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Papers by Irina Babaligea

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Peroxidase-mediated oxidation of l-dopa: A kinetic approach

A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-media... more A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-mediated oxidation of l-dopa was developed, and the rate constants for both enzymatic and non-enzymatic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It is demonstrated that the accumulation of p-topaquinone in significant amounts occurred in excess of hydrogen peroxide or during auto-oxidation of l-dopa, but changes in the ratio of initial concentrations of the reactants can reduce considerably the production of this intermediate.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Peroxidase-mediated oxidation of l-dopa: A kinetic approach

Biochemical Engineering Journal, 2010

A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-media... more A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-mediated oxidation of l-dopa was developed, and the rate constants for both enzymatic and non-enzymatic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It is demonstrated that the accumulation of p-topaquinone in significant amounts occurred in excess of hydrogen peroxide or during auto-oxidation of l-dopa, but changes in the ratio of initial concentrations of the reactants can reduce considerably the production of this intermediate.

Research paper thumbnail of Detecting Operational Inactivation of Horseradish Peroxidase using an Isoconversional Method

Chemical Engineering & Technology, 2010

Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxi... more Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxidation of 2-aminophenol with hydrogen peroxide were estimated using an isoconversional method. This method only requires the progress kinetic curves obtained at constant initial concentrations of the substrates. In order to investigate the possible pathways of low-reactive species compound III formation, a kinetic model was proposed and several rate constants were calculated using an optimization computing program. Generation of an oxygen reactive species in the reaction system was also considered in the reaction scheme. Sensitivity analysis, corroborated with the overall inactivation kinetics observed with the isoconversional method, allows the conclusion that the inactivation of the enzyme occurs mainly via the reaction of compound II with hydrogen peroxide.

Research paper thumbnail of Detecting Operational Inactivation of Horseradish Peroxidase using an Isoconversional Method

Chemical Engineering & Technology, 2010

Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxi... more Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxidation of 2-aminophenol with hydrogen peroxide were estimated using an isoconversional method. This method only requires the progress kinetic curves obtained at constant initial concentrations of the substrates. In order to investigate the possible pathways of low-reactive species compound III formation, a kinetic model was proposed and several rate constants were calculated using an optimization computing program. Generation of an oxygen reactive species in the reaction system was also considered in the reaction scheme. Sensitivity analysis, corroborated with the overall inactivation kinetics observed with the isoconversional method, allows the conclusion that the inactivation of the enzyme occurs mainly via the reaction of compound II with hydrogen peroxide.

Research paper thumbnail of Detecting Operational Inactivation of Horseradish Peroxidase using an Isoconversional Method

Chemical Engineering & Technology, 2010

Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxi... more Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxidation of 2-aminophenol with hydrogen peroxide were estimated using an isoconversional method. This method only requires the progress kinetic curves obtained at constant initial concentrations of the substrates. In order to investigate the possible pathways of low-reactive species compound III formation, a kinetic model was proposed and several rate constants were calculated using an optimization computing program. Generation of an oxygen reactive species in the reaction system was also considered in the reaction scheme. Sensitivity analysis, corroborated with the overall inactivation kinetics observed with the isoconversional method, allows the conclusion that the inactivation of the enzyme occurs mainly via the reaction of compound II with hydrogen peroxide. Figure 7. Experimental and simulated kinetic curves according to the proposed model; [OAP] 0 = 1 · 10 -4 M, [H 2 O 2 ] = 2.5 · 10 -5 M.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Peroxidase-mediated oxidation of l-dopa: A kinetic approach

Biochemical Engineering Journal, 2010

A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-media... more A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-mediated oxidation of l-dopa was developed, and the rate constants for both enzymatic and non-enzymatic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It is demonstrated that the accumulation of p-topaquinone in significant amounts occurred in excess of hydrogen peroxide or during auto-oxidation of l-dopa, but changes in the ratio of initial concentrations of the reactants can reduce considerably the production of this intermediate.

Research paper thumbnail of Inactivation path during the copper (II) catalyzed synthesis of Questiomycin A from oxidation of 2-aminophenol

Applied Catalysis A: General, 2012

The catalytic oxidation of 2-aminophenol (OAP) to 2-amino-3H-phenoxazin-3-one (APX, Questiomycin ... more The catalytic oxidation of 2-aminophenol (OAP) to 2-amino-3H-phenoxazin-3-one (APX, Questiomycin A) was the object of numerous studies partly due to antimicrobial properties of Questiomycin A and mostly because it can be used as a model for the synthesis of the naturally occurring antineoplastic agent Actinomycin D. Several copper complexes were used as dioxygen and/or substrates activators in order to mimic the activity of phenoxazinone synthase, but the reported assays failed to provide reasonable mechanistic features in media compatible with natural conditions. The main purposes of our work were to use simple copper salts to perform oxidation of OAP in oxygenated aqueous solutions and to develop a reaction scheme able to explain the low yields in APX along with the operational inactivation of the catalyst. A 11-step kinetic model able to describe the inactivation of copper(II) catalyst during oxidation of OAP to APX in oxygenated solutions was developed, and the rate constants for both catalytic and noncatalytic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It was demonstrated that the inactivation path can be assigned to formation of the stable bis(o-iminosemiquinonato)copper(II) complex, a compound reported as a moderate antimicrobial agent.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Peroxidase-mediated oxidation of l-dopa: A kinetic approach

A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-media... more A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-mediated oxidation of l-dopa was developed, and the rate constants for both enzymatic and non-enzymatic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It is demonstrated that the accumulation of p-topaquinone in significant amounts occurred in excess of hydrogen peroxide or during auto-oxidation of l-dopa, but changes in the ratio of initial concentrations of the reactants can reduce considerably the production of this intermediate.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Peroxidase-mediated oxidation of l-dopa: A kinetic approach

Biochemical Engineering Journal, 2010

A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-media... more A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-mediated oxidation of l-dopa was developed, and the rate constants for both enzymatic and non-enzymatic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It is demonstrated that the accumulation of p-topaquinone in significant amounts occurred in excess of hydrogen peroxide or during auto-oxidation of l-dopa, but changes in the ratio of initial concentrations of the reactants can reduce considerably the production of this intermediate.

