Synergistic Effects of Doping and Strain in Bismuth Catalysts for CO2 Electroreduction.

Doping is a recognized method for enhancing catalytic performance. The introduction of strains is a common consequence of doping, although it is often overlooked. Differentiating the impact of doping and strain on catalytic performance poses a significant challenge. In this study, Cu-doped Bi catalysts with substantial tensile strain are synthesized. The synergistic effects of doping and strain in bismuth result in a remarkable CO2RR performance. Under optimized conditions, Cu1/6-Bi demonstrates exceptional formate Faradaic efficiency (>95%) and maintains over 90% across a wide potential window of 900 mV. Furthermore, it delivers an industrial-relevant partial current density of -317 mA cm-2 at -1.2 VRHE in a flow cell, while maintaining its selectivity. Additionally, it exhibits exceptional long-term stability, surpassing 120 h at -200 mA cm-2. Through experimental and theoretical mechanistic investigations, it has been determined that the introduction of tensile strain facilitates the adsorption of *CO2, thereby enhancing the reaction kinetics. Moreover, the presence of Cu dopants and tensile strain further diminishes the energy barrier for the formation of *OCHO intermediate. This study not only offers valuable insights for the development of effective catalysts for CO2RR through doping, but also establishes correlations between doping, lattice strains, and catalytic properties of bismuth catalysts.

Esculin suppresses the PERK-eIF2α-CHOP pathway by enhancing SIRT1 expression in oxidative stress-induced rat chondrocytes, mitigating osteoarthritis progression in a rat model.

OBJECTIVE: Osteoarthritis (OA) is a degenerative disease characterized by the gradual degeneration of chondrocytes, involving endoplasmic reticulum (ER) stress. Esculin is a natural compound with antioxidant, anti-inflammatory and anti-tumor properties. However, its impact on ER stress in OA therapy has not been thoroughly investigated. We aim to determine the efficiency of Esculin in OA treatment and its underlying mechanism. METHODS: We utilized the tert-butyl hydroperoxide (TBHP) to establish OA model in chondrocytes. The expression of SIRT1, PERK/eIF2α pathway-related proteins, apoptosis-associated proteins and ER stress-related proteins were detected by Western blot and Real-time PCR. The apoptosis was evaluated by flow cytometry and terminal deoxynucleotidyl transferase-mediated dUTP nick-end labeling (TUNEL) staining. X-ray imaging, Hematoxylin & Eosin staining, Safranin O staining and immunohistochemistry were used to assess the pharmacological effects of Esculin in the anterior cruciate ligament transection (ACLT) rat OA model. RESULTS: Esculin downregulated the expression of PERK/eIF2α pathway-related proteins, apoptosis-associated proteins and ER stress-related proteins, while upregulated the expression of SIRT1 and Bcl2 in the TBHP-induced OA model in vitro. It was coincident with the results of TUNEL staining and flow cytometry. We further confirmed the protective effect of Esculin in the rat ACLT-related model. CONCLUSION: Our results suggest the potential therapeutic value of Esculin on osteoarthritis. It probably inhibits the PERK-eIF2α-ATF4-CHOP pathway by upregulating SIRT1, thereby mitigating endoplasmic reticulum stress and protecting chondrocytes from apoptosis.

Porphyrin-Thiophene Based Conjugated Polymer Cathode with High Capacity for Lithium-Organic Batteries.

Organic electrode materials are promising for next-generation energy storage materials due to their environmental friendliness and sustainable renewability. However, problems such as their high solubility in electrolytes and low intrinsic conductivity have always plagued their further application. Polymerization to form conjugated organic polymers can not only inhibit the dissolution of organic electrodes in the electrolyte, but also enhance the intrinsic conductivity of organic molecules. Herein, we synthesized a new conjugated organic polymer (COPs) COP500-CuT2TP (poly [5,10,15,20-tetra(2,2'-bithiophen-5-yl) porphyrinato] copper (II)) by electrochemical polymerization method. Due to the self-exfoliation behavior, the porphyrin cathode exhibited a reversible discharge capacity of 420 mAh g-1, and a high specific energy of 900 Wh Kg-1 with a first coulombic efficiency of 96 % at 100 mA g-1. Excellent cycling stability up to 8000 cycles without capacity loss was achieved even at a high current density of 5 A g-1. This highly conjugated structure promotes COP500-CuT2TP combined high energy density, high power density, and good cycling stability, which would open new opportunity for the designable and versatile organic electrodes for electrochemical energy storage.

