Oxygen-Binding Sites of Enriched Gold Nanoclusters for Capturing Mitochondrial Reverse Electrons.

Reverse electron transfer (RET), an abnormal backward flow of electrons from complexes III/IV to II/I of mitochondria, causes the overproduction of a reduced-type CoQ to boost downstream production of mitochondrial superoxide anions that leads to ischemia-reperfusion injury (IRI) to organs. Herein, we studied low-coordinated gold nanoclusters (AuNCs) with abundant oxygen-binding sites to form an electron-demanding trapper that allowed rapid capture of electrons to compensate for the CoQ/CoQH2 imbalance during RET. The AuNCs were composed of only eight gold atoms that formed a Cs-symmetrical configuration with all gold atoms exposed on the edge site. The geometry and atomic configuration enhance oxygen intercalation to attain a d-band electron deficiency in frontier orbitals, forming an unusually high oxidation state for rapid mitochondrial reverse electron capture under a transient imbalance of CoQ/CoQH2 redox cycles. Using hepatic IRI cells/animals, we corroborated that the CoQ-like AuNCs prevent inflammation and liver damage from IRI via recovery of the mitochondrial function.

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, CO2 electroreduction reaction (CO2RR) is spatially and temporally understood as a result of intricate interactions at the interface, in which the interfacial features are highly relevant. We start with the discussion of current understandings and model development associated with the charged electrochemical interface as well as its dynamic landscape. We further highlight the interactive dynamics from the interfacial field, catalyst surface charges and various gradients in electrolyte and interfacial water structures at interfaces under CO2RR working conditions, with emphasis on the interfacial-structure dependence of catalytic reactivity/selectivity. Significantly, a probing energy-dependent "in situ characterization map" for dynamic interfaces based on various complementary in situ/operando techniques is proposed, aiming to present a comprehensive picture of interfacial electrocatalysis and to provide a more unified research framework. Moreover, recent milestones in both experimental and theoretical aspects to establish the correct profile of electrochemical interfaces are stressed. Finally, we present key scientific challenges with related perspectives toward future opportunities for this exciting frontier.

[Research progress in raw and processed Raphani Semen and prediction of quality markers].

Raphani Semen, with both edible and medicinal values, is a typical Chinese herbal medicine with different effects before and after processing. The raw helps ascending and the cooked helps descending. This paper comprehensively summarizes the differences in chemical constituents and pharmacological effects between raw and processed Raphani Semen that are reported in recent years. Based on the principle of quality markers(Q-markers) of traditional Chinese medicines, the chemical constituent sources, chemical constituent detection techniques, and correlation between bidirectional regulatory efficacy and chemical constituents are compared between raw and processed Raphani Semen. The results suggest that sulforaphene and glucoraphanin could be used as candidate Q-markers of raw and processed Raphani Semen, respectively. This review is expected to provide a reference for further research on the processing, new drug development, and improvement of safety and effectiveness of Raphani Semen in clinical application.

Light-Induced Dynamic Activation of Copper/Silicon Interface for Highly Selective Carbon Dioxide Reduction.

Numerous studies have shown a fact that phase transformation and/or reconstruction are likely to occur and play crucial roles in electrochemical scenarios. Nevertheless, a decisive factor behind the diverse photoelectrochemical activity and selectivity of various copper/silicon photoelectrodes is still largely debated and missing in the community, especially the possibly dynamic behaviors of metal catalyst/semiconductor interface. Herein, through in situ X-ray absorption spectroscopy and transmission electron microscope, a model system of Cu nanocrystals with well-defined facets on black p-type silicon (BSi) is unprecedentedly demonstrated to reveal the dynamic phase transformation of forming irreversible silicide at Cu nanocrystal-BSi interface during photoelectrocatalysis, which is validated to originate from the atomic interdiffusion between Cu and Si driven by light-induced dynamic activation process. Significantly, the adaptive junction at Cu-Si interface is activated by an expansion of interatomic Cu-Cu distance for CO2 electroreduction, which efficiently restricts the C-C coupling pathway but strengthens the bonding with key intermediate of *CHO for CH4 yield, resulting in a remarkable 16-fold improvement in the product ratio of CH4/C2 products and an intriguing selectivity switch. This work offers new insights into dynamic structural transformations of metal/semiconductor junction and design of highly efficient catalysts toward photosynthesis.

