Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies
Understanding the conformational preferences of carbohydrates is crucial to explain the interactions with their biological targets and to improve their use as therapeutic agents. We present experimental data resolving the conformational landscape of the monosaccharide d-lyxose, for which quantum mec...
| Autores: | , , , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2019 |
| País: | España |
| Institución: | Universidad del País Vasco |
| Repositorio: | Addi. Archivo Digital para la Docencia y la Investigación |
| OAI Identifier: | oai:addi.ehu.eus:10810/71228 |
| Acceso en línea: | http://hdl.handle.net/10810/71228 |
| Access Level: | acceso abierto |
| Palabra clave: | carbohydrates rotational spectroscopy conformers |
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oai:addi.ehu.eus:10810/71228 |
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Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies Calabrese, Camilla Écija Verdejo, Patricia Compañón, Ismael Vallejo López, Montserrat Cimas, Álvaro Parra Santamaría, Maider Basterrechea Elguezabal, Francisco José Santos, José I. Jiménez Barbero, Jesús Lesarri, Alberto Corzana, Francisco Cocinero Pérez, Emilio José carbohydrates rotational spectroscopy conformers Understanding the conformational preferences of carbohydrates is crucial to explain the interactions with their biological targets and to improve their use as therapeutic agents. We present experimental data resolving the conformational landscape of the monosaccharide d-lyxose, for which quantum mechanical (QM) calculations offer model-dependent results. This study compares the structural preferences in the gas phase, determined by rotational spectroscopy, with those in solution, resolved by nuclear magnetic resonance (NMR) and molecular dynamics (MD) simulations. In contrast to QM calculations, d-lyxose adopts only pyranose forms in the gas phase, with the α-anomer exhibiting both the 4C1 and 1C4 chairs (60:40). The predominantly populated β-anomer shows the 4C1 form exclusively, as determined experimentally by isotopic substitution. In aqueous solution, the pyranose forms are also dominant. However, in contrast to the gas phase, the α-anomer as 1C4 chair is the most populated, and its solvation is more effective than for the β derivative. Markedly, the main conformers found in the gas phase and solution are characterized by the lack of the stabilizing anomeric effect. From a mechanistic perspective, both rotational spectroscopy and solid-state nuclear magnetic resonance (NMR) corroborate that α ↔ β or furanose ↔ pyranose interconversions are prevented in the gas phase. Combining microwave (MW) and NMR results provides a powerful method for unraveling the water role in the conformational preferences of challenging molecules, such as flexible monosaccharides. We thank MINECO (Project No. CTQ2017-89150-R), Ministerio de Ciencia, Innovación y Universidades (Nos. RTI2018-099592-B-C21 and PGC2018-098561-B-C22), Basque Government (No. PIBA 2018-11), the UPV/EHU (No. PPG17/10), Fundación BBVA, the EU (Marie-Sklodowska Curie ITN, ProteinConjugates, Grant Agreement No. 675007) for the financial support. C.C. thanks MINECO for a Juan de la Cierva contract. I.C. thanks Universidad de La Rioja for the FPI grant. The computational, laser, and NMR resources of the UPV/EHU were used in this work. We thank Dr. Imanol Usabiaga (Università di Bologna) for his help with theoretical calculations. ACS http://hdl.handle.net/10810/71228 |
| title |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies |
| spellingShingle |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies Calabrese, Camilla carbohydrates rotational spectroscopy conformers |
| title_short |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies |
| title_full |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies |
| title_fullStr |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies |
| title_full_unstemmed |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies |
| title_sort |
Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies |
| author |
Calabrese, Camilla |
| author_facet |
Calabrese, Camilla Écija Verdejo, Patricia Compañón, Ismael Vallejo López, Montserrat Cimas, Álvaro Parra Santamaría, Maider Basterrechea Elguezabal, Francisco José Santos, José I. Jiménez Barbero, Jesús Lesarri, Alberto Corzana, Francisco Cocinero Pérez, Emilio José |
| author_role |
author |
| author2 |
Écija Verdejo, Patricia Compañón, Ismael Vallejo López, Montserrat Cimas, Álvaro Parra Santamaría, Maider Basterrechea Elguezabal, Francisco José Santos, José I. Jiménez Barbero, Jesús Lesarri, Alberto Corzana, Francisco Cocinero Pérez, Emilio José |
| author2_role |
author author author author author author author author author author author |
| topic |
carbohydrates rotational spectroscopy conformers |
| topic_facet |
carbohydrates rotational spectroscopy conformers |
| description |
Understanding the conformational preferences of carbohydrates is crucial to explain the interactions with their biological targets and to improve their use as therapeutic agents. We present experimental data resolving the conformational landscape of the monosaccharide d-lyxose, for which quantum mechanical (QM) calculations offer model-dependent results. This study compares the structural preferences in the gas phase, determined by rotational spectroscopy, with those in solution, resolved by nuclear magnetic resonance (NMR) and molecular dynamics (MD) simulations. In contrast to QM calculations, d-lyxose adopts only pyranose forms in the gas phase, with the α-anomer exhibiting both the 4C1 and 1C4 chairs (60:40). The predominantly populated β-anomer shows the 4C1 form exclusively, as determined experimentally by isotopic substitution. In aqueous solution, the pyranose forms are also dominant. However, in contrast to the gas phase, the α-anomer as 1C4 chair is the most populated, and its solvation is more effective than for the β derivative. Markedly, the main conformers found in the gas phase and solution are characterized by the lack of the stabilizing anomeric effect. From a mechanistic perspective, both rotational spectroscopy and solid-state nuclear magnetic resonance (NMR) corroborate that α ↔ β or furanose ↔ pyranose interconversions are prevented in the gas phase. Combining microwave (MW) and NMR results provides a powerful method for unraveling the water role in the conformational preferences of challenging molecules, such as flexible monosaccharides. |
| publishDate |
2019 |
| format |
article |
| url |
http://hdl.handle.net/10810/71228 |
| eu_rights_str_mv |
openAccess |
| publisher |
ACS |
| institution |
Universidad del País Vasco |
| collection |
Addi. Archivo Digital para la Docencia y la Investigación |
| reponame_str |
Addi. Archivo Digital para la Docencia y la Investigación |
| instname_str |
Universidad del País Vasco |
| _version_ |
1878739622305988608 |
| publishDateSort |
2019 |
| author_browse |
Basterrechea Elguezabal, Francisco José Calabrese, Camilla Cimas, Álvaro Cocinero Pérez, Emilio José Compañón, Ismael Corzana, Francisco Jiménez Barbero, Jesús Lesarri, Alberto Parra Santamaría, Maider Santos, José I. Vallejo López, Montserrat Écija Verdejo, Patricia |
| publisherStr |
ACS |
| score |
6.8972664 |