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Direct characterization of bulk samples by internal extractive electrospray ionization mass spectrometry.

Zhang H, Gu H, Yan F, Wang N, Wei Y, Xu J, Chen H - Sci Rep (2013)

Bottom Line: The method allows both qualitative and quantitative analysis of analytes distributed in a 3-dimensional volume (e.g., 1 ~ 100 mm(3)) of various synthetic and biological matrices (e.g., chewing gum, leaves, fruits, roots, pork, lung tissues) without either mashing the sample or matrix separation.Using different extraction solvents, online chromatographic separation of chemicals inside the sample volume was observed during iEESI-MS analysis.The presented method is featured by the high speed of analysis, high sensitivity, low sample consumption and minimal sample preparation and/or degradation, offering unique possibilities for advanced applications in plant science, clinical diagnosis, catalyst studies, and materials science.

View Article: PubMed Central - PubMed

Affiliation: Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China Institute of Technology, Nanchang, Jiangxi 330013, China.

ABSTRACT
A straight-forward analytical strategy called internal extractive electrospray ionization mass spectrometry (iEESI-MS), which combines solvent extraction of chemicals inside a bulk sample with in situ electrospray ionization mass spectrometry, has been established to directly characterize the interior of a bulk sample with molecular specificity. The method allows both qualitative and quantitative analysis of analytes distributed in a 3-dimensional volume (e.g., 1 ~ 100 mm(3)) of various synthetic and biological matrices (e.g., chewing gum, leaves, fruits, roots, pork, lung tissues) without either mashing the sample or matrix separation. Using different extraction solvents, online chromatographic separation of chemicals inside the sample volume was observed during iEESI-MS analysis. The presented method is featured by the high speed of analysis, high sensitivity, low sample consumption and minimal sample preparation and/or degradation, offering unique possibilities for advanced applications in plant science, clinical diagnosis, catalyst studies, and materials science.

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Selective extraction of analytes distributed inside the bulk volume of a chewing gum using different solvents for iEESI-MS analysis.a) cyclohexane; b) water; c) methanol.
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f3: Selective extraction of analytes distributed inside the bulk volume of a chewing gum using different solvents for iEESI-MS analysis.a) cyclohexane; b) water; c) methanol.

Mentions: Selective extraction of analytes distributed inside the bulk volume of a raw sample is easily achieved in iEESI by using solvents with different polarity. For example, different analytes were selectively detected from a chewing gum with cyclohexane, water, or methanol as ESI solvent. Dramatically different mass spectra were observed, with regard to both signal composition and total ion intensity (Fig. 3). Generally low-intensity signals (~1.23 cps) were detected in the mass range of m/z 250–800 (Fig. 3a) from the chewing gum by iEESI-MS with cyclohexane, while considerably richer mass patterns with higher signal abundances (>103 cps) were obtained using water (Fig. 3b) and methanol (Fig. 3c) under the same experimental conditions. Since cyclohexane is not a very suitable solvent for ESI, the low signal density achieved using cyclohexane might be caused by the low efficiency of either ionization or extraction process of the iEESI. No signal of polar ingredients such as glucose (MW 180) and glycerol (MW 92) was detected by iEESI-MS using cyclohexane. More abundant signals were obtained by iEESI using water and, particularly, methanol as the extraction solvent. Therefore, we attribute the observed difference to the more efficient extraction of these compounds achieved by polar water and methanol solvents as compared to nonpolar cyclohexane. Polar molecules such as glucose (m/z 198 and 221), glycerol (m/z 115 and 131), menthol (m/z 157), menthone (m/z 155) and sucrose (m/z 360 and 381) were detected at high abundances in iEESI-MS with water and methanol as the extraction solvent, while the corresponding peaks were absent in the mass spectra using cyclohexane (Fig. 3a). Using water, the dominant mass rage in the mass spectrum was m/z 400–800 (Fig. 3b), while the iEESI-MS fingerprint obtained with methanol spanned a much wider m/z range (100–2000) (Fig. 3c).