Ni/Mg Dual Concentration-Gradient Surface Modification to Enhance Structural Stability and Electrochemical Performance of Li-Rich Layered Oxides.

Li-rich layered oxides (LRLOs), with the advantages of high specific capacity and low cost, are considered as candidates for the next-generation cathode of lithium-ion batteries (LIBs). Unfortunately, sluggish kinetics and interfacial degradation lead to capacity loss and voltage decay of the material during cycling. To address these issues, we propose a Ni/Mg dual concentration-gradient modification strategy for LRLOs. From the center to the surface of the modified materials, the contents of Ni and Mg are gradually increased while the content of Mn is decreased. The high Ni content on the surface increases the proportion of cationic redox, elevating the operating voltage and accelerating reaction kinetics. Moreover, the doped Mg on the surface of the material acting as a stabilizing pillar suppresses the migration of transition metals, stabilizing the layered structure. Therefore, the material with the Ni/Mg dual concentration-gradients delivers a superior electrochemical performance, exhibiting a suppressed voltage decay of 2.8 mV per cycle during 200 cycles (1 C, 2-4.8 V) and an excellent rate capability of 94.84 mAh/g at 7C. This study demonstrates a synergic design to construct high-performance LRLO cathode materials for LIBs.

Regulating Grind-Induced Lattice Distortion for Nickel-Rich Cathodes by Annealing.

The commercialization of high-performance nickel-rich cathodes always awaits a cost-effective, environmentally friendly, and large-scale preparation method. Despite a grinding process normally adopted in the synthesis of the nickel-rich cathodes, lattice distortion, rough surface, and sharp edge transformation inevitably occurr in the resultant samples. In this work, an additional annealing process is proposed that aims at regulating lattice distortion as well as achieving round and smoother morphologies without any structural or elemental modifications. Such a structural enhancement is favored for improved lithium diffusion and electrochemical stability during cycling. Consequently, the annealed cathodes demonstrate a considerable enhancement in capacity retention, escalating from 68.7% to 91.9% after 100 cycles at 1 C. Additionally, the specific capacity is significantly increased from 64 to 142 mAh g-1 at 5 C when compared to the unannealed cathodes. This work offers a straightforward and effective approach for reinforcing the electrochemical properties of nickel-rich cathodes.

Multiple Heteroatom-Hydrogen Bonds Bridging Electron Transport in Covalent Organic Framework-Based Supramolecular System for Photoreduction of CO2.

Supramolecular systems consisting of covalent organic frameworks (COFs) and Ni complex are designed for robust photocatalytic reduction of CO2 . Multiple heteroatom-hydrogen bonding between the COF and Ni complex is identified to play a decisive role in the photoexcited electron transfer across the liquid-solid interface. The diminution of steric groups on COF or metal complex can optimize catalytic performance, which is more attributable to the enhanced hydrogen-bond interaction rather than their intrinsic activity. The photosystem with relatively strong strength of hydrogen bonds exhibits remarkable photocatalytic CO2 -to-CO conversion, far superior to photosystems with supported atomic Ni or metal complex alone in the absence of hydrogen-bond effect. Such heteroatom-hydrogen bonds bridging electron transport pathway confers supramolecular system with high photocatalytic performance, providing an avenue to rationally design efficient and steadily available photosystems.

Spontaneous Desaturation of the Solvation Sheath for High-Performance Anti-Freezing Zinc-Ion Gel-Electrolyte.

