Chiral micelles for matrix-assisted DOSY

• Grant number: 21/05081-5
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• Start date: August 01, 2021
• End date: July 31, 2027
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Claudio Francisco Tormena
• Grantee: Tadeu Luiz Gomes Cabral
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant: 20/10246-0 - Nuclear magnetic resonance spectroscopy: from pulse sequences to structural assignments, AP.TEM
• Associated scholarship(s): 23/07116-6 - Investigation of enantiodiscrimination using computational approaches, BE.EP.DD

Abstract

Matrix-Assisted DOSY (MAD) has been used to differentiate molecules that diffuse at a similar rate, as it is often the case for isomers. The differentiation is based on modifying the solution matrix (i.e. the medium), by adding large compounds that interact with each isomer present in the sample with different strengths. Surfactants are typically used for this purpose. Our group has made significant contributions in this field, and the power of MAD was recently demonstrated in a preliminary study, where enantiomers were differentiated using a small chiral (BINOL) matrix compound. Due to the small difference in the interaction strength between enantiomers with BINOL, a high concentration of BINOL is required in comparison with enantiomers for differentiation of enantiomers in the diffusion dimension, limiting the application for soluble compounds in a non-polar organic solvent, typically chloroform. On top of that, BINOL is not large enough to meet the size required for MAD. Even when BINOL is strongly bonded to a molecule, changes in the diffusion coefficient are small, and the distinction is not achieved. We intend to use chiral amphiphile PS-750-M micelles to differentiate enantiomers using water and organic solvent. The PS-750-M micelles were chosen since it has been reported that PS-750-M can be used to selective direct monofluorination of indoles and arenes, allowing site-specific solubility of substrate and fluorine source in the micelle. (AU)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

GOMES CABRAL, TADEU LUIZ; DAL POGGETTO, GUILHERME; BRUSSOLO DA SILVA, JOO PEDRO; NILSSON, MATHIAS; TORMENA, CLAUDIO F.. Determining the Absolute Configuration of Small Molecules by Diffusion NMR Experiments. LANCET GASTROENTEROLOGY & HEPATOLOGY, v. 10, n. 2, p. 6-pg., 2025-02-01. (21/05081-5, 20/10246-0)

MATTIOLI, RENAN RODINI; SANTOS, CAMILA SOUZA; DE SOUZA, BRUNA BUTKE; BRANCO, PEDRO DOMINGUEZ; BOLT, ROBERT R. A.; RABY-BUCK, SARAH E.; CABRAL, TADEU LUIZ GOMES; TORMENA, CLAUDIO F.; BROWNE, DUNCAN L.; PASTRE, JULIO C.. On the Valorisation of Chitin-Derived Furans by Milling. CHEMSUSCHEM, v. N/A, p. 6-pg., 2024-10-30. (21/05081-5, 22/00774-5, 19/26450-9, 22/03872-8, 20/10246-0, 21/06661-5, 23/01238-2, 23/01232-4)

CABRAL, TADEU LUIZ GOMES; DA SILVA, JOAO PEDRO BRUSSOLO; TORMENA, CLAUDIO FRANCISCO; STEIN, MATTHIAS. Molecular Recognition and Chiral Discrimination from NMR and Multi-Scale Simulations. CHEMISTRY-A EUROPEAN JOURNAL, v. N/A, p. 13-pg., 2025-04-02. (23/07116-6, 20/10246-0, 21/05081-5)