Direct characterization of bulk samples by internal extractive electrospray ionization mass spectrometry.

Zhang H, Gu H, Yan F, Wang N, Wei Y, Xu J, Chen H - Sci Rep (2013)

Selective extraction of analytes distributed inside the bulk volume of a chewing gum using different solvents for iEESI-MS analysis.a) cyclohexane; b) water; c) methanol.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC3750536&req=5

f3: Selective extraction of analytes distributed inside the bulk volume of a chewing gum using different solvents for iEESI-MS analysis.a) cyclohexane; b) water; c) methanol.
Mentions: Selective extraction of analytes distributed inside the bulk volume of a raw sample is easily achieved in iEESI by using solvents with different polarity. For example, different analytes were selectively detected from a chewing gum with cyclohexane, water, or methanol as ESI solvent. Dramatically different mass spectra were observed, with regard to both signal composition and total ion intensity (Fig. 3). Generally low-intensity signals (~1.23 cps) were detected in the mass range of m/z 250–800 (Fig. 3a) from the chewing gum by iEESI-MS with cyclohexane, while considerably richer mass patterns with higher signal abundances (>103 cps) were obtained using water (Fig. 3b) and methanol (Fig. 3c) under the same experimental conditions. Since cyclohexane is not a very suitable solvent for ESI, the low signal density achieved using cyclohexane might be caused by the low efficiency of either ionization or extraction process of the iEESI. No signal of polar ingredients such as glucose (MW 180) and glycerol (MW 92) was detected by iEESI-MS using cyclohexane. More abundant signals were obtained by iEESI using water and, particularly, methanol as the extraction solvent. Therefore, we attribute the observed difference to the more efficient extraction of these compounds achieved by polar water and methanol solvents as compared to nonpolar cyclohexane. Polar molecules such as glucose (m/z 198 and 221), glycerol (m/z 115 and 131), menthol (m/z 157), menthone (m/z 155) and sucrose (m/z 360 and 381) were detected at high abundances in iEESI-MS with water and methanol as the extraction solvent, while the corresponding peaks were absent in the mass spectra using cyclohexane (Fig. 3a). Using water, the dominant mass rage in the mass spectrum was m/z 400–800 (Fig. 3b), while the iEESI-MS fingerprint obtained with methanol spanned a much wider m/z range (100–2000) (Fig. 3c).

Bottom Line: The method allows both qualitative and quantitative analysis of analytes distributed in a 3-dimensional volume (e.g., 1 ~ 100 mm(3)) of various synthetic and biological matrices (e.g., chewing gum, leaves, fruits, roots, pork, lung tissues) without either mashing the sample or matrix separation.Using different extraction solvents, online chromatographic separation of chemicals inside the sample volume was observed during iEESI-MS analysis.The presented method is featured by the high speed of analysis, high sensitivity, low sample consumption and minimal sample preparation and/or degradation, offering unique possibilities for advanced applications in plant science, clinical diagnosis, catalyst studies, and materials science.

View Article: PubMed Central - PubMed

Affiliation: Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China Institute of Technology, Nanchang, Jiangxi 330013, China.

ABSTRACT
A straight-forward analytical strategy called internal extractive electrospray ionization mass spectrometry (iEESI-MS), which combines solvent extraction of chemicals inside a bulk sample with in situ electrospray ionization mass spectrometry, has been established to directly characterize the interior of a bulk sample with molecular specificity. The method allows both qualitative and quantitative analysis of analytes distributed in a 3-dimensional volume (e.g., 1 ~ 100 mm(3)) of various synthetic and biological matrices (e.g., chewing gum, leaves, fruits, roots, pork, lung tissues) without either mashing the sample or matrix separation. Using different extraction solvents, online chromatographic separation of chemicals inside the sample volume was observed during iEESI-MS analysis. The presented method is featured by the high speed of analysis, high sensitivity, low sample consumption and minimal sample preparation and/or degradation, offering unique possibilities for advanced applications in plant science, clinical diagnosis, catalyst studies, and materials science.

Show MeSH
Related in: MedlinePlus