In Situ Real-Time Dendritic Growth Determination of Electrodeposits on Ultramicroelectrodes.

Monitoring the dendritic electrodeposition process is crucial in various fields such as energy storage devices and sensors. A variety of in situ dendritic growth monitoring methods have been developed, especially for battery applications, but they require specialized cells and equipment and are often invasive, making them unsuitable for various electrochemical systems and commercial batteries. To address these challenges, a real-time impedance analysis technique was used to determine dendritic electrodeposition on microelectrodes. The "effective size" of the electrodeposit was extracted from the impedance data, and the dendritic growth was assessed in real-time by comparing "effective size" to a theoretical radius assuming hemispherical growth. The technique was validated using scanning electron microscopy imaging and finite element method simulation. Initially applied to gold electrodeposition, the method was extended to zinc electrodeposition, demonstrating potential utilization for energy storage systems.

On-Site Formation of Functional Dopaminergic Presynaptic Terminals on Neuroligin-2-Modified Gold-Coated Microspheres.

Advancements in neural interface technologies have enabled the direct connection of neurons and electronics, facilitating chemical communication between neural systems and external devices. One promising approach is a synaptogenesis-involving method, which offers an opportunity for synaptic signaling between these systems. Janus synapses, one type of synaptic interface utilizing synaptic cell adhesion molecules for interface construction, possess unique features that enable the determination of location, direction of signal flow, and types of neurotransmitters involved, promoting directional and multifaceted communication. This study presents the first successful establishment of a Janus synapse between dopaminergic (DA) neurons and abiotic substrates by using a neuroligin-2 (NLG2)-mediated synapse-inducing method. NLG2 immobilized on gold-coated microspheres can induce synaptogenesis upon contact with spatially isolated DA axons. The induced DA Janus synapses exhibit stable synaptic activities comparable to that of native synapses over time, suggesting their suitability for application in neural interfaces. By calling for DA presynaptic organizations, the NLG2-immobilized abiotic substrate is a promising tool for the on-site detection of synaptic dopamine release.

Dual Function of N-Iodosuccinimide for C(sp3)-B Bond Activation.

A practical method for C(sp3)-B bond activation was developed. Using a combination of alkyl trifluoroborates and N-iodosuccinimide (NIS), various C(sp3)-heteroatom bonds were readily generated in an efficient manner. Mechanistic studies revealed the bifunctional ability of NIS: mediating the formation of reactive halogenated intermediates and activating them via halogen bonding. This electrophilic activation of the reaction center enables the utilization of general heteroatom nucleophiles, which are used in a limited capacity in traditional 1,2-metalate rearrangements.

Long-Range SECCM Enables High-Throughput Electrochemical Screening of High Entropy Alloy Electrocatalysts at Up-To-Industrial Current Densities.

High-entropy alloys (HEAs), especially in the form of compositional complex solid solutions (CCSS), have gained attention in the field of electrocatalysis. However, exploring their vast composition space concerning their electrocatalytic properties imposes significant challenges. Scanning electrochemical cell microscopy (SECCM) offers high-speed electrochemical analysis on surface areas with a lateral resolution down to tens of nm. However, high-precision piezo positioners often used for the motion of the tip limit the area of SECCM scans to the motion range of the piezo positioners which is typically a few tens of microns. To bridge this experimental gap, the study proposes a long-range SECCM system with a rapid gas-exchange environmental cell for high-throughput electrochemical characterization of 100 mm diameter HEA thin-film material libraries (ML) obtained by combinatorial co-sputtering. Due to the gas-liquid interface at the positioned SECCM droplet on the sample, high-throughput evaluation under industrial current density conditions becomes feasible. This allows the direct correlation between electrocatalytic activity and material composition with high statistical reliability. The multidimensional data obtained accelerates materials discovery, development, and optimization.

G-Quadruplex-Filtered Selective Ion-to-Ion Current Amplification for Non-Invasive Ion Monitoring in Real Time.

