PMID- 22885051 OWN - NLM STAT- MEDLINE DCOM- 20121203 LR - 20120827 IS - 1873-3778 (Electronic) IS - 0021-9673 (Linking) VI - 1256 DP - 2012 Sep 21 TI - High polar organic-inorganic hybrid coating stir bar sorptive extraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of seleno-amino acids and seleno-oligopeptides in biological samples. PG - 32-9 LID - 10.1016/j.chroma.2012.07.080 [doi] AB - In this work, partially sulfonated polystyrene-titania (PSP-TiO(2)) organic-inorganic hybrid stir bar coating was prepared by sol-gel and blending methods, and a new method of PSP-TiO(2) coating stir bar sorptive extraction (SBSE)-high performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) was established for the analysis of seleno-amino acids (selenocystine (SeCys(2)), methylseleno-cysteine (MeSeCys), selenomethionine (SeMet) and selenoethionine (SeEt)) and seleno-oligopeptides (gamma-glutamyl-Se-methyl-selenocysteine (gamma-GluMeSeCys) and selenodiglutathione (GS-Se-SG)) in biological samples. The prepared high polar PSP-TiO(2) hybrid coating avoided the swelling of PSP and cracking of TiO(2) coating by combining the good film-forming property of PSP with the high mechanical strength of TiO(2). The scanning electron microscope (SEM) showed that no obvious swelling and damage occurred for the PSP-TiO(2) hybrid stir bar coating after 30 extraction/desorption cycles. The preparation reproducibility of PSP-TiO(2) coated stir bar, evaluated with the relative standard deviations (RSDs), was in the range of 6.7-12.6% (n=5) in one batch, and 9.9-17.6% (n=7) among different batches. The limits of detection (LODs) of the developed method for six target selenium species were in the range of 50.2-185.5 ngL(-1) (as (77)Se) and 45.9-158.8 ngL(-1) (as (82)Se) with the RSDs within 4.9-11.7%. The dynamic linear range was found to cover three orders of magnitude with correlation coefficient of 0.9995-0.9999. The developed method was applied for the analysis of Certified Reference Material SELM-1 selenium enriched yeast and the determined values were in good agreement with the certified values. The method has also been applied for the analysis of seleno-amino acids and seleno-oligopeptides in human urine and garlic samples. Different from the conventional organic polymer SBSE coatings (such as polydimethylsiloxane, PDMS), the extraction mechanism of PSP-TiO(2) organic-inorganic hybrid SBSE coating was based on the cation exchange interaction, which made it feasible to directly extract high polar seleno-amino acids and seleno-oligopeptides in biological samples without derivatization. This coating could also be suitable for stir bar sorptive extraction of other cationic compounds from the environmental and biological samples. CI - Copyright (c) 2012 Elsevier B.V. All rights reserved. FAU - Mao, Xiangju AU - Mao X AD - Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China. FAU - Hu, Bin AU - Hu B FAU - He, Man AU - He M FAU - Chen, Beibei AU - Chen B LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20120801 PL - Netherlands TA - J Chromatogr A JT - Journal of chromatography. A JID - 9318488 RN - 0 (Oligopeptides) RN - 0 (Selenium Compounds) SB - IM MH - Chromatography, High Pressure Liquid/*methods MH - Hydrogen-Ion Concentration MH - Limit of Detection MH - Mass Spectrometry/*methods MH - Microscopy, Electron, Scanning MH - Oligopeptides/*chemistry MH - Reproducibility of Results MH - Selenium Compounds/*chemistry EDAT- 2012/08/14 06:00 MHDA- 2012/12/10 06:00 CRDT- 2012/08/14 06:00 PHST- 2012/06/15 00:00 [received] PHST- 2012/07/26 00:00 [revised] PHST- 2012/07/26 00:00 [accepted] PHST- 2012/08/14 06:00 [entrez] PHST- 2012/08/14 06:00 [pubmed] PHST- 2012/12/10 06:00 [medline] AID - S0021-9673(12)01153-3 [pii] AID - 10.1016/j.chroma.2012.07.080 [doi] PST - ppublish SO - J Chromatogr A. 2012 Sep 21;1256:32-9. doi: 10.1016/j.chroma.2012.07.080. Epub 2012 Aug 1.