Theory-Guided Design of Unconventional Phase Metal Heteronanostructures for Higher-Rate Stable Li-CO2 and Li-Air Batteries.

Lithium-carbon dioxide (Li-CO2) and Li-air batteries hold great potential in achieving carbon neutral given their ultrahigh theoretical energy density and eco-friendly features. However, these Li-gas batteries still suffer from low discharging-charging rate and poor cycling life due to sluggish decomposition kinetics of discharge products especially Li2CO3. Here we report the theory-guided design and preparation of unconventional phase metal heteronanostructures as cathode catalysts for high-performance Li-CO2/air batteries. The assembled Li-CO2 cells with unconventional phase 4H/face-centered cubic (fcc) ruthenium-nickel heteronanostructures deliver a narrow discharge-charge gap of 0.65 V, excellent rate capability and long-term cycling stability over 200 cycles at 250 mA g-1. The constructed Li-air batteries can steadily run for above 150 cycles in ambient air. Electrochemical mechanism studies reveal that 4H/fcc Ru-Ni with high-electroactivity facets can boost redox reaction kinetics and tune discharge reactions towards Li2C2O4 path, alleviating electrolyte/catalyst failures induced by the aggressive singlet oxygen from solo decomposition of Li2CO3.

Dealloying-Induced Zeolite-like Metal Framework of AB2 Laves Phase Intermetallic Electrocatalysts.

Exploring an efficient and robust electrocatalyst for hydrogen evolution reaction (HER) at high pH and temperature holds the key to the industrial application of alkaline water electrolysis (AWE). Herein, we design an open tunnel structure by dealloying a series of Laves phase intermetallics, i.e., MCo2 and MRu0.25Co1.75 (M = Sc and Zr). The dealloying process can induce a zeolite-like metal framework for ScCo2 and ScRu0.25Co1.75 by stripping Sc metal from the center of a tunnel structure. This structural engineering significantly lowers their overpotentials at a current density of 500 mA/cm2 (η500) ca. 80 mV in 1.0 M KOH. Through a simple process, ScRu0.25Co1.75 can be easily decorated on a carbon cloth substrate and only requires 132 mV to reach 500 mA/cm2. More importantly it can maintain activity over 1000 h in industrial conditions (6.0 M KOH at 333 K), showing its potential for practical industrial applications.

Lewis Acidic Support Boosts C-C Coupling in the Pulsed Electrochemical CO2 Reaction.

Copper-oxide electrocatalysts have been demonstrated to effectively perform the electrochemical CO2 reduction reaction (CO2RR) toward C2+ products, yet preserving the reactive high-valent CuOx has remained elusive. Herein, we demonstrate a model system of Lewis acidic supported Cu electrocatalyst with a pulsed electroreduction method to achieve enhanced performance for C2+ products, in which an optimized electrocatalyst could reach ∼76% Faradaic efficiency for C2+ products (FEC2+) at ∼-0.99 V versus reversible hydrogen electrode, and the corresponding mass activity can be enhanced by ∼2 times as compared to that of conventional CuOx. In situ time-resolved X-ray absorption spectroscopy investigating the dynamic chemical/physical nature of Cu during CO2RR discloses that an activation process induced by the KOH electrolyte during pulsed electroreduction greatly enriched the Cuδ+O/Znδ+O interfaces, which further reveals that the presence of Znδ+O species under the cathodic potential could effectively serve as a Lewis acidic support for preserving the Cuδ+O species to facilitate the formation of C2+ products, and the catalyst structure-property relationship of Cuδ+O/Znδ+O interfaces can be evidently realized. More importantly, we find a universality of stabilizing Cuδ+O species for various metal oxide supports and to provide a general concept of appropriate electrocatalyst-Lewis acidic support interaction for promoting C2+ products.

Reversibly Adapting Configuration in Atomic Catalysts Enables Efficient Oxygen Electroreduction.