Living cells efflux intracellular ions for maintaining cellular life, so intravital measurements of specific ion signals are of significant importance for studying cellular functions and pharmacokinetics. In this work, de novo synthesis of artificial K+ -selective membrane and its integration with polyelectrolyte hydrogel-based open-junction ionic diode (OJID) is demonstrated, achieving a real-time K+ -selective ion-to-ion current amplification in complex bioenvironments. By mimicking biological K+ channels and nerve impulse transmitters, in-line K+ -binding G-quartets are introduced across freestanding lipid bilayers by G-specific hexylation of monolithic G-quadruplex, and the pre-filtered K+ flow is directly converted to amplified ionic currents by the OJID with a fast response time at 100 ms intervals. By the synergistic combination of charge repulsion, sieving, and ion recognition, the synthetic membrane allows K+ transport exclusively without water leakage; it is 250× and 17× more permeable toward K+ than monovalent anion, Cl- , and polyatomic cation, N-methyl-d-glucamine+ , respectively. The molecular recognition-mediated ion channeling provides a 500% larger signal for K+ as compared to Li+ (0.6× smaller than K+ ) despite the same valence. Using the miniaturized device, non-invasive, direct, and real-time K+ efflux monitoring from living cell spheroids is achieved with minimal crosstalk, specifically in identifying osmotic shock-induced necrosis and drug-antidote dynamics.

Virus-templated redox nanowire network for enzyme electrode.

Viruses have unique coat proteins that are genetically modifiable. Their surface can serve as a nano-template on which electroactive molecules are immobilized. In this study, we report filamentous bacteriophage as a backbone to which redox mediators are covalently and densely tethered, constructing redox nanowire, i.e. an electron conducting biomaterial. The highly ordered coat proteins of a filamentous bacteriophage provide flexible and biocompatible platform to constitute a biohybrid redox nanowire. Incorporating bacteriophage and redox molecules form an entangled assembly of nanowires enabling facile electron transfer. Electron transfer among the molecular mediators in the entangled assembly originates apparent electron diffusion of which the electron transfer rate is comparable to that observed in conventional redox polymers. Programming peptide terminals suggests further enhancement in electron mediation by increasing redox species mobility. In addition, the redox nanowire film functions as a favorable matrix for enzyme encapsulation. The stability of the enzymes entrapped in this unique matrix is substantially improved.

Streamlining the interface between electronics and neural systems for bidirectional electrochemical communication.

Seamless neural interfaces conjoining neurons and electrochemical devices hold great potential for highly efficient signal transmission across neural systems and the external world. Signal transmission through chemical sensing and stimulation via electrochemistry is remarkable because communication occurs through the same chemical language of neurons. Emerging strategies based on synaptic interfaces, iontronics-based neuromodulation, and improvements in selective neurosensing techniques have been explored to achieve seamless integration and efficient neuro-electronics communication. Synaptic interfaces can directly exchange signals to and from neurons, in a similar manner to that of chemical synapses. Hydrogel-based iontronic chemical delivery devices are operationally compatible with neural systems for improved neuromodulation. In this perspective, we explore developments to improve the interface between neurons and electrodes by targeting neurons or sub-neuronal regions including synapses. Furthermore, recent progress in electrochemical neurosensing and iontronics-based chemical delivery is examined.

Reorganization energy in a polybromide ionic liquid measured by scanning electrochemical cell microscopy.

Room temperature ionic liquids (RT-ILs) are promising electrolytes for electrocatalysis. Understanding the effects of the electrode-electrolyte interface structure on electrocatalysis in RT-ILs is important. Ultrafast mass transport of redox species in N-methyl-N-ethyl-pyrrolidinium polybromide (MEPBr2n+1) enabled evaluation of the reorganization energy (λ), which reflects the solvation structure in the inner Helmholtz plane (IHP). λ was achieved by fitting the electron transfer rate-limited voltammogram at a Pt ultramicroelectrode (UME) to the Marcus-Hush-Chidsey model for heterogeneous electron transfer kinetics. However, it is time-consuming or even impossible to prepare electrode materials, including alloys of numerous compositions in the form of UME, for each experiment. Herein, we report a method to evaluate the λ of MEPBr2n+1 by scanning electrochemical cell microscopy (SECCM), which allows high throughput electrochemical measurements using a single electrode with high spatial resolution. Fast mass transport in the nanosized SECCM tip is critical for achieving heterogeneous electron transfer-limited voltammograms. Furthermore, investigating λ on a high-entropy alloy materials library composed of Pt, Pd, Ru, Ir, and Ag suggests a negative correlation between λ and the work function. Given that the potential of zero charge correlates with the work function of electrodes, this can be attributed to the surface-charge sensitive ionic structure in the IHP of MEPBr2n+1, modulating the solvation energy of the redox-active species in the IHP.

