Nuclear magnetic resonance spectroscopy: from pulse sequences to structural assignments

• Grant number: 20/10246-0
• Support Opportunities: Research Projects - Thematic Grants
• Duration: February 01, 2021 - January 31, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry
• Principal Investigator: Claudio Francisco Tormena
• Grantee: Claudio Francisco Tormena
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated researchers: Armando Juan Navarro Vázquez ; Bruno Linclau ; Francisco Paulo dos Santos ; Lars Mathias Nilsson ; Lucas Colucci Ducati ; Marco Antonio Barbosa Ferreira ; Watson Loh
• Associated scholarship(s): 24/00752-7 - Development of Palladium-Photoredox Catalyzed Trifluoromethylation Reactions Assisted by Statistical Tools, BP.DD; 23/13801-3 - Determination of electronic properties in heterocyclic rings through NMR parameters, BP.DR; 23/10838-3 - Chiral gold nanoparticles applied to enantiodiscrimination, BP.IC; + associated scholarships 23/12169-1 - Maintenance of computational infrastructure and user training, BP.TT; 22/14197-0 - Study of the structure and reactivity of catalytic systems of Pd-photoredox reactions assisted by machine learning techniques, BP.PD; 22/14697-2 - Enantiodiscrimination by MAD NMR using a chromatographic chiral stationary, BP.PD; 22/16223-8 - Investigation of the non-classical carbocations stability obtained from the epoxide ring opening, BP.IC; 22/13038-5 - Relaxation agent for speed up 13C NMR spectra for the Kinetic Isotope Effect measurements, BP.IC; 21/09687-5 - Assessment of conformational preferences on fluorine-containing molecules and study of transmission pathway for JFH couplings using Car-Parrinello molecular dynamics, BP.PD; 21/05081-5 - Chiral micelles for matrix-assisted DOSY, BP.DD; 21/05095-6 - Conformational preferences on fluorine-containing molecules, BP.DD - associated scholarships

Abstract

Since 2015 a thematic proposal (2015/08541-6) is in progress, related to the application of NMR beyond to structure assignments. During this period, our group developed and applied new pulse sequences, including those for DOSY and FESTA experiments to deal with structure assignment of compounds in mixtures, without the need for any physical separation. DOSY experiments were also used to study the effect of solvent ionic liquids, to absorb/capture CO2, and to differentiate enantiomers using a chiral matrixes. We have also explained, for the first time, the correct electronic effect (i.e. the source) responsible for observed experimental behaviour of 1H and 13C chemical shits (d) and even the correct transmission pathway of some coupling constants, and conformational preferences for small organic molecules. The mechanisms of important organic reactions were investigated by a synergistic effort of NMR and theoretical calculations.In the present proposal, we intend to go deeper in NMR methods development to: deal with mixtures introducing new 2D and 3D NMR experiments; apply HR-MAS approach for the measurement of RDC (Residual Dipolar Coupling) and RCSA (Residual Chemical Shift Anisotropy) using a single sample to get both isotropic an anisotropic parameters, avoiding the non-ideal approximations commonly used; HR-MAS NMR experiments will also be applied with chromatographic chiral stationary phase for Matrix-Assisted DOSY (MAD) measurements to differentiate enantiomers and evaluate the enantiomer interaction strength with the chromatographic chiral phases, chiral micelles will also be used an attractive alternative with very favourable NMR properties; measure and investigate the CO2 absorption in the presence of ionic liquid with high-pressure NMR DOSY; state-of-art theoretical calculations to describe, in term of electronic structure, the correct origin of observed NMR parameters; determine stable conformation with theoretical quantum chemistry of targeted fluorinated organic molecules and the interaction responsible for such stability; speeding up NMR experiments to get kinetic information for organic reaction mechanism investigation. In addition to the developments for high-field NMR, we also intend to adapt and further develop key methodologies for benchtop NMR, in collaboration with Nanalysis which is a leading manufacturer of commercial benchtop NMR spectrometers. We intend to continue the important work of delivering a better understanding of fundamental NMR parameters (´ and J) which is essential for a correct application of NMR for structure assignment and new NMR methodologies for the analysis of complex samples. Very important for the Brazilian industry and Academia is the high-level training in modern NMR, obtained by our research students at all levels, including PhD students and post-docs. We believe that the success achieved in the past five years puts us in a very credible position for continued support for the next five years. (AU)

