Search

The construction of p-n heterojunctions is expected to be one of the effective means to improve gas sensitivity. In this research, p-n heterojunctions are successfully constructed by metal oxides derived from metal-organic frameworks (MOFs). MOFs-derived bimetallic Co 3 O 4 /SnO 2 microspheres are prepared by precipitation. Gas-sensing performance shows that the Co 3 O 4 /SnO 2 sensor exhibits an extremely high response ( R a / R g = 641) to 20 ppm of n -butanol at 200 °C, which is 19 times that of pristine SnO 2 . It can detect n -butanol gas at low concentrations, has good selectivity to alcohol gas, and reduces the interference of benzene gas. The improved gas sensitivity can be attributed to the formation of a stable heterojunction between Co 3 O 4 and SnO 2 , resulting in a greater resistance change of Co 3 O 4 /SnO 2 . Co 3 O 4 /SnO 2 inherits the characteristic of high specific surface area of MOFs, which provides abundant sites for the reaction of the target gas and oxygen molecules. Finally, the gas-sensing mechanism of the Co 3 O 4 /SnO 2 -based sensor is discussed in detail.

Superinsulation aerogels are characterized by low tensile strength and brittleness due to their high porosity. To address these limitations, multiscale architectural design inspired by nacre can be employed. This materials design approach offers a promising strategy for enhancing the mechanical strength of aerogel thermal insulation. In this study, we present nacre-inspired multilayer cellulose-silica aerogel configurations. The cellulose "brick" network imparts structural strength to effectively redistribute energy, while the nanoporous "mortar" silica blocks heat transfer, maintaining insulation and fire retardance. The multilayer composites, with a layering configuration of five cellulose layers with four silica layers (5 + 4) and a cellulose layer thickness of 1.42 mm, exhibit a thermal conductivity of 31.3 mW/(m·K), a flexural modulus of 505 MPa, and an impact strength of 7.33 kJ/m 2 . The hydrophobic composite shows a water contact angle of 127°, enhanced soundproofing with a 27% noise reduction, and a carbon footprint of 0.49 kgCO 2 eq/kg. The multilayer cellulose-silica aerogel design provides a robust, eco-friendly thermal insulation solution for green building applications.

A three-dimensional (3D) hierarchical microfiber bundle-based scaffold integrated with silver nanowires (AgNWs) and porous polyurethane (PU) was designed for the Joule heater via a facile dip-coating method. The interconnected micrometer-sized voids and unique hierarchical structure benefit uniform AgNWs anchored and the formation of a high-efficiency 3D conductive network. As expected, this composite exhibits a superior electrical conductivity of 1586.4 S/m and the best electrothermal conversion performance of 118.6 °C at 2.0 V compared to reported wearable Joule heaters to date. Moreover, the durable microfiber bundle-PU network provides strong mechanical properties, allowing for the stable and durable electrothermal performance of such a composite to resist twisting, bending, abrasion, and washing. Application studies show that this kind of Joule heater is suitable for a wide range of applications, such as seat heating, a heating jacket, personal thermal management, etc.

Idiopathic pulmonary fibrosis (IPF) is a progressive and lethal lung disease with an elusive etiology. Aberrant activation of c-Jun N-terminal kinase 1 (JNK1) has been implicated in its pathogenesis. Through a combination of structure-based drug design and structure-activity relationship (SAR) optimization, a series of pyrimidine-2,4-diamine scaffold derivatives have been developed as potent JNK1 inhibitors. Compound E1 was identified with low nanomolar JNK1 inhibitory potency (IC 50 = 2.7 nM). The introduction of a dimethylamine side chain has significantly enhanced the ability of E1 to inhibit c-Jun phosphorylation, surpassing the clinical candidate CC-90001 . Molecular dynamics simulations revealed a binding free energy of -50.46 kcal/mol for E1 . Moreover, E1 displayed satisfactory pharmacokinetic properties, with a bioavailability of 69% in rats. Furthermore, compound E1 exerted significant antifibrotic effects in a bleomycin-induced IPF mouse model and prevented a TGF-β-induced epithelial-to-mesenchymal transition in vitro. These findings position E1 as a promising lead for further drug development targeting IPF.

