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.

Prediction of pathological complete response and prognosis in locally advanced rectal cancer.

Background: Colorectal cancer is currently the third most common malignant tumor and the second leading cause of cancer-related death worldwide. Neoadjuvant chemoradiotherapy (nCRT) is standard for locally advanced rectal cancer (LARC). Except for pathological examination after resection, it is not known exactly whether LARC patients have achieved pathological complete response (pCR) before surgery.

All-in-One: Plasmonic Janus Heterostructures for Efficient Cooperative Photoredox Catalysis.

Janus heterostructures consisting of multiple jointed components with distinct properties have gained growing interest in the photoredox catalytic field. Herein, we have developed a facile low-temperature method to gain anisotropic one-dimensional Au-tipped CdS (Au-CdS) nanorods (NRs), followed by assembling Ru molecular co-catalyst (RuN) onto the surface of the NRs. The CdS NRs decorated with plasmonic Au nanoparticles and RuN complex harness the virtues of metal-semiconductor and inorganic-organic interface, giving directional charge transfer channels, spatially separated reaction sites, and enhanced local electric field distribution.

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.

Optical enhancement mode 2 improves the detection rate of gastric neoplastic lesion in high-risk populations: A multicenter randomized controlled clinical study.

Objectives: Detection of early neoplastic lesions is crucial for improving the survival rates of patients with gastric cancer. Optical enhancement mode 2 is a new image-enhanced endoscopic technique that offers bright images and can improve the visibility of neoplastic lesions. This study aimed to compare the detection of neoplastic lesions with optical enhancement mode 2 and white-light imaging (WLI) in a high-risk population.

Efficient and Direct Functionalization of Allylic sp C-H Bonds with Concomitant CO Reduction.

Solar-driven CO reduction integrated with C-C/C-X bond-forming organic synthesis represents a substantially untapped opportunity to simultaneously tackle carbon neutrality and create an atom-/redox-economical chemical synthesis. Herein, we demonstrate the first cooperative photoredox catalysis of efficient and tunable CO reduction to syngas, paired with direct alkylation/arylation of unactivated allylic sp C-H bonds for accessing allylic C-C products, over SiO -supported single Ni atoms-decorated CdS quantum dots (QDs). Our protocol not only bypasses additional oxidant/reductant and pre-functionalization of organic substrates, affording a broad of allylic C-C products with moderate to excellent yields, but also produces syngas with tunable CO/H ratios (1 : 2-5 : 1).

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.

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.

Five-year follow-up on two revascularization methods used on patients with left main artery disease and/or multivessel coronary artery disease.

Background: Coronary artery bypass graft (CABG) and percutaneous coronary intervention (PCI) are the main treatment methods for left main artery disease (LMAD) and triple-vessel coronary artery disease (TVCAD).

Objective: This study aimed to evaluate the five-year post-treatment effects of CABG and PCI in patients with severe coronary vasculopathy.

Methods: A total of 430 patients with LMAD and/or triple-vessel coronary artery disease from November 2014 to July 2015 were enrolled retrospectively in the affiliated cardiovascular hospital of Shanxi Medical University and divided into the CABG group and PCI group.

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.

Functional and Phenotypic Diversity of Microglia: Implication for Microglia-Based Therapies for Alzheimer's Disease.

Alzheimer's disease (AD) is a progressive neurodegenerative disease and is closely associated with the accumulation of β-amyloid (Aβ) and neurofibrillary tangles (NFTs). Apart from Aβ and NFT pathologies, AD patients also exhibit a widespread microglial activation in various brain regions with elevated production of pro-inflammatory cytokines, a phenomenon known as neuroinflammation. In healthy central nervous system, microglia adopt ramified, "surveying" phenotype with compact cell bodies and elongated processes.

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.

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.

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.

Earth-Abundant MoS and Cobalt Phosphate Dual Cocatalysts on 1D CdS Nanowires for Boosting Photocatalytic Hydrogen Production.

Cocatalysts play a significant role in accelerating the catalytic reactions of semiconductor photocatalyst. In particular, a semiconductor assembled with dual cocatalysts, i.e.

3D graphene-based gel photocatalysts for environmental pollutants degradation.

Enormous research interest is devoted to fabricating three-dimensional graphene-based gels (3D GBGs) toward improved conversion of solar energy by virtue of the intrinsic properties of single graphene and 3D porous structure characteristics. Here, this concise minireview is primarily focused on the recent progress on applications of 3D GBGs, including aerogels and hydrogels, in photocatalytic degradation of pollutants from water and air, such as organic pollutants, heavy metal ions, bacteria and gaseous pollutants. In particular, the preponderances of 3D GBG photocatalysts for environmental pollutants degradation have been elaborated.