Single-atom catalysts (SACs) featuring M-N-C moieties have garnered significant attention as efficient electrocatalysts for the oxygen reduction reaction (ORR). However, the role of the dynamic M-N configuration of SACs induced by the derived frameworks under applied ORR potentials remains poorly understood. Herein, we conduct a comprehensive investigation using multiple operando techniques to assess the dynamic configurations of Cu SACs under various microstructural interface (MSI) regulations by anchoring atomic Cu on g-C3N4 and zeolitic imidazolate framework (ZIF) substrates. Cu SACs supported on g-C3N4 exhibit symmetric Cu-N configurations characterized by a reversibly adaptive nature under operational conditions, which leads to their excellent ORR catalytic activity. In contrast, the Cu-N configuration in ZIF-derived Cu SACs undergoes irreversible structural changes during the ORR process, in which the elongated Cu-N pair is unstable and breaks during the ORR, acting as a competing reaction against the ORR and resulting in high overpotential requirements. Crucially, operando time-resolved X-ray absorption spectroscopy (TR-XAS) and Raman results unequivocally reveal the reversibly adapting properties of the local Cu-N configuration in atomic Cu-anchored g-C3N4, which have been overlooked in numerous literatures. All findings provide valuable insights into the potential-driven characteristics of atomic electrocatalysts during target reactions and offer a systematic approach to study atomic electrocatalysts and their corresponding catalytic behaviors.

Atomic Interface Engineering of Single-Atom Pt/TiO2 -Ti3 C2 for Boosting Photocatalytic CO2 Reduction.

Solar-driven CO2 conversion into valuable fuels is a promising strategy to alleviate the energy and environmental issues. However, inefficient charge separation and transfer greatly limits the photocatalytic CO2 reduction efficiency. Herein, single-atom Pt anchored on 3D hierarchical TiO2 -Ti3 C2 with atomic-scale interface engineering is successfully synthesized through an in situ transformation and photoreduction method. The in situ growth of TiO2 on Ti3 C2 nanosheets can not only provide interfacial driving force for the charge transport, but also create an atomic-level charge transfer channel for directional electron migration. Moreover, the single-atom Pt anchored on TiO2 or Ti3 C2 can effectively capture the photogenerated electrons through the atomic interfacial PtO bond with shortened charge migration distance, and simultaneously serve as active sites for CO2 adsorption and activation. Benefiting from the synergistic effect of the atomic interface engineering of single-atom Pt and interfacial TiOTi, the optimized photocatalyst exhibits excellent CO2 -to-CO conversion activity of 20.5 µmol g-1  h-1 with a selectivity of 96%, which is five times that of commercial TiO2 (P25). This work sheds new light on designing ideal atomic-scale interface and single-atom catalysts for efficient solar fuel conversation.

Atomic Metal-Support Interaction Enables Reconstruction-Free Dual-Site Electrocatalyst.

Real bifunctional electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction have to be the ones that exhibit a steady configuration during/after reaction without irreversible structural transformation or surface reconstruction. Otherwise, they can be termed as "precatalysts" rather than real catalysts. Herein, through a strongly atomic metal-support interaction, single-atom dispersed catalysts decorating atomically dispersed Ru onto a nickel-vanadium layered double hydroxide (LDH) scaffold can exhibit excellent HER and OER activities. Both in situ X-ray absorption spectroscopy and operando Raman spectroscopic investigation clarify that the presence of atomic Ru on the surface of nickel-vanadium LDH is playing an imperative role in stabilizing the dangling bond-rich surface and further leads to a reconstruction-free surface. Through strong metal-support interaction provided by nickel-vanadium LDH, the significant interplay can stabilize the reactive atomic Ru site to reach a small fluctuation in oxidation state toward cathodic HER without reconstruction, while the atomic Ru site can stabilize the Ni site to have a greater structural tolerance toward both the bond constriction and structural distortion caused by oxidizing the Ni site during anodic OER and boost the oxidation state increase in the Ni site that contributes to its superior OER performance. Unlike numerous bifunctional catalysts that have suffered from the structural reconstruction/transformation for adapting the HER/OER cycles, the proposed Ru/Ni3V-LDH is characteristic of steady dual reactive sites with the presence of a strong metal-support interaction (i.e., Ru and Ni sites) for individual catalysis in water splitting and is revealed to be termed as a real bifunctional electrocatalyst.

