Rational Design of Cu-Doped Tetrahedron of Spinel Oxide for High-Performance Nitric Oxide Electrochemical Sensor.

The real-time detection of nitric oxide (NO) in living cells is essential to reveal its physiological processes. However, the popular electrochemical detection strategy is limited to the utilization of noble metals. The development of new detection candidates without noble metal species still maintaining excellent catalytic performance has become a big challenge. Herein, we propose a spinel oxide doped with heteroatom-Cu-doped Co3O4 (Cu-Co3O4) for the sensitive and selective detection of NO release from the living cells. The material is strategically designed with Cu occupying the tetrahedral (Td) center of Co3O4 through the formation of a Cu-O bond. The introduced Cu regulates the local coordination environment and optimizes the electronic structure of Co3O4, hybridizing with the N 2p orbital to enhance charge transfer. The CuTd site can well inhibit the current response to nitrite (NO2-), resulting in a high improvement in the electrochemical oxidation of NO. The selectivity of Cu-Co3O4 can be markedly improved by the pore size of the molecular sieve and the negative charge on the surface. The rapid transmission of electrons is due to the fact that Cu-Co3O4 can be uniformly and densely in situ grown on Ti foil. The rationally designed Cu-Co3O4 sensor displays excellent catalytic activity toward NO oxidation with a low limit of detection of 2.0 nM (S/N = 3) and high sensitivity of 1.9 µA nM-1 cm-2 in cell culture medium. The Cu-Co3O4 sensor also shows good biocompatibility to monitor the real-time NO release from living cells (human umbilical vein endothelial cells: HUVECs; macrophage: RAW 264.7 cells). It was found that a remarkable response to NO was obtained in different living cells when stimulated by l-arginine (l-Arg). Moreover, the developed biosensor could be used for real-time monitoring of NO released from macrophages polarized to a M1/M2 phenotype. This cheap and convenient doping strategy shows universality and can be used for sensor design of other Cu-doped transition metal materials. The Cu-Co3O4 sensor presents an excellent example through the design of proper materials to implement unique sensing requirements and sheds light on the promising strategy for electrochemical sensor fabrication.

Efficient visible-light-driven S-scheme AgVO3/Ag2S heterojunction photocatalyst for boosting degradation of organic pollutants.

The traditional semiconductor photocatalysts for solving the related environmental aggravation are often challenged by the recombination of photogenerated carriers. Designing an S-scheme heterojunction photocatalyst is one of the keys to tackling its practical application problems. This paper reports an S-scheme AgVO3/Ag2S heterojunction photocatalyst constructed via a straightforward hydrothermal approach that exhibits outstanding photocatalytic degradation performances to the organic dye Rhodamine B (RhB) and antibiotic Tetracycline hydrochloride (TC-HCl) driven by visible light. The results show that AgVO3/Ag2S heterojunction with a molar ratio of 6:1 (V6S) possesses the highest photocatalytic performances, 99% of RhB can be almost degraded by 0.1 g/L V6S within 25 min light illumination, and about 72% of TC-HCl can be photodegraded with the act of 0.3 g/L V6S under 120 min light irradiation. Meanwhile, the AgVO3/Ag2S system exhibits superior stability and maintains high photocatalytic activity after 5 repeated tests. Moreover, the EPR measurement and radical capture test identify that superoxide radicals and hydroxyl radicals mainly contribute to the photodegradation process. The present work demonstrates that constructing an S-scheme heterojunction can effectively inhibit the recombination of carriers, providing insights into the fabrication of applied photocatalysts for practical wastewater purification treatment.

A study of balloon type on calcified coronary lesion predilation: A finite element analysis.

Calcified coronary lesions have been one of the more difficult types of lesion for interventional treatment, and angioplasty is required to break the calcification before stent implantation so that the stent can expand smoothly, however, it remains unclear which type of angioplasty is optimal for different calcified lesions. In this study, a finite element approach was used to model normal balloons, cutting balloons, and AngioSculpt balloons. In addition, calcified lesions of different degrees, thicknesses, and lengths were modeled according to Intravascular ultrasound (IVUS) calcification grade. The above three balloons were used to pretreat calcified lesions, and the brittle fracture module for calcification was used to detect fracture success, to facilitate virtual stent implantation after predilation. The simulation results showed that with a thickness of less than 0.3 mm, balloons were unable to deal with calcified plaques in lesions of less than 120°, for 180° calcified lesions the cutting balloon fractured the calcified material at 1.2 MPa, the AngioSculpt balloon produced multiple fractures at 0.8 MPa for 270° calcified plaques, but was unable to fracture calcified lesions with a thickness of 0.4 mm. Based on these results, we conclude that the length of the lesion did not affect calcification fracture, while the thickness of the lesion did. In calcified lesions of approximately 180°, the cutting balloon showed the best predilation results, while the AngioSculpt balloon was optimal for 270°. In annular calcification, all three balloons were unable to fracture the lesion.

In Situ Reconstruction NiO Octahedral Active Sites for Promoting Electrocatalytic Oxygen Evolution of Nickel Phosphate.

