Electrochemical Rectification Research Articles

Electrowetting-Mediated Transport to Produce Electrochemical Transistor Action in Nanopore Electrode Arrays.

Understanding water behavior in confined volumes is important in applications ranging from water purification to healthcare devices. Especially relevant are wetting and dewetting phenomena which can be switched by external stimuli, such as light and electric fields. Here, these behaviors are exploited for electrochemical processing by voltage-directed ion transport in nanochannels contained within nanopore arrays in which each nanopore presents three electrodes. The top and middle electrodes (TE and ME) are in direct contact with the nanopore volume, but the bottom electrode (BE) is buried beneath a 70 nm silicon nitride (SiNx ) insulating layer. Electrochemical transistor operation is realized when small, defect-mediated channels are opened in the SiNx . These defect channels exhibit voltage-driven wetting that mediates the mass transport of redox species to/from the BE. When BE is held at a potential maintaining the defect channels in the wetted state, setting the potential of ME at either positive or negative overpotential results in strong electrochemical rectification with rectification factors up to 440. By directing the voltage-induced electrowetting of defect channels, these three-electrode nanopore structures can achieve precise gating and ion/molecule separation, and, as such, may be useful for applications such as water purification and drug delivery.

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries.

Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture, the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures.The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured, benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW), a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. While the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs, including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.

Redox Cycling in Individually Encapsulated Attoliter-Volume Nanopores.

Redox cycling electrochemistry in arrays of individually encapsulated attoliter-volume ( V ∼ 10 aL) nanopores is investigated and reported here. These nanopore electrode array (NEA) structures exhibit distinctive electrochemical behaviors not observed in open NEAs, which allow free diffusion of redox couples between the nanopore interior and bulk solution. Confined nanopore environments, generated by sealing NEAs with a layer of poly(dimethylsiloxane), are characterized by enhanced currents-up to 250-fold compared with open NEAs-owing to effective trapping of the redox couple inside the nanopores and to enhanced mass transport effects. In addition, electrochemical rectification ( ca. 1.5-6.3) was observed and is attributed to ion migration. Finite-element simulations were performed to characterize the concentration and electric potential gradients associated with the disk electrode, aqueous medium, and ring electrode inside the nanopores, and the results are consistent with experimental observations. The additional signal enhancement and redox-cycling-based rectification behaviors produced in these self-confined attoliter-volume nanopores are potentially useful in devising ultrasensitive sensors and molecular-based iontronic devices.

Stochastic pumping of ions based on colored noise in bacterial channels under acidic stress.

Fluctuation-driven ion transport can be obtained in bacterial channels with the aid of different types of colored noise including the biologically relevant Lorentzian one. Using the electrochemical rectification of the channel current as a ratchet mechanism we observe transport of ions up to their concentration gradient under conditions similar to that met in vivo, namely moderate pH gradients and asymmetrically charged lipid membranes. We find that depending on the direction of the concentration gradient the channel can pump either cations or anions from the diluted side to the concentrated one. We discuss the possible relevance of this phenomenon for the pH homeostasis of bacterial cells.

Multi-level logic gate operation based on amplified aptasensor performance.

Conventional electronic circuits can perform multi-level logic operations; however, this capability is rarely realized by biological logic gates. In addition, the question of how to close the gap between biomolecular computation and silicon-based electrical circuitry is still a key issue in the bioelectronics field. Here we explore a novel split aptamer-based multi-level logic gate built from INHIBIT and AND gates that performs a net XOR analysis, with electrochemical signal as output. Based on the aptamer-target interaction and a novel concept of electrochemical rectification, a relayed charge transfer occurs upon target binding between aptamer-linked redox probes and solution-phase probes, which amplifies the sensor signal and facilitates a straightforward and reliable diagnosis. This work reveals a new route for the design of bioelectronic logic circuits that can realize multi-level logic operation, which has the potential to simplify an otherwise complex diagnosis to a "yes" or "no" decision.

