Benchaporn Lertanantawong

Study of the underlying electrochemistry of polycrystalline gold electrodes in aqueous solution and electrocatalysis by large amplitude fourier transformed alternating current voltammetry.

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current (FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis.

Investigation of mediated oxidation of ascorbic acid by ferrocenemethanol using large-amplitude fourier transformed ac voltammetry under quasi-reversible electron-transfer conditions at an indium tin oxide electrode

The ability of the technique of large-amplitude Fourier transformed (FT) ac voltammetry to facilitate the quantitative evaluation of electrode processes involving electron transfer and catalytically coupled chemical reactions has been evaluated. Predictions derived on the basis of detailed simulations imply that the rate of electron transfer is crucial, as confirmed by studies on the ferrocenemethanol (FcMeOH)-mediated electrocatalytic oxidation of ascorbic acid. Thus, at glassy carbon, gold, and boron-doped diamond electrodes, the introduction of the coupled electrocatalytic reaction, while producing significantly enhanced dc currents, does not affect the ac harmonics. This outcome is as expected if the FcMeOH (0/+) process remains fully reversible in the presence of ascorbic acid. In contrast, the ac harmonic components available from FT-ac voltammetry are predicted to be highly sensitive to the homogeneous kinetics when an electrocatalytic reaction is coupled to a quasi-reversible electron-transfer process. The required quasi-reversible scenario is available at an indium tin oxide electrode. Consequently, reversible potential, heterogeneous charge-transfer rate constant, and charge-transfer coefficient values of 0.19 V vs Ag/AgCl, 0.006 cm s (-1) and 0.55, respectively, along with a second-order homogeneous chemical rate constant of 2500 M (-1) s (-1) for the rate-determining step in the catalytic reaction were determined by comparison of simulated responses and experimental voltammograms derived from the dc and first to fourth ac harmonic components generated at an indium tin oxide electrode. The theoretical concepts derived for large-amplitude FT ac voltammetry are believed to be applicable to a wide range of important solution-based mediated electrocatalytic reactions.

Non-protein coding RNA-based genosensor with quantum dots as electrochemical labels for attomolar detection of multiple pathogens

The ability of a diagnostic test to detect multiple pathogens simultaneously is useful to obtain meaningful information for clinical treatment and preventive measures. We report a highly sensitive and specific electrochemical biosensor assay for simultaneous detection of three gene targets using quantum dots (QDs). The targets are novel non-protein coding RNA (npcRNA) sequences of Vibrio cholerae, Salmonella sp. and Shigella sp., which cause diarrheal diseases. QDs (PbS, CdS, ZnS) were synthesized and functionalized with DNA probes that were specific to each pathogen. Electrochemical detection of QDs was performed using square wave anodic stripping voltammetry (SWASV). The QDs gave distinct peaks at 0.5 V (PbS), 0.75 V (CdS) and 1.1 V (ZnS). There was no interference in signal response when all three QDs were mixed and detected simultaneously. The detection limits of single and multiplex assays with linear targets and PCR products were in the attomolar ranges. The high assay sensitivity, in combination with specific npcRNA sequences as novel diagnostic targets, makes it a viable tool for detecting pathogens from food, environment and clinical samples.

Electrochemical genosensor assay using lyophilized gold nanoparticles/latex microsphere label for detection of Vibrio cholerae.

Vibrio cholerae is a Gram-negative bacterium that causes cholera, a diarrheal disease. Cholera is widespread in poor, under-developed or disaster-hit countries that have poor water sanitation. Hence, a rapid detection method for V. cholerae in the field under these resource-limited settings is required. In this paper, we describe the development of an electrochemical genosensor assay using lyophilized gold nanoparticles/latex microsphere (AuNPs-PSA) reporter label. The reporter label mixture was prepared by lyophilization of AuNPs-PSA-avidin conjugate with different types of stabilizers. The best stabilizer was 5% sorbitol, which was able to preserve the dried conjugate for up to 30 days. Three methods of DNA hybridization were compared and the one-step sandwich hybridization method was chosen as it was fastest and highly specific. The performance of the assay using the lyophilized reagents was comparable to the wet form for detection of 1aM to 1fM of linear target DNA. The assay was highly specific for V. cholerae, with a detection limit of 1fM of PCR products. The ability of the sensor is to detect LAMP products as low as 50ngµl(-1). The novel lyophilized AuNPs-PSA-avidin reporter label with electrochemical genosensor detection could facilitate the rapid on-site detection of V. cholerae.

Room Temperature Electrochemical Synthesis of Crystalline GaOOH Nanoparticles from Expanding Liquid Metals

Gallium oxyhydroxide (GaOOH) is a wide band gap semiconductor of interest for a variety of applications in electronics and catalysis where the synthesis of the crystalline form is usually achieved via hydrothermal routes. Here we synthesize GaOOH via the electrochemical oxidation of gallium based liquid metals in solutions of 0.1 M NaNO3 electrolyte with pH adjusted over the range of 7-8.4 with NaOH. This electrochemical approach employed under ambient conditions results in the formation of crystalline oblong shaped α-GaOOH nanoparticles from both liquid gallium and liquid galinstan which is a eutectic based on Ga, In, and Sn. The size and shape of the GaOOH particles could be controlled by the solution pH. The product is characterized with scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-visible spectroscopy, and photoluminescence spectroscopy. During the electrochemical oxidation process, the liquid metal drop was found to expand significantly in the case of galinstan due to a constant electrowetting effect which resulted in the continuous expulsion of nanomaterial from the expanding liquid metal droplet. This electrochemical approach may be applicable to other liquid metals for the fabrication of metal oxide nanomaterials and also demonstrates that significant chemical reactions may be occurring at the surface of liquid metals that are actuated under an applied electric field in aqueous electrolytes.

Fingerprinting Green Curry: An Electrochemical Approach to Food Quality Control

The detection and identification of multiple components in a complex sample such as food in a cost-effective way is an ongoing challenge. The development of on-site and rapid detection methods to ensure food quality and composition is of significant interest to the food industry. Here we report that an electrochemical method can be used with an unmodified glassy carbon electrode for the identification of the key ingredients found within Thai green curries. It was found that green curry presents a fingerprint electrochemical response that contains four distinct peaks when differential pulse voltammetry is performed. The reproducibility of the sensor is excellent as no surface modification is required and therefore storage is not an issue. By employing particle swarm optimization algorithms the identification of ingredients within a green curry could be obtained. In addition, the quality and freshness of the sample could be monitored by detecting a change in the intensity of the peaks in the fingerprint response.

CHAPTER 9:Nanomaterial-Based Electrochemical Sensors for Highly Sensitive Detection of Foodborne Pathogens

In this chapter we briefly survey the main foodborne pathogens in terms of their causes, symptoms and impact on human health. We have described the principles of detection for some important analytes by conventional means and by electrochemical biosensors using either immunoassay or nucleic acid assay. We provide a survey of the use of nanomaterials in such biosensors, both in terms of the possible electrode modifications that are available to increase the sensor response, and in terms of how nanomaterials can be used to construct labels for electrochemical biosensors.