.00 ng/L. Among these, 21 analytes fell within the concentration range of 1.50−375.0 ng/L, while 5 were detected in the range of 3.00−750.0 ng/L, the correlation coefficient was 0.99, within-and between-batch precision was less than 7.71% and 13.91%, respectively, and the extraction recoveries were higher than 92.64% . The method is simple, accurate, and sensitive, and can be used for cathinone detection and abuse monitoring.
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Figure 1. Total ion chromatogram (TIC) of the target analytes A:Blank redissolution solvent; B:Pure water; C:Pure water sample with the standard compounds; D:Wastewater sample fortified with the standard compounds; E:Wastewater sample
Table 1 Quantitative ion information of 26 cathinones substances and deuterated internal standard methyl cathinones-D3 compounds and SRM
No. IUPAC Name Compound Retention time/min SRM（m/z）（Collision energy） 1 Methcathinone-D3 MC-D3 3.78 167.1→149.2*(12eV) 167.1→1 34.1(22eV) 2 3,4-Methylenedioxy-N-methylcathinone Methylone 4.83 208.1→160.1*(25eV) 208.1→132.0(29eV) 3 4-Fluoromethcathinone 4-FMC 4.92 182.1→147.8*(35eV) 182.1→103.2(28eV) 4 N-Ethylaminopropiophenone Ethcathinone 5.11 178.1→160.1*(13eV) 178.1→132.1(18eV) 5 1-(1,3-Benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Dimethylone 5.38 222.1→147.1*(20eV) 222.1→177.1(15eV) 6 1-(1,3-Benzodioxol-5-yl)-2-(ethylamino)propan-1-one Ethylone 5.92 222.1→174.0*(19eV) 222.1→204.1(13eV) 7 1-(4-Methoxyphenyl)-2-(methylamino)propan-1-one 4-MeOMC 6.11 194.1→176.0*(13eV) 194.1→161.0(21eV) 8 2-(Methylamino)-1-phenylbutan-1-one Buphedrone 6.26 178.1→160.2*(12eV) 178.1→131.1(23eV) 9 1-(1,3-Benzodioxol-5-yl)-2-pyrrolidin-1-ylpropan-1-one MDPPP 6.57 248.1→147.2*(22eV) 248.1→98.1(27eV) 10 1-(1,3-Benzodioxol-5-yl)-2-(methylamino)butan-1-one Butylone 6.82 222.1→174.1*(18eV) 222.1→204.1(13eV) 11 2-(Ethylamino)-1-phenylbutan-1-one NEB 6.96 192.1→174.1*(13eV) 192.1→91.1(25eV) 12 1-(1,3-Benzodioxol-5-yl)-2-(dimethylamino)butan-1-one Dibutylone 7.08 236.1→191.0*(12eV) 236.1→86.2(20eV) 13 2-(Methylamino)-1-(3-methylphenyl)propan-1-one 3-MMC 7.14 178.1→160.2*(13eV) 178.1→145.1(21eV) 14 1-Phenyl-2-(1-pyrrolidinyl) butan-1-one α-PBP 7.26 218.15→91.1*(23eV) 218.15→112.1(26eV) 15 1-(1,3-Benzodioxol-5-yl)-2-pyrrolidin-1-ylbutan-1-one MDPBP 7.77 262.1→191.1*(17eV) 262.1→161.0(19eV) 16 2-(Ethylamino)-1-(4-methylphenyl)propan-1-one 4-MEC 8.18 192.1→174.1*(13eV) 192.1→144.2(28eV) 17 2-Pyrrolidin-1-yl-1-thiophen-2-ylpentan-1-one α-PVT 8.19 238.1→126.0*(16eV) 238.1→96.7(23eV) 18 2-(Methylamino)-1-phenylpentan-1-one Pentedrone 8.19 192.1→174.05*(13eV) 192.1→145.1(22eV) 19 1-(4-Chlorophenyl)-2-(ethylamino)propan-1-one 4-CEC 8.29 212.1→159.3*(21eV) 212.1→144.1(22eV) 20 1-(4-Methylphenyl)-2-methylaminobutan-1-one 4-MeBP 8.54 192.1→174.25*(12eV) 192.1→144.2(32eV) 21 1-(3,4-Dimethylphenyl)-2-methylaminopropan-1-one 3,4-DMMC 8.97 192.1→174.2*(13eV) 192.1→159.3(20eV) 22 1-Phenyl-2-(1-pyrrolidinyl)pentan-1-one α-PVP 9.01 232.2→91.1*(25eV) 232.2→126.2(28eV) 23 1-(1,3-Benzodioxol-5-yl)-2-(ethylamino)pentan-1-one N-ethylpentylone 9.01 250.1→174.0*(33eV) 250.1→145.1(39eV) 24 1-(1,3-Benzodioxol-5-yl)-2-pyrrolidin-1-ylpentan-1-one MDPV 9.37 276.2→174.9*(21eV) 276.2→204.6(19eV) 25 1-(4-Fluorophenyl)-2-pyrrolidin-1-ylpentan-1-one 4-F-α-PVP 9.61 250.2→109.0*(19eV) 250.2→126.1(23eV) 26 1-(4-Methoxyphenyl)-2-pyrrolidin-1-ylpentan-1-one 4-MeO-α-PVP 10.02 262.2→121.1*(25eV) 262.2→191.0(17eV) 27 1-Phenyl-2-(1-pyrrolidinyl)heptan-1-one α-PHPP 12.12 260.2→91.1*(26eV) 260.2→154.2(28eV) Ion pair with * is used as the quantitative ion and the other ion pair is used as the qualitative ion 
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