Engineering Lattice Disorder on a Photocatalyst: Photochromic BiOBr Nanosheets Enhance Activation of Aromatic C-H Bonds via Water Oxidation.

Solar-driven photocatalytic reactions can mildly activate hydrocarbon C-H bonds to produce value-added chemicals. However, the inefficient utilization of photogenerated carriers hinders the application. Here, we report reversible photochromic BiOBr (denoted as p-BiOBr) nanosheets that were colored by trapping photogenerated holes upon visible light irradiation and bleached by water oxidation to generate hydroxyl radicals, demonstrating enhanced carrier separation and water oxidation. The photocatalytic coupling and oxidation reactions of ethylbenzene were efficiently realized by p-BiOBr in a water-based medium under ambient temperature and pressure (apparent quantum yield is 14 times that of pristine BiOBr). The p-BiOBr nanosheets feature lattice disordered defects on the surface, providing rich uncoordinated catalytic sites and inducing structural distortions and lattice strain, which further leads to an altered band structure and significantly enhanced photocatalytic performances. These hole-trapping materials open up the possibility of substantially elevating the utilization efficiency of photogenerated holes for high-efficiency photocatalytic activation of various saturated C-H bonds.

Hetero-Atomic Pairs with a Distal Fe3+ -Site Boost Water Oxidation.

The hetero-atomic interaction has been the subject of many investigations, due to their heterogeneity, the individual roles of the atoms are still difficult to realize. Herein, an electrocatalyst with a hetero-atomic pair confined on a tungsten phosphide (WP) substrate so that the Fe3+ -site of the pair is distal to the surface is shown to deliver an extremely low overpotential of 192 mV at 10 mA cm-2 and one of the highest oxygen production turnover frequencies (TOF) of 2.1 s-1 at 300 mV under alkaline environment for the oxygen evolution reaction (OER). Operando characterization shows the Lewis acidic Fe3+ site boosts a large population of Co4+/3+ and the deprotonation of coordinated water, allowing simultaneously enhanced electron-transfer as well as the proton-transfer. A significant contribution from the WP substrate modulates the order of hydroxide transfer in the pre-equilibrium step (PES) and rate-determining-step (RDS), leading to a remarkable OER performance.

[Risk factors for recurrence after intravitreal anti-vascular endothelial growth factor injection for retinopathy of prematurity]. / çŽ»ç’ƒä½“è ”å† æ³¨å°„æŠ—è¡€ç®¡å† çš®ç”Ÿé•¿å› å­æ²»ç–—æ—©äº§å„¿è§†ç½‘è†œç— å¤å‘çš„å±é™©å› ç´ åˆ†æž.

OBJECTIVES: To investigate the efficacy of intravitreal anti-vascular endothelial growth factor (anti-VEGF) injection in the treatment of retinopathy of prematurity (ROP) and the risk factors for recurrence. METHODS: A retrospective analysis was performed on the medical data of 159 infants with ROP who were born in the First Affiliated Hospital of Zhengzhou University and underwent anti-VEGF treatment from January 2016 to December 2021. According to the presence or absence of recurrence within the follow-up period after initial anti-VEGF treatment, they were divided into a recurrence group with 24 infants and a non-recurrence group with 135 infants. The medical data were compared between the two groups, and a multivariate logistic regression analysis was used to investigate the risk factors for the recurrence of ROP after anti-VEGF treatment. RESULTS: After one-time anti-VEGF treatment, all 159 infants showed regression of plus disease. Recurrence was observed in 24 infants (15.1%) after anti-VEGF treatment, with a mean interval of (8.4±2.6) weeks from treatment to recurrence. The multivariate logistic regression analysis showed that preoperative fundus hemorrhage and prolonged total oxygen supply time were risk factors for the recurrence of ROP (P<0.05), while gestational hypertension was a protective factor (P<0.05). CONCLUSIONS: Intravitreal anti-VEGF injection is effective for ROP. Preoperative fundus hemorrhage and long duration of oxygen therapy may increase the risk of ROP recurrence, and further studies are needed to investigate the influence of gestational hypertension on the recurrence of ROP.

