Interface Synergy of Exposed Oxygen Vacancy and Pd Lewis Acid Sites Enabling Superior Cooperative Photoredox Synthesis.

Photo-driven cross-coupling of o-arylenediamines and alcohols has emerged as an alternative for the synthesis of bio-active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (V) and Pd Lewis acid sites for benzimidazole and hydrogen (H) coproduction over Pd-loaded TiO nanospheres with the highest photoredox activity compared to previous works so far.

Bimetallic Single Atom/Nanoparticle Ensemble for Efficient Photochemical Cascade Synthesis of Ethylene from Methane.

Light-driven photoredox catalysis presents a promising approach for the activation and conversion of methane (CH) into high value-added chemicals under ambient conditions. However, the high C-H bond dissociation energy of CH and the absence of well-defined C-H activation sites on catalysts significantly limit the highly efficient conversion of CH toward multicarbon (C) hydrocarbons, particularly ethylene (CH). Herein, we demonstrate a bimetallic design of Ag nanoparticles (NPs) and Pd single atoms (SAs) on ZnO for the cascade conversion of CH into CH with the highest production rate compared with previous works.

Frequency properties of channeled spectropolarimetry: an information theory perspective.

Channeled spectropolarimetry (CSP) has emerged as a notable technique due to its unique capacity to instantaneously measure either the polarization state of light or the Mueller matrix of a sample over a broad spectral range. Leveraging the quasi-linear relation between phase retardances of thick birefringent retarders and wavenumber, the target signal undergoes wavelength encoding. For the first time, we present a theoretical framework for the general CSP from a perspective of information theory.

Performance Optimization of Ionic Polymer Sensors through Characteristic Regulation of Chemically Prepared Interfacial Electrodes.

Ionic polymer sensors (IPSs) have broad application prospects in health monitoring, environmental perception, and human-computer interaction. The performance of IPSs with chemically prepared electrodes is generally superior to that with physically prepared electrodes due to the area difference of the electric double layer (EDL), but the effects of the electrode characteristics prepared by chemical methods on the performance of IPSs have not been revealed. Therefore, in this paper, we studied the impact of the characteristics of chemically prepared electrodes on the performance of IPSs and realized the performance optimization of IPSs through electrode characteristic regulation.

Effect of Initial Crack Position on Crack Propagation Behaviors of Heavy-Duty Transmission Gear.

The tooth bending fatigue fracture is caused by the alternating loads for the heavy-duty transmission gears. The crack initiation and propagation are the two major parts in the failure process. The crack propagation behavior is mainly affected by initial crack position except for the load and material properties.

Spatially and temporally understanding dynamic solid-electrolyte interfaces in carbon dioxide electroreduction.

The ubiquity of solid-liquid interfaces in nature and the significant role of their atomic-scale structure in determining interfacial properties have led to intensive research. Particularly in electrocatalysis, however, a molecular-level picture that clearly describes the dynamic interfacial structures and organizations with their correlation to preferred reaction pathways in electrochemical reactions remains poorly understood. In this review, CO electroreduction reaction (CORR) is spatially and temporally understood as a result of intricate interactions at the interface, in which the interfacial features are highly relevant.

Multi-spectral snapshot diffraction-based overlay metrology.

Diffraction-based overlay (DBO) metrology has been successfully introduced to deal with the tighter overlay control in modern semiconductor manufacturing. Moreover, DBO metrology typically needs to be performed at multiple wavelengths to achieve accurate and robust measurement in the presence of overlay target deformations. In this Letter, we outline a proposal for multi-spectral DBO metrology based on the linear relation between the overlay errors and the combinations of off-diagonal-block Mueller matrix elements ΔM = M - ( - 1)M (i = 1, 2; j = 3, 4) associated with the zeroth-order diffraction of overlay target gratings.

New Radical Route and Insight for the Highly Efficient Synthesis of Benzimidazoles Integrated with Hydrogen Evolution.

Benzimidazoles are a versatile class of scaffolds with important biological activities, whereas their synthesis in a lower-cost and more efficient manner remains a challenge. Here, we demonstrate a conceptually new radical route for the high-performance photoredox coupling of alcohols and diamines to synthesize benzimidazoles along with stoichiometric hydrogen (H ) over Pd-decorated ultrathin ZnO nanosheets (Pd/ZnO NSs). The mechanistic study reveals the unique advantage of ZnO NSs over other supports and particularly that the features of Pd nanoparticles in facilitating the cleavage of the α-C-H bond of alcohols and adsorbing subsequently-generated C-centered radicals hold the key to turning on the reaction.

Exposed Zinc Sites on Hybrid ZnIn S @CdS Nanocages for Efficient Regioselective Photocatalytic Epoxide Alcoholysis.

