First-in-human evaluation of an independently developed Chinese robot-assisted system for percutaneous coronary intervention.

BACKGROUND: Several studies have proved the safety and feasibility of robot-assisted percutaneous coronary intervention (PCI) in reducing the occupational hazards of interventionists while achieving precision medicine. However, an independently developed robot-assisted system for PCI in China has not yet emerged. This study aimed to evaluate the safety and feasibility of a robot-assisted system for elective PCI in China. METHODS: This preclinical trial included 22 experimental pigs and preliminarily supported the safety and feasibility of the ETcath200 robot-assisted system for PCI. Then, eleven patients with coronary heart disease who met the inclusion criteria and had clinical indications for elective PCI were enrolled. PCI was performed using a robot-assisted system. The primary outcomes were clinical success (defined as visual estimated residual stenosis < 30% after PCI and no major adverse cardiovascular events during hospitalization and within 30 days after PCI) and technical success (defined as the ability to use the robot-assisted system to complete PCI successfully without conversion to the traditional manual PCI). RESULTS: Eleven patients were included in this clinical trial. A drug-eluting stent with a diameter of 3 mm (interquartile range: 2.75-3.5 mm) and a length of 26 mm (interquartile range: 22-28 mm) was deployed in all patients. The clinical success rate was 100%, with no PCI-related complications and no in-hospital or 30-day major adverse cardiovascular events, and the technical success rate was 100%. CONCLUSIONS: The results strongly suggest that the use of the independently developed robot-assisted system in China for elective PCI is feasible, safe, and effective.

Direct Oxygen Transfer from H2 O to Cyclooctene over Electron-Rich RuO2 Nanocrystals for Epoxidation and Hydrogen Evolution.

Production of more than 20 million tons of epoxides per year from olefins suffers from low atom economy due to the use of oxidants and complex catalysts with unsatisfactory selectivity, leading to huge environmental and economic costs. We present a proof-of-concept application of electron-rich RuO2 nanocrystals to boost the highly selective epoxidation of cyclooctene via direct oxygen transfer from water as the sole oxygen source under mild conditions. The enhanced electron enrichment of RuO2 nanocrystals via the Schottky effect with nitrogen-doped carbons largely promotes the capture and activation of cyclooctene to give a high turnover frequency (260 h-1 ) of cyclooctene oxide, far surpassing the reported values (<20 h-1 ) of benchmarked catalysts at room temperature with oxidants. Our electron-rich RuO2 electrocatalysts enable efficient and durable hydrogen production (Faradaic efficiency >90 %) on the cathode without impacting on the selectivity to epoxide (>99 %) on the anode.

Facilitating Hot Electron Injection from Graphene to Semiconductor by Rectifying Contact for Vis-NIR-Driven H2 O2 Production.

Solar-driven production of hydrogen peroxide (H2 O2 ), as an important industrial chemical oxidant with an extensive range of applications, from oxygen reduction is a sustainable alternative to mainstream anthraquinone oxidation and direct hydrogenation of dioxygen methods. The efficiency of solar to hydrogen peroxide over semiconductor-based photocatalysts is still largely limited by the narrow light absorption to visible light. Here, the authors proposed and demonstrate the proof-of-concept application of light-generated hot electrons in a graphene/semiconductor (exemplified with widely used TiO2 ) dyad to largely extend visible light spectra up to 800 nm for efficient H2 O2 production. The well-designed graphene/semiconductor heterojunction has a rectifying interface with a zero barrier for the hot electron injection, largely boosting excited hot electrons with an average lifetime of ≈0.5 ps into charge carriers with a long fluorescent lifetime (4.0 ns) for subsequent H2 O2 production. The optimized dyadic photocatalyst can provide an H2 O2 yield of 0.67 mm g-1  h-1 under visible light irradiation (λ ≥ 400 nm), which is 20 times of the state-of-the-art noble-metal-free titanium oxide-based photocatalyst, and even achieves an H2 O2 yield of 0.14 mm g-1  h-1 upon photoexcitation by near-infrared-region light (≈800 nm).

