2013
DOI: 10.1002/anie.201302870
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Rapid Removal of Matrices from Small‐Volume Samples by Step‐Voltage Nanoelectrospray

Abstract: Matrix unloaded: By changing from fixed-voltage (left) to step-voltage nanoelectrospray (right), the mass-spectrometric analysis of small-volume physiological samples is possible. Separation and ionization are achieved in one process, which avoids sample loss and dilution and prevents interference by the matrix. The result is high sensitivity even for samples at the nanoliter level.

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Cited by 56 publications
(54 citation statements)
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“…Typical mass spectra (Figure e) of zone 1 are very noisy; the spectrum of zone 2 is very clean with the analyte peptides displaying very high SNR and enhanced signal intensity, while the spectrum of zone 3 shows matrix peaks. These results are consistent with the following proposed mechanism, based on our prior study of this effect: during electrophoresis (−5 kV voltage applied to the electrode) a strong static electrical field in the solution pulls small cations and positively charged complexes into zone 3 (they show up later as the interference peaks in the MS of zone 3); the initial negative potential also pushes small anions into zone 1 so cleaning the analyte in zone 2 of interfering negatively charged ions. By removal of the high mobility ions from zone 2, a commensurate narrowing of the bandwidth and preconcentration of weak electrolytes (e.g.…”
Section: Figuresupporting
confidence: 90%
“…Typical mass spectra (Figure e) of zone 1 are very noisy; the spectrum of zone 2 is very clean with the analyte peptides displaying very high SNR and enhanced signal intensity, while the spectrum of zone 3 shows matrix peaks. These results are consistent with the following proposed mechanism, based on our prior study of this effect: during electrophoresis (−5 kV voltage applied to the electrode) a strong static electrical field in the solution pulls small cations and positively charged complexes into zone 3 (they show up later as the interference peaks in the MS of zone 3); the initial negative potential also pushes small anions into zone 1 so cleaning the analyte in zone 2 of interfering negatively charged ions. By removal of the high mobility ions from zone 2, a commensurate narrowing of the bandwidth and preconcentration of weak electrolytes (e.g.…”
Section: Figuresupporting
confidence: 90%
“…[1][2][3][4] The multi-stage pretreatment procedures are usually laborious, timeconsuming, and expensive in operation and commonly suffer from sample losses and chemical contamination. Significant efforts are being made to develop more practical and versatile approaches for chemical preconcentration and purification relying on the recent advances in adsorbent materials, [5][6][7] microfluidics, 8 nanotechnology, 9 micro-extraction, 10 crystallization, 11 electrospray ionization (ESI) [12][13][14] and matrix-assisted laser desorption/ionization (M ALDI). 15 -17 It has been earlier discovered that the concentration of organic solutes in bursting bubble aerosols above the sea surface is increased by more than two orders of magnitude relative to the bulk seawater whereas the chemical enrichment of inorganic constituents (including Na + , M g 2+ , Ca 2+ , K + , Cl -, and SO 4 2-) is limited to a few percent if occurs at all.…”
Section: Introductionmentioning
confidence: 99%
“…2). Besides, our method could avoid the matrix effects caused by the complexity of the sample33, even if sample purification was not conducted, because 1) some matrix, such as salts, could not dissolve into pure methanol, resulting in some tolerance of matrix effects; 2) single reaction monitoring (SRM) was always utilized to identify Cyt and 5mCyt in MS 2 spectra. Therefore, SRM were always used to identify Cyt and 5mCyt while the samples were ionized.…”
Section: Resultsmentioning
confidence: 99%