Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry
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-d...
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2025-03-01
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| author | Berlane G. Santos Fernanda P. Carli Claudimir L. do Lago Ivano G. R. Gutz Lúcio Angnes |
| author_facet | Berlane G. Santos Fernanda P. Carli Claudimir L. do Lago Ivano G. R. Gutz Lúcio Angnes |
| author_sort | Berlane G. Santos |
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| description | 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)<sub>6</sub>]<sup>3−</sup>/<sup>4−</sup>, in sodium acetate as an electrolyte adjusted to pH 8.2. In the presence of dissolved CO<sub>2</sub> in equilibrium with bicarbonate, there is a decrease in the ferrocyanide peak current with time (~30% in 60 min), attributed to the formation of hemiester 2-mercapto ethyl carbonate at the GE-ME/solution interface. Similarly, dissolved CO<sub>2</sub> 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 BaCO<sub>3</sub> precipitation and consequent dissociation of the hemiester, attested by the recovery of the initial ferricyanide DPV signal. With the positively charged redox probe [Ru(NH<sub>3</sub>)<sub>6</sub>]<sup>2+</sup>, no decrease in the DPV peak was observed during the formation of the hemiester by reaction with bicarbonate. The repulsion of [Fe(CN)<sub>6</sub>]<sup>3−</sup>, but not of [Ru(NH3)<sub>6</sub>]<sup>2+</sup>, 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. |
| format | Article |
| id | doaj-art-edff148ca2ac434d8d00a6fa068c6ec0 |
| institution | DOAJ |
| issn | 2227-9040 |
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| publishDate | 2025-03-01 |
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| spelling | doaj-art-edff148ca2ac434d8d00a6fa068c6ec02025-08-20T02:42:46ZengMDPI AGChemosensors2227-90402025-03-011339310.3390/chemosensors13030093Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and ElectrochemistryBerlane G. Santos0Fernanda P. Carli1Claudimir L. do Lago2Ivano G. R. Gutz3Lúcio Angnes4Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo 05508-000, SP, BrazilDepartment of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo 05508-000, SP, BrazilDepartment of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo 05508-000, SP, BrazilDepartment of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo 05508-000, SP, BrazilDepartment of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo 05508-000, SP, BrazilThis 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)<sub>6</sub>]<sup>3−</sup>/<sup>4−</sup>, in sodium acetate as an electrolyte adjusted to pH 8.2. In the presence of dissolved CO<sub>2</sub> in equilibrium with bicarbonate, there is a decrease in the ferrocyanide peak current with time (~30% in 60 min), attributed to the formation of hemiester 2-mercapto ethyl carbonate at the GE-ME/solution interface. Similarly, dissolved CO<sub>2</sub> 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 BaCO<sub>3</sub> precipitation and consequent dissociation of the hemiester, attested by the recovery of the initial ferricyanide DPV signal. With the positively charged redox probe [Ru(NH<sub>3</sub>)<sub>6</sub>]<sup>2+</sup>, no decrease in the DPV peak was observed during the formation of the hemiester by reaction with bicarbonate. The repulsion of [Fe(CN)<sub>6</sub>]<sup>3−</sup>, but not of [Ru(NH3)<sub>6</sub>]<sup>2+</sup>, 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.https://www.mdpi.com/2227-9040/13/3/93hemiesterCO<sub>2</sub>alcoholcarbonic acidself-assembled monolayer |
| spellingShingle | Berlane G. Santos Fernanda P. Carli Claudimir L. do Lago Ivano G. R. Gutz Lúcio Angnes Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry Chemosensors hemiester CO<sub>2</sub> alcohol carbonic acid self-assembled monolayer |
| title | Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry |
| title_full | Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry |
| title_fullStr | Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry |
| title_full_unstemmed | Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry |
| title_short | Proving the Formation of Carbonic Acid Hemiesters Using Self-Assembled Monolayers and Electrochemistry |
| title_sort | proving the formation of carbonic acid hemiesters using self assembled monolayers and electrochemistry |
| topic | hemiester CO<sub>2</sub> alcohol carbonic acid self-assembled monolayer |
| url | https://www.mdpi.com/2227-9040/13/3/93 |
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