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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Polyhydroxamicalkanoate as a bioinspired acetylcholinesterase-based catalyst for acetylthiocholine hydrolysis and organophosphorus dephosphorylation: experimental studies and theoretical insights

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Autor(es):
Sgobbi, Livia F. ; Zibordi-Besse, Larissa ; Rodrigues, Bruno V. M. ; Razzino, Claudia A. ; Da Silva, Juarez L. F. ; Machado, Sergio A. S.
Número total de Autores: 6
Tipo de documento: Artigo Científico
Fonte: CATALYSIS SCIENCE & TECHNOLOGY; v. 7, n. 15, p. 3388-3398, AUG 7 2017.
Citações Web of Science: 1
Resumo

Acetylcholinesterase (AChE)-based biosensing methods are limited due to facile denaturation and leakage during the immobilization process. Accordingly, enzyme mimics have demonstrated extensive potential in versatile catalysis applications, since they provide desirable advantages over natural enzymes, including low-cost scalable production combined with flexible experimental conditions. Herein, we investigate the performance of a functionalized polyacrylamide, polyhydroxamicalkanoate (PHA) for the hydrolysis of the acetylthiocholine (ATCh) substrate as well as paraoxon-ethyl dephosphorylation. Polyhydroxamicalkanoate contains hydroxamic and carboxyl groups inserted along its backbone acting as an active site. This mimetic model exhibited significant rate enhancements for ATCh hydrolysis of over 10(8)-fold in pH 7.0 and over 10(7)-fold in pH 8.0. In this contribution, density functional theory calculations were employed to explore, at the atomistic level, the interactions between the bio-inspired AChE material with ATCh in addition to paraoxon- ethyl. Vibrational analysis validates our structural models for ATCh, paraoxon- ethyl and PHA. Remarkably, the adsorption energy of paraoxon- ethyl-PHA is 3-fold higher than that of ATCh-PHA. The foregoing result implies that paraoxon- ethyl strongly inhibits the polymeric active site in comparison with ATCh due to a covalent bond between the phosphorus atom in the pesticide and the oxygen atom in the hydroxamate moiety in PHA, releasing p-nitrophenolate. This study sheds light on the interaction mechanism that an AChE-based bioinspired polymer undergoes in ATCh hydrolysis and paraoxon- ethyl dephosphorylation. The modeling strategy consolidates the experimental outcomes which reveals the potential application of this biomimetic PHA polymer as an alternative for biosensing approaches. (AU)

Processo FAPESP: 15/08523-8 - Desenvolvimento de um nanosensor fluorescente a partir da eletrofiação de PVA e quantum dots de grafeno: aplicação na detecção de biomarcadores de Alzheimer
Beneficiário:Bruno Vinícius Manzolli Rodrigues
Linha de fomento: Bolsas no Brasil - Pós-Doutorado
Processo FAPESP: 13/20701-3 - Desenvolvimento de uma plataforma amperométrica modificada com compósito grafeno/pontos quânticos emitindo em comprimentos de onda diferente para detecção de pesticidas i
Beneficiário:Lívia Flório Sgobbi
Linha de fomento: Bolsas no Exterior - Estágio de Pesquisa - Doutorado
Processo FAPESP: 12/08750-6 - Desenvolvimento de um biossensor mimético descartável para pesticidas organofosforados e carbamatos para o controle de qualidade de águas de abastecimento
Beneficiário:Lívia Flório Sgobbi
Linha de fomento: Bolsas no Brasil - Doutorado