Research paper thumbnail of Detecting Operational Inactivation of Horseradish Peroxidase using an Isoconversional Method

Chemical Engineering & Technology, 2010

Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxi... more Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxidation of 2-aminophenol with hydrogen peroxide were estimated using an isoconversional method. This method only requires the progress kinetic curves obtained at constant initial concentrations of the substrates. In order to investigate the possible pathways of low-reactive species compound III formation, a kinetic model was proposed and several rate constants were calculated using an optimization computing program. Generation of an oxygen reactive species in the reaction system was also considered in the reaction scheme. Sensitivity analysis, corroborated with the overall inactivation kinetics observed with the isoconversional method, allows the conclusion that the inactivation of the enzyme occurs mainly via the reaction of compound II with hydrogen peroxide.

Research paper thumbnail of Detecting Operational Inactivation of Horseradish Peroxidase using an Isoconversional Method

Chemical Engineering & Technology, 2010

Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxi... more Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxidation of 2-aminophenol with hydrogen peroxide were estimated using an isoconversional method. This method only requires the progress kinetic curves obtained at constant initial concentrations of the substrates. In order to investigate the possible pathways of low-reactive species compound III formation, a kinetic model was proposed and several rate constants were calculated using an optimization computing program. Generation of an oxygen reactive species in the reaction system was also considered in the reaction scheme. Sensitivity analysis, corroborated with the overall inactivation kinetics observed with the isoconversional method, allows the conclusion that the inactivation of the enzyme occurs mainly via the reaction of compound II with hydrogen peroxide.

Research paper thumbnail of Detecting Operational Inactivation of Horseradish Peroxidase using an Isoconversional Method

Chemical Engineering & Technology, 2010

Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxi... more Kinetic parameters of operational inactivation of horseradish peroxidase during the enzymatic oxidation of 2-aminophenol with hydrogen peroxide were estimated using an isoconversional method. This method only requires the progress kinetic curves obtained at constant initial concentrations of the substrates. In order to investigate the possible pathways of low-reactive species compound III formation, a kinetic model was proposed and several rate constants were calculated using an optimization computing program. Generation of an oxygen reactive species in the reaction system was also considered in the reaction scheme. Sensitivity analysis, corroborated with the overall inactivation kinetics observed with the isoconversional method, allows the conclusion that the inactivation of the enzyme occurs mainly via the reaction of compound II with hydrogen peroxide. Figure 7. Experimental and simulated kinetic curves according to the proposed model; [OAP] 0 = 1 · 10 -4 M, [H 2 O 2 ] = 2.5 · 10 -5 M.

Research paper thumbnail of Oxidase–peroxidase reaction: kinetics of peroxidase-catalysed oxidation of 2-aminophenol

Bioprocess and Biosystems Engineering, 2008

Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobi... more Possible reaction pathways that may lead to horseradish peroxidase inactivation during the aerobic oxidation of 2-aminophenol were investigated using extended kinetic curves. A kinetic model involving the formation of a low-reactive species, Compound III, was proposed and several rate constants were calculated using an optimisation computing program. Sensitivity analysis allowed to conclude that both oxidase and peroxidase cycles occur in 2-aminophenol oxidation.

Research paper thumbnail of Peroxidase-mediated oxidation of l-dopa: A kinetic approach

Biochemical Engineering Journal, 2010

A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-media... more A kinetic model able to adequately describe the accumulation of p-topaquinone in peroxidase-mediated oxidation of l-dopa was developed, and the rate constants for both enzymatic and non-enzymatic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It is demonstrated that the accumulation of p-topaquinone in significant amounts occurred in excess of hydrogen peroxide or during auto-oxidation of l-dopa, but changes in the ratio of initial concentrations of the reactants can reduce considerably the production of this intermediate.

Research paper thumbnail of Inactivation path during the copper (II) catalyzed synthesis of Questiomycin A from oxidation of 2-aminophenol

Applied Catalysis A: General, 2012

The catalytic oxidation of 2-aminophenol (OAP) to 2-amino-3H-phenoxazin-3-one (APX, Questiomycin ... more The catalytic oxidation of 2-aminophenol (OAP) to 2-amino-3H-phenoxazin-3-one (APX, Questiomycin A) was the object of numerous studies partly due to antimicrobial properties of Questiomycin A and mostly because it can be used as a model for the synthesis of the naturally occurring antineoplastic agent Actinomycin D. Several copper complexes were used as dioxygen and/or substrates activators in order to mimic the activity of phenoxazinone synthase, but the reported assays failed to provide reasonable mechanistic features in media compatible with natural conditions. The main purposes of our work were to use simple copper salts to perform oxidation of OAP in oxygenated aqueous solutions and to develop a reaction scheme able to explain the low yields in APX along with the operational inactivation of the catalyst. A 11-step kinetic model able to describe the inactivation of copper(II) catalyst during oxidation of OAP to APX in oxygenated solutions was developed, and the rate constants for both catalytic and noncatalytic branch were estimated either experimentally or using a computing program for detailed kinetic simulation. It was demonstrated that the inactivation path can be assigned to formation of the stable bis(o-iminosemiquinonato)copper(II) complex, a compound reported as a moderate antimicrobial agent.