Electrochemical activation strategy is very effective to improve the intrinsic catalytic activity of metal phosphate toward the sluggish oxygen evolution reaction (OER) for water electrolysis. However, it is still challenging to operando trace the activated reconstruction and corresponding electrocatalytic dynamic mechanisms. Herein, a constant voltage activation strategy is adopted to in situ activate Ni2 P4 O12 , in which the break of NiONi bond and dissolution of PO4 3- groups could optimize the lattice oxygen, thus reconstructing an irreversible amorphous Ni(OH)2 layer with a thickness of 1.5-3.5 nm on the surface of Ni2 P4 O12 . The heterostructure electrocatalyst can afford an excellent OER activity in alkaline media with an overpotential of 216.5 mV at 27.0 mA cm-2 . Operando X-ray absorption fine structure spectroscopy analysis and density functional theory simulations indicate that the heterostructure follows a nonconcerted proton-electron transfer mechanism for OER. This activation strategy demonstrates universality and can be used to the surface reconstruction of other metal phosphates.

Influence of different postballoon expansion procedures: A finite element analysis.

BACKGROUND: Postballoon expansion is considered as an appropriate procedure for adequate stent expansion for coronary bifurcation lesions. Two postballoon expansion procedures are currently recommended: proximal optimization technique (POT)/side/POT and POT/kiss/POT. However, the effects of the two postballoon expansion treatments are different. There is a lack of biomechanical study to quantify the difference. PURPOSE: It is recognized that biomechanical factors influence the occurrence of Major Cardiovascular Adverse Events (MACE), which includes recurrent angina pectoris, acute myocardial infarction and coronary heart disease death. The current paper evaluated the two postexpansion strategies and quantified biomechanical parameters to provide a basis for clinical decisions. METHODS: Based on the CT angiography (CTA) data of a patient diagnosed with coronary bifurcation lesions, a personalized coronary bifurcation lesion model was constructed, and the surgical procedure after two expansions was simulated. The POT/side/POT and POT/kiss/POT expansion procedures were analyzed from the perspective of biomechanics through finite element analysis. The biomechanics factors, including the percentage of stent malapposition and stent occlusion at the side branch (SB) opening, the stent ellipse index of proximal main vessel (PMV) segment, the minimum lumen area of the stent vessel segment and the stress distribution of the vessel wall, were used to quantify clinician concerns about factors affecting patient outcomes. The factors include stent adhesion, SB open stent occlusion, poor stent deformation, patency effect of vessel stenosis, and vessel wall damage. RESULTS: Both postexpansion procedures were successfully simulated. The malapposition rate during POT/side/POT was larger (1.2% vs. 0.42%) and stent occlusion at the SB opening from the cross-section perpendicular to the SB opening after the POT/side/POT procedure was 0.20%, compared with 0.00% after POT/kiss/POT. POT/kiss/POT produced a larger PMV segment stent ellipse index. Minimum lumen area after POT/side/POT was 5.6 mm2 and after POT/kiss/POT 5.9 mm2 . POT/kiss/POT produces an effect of greater vascular stress than POT/side/POT. CONCLUSION: Numerical simulations provide a quantitative analysis to inform clinicians of the differences between preoperative planning and surgical procedures. Biomechanical analysis of the differences between the two postexpansion strategies found that the POT/kiss/POT procedure resulted in better stent fit, less occlusion of the SB open stent and better vascular patency but also resulted in poor stent deformation and caused greater vessel wall stress. The current study informs rationales for clinical understanding of postexpansion strategies.

High-performance self-supporting AgCoPO4/CFP for hydrogen evolution reaction under alkaline conditions.

Electrochemical water decomposition to produce hydrogen is a promising approach for renewable energy storage. It is vital to develop a catalyst with low overpotential, low cost and high stability for hydrogen evolution reaction (HER) under alkaline conditions. Herein, we used a simple hydrothermal method to obtain a AgCo(CO)4 precursor on the surface of carbon fiber paper (CFP). After thermal phosphorization, the self-supporting catalyst AgCoPO4/CFP was obtained, which greatly improved the HER catalytic performance under alkaline conditions. At 10 mA cm-2, it showed an overpotential of 32 mV. The Tafel slope was 34.4 mV dec-1. The high catalytic performance of AgCoPO4/CFP may be due to the hydrophilic surface promoting effective contact with the electrolyte and the synergistic effect of the two metals, which accelerated electron transfer and thus promoted hydrogen evolution reaction. In addition, it showed an outstanding urea oxidation reaction (UOR) activity. After adding 0.5 M urea, the over-potential of the AgCoPO4/CFP assembled electrolytic cell was only 1.45 V when the current density reached 10 mA cm-2, which was much lower than that required for overall water splitting. This work provides a new method for the design and synthesis of efficient HER electrocatalysts.

Hierarchical CoP Nanostructures on Nickel Foam as Efficient Bifunctional Catalysts for Water Splitting.

