Scanning electrochemical cell microscopy : a versatile technique for nanoscale electrochemistry and functional imaging

Scanning electrochemical cell microscopy (SECCM) is a new pipette-based imaging technique purposely designed to allow simultaneous electrochemical, conductance, and topographical visualization of surfaces and interfaces. SECCM uses a tiny meniscus or droplet, confined between the probe and the surface, for high-resolution functional imaging and nanoscale electrochemical measurements. Here we introduce this technique and provide an overview of its principles, instrumentation, and theory. We discuss the power of SECCM in resolving complex structure-activity problems and provide considerable new information on electrode processes by referring to key example systems, including graphene, graphite, carbon nanotubes, nanoparticles, and conducting diamond. The many longstanding questions that SECCM has been able to answer during its short existence demonstrate its potential to become a major technique in electrochemistry and interfacial science

Carbon fibre composites: integrated electrochemical sensors for wound management

The applicability of employing a carbon fibre mesh as an electrochemical sensing substructure for assessing urate transformations within wound exudates is evaluated. Prototype sensor assemblies have been designed and their response characteristics towards uric acid and other common physiological components are detailed. Modification of the carbon fibre sensor through surface anodisation and the application of cellulose acetate permselective barriers have been shown to lead to optimized responses and much greater sensitivity (1440% increase) and specificity. These could enable the accurate periodic monitoring of uric acid in wound fluid. The performance characteristics of the composite sensors in whole blood, serum and blister fluid have been investigated

Electrically Guided DNA Immobilization and Multiplexed DNA Detection with Nanoporous Gold Electrodes.

Molecular diagnostics have significantly advanced the early detection of diseases, where the electrochemical sensing of biomarkers (e.g., DNA, RNA, proteins) using multiple electrode arrays (MEAs) has shown considerable promise. Nanostructuring the electrode surface results in higher surface coverage of capture probes and more favorable orientation, as well as transport phenomena unique to nanoscale, ultimately leading to enhanced sensor performance. The central goal of this study is to investigate the influence of electrode nanostructure on electrically-guided immobilization of DNA probes for nucleic acid detection in a multiplexed format. To that end, we used nanoporous gold (np-Au) electrodes that reduced the limit of detection (LOD) for DNA targets by two orders of magnitude compared to their planar counterparts, where the LOD was further improved by an additional order of magnitude after reducing the electrode diameter. The reduced electrode diameter also made it possible to create a np-Au MEA encapsulated in a microfluidic channel. The electro-grafting reduced the necessary incubation time to immobilize DNA probes into the porous electrodes down to 10 min (25-fold reduction compared to passive immobilization) and allowed for grafting a different DNA probe sequence onto each electrode in the array. The resulting platform was successfully used for the multiplexed detection of three different biomarker genes relevant to breast cancer diagnosis

Characterization of gold nanoparticle layer deposited on gold electrode by various techniques for improved sensing abilities

The deposition of gold nanoparticles (AuNPs) on the surface of gold electrode is believed to enhance the electrochemical characteristics of the surface. According to the existing literature, this could be performed in various ways. The purpose of the current study was to compare these results and report the most effective technique. In this regard, the layer-by-layer deposition, self-assembled monolayer technique and electro deposition method were investigated. Our results showed that cyclic voltammetry electrodeposition of AuNPs causes an observable increase in the peak current, causing improved electrode kinetics and a reduction in the oxidation potential (thermodynamically feasible reaction). These modified electrodes also showed several advantages with respect to stability and reproducibility

Fabrication and electrochemical characterization of highly efficient hierarchically assembled hybrid two-dimensional nanointerfaces for electrochemical biosensing and bioelectronics

