Banca de DEFESA: PEDRO TENDRIH SODRÉ

Uma banca de DEFESA de DOUTORADO foi cadastrada pelo programa.
DISCENTE : PEDRO TENDRIH SODRÉ
DATA : 26/11/2024
HORA: 14:00
LOCAL: Auditório 801 no 8º andar do Bloco B da Universidade Federal do ABC
TÍTULO:

Atomistic and coarse-grained molecular simulations of proline containing lipopeptides: applications to biocatalysis and biosensors

PÁGINAS: 153
RESUMO:

This thesis encompasses several applications towards a better understanding on how lipopeptide aggregate structures can be used to enhance aldol catalysis and pesticide detection. In our first application, we focus on understanding on how proline containing lipopeptides aggregates can enhance catalysis. L-Proline functions as enantioselective organocatalyst towards aldol reactions, resulting in products with great selectivity towards the S stereochemistry. PRWGC18 and PRWGC18-2 are L-Proline containing lipopeptide molecules can act as organocatalyst in aqueous solution, producing mostly anti products with major (S,R) stereochemistry. They self-assemble in aqueous solutions, originating aggregate structures that further enhances both reaction yields and stereochemistry. In this work we used atomistic molecular dynamics simulations to investigate the role of the aggregate in enhancing the enantiomeric excess of a prototype aldol reaction between cyclohexanone and paranitrobenzaldehyde. Density Functional Theory and DLPNO-CCSD calculations using simplified models along molecular dynamics simulations showed that the aggregate environment enhances the the (S,R) product formation by increasing the number of putative reactive encounters and facilitates the reaction by providing an environment where trifluoroacetic acid could participate in the reaction through a tri-molecular a proton shuttle mechanism. On a second application, we employ atomistic molecular dynamics calculations to describe the glyphosate detection mechanism by PRWGC18 and SPRWGC18 lipopeptide aggregates. Our simulations revealed a strongly pH dependent detection mechanism that favors the SPRWGC18 sequence when compared to PRWGC18. Finally, coarse-grained simulations on the form of Hybrid Particle-Field are used to fit SAXS data using Bayesian Metainference, a technique that aims to generate a unique dynamics that reproduce the experimental SAXS signal. We investigate the concentration and pH effect influence on the aggregation phases and on the experimental SAXS data and how they can affect the aggregate morphology

MEMBROS DA BANCA:
Presidente - Interno ao Programa - 1544403 - MAURICIO DOMINGUES COUTINHO NETO
Membro Titular - Examinador(a) Externo à Instituição - LUIS GUSTAVO DIAS - USP
Membro Titular - Examinador(a) Externo à Instituição - RICARDO LUIS LONGO - UFPE
Membro Titular - Examinador(a) Externo à Instituição - THEREZA AMÉLIA SOARES - USP
Membro Titular - Examinador(a) Externo à Instituição - GUSTAVO TROIANO FELICIANO - UNESP
Membro Suplente - Examinador(a) Externo ao Programa - 1676356 - ANTONIO SERGIO KIMUS BRAZ
Membro Suplente - Examinador(a) Externo à Instituição - ANDRE FARIAS DE MOURA - UFSCAR