Ultradense Electrochemical Chips with Arrays of Nanostructured Microelectrodes to Enable Sensitive Diffusion-Limited Bioassays.

Nanostructured microelectrodes (NMEs) are an attractive alternative to yield sensitive bioassays in unprocessed samples. However, although valuable for different applications, nanoporous NMEs usually cannot boost the sensitivity of diffusion-limited analyses because of the enlarged Debye length within the nanopores, which reduces their accessibility. To circumvent this limitation, nanopore-free gold NMEs were electrodeposited from 45 µm SU-8 apertures, featuring nanoridged microspikes on a recessed surface of gold thin film while carrying interconnected crown-like and spiky structures along the edge of a SU-8 passivation layer. These structures were grown onto ultradense, vertical array chips that offer a promising strategy for translating reproducible, high-resolution, and cost-effective sensors into real-world applications. The NMEs yielded reproducible analyses, while machine learning allowed us to predict the analytical responses from NME electrodeposition data. By taking advantage of the high surface area and accessible structure of the NMEs, these structures provided a sensitivity for [Fe(CN)6]3-/4- that was 5.5× higher than that of bare WEs while also delivering a moderate antibiofouling property in undiluted human plasma. As a proof of concept, these electrodes were applied toward the fast (22 min) and simple determination of Staphylococcus aureus by monitoring the oxidation of [Fe(CN)6]4-, which acted as a cellular respiration rate redox reporter. The sensors also showed a wide dynamic range, spanning 5 orders of magnitude, and a calculated limit of detection of 0.2 CFU mL-1.

Single-Response Duplexing of Electrochemical Label-Free Biosensor from the Same Tag.

Multiplexing is a valuable strategy to boost throughput and improve clinical accuracy. Exploiting the vertical, meshed design of reproducible and low-cost ultra-dense electrochemical chips, the unprecedented single-response multiplexing of typical label-free biosensors is reported. Using a cheap, handheld one-channel workstation and a single redox probe, that is, ferro/ferricyanide, the recognition events taking place on two spatially resolved locations of the same working electrode can be tracked along a single voltammetry scan by collecting the electrochemical signatures of the probe in relation to different quasi-reference electrodes, Au (0 V) and Ag/AgCl ink (+0.2 V). This spatial isolation prevents crosstalk between the redox tags and interferences over functionalization and binding steps, representing an advantage over the existing non-spatially resolved single-response multiplex strategies. As proof of concept, peptide-tethered immunosensors are demonstrated to provide the duplex detection of COVID-19 antibodies, thereby doubling the throughput while achieving 100% accuracy in serum samples. The approach is envisioned to enable broad applications in high-throughput and multi-analyte platforms, as it can be tailored to other biosensing devices and formats.

Recent Advances in Bio-Templated Metallic Nanomaterial Synthesis and Electrocatalytic Applications.

Developing metallic nanocatalysts with high reaction activity, selectivity and practical durability is a promising and active subfield in electrocatalysis. In the classical "bottom-up" approach to synthesize stable nanomaterials by chemical reduction, stabilizing additives such as polymers or organic surfactants must be present to cap the nanoparticle to prevent material bulk aggregation. In recent years, biological systems have emerged as green alternatives to support the uncoated inorganic components. One key advantage of biological templates is their inherent ability to produce nanostructures with controllable composition, facet, size and morphology under ecologically friendly synthetic conditions, which are difficult to achieve with traditional inorganic synthesis. In addition, through genetic engineering or bioconjugation, bio-templates can provide numerous possibilities for surface functionalization to incorporate specific binding sites for the target metals. Therefore, in bio-templated systems, the electrocatalytic performance of the formed nanocatalyst can be tuned by precisely controlling the material surface chemistry. With controlled improvements in size, morphology, facet exposure, surface area and electron conductivity, bio-inspired nanomaterials often exhibit enhanced catalytic activity towards electrode reactions. In this Review, recent research developments are presented in bio-approaches for metallic nanomaterial synthesis and their applications in electrocatalysis for sustainable energy storage and conversion systems.