Abstract : Two dimensional (2D) materials have provided a new era to biosensors research. Biosensors are functional biodevices which include the integration of biology with electronics. The integration of 2D materials with other nanomaterials has transformed the understanding of the biological and electronics world and has paved a way for the design and fabrication of novel 2D nanointerfaces. The use of 2D nanointerfaces has given great success to biosensors and bioelectronics field which ultimately impacts on biomedical diagnosis and sensing applications. The superior properties of 2D materials such as large surface area, ease of hybridization, good biocompatibility, and high electron transfer properties make them ideal interface materials for the design and fabrication of bioelectronic devices including biosensors. The thesis focused on the fabrication of 2D nanointerfaces by combining two 2D hybrid materials and then nanostructuring with metal nanoparticles for better electron transfer within the interface which is followed by immobilization of enzyme as a bio-recognition element for biosensing purposes. The conjugation of the 2D hybrid nanointerface materials was achieved through the self-assembly technique. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used in the study for characterization of the 2D hybrid nanointerface structures and chronoamperometry studies were employed to investigate the electrobiocatalytic properties of the 2D hybrid nanointerfaces structures. Structural characterization was done by using X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques for morphological details of 2D hybrid nanointerfaces structures. The fabrication of bioelectrodes was achieved by using the conjugated 2D hybrid nanointerface materials. ix There are three different segments in this research study. All of these different segments involved the use of 2D materials for bioelectronics purposes. The first phase involved the fabrication of smart hierarchically self-assembled 2D electrobiocatalytic interface system based on the combination of gold nanoparticles (AuNPs) doped graphene oxide (GO)-molybdenum disulfide (MoS2) layered nanohybrid, conjugated with poly (N-isopropylacrylamide, PNIPAAm) resulting in GO/AuNPs/MoS2/PNIPAAm interface. The introduction of PNIPAAm improved the stability of the self-assembled GO/AuNPs/MoS2 interface structure. Horseradish peroxidase (HRP) was subsequently immobilized on the GO/AuNPs/MoS2/PNIPAAm interface through electrostatic interactions giving GO/AuNPs/MoS2/PNIPAAm/Peroxidase electrobiocatalytic interface system as a platform for electrobiocatalysis reactions for biosensing applications. Morphological characterization of GO/AuNPs/MoS2/PNIPAAm indicates that this 2D nanointerface structure has a wide surface area for enzyme immobilization due to their flake-like structure. CV showed diffusion-controlled electron transfer properties at the interface. The electrobiocatalytic activity of the nanohybrid interface structure was studied using hydrogen peroxide (H2O2) as a model analyte. The fabricated bioelectrode exhibits a wide linear response to the detection of H2O2 from 1.57 to 11.33 mM, with a detection limit of 3.34 mM (S/N=3) and a capacitance of 8.6 F/cm2. The second phase of the study involved the fabrication of hybrid dual 2D-nanohybrid structure through self-assembly combination AuNPs with hybrid 2D materials consisting of boron nitride (BN) and tungsten disulphide (WS2) as a nanointerface system for electrochemical biosensing. HRP was immobilized on the hybrid dual 2Dnanoparticle systems to form a biointerface. Structural characterization showed high crystallinity in the fabricated structure, while morphological characterization confirmed x the high surface to volume area of the hybrid material and the presence of welldispersed AuNPs. Electrochemical characterization also confirmed that the fabricated HRP/BN/WS2/AuNPs/GC bioelectrode exhibited excellent electron transfer properties at the interface. The electrobiocatalytic activity of the nanohybrid interface structure was studied using H2O2 as a model analyte. The fabricated bioelectrode exhibited a wide linear range from 0.15 mM to 15.01 mM towards detection of H2O2 with a limit of detection of 3.0 mM (S/N = 3) and a sensitivity of 19.16 μA/mM/cm2. Theoretical studies of the BN/Au/WS2(001) nanohybrid structure was carried out using density functional theory (DFT) calculation for confirming the charge transport mobility and conductivity of the fabricated material. DFT calculations combined with the experimental studies showed that the self-assembled combination of the BN/Au/WS2(001) nanocomposite enhances the performance of the fabricated biosensor due to an introduced new electronic state emanating from the N 2p orbital. The third phase of the study involved the synthesis of acetylene sourced graphene (Gr) by chemical vapour deposition (CVD) method. Self-assembly method was used to prepare the 2D nanohybrid interfaces, which consist of Gr, WS2, AuNPs and HRP for fabricating electrochemical biosensor for detection of H2O2. The XRD results revealed that Gr/WS2/AuNPs nanohybrid structure has good crystalline nature. CV and electrochemical impedance spectroscopy results showed that due to the incorporation of AuNPs, the redox properties of Gr/WS2/AuNPs/HRP conjugate 2D hybrid structure improved in comparison to Gr/WS2/HRP. The same trend was observed in the chronoamperometric results. The Gr/WS2/AuNPs/HRP/GCE modified bioelectrode exhibited a good electrobiocatalytic performance towards the detection of H2O2 over a relatively wider linear range (0.40 mM to 23 mM), with a higher xi sensitivity (11.07 μA/mM/cm2) than that of Gr/WS2/HRP/GCE modified bioelectrode (9.23 μA/mM/cm2). The results have shown that electrobiocatalytic reactions can be controlled by modifying the nanohybrid interfaces.D.Phil. (Chemistr

