CESPU, Instituto de Investigação e Formação Avançada em Ciências e Tecnologias da Saúde, Rua Central de Gandra, 1317 Gandra, PRD, Portugal; Laboratório de Química Orgânica e Farmacêutica, Departamento de Ciências Químicas, Faculdade de Farmácia, Universidade do Porto, Rua de Jorge Viterbo Ferreira, 228, Porto, Portugal.
CESPU, Instituto de Investigação e Formação Avançada em Ciências e Tecnologias da Saúde, Rua Central de Gandra, 1317 Gandra, PRD, Portugal; Centro Interdisciplinar de Investigação Marinha e Ambiental (CIIMAR), Terminal de Cruzeiros do Porto de Leixões, Avenida General Norton de Matos, s/n, Matosinhos, Portugal.
J Chromatogr B Analyt Technol Biomed Life Sci. 2019 Sep 1;1125:121731. doi: 10.1016/j.jchromb.2019.121731. Epub 2019 Jul 24.
Currently, consumption of illicit drugs and pharmaceuticals has increased significantly. Many of these substances are chiral and can be available as racemates or enantiomerically pure. Determination of the enantiomeric fraction (EF) in wastewater is useful for: i) distinguishing between the consumption of prescribed and illicit drugs; ii) identification of possible local of illegal synthesis; iii) illegal discharge of sewage and estimation of illicit drugs and pharmaceuticals consumption by a community (wastewater-based epidemiology). This work describes the development of an indirect method by gas chromatography-mass spectrometry (GC-MS) for enantiomeric quantification of chiral substances namely psychoactive drugs and β-blockers based on the formation of diastereomers using (R)-(-)-α-methoxy-α-(trifluoromethyl)phenylacetyl chloride ((R)-MTPA-Cl) as chiral derivatization reagent. The developed method presented linearity (R > 0.99) for 20 compounds, 9 diastereomer pairs and paroxetine (PAR) and sertraline (SER). Recovery ranged from 80.7 to 114.5% (RSD < 9.1%) and accuracy between 84.6 and 118% (RSD < 9.9%). The limits of detection (LOD) varied from 0.03 and 26.0 ngL and limits of quantification (LOQ) from 0.15 and 104 ngL. Results showed the occurrence of amphetamine (AMP), illicit drugs as 3,4-methylenedioxymethamphetamine (MDMA) and methamphetamine (MAMP), alprenolol (ALP), norfluoxetine (NFLX), (SER), metoprolol (MET) and propranolol (PHO) at concentrations ranging from 21.7 ngL (MDMA) to 622 ngL (PHO). Measured concentrations were used to estimate the drug loads of the target chiral substances in a specific population. The EF was determined providing valuable information about the consumption and origin of the target drugs.
目前，非法药物和药品的消费明显增加。这些物质中有许多是手性的，可以作为外消旋体或对映体纯物质存在。在废水中测定对映体分数（EF）可用于：i）区分规定药物和非法药物的消费；ii）确定可能的非法合成地点；iii）非法排放污水和估算社区（基于污水的流行病学）的非法药物和药品消费。本工作描述了一种间接方法的发展，该方法通过气相色谱-质谱法（GC-MS），使用（R）-（-）-α-甲氧基-α-（三氟甲基）苯乙酰氯（（R）-MTPA-Cl）作为手性衍生化试剂，通过形成非对映异构体来对手性物质（即精神活性药物和β-受体阻滞剂）进行对映体定量。所开发的方法对于 20 种化合物、9 对非对映体和帕罗西汀（PAR）和舍曲林（SER）具有线性性（R > 0.99）。回收率范围为 80.7%至 114.5%（RSD < 9.1%），准确度为 84.6%至 118%（RSD < 9.9%）。检测限（LOD）范围为 0.03 至 26.0 ngL，定量限（LOQ）范围为 0.15 至 104 ngL。结果表明，在浓度范围为 21.7 ngL（MDMA）至 622 ngL（PHO）时，出现了安非他命（AMP）、非法药物如 3,4-亚甲二氧基甲基苯丙胺（MDMA）和甲基苯丙胺（MAMP）、阿普洛尔（ALP）、诺氟西汀（NFLX）、（SER）、美托洛尔（MET）和普萘洛尔（PHO）。所测量的浓度用于估算特定人群中目标手性物质的药物负荷。测定对映体分数（EF）提供了有关目标药物消费和来源的有价值信息。