Enhanced adhesion of functional layers by controlled electrografting of ethylenediamine on ITO for electrochemical immunoassay in microfluidic channel.

Two-electrode (2E) system of the interdigitated electrode array (IDA), which operates neither reference nor counter electrodes, has great potential to miniaturize multiplex immunoassay in a microfluidic chip for point-of-care testing. However, it is necessary to firmly immobilize the mediator layer on IDA made of indium tin oxide (ITO) which is chemically inert. It is important because the mediator determines the electrochemical potential in the 2E system, but the layer is easy to be detached during the washing processes of immunoassay. Here, we controlled the concentration of ethylenediamine (EDA) to generate a permeable and robust film to adhere to mediators on the ITO IDA chip. Electrooxidation of EDA yielded thin oligomeric ethyleneimine (OEI) film and it provided amine groups for immobilizing the mediator, poly(toluidine blue) (pTB), via common conjugation reaction. Despite repeated flows in the microchannel, which are essential for sensitive immunoassay, the pTB/OEI layer was hardly washed and still remained on the ITO IDA. Myoglobin was measured down to âˆ¼ pg/mL level. Therefore, the ITO IDA modified with the OEI film in the 2E system constituted a stable platform that withstands washing steps for sensitive electrochemical detection in the miniaturized immunoassay.

Iontronic analog of synaptic plasticity: Hydrogel-based ionic diode with chemical precipitation and dissolution.

In this study, an aqueous nonlinear synaptic element showing plasticity behavior is developed, which is based on the chemical processes in an ionic diode. The device is simple, fully ionic, and easily configurable, requiring only two terminals-for input and output-similar to biological synapses. The key processes realizing the plasticity features are chemical precipitation and dissolution, which occur at forward- or reverse-biased ionic diode junctions in appropriate reservoir electrolytes. Given that the precipitate acts as a physical barrier in the circuit, the above processes change the diode conductivity, which can be interpreted as adjusting "synaptic weight" of the system. By varying the operating conditions, we first demonstrate the four types of plasticity that can be found in biological system: long-term potentiation/depression and short-term potentiation/depression. The plasticity of the proposed iontronic device has characteristics similar to those of neural synapses. To demonstrate its potential use in comparatively complex information processing, we develop a precipitation-based iontronic synapse (PIS) capable of both potentiation and depression. Finally, we show that the postsynaptic signals from the multiple excitatory or inhibitory PISs can be integrated into the total "dendritic" current, which is a function of time and input history, as in actual hippocampal neural circuits.

Heterogeneous electron transfer reorganization energy at the inner Helmholtz plane in a polybromide redox-active ionic liquid.

In ionic liquids (ILs), the electric double layer (EDL) is where heterogeneous electron transfer (ET) occurs. Nevertheless, the relationship between the EDL structure and its kinetics has been rarely studied, especially for ET taking place in the inner Helmholtz plane (IHP). This is largely because of the lack of an appropriate model system for experiments. In this work, we determined the reorganization energy (λ) of Br2 reduction in a redox-active IL 1-ethyl-1-methylpyrrolidinium polybromide (MEPBr2n+1) based on the Marcus-Hush-Chidsey model. Exceptionally fast mass transport of Br2 in MEPBr2n+1 allows voltammograms to be obtained in which the current plateau is regulated by electron-transfer kinetics. This enables investigation of the microscopic environment in the IHP of the IL affecting electrocatalytic reactions through reorganization energy. As a demonstration, TiO2-modified Pt was employed to show pH-dependent reorganization energy, which suggests the switch of major ions at the IHP as a function of surface charges of electrodes.