Boosting Mass Exchange between Pd/NC and MoC/NC Dual Junctions via Electron Exchange for Cascade CO2 Fixation.

Merging existing catalysts together as a cascade catalyst may achieve "one-pot" synthesis of complex but functional molecules by simplifying multistep reactions, which is the blueprint of sustainable chemistry with low pollutant emission and consumption of energy and materials only when the smooth mass exchange between different catalysts is ensured. Effective strategies to facilitate the mass exchange between different active centers, which may dominate the final activity of various cascade catalysts, have not been reached until now, even though charged interfaces due to work function driven electron exchange have been widely observed. Here, we successfully constructed mass (reactants and intermediates) exchange paths between Pd/N-doped carbon and MoC/N-doped carbon induced by interfacial electron exchange to trigger the mild and cascade methylation of amines using CO2 and H2. Theoretical and experimental results have demonstrated that the mass exchange between electron-rich MoC and electron-deficient Pd could prominently improve the production of N,N-dimethyl tertiary amine, which results in a remarkably high turnover frequency value under mild conditions, outperforming the state-of-the-art catalysts in the literature by a factor of 5.9.

Heterojunction-Based Electron Donators to Stabilize and Activate Ultrafine Pt Nanoparticles for Efficient Hydrogen Atom Dissociation and Gas Evolution.

Platinum (Pt) is the most effective bench-marked catalyst for producing renewable and clean hydrogen energy by electrochemical water splitting. There is demand for high HER catalytic activity to achieve efficient utilization and minimize the loading of Pt in catalysts. In this work, we significantly boost the HER mass activity of Pt nanoparticles in Ptx /Co to 8.3 times higher than that of commercial Pt/C by using Co/NC heterojunctions as a heterogeneous version of electron donors. The highly coupled interfaces between Co/NC and Pt metal enrich the electron density of Pt nanoparticles to facilitate the adsorption of H+ , the dissociation of Pt-H bonds and H2 release, giving the lowest HER overpotential of 6.9 mV vs. RHE at 10 mA cm-2 in acid among reported HER electrocatalysts. Given the easy scale-up synthesis due to the stabilization of ultrafine Pt nanoparticles by Co/NC solid ligands, Ptx /Co can even be a promising substitute for commercial Pt/C for practical applications.

Schottky Barrier-Induced Surface Electric Field Boosts Universal Reduction of NOx - in Water to Ammonia.

NOx - reduction acts a pivotal part in sustaining globally balanced nitrogen cycle and restoring ecological environment, ammonia (NH3 ) is an excellent energy carrier and the most valuable product among all the products of NOx - reduction reaction, the selectivity of which is far from satisfaction due to the intrinsic complexity of multiple-electron NOx - -to-NH3 process. Here, we utilize the Schottky barrier-induced surface electric field, by the construction of high density of electron-deficient Ni nanoparticles inside nitrogen-rich carbons, to facilitate the enrichment and fixation of all NOx - anions on the electrode surface, including NO3 - and NO2 - , and thus ensure the final selectivity to NH3 . Both theoretical and experimental results demonstrate that NOx - anions were continuously captured by the electrode with largely enhanced surface electric field, providing excellent Faradaic efficiency of 99 % from both electrocatalytic NO3 - and NO2 - reduction. Remarkably, the NH3 yield rate could reach the maximum of 25.1 mg h-1 cm-2 in electrocatalytic NO2 - reduction reaction, outperforming the maximum in the literature by a factor of 6.3 in neutral solution. With the universality of our electrocatalyst, all sorts of available electrolytes containing NOx - pollutants, including seawater or wastewater, could be directly used for ammonia production in potential through sustainable electrochemical technology.

Electrochemical activation of C-H by electron-deficient W2C nanocrystals for simultaneous alkoxylation and hydrogen evolution.

