Single-step salt-template-based scalable production of 2D carbon sheets heterostructured with nickel nanocatalysts for lowering overpotential of hydrogen evolution reaction.

Non-precious metals have been considered as suitable alternatives for high-performance hydrogen evolution reactions (HER). Although the incorporation of carbon substances is shown to improve the number of active sites, electron transfer pathways, and long-term stability, there have been rare reports on their single-step scalable production. Herein, we realize free-standing two-dimensional (2D) carbon sheets heterostructured with nickel (Ni) nanocatalysts by pyrolyzing ultrathin layers of acetate tetrahydrate (i.e. the single precursor for both Ni and C sources) over water-soluble salt crystals. Such a salt-templated methodology is environmentally friendly and readily scalable without the implementation of sophisticated equipment. The resulting 2D carbon sheets exhibit an average small thickness of âˆ¼ 3 nm and lateral dimensions with tens of micrometers, where a large number of nano-sized Ni particles with an average diameter of 14 nm are uniformly dispersed. Such 2D Ni-C sheets demonstrate a small overpotential of 111 mV at 10 mA/cm2 and a low Tafel slope of 86 mV/dec for HER in 1 M KOH, which is significantly improved over those of reported non-precious metals composited with carbon substances. This work offers new insight into the design and practical production of non-precious metal matrixes for economical HER.

In Silico Analysis of Glucose Oxidase from Aspergillus niger: Potential Cysteine Mutation Sites for Enhancing Protein Stability.

Glucose oxidase (GOx) holds considerable advantages for various applications. Nevertheless, the thermal instability of the enzyme remains a grand challenge, impeding the success in applications outside the well-controlled laboratories, particularly in practical bioelectronics. Many strategies to modify GOx to achieve better thermal stability have been proposed. However, modification of this enzyme by adding extra disulfide bonds is yet to be explored. This work describes the in silico bioengineering of GOx from Aspergillus niger by judiciously analyzing characteristics of disulfide bonds found in the Top8000 protein database, then scanning for amino acid residue pairs that are suitable to be replaced with cysteines in order to establish disulfide bonds. Next, we predicted and assessed the mutant GOx models in terms of disulfide bond quality (bond length and α angles), functional impact by means of residue conservation, and structural impact as indicated by Gibbs free energy. We found eight putative residue pairs that can be engineered to form disulfide bonds. Five of these are located in less conserved regions and, therefore, are unlikely to have a deleterious impact on functionality. Finally, two mutations, Pro149Cys and His158Cys, showed potential for stabilizing the protein structure as confirmed by a structure-based stability analysis tool. The findings in this study highlight the opportunity of using disulfide bond modification as a new alternative technique to enhance the thermal stability of GOx.

Cavitas electrochemical sensors for the direct determination of salivary thiocyanate levels.

Noninvasive diagnosis using salivary samples to detect thiocyanate provides vital information on individual health. This article demonstrates the first example of a wearable sensing device to noninvasively assess thiocyanate levels. The customized screen-printed electrode system is integrated into a form of a mouthguard squarewave-voltammetric sensor toward the convenient and fast detection of the salivary biomarker within 15 s. The sensor with a protective film to mitigate the effect of biofouling offers high sensitivity and selectivity toward the detection of thiocyanate ions. Partial least square regression is applied to analyze the high-order squarewave-voltammetric data over the applied potential range of 0-1.75 V vs Ag/AgCl and quantify the thiocyanate concentration in a complex matrix. The mouthguard sensor operating under physiological conditions can monitor a wide range of thiocyanate (up to 11 mM) with a low detection limit of 30 µM. The demonstration introduces a unique approach, that obviates the requirement for blood sampling, to study thiocyanate levels of healthy people, cigarette smokers, or people with other health conditions. It is envisioned that the new cavitas device possesses a substantial promise for diverse biomedical diagnosis applications.

Fully edible biofuel cells.

The first example of a fully edible biofuel cell (BFC), based solely on highly biocompatible food materials without any additional external mediators, is described. The new BFC energy-harvesting approach relies on a variety of edible plant/mushroom extract/vegetable oil/charcoal paste biocatalytic electrodes and represents an attractive route for energy harvesting towards ingestible biomedical devices. The edible BFC anode and cathode paste materials consist of biocatalytic rich mushroom, apple, plum and banana plant tissues, along with dietary activated charcoal and water-immiscible olive oil, corn oil, and sesame oil for creating the paste matrix. The ethanol/O2 BFC relies on a bioanode, based on ethanol oxidation induced by the intrinsic biocatalytic activity of its mushroom component, along with a biocathode based on oxygen-reducing apple extract containing polyphenol-oxidase and phenolic compounds. The integrated natural catalytic system and selective biocatalytic activity of the natural extracts offer successful operation of BFCs without any extra mediators or membrane separating the anode and the cathode. The mushroom/apple/olive oil-based BFC displays a favorable power density of 282 µW cm-2 with an open circuit voltage (OCV) of 0.24 V. The power and OCV signals are linearly proportional to ethanol levels and indicate promise for self-powered alcohol sensing. The food-based BFCs were reproducible and able to maintain a power performance of over 80% of their initial output for four hours. These edible energy-harvesting BFCs hold great promise for the next-generation of ingestible devices and smart self-powered biosensors for monitoring health and the digestive system.

Pure Nanoscale Morphology Effect Enhancing the Energy Storage Characteristics of Processable Hierarchical Polypyrrole.

We report a new synthesis approach for the precise control of wall morphologies of colloidal polypyrrole microparticles (PPyMPs) based on a time-dependent template-assisted polymerization technique. The resulting PPyMPs are water processable, allowing the simple and direct fabrication of multilevel hierarchical PPyMPs films for energy storage via a self-assembly process, whereas convention methods creating hierarchical conducting films based on electrochemical polymerization are complicated and tedious. This approach allows the rational design and fabrication of PPyMPs with well-defined size and tunable wall morphology, while the chemical composition, zeta potential, and microdiameter of the PPyMPs are well characterized. By precisely controlling the wall morphology of the PPyMPs, we observed a pure nanoscale morphological effect of the materials on the energy storage performance. We demonstrated by controlling purely the wall morphology of PPyMPs to around 100 nm (i.e., thin-walled PPyMPs) that the thin-walled PPyMPs exhibit typical supercapacitor characteristics with a significant enhancement of charge storage performance of up to 290% compared to that of thick-walled PPyMPs confirmed by cyclic voltametry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. We envision that the present design concept could be extended to different conducting polymers as well as other functional organic and inorganic dopants, which provides an innovative model for future study and understanding of the complex physicochemical phenomena of energy-related materials.