A Unified Synthetic Strategy to Introduce Heteroatoms via Electrochemical Functionalization of Alkyl Organoboron Reagents.

Based on systematic electrochemical analysis, an integrated synthetic platform of C(sp3)-based organoboron compounds was established for the introduction of heteroatoms. The electrochemically mediated bond-forming strategy was shown to be highly effective for the functionalization of sp3-hybridized carbon atoms with significant steric hindrance. Moreover, virtually all the nonmetallic heteroatoms could be utilized as reaction partners using one unified protocol. The observed reactivity stems from the two consecutive single-electron oxidations of the substrate, which eventually generates an extremely reactive carbocation as the key intermediate. The detailed reaction profile could be elucidated through multifaceted electrochemical studies. Ultimately, a new dimension in the activation strategies for organoboron compounds was accomplished through the electrochemically driven reaction development.

Paper-based electrochromic glucose sensor with polyaniline on indium tin oxide nanoparticle layer as the optical readout.

Surging interests in point-of-care diagnostics have led to the development of many lightweight and cost-effective paper-based sensors. Particularly, sensors using colorimetric readouts are considered highly advantageous because no additional detector or device is required for signal display. Herein, we introduce an electrochemically operated colorimetric sensor that can compensate for the disadvantages of traditional colorimetry, hence enhancing response time, reusability and color uniformity. On a single paper substrate, carbon/graphite paste was screen printed to form the working and counter electrodes, and Ag/AgCl ink was applied for the reference electrode. Prussian blue and Glucose oxidase were employed on the one of the carbon electrodes for the detection of analytes, hydrogen peroxide and glucose. For the colorimetric readout, indium tin oxide nanoparticles and polyaniline were consecutively introduced on the other carbon electrode, which is used as the counter electrode. The color change of electrochromic polyaniline could be clearly observed, and its application as a colorimetric sensor was demonstrated by the quantitative analyses of hydrogen peroxide and glucose. This paper-based electrochromic glucose sensor showed a short response time of 30 s and exhibited a detection limit of 126 µM for glucose. Along with its rapid and easy detection by incorporating the merits of electrochemical sensing and colorimetry, the paper-based electrochromic sensor could potentially contribute to the development of point-of-care devices by combination with portable power sources.

Adopting Back Reduction Current as an Additional Output Signal for Achieving Photoelectrochemical Differentiated Detection.

Photoelectrochemical (PEC) sensors are usually based on a single output signal, that is, the photocurrent change caused by the (photoelectro)chemical reaction between target analytes and photoelectrodes. However, the photocurrent may be influenced by redox species other than the target analyte; therefore, modifying the surface of photoelectrodes with probes that selectively bind to the analyte is essential. Moreover, even though various surface modification methods have been developed, distinguishing molecularly similar chemicals using PEC sensing systems remains a significant challenge. To address these selectivity issues, we proposed a photoanode-based PEC sensor that utilizes a cathodic transient current as a second output signal in addition to the photocurrent, which arises from the back reduction of photo-oxidized species. Factors influencing the back reduction were investigated by observing the transient photocurrent of hematite photoanodes in the presence of model redox probes. The chemical environment around the electrode-electrolyte interface was manipulated by altering the electrolyte composition or modifying the electrode surface. The favorable interaction between the electrode surface and redox species led to an increase in the extent of back reduction and the cathodic transient current. In addition, the extent of back reduction also depends on the chemical identity of the redox species, such as the kinetics of subsequent chemical reactions. Therefore, the synergistic combination of the photocurrent and the cathodic transient current enabled the differentiated detection of various catecholamine neurotransmitters with a single pristine photoelectrode, which has never been achieved using traditional PEC methods. Revisiting the transient photocurrent can complement conventional PEC applications and offers possibilities for more effective semiconductor-based applications.

Revisiting Thin-Layer Electrochemistry in a Chip-Type Cell for the Study of Electro-organic Reactions.

