Structural and Biomimetic Chemical Kinetics: Kinetic Magnitudes Include Structural Information

Abstract

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.

Biomimetic Conducting Polymers: Synthesis, Materials, Properties, Functions, and Devices

“…7b) The slope (dQ/dt = dQ/Fdt = dn/dt, mol L −1 s −1 , where F is the Faraday's constant and n the number of moles of both, electron and exchanged balancing counterions) at the inflexion point is the initial oxidation rate, R. This slope is the current (dQ/dt = i) at the chronoamperometric maximum. 28,86 In this way Eq. (16) indicates the experimental procedure to check if, at the chronoamperometric maxima, the reaction occurs under chemical kinetic control.…”

“…5b) includes information about different structural aspects that also can be used for information storage. 6,28,86 …”

“…4c). 17,28 When the chains take part of a film, the conformational movements, driven by the reactions, generate or destroy free volume to lodge or expel counterions and solvent: the material swells by oxidation (Figs. 9a-c) and shrinks (Figs.…”

“…Equations (14)(15)(16)(17) state that the activation energy, the kinetic coefficient, and the reaction order of any reaction driving conformational and structural movements include quantitative structural information. The chemical kinetics becomes structural chemical kinetics 28 envisaging a quantitative description and prediction of many biological reactions inducing health and illnesses by right folding, un-folding, or misfolding of proteins, enzymes, or nucleic acids.…”

Effect of the Electrolyte Concentration and Substrate on Conducting Polymer Actuators

“…4d) film shrinking, closing and compaction by expulsion of counterions and water. 32,40 The subsequent film reduction with the entrance of cations starts by nucleation-relaxation giving a maximum or a shoulder on the chronoamperometric responses. Faster nucleationrelaxation processes occur when the concentration rises up to 0.6-1M.…”