Enantiomer Differentiation of Amino Acid Stereoisomers by Structural Mass Spectrometry Using Noncovalent Trinuclear Copper Complexes.
Saved in:
| Title: | Enantiomer Differentiation of Amino Acid Stereoisomers by Structural Mass Spectrometry Using Noncovalent Trinuclear Copper Complexes. |
|---|---|
| Authors: | Zlibut, Emanuel1 (AUTHOR), May, Jody C.1 (AUTHOR), McLean, John A.1 (AUTHOR) john.a.mclean@vanderbilt.edu |
| Source: | Journal of the American Society for Mass Spectrometry. 6/1/2022, Vol. 33 Issue 6, p996-1002. 7p. |
| Abstract: | Previous work has demonstrated that copper complexation strategies can be used with tandem MS (MS/MS) and, more recently, ion mobility-mass spectrometry (IM-MS) to differentiate chiral isomers based upon enantiomeric-specific binding. In this study, we investigate the separation of chiral amino acids (AAs) forming trinuclear complexes that can be directly resolved by IM-MS analyses. Twenty standard AAs of both d- and l-chirality were investigated. Specific AAs including d/l-histidine, d/l-proline, d/l-glutamine, d/l-tyrosine, and d/l-tryptophan were evaluated as "chiral selectors" that, when combined with copper, were found to promote selective complexation with specific AA enantiomers. Significant enantiomer differentiation was observed in the IM spectra for hydrophobic AAs acids with peak-to-peak resolutions ranging from 0.63 to 1.15. Among the chiral selectors investigated, histidine provided the best enantioselectivity, followed by tryptophan, suggesting the aromatic structure plays an important role in forming chiral-specific ion complexes. Unlike MS/MS methods where chiral selectors with l-stereochemistry enhance the differentiation, the chirality of the selector was found to have no significant effect on observed IM separation with both d- and l-selectors providing similar resolutions but with inverted IM arrival time ordering. To investigate the structural differences between resolvable chiral complexes, a combination of MS/MS, collision cross-section (CCS) measurements, and molecular mechanics techniques was used. Candidate trinuclear structures of the stoichiometry [(Cu2+)3(d/lIle)3(lHis)2 – 5H]+ were constructed with guidance from empirical MS/MS results. Of the 48 theoretical structures generated, one enantiomeric cluster pair yielded close correlation (<1%) with experimental CCS measurements, suggesting the most enantioselective ion complexes observed in this work are bridged by three coppers. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of the American Society for Mass Spectrometry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
|---|---|
| Header | DbId: egs DbLabel: Engineering Source An: 158161327 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Enantiomer Differentiation of Amino Acid Stereoisomers by Structural Mass Spectrometry Using Noncovalent Trinuclear Copper Complexes. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Zlibut%2C+Emanuel%22">Zlibut, Emanuel</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22May%2C+Jody+C%2E%22">May, Jody C.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22McLean%2C+John+A%2E%22">McLean, John A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> john.a.mclean@vanderbilt.edu</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Society+for+Mass+Spectrometry%22">Journal of the American Society for Mass Spectrometry</searchLink>. 6/1/2022, Vol. 33 Issue 6, p996-1002. 7p. – Name: Abstract Label: Abstract Group: Ab Data: Previous work has demonstrated that copper complexation strategies can be used with tandem MS (MS/MS) and, more recently, ion mobility-mass spectrometry (IM-MS) to differentiate chiral isomers based upon enantiomeric-specific binding. In this study, we investigate the separation of chiral amino acids (AAs) forming trinuclear complexes that can be directly resolved by IM-MS analyses. Twenty standard AAs of both d- and l-chirality were investigated. Specific AAs including d/l-histidine, d/l-proline, d/l-glutamine, d/l-tyrosine, and d/l-tryptophan were evaluated as "chiral selectors" that, when combined with copper, were found to promote selective complexation with specific AA enantiomers. Significant enantiomer differentiation was observed in the IM spectra for hydrophobic AAs acids with peak-to-peak resolutions ranging from 0.63 to 1.15. Among the chiral selectors investigated, histidine provided the best enantioselectivity, followed by tryptophan, suggesting the aromatic structure plays an important role in forming chiral-specific ion complexes. Unlike MS/MS methods where chiral selectors with l-stereochemistry enhance the differentiation, the chirality of the selector was found to have no significant effect on observed IM separation with both d- and l-selectors providing similar resolutions but with inverted IM arrival time ordering. To investigate the structural differences between resolvable chiral complexes, a combination of MS/MS, collision cross-section (CCS) measurements, and molecular mechanics techniques was used. Candidate trinuclear structures of the stoichiometry [(Cu2+)3(d/lIle)3(lHis)2 – 5H]+ were constructed with guidance from empirical MS/MS results. Of the 48 theoretical structures generated, one enantiomeric cluster pair yielded close correlation (<1%) with experimental CCS measurements, suggesting the most enantioselective ion complexes observed in this work are bridged by three coppers. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Society for Mass Spectrometry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=158161327 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/jasms.2c00059 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 7 StartPage: 996 Titles: – TitleFull: Enantiomer Differentiation of Amino Acid Stereoisomers by Structural Mass Spectrometry Using Noncovalent Trinuclear Copper Complexes. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Zlibut, Emanuel – PersonEntity: Name: NameFull: May, Jody C. – PersonEntity: Name: NameFull: McLean, John A. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 06 Text: 6/1/2022 Type: published Y: 2022 Identifiers: – Type: issn-print Value: 10440305 Numbering: – Type: volume Value: 33 – Type: issue Value: 6 Titles: – TitleFull: Journal of the American Society for Mass Spectrometry Type: main |
| ResultId | 1 |
