Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry

Autor(es)

Santos, Berlane G. ; Carli, Fernanda P. ; do Lago, Claudimir L. ; Gutz, Ivano G. R. ; Angnes, Lucio

• Tipo de documento: Artigo Científico
• Fonte: CHEMOSENSORS; v. 13, n. 3, p. 12-pg., 2025-03-06.

Resumo

This study demonstrates, for the first time, the formation of a hemiester of carbonic acid on self-assembled monolayers using voltammetric techniques and redox probes. A gold electrode (GE) was modified with 2-mercaptoethanol (ME) through self-assembly. With this modified electrode (GE-ME), a well-defined peak was observed by differential pulse voltammetry (DPV) for the negatively charged redox probe, ferricyanide/ferrocyanide, [Fe(CN)(6)](3-)/(4-), in sodium acetate as an electrolyte adjusted to pH 8.2. In the presence of dissolved CO2 in equilibrium with bicarbonate, there is a decrease in the ferrocyanide peak current with time (similar to 30% in 60 min), attributed to the formation of hemiester 2-mercapto ethyl carbonate at the GE-ME/solution interface. Similarly, dissolved CO2 and bicarbonate also affect the electrochemical impedance measurements by increasing resistance to the charge transfer process with time (elevation of Rct values), compatible with the formation of the hemiester. The addition of barium salt led to the displacement of the equilibrium towards BaCO3 precipitation and consequent dissociation of the hemiester, attested by the recovery of the initial ferricyanide DPV signal. With the positively charged redox probe [Ru(NH3)(6)](2+), no decrease in the DPV peak was observed during the formation of the hemiester by reaction with bicarbonate. The repulsion of [Fe(CN)(6)](3-), but not of [Ru(NH3)(6)](2+), suggests that the formed species is the negatively charged 2-mercapto-ethyl carbonate, i.e., the hemiester with a dissociated proton. Due to the lack of a voltammetric signal from the hemiester itself, the formation of a self-assembled layer of thio-alcohol followed by the gradual formation of the corresponding carbonic acid hemiester allowed us to reach an elegant way of electrochemically demonstrating the formation of these species. (AU)

• Processo FAPESP: 19/22126-2 - Comportamento eletroquímico de hemiésteres do ácido carbônico em meio aquoso
• Beneficiário: Berlane Gomes Santos
• Modalidade de apoio: Bolsas no Brasil - Doutorado
• Processo FAPESP: 17/13137-5 - Formação e propriedades de hemiésteres do ácido carbônico em meio aquoso
• Beneficiário: Claudimir Lucio Do Lago
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 14/50867-3 - INCT 2014: Instituto Nacional de Ciência e Tecnologia de Bioanalítica
• Beneficiário: Marco Aurelio Zezzi Arruda
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 12/50259-8 - Grafeno: fotônica e opto-eletrônica: colaboração UPM-NUS
• Beneficiário: Antonio Helio de Castro Neto
• Modalidade de apoio: Auxílio à Pesquisa - Programa SPEC