In recent years, gel-electrolyte becomes pivotal in preventing hydrogen evolution, reducing dendrite growth, and protecting the zinc metal anode for zinc-ion batteries. Herein, a polyvinyl alcohol-based water-organic hybrid gel electrolyte with Agar and dimethyl sulfoxide is designed to construct the spontaneous desaturation of the solvation sheath for reducing hydrogen evolution and dendrite growth at room temperature and even low temperature. According to experimental characterization and theoretical calculations, the well binding between multihydroxy polymer and H2 O is achieved in the hybrid desaturated gel-electrolyte to regulate the inner and outer sheath. The ionic conductivity of hybrid gel-electrolyte reaches 7.4 mS cm-1 even at -20 °C with only 0.5 m zinc trifluoromethanesulfonate (Zn(OTf)2 ). The Zn symmetric cells cycle over 1200 h under 26 and -20 °C with improved mechanical properties and electrochemical performance. The asymmetric Zn || Cu cell with hybrid gel electrolyte reaches ≈99.02% efficiency after 250 cycles. The capacity of full cell is maintained at around 74 mAh g-1 with almost unchanged retention rate from 50 to 300 cycles at -20 °C. This work provides an effective strategy for desaturated solvation to reach anti-freezing and high-density Zn energy storage devices.

Atomic-Scale Insights into the Self-Assembly of Alternating AlN/TiN Lamellar Nanostructures via Spinodal Decomposition in AlTiN Coating.

The self-assembly mechanism of alternating AlN/TiN nano-lamellar structures in AlTiN coating is still a mystery, though this coating has been widely used in industry. Here, by using the phase-field crystal method, we studied the atomic-scale mechanisms of the formation of nano-lamellar structures during spinodal decomposition transformation of an AlTiN coating. The results show that the formation of a lamella is characterized by four distinct stages including the generation of dislocations (stage I), formation of islands (stage II), merging of islands (stage III), and flattening of lamellae (stage IV). The locally periodic fluctuation of the concentration along the lamella leads to the generation of periodically distributed misfit dislocations and then AlN/TiN islands, while the fluctuation of the composition in the direction normal to the lamella is responsible for the merging of islands and flattening of a lamella and more importantly the cooperative growth between neighboring lamellae. Moreover, we found that misfit dislocations play a crucial role in all the four stages, promoting the cooperative growth of TiN and AlN lamellae. Our results demonstrate that the TiN and AlN lamellae could be produced through the cooperative growth of AlN/TiN lamellae in spinodal decomposition of the AlTiN phase.

In situself-assembly fabrication of ultrathin sheet-like CuS modified g-C3N4heterojunction and its enhanced visible-light photocatalytic performance.

Photocatalysts with heterojunction structure have been widely used for organic degradation. In this study, CuS/g-C3N4heterojunction was formed byin situself-assembly via a simply hydrothermal method. A series of characterizations were applied to analyzing the morphology, structure, optical properties and photo-induced electron transfer of the samples. The effect of CuS mass ratio in the CuS/g-C3N4composite on methyl blue (10 mg l-1) degradation under visible-light illumination was discussed. When CuS mass ratio was 60%, CuS/g-C3N4behaved the highest photocatalytic efficiency which is 17 times higher than that of pure g-C3N4, and the optimal heterojunction exhibited promising photocatalytic stability as well. The synthesized CuS/g-C3N4with intimate contact and promising photocatalytic performance provides important implications on analogous researches on g-C3N4-based heterojunctions for photocatalytic applications.

DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal-Dioxygen Complexes: Distinct Mechanisms and Reaction Rules.

