2026-04-22T21:34:17Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/509402022-02-01T12:02:56Zcom_10324_1186com_10324_931com_10324_894col_10324_1404

Saragi, Rizalina Tama Juanes San José, Marcos Abad, José Luis Pinacho Gómez, Ruth Rubio García, José Emiliano Lesarri Gómez, Alberto Eugenio 2021-12-14T10:22:34Z 2021-12-14T10:22:34Z 2022 Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2022, vol. 267, part 2, 120531 1386-1425 https://uvadoc.uva.es/handle/10324/50940 10.1016/j.saa.2021.120531 Producción Científica Chirality is determinant for sphingosine biofunctions and pharmacological activity, yet the reasons for the biological chiral selection are not well understood. Here, we characterized the intra- and intermolecular interactions at the headgroup of the cytotoxic anhydrophytosphingosine jaspine B, revealing chirality-dependent correlations between the puckering of the ring core and the formation of amino-alcohol hydrogen bond networks, both in the monomer and the monohydrate. Following the specific synthesis of a shortened 3-carbon side-chain molecule, denoted jaspine B3, six different isomers were observed in a jet expansion using broadband (chirped-pulsed) rotational spectroscopy. Additionally, a single isomer of the jaspine B3 monohydrate was observed, revealing the insertion of water in between the hydroxy and amino groups and the formation of a network of O-H···N-H···Oring hydrogen bonds. The specific jaspine B3 stereochemistry thus creates a double-faced molecule where the exposed lone-pair electrons may easily catalyze the formation of intermolecular aggregates and determine the sphingosine biological properties. Ministerio de Ciencia, Innovación y Universidades - Fondo Europeo de Desarrollo Regional (grant PGC2018-098561-B-C22) application/pdf eng Elsevier info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2021 The Authors Attribution-NonCommercial-NoDerivatives 4.0 Internacional Noncovalent interactions Interacciones no covalentes Sphingosines Esfingosina Rotational spectroscopy Espectroscopía rotacional Chirality-Puckering correlation and intermolecular interactions in Sphingosines: Rotational spectroscopy of jaspine B3 and its monohydrate info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion https://www.sciencedirect.com/science/article/pii/S1386142521011082?via%3Dihub SI