Chiroptical methods for the characterization of micro- and macromolecules from natural sources

• Grant number: 11/22339-4
• Support Opportunities: Scholarships in Brazil - Post-Doctorate
• Effective date (Start): May 01, 2012
• Effective date (End): April 30, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Vanderlan da Silva Bolzani
• Grantee: João Marcos Batista Junior
• Host Institution: Instituto de Química (IQ). Universidade Estadual Paulista (UNESP). Campus de Araraquara. Araraquara , SP, Brazil
• Associated scholarship(s): 12/13739-1 - Vibrational optical activity as a probe to molecular chirality, BE.EP.PD

Abstract

The exact orientation of the atoms of a given molecule in space, i.e. the absolute configuration (AC) has been a complex and intriguing problem to be solved. This feature is especially critical for bioactive natural products, which are predominantly chiral. Although there are several methods capable of determining AC of chiral compounds, many present requirements that may limit their application, such as the presence of high quality single crystals for X-ray analysis, and derivatizations for NMR methods and stereoselective organic synthesis. Based on that, the determination of AC of chiral molecules may be a challenge even in well established research institutions such as the Institute of Chemistry of UNESP in Araraquara. Thus, in this project we propose the use of a combination of chiroptical methods, such as optical rotation (OR), optical rotatory dispersion (ORD), electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA), all in association with quantum mechanical calculations for reliable predictions of theoretical spectra, in order to determine unambiguously the absolute configuration and solution-state conformations of natural products isolated at NuBBE (Nucleus for Bioassays, Biosynthesis and Ecophysiology of Natural Products) This approach is essential in the identification of new molecular entities (NMEs). Moreover, the use of vibrational optical activity, which is represented by VCD and ROA, will also allow the characterization of secondary structures of peptides and proteins from plant species. Therefore, this project is aimed at the application of chiroptical methods and modern computational tools to solve stereochemical problems of natural products, both scantily explored in Brazil.

Scientific publications

(4)

(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)

FREITAS, GIOVANA C.; BATISTA, JR., JOAO M.; FRANCHI, JR., GILBERTO C.; NOWILL, ALEXANDRE E.; YAMAGUCHI, LYDIA F.; VILCACHAGUA, JANAINA D.; FAVARO, DENIZE C.; FURLAN, MAYSA; GUIMARAES, ELSIE F.; JEFFREY, CHRISTOPHER S.; et al. Cytotoxic non-aromatic B-ring flavanones from Piper carniconnectivum C. DC.. Phytochemistry, v. 97, p. 81-87, JAN 2014. (11/22339-4)

BATISTA, ANDREA N. L.; BATISTA, JR., JOAO M.; BOLZANI, VANDERLAN S.; FURLAN, MAYSA; BLANCH, EWAN W.. Selective DMSO-induced conformational changes in proteins from Raman optical activity. Physical Chemistry Chemical Physics, v. 15, n. 46, p. 20147-20152, 2013. (12/13739-1, 13/07600-3, 12/16484-4, 11/22339-4)

BATISTA, JR., JOAO M.; BLANCH, EWAN W.; BOLZANI, VANDERLAN DA SILVA. Recent advances in the use of vibrational chiroptical spectroscopic methods for stereochemical characterization of natural products. NATURAL PRODUCT REPORTS, v. 32, n. 9, p. 1280-1302, 2015. (11/22339-4, 13/07600-3, 14/25222-9, 14/50304-9)

PINTO, MERI EMILI F.; BATISTA, JR., JOAO M.; KOEHBACH, JOHANNES; GAUR, PRATIBHA; SHARMA, ABHINAY; NAKABASHI, MYNA; CILLI, EDUARDO MAFFUD; GIESEL, GUILHERME M.; VERLI, HUGO; GRUBER, CHRISTIAN W.; et al. Ribifolin, an Orbitide from Jatropha ribifolia, and Its Potential Antimalarial Activity. Journal of Natural Products, v. 78, n. 3, p. 374-380, MAR 2015. (11/22339-4, 13/07600-3, 12/13739-1)