title: TiO₂ nanoparticles functionalized monolithic capillary microextraction online coupled with inductively coupled plasma mass spectrometry for the analysis of Gd ion and Gd-based contrast agents in human urine.
abstract: In this work, a novel method of TiO2 nanoparticles (NPs) functionalized monolithic capillary microextraction (CME) online coupling with inductively coupled plasma mass spectrometry (ICPMS) was developed for the sequential determination of Gd(3+) and Gd-based contrast agents in human urine samples. The monolithic capillary was prepared by embedding anatase TiO2 NPS in the poly(methacrylic acid-ethylene glycol dimethacrylate) (MAA-EDMA) framework. The Gd(3+) and Gd-based contrast agents (such as gadolinium-diethylene triamine pentaacetic acid (Gd-DTPA) and Gd-DTPA-bismethylamide (Gd-DTPA-BMA)) display different adsorption behaviors on the prepared monolithic capillary which possesses the adsorption properties of both anatase TiO2 NPS and poly(MAA-EDMA) monolith. Under the optimized conditions, the limits of detection (LODs) were found to be 3.6, 3.2, and 4.5 ng L(-1) for Gd(3+), Gd-DTPA, and Gd-DTPA-BMA, respectively, which are the lowest up to date. The enrichment factor was 25-fold with the sample throughput of 5 h(-1). The proposed method was validated by the analysis of Gd(3+) and Gd-DTPA in the healthy human urine samples as well as Gd(3+) and Gd-DTPA-BMA in patient urine samples. It was found that only a small amount of the free Gd(3+) was released from Gd-DTPA-BMA, and accurate results could be obtained since no oxidation/reduction or subtraction is involved in this method. This method is simple, sensitive, and rapid and provides a very attractive nonchromatography strategy for the speciation of Gd(3+) and Gd-based contrast agents in urine samples.
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Xiaolan
authors.initials: X
authors.lastname: Liu
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Beibei
authors.initials: B
authors.lastname: Chen
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Lin
authors.initials: L
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Shiyao
authors.initials: S
authors.lastname: Song
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Yabing
authors.initials: Y
authors.lastname: Cai
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Man
authors.initials: M
authors.lastname: He
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University , Wuhan, Hubei 430072, China.
authors.forename: Bin
authors.initials: B
authors.lastname: Hu
mesh_terms: D003287:Contrast Media / Q000032:analysis*; D005682:Gadolinium / Q000032:analysis*; D006801:Humans; D020407:Internet; D007477:Ions / Q000032:analysis; D013058:Mass Spectrometry; D053758:Nanoparticles / Q000737:chemistry*; D052617:Solid Phase Microextraction; D014025:Titanium / Q000737:chemistry*; D016482:Urinalysis / Q000379:methods*
chemical_list: D003287:Contrast Media; D007477:Ions; C009495:titanium dioxide; D005682:Gadolinium; D014025:Titanium