title: A novel solid-phase microextraction method based on polymer monolith frit combining with high-performance liquid chromatography for determination of aldehydes in biological samples.
abstract: In this work, a polypropylene frit with porous network structure (20 μm pole size) was first utilized as the mould of polymer monolithic material, poly(methacrylic acid-co-ethylene glycol dimethacrylate) (MAA-co-EDMA) monolith was synthesized within channels and macropores of the frit. A simple and sensitive solid-phase microextraction method based on polymer monolith frit coupled with high-performance liquid chromatography (HPLC) was established and applied to analysis of hexanal and heptanal in biological samples (human urine and serum). In the method, small molecule metabolites (aldehydes) in biological samples derivatized with 2,4-dinitrophenylhydrazine (DNPH), and the formed hydrazones were extracted simultaneously on the monolithic frit and thereafter ultrasound-assisted desorbed with acetonitrile as elution solvent. The experimental parameters with regard to polymerization, derivatization and extraction were investigated. Under the optimal conditions, the linearity was in the range of 0.02-5.0 μmol L(-1) (r=0.9994) for both hexanal and heptanal and the limits of detection (S/N=3) were 0.81 nmol L(-1) for hexanal and 0.76 nmol L(-1) for heptanal. The relative standard deviations (RSDs, n=5) were less than 6.5% for the same monolithic frit and less than 8.9% for the different monolithic frits. Satisfactory recoveries ranging from 70.71% to 88.73% were obtained for the urine samples. The method possesses many advantages including simple setup, fast analysis, low cost, sufficient sensitivity, good biological compatibility and less organic solvent consumption. The proposed method is a useful assistant tool in the clinical early diagnosis of lung disease by monitoring aldehyde biomarker candidates in complex biological samples.
authors.affiliation: Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China. huixu@mail.ccnu.edu.cn
authors.forename: Hui
authors.initials: H
authors.lastname: Xu
authors.forename: Shuyu
authors.initials: S
authors.lastname: Wang
authors.forename: Ganbing
authors.initials: G
authors.lastname: Zhang
authors.forename: Shiqiang
authors.initials: S
authors.lastname: Huang
authors.forename: Dandan
authors.initials: D
authors.lastname: Song
authors.forename: Yanping
authors.initials: Y
authors.lastname: Zhou
authors.forename: Guangdou
authors.initials: G
authors.lastname: Long
mesh_terms: D000447:Aldehydes / Q000032:analysis* / Q000097:blood / Q000652:urine; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D006801:Humans; D010659:Phenylhydrazines / Q000737:chemistry; D011126:Polypropylenes / Q000737:chemistry*; D052617:Solid Phase Microextraction / Q000379:methods*; D013696:Temperature
chemical_list: D000447:Aldehydes; D010659:Phenylhydrazines; D011126:Polypropylenes; C004787:2,4-dinitrophenylhydrazine; C046204:heptanal; C010463:n-hexanal