Project description:Here we report the direct observation and quantitative analysis of single redox events on a modified indium-tin oxide (ITO) electrode. The key in the observation of single redox events are the use of a fluorogenic redox species and the nanoconfinement and hindered redox diffusion inside 3-nm-diameter silica nanochannels. A simple electrochemical process was used to grow an ultrathin silica film (∼100 nm) consisting of highly ordered parallel nanochannels exposing the electrode surface from the bottom. The electrode-supported 3-nm-diameter nanochannels temporally trap fluorescent resorufin molecules resulting in hindered molecular diffusion in the vicinity of the electrode surface. Adsorption, desorption, and heterogeneous redox events of individual resorufin molecules can be studied using total-internal reflection fluorescence (TIRF). The rate constants of adsorption and desorption processes of resorufin were characterized from single-molecule analysis to be (1.73 ± 0.08) × 10-4 cm·s-1 and 15.71 ± 0.76 s-1, respectively. The redox events of resorufin to the non-fluorescent dihydroresorufin were investigated by analyzing the change in surface population of single resorufin molecules with applied potential. The scan-rate-dependent molecular counting results (single-molecule fluorescence voltammetry) indicated a surface-controlled electrochemical kinetics of the resorufin reduction on the modified ITO electrode. This study demonstrates the great potential of mesoporous silica as a useful modification scheme for studying single redox events on a variety of transparent substrates such as ITO electrodes and gold or carbon film coated glass electrodes. The ability to electrochemically grow and transfer mesoporous silica films onto other substrates makes them an attractive material for future studies in spatial heterogeneity of electrocatalytic surfaces.
Project description:This manuscript investigates the chemical and structural stability of 3D printing materials (3DPMs) frequently used in electrochemistry. Four 3D printing materials were studied: Clear photopolymer, Elastic photopolymer, PET filament, and PLA filament. Their stability, solubility, structural changes, flexibility, hardness, and color changes were investigated after exposure to selected organic solvents and supporting electrolytes. Furthermore, the available potential windows and behavior of redox probes in selected supporting electrolytes were investigated before and after the exposure of the 3D-printed objects to the electrolytes at various working electrodes. Possible electrochemically active interferences with an origin from the 3DPMs were also monitored to provide a comprehensive outline for the use of 3DPMs in electrochemical platform manufacturing.
Project description:BackgroundSpatial neglect is a neurocognitive disorder that affects perception, representation, and/or motor planning. Neglect dyslexia in spatial neglect after right hemisphere damage may co-occur with, or be dissociated from, other spatial neglect signs. Previous neglect dyslexia research focused on word-level stimuli and reading errors. Using single words for assessment may leave some people with neglect dyslexia undiagnosed, and assessment materials that are closer to texts read in real life may better capture neglect dyslexia.MethodThe authors tested reading in 67 right hemisphere stroke survivors with 4 types of text materials: words, phrases, an article, and a menu.ResultsAccuracy on reading the menu and article texts was significantly poorer than reading the words and phrases. The hypothesis that assessment materials with ecological validity such as reading a menu and reading an article may be more challenging than reading single words and phrases was supported.ConclusionResults suggest that neglect dyslexia assessment after stroke should include text materials comparable to those read in everyday life. Increasing the spatial extent of training materials in future research might also yield better functional generalization after right brain stroke.
Project description:Bioelectrochemical systems (BESs) have been studied extensively during the past decades owing primarily to their versatility and potential in addressing the water-energy-resource nexus. In stark contrast to the significant advancements that have been made in developing innovative processes for pollution control and bioresource/bioenergy recovery, minimal progress has been achieved in demonstrating the feasibility of BESs in scaled-up applications. This lack of scaled-up demonstration could be ascribed to the absence of suitable electrode modules (EMs) engineered for large-scale application. In this study, we report a scalable composite-engineered EM (total volume of 1 m3), fabricated using graphite-coated stainless steel and carbon felt, that allows integrating BESs into mainstream wastewater treatment technologies. The cost-effectiveness and easy scalability of this EM provides a viable and clear path to facilitate the transition between the success of the lab studies and applications of BESs to solve multiple pressing environmental issues at full-scale.
Project description:Altering electrochemical interfaces by using electrolyte effects or so-called "electrolyte engineering" provides a versatile means to modulate the electrochemical response. However, the long-standing challenge is going "beyond cyclic voltammetry" where electrolyte effects are interrogated from the standpoint of the interfacial properties of the electrode/electrolyte interface. Here, we employ ferrocene-terminated self-assembled monolayers as a molecular probe and investigate how the anion-dictated electrochemical responses are translated in terms of the electronic and structural properties of the electrode/monolayer/electrolyte interface. We utilise a photoelectron-based spectroelectrochemical approach that is capable of capturing "snapshots" into (1) anion dependencies of the ferrocene/ferrocenium (Fc/Fc+) redox process including ion-pairing with counter anions (Fc+-anion) caused by differences in Fc+-anion interactions and steric constraints, and (2) interfacial energetics concerning the electrostatic potential across the electrode/monolayer/electrolyte interface. Our work can be extended to provide electrolyte-related structure-property relationships in redox-active polymers and functionalised electrodes for pseudocapacitive energy storage.
