Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects
- Autores
- Martinez, María Victoria; Coneo Rodriguez, Rusbel; Baena Moncada, Angelica Maria; Rivarola, Claudia Rosana; Bruno, Mariano Martín; Miras, Maria Cristina; Barbero, César Alfredo
- Año de publicación
- 2016
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- The retention, release, and detection of metallic complexes in polymeric hydrogels are of interest in drug delivery, analytical chemistry, and water remediation. The electrochemistry of the redox complexes inside the hydrogel could be affected by the viscoelastic properties of the gel, local ionic force and pH, and interactions (e.g., hydrophobic) between the complex and the polymer chains. In this work, it is shown that a simple setup, consisting of a disk electrode pressed on the hydrogel, allows to perform electrochemistry of a redox couple: Tris(1,10-phenanthroline)iron(II) (Fe(phen)3 2+) inside a hydrogel matrix. The behavior is compared with the same couple in solution, and it is found that the electrochemical properties of the redox couple are strongly affected by the presence of the hydrogel matrix. The cyclic voltammogram of the hydrogel loaded with complex shows a response, which suggests electrochemical-chemical mechanism. The chemical step is likely linked to a catalytic oxidation of free hydrated Fe2+ ions present inside the hydrogel together with the redox complex. Since Fe2+ ions have small charge transfer constants on the glassy carbon electrodes, only the catalytic current is observed. Indeed, when excess ligand (phenanthroline) is absorbed inside the hydrogel, the measured cyclic voltammograms show a single reversible oxidation/reduction step. It seems that the complexation equilibrium shifts toward the complex, making the free iron concentration negligible. Accordingly, the cyclic voltammetry shape and peak potential difference agree with a reversible oxidation/reduction. Additionally, the peak currents of the cyclic voltammograms show a linear dependence with the square root of time, as predicted by a Randles-Sevcik equation. However, the measured currents are smaller than the simulated ones. The differences are in agreement with simulations of the cyclic voltammograms where the migration of the redox species is considered. Chronoamperometry is used to measure the mass transport of redox species inside the hydrogel. It is found that the current transients still obey Cottrell?s equation, but the diffusion coefficients obtained from the slopes of Cottrell?s plots have to be corrected for migration effects. The effective diffusion coefficient of Fe(phen)3 2+ measured inside the hydrogel (DRed-hydrogel = 5.5 (±0.5) × 10−8 cm2 s−1) is ca. 80 times smaller than the one measured in solution (DRed-solution = 4.4 (±0.5) × 10−6 cm2 s−1). The simple setup has a true semi-infinite boundary condition, which allows characterizing the hydrogel in the same condition as the bulk material and easily changing both the redox species and the hydrogel structure.
Fil: Martinez, María Victoria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Coneo Rodriguez, Rusbel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Baena Moncada, Angelica Maria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Rivarola, Claudia Rosana. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Bruno, Mariano Martín. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Miras, Maria Cristina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Barbero, César Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina - Materia
-
HYDROGEL
IRON
PARTITION
PHENANTHROLINE - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/114275
Ver los metadatos del registro completo
id |
CONICETDig_7ee0264452073bcd9e2fd05d0198d3de |
---|---|
oai_identifier_str |
oai:ri.conicet.gov.ar:11336/114275 |
network_acronym_str |
CONICETDig |
repository_id_str |
3498 |
network_name_str |
CONICET Digital (CONICET) |
spelling |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effectsMartinez, María VictoriaConeo Rodriguez, RusbelBaena Moncada, Angelica MariaRivarola, Claudia RosanaBruno, Mariano MartínMiras, Maria CristinaBarbero, César AlfredoHYDROGELIRONPARTITIONPHENANTHROLINEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The retention, release, and detection of metallic complexes in polymeric hydrogels are of interest in drug delivery, analytical chemistry, and water remediation. The electrochemistry of the redox complexes inside the hydrogel could be affected by the viscoelastic properties of the gel, local ionic force and pH, and interactions (e.g., hydrophobic) between the complex and the polymer chains. In this work, it is shown that a simple setup, consisting of a disk electrode pressed on the hydrogel, allows to perform electrochemistry of a redox couple: Tris(1,10-phenanthroline)iron(II) (Fe(phen)3 2+) inside a hydrogel matrix. The behavior is compared with the same couple in solution, and it is found that the electrochemical properties of the redox couple are strongly affected by the presence of the hydrogel matrix. The cyclic voltammogram of the hydrogel loaded with complex shows a response, which suggests electrochemical-chemical mechanism. The chemical step is likely linked to a catalytic oxidation of free hydrated Fe2+ ions present inside the hydrogel together with the redox complex. Since Fe2+ ions have small charge transfer constants on the glassy carbon electrodes, only the catalytic current is observed. Indeed, when excess ligand (phenanthroline) is absorbed inside the hydrogel, the measured cyclic voltammograms show