Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation
Dehydrogenation and deprotonation of sucrose and trehalose molecules in vacuum is theoretically studied by using ab initio calculations in the framework of the density functional theory. The differences in the structural, electronic, energetic and vibrational properties of dehydrogenated and deproto...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
The Royal Society
2022-10-01
|
| Series: | Royal Society Open Science |
| Subjects: | |
| Online Access: | https://royalsocietypublishing.org/doi/10.1098/rsos.220436 |
| _version_ | 1827639207493894144 |
|---|---|
| author | Bohdan Andriyevsky Nathalie Tarrat Juan Cortés Johann Christian Schön |
| author_facet | Bohdan Andriyevsky Nathalie Tarrat Juan Cortés Johann Christian Schön |
| author_sort | Bohdan Andriyevsky |
| collection | DOAJ |
| description | Dehydrogenation and deprotonation of sucrose and trehalose molecules in vacuum is theoretically studied by using ab initio calculations in the framework of the density functional theory. The differences in the structural, electronic, energetic and vibrational properties of dehydrogenated and deprotonated molecules are discussed, depending on the site from which the hydrogen atom or the proton has been removed. The dehydrogenated molecules are found to be stable, regardless of which hydrogen atom is removed. This contrasts with the instability of the deprotonated molecules, where break-ups or structural reorganizations of the molecule are observed in 20–30% of the cases, but only when the hydrogen atom whose proton is removed was bonded to a carbon atom. Considering the stability and possible rearrangements of the hydrogen network of the deprotonated/dehydrogenated molecule, the formation of additional hydrogen-bridge bonds compared with the nominal molecule appears to be more pronounced for the deprotonated molecules than for the dehydrogenated ones. Moreover, our calculations show that the hydrogen-transfer energy barriers are usually larger for the deprotonated molecules than for the dehydrogenated ones. Finally, compared with the nominal molecule, the vibrational frequency spectrum is shifted to lower frequencies for both the dehydrogenated and the deprotonated molecules. |
| first_indexed | 2024-03-09T16:35:20Z |
| format | Article |
| id | doaj.art-8502153356724dfdb3f5dca3cd6a6d6a |
| institution | Directory Open Access Journal |
| issn | 2054-5703 |
| language | English |
| last_indexed | 2024-03-09T16:35:20Z |
| publishDate | 2022-10-01 |
| publisher | The Royal Society |
| record_format | Article |
| series | Royal Society Open Science |
| spelling | doaj.art-8502153356724dfdb3f5dca3cd6a6d6a2023-11-24T14:57:05ZengThe Royal SocietyRoyal Society Open Science2054-57032022-10-0191010.1098/rsos.220436Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigationBohdan Andriyevsky0Nathalie Tarrat1Juan Cortés2Johann Christian Schön3Faculty of Electronics and Computer Science, Koszalin University of Technology, Śniadeckich Street 2, 74-453 Koszalin, PolandCEMES, Université de Toulouse, CNRS, 29 rue Jeanne Marvig, 31055 Toulouse, FranceLAAS-CNRS, Université de Toulouse, CNRS, 31400 Toulouse, FranceMax Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, GermanyDehydrogenation and deprotonation of sucrose and trehalose molecules in vacuum is theoretically studied by using ab initio calculations in the framework of the density functional theory. The differences in the structural, electronic, energetic and vibrational properties of dehydrogenated and deprotonated molecules are discussed, depending on the site from which the hydrogen atom or the proton has been removed. The dehydrogenated molecules are found to be stable, regardless of which hydrogen atom is removed. This contrasts with the instability of the deprotonated molecules, where break-ups or structural reorganizations of the molecule are observed in 20–30% of the cases, but only when the hydrogen atom whose proton is removed was bonded to a carbon atom. Considering the stability and possible rearrangements of the hydrogen network of the deprotonated/dehydrogenated molecule, the formation of additional hydrogen-bridge bonds compared with the nominal molecule appears to be more pronounced for the deprotonated molecules than for the dehydrogenated ones. Moreover, our calculations show that the hydrogen-transfer energy barriers are usually larger for the deprotonated molecules than for the dehydrogenated ones. Finally, compared with the nominal molecule, the vibrational frequency spectrum is shifted to lower frequencies for both the dehydrogenated and the deprotonated molecules.https://royalsocietypublishing.org/doi/10.1098/rsos.220436moleculessucrosetrehalosedehydrogenationdeprotonationdensity functional theory |
| spellingShingle | Bohdan Andriyevsky Nathalie Tarrat Juan Cortés Johann Christian Schön Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation Royal Society Open Science molecules sucrose trehalose dehydrogenation deprotonation density functional theory |
| title | Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation |
| title_full | Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation |
| title_fullStr | Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation |
| title_full_unstemmed | Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation |
| title_short | Dehydrogenation versus deprotonation of disaccharide molecules in vacuum: a thorough theoretical investigation |
| title_sort | dehydrogenation versus deprotonation of disaccharide molecules in vacuum a thorough theoretical investigation |
| topic | molecules sucrose trehalose dehydrogenation deprotonation density functional theory |
| url | https://royalsocietypublishing.org/doi/10.1098/rsos.220436 |
| work_keys_str_mv | AT bohdanandriyevsky dehydrogenationversusdeprotonationofdisaccharidemoleculesinvacuumathoroughtheoreticalinvestigation AT nathalietarrat dehydrogenationversusdeprotonationofdisaccharidemoleculesinvacuumathoroughtheoreticalinvestigation AT juancortes dehydrogenationversusdeprotonationofdisaccharidemoleculesinvacuumathoroughtheoreticalinvestigation AT johannchristianschon dehydrogenationversusdeprotonationofdisaccharidemoleculesinvacuumathoroughtheoreticalinvestigation |