It is important but challenging to elucidate the electrochemical reaction mechanisms of organic compounds using electroanalytical methods. Particularly, a rapid and straightforward method that provides information on reaction intermediates or other key electrochemical parameters may be useful. In this work, we exploited the advantages of classic thin-layer electrochemistry to develop a thin-layer electroanalysis microchip (TEAM). The TEAM provided better-resolved voltammetric peaks than under semi-infinite diffusion conditions owing to its small height. Importantly, rapid and accurate determination of the number of electrons transferred, n, was enabled by mechanically confining the microliter-scale volume analyte at the electrode, while securing ionic conduction using polyelectrolyte gels. The performance of the TEAM was validated using voltammetry and coulometry of standard redox couples. Utilizing the TEAM, a (spectro)electrochemical analysis of FM 1-43, an organic dye widely used in neuroscience, was successfully performed. Moreover, the TEAM was applied to study the electrochemical oxidation mechanism of pivanilides and alkyltrifluoroborate salts with different substituents and solvents. This work suggests that TEAM is a promising tool to provide invaluable mechanistic information and promote the rational design of electrosynthetic strategies.

Functional Integration of Catalysts with Si Nanowire Photocathodes for Efficient Utilization of Photogenerated Charge Carriers.

Low-cost catalysts with high activity and durability are necessary to achieve efficient large-scale energy conversion in photoelectrochemical cell (PEC) systems. An additional factor that governs the construction of photoelectrodes for PECs is the spatial control of the catalysts for efficient utilization of photogenerated charge carriers. Here, we demonstrate spatial decoupling of the light-absorbing and catalytic components in hierarchically structured Si-based photocathodes for the hydrogen evolution reaction (HER). By simply modifying a well-known metal-assisted chemical etching procedure, we fabricated a Si nanowire (NW) array-based photocathode with Ag-Pt catalysts at the base and small amounts of the Pt catalyst at the NW tips. This approach simultaneously mitigates the parasitic light absorption by the catalytic layers and recombination of charge carriers owing to the long transport distance, resulting in improved photoelectrochemical HER performance under simulated AM 1.5G illumination.

Enhanced H2 Evolution at Patterned MoSx-Modified Si-Based Photocathodes by Incorporating the Interfacial 3D Nanostructure of Ag.

Photoelectrochemical cells represent one of the promising ways to renewably produce hydrogen (H2) as a future chemical fuel. The design of a catalyst/semiconductor junction for the hydrogen evolution reaction (HER) requires various factors for high performance. In catalytic materials, an intrinsic activity with fast charge-transfer kinetics is important. Additionally, their thermodynamic property and physical adhesion should be compatible with the underlying semiconductor for favorable band alignment and stability during vigorous H2 bubble formation. Moreover, catalysts, especially non-noble materials that demand a large amount of loading, should be adequately dispersed on the semiconductor surface to allow sufficient light absorption to generate excitons. One of the methods to simultaneously satisfy these conditions is to adopt an interfacial layer between the semiconductor and active materials in HER. The interfacial layer efficiently extracts the electrons from the semiconductor and conveys those to the catalytically active surface. We demonstrate Ag as a 3D interfacial nanostructure of patterned MoSx catalysts for photoelectrochemical HER. The nanostructured porous Ag layer was introduced by a simple chemical process, followed by photoelectrochemical deposition of MoSx to form MoSx/Ag nanostructures in cross-shaped catalyst pattern arrays. Ag modulated the surface electronic property of MoSx to improve the reaction kinetics as well as helped a charge transport at the Ag|p-Si(100) junction. The physically stable adhesion of catalysts was also achieved despite the ∼40 nm thick catalysts owing to the interfacial Ag nanostructure. This work contributes to further understand the complex multistep HER from light absorption to charge transfer to protons, helping to develop cost-effective and efficient photocathodes.

Electrochemistry of the Silicon Oxide Dielectric Layer: Principles, Electrochemical Reactions, and Perspectives.