Photocatalytic epoxide alcoholysis through C-O bond cleavage and formation has emerged as an alternative to synthesizing anti-tumoral pharmaceuticals and fine chemicals. However, the lack of crucial evidence to interpret the interaction between reactants and photocatalyst surface makes it challenging for photocatalytic epoxide alcoholysis with both high activity and regioselectivity. In this work, we report the hierarchical ZnIn S @CdS photocatalyst for epoxide alcoholysis with high regioselectivity nearly 100 %.

Heterostructure-Engineered Semiconductor Quantum Dots toward Photocatalyzed-Redox Cooperative Coupling Reaction.

Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis. Here, we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catalysis toward the oxidation of 1-phenylethanol to acetophenone/2,3-diphenyl-2,3-butanediol (pinacol) integrated with the reduction of protons to H. The strong interaction and typical type-I band-position alignment between CdS quantum dots and ZnS quantum dots result in efficient separation and transfer of electron-hole pairs, thus distinctly enhancing the coupled photocatalyzed-redox activity and stability.

Nanoscale Assembly of CdS/BiVO Hybrids for Coupling Selective Fine Chemical Synthesis and Hydrogen Production under Visible Light.

Simultaneously utilizing photogenerated electrons and holes in one photocatalytic system to synthesize value-added chemicals and clean hydrogen (H) energy meets the development requirements of green chemistry. Herein, we report a binary material of CdS/BiVO combining one-dimensional (1D) CdS nanorods (NRs) with two-dimensional (2D) BiVO nanosheets (NSs) constructed through a facile electrostatic self-assembly procedure for the selectively photocatalytic oxidation of aromatic alcohols integrated with H production, which exhibits significantly enhanced photocatalytic performance. Within 2 h, the conversion of aromatic alcohols over CdS/BiVO-25 was approximately 9-fold and 40-fold higher than that over pure CdS and BiVO, respectively.

Engineering Semiconductor Quantum Dots for Selectivity Switch on High-Performance Heterogeneous Coupling Photosynthesis.

Semiconductor-based photoredox catalysis brings an innovative strategy for sustainable organic transformation (e.g., C-C/C-X bond formation), via radical coupling under mild conditions.

Embedded growth of colorful CsPbX(X = Cl, Br, I) nanocrystals in metal-organic frameworks at Room Temperature.

Herein, we develop a novel strategy for preparing all-inorganic cesium lead halide (CsPbX, X = Cl, Br, I) perovskite nanocrystals (NCs)@Zn-based metal-organic framework (MOF) composites through interfacial synthesis. The successful embedding of fluorescent perovskite NCs in Zn-MOFs is due to theconfined growth, which is attributed to the re-nucleation of water-triggered phase transformation from CsPbBrto CsPbBr. The controllable synthesis of mixed-halide based composites with various emission wavelength can be achieved by adding the desired amount of halide (Cl or I) salts in the re-nucleation process.

Downregulation of microRNA-21 contributes to decreased collagen expression in venous malformations via transforming growth factor-β/Smad3/microRNA-21 signaling feedback loop.

Objective: Venous malformations (VMs) are the most frequent vascular malformations and are characterized by dilated and tortuous veins with a dysregulated vascular extracellular matrix. The purpose of the present study was to investigate the potential involvement of microRNA-21 (miR-21), a multifunctional microRNA tightly associated with extracellular matrix regulation, in the pathogenesis of VMs.

Methods: The expression of miR-21, collagen I, III, and IV, transforming growth factor-β (TGF-β), and Smad3 (mothers against decapentaplegic homolog 3) was evaluated in VMs and normal skin tissue using in situ hybridization, immunohistochemistry, Masson trichrome staining, and real-time polymerase chain reaction.

Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts.

Merging hydrogen (H) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H fuel and high-value chemicals can be coproduced under mild conditions using light as the sole energy input. Following this dual-functional photocatalytic strategy, a dreamlike reaction pathway for constructing C-C/C-X (X = C, N, O, S) bonds from abundant and readily available X-H bond-containing compounds with concomitant release of H can be readily fulfilled without the need of external chemical reagents, thus offering a green and fascinating organic synthetic strategy. In this review, we begin by presenting a concise overview on the general background of traditional photocatalytic H production and then focus on the fundamental principles of cooperative photoredox coupling of selective organic synthesis and H production by simultaneous utilization of photoexcited electrons and holes over semiconductor-based catalysts to meet the economic and sustainability goal.

Roles of Graphene Oxide in Heterogeneous Photocatalysis.

Graphene oxide (GO) has been widely utilized as the precursor of graphene (GR) to fabricate GR-based hybrid photocatalysts for solar-to-chemical energy conversion. However, until now, the properties and roles that GO played in heterogeneous photocatalysis have remained relatively elusive. In this Review, we start with a brief discussion of synthesis and structure of GO.

Nanostructured metal phosphides: from controllable synthesis to sustainable catalysis.