Aldehyde deformylations occurring in organisms are catalyzed by metalloenzymes through metal-dioxygen active cores, attracting great interest to study small-molecule metal-dioxygen complexes for understanding relevant biological processes and developing biomimetic catalysts for aerobic transformations. As the known deformylation mechanisms, including nucleophilic attack, aldehyde α-H-atom abstraction, and aldehyde hydrogen atom abstraction, undergo outer-sphere pathways, we herein report a distinct inner-sphere mechanism based on density functional theory (DFT) mechanistic studies of aldehyde deformylations with a copper (II)-superoxo complex. The inner-sphere mechanism proceeds via a sequence mainly including aldehyde end-on coordination, homolytic aldehyde C-C bond cleavage, and dioxygen O-O bond cleavage, among which the C-C bond cleavage is the rate-determining step with a barrier substantially lower than those of outer-sphere pathways. The aldehyde C-C bond cleavage, enabled through the activation of the dioxygen ligand radical in a second-order nucleophilic substitution (SN2)-like fashion, leads to an alkyl radical and facilitates the subsequent dioxygen O-O bond cleavage. Furthermore, we deduced the rules for the reactions of metal-dioxygen complexes with aldehydes and nitriles via the inner-sphere mechanism. Expectedly, our proposed inner-sphere mechanisms and the reaction rules offer another perspective to understand relevant biological processes involving metal-dioxygen cores and to discover metal-dioxygen catalysts for aerobic transformations.

Three-dimensional transistor arrays for intra- and inter-cellular recording.

Electrical impulse generation and its conduction within cells or cellular networks are the cornerstone of electrophysiology. However, the advancement of the field is limited by sensing accuracy and the scalability of current recording technologies. Here we describe a scalable platform that enables accurate recording of transmembrane potentials in electrogenic cells. The platform employs a three-dimensional high-performance field-effect transistor array for minimally invasive cellular interfacing that produces faithful recordings, as validated by the gold standard patch clamp. Leveraging the high spatial and temporal resolutions of the field-effect transistors, we measured the intracellular signal conduction velocity of a cardiomyocyte to be 0.182 m s-1, which is about five times the intercellular velocity. We also demonstrate intracellular recordings in cardiac muscle tissue constructs and reveal the signal conduction paths. This platform could provide new capabilities in probing the electrical behaviours of single cells and cellular networks, which carries broad implications for understanding cellular physiology, pathology and cell-cell interactions.

Donor-Acceptor Pairs in Covalent Organic Frameworks Promoting Electron Transfer for Metal-Free Photocatalytic Organic Synthesis.

The donor-acceptor-type covalent organic frameworks (COFs) have recently gained increasing interest in photocatalysis, but the photoinduced electron-transfer regimes in the COFs are underexplored. Herein, we demonstrate a designed porphyrinic COF possessing a donor-acceptor structure together with its photocatalytic performance in aerobic coupling of primary amines. The COF could be photoexcited by the full range of visible light to generate electron-hole pairs that could be separated by donor-acceptor pairs. Electron transfer as the mechanism of the reaction from anthracene unit to porphyrin unit was revealed by natural transition orbitals analyses. The electrons migrate to the adsorbed O2 to generate reactive oxidative species. The COF displays remarkable photocatalytic activities in the coupling of amines to imines, which can be explained mainly by the sufficient charge separation and mobility, benefiting from the donor-acceptor pairs in the COF and their interactions to the reactants and intermediates.

Transparent, Flexible Plasmonic Ag NP/PMMA Substrates Using Chemically Patterned Ferroelectric Crystals for Detecting Pesticides on Curved Surfaces.

