PMID- 22148170 OWN - NLM STAT- MEDLINE DCOM- 20120515 LR - 20211004 IS - 1520-6882 (Electronic) IS - 0003-2700 (Linking) VI - 84 IP - 2 DP - 2012 Jan 17 TI - Enhancing the coverage of the urinary metabolome by sheathless capillary electrophoresis-mass spectrometry. PG - 885-92 LID - 10.1021/ac202407v [doi] AB - Sheathless capillary electrophoresis-mass spectrometry (CE-MS), using a porous tip sprayer, is proposed for the first time for highly sensitive metabolic profiling of human urine. A representative metabolite mixture and human urine were used for evaluation of the sheathless CE-MS platform. For test compounds, relative standard deviations (RSDs) for migration times and peak areas were below 2% and 12%, respectively, and an injection volume of only approximately 8 nL resulted in detection limits between 11 and 120 nM. Approximately 900 molecular features were detected in human urine by sheathless CE-MS whereas about 300 molecular features were found with classical sheath-liquid CE-MS. This difference can probably be attributed to an improved ionization efficiency and increased sensitivity at low flow-rate conditions. The integration of transient-isotachophoresis (t-ITP) as an in-capillary preconcentration procedure in sheathless CE-MS further resulted in subnanomolar limits of detection for compounds of the metabolite mixture, and more than 1300 molecular features were observed in urine. Compared to the classical CE-MS approaches, the integration of t-ITP combined with the use of a sheathless interface provides up to 2 orders of magnitude sensitivity improvement. Hence, sheathless CE-MS can be used for in-depth metabolic profiling of biological samples, and we anticipate that this approach will yield unique information in the field of metabolomics. FAU - Ramautar, Rawi AU - Ramautar R AD - Biomolecular Mass Spectrometry Unit, Department of Parasitology, Leiden University Medical Center, Leiden, The Netherlands. R.Ramautar@lumc.nl FAU - Busnel, Jean-Marc AU - Busnel JM FAU - Deelder, Andre M AU - Deelder AM FAU - Mayboroda, Oleg A AU - Mayboroda OA LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20111230 PL - United States TA - Anal Chem JT - Analytical chemistry JID - 0370536 RN - 0 (Biomarkers) SB - IM MH - Biomarkers/*urine MH - Electrophoresis, Capillary/*methods MH - Humans MH - Isotachophoresis MH - *Metabolome MH - *Metabolomics MH - Spectrometry, Mass, Electrospray Ionization/*methods MH - Urine/*chemistry EDAT- 2011/12/14 06:00 MHDA- 2012/05/16 06:00 CRDT- 2011/12/14 06:00 PHST- 2011/12/14 06:00 [entrez] PHST- 2011/12/14 06:00 [pubmed] PHST- 2012/05/16 06:00 [medline] AID - 10.1021/ac202407v [doi] PST - ppublish SO - Anal Chem. 2012 Jan 17;84(2):885-92. doi: 10.1021/ac202407v. Epub 2011 Dec 30.