Metal phosphides (MPs) with unique and desirable physicochemical properties provide promising potential in practical applications, such as the catalysis, gas/humidity sensor, environmental remediation, and energy storage fields, especially for transition metal phosphides (TMPs) and MPs consisting of group IIIA and IVA metal elements. Most studies, however, on the synthesis of MP nanomaterials still face intractable challenges, encompassing the need for a more thorough understanding of the growth mechanism, strategies for large-scale synthesis of targeted high-quality MPs, and practical achievement of functional applications. This review aims at providing a comprehensive update on the controllable synthetic strategies for MPs from various metal sources.

Coupling Strategy for CO Valorization Integrated with Organic Synthesis by Heterogeneous Photocatalysis.

Photocatalytic reduction of CO to solar fuels and/or fine chemicals is a promising way to increase the energy supply and reduce greenhouse gas emissions. However, the conventional reaction system for CO photoreduction with pure H O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, or cost-ineffective atom economy. A recent surge of developments, in which photocatalytic CO valorization is integrated with selective organic synthesis into one reaction system, indicates an efficient modus operandi that enables sufficient utilization of photogenerated electrons and holes to achieve the goals for sustainable economic and social development.

Molecular Understanding of Electrochemical-Mechanical Responses in Carbon-Coated Silicon Nanotubes during Lithiation.

Carbon-coated silicon nanotube (SiNT@CNT) anodes show tremendous potential in high-performance lithium ion batteries (LIBs). Unfortunately, to realize the commercial application, it is still required to further optimize the structural design for better durability and safety. Here, the electrochemical and mechanical evolution in lithiated SiNT@CNT nanohybrids are investigated using large-scale atomistic simulations.

Cooperative Syngas Production and C-N Bond Formation in One Photoredox Cycle.

Solar-driven syngas production by CO reduction provides a sustainable strategy to produce renewable feedstocks. However, this promising reaction often suffers from tough CO activation, sluggish oxidative half-reaction kinetics and undesired by-products. Herein, we report a function-oriented strategy of deliberately constructing black phosphorus quantum dots-ZnIn S (BP/ZIS) heterostructures for solar-driven CO reduction to syngas, paired with selectively oxidative C-N bond formation, in one redox cycle.

Rationally designed transition metal hydroxide nanosheet arrays on graphene for artificial CO reduction.

The performance of transition metal hydroxides, as cocatalysts for CO photoreduction, is significantly limited by their inherent weaknesses of poor conductivity and stacked structure. Herein, we report the rational assembly of a series of transition metal hydroxides on graphene to act as a cocatalyst ensemble for efficient CO photoreduction. In particular, with the Ru-dye as visible light photosensitizer, hierarchical Ni(OH) nanosheet arrays-graphene (Ni(OH)-GR) composites exhibit superior photoactivity and selectivity, which remarkably surpass other counterparts and most of analogous hybrid photocatalyst system.

Patterning Ag nanoparticles by selective wetting for fine size Cu-Ag-Cu bonding.

Metal nanoparticles (NPs) are promising bonding materials to replace Sn alloys in fine size Cu-Cu bonding. However, the method of rapidly patterning NPs on solder joints with sizes less than 30 µm is one of the main barriers that impede the practical applications of NPs in Cu-Cu bonding, especially in mass production. In this paper, a novel method of patterning Ag NPs on Cu pads by selective wetting was introduced.

A unique coordination-driven route for the precise nanoassembly of metal sulfides on metal-organic frameworks.

Incorporating different materials, such as metal sulfides, with metal-organic frameworks (MOFs) to develop MOF-based multifunctional composites with enhanced performance is an important area of research. However, the intrinsically high interfacial energy barrier significantly restricts the heterogeneous nucleation and nanoassembly of metal sulfides onto MOFs during the wet chemistry synthesis process. Herein, taking advantage of the natural tailorability of MOFs, the precise and controllable growth of metal sulfide nanoparticles (NPs) (CdS, ZnS, CuS and Ag2S) at the coordinatively unsaturated metal sites (CUSs) of MOFs to form MOF@metal sulfide composites under mild conditions is achieved via a cysteamine-assisted coordination-driven route.

Downregulation of lysyl oxidase in venous malformations: Association with vascular destabilization and sclerotherapy.

Venous malformations (VM) are localized defects in vascular morphogenesis manifested by dilated venous channels with reduced perivascular cell coverage. As a vital enzyme for extracellular matrix (ECM) deposition, lysyl oxidase (LOX) plays important roles in vascular development and diseases. However, the expression and significance of LOX are unknown in VM.

Controllable Synthesis of All Inorganic Lead Halide Perovskite Nanocrystals with Various Appearances in Multiligand Reaction System.

All inorganic cesium lead halide (CsPbX, X = Cl, Br, I) perovskite nanocrystals (PNCs) exhibit promising applications in light-emitting devices due to their excellent photophysical properties. Herein, we developed a low-cost and convenient method for the preparation of CsPbX PNCs in a multiligand-assisted reaction system where peanut oil is applied as a ligand source. The mixed-halide PNCs with tunable optical-band gap were prepared by mixing the single-halide perovskite solutions at room temperature.