Transparent and flexible surface-enhanced Raman scattering (SERS) substrates have attracted much interest for the detection of probe molecules on the curved surfaces of real samples, but a facile route to fabricate such substrates is still lacking. Herein, we present a rationally designed, high-performance flexible SERS substrate fabricated using a simple drop and peel-off technique for the ultrasensitive detection of pesticides. The proposed SERS substrate consists of a polymethyl methacrylate (PMMA) film anchored with plasmonic silver nanoparticles (Ag NPs), which are photoreduced using chemically patterned ferroelectric templates. The photoreduced Ag NPs extracted onto the PMMA film offer strong electromagnetic enhancement and produce intensive hotspots for the effective enhancement of the Raman signal. They provide superior SERS performance for the detection of parathion (PT) and fenitrothion (FNT) at trace-level concentrations of 10-9 M and 10-10 M with excellent enhancement factors in the order of 108 and 109, respectively. Moreover, the Ag NP/PMMA SERS substrate has good spot-to-spot uniformity and batch-to-batch reproducibility with the reservation of high detection sensitivity even after the mechanical deformation of bending and torsion up to 50 cycles. The multiplex detection ability is also investigated for the simultaneous detection of PT and FNT. To ensure the practical feasibility, the in-situ, real-time detection of PT and FNT on the curved surfaces of tomato and lemon using a fiber-coupled Raman probe is performed with limits of detection of 4.24 × 10-8 M and 2.74 × 10-9 M. The proposed Ag NP/PMMA flexible SERS substrate possesses unique features, such as easy fabrication through a simple, economical, rapid process, and facilitates straightforward implementation of in-situ SERS detection on curved fruit/vegetable surfaces.

Mechanism of Pd-catalysed C(sp3)-H arylation of thioethers with Ag(I) additives.

Mechanistic studies reveal that Pd-catalyzed C(sp3)-H arylation of thioethers with silver(i) additives takes place via C(sp3)-H activation, oxidative addition and reductive elimination, wherein all steps proceed via the heterodimeric Pd-Ag pathway. Besides, the active heterodimeric Pd-Ag species are detected by mass spectrometry via control experiments.

Bandgap Engineering of an Aryl-Fused Tetrathianaphthalene for Visible-Blind Organic Field-Effect Transistors.

Stability problem of organic semiconductors (OSCs) because of photoabsorption has become a major barrier to large scale applications in organic field-effect transistors (OFETs). It is imperative to design OSCs which are insensitive to visible and near-infrared (VNIR) light to obtain both environmental and operational stability. Herein, taking a 2,3,8,9-tetramethoxy [1,4]benzodithiino[2,3-b][1,4]benzodithiine (TTN2) as an example, we show that controlling molecular configuration is an effective strategy to tune the bandgaps of OSCs for visible-blind OFETs. TTN2 adopts an armchair-like configuration, which is different from the prevailing planar structure of common OSCs. Because of the large bandgap, TTN2 exhibits no photoabsorption in the VNIR region and OFETs based on TTN2 show high environmental stability. The devices worked well after being stored in ambient air, (i.e. in the presence of oxygen and water) and light for over two years. Moreover, the OFETs show no observable response to light irradiation from 405-1,020 nm, which is also favorable for high operational stability.

Mechanistic studies of Cp*Ir(III)/Cp*Rh(III)-catalyzed branch-selective allylic C-H amidation: why is Cp*Ir(III) superior to Cp*Rh(III)?

Density functional theory calculations have revealed the mechanism and origins of the reactivity and regioselectivity of the Cp*Ir(iii)/Cp*Rh(iii)-catalyzed allylic C-H amidation of alkenes and dioxazolones. Generally, the catalytic cycle consists of alkene coordination, C(sp3)-H activation, dioxazolone oxidative addition, reductive elimination and proto-demetallation to give the final amidation product. The C-H activation is found to be the rate-determining step, and it controls the reactivity of the reaction. For the Cp*Ir(iii)-catalyzed system, the C-H activation undergoes an Ir(iii)-assisted proton transfer process with a low energy barrier, elucidating its high reactivity. In contrast, the C-H activation step is more like a direct deprotonation in the Cp*Rh(iii)-catalyzed system, which is responsible for its higher barrier and lower reactivity. The branched-selectivity arises from the electronic effect of the alkyl group on the charge distribution over the allylic moiety. Herein, iridium(v) polarizes the allylic group greater than that of the rhodium(v) system, which accounts for its good regioselectivity. The mechanistic insights will be useful for the further development of transition metal-catalyzed selective C-H amination reactions.