Electrochemistry of the silicon oxide dielectric layer, a notable insulator often used as a gate oxide, is counterintuitive, but addresses fundamental questions to yield novel scientific discoveries. In this minireview, the fundamental electron transfer mechanism of silicon oxide in the electrolyte solution is elucidated. The possible electrochemical reactions to date are discussed in detail, providing numerous potential areas of application which are elaborated and justified. This minireview not only provides background but also guides future research.

Bioaerosol monitoring by integrating DC impedance microfluidic cytometer with wet-cyclone air sampler.

The recent outbreak of COVID-19 has highlighted the seriousness of airborne diseases and the need for a proper pathogen detection system. Compared to the ample amount of research on biological detection, work on integrated devices for air monitoring is rare. In this work, we integrated a wet-cyclone air sampler and a DC impedance microfluidic cytometer to build a cyclone-cytometer integrated air monitor (CCAM). The wet-cyclone air sampler sucks the air and concentrates the bioaerosols into 10 mL of aqueous solvent. After 5 min of air sampling, the bioaerosol-containing solution was conveyed to the microfluidic cytometer for detection. The device was tested with aerosolized microbeads, dust, and Escherichia coli (E. coli). CCAM is shown to differentiate particles from 0.96 to 2.95 µm with high accuracy. The wet cyclone air-sampler showed a 28.04% sampling efficiency, and the DC impedance cytometer showed 87.68% detection efficiency, giving a total of 24.59% overall CCAM efficiency. After validation of the device performance, CCAM was used to detect bacterial aerosols and their viability without any separate pretreatment step. Differentiation of dust, live E. coli, and dead E. coli was successfully performed by the addition of BacLight bacterial viability reagent in the sampling solvent. The usage could be further extended to detection of specific species with proper antibody fluorescent label. A promising strategy for aerosol detection is proposed through the constructive integration of a DC impedance microfluidic cytometer and a wet-cyclone air sampler.

Universal Suzuki-Miyaura Catalyst-Transfer Polymerization for Precision Synthesis of Strong Donor/Acceptor-Based Conjugated Polymers and Their Sequence Engineering.

Catalyst-transfer polymerization has revolutionized the field of polymer synthesis due to its living character, but for a given catalyst system, the polymer scope is rather narrow. Herein we report a highly efficient Suzuki-Miyaura catalyst-transfer polymerization (SCTP) that covers a wide range of monomers from electron-rich (donor, D) to electron-deficient (acceptor, A) (hetero)arenes by rationally designing boronate monomers and using commercially available Buchwald RuPhos and SPhos Pd G3 precatalysts. Initially, we optimized the controlled polymerization of 3,4-propylenedioxythiophene (ProDOT), benzotriazole (BTz), quinoxaline (QX), and 2,3-diphenylquinoxaline (QXPh) by introducing new boronates, such as 4,4,8,8-tetramethyl-1,3,6,2-dioxazaborocane and its N-benzylated derivative, to modulate the reactivity and stability of the monomers. As a result, PProDOT, PBTz, PQX, and PQXPh were prepared with controlled molecular weight and narrow dispersity (D < 1.29) in excellent yield (>85%). A detailed investigation of the polymer structures using 1H NMR and MALDI-TOF spectrometry supported the chain-growth mechanism and the high initiation efficiency of the SCTP method. In addition, the use of RuPhos-Pd showing excellent catalyst-transfer ability on both D/A monomers led to unprecedented controlled D-A statistical copolymerization, thereby modulating the HOMO energy level (from -5.11 to -4.80 eV) and band gap energy (from 1.68 to 1.91 eV) of the resulting copolymers. Moreover, to demonstrate the living nature of SCTP, various combinations of D-A and A-A block copolymers (PBTz-b-PProDOT, PQX-b-PProDOT, and PQX-b-PBTz) were successfully prepared by the sequential addition method. Finally, simple but powerful one-shot D-A block copolymerization was achieved by maximizing the rate difference between a fast-propagating pinacol boronate donor and a slow-propagating acceptor to afford well-defined poly(3-hexylthiophene)-b-poly(benzotriazole).