The application of neural networks to anodic stripping voltammetry to improve trace metal analysis

This thesis describes a novel application of an artificial neural network and links together the two diverse disciplines of electroanalytical chemistry and information sciences. The artificial neural network is used to process data obtained from a Differential Pulse Anodic Stripping (DPAS) electroanalytical scan and produces as an output, predictions of lead concentration in samples where the concentration is less than 100 parts per billion. A comparative study of several post analysis processing techniques is presented, both traditional and neural. Through this it is demonstrated that by using a neural network, both the accuracy and the precision of the concentration predictions are increased by a factor of approximately two, over those obtained using a traditional, peak height calibration curve method. Statistical justification for these findings is provided Furthermore it is shown that, by post processing with a neural network, good quantitative predictions of heavy metal concentration may be made from instrument responses so poor that, if using tradition methods of calibration, the analytical scan would have had to be repeated. As part of the research the author has designed and built a complete computer controlled analytical instrument which provides output both to a graphical display and to the neural network. This instrument, which is fully described in the text, is operated via a mouse driven user interface written by the author

Biosensors and Nanobiosensors: Design and Applications

The goal of this chapter is to cover the full scope of biosensors. It offers a survey of the principles, design, operation, and biomedical applications of the most popular types of biosensing devices in use today. By discussing recent research and future trends based on many excellent books and reviews, it is hoped to give the readers a comprehensive view on this fast growing field

Development of novel techniques for monitoring anti-oxidant thiols

The clinical exploitation of physiological biomarkers could yield considerableimprovements in diagnosis and treatment providing their measurement can be conducted peedily and preferably at the point of care. The project has sought to investigate the development of new methods that could allow such measurements to be made. The various biomarkers that could be exploited as the basis of a general “index” of physiological wellbeing have been identified and their potential clinical merit critically appraised. Anti-oxidant sulphur compounds (cysteine, glutathione, sulphite) were selected as potential targets on the basis of their physiological role in protecting the body from damage by free radicals. The variation in their concentration within biofluids is widely acknowledged as a useful diagnostic gauge as to the degree of oxidative stress that an individual may be experiencing. The main problem, from a clinical perspective, is the lack of a suitable procedure for monitoring their concentration speedily at, or by, the patient. A brief assessment of the various electroanalytical options (encompassing voltammetric, amperometric and potentiometric methodologies) available for the detection of the sulphur anti-oxidants has been conducted. A potentiometric detection strategy was found to offer numerous advantages and a novel indicator family based on quinone interaction adopted and forms the foundation of the work presented herein. The reaction mechanism has been elucidated and the analytical applicability of the system investigated using a variety of techniques – covering both chromatographic, spectroscopic and electrochemical methodologies

Screen Printed Carbon Electrode Based Microfluidic Biosensor for Sweat Cortisol Detection

A simple, cost-effective, microfluidic, field-deployable biosensor with screen printed carbon electrode (SPCE) was developed for detection of sweat cortisol with point of care applications. Cortisol detection in artificial sweat is an important screening tool for diagnosis and monitoring of various health conditions like Addison’s disease, stress disorder, and Cushing’s syndrome. A self-assembled monolayer of graphene oxide (GO) is functionalized on SPCE electrode, onto which cortisol antibodies are immobilized for cortisol detection. Microfluidic system ensured precise and controlled flow of reagents and antibodies. Electrochemical measurement is done using cyclic voltammetry, as a function of cortisol concentrations. Cyclic voltammetry measurement gives current magnitude with applied voltage as a function of time. Scanning Electron Microscopy (SEM) imaging shows the change in surface morphology with the addition of antibody, compared to bare electrode functionalized with GO. The images confirm the antibody binding to selfassembled GO nanosurface on the working electrode. Raman imaging also supports the advantages of surface functionalization with antibodies. It shows presence of GO and antibodies on the biosensor surface suggesting GO self-assembly and antibodies immobilization. Atomic Force Microscopy (AFM) imaging shows surface topography of the developed sensor upon immobilization of self-assembled GO. The evenly distributed GO provided more surface area for antibodies immobilization. Cortisol was detected in the linear range of 0.1 ng/ml to 150 ng/ml, where current magnitude decreased with increasing cortisol concentration due to reduction in number of free electrons. The developed microfluidic biosensor for cortisol detection formed the base for sweat cortisol sensor with POC applications, and can also be used in personalized health diagnosis or monitoring