UV-Visible and Electrochemical Monitoring of Carbon Monoxide Release by Donor Complexes to Myoglobin Solutions and to Electrodes Modified with Films Containing Hemin
- Obirai, Joseph C, Hamadi, Sara, Ithurbide, Aurélie, Wartelle, Corinne, Nyokong, Tebello, Zagal, José, Top, Siden, Bedioui, Fethi
- Authors: Obirai, Joseph C , Hamadi, Sara , Ithurbide, Aurélie , Wartelle, Corinne , Nyokong, Tebello , Zagal, José , Top, Siden , Bedioui, Fethi
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283906 , vital:56001 , xlink:href="https://doi.org/10.1002/elan.200603571"
- Description: This study reports on the evaluation of the CO donating behavior of tricarbonyl dichloro ruthenium(II) dimer ([Ru(CO)3Cl2]2) and 1,3-dimethoxyphenyl tricarbonyl chromium (C6H3(MeO)2Cr(CO)3) complex by UV-visible technique and electrochemical technique. The CO release was monitored by following the modifications of the UV-visible features of MbFe(II) in phosphate buffer solution and the redox features of reduced Hemin, HmFe(II), confined at the surface of a vitreous carbon electrode. In the latter case, the interaction between the hemin-modified electrode and the released CO was seen through the observation of an increase of the reduction current related to the FeIII/FeII redox process of the immobilized porphyrin. While the ruthenium-based complex, ([Ru(CO)3Cl2]2), depended on the presence of Fe(II) species to release CO, it was found that the chromium-based complex released spontaneously CO. This was facilitated by illuminating and/or simple stirring of the solution containing the complex.
- Full Text:
- Date Issued: 2006
- Authors: Obirai, Joseph C , Hamadi, Sara , Ithurbide, Aurélie , Wartelle, Corinne , Nyokong, Tebello , Zagal, José , Top, Siden , Bedioui, Fethi
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283906 , vital:56001 , xlink:href="https://doi.org/10.1002/elan.200603571"
- Description: This study reports on the evaluation of the CO donating behavior of tricarbonyl dichloro ruthenium(II) dimer ([Ru(CO)3Cl2]2) and 1,3-dimethoxyphenyl tricarbonyl chromium (C6H3(MeO)2Cr(CO)3) complex by UV-visible technique and electrochemical technique. The CO release was monitored by following the modifications of the UV-visible features of MbFe(II) in phosphate buffer solution and the redox features of reduced Hemin, HmFe(II), confined at the surface of a vitreous carbon electrode. In the latter case, the interaction between the hemin-modified electrode and the released CO was seen through the observation of an increase of the reduction current related to the FeIII/FeII redox process of the immobilized porphyrin. While the ruthenium-based complex, ([Ru(CO)3Cl2]2), depended on the presence of Fe(II) species to release CO, it was found that the chromium-based complex released spontaneously CO. This was facilitated by illuminating and/or simple stirring of the solution containing the complex.
- Full Text:
- Date Issued: 2006
Volcano correlations for the reactivity of surface-confined cobalt N4-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate
- Claußen, Jan A, Ochoa, Gonzalo, Páez, Maritza, Costamagno, Juan, Gulppi, Miguel, Nyokong, Tebello, Bedioui, Fethi, Zagal, José H
- Authors: Claußen, Jan A , Ochoa, Gonzalo , Páez, Maritza , Costamagno, Juan , Gulppi, Miguel , Nyokong, Tebello , Bedioui, Fethi , Zagal, José H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268688 , vital:54222 , xlink:href="https://doi.org/10.1007/s10008-007-0336-y"
- Description: We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B12, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin larger than Co–tetrasulfonatotetraphenylporphyrin larger than Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B12 exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N4-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site.
- Full Text:
- Date Issued: 2008
- Authors: Claußen, Jan A , Ochoa, Gonzalo , Páez, Maritza , Costamagno, Juan , Gulppi, Miguel , Nyokong, Tebello , Bedioui, Fethi , Zagal, José H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268688 , vital:54222 , xlink:href="https://doi.org/10.1007/s10008-007-0336-y"
- Description: We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B12, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin larger than Co–tetrasulfonatotetraphenylporphyrin larger than Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B12 exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N4-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site.
- Full Text:
- Date Issued: 2008