Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers
Accurate modeling of small molecules substantially reduces the logistical effort and time consumption to discover and then obtain chemicals with various applications. Molecular stereochemistry is fundamentally involved in the intermolecular interactions that give rise to biological activity. Establi...
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MDPI AG
2023-06-01
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| Series: | Applied Sciences |
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| Online Access: | https://www.mdpi.com/2076-3417/13/13/7530 |
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| author | Carolina Cojocariu Nicolae Dinca Marius Georgescu Eugen Sisu Alina Serb Mihai-Cosmin Pascariu |
| author_facet | Carolina Cojocariu Nicolae Dinca Marius Georgescu Eugen Sisu Alina Serb Mihai-Cosmin Pascariu |
| author_sort | Carolina Cojocariu |
| collection | DOAJ |
| description | Accurate modeling of small molecules substantially reduces the logistical effort and time consumption to discover and then obtain chemicals with various applications. Molecular stereochemistry is fundamentally involved in the intermolecular interactions that give rise to biological activity. Establishing the configuration of the asymmetric carbon in diastereomers can be decisive in drug design. In the presented analytical technique, on the basis of quantitative structure–fragmentation relationship (QSFR), mass–energy profiles obtained by electron ionization mass spectrometry (EI-MS) for analytes are used, along with some profiles for candidate structures calculated by quantum chemical (QC) methods. Our paper establishes the analytical conditions that lead to the best matching scores of such profiles corresponding to the actual structures for some isomers of acetalized monosaccharides. The optimization was achieved by group validation of five analytes, using four independent variables: the QC method, the descriptor of calculated energy, the impact energy of electrons, and the descriptor of experimental energy. The true structures were obtained using experimental profiles obtained at low electronic impact energies, and profiles were calculated using the DFT (B3LYP/6-31G) and RM1 QC methods. The double quantification of the ionic mass and the energy that generates it, for only a few primary ions of the mass spectrum, even allows the differentiation of acetalized diastereomers. |
| first_indexed | 2024-03-11T01:47:17Z |
| format | Article |
| id | doaj.art-9a55e7b47d8e41d8a40fb203edc8431a |
| institution | Directory Open Access Journal |
| issn | 2076-3417 |
| language | English |
| last_indexed | 2024-03-11T01:47:17Z |
| publishDate | 2023-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Applied Sciences |
| spelling | doaj.art-9a55e7b47d8e41d8a40fb203edc8431a2023-11-18T16:07:43ZengMDPI AGApplied Sciences2076-34172023-06-011313753010.3390/app13137530Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide IsomersCarolina Cojocariu0Nicolae Dinca1Marius Georgescu2Eugen Sisu3Alina Serb4Mihai-Cosmin Pascariu5Department of Biochemistry and Pharmacology, “Victor Babes” University of Medicine and Pharmacy, RO-300041 Timisoara, RomaniaDepartment of Technical and Natural Sciences, Faculty of Food Engineering, Tourism and Environmental Protection, “Aurel Vlaicu” University, RO-310330 Arad, RomaniaDepartment of Functional Sciences, “Victor Babes” University of Medicine and Pharmacy, RO-300041 Timisoara, RomaniaDepartment of Biochemistry and Pharmacology, “Victor Babes” University of Medicine and Pharmacy, RO-300041 Timisoara, RomaniaDepartment of Biochemistry and Pharmacology, “Victor Babes” University of Medicine and Pharmacy, RO-300041 Timisoara, RomaniaDepartment of Pharmaceutical Sciences, Faculty of Pharmacy, “Vasile Goldiș” Western University, RO-310414 Arad, RomaniaAccurate modeling of small molecules substantially reduces the logistical effort and time consumption to discover and then obtain chemicals with various applications. Molecular stereochemistry is fundamentally involved in the intermolecular interactions that give rise to biological activity. Establishing the configuration of the asymmetric carbon in diastereomers can be decisive in drug design. In the presented analytical technique, on the basis of quantitative structure–fragmentation relationship (QSFR), mass–energy profiles obtained by electron ionization mass spectrometry (EI-MS) for analytes are used, along with some profiles for candidate structures calculated by quantum chemical (QC) methods. Our paper establishes the analytical conditions that lead to the best matching scores of such profiles corresponding to the actual structures for some isomers of acetalized monosaccharides. The optimization was achieved by group validation of five analytes, using four independent variables: the QC method, the descriptor of calculated energy, the impact energy of electrons, and the descriptor of experimental energy. The true structures were obtained using experimental profiles obtained at low electronic impact energies, and profiles were calculated using the DFT (B3LYP/6-31G) and RM1 QC methods. The double quantification of the ionic mass and the energy that generates it, for only a few primary ions of the mass spectrum, even allows the differentiation of acetalized diastereomers.https://www.mdpi.com/2076-3417/13/13/7530mass–energy profilesmass spectrometry (MS)quantitative structure–fragmentation relationship (QSFR)molecule recognitiondiastereomers |
| spellingShingle | Carolina Cojocariu Nicolae Dinca Marius Georgescu Eugen Sisu Alina Serb Mihai-Cosmin Pascariu Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers Applied Sciences mass–energy profiles mass spectrometry (MS) quantitative structure–fragmentation relationship (QSFR) molecule recognition diastereomers |
| title | Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers |
| title_full | Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers |
| title_fullStr | Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers |
| title_full_unstemmed | Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers |
| title_short | Mass–Energy Profiles Obtained by Quantum Chemical Computing Applied in Mass Spectrometry: A Case Study with Identification of a Group of Acetalized Monosaccharide Isomers |
| title_sort | mass energy profiles obtained by quantum chemical computing applied in mass spectrometry a case study with identification of a group of acetalized monosaccharide isomers |
| topic | mass–energy profiles mass spectrometry (MS) quantitative structure–fragmentation relationship (QSFR) molecule recognition diastereomers |
| url | https://www.mdpi.com/2076-3417/13/13/7530 |
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