title: Profiling of cis-diol-containing nucleosides and ribosylated metabolites by boronate-affinity organic-silica hybrid monolithic capillary liquid chromatography/mass spectrometry.
abstract: RNA contains a large number of modified nucleosides. In the metabolic re-exchange of RNA, modified nucleosides cannot be recycled and are thus excreted from cells into biological fluids. Determination of endogenous modified nucleosides in biological fluids may serve as non-invasive cancers diagnostic methods. Here we prepared boronate-affinity organic-silica hybrid capillary monolithic column (BOHCMC) that exhibited excellent selectivity toward the cis-diol-containing compounds. We then used the prepared BOHCMC as the on-line solid-phase microextraction (SPME) column and developed an on-line SPME-LC-MS/MS method to comprehensively profile cis-diol-containing nucleosides and ribosylated metabolites in human urine. Forty-five cis-diol-containing nucleosides and ribosylated metabolites were successfully identified in human urine. And five ribose conjugates, for the first time, were identified existence in human urine in the current study. Furthermore, the relative quantification suggested 4 cis-diol-containing compounds (5'-deoxy-5'-methylthioadensine, N(4)-acetylcytidine, 1-ribosyl-N-propionylhistamine and N(2),N(2),7-trimethylguanosine) increased more than 1.5 folds in all the 3 types of examined cancers (lung cancer, colorectal cancer, and nasopharyngeal cancer) compared to healthy controls. The on-line SPME-LC-MS/MS method demonstrates a promising method for the comprehensive profiling of cis-diol-containing ribose conjugates in human urines, which provides an efficient strategy for the identification and discovery of biomarkers and may be used for the screening of cancers.
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
authors.forename: Han-Peng
authors.initials: HP
authors.lastname: Jiang
authors.affiliation: 1] Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China [2] Department of Pathology, Hubei Cancer Hospital, Wuhan 430079, China.
authors.forename: Chu-Bo
authors.initials: CB
authors.lastname: Qi
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
authors.forename: Jie-Mei
authors.initials: JM
authors.lastname: Chu
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
authors.forename: Bi-Feng
authors.initials: BF
authors.lastname: Yuan
authors.affiliation: Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
authors.forename: Yu-Qi
authors.initials: YQ
authors.lastname: Feng
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D016022:Case-Control Studies; D002846:Chromatography, Affinity / Q000379:methods*; D002853:Chromatography, Liquid / Q000379:methods*; D006801:Humans; D055442:Metabolome; D009705:Nucleosides / Q000032:analysis*; D012266:Ribose / Q000652:urine*; D012822:Silicon Dioxide / Q000737:chemistry; D052617:Solid Phase Microextraction; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D000438:Alcohols; D001897:Boronic Acids; D009705:Nucleosides; D012266:Ribose; D012822:Silicon Dioxide