Electrochemical biosensor based on microfabricated electrode arrays for life sciences applications

In developing a biosensor, the utmost important aspects that need to be emphasized are the specificity and selectivity of the transducer. These two vital prerequisites are of paramount in ensuring a robust and reliable biosensor. Improvements in electrochemical sensors can be achieved by using microelectrodes and to modify the electrode surface (using chemical or biological recognition layers to improve the sensitivity and selectivity). The fabrication and characterisations of silicon-based and glass-based gold microelectrode arrays with various geometries (band and disc) and dimension (ranging from 10 μm-100 nm) were reported. It was found that silicon-based transducers of 10 μm gold microelectrode array exhibited the most stable and reproducible electrochemical measurements hence this dimension was selected for further study. Chemical electrodeposition on both 10 μm microband and microdisc were found viable by electro-assisted self-assembled sol-gel silica film and nanoporous-gold electrodeposition respectively. The fabrication and characterisations of on-chip electrochemical cell was also reported with a fixed diameter/width dimension and interspacing variation. With this regard, the 10 μm microelectrode array with interspacing distance of 100 μm exhibited the best electrochemical response. Surface functionalisations on single chip of planar gold macroelectrodes were also studied for the immobilisation of histidine-tagged protein and antibody. Imaging techniques such as atomic force microscopy, fluorescent microscopy or scanning electron microscope were employed to complement the electrochemical characterisations. The long-chain thiol of self-assembled monolayer with NTA-metal ligand coordination was selected for the histidine-tagged protein while silanisation technique was selected for the antibody immobilisation. The final part of the thesis described the development of a T-2 labelless immunosensor using impedimetric approach. Good antibody calibration curve was obtained for both 10 μm microband and 10 μm microdisc array. For the establishment of the T-2/HT-2 toxin calibration curve, it was found that larger microdisc array dimension was required to produce better calibration curve. The calibration curves established in buffer solution show that the microelectrode arrays were sensitive and able to detect levels of T-2/HT-2 toxin as low as 25 ppb (25 μg kg-1) with a limit of quantitation of 4.89 ppb for a 10 μm microband array and 1.53 ppb for the 40 μm microdisc array.

The role of structure in the electrochemical performance of nanostructured metal oxides for lithium ion battery anodes

The Li-ion battery has for a number of years been a key factor that has enabled an ever increasing number of modern consumer devices, while in recent years has also been sought to power a range of emerging electric and hybrid electric vehicles. Due to their importance and popularity, a number of characteristics of Li-ion batteries have been subjected to intense work aimed at radical improvement. Although electrode material selection intrinsically defines characteristics like maximum capacity or voltage, engineering of the electrode structure may yield significant improvements to the lifetime performance of the battery, which would not be available if the material was used in its bulk form. The body of work presented in this thesis describes the relationship between the structure of electrochemically active materials and the course of the electrochemical processes occurring within the electrode. Chapter one describes the motivation behind the research presented herein. Chapter two serves to highlight a number of key advancements which have been made and detailed in the literature over recent years, pertaining to the use of nanostructured materials in Li-ion technology. Chapter three details methods and techniques applied in developing the body of work presented in this thesis. Chapter four details structural, molecular and electrochemical characteristics of tin oxide nanoparticle based electrodes, with particular emphasis on the relationship between the size distribution and the electrode performance. Chapter five presents findings of structural, electrochemical and optical study of indium oxide nanoparticles grown on silicon by molecular beam epitaxy. In chapter 6, tin oxide inverted opal electrodes are investigated for the conduct of the electrochemical performance of the electrodes under varying rate of change of potential. Chapter 7 presents the overall conclusions drawn from the results presented in this thesis, coupled with an indication of potential future work which may be explored further.

