Logarithmic relaxation of electrochemical insulating-to-conducting conversion at polyaniline films: interpretation by electric percolation

Aoki, Koichi; Cao, Junyan; Hoshino, Yoshimasa

doi:10.1016/0013-4686(94)e0181-x

Cited by 77 publications

(34 citation statements)

References 29 publications

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“…Those responses from conducting polymers were considered anomalous voltammetric responses: deeper reduced initial states require higher energy (higher anodic potentials) to start their re‐oxidization while, according with Nernst equation, a lower equilibrium potential (lower energy) should be expected for a higher concentration of the reduced species. Different CPs exchanging anions during electrochemical reactions in different electrolytes give similar “anomalous” voltammetric responses to those depicted by Figure after reduction until rising cathodic potential limits ,,,,,,…”

Section: Identification Of Different Reaction‐driven Structural Effecmentioning

confidence: 55%

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Structural and Conformational Chemistry from Electrochemical Molecular Machines. Replicating Biological Functions. A Review

Otero

2017

The Chemical Record

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Each constitutive chain of a conducting polymer electrode acts as a reversible multi-step electrochemical molecular motor: reversible reactions drive reversible conformational movements of the chain. The reaction-driven cooperative actuation of those molecular machines generates, or destroys, inside the film the free volume required to lodge/expel balancing counterions and solvent: reactions drive reversible film volume variations, which basic structural components are here identified and quantified from electrochemical responses. The content of the reactive dense gel (chemical molecular machines, ions and water) mimics that of the intracellular matrix in living functional cells. Reaction-driven properties (composition-dependent properties) and devices replicate biological functions and organs. An emerging technological world of soft, wet, reaction-driven, multifunctional and biomimetic devices and the concomitant zoomorphic or anthropomorphic robots is presented.

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Section: Identification Of Different Reaction‐driven Structural Effecmentioning

confidence: 55%

“…As a consequence, it was proposed that during electrochemical reductions the material conductivity changes from conducting (oxidized state) to insulator (reduced state). This is the origin of the conducting/insulator transition model ,,. It was accepted that after reduction the film couldn't be re‐oxidized.…”

Section: Dense Gel Electrodesmentioning

confidence: 99%

Structural and Conformational Chemistry from Electrochemical Molecular Machines. Replicating Biological Functions. A Review

Otero

2017

The Chemical Record

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“…The results seem to contradict electrochemical principles: deeper reduced initial states and larger potential steps produce slower reaction rates, requiring longer times for the film oxidation completion. Similar unexpected results (chronoamperometric or voltammetric) from different conducting polymers were named from the eighties anomalous results, memory effect, relaxation processes, asymmetric processes, and so on 45, 56, 63, 64, 67–98…”

Section: Reaction Kineticsmentioning

confidence: 55%

Structural and Biomimetic Chemical Kinetics: Kinetic Magnitudes Include Structural Information

Otero

Martínez

2012

Adv Funct Materials

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Electrochemical reactions in fi lms of conducting polymers involve reactive chains, exchanging ions and solvent with the electrolyte under current fl ow. The reaction induces structural changes: conformational movements in chains and swelling, shrinking, compaction, and relaxation processes in the reactive dense gel. Conformational movements and structural changes induced by reactions are not included by today's chemical kinetic models. Using different packed conformations as initial states for the study of the reaction kinetics in fi lms of different conducting polymers, rate coeffi cients, activation energies, and reaction orders related to the concentration of active centers in the fi lm change with the structure of the selected initial state. The kinetic magnitudes include and quantify conformational and structural energetic states. Therefore, the reaction activation energy includes the constant reaction activation energy and the conformational energy of the initial packed state. The electrochemically stimulated conformational relaxation model describes the empirical variation of the kinetic magnitudes.

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“…We have investigated the use of composite films of poly(aniline) with a polyanion such as poly(vinylesulfonate) [12]. In these composites deprotonation of the emeraldine form can only occur if cations from the solution enter the film to maintain electroneutrality [14,15].…”

Section: Introductionmentioning

confidence: 99%

The measurement of alkaline phosphatase at nanomolar concentration within 70 s using a disposable microelectrochemical transistor

Astier

Bartlett

2004

Bioelectrochemistry

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Logarithmic relaxation of electrochemical insulating-to-conducting conversion at polyaniline films: interpretation by electric percolation

Cited by 77 publications

References 29 publications

Structural and Conformational Chemistry from Electrochemical Molecular Machines. Replicating Biological Functions. A Review

Structural and Conformational Chemistry from Electrochemical Molecular Machines. Replicating Biological Functions. A Review

Structural and Biomimetic Chemical Kinetics: Kinetic Magnitudes Include Structural Information

The measurement of alkaline phosphatase at nanomolar concentration within 70 s using a disposable microelectrochemical transistor

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