In Situ Identifying the Dynamic Structure behind Activity of Atomically Dispersed Platinum Catalyst toward Hydrogen Evolution Reaction.

Single-atom catalysts (SAs) with the maximum atom utilization and breakthrough activities toward hydrogen evolution reaction (HER) have attracted considerable research interests. Uncovering the nature of single-atom metal centers under operating electrochemical condition is highly significant for improving their catalytic performance, yet is poorly understood in most studies. Herein, Pt single atoms anchoring on the nitrogen-carbon substrate (PtSA /N-C) as a model system are utilized to investigate the dynamic structure of Pt single-atom centers during the HER process. Via in situ/operando synchrotron X-ray absorption spectroscopy and X-ray photoelectron spectroscopy, an intriguing structural reconstruction at atomic level is identified in the PtSA /N-C when it is subjected to the repetitive linear sweep voltammetry and cyclic voltammetry scanning. It demonstrates that the PtN bonding tends to be weakened under cathodic potentials, which induces some Pt single atoms to dynamically aggregate into forming small clusters during the HER reaction. More importantly, experimental evidence and/or indicator is offered to correlate the observed Tafel slope with the dynamic structure of Pt catalysts. This work provides an evident understanding of SAs under electrocatalytic process and offers informative insights into constructing efficient catalysts at atomic level for electrochemical water-splitting system.

Heterocyclic-Additive-Activated Dinuclear Dysprosium Electrocatalysts for Heterogeneous Water Oxidation.

Heterogeneous catalysis based on air-stable lanthanide complexes is relatively rare, especially for electrochemical water oxidation and reduction. Therefore, it is highly desired to investigate the synergy caused by cocatalysts on the lanthanide complex family for heterogeneous catalysis because of their structural diversity, air/moisture insensitivity, and easy preparation under an air atmosphere. Two mononuclear and three dinuclear dysprosium complexes containing a series of Schiff-base ligands have been demonstrated as robust electrocatalysts for triggering heterogeneous water oxidation in alkaline solution, in which the complex [Dy2(hmb)2(OAc)4]·MeCN(3) was revealed to have the best activity toward heterogeneous water oxidation among all five complexes in the present study. The molecular activation of dysprosium complexes has also been investigated with a series of N-containing heterocyclic additives [i.e., 4-(dimethylamino)pyridine (DMAP), bis(triphenylphosphine)iminium chloride ([PPN]Cl), indole, and quinoline]. In particular, the corresponding overpotential was effectively enhanced by 211 mV (at a current density of 10 mA cm-2) with the assistance of DMAP. On the basis of electrochemical and ex situ/in situ spectroscopic investigations, the best catalyst, DMAP-complex 3 on a carbon paper electrode, was confirmed with well-maintained molecular identity during heterogeneous water oxidation free of forming any dysprosium oxide and/or undesired products.

Linking the Dynamic Chemical State of Catalysts with the Product Profile of Electrocatalytic CO2 Reduction.

The promoted activity and enhanced selectivity of electrocatalysts is commonly ascribed to specific structural features such as surface facets, morphology, and atomic defects. However, unraveling the factors that really govern the direct electrochemical reduction of CO2 (CO2 RR) is still very challenging since the surface state of electrocatalysts is dynamic and difficult to predict under working conditions. Moreover, theoretical predictions from the viewpoint of thermodynamics alone often fail to specify the actual configuration of a catalyst for the dynamic CO2 RR process. Herein, we re-survey recent studies with the emphasis on revealing the dynamic chemical state of Cu sites under CO2 RR conditions extracted by in situ/operando characterizations, and further validate a critical link between the chemical state of Cu and the product profile of CO2 RR. This point of view provides a generalizable concept of dynamic chemical-state-driven CO2 RR selectivity that offers an inspiration in both fundamental understanding and efficient electrocatalysts design.

Electrocatalytic Methane Functionalization with d0 Early Transition Metals Under Ambient Conditions.

