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...

Descripción completa

Detalles Bibliográficos
Autores: 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
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
id ES_c4fc2bf16626a4bf4a5ceb293107e93e
oai_identifier_str oai:addi.ehu.eus:10810/71228
network_acronym_str ES
network_name_str España
repository_id_str
spelling Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR SpectroscopiesCalabrese, CamillaÉcija Verdejo, PatriciaCompañón, IsmaelVallejo López, MontserratCimas, ÁlvaroParra Santamaría, MaiderBasterrechea Elguezabal, Francisco JoséSantos, José I.Jiménez Barbero, JesúsLesarri, AlbertoCorzana, FranciscoCocinero Pérez, Emilio Josécarbohydratesrotational spectroscopyconformersUnderstanding 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.ACS202520252019info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/71228reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoIngléshttps://doi.org/10.1021/acs.jpclett.9b00978info:eu-repo/semantics/openAccess© 2019 American Chemical Societyoai:addi.ehu.eus:10810/712282026-06-18T09:23:17Z
dc.title.none.fl_str_mv Conformational Behavior of D-Lyxose in Gas and Solution Phases by Rotational and NMR Spectroscopies
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
dc.creator.none.fl_str_mv 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 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
dc.subject.none.fl_str_mv carbohydrates
rotational spectroscopy
conformers
topic 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
dc.date.none.fl_str_mv 2019
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/71228
url http://hdl.handle.net/10810/71228
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1021/acs.jpclett.9b00978
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
© 2019 American Chemical Society
eu_rights_str_mv openAccess
rights_invalid_str_mv © 2019 American Chemical Society
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869418949446205440
score 15.81155

Similares en LA Referencia