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

Chirality-Puckering correlation and intermolecular interactions in Sphingosines: Rotational spectroscopy of jaspine B3 and its monohydrate Saragi, Rizalina Tama Juanes San José, Marcos Abad, José Luis Pinacho Gómez, Ruth Rubio García, José Emiliano Lesarri Gómez, Alberto Eugenio Noncovalent interactions Interacciones no covalentes Sphingosines Esfingosina Rotational spectroscopy Espectroscopía rotacional 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) 2021-12-14T10:22:34Z 2021-12-14T10:22:34Z 2022 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 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 eng https://www.sciencedirect.com/science/article/pii/S1386142521011082?via%3Dihub Attribution-NonCommercial-NoDerivatives 4.0 Internacional info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2021 The Authors application/pdf Elsevier https://uvadoc.uva.es/bitstream/10324/50940/4/Chirality-puckering-correlation.pdf.jpg Hispana TEXT http://creativecommons.org/licenses/by-nc-nd/4.0/ UVaDOC. Repositorio Documental de la Universidad de Valladolid https://uvadoc.uva.es/handle/10324/50940