| Full text | |
| Author(s): |
Santos, Berlane G.
;
Carli, Fernanda P.
;
do Lago, Claudimir L.
;
Gutz, Ivano G. R.
;
Angnes, Lucio
Total Authors: 5
|
| Document type: | Journal article |
| Source: | CHEMOSENSORS; v. 13, n. 3, p. 12-pg., 2025-03-06. |
| Abstract | |
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) | |
| FAPESP's process: | 19/22126-2 - Electrochemical behavior of carbonic acid hemiesters in aqueous medium |
| Grantee: | Berlane Gomes Santos |
| Support Opportunities: | Scholarships in Brazil - Doctorate |
| FAPESP's process: | 17/13137-5 - Formation and properties of hemiesters of carbonic acid in aqueous medium |
| Grantee: | Claudimir Lucio Do Lago |
| Support Opportunities: | Research Projects - Thematic Grants |
| FAPESP's process: | 14/50867-3 - INCT 2014: National Institute of Science and Technology in Bioanalysis |
| Grantee: | Marco Aurelio Zezzi Arruda |
| Support Opportunities: | Research Projects - Thematic Grants |
| FAPESP's process: | 12/50259-8 - Graphene: photonics and opto-electronics: UPM-NUS collaboration |
| Grantee: | Antonio Helio de Castro Neto |
| Support Opportunities: | Research Projects - SPEC Program |