Novel same-metal three electrode system for cyclic voltammetry studies.

Conventional three-electrode systems used in electrochemical measurement demand time-consuming and maintenance intensive procedures to enable accurate and repeatable electrochemical measurements. Traditionally, different metal configurations are used to establish the electrochemical gradient required to acquire the redox activity, and vary between different electrochemical measurement platforms. However, in this work, we report using the same metal (gold) for the counter, working and reference electrodes fabricated on a miniaturized printed circuit board (PCB) for a much simpler design. Potassium ferricyanide, widely used as a redox probe for electrochemical characterization, was utilized to acquire cyclic voltametric profiles using both the printed circuit board-based gold-gold-gold three-electrode and conventional three-electrode systems (glassy carbon electrode or graphite foil as the working electrode, platinum wire as the counter electrode, and Ag/AgCl as the reference electrode). The results show that both types of electrode systems generated similar cyclic voltammograms within the same potential window (-0.5 to +0.7 V). However, the novel PCB-based same-metal three-electrode electrochemical cell only required a few activation cycles and exhibited impressive cyclic voltametric repeatability with higher redox sensitivity and detection window, while using only trace amounts of solutions/analytes.

Langmuir-Blodgett Graphene-Based Films for Algal Biophotovoltaic Fuel Cells.

The prevalence of photosynthesis, as the major natural solar energy transduction mechanism or biophotovoltaics (BPV), has always intrigued mankind. Over the last decades, we have learned to extract this renewable energy through continuously improving solid-state semiconductive devices, such as the photovoltaic solar cell. Direct utilization of plant-based BPVs has, however, been almost impracticable so far. Nevertheless, the electrochemical platform of fuel cells (FCs) relying on redox potentials of algae suspensions or biofilms on functionalized anode materials has in recent years increasingly been demonstrated to produce clean or carbon-negative electrical power generators. Interestingly, these algal BPVs offer unparalleled advantages, including carbon sequestration, bioremediation and biomass harvesting, while producing electricity. The development of high performance and durable BPVs is dependent on upgraded anode materials with electrochemically dynamic nanostructures. However, the current challenges in the optimization of anode materials remain significant barriers towards the development of commercially viable technology. In this context, two-dimensional (2D) graphene-based carbonaceous material has widely been exploited in such FCs due to its flexible surface functionalization properties. Attempts to economically improve power outputs have, however, been futile owing to molecular scale disorders that limit efficient charge coupling for maximum power generation within the anodic films. Recently, Langmuir-Blodgett (LB) film has been substantiated as an efficacious film-forming technique to tackle the above limitations of algal BPVs; however, the aforesaid technology remains vastly untapped in BPVs. An in-depth electromechanistic view of the fabrication of LB films and their electron transference mechanisms is of huge significance for the scalability of BPVs. However, an inclusive review of LB films applicable to BPVs has yet to be undertaken, prohibiting futuristic applications. Consequently, we report an inclusive description of a contextual outline, functional principles, the LB film-formation mechanism, recent endeavors in developing LB films and acute encounters with prevailing BPV anode materials. Furthermore, the research and scale-up challenges relating to LB film-integrated BPVs are presented along with innovative perceptions of how to improve their practicability in scale-up processes.

Understanding the electronic properties of single- and double-stranded DNA.

Understanding the charge transfer mechanism through deoxyribonucleic acid (DNA) molecules remains a challenge for numerous theoretical and experimental studies in order to be utilized in nanoelectronic devices. Various methods have attempted to investigate the conductivity of double-stranded (ds-) and single-stranded DNA (ssDNA) molecules. However, different electronic behaviors of these molecules are not clearly understood due to the complexity and lack of accuracy of the methods applied in these studies. In this work however, we demonstrated an electronic method to study the electrical behavior of synthetic ssDNA or dsDNA integrated within printed circuit board (PCB)-based metal (gold)-semiconductor (DNA) Schottky junctions. The results obtained in this work are in agreement with other studies reporting dsDNA as having higher conductivity than ssDNA as observed by us in the range of 4-6µA for the former and 2-3µA for the latter at an applied bias of 3V. Selected solid-state parameters such as turn-on voltage, series resistance, shunt resistance, ideality factor, and saturation current were also calculated for the specifically designed ss- and dsDNA sequences using the thermionic emission model. The results also showed that the highest conductance was observed for dsDNA with guanine and cytosine base pairs, while the lowest conductance was for ssDNA with adenine and thymine bases. We believe the results of this preliminary work involving the gold-DNA Schottky junction may allow the interrogation of DNA charge transfer mechanisms and contribute to better understanding its elusive electronic properties.

Printed-Circuit-Board-Based Two-Electrode System for Electronic Characterization of Proteins.

Proteins have been increasingly suggested as suitable candidates for the fabrication of biological computers and other biomolecular-based electronic devices mainly due to their interesting structure-related intrinsic electrical properties. These natural biopolymers are environmentally friendly substitutes for conventional inorganic materials and find numerous applications in bioelectronics. Effective manipulation of protein biomolecules allows for accurate fabrication of nanoscaled device dimensions for miniaturized electronics. The prerequisite, however, demands an interrogation of its various electronic properties prior to understanding the complex charge transfer mechanisms in protein molecules, the knowledge of which will be crucial toward development of such nanodevices. One significantly preferred method in recent times involves the utilization of solid-state sensors where interactions of proteins could be investigated upon contact with metals such as gold. Therefore, in this work, proteins (hemoglobin and collagen) were integrated within a two-electrode system, and the resulting electronic profiles were investigated. Interestingly, structure-related electronic profiles representing semiconductive-like behaviors were observed. These characteristic electronic profiles arise from the metal (Au)-semiconductor (protein) junction, clearly demonstrating the formation of a Schottky junction. Further interpretation of the electronic behavior of proteins was done by the calculation of selected solid-state parameters. For example, the turn-on voltage of hemoglobin was measured to occur at a lower turn-on voltage, indicating the possible influence of the hem group present as a cofactor in each subunit of this tetrameric protein.