Electroactive polymers made by loading redox ions inside crosslinked polymeric hydrogels. Effects of hydrophobic interactions and solvent dynamics

Martínez, María Vanina; Bruno, Mariano M.; Miras, M.C.; Barbero, C.

doi:10.1016/j.electacta.2016.10.007

Cited by 10 publications

(22 citation statements)

References 84 publications

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“…The analyte loaded into the hydrogel was electrochemically sensed by a working electrode made of flat glassy carbon pressed slightly on the hydrogel. The results showed that the redox molecules are present fulfill the semi‐infinite diffusion boundary conditions, therefore the data analysis can be performed using the theoretical framework for electrochemical measurements in liquid solvents 40 . Additionally, the agreement with Marcus theory model on the dependence of charge transfer on hydrogel viscosity strongly suggests an intimate contact of the flat (albeit with micrometric sized rugosity) carbon surface with the hydrogel matrix 39 .…”

Section: Introductionmentioning

confidence: 68%

“…Electrochemical measurements on the hydrogel were performed by using the setup proposed by Martinez et al 40 (Figure 2). A Pt grid was used as the counter electrode (CE), an Ag/AgCl (KCl saturated solution) inside a glass Luggin capillary was used as a reference electrode (RE).…”

Section: Methodsmentioning

confidence: 99%

“…Recently, our research group reported a novel simple experimental setup for electrochemical sensing of organic and inorganic redox analytes (e.g., nitrite, arsenite, dopamine, and tris(phenanthroline)iron(II) complex) by employing polymeric crosslinked matrices 29,40,41 . The analyte loaded into the hydrogel was electrochemically sensed by a working electrode made of flat glassy carbon pressed slightly on the hydrogel.…”

Section: Introductionmentioning

confidence: 99%

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A modular platform based on electrospun carbon nanofibers and poly(N‐isopropylacrylamide) hydrogel for sensor applications

Abel

Martínez

Bruno

et al. 2021

Polymers for Advanced Techs

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Modular sensor platforms are a fashion approach that allows the use of advanced materials to promote the evolution of portable electrochemical sensors. A modular platform building by the combination of carbonized poly(acrylonitrile) electrospun mat (C‐PAN; fiber diameter ca. 300 nm) and a poly(N‐isopropylacrylamide; PNIPAm) hydrogel was assayed. The individual components of the platform were physicochemically characterized before assembling. The swelling behavior and the capacity of sorption of a redox complex tris(1,10‐phenanthroline)iron(II) of the polymeric hydrogel were evaluated. Moreover, the morphological aspects of the electrospun fibers before and after carbonization were analyzed. Finally, cyclic voltammetry and chronocoulometry experiments were performed to analyze the electrochemical performance of the modular platform. In this work, we demonstrated that the platform takes advantage of the3D structure of the electrospun mat and the selective sorption of the hydrogel for the electrochemical sensing target analyte. The iron sensing using its complexation into the tris(1,10‐phenanthroline)iron(II) redox complex was assessed by differential pulse voltammetry (DPV). The anodic peak current showed a linear relation versus iron complex concentration in the range of 10–80 μmol L−1 with a detection limit of 0.103 μmol L−1. All the results herein presented suggest that a synergistic combination of large surface area carbon fiber electrodes and ion retaining hydrogel has been achieved.

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Section: Introductionmentioning

confidence: 68%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A modular platform based on electrospun carbon nanofibers and poly(N‐isopropylacrylamide) hydrogel for sensor applications

Abel

Martínez

Bruno

et al. 2021

Polymers for Advanced Techs

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“…This pH change can induce either precipitation by discharging the polyelectrolytes [ 24 , 25 ] or enabling complexation and subsequent precipitation with other polyelectrolytes or multivalent ions upon charging [ 1 , 2 ]. Another way of introducing electrochemical stimulation in those systems is the complex formation of polyelectrolytes with electroactive counterions [ 26 , 27 ]. As in previous works, we use this modular approach to perform a counterion valency-induced deposition (CVID) of cationic polyelectrolytes interacting with hexacyanoferrate ions [ 28 ].…”