Electrochemical and FTIR characterization of the self-assembled monolayer of 2-mercaptobenzimidazole on Au(1 1 1)

The behaviour of a self-assembled monolayer of 2-mercaptobenzimidazole (MBI) at the Au(111) electrode has been examined using cyclic voltammetry and in situ FTIR spectroscopy. The charge associated with the reductive desorption is pH independent while the oxidative partial redeposition charge increases when the pH is lowered. This is due to differences between the nature and the solubility of the MBI desorption product. In alkaline and neutral media MBI desorbs as the thiolate. In contrast, in acidic solutions the thiol is the desorbed product. Subtractively normalized interfacial reflection Fourier transform absorption spectroscopy (SNIFTIRS) has been applied to investigate the MBI monolayer in contact with aqueous solutions of different pH. The SNIFTIRS data are in agreement with the electrochemical results. Moreover, quantitative analysis of the IR data provided evidence that adsorbed MBI molecules assume a tilted orientation with an angle of 60±5° between the C2 axis of the molecule and the direction normal to the gold surface. © 2003 Elsevier B.V. All rights reserved.

Probing the Electrochemical Interface by In Situ Infrared Spectroscopy

info:eu-repo/semantics/published

Barnacle cement: a polymerization model based on evolutionary concepts.

Enzymes and biochemical mechanisms essential to survival are under extreme selective pressure and are highly conserved through evolutionary time. We applied this evolutionary concept to barnacle cement polymerization, a process critical to barnacle fitness that involves aggregation and cross-linking of proteins. The biochemical mechanisms of cement polymerization remain largely unknown. We hypothesized that this process is biochemically similar to blood clotting, a critical physiological response that is also based on aggregation and cross-linking of proteins. Like key elements of vertebrate and invertebrate blood clotting, barnacle cement polymerization was shown to involve proteolytic activation of enzymes and structural precursors, transglutaminase cross-linking and assembly of fibrous proteins. Proteolytic activation of structural proteins maximizes the potential for bonding interactions with other proteins and with the surface. Transglutaminase cross-linking reinforces cement integrity. Remarkably, epitopes and sequences homologous to bovine trypsin and human transglutaminase were identified in barnacle cement with tandem mass spectrometry and/or western blotting. Akin to blood clotting, the peptides generated during proteolytic activation functioned as signal molecules, linking a molecular level event (protein aggregation) to a behavioral response (barnacle larval settlement). Our results draw attention to a highly conserved protein polymerization mechanism and shed light on a long-standing biochemical puzzle. We suggest that barnacle cement polymerization is a specialized form of wound healing. The polymerization mechanism common between barnacle cement and blood may be a theme for many marine animal glues.

Design and synthesis of hierarchical MnO2 nanospheres/carbon nanotubes/conducting polymer ternary composite for high performance electrochemical electrodes.

For efficient use of metal oxides, such as MnO(2) and RuO(2), in pseudocapacitors and other electrochemical applications, the poor conductivity of the metal oxide is a major problem. To tackle the problem, we have designed a ternary nanocomposite film composed of metal oxide (MnO(2)), carbon nanotube (CNT), and conducting polymer (CP). Each component in the MnO(2)/CNT/CP film provides unique and critical function to achieve optimized electrochemical properties. The electrochemical performance of the film is evaluated by cyclic voltammetry, and constant-current charge/discharge cycling techniques. Specific capacitance (SC) of the ternary composite electrode can reach 427 F/g. Even at high mass loading and high concentration of MnO(2) (60%), the film still showed SC value as high as 200 F/g. The electrode also exhibited excellent charge/discharge rate and good cycling stability, retaining over 99% of its initial charge after 1000 cycles. The results demonstrated that MnO(2) is effectively utilized with assistance of other components (fFWNTs and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) in the electrode. Such ternary composite is very promising for the next generation high performance electrochemical supercapacitors.

Acid-base and electrochemical properties of manganese meso(ortho- and meta-N-ethylpyridyl)porphyrins: potentiometric, spectrophotometric and spectroelectrochemical study of protolytic and redox equilibria.

The difference in electrostatics and reduction potentials between manganese ortho-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP) and manganese meta-tetrakis(N-ethylpyridinium-3-yl)porphyrin (MnTE-3-PyP) is a challenging topic, particularly because of the high likelihood for their clinical development. Hence, a detailed study of the protolytic and electrochemical speciation of Mn(II-IV)TE-2-PyP and Mn(II-IV)TE-3-PyP in a broad pH range has been performed using the combined spectrophotometric and potentiometric methods. The results reveal that in aqueous solutions within the pH range ∼2-13 the following species exist: (H(2)O)Mn(II)TE-m-PyP(4+), (HO)Mn(II)TE-m-PyP(3+), (H(2)O)(2)Mn(III)TE-m-PyP(5+), (HO)(H(2)O)Mn(III)TE-m-PyP(4+), (O)(H(2)O)Mn(III)TE-m-PyP(3+), (O)(H(2)O)Mn(IV)TE-m-PyP(4+) and (O)(HO)Mn(IV)TE-m-PyP(3+) (m = 2, 3). All the protolytic equilibrium constants that include the accessible species as well as the thermodynamic parameters for each particular protolytic equilibrium have been determined. The corresponding formal reduction potentials related to the reduction of the above species and the thermodynamic parameters describing the accessible reduction couples were calculated as well.