Electrochemical current rectification–a novel signal amplification strategy for highly sensitive and selective aptamer-based biosensor

Electrochemical aptamer-based (E-AB) sensors represent an emerging class of recently developed sensors. However, numerous of these sensors are limited by a low surface density of electrode-bound redox-oligonucleotides which are used as probe. Here we propose to use the concept of electrochemical current rectification (ECR) for the enhancement of the redox signal of E-AB sensors. Commonly, the probe-DNA performs a change in conformation during target binding and enables a nonrecurring charge transfer between redox-tag and electrode. In our system, the redox-tag of the probe-DNA is continuously replenished by solution-phase redox molecules. A unidirectional electron transfer from electrode via surface-linked redox-tag to the solution-phase redox molecules arises that efficiently amplifies the current response. Using this robust and straight-forward strategy, the developed sensor showed a substantial signal amplification and consequently improved sensitivity with a calculated detection limit of 114nM for ATP, which was improved by one order of magnitude compared with the amplification-free detection and superior to other previous detection results using enzymes or nanomaterials-based signal amplification. To the best of our knowledge, this is the first demonstration of an aptamer-based electrochemical biosensor involving electrochemical rectification, which can be presumably transferred to other biomedical sensor systems.

Tuning Electrochemical Rectification via Quantum Dot Assemblies

A novel approach to tuning electrochemical rectification using 2D assemblies of quantum dots (QDs) is presented. Asymmetric enhancement of the oxidation and reduction currents in the presence of the Fe(CN)(6)(3-/4-) redox couple is observed upon adsorption of QDs at thiol-modified Au electrodes. The extent of the electrochemical rectification is dependent on the average QD size. A molecular blocking layer is generated by self-assembling 11-mercaptoundecanoic acid (MUA) and an ultrathin film of poly(diallyldimethylammonium chloride) (PDADMAC) on the electrode. The polycationic film allows the electrostatic adsorption of 3-mercaptopropionic acid (MPA)-stabilized CdTe QDs, generating 2D assemblies with approximately 0.4% coverage. The QD adsorption activates a fast charge transfer across the blocking layer in which the reduction process is more strongly enhanced than the oxidation reaction. The partial electrochemical rectification is rationalized in terms of the relative position of the valence (VB) and conduction band (CB) edges with respect to the redox Fermi energy (ε(redox)). Quantitative analysis of the exchange current density obtained from electrochemical impedance spectroscopy demonstrates that the enhancement of charge transport across the molecular barrier is strongly dependent on the position of the QD valence band edge relative to ε(redox). The average electron tunneling rate constant through the QD assemblies is estimated on the basis of the Gerischer model for electron transfer.

Electrochemical current rectification at bio-functionalized electrodes

In the present paper, we demonstrate the electrochemical rectification of a redox current which is transferred between redox probes (ferricyanide) in solution and a gold electrode functionalized with the biomolecular redox mediator microperoxidase-11 (MP-11). MP-11 is the redox active, heme-containing domain of the biological electron shuttle cytochrome c (cyt c). In our system, a unidirectional current develops due to selective electron transport from the bio-functionalized electrode to ferricyanide such that MP-11 controls the read-out of our coupled redox system. The electrode was functionalized by adding a monolayer of undecanethiol (UDT) to promote the physisorption of MP-11 and inhibit the direct electron transfer between redox probe and electrode. The relative position of redox donator, mediator, and acceptor equilibrium potentials defines the charge transport and a potential-dependent electrochemical current rectification. The results of our investigations demonstrate that functional building blocks of proteins can be reassembled into new conceptual devices with operation modes deviating from their native function, which could prove highly useful in future design of biosensors and bioelectronic systems.