Scientific publications

(21)

(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)

SOARES, JOAO VITOR; DAL POGGETTO, GUILHERME; VIESSER, RENAN V.; COUTO, UENIFER R.; TORMENA, CLAUDIO F.. Stereoelectronic interactions: A booster for (4)J(HF) transmission. Magnetic Resonance in Chemistry, v. 60, n. 5, p. 8-pg., 2022-01-22. (15/08541-6, 17/20890-1, 20/10246-0, 16/24331-4, 18/19253-0)

BATISTA, PATRICK R.; PENNA, TATIANA C.; DUCATI, LUCAS C.; CORRERA, THIAGO C.. p-Aminobenzoic acid protonation dynamics in an evaporating droplet by ab initio molecular dynamics. Physical Chemistry Chemical Physics, v. 23, n. 35, AUG 2021. (17/20262-0, 20/10246-0, 19/25634-9, 18/07308-4, 15/08539-1, 14/15962-5)

BONATO, LUIZ GUSTAVO; DAL POGGETTO, GUILHERME; MORAL, RAPHAEL FERNANDO; DE CARVALHO VALE, BRENER RODRIGO; GERMINO, JOSE CARLOS; ALMEIDA, DIOGO BURIGO; SANTIAGO, PATRICIA; FERNANDEZ, PABLO SEBASTIAN; TORMENA, CLAUDIO FRANCISCO; PADILHA, LAZARO A.; et al. Photostability of amine-free CsPbBr3 perovskite nanocrystals under continuous UV illumination. JOURNAL OF MATERIALS CHEMISTRY C, v. 11, n. 24, p. 12-pg., 2023-03-06. (20/10246-0, 21/13262-0, 17/11986-5, 20/16077-6, 18/15574-6, 19/22576-8, 19/25765-6, 20/04431-0)

KAWAKAMI, MANAMI; SCHULZ, KARL H. G.; VARNI, ANTHONY J.; TORMENA, CLAUDIO F.; GIL, ROBERTO R.; NOONAN, KEVIN J. T.. Statistical copolymers of thiophene-3-carboxylates and selenophene-3-carboxylates; Se-77 NMR as a tool to examine copolymer sequence in selenophene-based conjugated polymers. Polymer Chemistry, v. 13, n. 37, p. 9-pg., 2022-08-09. (20/10246-0)

BARBOZA, AMANDA ALINE; DANTAS, JULIANA ARANTES; COSTA, MATEUS OLIVEIRA; CHIAVEGATTI, ATTILIO; DE MELO JARDIM, GUILHERME AUGUSTO; BARBOSA FERREIRA, MARCO ANTONIO. Recent Advances in Palladium-Catalyzed Oxidative Couplings in the Synthesis/Functionalization of Cyclic Scaffolds Using Molecular Oxygen as the Sole Oxidant. SYNTHESIS-STUTTGART, v. 54, n. 09, p. 22-pg., 2022-01-25. (14/50249-8, 20/10246-0, 20/01255-6)

BARBOZA, AMANDA A.; DANTAS, JULIANA A.; JARDIM, GUILHERME A. M.; NETO, ATTILIO C.; OLIVEIRA, WILLIAN X. C.; GENSCH, TOBIAS; FERREIRA, MARCO A. B.. Synthesis of Dihydropyrazoles via Pd-Catalyzed Heterocyclization/Carbonylation Reaction: Development and Parameterization Studies. CHEMCATCHEM, v. 14, n. 20, p. 5-pg., 2022-10-01. (20/01255-6, 20/10246-0, 20/13563-7)