Surface Insulation Resistance Degradation and Electrochemical Migration on Printed Circuit Boards

Widespread adoption of lead-free materials and processing for printed circuit board (PCB) assembly has raised reliability concerns regarding surface insulation resistance (SIR) degradation and electrochemical migration (ECM). As PCB conductor spacings decrease, electronic products become more susceptible to these failures mechanisms, especially in the presence of surface contamination and flux residues which might remain after no-clean processing. Moreover, the probability of failure due to SIR degradation and ECM is affected by the interaction between physical factors (such as temperature, relative humidity, electric field) and chemical factors (such as solder alloy, substrate material, no-clean processing). Current industry standards for assessing SIR reliability are designed to serve as short-term qualification tests, typically lasting 72 to 168 hours, and do not provide a prediction of reliability in long-term applications. The risk of electrochemical migration with lead-free assemblies has not been adequately investigated. Furthermore, the mechanism of electrochemical migration is not completely understood. For example, the role of path formation has not been discussed in previous studies. Another issue is that there are very few studies on development of rapid assessment methodologies for characterizing materials such as solder flux with respect to their potential for promoting ECM. In this dissertation, the following research accomplishments are described: 1). Long-term temp-humidity-bias (THB) testing over 8,000 hours assessing the reliability of printed circuit boards processed with a variety of lead-free solder pastes, solder pad finishes, and substrates. 2). Identification of silver migration from Sn3.5Ag and Sn3.0Ag0.5Cu lead-free solder, which is a completely new finding compared with previous research. 3). Established the role of path formation as a step in the ECM process, and provided clarification of the sequence of individual steps in the mechanism of ECM: path formation, electrodeposition, ion transport, electrodeposition, and filament formation. 4). Developed appropriate accelerated testing conditions for assessing the no-clean processed PCBs' susceptibility to ECM: a). Conductor spacings in test structures should be reduced in order to reflect the trend of higher density electronics and the effect of path formation, independent of electric field, on the time-to-failure. b). THB testing temperatures should be modified according to the material present on the PCB, since testing at 85oC can cause the evaporation of weak organic acids (WOAs) in the flux residues, leading one to underestimate the risk of ECM. 5). Correlated temp-humidity-bias testing with ion chromatography analysis and potentiostat measurement to develop an efficient and effective assessment methodology to characterize the effect of no-clean processing on ECM.

Does an incremental filling technique reduce polymerization shrinkage stresses

It is widely accepted that volumetric contraction and solidification during the polymerization process of restorative composites in combination with bonding to the hard tissue result in stress transfer and inward deformation of the cavity walls of the restored tooth. Deformation of the walls decreases the size of the cavity during the filling process. This fact has a profound influence on the assumption-raised and discussed in this paper-that an incremental filling technique reduces the stress effect of composite shrinkage on the tooth. Developing stress fields for different incremental filling techniques are simulated in a numerical analysis. The analysis shows that, in a restoration with a well-established bond to the tooth-as is generally desired-incremental filling techniques increase the deformation of the restored tooth. The increase is caused by the incremental deformation of the preparation, which effectively decreases the total amount of composite needed to fill the cavity. This leads to a higher-stressed tooth-composite structure. The study also shows that the assessment of intercuspal distance measurements as well as simplifications based on generalization of the shrinkage stress state cannot be sufficient to characterize the effect of polymerization shrinkage in a tooth-restoration complex. Incremental filling methods may need to be retained for reasons such as densification, adaptation, thoroughness of cure, and bond formation. However, it is very difficult to prove that incrementalization needs to be retained because of the abatement of shrinkage effects.