Redox Mediation and Electron Transfer through Supramolecular Arrays of Ferrocene-Labeled Streptavidin on Biotinylated Gold Electrodes

In this work we have studied electron transfer between ferrocyanide species in solution and Au electrodes redox-mediated by ferrocene labels linked to supramolecular bioconjugates. This configuration leads to the so-called electrochemical rectification where the ferrocyanide oxidation is mediated by electrogenerated ferricenium, as evidenced by a unidirectional current flux. Our aims were focused at gaining insight into the molecular aspects of the rectified current and exploring the limits of the electrocatalytic amplification when bioconjugates are used as a platform. We used the Alleman−Weber−Creager model to rationalize and describe in a more quantitative manner the influence of the donor species in solution on the measured electrocatalytic current. Moreover, this model enabled us to estimate homogeneous and heterogeneous rate constants associated with the electron transfer process. We observed that the characteristics of the redox-mediated amplification are highly dependent on the concentration of donor species. This can be described in two regimes depending on whether the bimolecular reaction (kcross) or the electrogeneration of the mediator (ko) is the limiting step in the overall electron transfer process. The estimation of kcross is in good agreement with that calculated from Marcus theory. On the other hand, the ko values suggest that electron transfer between the redox labels in the protein conjugate and the Au electrode is mainly controlled by electron tunneling through the biotinylated platform.

Current rectification by mediating electroactive polymers

In this work we briefly review the theoretical basis for the electrochemical rectification in mediated redox reactions at redox polymer modified electrodes. Electrochemical rectification may have two distinct origins. It is either caused by a slow kinetics of the reaction between the external redox couple and the mediator or it is originated by a slow electronic transport within the film under an unfavorable thermodynamic condition. We show experimental results for the redox mediation reaction of poly( o-aminophenol) (POAP) on the Fe 2+/3+ and on the Fe(CN) 6 3−/4− redox couples in solution that prove the proposed mechanisms of electrochemical rectification.

Redox mediation at electroactive polymer coated electrodes: Mechanistic diagnosis criteria from steady state polarization curves

In this work, we analyze the i–E response of a redox mediator modified electrode in steady state and in the absence of permeation of the reactants into the film. We show that, besides some kinetic criteria existing in the literature based on the behavior of the limiting currents, there are others based on the entire i–E response. This analysis allows to explain several features of the i–E curve, yet unexplained, such as the shift of the half wave potential, electrochemical rectification, the shape of the Koutecky–Levich plots and the shape of the E vs. ln [(iL − i)/i] plots. From them, it is possible to determine, almost unmistakably, the type of kinetic control and to obtain the corresponding kinetic parameters.

산화환원 화학 종이 단 분자 층으로 화학 흡착된 전극에서의 전기화학적 정류

산화환원 화학 종이 화학적으로 흡착 된 전극에서의 전자 이동 현상은 흡착 화학 종이 전극표면에 흡착 되기 전과는 다르게 흡착 된 산화환원 화학 종의 전자 이동 특성에 전적으로 의존한다. 이러한 전극 표면에서의 전자이동에 관한 기본적인 변화는 전자 이동 현상에 관한 기초 연구를 넘어 전기화학 촉매, 전기화학적 바이오센서, 분자전자공학 등에 유용한 지식이 되고 있다. 본 고에서는 산화환원 화학 종이 자기 조립 막을 형성하여 화학적으로 흡착 된 전극을 사용 할 때 전극/용액 계면에서 관측 되는 전기화학 정류 전류와 전압 사이의 관계에 대한 상관관계를 소개 한다. Electrochemical rectification at electrode chemically modified with redox active agents isolated at monolayer level was considered. Formulation of the rising part of linear sweep voltammogram at steady and rotating disc electrode was introduced.

A pH-Tunable Nanofluidic Diode: Electrochemical Rectification in a Reconstituted Single Ion Channel

We report pH-dependent electrochemical rectification in a protein ion channel (the bacterial porin OmpF) reconstituted on a planar phospholipid membrane. The measurements performed at single-channel level show that the electric current is controlled by the protein fixed charge and it can be tuned by adjusting the local pH. Under highly asymmetric pH conditions, the channel behaves like a liquid diode. Unlike other nanofluidic devices that display also asymmetric conductance, here the microscopic charge distribution of the system can be explored by using the available high-resolution (2.4 A) channel crystallographic structure. Continuum electrostatics calculations confirm the hypothesized bipolar structure of the system. The selective titration of the channel residues is identified as the underlying physicochemical mechanism responsible for current rectification.