Project description:The ubiquity of graphitic materials in electrochemistry makes it highly desirable to probe their interfacial behavior under electrochemical control. Probing the dynamics of molecules at the electrode/electrolyte interface is possible through spectroelectrochemical approaches involving surface-enhanced infrared absorption spectroscopy (SEIRAS). Usually, this technique can only be done on plasmonic metals such as gold or carbon nanoribbons, but a more convenient substrate for carbon electrochemical studies is needed. Here, we expanded the scope of SEIRAS by introducing a robust hybrid graphene-on-gold substrate, where we monitored electrografting processes occurring at the graphene/electrolyte interface. These electrodes consist of graphene deposited onto a roughened gold-sputtered internal reflection element (IRE) for attenuated total reflectance (ATR) SEIRAS. The capabilities of the graphene-gold IRE were demonstrated by successfully monitoring the electrografting of 4-amino-2,2,6,6-tetramethyl-1-piperidine N-oxyl (4-amino-TEMPO) and 4-nitrobenzene diazonium (4-NBD) in real time. These grafts were characterized using cyclic voltammetry and ATR-SEIRAS, clearly showing the 1520 and 1350 cm-1 NO2 stretches for 4-NBD and the 1240 cm-1 C-C, C-C-H, and N-Ȯ stretch for 4-amino-TEMPO. Successful grafts on graphene did not show the SEIRAS effect, while grafting on gold was not stable for TEMPO and had poorer resolution than on graphene-gold for 4-NBD, highlighting the uniqueness of our approach. The graphene-gold IRE is proficient at resolving the spectral responses of redox transformations, unambiguously demonstrating the real-time detection of surface processes on a graphitic electrode. This work provides ample future directions for real-time spectroelectrochemical investigations of carbon electrodes used for sensing, energy storage, electrocatalysis, and environmental applications.
Project description:Conventional electrodes in typical photodetectors only conduct electrical signals and introduce high optical reflection, impacting the optical-to-electrical conversion efficiency. The created surface solar harvester with a multi-functional folded electrode (MFFE) realizes both a three-dimensional Schottky junction with a larger light detecting area as well as low optical reflection from 300 nm (ultra-violet light) to 1100 nm (near-infrared light) broadly without an additional anti-reflection layer. The MFFE needs silicon etching following the lithography process. The metal silver was deposited over structured silicon, completing the whole device simply. According to the experimental results, the width ratio of the bottom side to the top side in MFFE was 15.75, and it showed an optical reflection of 5-7% within the major solar spectrum of AM1.5G by the gradient refractive index effect and the multi-scattering phenomenon simultaneously. While the perovskite materials were deposited over the MFFE structure of the solar harvester, the three-dimensional electrode with lower optical reflection benefitted the perovskite solar cell with a larger detecting area and an additional anti-reflection function to absorb solar energy more efficiently. In this concept, because of the thin stacked film in the perovskite solar cell, the solar energy could be harvested by the prepared Schottky junction of the solar harvester again, except for the optical absorption of the perovskite materials. Moreover, the perovskite materials deposited over the MFFE structure could not absorb near-infrared (NIR) energies to become transparent. The NIR light could be harvested by the light detecting junction of the solar harvester to generate effective photocurrent output additionally for extending the detection capability of perovskite solar cell further. In this work, the concept of integration of a conventional perovskite solar cell with a silicon-based solar harvester having an MFFE structure was proposed and is expected to harvest broadband light energies under low optical reflection and enhance the solar energy conversion efficiency.
Project description:The majority of available systems for vagus nerve stimulation use helical stimulation electrodes, which cover the majority of the circumference of the nerve and produce largely uniform current density within the nerve. Flat stimulation electrodes that contact only one side of the nerve may provide advantages, including ease of fabrication. However, it is possible that the flat configuration will yield inefficient fiber recruitment due to a less uniform current distribution within the nerve. Here we tested the hypothesis that flat electrodes will require higher current amplitude to activate all large-diameter fibers throughout the whole cross-section of a nerve than circumferential designs. Computational modeling and in vivo experiments were performed to evaluate fiber recruitment in different nerves and different species using a variety of electrode designs. Initial results demonstrated similar fiber recruitment in the rat vagus and sciatic nerves with a standard circumferential cuff electrode and a cuff electrode modified to approximate a flat configuration. Follow up experiments comparing true flat electrodes to circumferential electrodes on the rabbit sciatic nerve confirmed that fiber recruitment was equivalent between the two designs. These findings demonstrate that flat electrodes represent a viable design for nerve stimulation that may provide advantages over the current circumferential designs for applications in which the goal is uniform activation of all fascicles within the nerve.