a single reversible oxidation/reduction step. It seems that the complexation equilibrium shifts toward the complex, making the free iron concentration negligible. Accordingly, the cyclic voltammetry shape and peak potential difference agree with a reversible oxidation/reduction. Additionally, the peak currents of the cyclic voltammograms show a linear dependence with the square root of time, as predicted by a Randles-Sevcik equation. However, the measured currents are smaller than the simulated ones. The differences are in agreement with simulations of the cyclic voltammograms where the migration of the redox species is considered. Chronoamperometry is used to measure the mass transport of redox species inside the hydrogel. It is found that the current transients still obey Cottrell?s equation, but the diffusion coefficients obtained from the slopes of Cottrell?s plots have to be corrected for migration effects. The effective diffusion coefficient of Fe(phen)3 2+ measured inside the hydrogel (DRed-hydrogel = 5.5 (±0.5) × 10−8 cm2 s−1) is ca. 80 times smaller than the one measured in solution (DRed-solution = 4.4 (±0.5) × 10−6 cm2 s−1). The simple setup has a true semi-infinite boundary condition, which allows characterizing the hydrogel in the same condition as the bulk material and easily changing both the redox species and the hydrogel structure.Fil: Martinez, María Victoria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Coneo Rodriguez, Rusbel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Baena Moncada, Angelica Maria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Rivarola, Claudia Rosana. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bruno, Mariano Martín. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Miras, Maria Cristina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Barbero, César Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaSpringer2016-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/114275Martinez, María Victoria; Coneo Rodriguez, Rusbel; Baena Moncada, Angelica Maria; Rivarola, Claudia Rosana; Bruno, Mariano Martín; et al.; Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects; Springer; Journal of Solid State Electrochemistry (print); 20; 7-2016; 2951-29601432-8488CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/ 10.1007/s10008-016-3312-6info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1007%2Fs10008-016-3312-6info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:34:41Zoai:ri.conicet.gov.ar:11336/114275instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:34:41.993CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
title |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
spellingShingle |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects Martinez, María Victoria HYDROGEL IRON PARTITION PHENANTHROLINE |
title_short |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
title_full |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
title_fullStr |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
title_full_unstemmed |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
title_sort |
Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects |
dc.creator.none.fl_str_mv |
Martinez, María Victoria Coneo Rodriguez, Rusbel Baena Moncada, Angelica Maria Rivarola, Claudia Rosana Bruno, Mariano Martín Miras, Maria Cristina Barbero, César Alfredo |
author |
Martinez, María Victoria |
author_facet |
Martinez, María Victoria Coneo Rodriguez, Rusbel Baena Moncada, Angelica Maria Rivarola, Claudia Rosana Bruno, Mariano Martín Miras, Maria Cristina Barbero, César Alfredo |
author_role |
author |
author2 |
Coneo Rodriguez, Rusbel Baena Moncada, Angelica Maria Rivarola, Claudia Rosana Bruno, Mariano Martín Miras, Maria Cristina Barbero, César Alfredo |
author2_role |
author author author author author author |
dc.subject.none.fl_str_mv |
HYDROGEL IRON PARTITION PHENANTHROLINE |
topic |
HYDROGEL IRON PARTITION PHENANTHROLINE |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
The retention, release, and detection of metallic complexes in polymeric hydrogels are of interest in drug delivery, analytical chemistry, and water remediation. The electrochemistry of the redox complexes inside the hydrogel could be affected by the viscoelastic properties of the gel, local ionic force and pH, and interactions (e.g., hydrophobic) between the complex and the polymer chains. In this work, it is shown that a simple setup, consisting of a disk electrode pressed on the hydrogel, allows to perform electrochemistry of a redox couple: Tris(1,10-phenanthroline)iron(II) (Fe(phen)3 2+) inside a hydrogel matrix. The behavior is compared with the same couple in solution, and it is found that the electrochemical properties of the redox couple are strongly affected by the presence of the hydrogel matrix. The cyclic voltammogram of the hydrogel loaded with complex shows a response, which suggests electrochemical-chemical mechanism. The chemical step is likely linked to a catalytic oxidation of free hydrated Fe2+ ions present inside the hydrogel together with the redox complex. Since Fe2+ ions have small charge transfer constants on the glassy carbon electrodes, only the catalytic current is observed. Indeed, when excess ligand (phenanthroline) is absorbed inside the hydrogel, the measured cyclic voltammograms show a single reversible oxidation/reduction step. It seems that the complexation equilibrium shifts toward the complex, making the free iron concentration negligible. Accordingly, the cyclic voltammetry shape and peak potential difference agree