Electrochemical rectification at electrode surface modified with poly (acrylic acid) and decane thiol

Gold surface modified with a two-component system consisting of poly (acrylic acid) (PAA) by electropolymerizing acrylic acid (AA) and decane thiol (DT), further functionalized with ferrocene monocarboxylic acid (FMC) through covalent linkage, was used to demonstrate mediated electron transfer resulting in a unidirectional flow of current. The electrode surface was modified using two different configurations. In Configuration 1 (Config. 1), electrode surface modified with FMC showed rectification behavior when contacted with a solution containing methylene blue (MB). In Configuration 2, redox-active bilayer was constructed using polyvinyl pyrollidone (PVP) and hexaamineruthernium (II) chloride [Ru(NH3)6]2+ showed rectification characteristics. The continuous rectification property of the redox-active bilayer is achieved by releasing the trapped [Ru(NH3)6]3+ in the outer layer using a reductant (ascorbic acid). Spectroelectrochemical measurements were made to study the reduction property of the ascorbic acid. Atomic force microscopic images and impedance measurements were also made on the modified electrode surfaces to explore the compactness of the first layer (PAA and PAA/DT).

Surface Microscopic Structure and Electrochemical Rectification of a Branched Alkanethiol Self-Assembled Monolayer

The tert-butanethiol self-assembled monolayers (SAMs) on Au(111) surfaces were prepared from various solvents and investigated by a combination of scanning tunneling microscopy (STM) and electrochemistry in aqueous environments. High-resolution STM images reveal a (radical(7) x radical(7))R19 degrees surface lattice structure, in contrast with the conventional lattice (radical(3) x radical(3))R30 degrees structure for straight-chain alkanethiol SAMs. Interestingly, such a branched monolayer shows electrochemical rectification toward redox probes. We suggest that electrochemical rectification could be a general characteristic of short-chain branched alkanthiol SAMs, and originate in localized electronic effects.

Polymer-based bilayer interfaces for electrochemical rectification

In this paper, the electrochemical current rectification phenomenon exhibited at an electrochemical interface constituted by a glassy carbon electrode covered with a bilayer of polymer films is discussed. The authors have shown that Methylene Blue (MB) redox species can be confined to a very thin insulating polymer film formed from orthophenylene diamine. The poly(opd) film exhibited excellent blocking properties to redox molecules in solution. On the other hand, the insulating poly(opd) film trapped with MB could mediate electron transfer between the redox molecules in solution and the electrode. Further, a second polymeric layer (Nafion film) trapped with ferrocene redox species was formed as the outer layer over the inner poly (opd) film containing MB. This bilayer-modified electrode, due to the significant difference in the redox potentials of the MB and ferrocene species immobilized in the inner and outer layers, respectively, exhibits unidirectional current flow and the results of the voltammetric investigations on the modified electrodes are described in this communication.

The Redox‐Reaction [Fe(CN)6]3‐/4‐ on Electrodes Coated with Fixed Charge Polymer Films — Observation of Membrane Permeability Modulation by the Electrode Potential

AbstractThin films of anion exchangers were prepared from quaternized polyvinylpyridine on glassy carbon and Pt electrodes. To render the polymer insoluble in aqueous electrolytes it was cross‐linked chemically or by exposing the coated electrodes to synchrotron‐radiation. With these electrodes the redox system [Fe(CN)6]3‐/4‐ was investigated with electrochemical methods, including the rotated ring/disk technique. The high equilibrium concentration of [Fe(CN)6]3‐ in the polymer matrix leads to extensive cross‐linking and desolvation of the film rendering its permeability low. During cathodic reduction a large fraction of the produced [Fe(CN)6]4‐ leaves the polymer phase. Anions from the background electrolyte replace the redox‐system; the film swells. The electrochemical phenomena associated with this reversible film structure change are discussed, in particular, a remarkable electrochemical rectification effect.