Section: Introductionmentioning

confidence: 99%

Influence of Polycation Composition on Electrochemical Film Formation

et al. 2018

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The effect of polyelectrolyte composition on the electrodeposition onto platinum is investigated using a counterion switching approach. Film formation of preformed polyelectrolytes is triggered by oxidation of hexacyanoferrates(II) (ferrocyanide), leading to polyelectrolyte complexes, which are physically crosslinked by hexacyanoferrate(III) (ferricyanide) ions due to preferential ferricyanide/polycation interactions. In this study, the electrodeposition of three different linear polyelectrolytes, namely quaternized poly[2-(dimethylamino)ethyl methacrylate] (i.e., poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride}; PMOTAC), quaternized poly[2-(dimethylamino)ethyl acrylate] (i.e., poly{[2-(acryloyloxy)ethyl]trimethylammonium chloride}; POTAC), quaternized poly[N-(3-dimethylaminopropyl)methacrylamide] (i.e., poly{[3-(methacrylamido)propyl]trimethylammonium chloride}; PMAPTAC) and different statistical copolymers of these polyelectrolytes with N-(3-aminopropyl)methacrylamide (APMA), are studied. Hydrodynamic voltammetry utilizing a rotating ring disk electrode (RRDE) shows the highest deposition efficiency DE for PMOTAC over PMAPTAC and over POTAC. Increasing incorporation of APMA weakens the preferred interaction of the quaternized units with the hexacyanoferrate(III) ions. At a sufficient APMA content, electrodeposition can thus be prevented. Additional electrochemical quartz crystal microbalance measurements reveal the formation of rigid polyelectrolyte films being highly crosslinked by the hexacyanoferrate(III) ions. Results indicate a different degree of water incorporation into these polyelectrolyte films. Hence, by adjusting the polycation composition, film properties can be tuned, while different chemistries can be incorporated into these electrodeposited thin hydrogel films.

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“…Recently, developed a simple experimental setup where a hydrogel matrix is used to load redox active substances, which they characterized by employing electrochemical techniques. The results show that the redox probes are present as dilute solutions and the hydrogel dimensions fulfill the semi-infinite diffusion boundary conditions, therefore the data analysis can be performed using the theoretical framework for electrochemical measurements in liquid solvents in the semi-infinite regime [31,32]. This is in contrast with modified electrodes where complex data analysis is required [34], since the diffusion is constrained by the finite thickness of the films.Consider the above mentioned, the incorporation of GO into a soft matrix based on crosslinked acrylamides to obtain a nanocomposite (NanoC) that works as an active material is shown.…”

mentioning

confidence: 99%

Hydrogel-Graphene Oxide Nanocomposites as Electrochemical Platform to Simultaneously Determine Dopamine in Presence of Ascorbic Acid Using an Unmodified Glassy Carbon Electrode

et al. 2018

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The detection of dopamine, an important neurotransmitter in the central nervous system, is relevant because low levels of dopamine can cause brain disorders. Here, a novel electrochemical platform made of a hydrogel–graphene oxide nanocomposite was employed to electrochemically determine simultaneously dopamine (DA) and ascorbic acid (AA). Unlike previous work, where the base electrode is modified, the active material (graphene oxide, GO) was dispersed in the hydrogel matrix, making an active nanocomposite where the electrochemical detection occurs. The GO, hydrogel and nanocomposite synthesis is described. Dynamic Light Scattering, UV-visible and FTIR spectroscopies showed that the synthesized GO nanoparticles present 480 nm of diagonal size and a few sheets in height. Moreover, the polymer swelling, the adsorption capacity and the release kinetic of DA and AA were evaluated. The nanocomposite showed lower swelling capacity, higher DA partition coefficient and faster DA release rate than in the hydrogel. The electrochemical measurement proved that both materials can be employed to determine DA and AA. Additionally, the nanocomposite platform allowed the simultaneous determination of both molecules showing two well separated anodic peaks. This result demonstrates the importance of the incorporation of the nanomaterial inside of the hydrogel and proves that the nanocomposite can be used as a platform in an electrochemical device to determinate DA using an unmodified glassy carbon electrode.

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Electroactive polymers made by loading redox ions inside crosslinked polymeric hydrogels. Effects of hydrophobic interactions and solvent dynamics

Cited by 10 publications

References 84 publications

A modular platform based on electrospun carbon nanofibers and poly(N‐isopropylacrylamide) hydrogel for sensor applications

A modular platform based on electrospun carbon nanofibers and poly(N‐isopropylacrylamide) hydrogel for sensor applications

Influence of Polycation Composition on Electrochemical Film Formation

Hydrogel-Graphene Oxide Nanocomposites as Electrochemical Platform to Simultaneously Determine Dopamine in Presence of Ascorbic Acid Using an Unmodified Glassy Carbon Electrode

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