Adsorption of 1,10-Phenanthroline within a Dodecanethiol Monolayer:  An Approach to a Switchable Electrode Surface

Hou, Kuang-Yu; Yu, Lei; Severson, Mark W.; Zeng, Xiangqun

doi:10.1021/jp044948h

Cited by 18 publications

(10 citation statements)

References 45 publications

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“…Modified electrodes functionalized with stimuli‐responsive materials attached to electrode surfaces as self‐assembled monolayers or thin‐films allowed switchable/tunable properties controlled by external signals 36–38, thus resulting in electrocatalytic and bioelectrocatalytic systems with variable activity controlled by external signals. Depending on the material properties, various modified electrode surfaces with the switchable behavior controlled by light signals 39, magnetic field 40, 41, temperature changes 42, applied electrical potential 43, 44 and chemical/biochemical inputs 45, 46 have been designed. The present paper gives a short overview of switchable bioelectrocatalytic interfaces changing their properties in response to pH changes and glimpses of the diverse challenges and opportunities in the near future.…”

Section: Introductionmentioning

confidence: 99%

Switchable Bioelectrocatalysis Controlled by pH Changes

2015

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1IntroductionModified electrodes,i ntroduced in 1970-80s,w ere originally aimed at achieving electrocatalytic,b ioelectrocatalytic and photoelectrocatalytic properties [1][2][3].R apid development of various chemically modified electrodes [4], particularly usings elf-assembling methods of surface modification pioneered in the 1980s [5,6],r esulted in the progress of bioelectrocatalytic systems [7,8] utilized in biosensors [9,10] and biofuel cells [11,12].N umerous review papers [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] 2Monolayer Modified Electrodes with Bioelectrocatalytic Activity Controlled by pH ValueInterfacial electron transfer reactions of charged redox speciesa re controlled by the electrode charge( Frumkin effect) [47].T his phenomenon was used to controlb ioelectrocatalytic reactionsb yv aryingt he electrodec harge on surfaces modified with self-assembled monolayers.F or example,agold electrodef unctionalized with as elf-assembled 4-aminothiophenol monolayer demonstrated different kinetics for pyrroloquinoline quinone (PQQ) redox reactions for protonated (positively charged) and deprotonated (neutral)amino groups [48].T he PQQ molecules carrying three negative charges due to dissociated carboxylic groups were electrostatically attracted to the positively charged protonated amino groupso nt he electrode surface,w hile their interactionw ith the neutral amino groups was much weaker,F igure 1. This resulted in facilitation of the electron transfer reaction on the positively charged electrode surface,t hus demonstrating ar eversible PQQ redox reaction followedb yc yclic voltammetry [49].O nt he other hand, ac yclic voltammogram of soluble PQQ on the neutrale lectrode surface demonstrated poor defined and electrochemically irreversible redox process.S ince PQQ isa ne fficient electrocatalyst of oxidation of NADH and NADPH [50],t he primarye lectrochemical reaction of PQQw as extended to an electrocatalytico xidationo fN ADPH mediated by PQQ [48]. Reversible activation and inhibition of the electrocatalytic process was observed when pH was cyclically changed between pH 5.5 and 6.8 resultingi np rotonated and deprotonated amino groups, respectively,F igure 1. Many other systems with pH-controlled bioelectrocatalytic processes proceeding at monolayer-modified electrodes with variable charges have been reported, particularly including photo-activatedi nterfaces with photoisomerizable moieties that allowed double control of the electrochemical processes by light signalsa nd pH changes [51,52]. Abstract:Application of stimuli-responsive materials,particularly basedo np H-sensitive monolayers and thinfilms,t os witchable bioelectrocatalysis is briefly overviewed in the paper. Thes witchable systems are exemplified with amino-functionalized self-assembled monolayers,p olyelectrolyte brushes and complex biomolecular assemblies organized on electrode surfaces and demonstrating differente lectrochemical properties dependingo np H values.T he pH variation was achieved in situ due to biocataly...

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Section: Introductionmentioning

confidence: 99%

Switchable Bioelectrocatalysis Controlled by pH Changes

2015

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“…In particular, light signals applied on interfaces functionalized with photoisomerizable species,17 magnetic field applied at electrode surfaces loaded with magnetic particles21 or magnetic nanowires22 and electrical potentials producing chemical changes at the modified electrode surfaces23 were used to switch/tune the electrochemical properties of the modified electrodes. Moreover, chemical24 and biochemical25 inputs of different complexity have been used to switch ON/OFF modified electrode interfaces for specific electrochemical transformations. Introduction of the novel concept of unconventional chemical26 and biochemical27 computing to the area of electrochemistry has resulted in further increase of complexity of the signal‐responsive electrode interfaces, thus allowing their programmed activation–deactivation to be controlled by numerous biochemical/physiological signals 28,29…”

Section: Introductionmentioning

confidence: 99%

Switchable electrode interfaces controlled by physical, chemical and biological signals

Bocharova

Katz

2011

The Chemical Record

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Electrode interfaces functionalized with various signal-responsive materials have been designed to allow switchable properties of the modified electrodes. External signals of different nature (electrical potential, magnetic field, light, chemical/biochemical inputs) were applied to reversibly activate-deactivate the electrode interfaces upon demand. Multifunctional properties of the modified interfaces have allowed their responses to complex combinations of external signals. Further increase of their complexity has been achieved by integrating the signalresponsive interfaces with unconventional biomolecular computing systems logically processing multiple biochemical signals. This approach has resulted in electrochemical systems controlled by complex variations of biomarkers corresponding to different physiological conditions, thus allowing biological control over electronic systems. The switchable electrodes have been integrated with various "smart" biosensing and signal-processing systems and have been used to assemble biofuel cells producing power on demand.

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“…Light signals [18,19], magnetic field applied at electrode surfaces loaded with magnetic particles [20,21] or magnetic nanowires [22] and electrical potentials generating chemical changes at the electrode interfaces [23] were used to alternate reversibly electrochemical properties of the modified electrodes. Chemical [24] or biochemical [25] signals resulting in the reversible changes of the interfacial properties were also used to switch the electrode activity ON/OFF for electrochemical transformations.…”

Section: Introductionmentioning

confidence: 99%

Modified Electrodes with Switchable Selectivity for Cationic and Anionic Redox Species

et al. 2009

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The modified electrode functionalized with a mixed-polymer brush composed of poly(2-vinylpyridine) and polyacrylic acid tethered to the surface demonstrated switchable interfacial properties discriminating negatively and positively charged redox species. The switchable electrochemical process was characterized by differential pulse voltammetry and Faradaic impedance spectroscopy. The electrochemical system was discussed as a model of an electrochemical multiplexer with two chemical redox inputs, the pH input operating as the selecting signal and one electronic output signal readable by the impedance spectroscopy in the form of the interfacial resistance. The modified electrode represents a novel component for integration with biocatalytic and biocomputing systems aiming at biochemically and electronically controlled actuators.

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Adsorption of 1,10-Phenanthroline within a Dodecanethiol Monolayer: An Approach to a Switchable Electrode Surface

Cited by 18 publications

References 45 publications

Switchable Bioelectrocatalysis Controlled by pH Changes

Switchable Bioelectrocatalysis Controlled by pH Changes

Switchable electrode interfaces controlled by physical, chemical and biological signals

Modified Electrodes with Switchable Selectivity for Cationic and Anionic Redox Species

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