The undesirable loss of methane (CH4 ) at remote locations welcomes approaches that ambiently functionalize CH4 on-site without intense infrastructure investment. Recently, we found that electrochemical oxidation of vanadium(V)-oxo with bisulfate ligand leads to CH4 activation at ambient conditions. The key question is whether such an observation is a one-off coincidence or a general strategy for electrocatalyst design. Here, a general scheme of electrocatalytic CH4 activation with d0 early transition metals is established. The pre-catalysts' molecular structure, electrocatalytic kinetics, and mechanism were detailed for titanium (IV), vanadium (V), and chromium (VI) species as model systems. After a turnover-limiting one-electron electrochemical oxidation, the yielded ligand-centered cation radicals activate CH4 with low activation energy and high selectivity. The reactivities are universal among early transition metals from Period 4 to 6, and the reactivities trend for different early transition metals correlate with their d orbital energies across periodic table. Our results offer new chemical insights towards developing advanced ambient electrocatalysts of natural gas.

A Universal Approach for Controllable Synthesis of n-Specific Layered 2D Perovskite Nanoplates.

2D perovskites with chemical formula A'2 An-1 Bn X3n+1 have recently attracted considerable attention due to their tunable optical and electronic properties, which can be attained by varying the chemical composition. While high color-purity emitting perovskite nanomaterials have been accomplished through changing the halide composition, the preparation of single-phase, specific n-layer 2D perovskite nanomaterials is still pending because of the fast nucleation process of nanoparticles. We demonstrate a facile, rational and efficacious approach to synthesizing single-phase 2D perovskite nanoplates with a designated n number for both lead- and tin-based perovskites through kinetic control. Casting carboxylic acid additives in the reaction medium promotes selective formation of the kinetic product-multilayer 2D perovskite-in preference to the single-layer thermodynamic product. For the n-specific layered 2D perovskites, decreasing the number of octahedral layers per inorganic sheet leads to an increase of photoluminescence energy, radiative decay rate, and a significant boost in photostability.

Materials Engineering of Violin Soundboards by Stradivari and Guarneri.

We investigated the material properties of Cremonese soundboards using a wide range of spectroscopic, microscopic, and chemical techniques. We found similar types of spruce in Cremonese soundboards as in modern instruments, but Cremonese spruces exhibit unnatural elemental compositions and oxidation patterns that suggest artificial manipulation. Combining analytical data and historical information, we may deduce the minerals being added and their potential functions-borax and metal sulfates for fungal suppression, table salt for moisture control, alum for molecular crosslinking, and potash or quicklime for alkaline treatment. The overall purpose may have been wood preservation or acoustic tuning. Hemicellulose fragmentation and altered cellulose nanostructures are observed in heavily treated Stradivari specimens, which show diminished second-harmonic generation signals. Guarneri's practice of crosslinking wood fibers via aluminum coordination may also affect mechanical and acoustic properties. Our data suggest that old masters undertook materials engineering experiments to produce soundboards with unique properties.

Mechanism of Oxygen Evolution Catalyzed by Cobalt Oxyhydroxide: Cobalt Superoxide Species as a Key Intermediate and Dioxygen Release as a Rate-Determining Step.

The oxygen evolution reaction (OER) is the performance-limiting half reaction of water splitting, which can be used to produce hydrogen fuel using renewable energies. Whereas a number of transition metal oxides and oxyhydroxides have been developed as promising OER catalysts in alkaline medium, the mechanisms of OER on these catalysts are not well understood. Here we combine electrochemical and in situ spectroscopic methods, particularly operando X-ray absorption and Raman spectroscopy, to study the mechanism of OER on cobalt oxyhydroxide (CoOOH), an archetypical unary OER catalyst. We find the dominating resting state of the catalyst as a Co(IV) species CoO2. Through oxygen isotope exchange experiments, we discover a cobalt superoxide species as an active intermediate in the OER. This intermediate is formed concurrently to the oxidation of CoOOH to CoO2. Combing spectroscopic and electrokinetic data, we identify the rate-determining step of the OER as the release of dioxygen from the superoxide intermediate. The work provides important experimental fingerprints and new mechanistic perspectives for OER catalysts.