CASSIA CHIARI; CLÁUDIO F. TORMENA. UMA NOVA ERA DA INCORPORAÇÃO DE ÁTOMO DE FLÚOR EM COMPOSTOS ORGÂNICOS: MÉTODOS MODERNOS E USO DA ESPECTROSCOPIA DE RESSONÂNCIA MAGNÉTICA DE 19F. Química Nova, v. 47, n. 4, 2024-02-29. (20/10246-0, 21/05095-6)

KAWAMURA, MEIRE Y.; ALEGRE-REQUENA, JUAN, V; BARBOSA, THAIS M.; TORMENA, CLAUDIO F.; PATON, ROBERT S.; FERREIRA, MARCO A. B.. Mechanistic Aspects on [3+2] Cycloaddition (32CA) Reactions of Azides to Nitroolefins: A Computational and Kinetic Study. CHEMISTRY-A EUROPEAN JOURNAL, v. 28, n. 69, p. 9-pg., 2022-10-19. (17/01754-0, 20/10246-0, 20/01255-6)

ALVES, TANIA M. F.; JARDIM, GUILHERME A. M.; FERREIRA, MARCO A. B.. A green metal-free ``one-pot{''} microwave assisted synthesis of 1,4-dihydrochromene triazoles. RSC ADVANCES, v. 11, n. 17, p. 10336-10339, MAR 18 2021. (14/50249-8, 20/01255-6, 20/10246-0)

BARBOZA, AMANDA A.; CHIAVEGATTI NETO, ATTILIO; ROSSET, ISAC G.; JARDIM, GUILHERME A. M.; FERREIRA, MARCO A. B.. Synthesis of 3-Carbonyl Trisubstituted Furans via Pd-Catalyzed Aerobic Cycloisomerization Reaction: Development and Mechanistic Studies. Journal of Organic Chemistry, v. 86, n. 5, p. 3923-3942, MAR 5 2021. (14/50249-8, 20/10246-0, 20/01255-6)

CHIAVEGATTI NETO, ATTILIO; SOARES, KELLY CINTRA; SANTOS, MAIARA DA SILVA; AIMOLA, TULIO JARDINI; FERREIRA, ANTONIO GILBERTO; JARDIM, GUILHERME A. M.; TORMENA, CLAUDIO FRANCISCO; PAIXAO, MARCIO WEBER; BARBOSA FERREIRA, MARCO ANTONIO. Mechanistic investigation of enolate/stabilized vinylogous carbanion-mediated organocatalytic azide (3+2) cycloaddition reactions for the synthesis of 1,2,3-triazoles. ORGANIC & BIOMOLECULAR CHEMISTRY, v. N/A, p. 8-pg., 2022-03-30. (14/15839-9, 18/01211-9, 20/10246-0, 14/50249-8, 20/01255-6, 16/24726-9, 20/13563-7)

APARECIDO DOS SANTOS-PINTO, JOSE ROBERTO; ESTEVES, FRANCIELE GREGO; TORMENA, CLAUDIO FRANCISCO; PEREZ-RIVEROL, AMILCAR; LASA, ALEXIS MUSACCHIO; BUENO, ODAIR CORREA; PALMA, MARIO SERGIO. Proteomic characterization of the fibroin-based silk fibers produced by weaver ant Camponotus textor. JOURNAL OF PROTEOMICS, v. 261, p. 13-pg., 2022-06-15. (17/22405-3, 13/26451-9, 17/10373-0, 16/16212-5, 20/10246-0, 16/10430-0, 15/08541-6)

FERNANDES, VITOR A.; LIMA, RAFAELY N.; BROTERSON, YOISEL B.; KAWAMURA, MEIRE Y.; ECHEMENDIA, RADELL; DE LA TORRE, ALEXANDER F.; FERREIRA, MARCO A. B.; RIVERA, DANIEL G.; PAIXAO, MARCIO W.. Direct access to tetrasubstituted cyclopentenyl scaffolds through a diastereoselective isocyanide-based multicomponent reaction. CHEMICAL SCIENCE, v. 12, n. 48, SEP 2021. (15/17141-1, 17/01754-0, 14/50249-8, 20/01255-6, 20/10246-0, 19/01973-9)