with a reversible oxidation/reduction. Additionally, the peak currents of the cyclic voltammograms show a linear dependence with the square root of time, as predicted by a Randles-Sevcik equation. However, the measured currents are smaller than the simulated ones. The differences are in agreement with simulations of the cyclic voltammograms where the migration of the redox species is considered. Chronoamperometry is used to measure the mass transport of redox species inside the hydrogel. It is found that the current transients still obey Cottrell?s equation, but the diffusion coefficients obtained from the slopes of Cottrell?s plots have to be corrected for migration effects. The effective diffusion coefficient of Fe(phen)3 2+ measured inside the hydrogel (DRed-hydrogel = 5.5 (±0.5) × 10−8 cm2 s−1) is ca. 80 times smaller than the one measured in solution (DRed-solution = 4.4 (±0.5) × 10−6 cm2 s−1). The simple setup has a true semi-infinite boundary condition, which allows characterizing the hydrogel in the same condition as the bulk material and easily changing both the redox species and the hydrogel structure. Fil: Martinez, María Victoria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Coneo Rodriguez, Rusbel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Baena Moncada, Angelica Maria. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Rivarola, Claudia Rosana. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Bruno, Mariano Martín. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Miras, Maria Cristina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Barbero, César Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina |
description |
The retention, release, and detection of metallic complexes in polymeric hydrogels are of interest in drug delivery, analytical chemistry, and water remediation. The electrochemistry of the redox complexes inside the hydrogel could be affected by the viscoelastic properties of the gel, local ionic force and pH, and interactions (e.g., hydrophobic) between the complex and the polymer chains. In this work, it is shown that a simple setup, consisting of a disk electrode pressed on the hydrogel, allows to perform electrochemistry of a redox couple: Tris(1,10-phenanthroline)iron(II) (Fe(phen)3 2+) inside a hydrogel matrix. The behavior is compared with the same couple in solution, and it is found that the electrochemical properties of the redox couple are strongly affected by the presence of the hydrogel matrix. The cyclic voltammogram of the hydrogel loaded with complex shows a response, which suggests electrochemical-chemical mechanism. The chemical step is likely linked to a catalytic oxidation of free hydrated Fe2+ ions present inside the hydrogel together with the redox complex. Since Fe2+ ions have small charge transfer constants on the glassy carbon electrodes, only the catalytic current is observed. Indeed, when excess ligand (phenanthroline) is absorbed inside the hydrogel, the measured cyclic voltammograms show a single reversible oxidation/reduction step. It seems that the complexation equilibrium shifts toward the complex, making the free iron concentration negligible. Accordingly, the cyclic voltammetry shape and peak potential difference agree with a reversible oxidation/reduction. Additionally, the peak currents of the cyclic voltammograms show a linear dependence with the square root of time, as predicted by a Randles-Sevcik equation. However, the measured currents are smaller than the simulated ones. The differences are in agreement with simulations of the cyclic voltammograms where the migration of the redox species is considered. Chronoamperometry is used to measure the mass transport of redox species inside the hydrogel. It is found that the current transients still obey Cottrell?s equation, but the diffusion coefficients obtained from the slopes of Cottrell?s plots have to be corrected for migration effects. The effective diffusion coefficient of Fe(phen)3 2+ measured inside the hydrogel (DRed-hydrogel = 5.5 (±0.5) × 10−8 cm2 s−1) is ca. 80 times smaller than the one measured in solution (DRed-solution = 4.4 (±0.5) × 10−6 cm2 s−1). The simple setup has a true semi-infinite boundary condition, which allows characterizing the hydrogel in the same condition as the bulk material and easily changing both the redox species and the hydrogel structure. |
publishDate |
2016 |
dc.date.none.fl_str_mv |
2016-07 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/114275 Martinez, María Victoria; Coneo Rodriguez, Rusbel; Baena Moncada, Angelica Maria; Rivarola, Claudia Rosana; Bruno, Mariano Martín; et al.; Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects; Springer; Journal of Solid State Electrochemistry (print); 20; 7-2016; 2951-2960 1432-8488 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/114275 |
identifier_str_mv |
Martinez, María Victoria; Coneo Rodriguez, Rusbel; Baena Moncada, Angelica Maria; Rivarola, Claudia Rosana; Bruno, Mariano Martín; et al.; Electrochemistry of Tris(1,10-phenanthroline)iron(II) inside a polymeric hydrogel. Coupled chemical reactions and migration effects; Springer; Journal of Solid State Electrochemistry (print); 20; 7-2016; 2951-2960 1432-8488 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/ 10.1007/s10008-016-3312-6 info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1007%2Fs10008-016-3312-6 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Springer |
publisher.none.fl_str_mv |
Springer |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
_version_ |
1844613075180716032 |
score |
13.070432 |