The activation of C-H bonds is a central challenge in organic chemistry and usually a key step for the retro-synthesis of functional natural products due to the high chemical stability of C-H bonds. Electrochemical methods are a powerful alternative for C-H activation, but this approach usually requires high overpotential and homogeneous mediators. Here, we design electron-deficient W2C nanocrystal-based electrodes to boost the heterogeneous activation of C-H bonds under mild conditions via an additive-free, purely heterogeneous electrocatalytic strategy. The electron density of W2C nanocrystals is tuned by constructing Schottky heterojunctions with nitrogen-doped carbon support to facilitate the preadsorption and activation of benzylic C-H bonds of ethylbenzene on the W2C surface, enabling a high turnover frequency (18.8 h-1) at a comparably low work potential (2 V versus SCE). The pronounced electron deficiency of the W2C nanocatalysts substantially facilitates the direct deprotonation process to ensure electrode durability without self-oxidation. The efficient oxidation process also boosts the balancing hydrogen production from as-formed protons on the cathode by a factor of 10 compared to an inert reference electrode. The whole process meets the requirements of atomic economy and electric energy utilization in terms of sustainable chemical synthesis.

sDR5-Fc inhibits macrophage M1 polarization by blocking the glycolysis.

BACKGROUND: M1 polarization of macrophages is an important pathological process in myocardial ischemia reperfusion injury, which is the major obstacle for the treatment of acute myocardial infarction. Currently, the strategies and mechanisms of inhibiting M1 polarization are poorly explored. This study aims to investigate the role of soluble death receptor 5-Fc (sDR5-Fc) in regulating M1 polarization of macrophages under extreme conditions and explore the mechanisms from the aspect of glycolysis. METHODS: Extreme conditions were induced in RAW264.7 cells. Real-time quantitative polymerase chain reaction and western blot were used to detect the expression of mRNA and proteins, respectively. Cell counting kit-8 was used to investigate the proliferation activity of cells. Expression levels of inflammatory cytokines were determined by enzyme-linked immunosorbent assay. RESULTS: We found that sDR5-Fc rescues the proliferation of macrophages under extreme conditions, including nutrition deficiency, excessive peroxide, and ultraviolet irradiation. In addition, administration of sDR5-Fc inhibits the M1 polarization of macrophages induced by lipopolysaccharide (LPS) and interferon-gamma (IFN-γ), as the expression of M1 polarization markers CD86, CXC motif chemokine ligand 10, matrix metalloproteinase 9, and tumor necrosis factor-α, as well as the secretion of inflammatory factors interleukin (IL)-1ß and IL-6, were significantly decreased. By further investigation of the mechanisms, the results showed that sDR5-Fc can recover the LPS and IFN-γ induced pH reduction, lactic acid elevation, and increased expression of hexokinase 2 and glucose transporter 1, which were markers of glycolysis in macrophages. CONCLUSIONS: sDR5-Fc inhibits the M1 polarization of macrophages by blocking the glycolysis, which provides a new direction for the development of strategies in the treatment of myocardial ischemia reperfusion injury.

Designed electron-deficient gold nanoparticles for a room-temperature Csp3-Csp3 coupling reaction.

Stille cross-coupling reactions catalysed by an ideal catalyst combining the high activity of homogeneous catalysts and the reusability of heterogeneous catalysts are of great interest for C-C bond formation, which is a widely used reaction in fine chemistry. Despite great effort to increase the utilization ratio of surface metal atoms, the activity of heterogeneous catalysts under mild conditions remains unsatisfactory. Herein, we design a proof-of-concept strategy to trigger the room-temperature activity of heterogeneous Au catalysts by decreasing the electron density at the interface of a rationally designed Schottky heterojunction of Au metals and boron-doped carbons. The electron-deficient Au nanoparticles formed as a result of the rectifying contact with boron-doped carbons facilitate the autocleavage of C-Br bonds for highly efficient C-C coupling reactions of alkylbromides and allylstannanes with a TOF value of 5199 h-1 at room temperature, surpassing that of the state-of-the-art homogeneous catalyst.

Phosphazene-derived stable and robust artificial SEI for protecting lithium anodes of Li-O2 batteries.

