Abstract
The fabrication of a novel sheathless interface for capillary electrophoresis–electrospray–mass spectrometry (CE–ESI–MS) is described. A programmable CO2 laser was used to ablate small channels in the walls of a polyimide capillary near the terminus. Subsequent exposure of the channel region to a cellulose acetate solution followed by drying resulted in the formation of an electrically conductive semi-permeable membrane. Application of an appropriate voltage to the reservoir resulted in the simultaneous establishment of an electrical connection for CE and ESI. Interface viability was demonstrated by conducting a CE separation of a peptide mixture, with detection accomplished via positive ion mode ESI–MS. For the peptide Val-Tyr-Val, a limit of detection of 0.1 femtomole (S/N 3) was achieved using single reaction monitoring. Attributes of the interface include structural robustness, ease of fabrication, minimal interface dead volume, and the ability to alter post-separation analyte ionization status by use of appropriate buffers in the interface reservoir.
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Coon JJ, Zurbig P, Dakna M, Dominiczak AF, Decramer S, Fliser D, Frommberger M, Golovko I, Good DM, Herget-Rosenthal S, Jankowski J, Julian BA, Kellmann M, Kolch W, Massy Z, Novak J, Rossing K, Schanstra JP, Schiffer E, Theodorescu D, Vanholder R, Weissinger EM, Mischak H (2008) CE–MS analysis of the human urinary proteome for biomarker discovery and disease diagnostics. Proteom Clin Appl 2:964–974
Pont L, Benavente F, Barbosa J, Sanz-Nebot VJ (2013) An update for human blood plasma pretreatment for optimized recovery of low-molecular-mass peptides prior to CE–MS and SPE–CE–MS. J Sep Sci 36:3896–3902
Redman EA, Ramos-Payan M, Mellors JS, Ramsey JM (2016) Analysis of hemoglobin glycation using microfluidic CE–MS: a rapid, mass spectrometry compatible method for assessing diabetes management. Anal Chem 88:5324–5330
Maxwell EJ, Chen DD (2008) Twenty years of interface development for capillary electrophoresis-electrospray ionization-mass spectrometry. Anal Chim Acta 627:25–33
Smith RD, Barinaga CJ, Udseth HR (1988) Improved electrospray ionization interface for capillary zone electrophoresis-mass spectrometry. Anal Chem 60:1948–1952
Fang L, Zhang R, Williams ER, Zare RN (1994) On-line time of flight mass spectrometric analysis of peptides separated by capillary electrophoresis. Anal Chem 66:3696–3701
Bendahl L, Honore SH, Olsen J (2002) A new sheathless electrospray interface for coupling of capillary electrophoresis to ion-trap mass spectrometry. 16:2333–2340
Chen YR, Her GR (2003) A simple method for fabrication of silver-coated sheathless electrospray emitters. Rapid Commun Mass Spectrom 17:437–441
Zamfir AD, Dinca N, Sisu E, Peter- Katalinić J (2006) Copper-coated microsprayer interface for on-line sheathless capillary electrophoresis mass spectrometry for carbohydrates. J Sep Sci 29:414–422
Severs JC, Smith RD (1997) Characterization of microdialysis junction for capillary electrophoresis/microelectrospray ionization mass spectrometry. Anal Chem 69:2154–2158
Cao P, Moini M (1997) A novel sheathless interface for capillary electrophoresis/electrospray ionization mass spectrometry using an in-capillary electrode. J Am Soc Mass Spectrom 8:561–564
Moini M (2007) Simplifying CE–MS operation. 2. Interfacing low-flow separation techniques to mass spectrometry using a porous tip. Anal Chem 79:4241–4246
Marginean I, Keqi T, Smith RD, Kelly RT (2014) Picoelectrospray ionization mass spectrometry using narrow-bore chemically etched emitters. J Am Soc Mass Spectrom 25:30–36
Wang C, Lee CS, Smith RD, Tang K (2013) Capillary isotachophoresis-nanoelectrospray ionization-selected reaction monitoring MS via a novel sheathless interface for high sensitivity sample quantification. Anal Chem 85:7308–7315
Mellors JS, Gorbounov V, Ramsey RS, Ramsey JM (2008) Fully integrated glass microfluidic device for performing high-efficiency capillary electrophoresis and electrospray ionization mass spectrometry. Anal Chem 80:6881–6887
Mellors JS, Jorabchi K, Smith LM, Ramsey JM (2010) Integrated microfluidic device for automated single cell analysis using electrophoretic separation and electrospray ionization mass spectrometry. Anal Chem 82:967–973
Redman EA, Batz NG, Mellors JS, Ramsey JM (2015) Integrated microfluidic capillary electrophoresis-electrospray ionization devices with online MS detection for the separation and characterization of intact monoclonal antibody variants. Anal Chem 87:2264–2272
Osbourn DM, Lunte CE (2001) Cellulose acetate decoupler for on-column electrochemical detection in capillary electrophoresis. Anal Chem 73:5961–5964
Yuan J, Dunn D, Clipse NM, Newton R Jr (2009) Formulation effects on the thermomechanical properties and permeability of free films and coating films. Pharm Technol 33:88–100
O’Shea TJ, Greenhagen RD, Lunte SM, Lunte CE, Smyth MR, Radzik DM, Watanabe N (1992) Capillary electrophoresis with electrochemical detection employing an on-column nafion joint. J Chromatogr 593:305–312
Wu Y-T, Chen Y-C (2005) Sheathless capillary electrophoresis/electrospray ionization mass spectrometry using a pulled bare fused-silica capillary as the electrospray emitter. Anal Chem 77:2071–2077
Soga T, Ohashi Y, Ueno Y, Naroka H, Tomita M, Nishioka T (2003) Quantitative metabolome analysis using capillary electrophoresis mass spectrometry. Proteome Res 2:488–494
Melanson JE, Baryla NE, Lucy CA (2001) Dynamic capillary for electroosmotic flow control in capillary electrophoresis. Trends Anal Chem 20:365–374
Zhou J, Lunte SM (1995) Membrane-based on-column mixer for capillary electrophoresis/electrochemistry. Anal Chem 67:13–18
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Johnson, R.T., To, N.H., Stobaugh, J.F. et al. The Development of a Sheathless Interface for Capillary Electrophoresis Electrospray Ionization Mass Spectrometry Using a Cellulose Acetate Cast Capillary. Chromatographia 80, 1061–1067 (2017). https://doi.org/10.1007/s10337-017-3326-y
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DOI: https://doi.org/10.1007/s10337-017-3326-y