Cruz Jonas Carneiro, Rosa Mariana Azevedo, Morés Lucas, Carasek Eduardo, Crippa José Alexandre de Souza, Figueiredo Eduardo Costa, Queiroz Maria Eugênia Costa
Departamento de Química - Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, São Paulo, 14040-901, Brazil.
Laboratory of Toxicant and Drug Analyses - LATF, Gabriel Monteiro da Silva St. 700, Federal University of Alfenas - Unifal-MG, 37130-000, Alfenas, MG, Brazil.
Anal Chim Acta. 2022 Sep 15;1226:340160. doi: 10.1016/j.aca.2022.340160. Epub 2022 Jul 20.
This manuscript describes the development of magnetic restricted-access carbon nanotubes (M-RACNTs) for use as SPME sorbent to determine cannabidiol (CBD) and delta-9-tetrahydrocannabinol (THC) in human plasma samples by UHPLC-MS/MS. The adsorptive phase was immobilized on an SPME device by electromagnetic interactions between the M-RACNTs and a cylindrical neodymium magnet (3-mm diameter x 8-mm height) attached to a stainless-steel rod (3-mm diameter x 40-mm height). The M-RACNTs were synthesized by incorporating FeO magnetic nanoparticles (MNPs) into commercial carbon nanotubes (CNTs); then the surface of the resulting sorbent was further coated with a layer of bovine serum albumin (BSA). Characterization techniques (SEM, FTIR, and Zeta potential) confirmed the presence of both MNPs and BSA layer dispersed through the structure of the CNTs. The M-RACNTs presented adequate sorption capacity, stable physical/chemical characteristics, and appropriate magnetic properties. Protein exclusion capacity (about 98.5%) was attributed to the chemical diffusion barrier created by the BSA network at the outer surface of the sorbent. The SPME parameters (sample pH, equilibrium time, and desorption conditions) were optimized by design of experiments (fraction factorial planning). The method (validated according to the FDA guidelines) presented adequate selectivity and linearity (coefficient of determination higher than 0.99) at concentrations ranging from the lower limit of quantification (LLOQ) (10 ng mL) to the upper limit of quantification (ULOQ) (300 ng mL) for both CBD and THC. Precision and accuracy varied from 4.47 to 19.84% (LLOQ) and -6.90 to 17.78% (LLOQ), respectively. Carry-over and matrix effect were not significant. The method was successfully applied to determine plasmatic CBD levels in healthy volunteers attending a single session of oral drug administration and THC levels in frequent cannabis smokers.
本手稿描述了磁性受限 access 碳纳米管（M-RACNTs）的开发，其用作固相微萃取（SPME）吸附剂，通过超高效液相色谱-串联质谱（UHPLC-MS/MS）测定人血浆样品中的大麻二酚（CBD）和 Δ⁹-四氢大麻酚（THC）。吸附相通过 M-RACNTs 与附着在不锈钢棒（直径 3 毫米×高度 40 毫米）上的圆柱形钕磁铁（直径 3 毫米×高度 8 毫米）之间的电磁相互作用固定在 SPME 装置上。M-RACNTs 通过将 FeO 磁性纳米颗粒（MNPs）掺入商业碳纳米管（CNTs）中合成；然后在所得吸附剂的表面进一步涂覆一层牛血清白蛋白（BSA）。表征技术（扫描电子显微镜、傅里叶变换红外光谱和 ζ 电位）证实了 MNPs 和 BSA 层均存在于 CNTs 的结构中。M-RACNTs 具有足够的吸附能力、稳定的物理/化学特性和合适的磁性。蛋白质排斥能力（约 98.5%）归因于吸附剂外表面 BSA 网络形成的化学扩散屏障。通过实验设计（分数析因规划）优化了 SPME 参数（样品 pH 值、平衡时间和解吸条件）。该方法（根据 FDA 指南进行验证）在 CBD 和 THC 浓度范围从定量下限（LLOQ）（10 ng/mL）到定量上限（ULOQ）（300 ng/mL）时具有足够的选择性和线性（决定系数高于 0.99）。精密度和准确度分别在 4.47%至 19.84%（LLOQ）和 -6.90%至 17.78%（LLOQ）之间变化。残留和基质效应不显著。该方法成功应用于测定单次口服给药的健康志愿者的血浆 CBD 水平以及频繁吸食大麻者的 THC 水平。