A stable artificial solid electrolyte interphase (ASEI) containing phosphazene and perfluoroalkoxy groups was designed to protect Li anodes. The ASEI with high ionic conductivity and mechanical robustness successfully suppressed the growth of Li dendrites, significantly enhancing the electrochemical performance of the Li-O2 batteries.

Electrochemical Reduction of N2 into NH3 by Donor-Acceptor Couples of Ni and Au Nanoparticles with a 67.8% Faradaic Efficiency.

The traditional NH3 production method (Haber-Bosch process) is currently complemented by electrochemical synthesis at ambient conditions, but the rather low selectivity (as indicated by the Faradaic efficiency) for the electrochemical reduction of molecular N2 into NH3 impedes the progress. Here, we present a powerful method to significantly boost the Faradaic efficiency of Au electrocatalysts to 67.8% for the nitrogen reduction reaction (NRR) by increasing their electron density through the construction of inorganic donor-acceptor couples of Ni and Au nanoparticles. The unique role of the electron-rich Au centers in facilitating the fixation and activation of N2 was also investigated via theoretical simulation methods and then confirmed by experimental results. The highly coupled Au and Ni nanoparticles supported on nitrogen-doped carbon are stable for reuse and long-term performance of the NRR, making the electrochemical process more sustainable for practical application.

Nitrogen-thermal modification of the bifunctional interfaces of transition metal/carbon dyads for the reversible hydrogenation and dehydrogenation of heteroarenes.

A nitrogen-thermal approach via the reaction between transition metal species and N dopants affords us the ability to optimize the tradeoff between the number of exposed transition metal/carbon (exemplified by cobalt in this work) boundaries and the most pronounced interfacial rectifying contact to achieve the highly efficient and selective hydrogenation and dehydrogenation of N-heterocycle compounds in a reversible manner.

Boosting selective nitrogen reduction to ammonia on electron-deficient copper nanoparticles.

Production of ammonia is currently realized by the Haber-Bosch process, while electrochemical N2 fixation under ambient conditions is recognized as a promising green substitution in the near future. A lack of efficient electrocatalysts remains the primary hurdle for the initiation of potential electrocatalytic synthesis of ammonia. For cheaper metals, such as copper, limited progress has been made to date. In this work, we boost the N2 reduction reaction catalytic activity of Cu nanoparticles, which originally exhibited negligible N2 reduction reaction activity, via a local electron depletion effect. The electron-deficient Cu nanoparticles are brought in a Schottky rectifying contact with a polyimide support which retards the hydrogen evolution reaction process in basic electrolytes and facilitates the electrochemical N2 reduction reaction process under ambient aqueous conditions. This strategy of inducing electron deficiency provides new insight into the rational design of inexpensive N2 reduction reaction catalysts with high selectivity and activity.

Oriented arrays of Co3O4 nanoneedles for highly efficient electrocatalytic water oxidation.

We described an effective way to generate a Co3O4 mesocrystal array with well-developed porosity, simply by uniting a coupled interface with hydrazine treatment. Due to the fast electron transfer and sufficient active sites, the Ti mesh-supported Co3O4 nanoneedles electrode could provide a current density of 49.9 mA cm-2 at 570 mV OER overpotential and has exceptionally high stability.

Grouping Effect of Single Nickel-N4 Sites in Nitrogen-Doped Carbon Boosts Hydrogen Transfer Coupling of Alcohols and Amines.

As a new type of heterogeneous catalyst with "homogeneous-like" activity, single-site transition-metal materials are usually treated as integrated but separate active centers. A novel grouping effect is reported for single Ni-N4 sites in nitrogen-doped carbon (Ni/NC), where an effective ligand-stabilized polycondensation method endows Ni/NC nanocatalysts with a high content of single-site Ni up to 9.5 wt %. The enhanced electron density at each single Ni-N4 site promotes a highly efficient hydrogen transfer, which is exemplified by the coupling of benzyl alcohol and aniline into N-benzylaniline with a turnover frequency (TOF) value of 7.0 molN-benzylaniline molmetal -1 h-1 ; this TOF outpaces that of reported stable non-noble-metal-based catalysts by a factor of 2.