ALVES, TANIA M. F.; JARDIM, GUILHERME A. M.; FERREIRA, MARCO A. B.. A green metal-free "one-pot" microwave assisted synthesis of 1,4-dihydrochromene triazoles. RSC ADVANCES, v. 11, n. 17, p. 4-pg., 2021-03-18. (14/50249-8, 20/10246-0, 20/01255-6)

LIU, SHIWEN; TORMENA, CLAUDIO F.; HAMMOND, GERALD B.; XU, BO. Broadly Applicable Ion Pair-Assisted Nucleophilic Substitution of sp(3)-Carbon Electrophiles with Alkynyltrifluoroborates. ORGANIC LETTERS, v. 24, n. 34, p. 6-pg., 2022-09-02. (20/10246-0)

MYCROFT, CORAL; DAL POGGETTO, GUILHERME; BARBOSA, THAIÏS M.; TORMENA, CLAÏUDIO F.; NILSSON, MATHIAS; MORRIS, GARETH A.; CASTANAR, LAURA. Rapid Measurement of Heteronuclear Coupling Constants in Complex NMR Spectra. Journal of the American Chemical Society, v. 145, n. 36, p. 8-pg., 2023-08-31. (14/12776-6, 11/14301-7, 18/19253-0, 20/10246-0)

JARDIM, GUILHERME A. M.; DANTAS, JULIANA A.; BARBOZA, AMANDA A.; PAIXAO, MARCIO W.; FERREIRA, MARCO A. B.. Light-Driven Palladium-Radical Hybrid Species: Mechanistic Aspects and Recent Examples. SYNTHESIS-STUTTGART, v. 54, n. 21, p. 17-pg., 2022-08-22. (20/10246-0, 20/01255-6, 21/06099-5)

DIAS, MARIANA A.; BATISTA, PATRICK R.; DUCATI, LUCAS C.; MONTAGNER, CASSIANA C.. Insights into sorption and molecular transport of atrazine, testosterone, and progesterone onto polyamide microplastics in different aquatic matrices. Chemosphere, v. 318, p. 10-pg., 2023-02-01. (18/21733-0, 14/50951-4, 17/17750-3, 20/10246-0, 15/18790-3, 08/57808-1, 18/07308-4)

OBEID, GUILHERME; MORAES, GUSTAVO O.; PENNA, TATIANA C.; SCHENBERG, LEONARDO A.; DUCATI, LUCAS C.; CORRERA, THIAGO C.. Solvation effects on glyphosate protonation and deprotonation states evaluated by mass spectrometry and explicit solvation simulations. Journal of Chemical Physics, v. 158, n. 5, p. 12-pg., 2023-02-07. (20/10246-0, 19/12808-9, 17/20262-0, 17/17750-3, 15/08539-1, 19/18727-0, 19/25634-9, 20/08894-4, 21/06726-0, 14/15962-5)

SURBELLA, ROBERT G.; DUCATI, LUCAS C.; SCHOFIELD, MARK H.; MCNAMARA, BRUCE K.; PELLEGRINI, KRISTI L.; CORBEY, JORDAN F.; SCHWANTES, JON M.; AUTSCHBACH, JOCHEN; CAHILL, CHRISTOPHER L.. Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal-Ligand Bonding. Inorganic Chemistry, v. N/A, p. 9-pg., 2022-10-28. (17/17750-3, 20/10246-0)

WESTPHAL, REGINA; VENTURINI FILHO, ECLAIR; LOUREIRO, LAIZA BRUZADELLE; TORMENA, CLAUDIO FRANCISCO; PESSOA, CLAUDIA; GUIMARAES, CELINA DE JESUS; MANSO, MARIANA PALMEIRA; FIOROT, RODOLFO GOETZE; CAMPOS, VINICIUS RANGEL; LAMOUNIER CAMARGOS RESENDE, JACKSON ANTONIO; et al. Green Synthesis of Spiro Compounds with Potential Anticancer Activity through Knoevenagel/Michael/Cyclization Multicomponent Domino Reactions Organocatalyzed by Ionic Liquid and Microwave-Assisted. Molecules, v. 27, n. 22, p. 15-pg., 2022-11-01. (20/10246-0)