Zinc Manganate: Synthesis, Characterization, and Electrochemical Application toward Flufenamic Acid Detection.

The construction of novel electrocatalysts for efficient and economic electrochemical sensors is continuously a significant conceptual barrier for the point-of-care technology. Binary metal oxides with heterostructures have gained plenty of attention due to their promising physicochemical properties. Herein, we develop a rapid and sensitive electrochemical probe for the detection of flufenamic acid (FFA) by using a zinc manganate (ZnMnO)-modified electrode. The formation of ZnMnO was confirmed by various analytical techniques, such as X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and field-emission scanning electron microscopy with energy dispersive X-ray spectroscopy and elemental mapping. The ZnMnO-based electrocatalyst, which was used for the electrochemical detection of FFA, shows better performance than the previously reported electrode materials. The ZnMnO assay shows a linear quantitative range from 0.05 to 116 µM with a limit of detection of 0.003 µM and sensitivity of 0.385 µA µM-1 cm-2. Its good electrochemical performance can be ascribed to the large surface area, rapid charge mass transfer, copious active sites, and high carrier mobility. The electrochemical study displays that the fabricated ZnMnO-based sensor has the potential to be applied in the clinical analysis. This work constructs an advanced functional electrode material with a microscale architecture for the point-of-care technology.

Cocrystal Engineering: Toward Solution-Processed Near-Infrared 2D Organic Cocrystals for Broadband Photodetection.

Large-area 2D cocrystals with strong near-infrared (NIR) absorption have been designed and prepared. Driven by the intermolecular charge-transfer (CT) interactions, zinc tetraphenylporphyrin (donor) and C60 (acceptor) self-assemble into a NIR cocrystal with absorption wavelength up to 1080 nm. By tailoring the growth solvents and processes, the cocrystal morphologies can be tuned from 1D nanowires, 2D nanosheets to large-area 2D cocrystal films with length reaching several millimeters. Owing to the highly ordered donor-acceptor arrangement, the CT absorption in the 2D cocrystals is enhanced and is comparable to singlet absorption. The uniform 2D cocrystals, with enhanced CT absorption in the NIR region, displays a high responsivity of 2424 mA W-1 to NIR light and a fast response time of 0.6 s. The excellent device performance is attributed to the generation of long-lived free charge carriers as revealed by transient absorption spectroscopy and optimization of device configuration.

Silver-Promoted Direct Phosphorylation of Bulky C(sp2)-H Bond to Build Fully Substituted ß-Phosphonodehydroamino Acids.

A general and practical cross-dehydrogenative coupling protocol between readily available trisubstituted α,ß-dehydro α-amino carboxylic esters and H-phosphites is described. This C(sp2)-H phosphorylation reaction proceeds with absolute Z-selectivity promoted by silver salt in a radical relay manner. The bulky tetrasubstituted ß-phosphonodehydroamino acids were obtained in grams and added new modules to the toolkit for peptide modifications.

Establishing the carrier scattering phase diagram for ZrNiSn-based half-Heusler thermoelectric materials.

Chemical doping is one of the most important strategies for tuning electrical properties of semiconductors, particularly thermoelectric materials. Generally, the main role of chemical doping lies in optimizing the carrier concentration, but there can potentially be other important effects. Here, we show that chemical doping plays multiple roles for both electron and phonon transport properties in half-Heusler thermoelectric materials. With ZrNiSn-based half-Heusler materials as an example, we use high-quality single and polycrystalline crystals, various probes, including electrical transport measurements, inelastic neutron scattering measurement, and first-principles calculations, to investigate the underlying electron-phonon interaction. We find that chemical doping brings strong screening effects to ionized impurities, grain boundary, and polar optical phonon scattering, but has negligible influence on lattice thermal conductivity. Furthermore, it is possible to establish a carrier scattering phase diagram, which can be used to select reasonable strategies for optimization of the thermoelectric performance.