A highly active and cheap catalyst is also key to hydrogen production by water splitting. However, most of the high-efficiency catalysts reported to date only are catalytically active for either the hydrogen evolution reaction (HER) or the oxygen evolution reaction (OER), which makes the development of multifunctional catalysts more meaningful. Here, for the first time, Co(CO3 )0.5 OH. 0.11 H2 O (CHCH) as precursor with different microstructures on the surface of nickel foam (NF) was obtained using a facile hydrothermal method. The CoP/NF catalyst was obtained after thermal phosphating that retained the microhierarchical structure of the precursor and greatly improved the catalytic performance, with a highly efficiency performance as HER and OER dual-functional catalyst. Density functional theory (DFT) calculations showed that the possible reason for the excellent performance of the CoP/NF layered structure is an increase in the number of of surface defects and an increased active surface area. The results reported in this paper show that CoP/NF, a layered bifunctional electrocatalyst, is a cost-effective and efficient water-splitting electrode. This finding can offer the opportunity for the commercial use of excess electric energy for large-scale water splitting hydrogen production.

Effect of Y Addition on the Microstructure and Mechanical Properties of ZM31 Alloy.

Effects of different Y contents (0, 0.3, 0.7, 1.5, 3, 5 and 10 wt.%) on the microstructure, thermal stability and mechanical properties of Mg-3Zn-1Mn (ZM31) alloys were systematically studied. The existence form and action mechanism of Y in the experimental alloys were investigated. The results revealed that with the change of Y content, the main phases of the ZM31-xY alloys changed from Mg7Zn3 phase, I-phase, I + W-phase, W-phase, W + LPSO phase to LPSO phase. When Y content was low (≤1.5%), hot extrusion could break up the residual phases after homogenization to form dispersed fine rare-earth phase particles, and fine second phases would also precipitate in the grain, which could inhibit the grain growth. When Y content was high (≥3%), the experimental alloys were only suitable for high-temperature extrusion due to the formation of the high heat stable rare-earth LPSO phase. In addition, Y could evidently enhance the mechanical properties of the as-extruded ZM31 alloy, of which the ZM31-10Y alloy had the best mechanical properties, that is, the tensile and yield strengths are 403 MPa and 342 MPa. The high strengths of the alloys were mainly determined by fine grain strengthening, rare-earth phase strengthening and dispersion strengthening of fine α-Mn particles.

Effect of Ti Transition Layer Thickness on the Structure, Mechanical and Adhesion Properties of Ti-DLC Coatings on Aluminum Alloys.

Multilayers of Ti doped diamond-like carbon (Ti-DLC) coatings were deposited on aluminum alloys by filtered cathodic vacuum arc (FCVA) technology using C2H2 as a reactive gas. The effect of different Ti transition layer thicknesses on the structure, mechanical and adhesion properties of the coatings, was investigated by scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), nanoindentation and a scratch tester. The results showed that the Ti transition layer could improve interfacial transition between the coating and the substrate, which was beneficial in obtaining excellent adhesion of the coatings. The Ti transition layer thickness had no significant influence on the composition and structure of the coatings, whereas it affected the distortion of the sp²-C bond angle and length. Nanoindentation and scratch test results indicated that the mechanical and adhesion properties of the Ti-DLC coatings depended on the Ti transition layer thickness. The Ti transition layer proved favorable in decreasing the residual compressive stress of the coating. As the Ti transition layer thickness increased, the hardness value of the coating gradually decreased. However, its elastic modulus and adhesion exhibited an initial decrease followed by an increasing fluctuation. Among them, the Ti-DLC coating with a Ti transition layer thickness of 1.1 µm exhibited superior mechanical properties.

Flower-Like Nickel Phosphide Microballs Assembled by Nanoplates with Exposed High-Energy (0 0 1) Facets: Efficient Electrocatalyst for the Hydrogen Evolution Reaction.

The fabrication of low-cost and earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) over a broad pH range is attractive. In this work, a facile precursor route is developed to synthesize flower-like nickel phosphide microballs with a diameter of approximately 12 µm. With a controlled phosphorization temperature, flower-like nickel phosphide microballs with different crystalline structures (Ni5 P4 and Ni2 P) were obtained easily. Flower-like Ni5 P4 microballs possessed two advantageous features for enhanced HER: fast vectorial electron transfer path along the building block nanoplates and enhanced inherent catalytic activity of each active site for high-energy (0 0 1) facets. The flower-like Ni5 P4 microballs electrocatalyst thus displayed excellent activity for the HER with a low overpotential (η) of 35.4 mV to reach current densities of 10 mA cm-2 and a small Tafel slope of 48 mV dec-1 in acid solution. In addition, it showed excellent activity in 1 m KOH with η=47 mV at 10 mA cm-2 . DFT studies indicated that the free energy of hydrogen adsorbed on the Ni site of Ni5 P4 was 0.152 eV, which is smaller than that of the Ni site of Ni2 P (0.182 eV). Therefore, flower-like Ni5 P4 microballs exhibited better HER activity than Ni2 P, which is consistent with our HER data. This hierarchical structure with exposed high-energy (0 0 1) facets paves the way to design and synthesize low-cost, high-performance catalysts for the HER.