Charge Storage in Graphene Oxide: Impact of the Cation on Ion Permeability and Interfacial Capacitance.

The charge storage and membrane applications of graphene oxide (GO) materials are dictated by its intrinsic material properties. Structure-function relationships correlating periodic parameters, such as the hydrated ion radius and ion-GO interactions, are currently lacking yet are needed to provide insight on the charge storage and ion transport mechanism. We report the use of scanning ion conductance microscopy to measure the ion permeability of GO films and evaluate its relationship with the measured capacitance. We demonstrate that species (namely K+) with strong electrostatic interactions with the oxygen functionalities of GO provide the benefit of higher capacitance but suffer from inhibited ion mobility due to constriction of the GO interlayer spacing.

Biosynthesized silver nanorings as a highly efficient and selective electrocatalysts for CO2 reduction.

Inspiration from nature has driven the development and applications of greener inorganic nanomaterials prepared using biotemplates in the field of nanoscience. In this study, we report the superiority of using a biosynthesized silver nanoring material for CO formation in CO2 saturated KHCO3. Compared to bulk silver and free silver nanoparticles prepared by pure chemical reduction, this silver nanoring (assembled on tobacco mosaic virus coat protein) exhibits significantly enhanced activity and selectivity for the conversion of CO2 to CO. The highest CO faradaic efficiency reaches 95.0% at an overpotential of 910 mV. Additionally, the CO partial current density is 2.7-fold higher than that of the free silver nanoparticles. We believe that the improved catalytic performance is related to the structuring ligand effect of the protein. The numerous functional groups on the protein may tune the reaction activity by influencing the binding energies of the intermediate species from CO2 reduction or hydrogen evolution.

Correction: Biosynthesized silver nanorings as a highly efficient and selective electrocatalysts for CO2 reduction.

Correction for 'Biosynthesized silver nanorings as a highly efficient and selective electrocatalysts for CO2 reduction' by Yani Pan et al., Nanoscale, 2019, 11, 18595-18603.

Pd-M/C (M = Pd, Cu, Pt) Electrocatalysts for Oxygen Reduction Reaction in Alkaline Medium: Correlating the Electronic Structure with Activity.

The increasing global needs for clean and renewable energy have fostered the design of new and highly efficient materials for fuel cells applications. In this work, Pd-M (M = Pd, Cu, Pt) and Pt nanoparticles were prepared by a green synthesis method. The carbon-supported nanoparticles were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) in alkaline medium. A comprehensive electronic and structural characterization of these materials was achieved using X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Their electrochemical properties were investigated by cyclic voltammetry, while their activities for the ORR were characterized using steady-state polarization experiments. The results revealed that the bimetallic nanoparticles consist of highly crystalline nanoalloys with size around 5 nm, in which the charge transfer involving Pd and M atoms affects the activity of the electrocatalysts. Additionally, the samples with higher ORR activity are those whose d-band center is closer to the Fermi level.

The borohydride oxidation reaction on La-Ni-based hydrogen-storage alloys.

This work provides insights into the processes involved in the borohydride oxidation reaction (BOR) in alkaline media on metal hydride alloys formed by LaNi(4.7)Sn(0.2)Cu(0.1) and LaNi(4.78)Al(0.22) with and without deposited Pt, Pd, and Au. The results confirm the occurrence of hydrolysis of the borohydride ions when the materials are exposed to BH(4)(-) and a continuous hydriding of the alloys during BH(4)(-) oxidation measurements at low current densities. The activity for the direct BOR is low in both bare metal hydride alloys, but the rate of the BH(4)(-) hydrolysis and the hydrogen-storage capacity are higher, while the rate of H diffusion is slower for bare LaNi(4.78) Al(0.22). The addition of Pt and Pd to both alloys results in an increase of the BH(4)(-) hydrolysis, but the H(2) formed is rapidly oxidized at the Pt-modified catalysts. In the case of Au modification, a small increase in the BH(4)(-) hydrolysis is observed as compared to the bare alloys. The presence of Au and Pd also leads to a reduction of the rates of alloy hydriding/de-hydriding.