Application of electrochemical impedance spectroscopy for studying of enzyme kinetics

Vidaković‐Koch, Tanja; Mittal, Vinit K.; Varničić, Miroslava; Thi, Quynh Nga Do; Sundmacher, Kai

doi:10.1016/j.electacta.2013.03.026

Cited by 20 publications

(14 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The frequency-dependent resistance arises from the capacitance C e (as 1/ωC): it reflects engagement of the cyclic contribution from reversible chemical steps ranging from binding/release of H 2 to atom/ion transfer, as well as electron transfers that are tightly coupled to these steps (30,31). Expressed another way, R e represents the DC resistance always offered by the combined electron relay and active site, whereas C e is analogous to a time-dependent charging and discharging of the active site (this is a Faradaic process because catalytic cycling allows electrons to flow).…”

Section: Electrochemical Impedance Spectroscopymentioning

confidence: 99%

Frequency and potential dependence of reversible electrocatalytic hydrogen interconversion by [FeFe]-hydrogenases

Pandey

Islam

Happe

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

The kinetics of hydrogen oxidation and evolution by [FeFe]hydrogenases have been investigated by electrochemical impedance spectroscopy-resolving factors that determine the exceptional activity of these enzymes, and introducing an unusual and powerful way of analyzing their catalytic electron transport properties. Attached to an electrode, hydrogenases display reversible electrocatalytic behavior close to the 2H + /H 2 potential, making them paradigms for efficiency: the electrocatalytic "exchange" rate (measured around zero driving force) is therefore an unusual parameter with theoretical and practical significance. Experiments were carried out on two [FeFe]-hydrogenases, CrHydA1 from the green alga Chlamydomonas reinhardtii, which contains only the active-site "H cluster," and CpI from the fermentative anaerobe Clostridium pasteurianum, which contains four low-potential FeS clusters that serve as an electron relay in addition to the H cluster. Data analysis yields catalytic exchange rates (at the formal 2H + /H 2 potential, at 0°C) of 157 electrons (78 molecules H 2 ) per second for CpI and 25 electrons (12 molecules H 2 ) per second for CrHydA1. The experiments show how the potential dependence of catalytic electron flow comprises frequency-dependent and frequency-independent terms that reflect the proficiencies of the catalytic site and the electron transfer pathway in each enzyme. The results highlight the "wire-like" behavior of the Fe-S electron relay in CpI and a low reorganization energy for electron transfer on/off the H cluster.hydrogen | electrocatalysis | impedance spectroscopy | hydrogenase | electron transfer

show abstract

Section: Electrochemical Impedance Spectroscopymentioning

confidence: 99%

Frequency and potential dependence of reversible electrocatalytic hydrogen interconversion by [FeFe]-hydrogenases

Pandey

Islam

Happe

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

show abstract

“…This wide range of fields includes typically electrochemistry related fields as fuel cells [5][6][7][8][9][10][11][12], batteries [13][14][15][16][17], coatings [18][19][20], electrochemical sensors [21][22][23][24][25][26] and supercapacitors [27][28][29][30][31]. But it also includes fields not traditionally linked to electrochemistry as enzymatic kinetics [32], biochemistry [33][34][35], food quality control [36], cancer detection [37][38] and immunology [39][40], amongst others. This electrochemical technique was first introduced in wet-electrochemistry in the late sixties of last century; and then, during the seventies, it was adopted by the solid state researchers [41].…”

Section: Introductionmentioning

confidence: 99%

Application of a Montecarlo based quantitative Kramers-Kronig test for linearity assessment of EIS measurements

Giner-Sanz

Ortega

Pérez-Herranz

2016

Electrochimica Acta

View full text Add to dashboard Cite

Electrochemical Impedance Spectroscopy (EIS) is a very powerful tool to study the behaviour of electrochemical systems. Three conditions must be fulfilled during EIS measurements: causality, linearity, and stability. If any of these conditions is not achieved, then the conclusions obtained from the analysis of the measured spectra may be biased, or even misguided. For this reason, the verification of the compliance of these conditions is critical before accepting any analysis performed on an experimental spectrum. In a previous work, an experimental spectrum quantitative validation technique based on Kramers-Kronig relations was presented. The validation method consists in a Kramers-Kronig (KK) validation test, by equivalent electrical circuit fitting, coupled with a Montecarlo error propagation method. The validation technique builds a consistency region for a given confidence level that allows to discriminate between the individual points of the EIS spectrum that are consistent with the four fundamental hypotheses, and the inconsistent ones. The aim of this work is to validate experimentally if the quantitative validation technique is able to detect nonlinearities. In order to achieve this goal, the EIS spectrum of a markedly nonlinear system was measured experimentally using different perturbation amplitudes. The validation technique was applied to each one of the measured spectra. The method successfully managed to identify large nonlinearities; but did not detect slight ones.

show abstract

“…It has been applied to a wide range of different fields as fuel cells [5][6][7][8][9][10], batteries [11][12], coatings [13][14], electrochemical reaction kinetics [15], electrochemical sensors [16][17][18][19], supercapacitors [20][21][22] and dielectrics [23]. This electrochemical measurement technique has also been used in fields that are not traditionally linked to electrochemistry as enzymatic kinetics [24], cancer detection [25], biochemistry [26][27] and immunology [28][29] amongst others. The large spectrum of fields in which EIS has been applied is explained by the fact that this electrochemical method allows to deconvolve the different physic-chemical phenomena taking place in a given system [4].…”

Section: Introductionmentioning

confidence: 99%

Total harmonic distortion based method for linearity assessment in electrochemical systems in the context of EIS

Giner-Sanz

Ortega

Pérez-Herranz

2015

Electrochimica Acta

View full text Add to dashboard Cite

ElsevierGiner Sanz, JJ.; Ortega Navarro, EM.; Pérez-Herranz, V. (2015). Total harmonic distortion based method for linearity assessment in electrochemical systems in the context of EIS. Electrochimica Acta. 186:598-612. doi:10.1016Acta. 186:598-612. doi:10. /j.electacta.2015 Electrochemical Impedance Spectroscopy (EIS) is a widely used electrochemical measurement technique that has been used in a great spectrum of fields since it allows deconvolving the individual physic-chemical processes that take place in a given system. Ohm's generalized law, and thus the impedance concept, are only valid if 4 conditions are fulfilled: causality, finiteness, stationarity and linearity. In the case that any of these conditions is not achieved, the obtained impedance spectra will present distortions that may lead to biased or even erroneous results and conclusions. For this reason it is crucial to verify if the 4 conditions are fulfilled, before accepting the results extracted from impedance spectra. In this work, a linearity assessment quantitative method based in the total harmonic distortion (THD) parameter is presented and verified experimentally. The experimental validation of the implemented method showed that the implemented method is able to assess quantitatively the linearity of the system. In addition, it is also able to determine the threshold frequency above which the system will not present significant nonlinear effects even for large perturbation amplitudes. It was observed that the THD method is more sensitive to nonlinear effects than the spectra themselves.

show abstract

Application of electrochemical impedance spectroscopy for studying of enzyme kinetics

Cited by 20 publications

References 25 publications

Frequency and potential dependence of reversible electrocatalytic hydrogen interconversion by [FeFe]-hydrogenases

Frequency and potential dependence of reversible electrocatalytic hydrogen interconversion by [FeFe]-hydrogenases

Application of a Montecarlo based quantitative Kramers-Kronig test for linearity assessment of EIS measurements

Total harmonic distortion based method for linearity assessment in electrochemical systems in the context of EIS

Contact Info

Product

Resources

About