Inorganic–organic hybrid coating material for the online in‐tube solid‐phase microextraction of monohydroxy polycyclic aromatic hydrocarbons in urine

Abstract

An inorganic-organic hybrid nanocomposite (zinc oxide/polypyrrole) that represents a novel kind of coating for in-tube solid-phase microextraction is reported. The composite coating was prepared by a facile electrochemical polymerization strategy on the inner surface of a stainless-steel tube. Based on the coated tube, a novel online in-tube solid-phase microextraction with liquid chromatography and mass spectrometry method was developed and applied for the extraction of three monohydroxy polycyclic aromatic hydrocarbons in human urine. The coating displayed good extraction ability toward monohydroxy polycyclic aromatic hydrocarbons. In addition, long lifespan, excellent stability, and good compression resistance were also obtained for the coating. The experimental conditions affecting the extraction were optimized systematically. Under the optimal conditions, the limits of detection and quantification were in the range of 0.039-0.050 and 0.130-0.167 ng/mL, respectively. Good linearity (0.2-100 ng/mL) was obtained with correlation coefficients larger than 0.9967. The repeatability, expressed as relative standard deviation, ranged between 2.5% and 9.4%. The method offered the advantage of process simplicity, rapidity, automation, and sensitivity in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities of Hubei province. An acceptable recovery of monohydroxy polycyclic aromatic hydrocarbons (64-122%) represented the additional attractive features of the method in real urine analysis.

Determination of trace hydroxyl polycyclic aromatic hydrocarbons in urine using graphene oxide incorporated monolith solid‐phase extraction coupled with LC‐MS/MS

“…The intra‐ and inter‐day precisions (RSD) ranged from 2.4 to 8.7% and 2.9 to 9.9%, respectively. As overviewed in Table , LODs (0.02–0.1 ng/mL) and recoveries (77.5–97.1%) for the target compounds are comparable with the other reported results obtained by LC‐MS/MS for the similar multi‐analyte determination of OH‐PAHs in urine samples .…”

Recent Applications and Newly Developed Strategies of Solid-Phase Microextraction in Contaminant Analysis: Through the Environment to Humans

“…In another study by Naccarato et al, the Generally speaking, urine is undoubtedly the preferred matrix among the analyzed biological fluids because of its greater biological half-life and its less invasive sampling. This trend is confirmed in the last lustrum since most of the published works on this topic have been directed, as well as to the assay of markers of several pathological conditions [210][211][212], toward the determination of several contaminants in urine samples [14,74,83,[213][214][215][216][217][218][219]. Few studies focused on hair [220][221][222], three papers were published about analysis in blood/serum [29,223,224], and one regarding meconium [225].…”

“…The satisfactory results achieved in terms of the lifetime of coatings and validation parameters created not only new alternatives for polycyclic aromatic hydrocarbon exposure assessment but also opened new perspectives for the application of direct immersion solid-phase microextraction to the analysis of bio-clinical matrices. As for food analysis, various coatings were proposed for the analysis of urine, such as C 18 /PAN [213], layered double hydroxide/graphene (LDH-G) [218], inorganic-organic hybrid nanocomposite [219], and cross-linked PIL [83] for the determination of hydroxylated PAHs as metabolites of PAHs [213,219], organochlorine pesticides [218], and endocrine-disrupting chemicals [83]. In the study proposed by Yang et al [213], an improved low-cost direct SPME-MS technique with glass capillary was further developed for the determination of five typical OH-PAHs in urine samples using a C18-SPME fiber, which then was inserted into a prefilled glass-capillary with spray solvent to generate ions for MS analysis.…”

Bioanalytical HPLC Applications of In-Tube Solid Phase Microextraction: A Two-Decade Overview

“…Other materials that have been employed as coating materials for capillary columns include β-cyclodextrin [117], titania (TiO 2 ) [118], polydopamine/dialdehyde starch/chitosan composite [112], Fe 3 O 4 /SiO 2 /layered double (Cu-Cr) hydroxide nanoparticles [113], Cu-Cr-Al ternary layered double hydroxide/polythiophene coating [119], polypyrrole [120][121][122][123][124][125][126][127][128][129], sol-gel materials [130], and Fe 3 O 4 /SiO 2 [131].…”

“…A hybrid inorganic-organic zinc oxide/polypyrrole coating material has been also synthesized and evaluated for the online in-tube SPME of monohydroxy polycyclic aromatic hydrocarbons in urine. The hybrid sorbent combined the large surface area of zinc oxide nanorods and the porous structure of polypyrrole to provide a stable coating with a long lifespan [129].…”