RT info:eu-repo/semantics/article
T1 Chirality-Puckering correlation and intermolecular interactions in Sphingosines: Rotational spectroscopy of jaspine B3 and its monohydrate
A1 Saragi, Rizalina Tama
A1 Juanes San José, Marcos
A1 Abad, José Luis
A1 Pinacho Gómez, Ruth
A1 Rubio García, José Emiliano
A1 Lesarri Gómez, Alberto Eugenio
K1 Noncovalent interactions
K1 Interacciones no covalentes
K1 Sphingosines
K1 Esfingosina
K1 Rotational spectroscopy
K1 Espectroscopía rotacional
AB 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.
PB Elsevier
SN 1386-1425
YR 2022
FD 2022
LK https://uvadoc.uva.es/handle/10324/50940
UL https://uvadoc.uva.es/handle/10324/50940
LA eng
NO Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2022, vol. 267, part 2, 120531
NO Producción Científica
DS UVaDOC
RD 16-ago-2024