title: Rapid and selective screening for sulfhydryl analytes in plasma and urine using surface-enhanced transmission mode desorption electrospray ionization mass spectrometry.
abstract: Nylon mesh substrates were derivatized to include VICAT(SH), a biotinylated reagent that contains both a photolabile linking group and a thiol specific capture agent. The enhanced mesh substrates were then used to capture sulfhydryl analytes directly from urine and plasma samples via covalent reaction between the reactive thiols of the analytes and the iodoacetaminyl unit of VICAT(SH). Photocleavage of the labile linker was followed by direct analysis of the mesh surface via transmission mode desorption electrospray ionization (TM-DESI). This chemoselective capture method promoted enrichment of sulfhydryl analytes and reduced matrix interferences, thereby resulting in increased analytical performance of surface enhanced TM-DESI-MS when compared to standard DESI-MS. The present work describes the manufacture of the derivatized mesh substrates and the quality control assessments made during the manufacturing process, the optimization of the chemoselective capture method, and results of experiments pertinent to biological applications. Integration of the chemoselective capture materials with ambient ionization and tandem mass spectrometry results in a powerful combination of speed and selectivity for targeted analyte screening.
authors.affiliation: Department of Chemistry and Biochemistry, University of Texas at Austin, University Station A5300, Austin, Texas 78712, USA.
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Chipuk
authors.forename: Michael H
authors.initials: MH
authors.lastname: Gelb
authors.forename: Jennifer S
authors.initials: JS
authors.lastname: Brodbelt
mesh_terms: D004364:Pharmaceutical Preparations / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D004364:Pharmaceutical Preparations; D013438:Sulfhydryl Compounds
references.citation: Anal Chem. 2007 Aug 1;79(15):5878-87
references.pmid: 17602570
references.citation: J Pharm Biomed Anal. 2009 Oct 15;50(3):384-91
references.pmid: 19525082
references.citation: Nat Methods. 2007 May;4(5):429-35
references.pmid: 17417646
references.citation: Nucleic Acids Res. 1999 Dec 1;27(23):4626-31
references.pmid: 10556319
references.citation: Anal Chem. 2007 Nov 1;79(21):8327-32
references.pmid: 17918908
references.citation: Anal Chem. 2009 Sep 15;81(18):7618-24
references.pmid: 19746995
references.citation: Proc Natl Acad Sci U S A. 1995 Aug 1;92(16):7590-4
references.pmid: 7638235
references.citation: J Chromatogr B Analyt Technol Biomed Life Sci. 2003 Nov 25;797(1-2):305-19
references.pmid: 14630157
references.citation: J Am Soc Mass Spectrom. 2009 Apr;20(4):584-92
references.pmid: 19112027
references.citation: Anal Chem. 2007 Mar 1;79(5):2150-7
references.pmid: 17269655
references.citation: J Am Chem Soc. 2007 Dec 26;129(51):15780-2
references.pmid: 18052286
references.citation: Nat Mater. 2008 Jun;7(6):442-53
references.pmid: 18497851
references.citation: J Chromatogr. 1991 Jan 2;562(1-2):639-45
references.pmid: 2026726
references.citation: Proteomics. 2009 Mar;9(6):1518-23
references.pmid: 19294621
references.citation: Bioconjug Chem. 2004 Mar-Apr;15(2):380-8
references.pmid: 15025535
references.citation: Proc Natl Acad Sci U S A. 1971 Sep;68(9):2153-7
references.pmid: 5289374
references.citation: Methods Enzymol. 2009;463:417-38
references.pmid: 19892186
references.citation: Mass Spectrom Rev. 1997 Nov-Dec;16(6):353-76
references.pmid: 9703694
references.citation: Mass Spectrom Rev. 2004 Jan-Feb;23(1):34-44
references.pmid: 14625891
references.citation: Anal Chem. 2010 Jan 1;82(1):16-8
references.pmid: 19902914
references.citation: Methods Mol Biol. 1995;42:1-218
references.pmid: 7655571
references.citation: Proc Natl Acad Sci U S A. 2003 Jan 21;100(2):409-13
references.pmid: 12515854
references.citation: J Am Soc Mass Spectrom. 2008 Nov;19(11):1612-20
references.pmid: 18684639
references.citation: Comp Biochem Physiol B Biochem Mol Biol. 2002 Dec;133(4):523-35
references.pmid: 12470816
references.citation: Rapid Commun Mass Spectrom. 1996;10(13):1688-92
references.pmid: 8914339
references.citation: Anal Chem. 2002 Mar 15;74(6):1349-54
references.pmid: 11922303
references.citation: Anal Chem. 1999 May 15;71(10):2014-20
references.pmid: 10361500
references.citation: Anal Bioanal Chem. 2006 Jul;385(5):855-60
references.pmid: 16791565
references.citation: J Agric Food Chem. 2008 Jan 23;56(2):333-6
references.pmid: 18092755
references.citation: Cancer Invest. 2007 Mar;25(2):117-23
references.pmid: 17453823
references.citation: Analyst. 2008 Nov;133(11):1481-5
references.pmid: 18936823
references.citation: J Mass Spectrom. 2005 Oct;40(10):1261-75
references.pmid: 16237663
references.citation: Br J Clin Pharmacol. 1984 Mar;17(3):243-50
references.pmid: 6324834
references.citation: ACS Nano. 2008 Jan;2(1):7-18
references.pmid: 19206542
references.citation: Science. 2004 Oct 15;306(5695):471-3
references.pmid: 15486296
references.citation: Science. 2006 Mar 17;311(5767):1566-70
references.pmid: 16543450
references.citation: Anal Chem. 2007 Sep 15;79(18):7131-8
references.pmid: 17705399
references.citation: Anal Chem. 2002 Jul 15;74(14):3429-33
references.pmid: 12139050
references.citation: Biomed Chromatogr. 2003 Jul;17(5):285-91
references.pmid: 12884392
references.citation: Enzyme Microb Technol. 2001 Feb 1;28(2-3):225-232
references.pmid: 11166816
references.citation: Anal Biochem. 2008 Apr 15;375(2):187-95
references.pmid: 18162165
references.citation: Anal Chem. 1995 Mar 1;67(5):843-8
references.pmid: 7762820
references.citation: Anal Bioanal Chem. 2005 Mar;381(5):1095-100
references.pmid: 15744519
references.citation: Anal Chem. 2004 Jul 15;76(14):4104-11
references.pmid: 15253649
references.citation: Anal Biochem. 1981 Apr;112(2):195-203
references.pmid: 6266278
references.citation: J Mol Biol. 1975 Nov 5;98(3):503-17
references.pmid: 1195397
references.citation: Anal Chem. 2005 Apr 15;77(8):2297-302
references.pmid: 15828760