Organic contaminants with lower Hammett constants are typically more prone to being attacked by reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, the interactions of an organic contaminant with catalytic centers and participating ROS are complex and lack an in-depth understanding. In this work, we observed an abnormal phenomenon in AOPs that the degradation of electron-rich phenolics, such as 4-methoxyphenol, acetaminophen, and 4-presol, was unexpectedly slower than electron-deficient phenolics in a Mn(II)/nitrilotriacetic acid/peroxymonosulfate (Mn(II)/NTA/PMS) system. The established quantitative structure-activity relationship revealed a volcano-type dependence of the degradation rates on the Hammett constants of pollutants. Leveraging substantial analytical techniques and modeling analysis, we concluded that the electron-rich phenolics would inhibit the generation of both primary (Mn(III)NTA) and secondary (Mn(V)NTA) high-valent manganese species through complexation and competition effects. Specifically, the electron-rich phenolics would form a hydrogen bond with Mn(II)/NTA/PMS through outer-sphere interactions, thereby reducing the electrophilic reactivity of PMS to accept the electron transfer from Mn(II)NTA, and slowing down the generation of reactive Mn(III)NTA. Furthermore, the generated Mn(III)NTA is more inclined to react with electron-rich phenolics than PMS due to their higher reaction rate constants (8314 ± 440, 6372 ± 146, and 6919 ± 31 M -1 s -1 for 4-methoxyphenol, acetaminophen, and 4-presol, respectively, as compared with 671 M -1 s -1 for PMS). Consequently, the two-stage inhibition impeded the generation of Mn(V)NTA. In contrast, the complexation and competition effects are insignificant for electron-deficient phenolics, leading to declined reaction rates when the Hammett constants of pollutants increase. For practical applications, such complexation and competition effects would cause the degradation of electron-rich phenolics to be more susceptible to water matrixes, whereas the degradation of electron-deficient phenolics remains largely unaffected. Overall, this study elucidated the intricate interaction mechanisms between contaminants and reactive metal species at both the electronic and kinetic levels, further illuminating their implications for practical treatment.

Biomedical-device-associated infection (BAI) is undoubtedly a major concern and a serious challenge in modern medicine. Therefore, the development of biomedical materials that are capable of resisting or killing bacteria is of great importance. In this work, a croconaine-functionalized polymer with antifouling and near-infrared (NIR) photothermal bactericidal properties was prepared and facilely modified on polypropylene (PP) to combat medical device infections. Croconaine dye is elaborately modified as a "living" initiator, termed CR-4EBiB, for preparing amphiphilic block polymers by atom transfer radical polymerization (ATRP). In the formed polymer coating, the hydrophobic block can strongly adhere to the surface of the PP substrate, whereas the hydrophilic block is located on the outer layer by solvent-induced resistance to bacterial adhesion. Under the irradiation of an NIR laser (808 nm), the croconaine dye in the coating achieved maximum conversion of light to heat to effectively kill E. coli , S. aureus , and methicillin-resistant Staphylococcus aureus (MRSA). This work provides a facile and promising strategy for the development of implantable antibacterial biomedical materials.

Irreversible bone defects resulting from trauma, infection, and degenerative illnesses have emerged as a significant health concern. Structurally and functionally controllable hydrogels made by bone tissue engineering (BTE) have become promising biomaterials. Natural proteins are able to establish connections with autologous proteins through unique biologically active regions. Hydrogels based on proteins can simulate the bone microenvironment and regulate the biological behavior of stem cells in the tissue niche, making them candidates for research related to bone regeneration. This article reviews the biological functions of various natural macromolecular proteins (such as collagen, gelatin, fibrin, and silk fibroin) and highlights their special advantages as hydrogels. Then the latest research trends on cross-linking modified macromolecular protein hydrogels with improved mechanical properties and composite hydrogels loaded with exogenous micromolecular proteins have been discussed. Finally, the applications of protein hydrogels, such as 3D printed hydrogels, microspheres, and injectable hydrogels, were introduced, aiming to provide a reference for the repair of clinical bone defects.

Electrochemical nitrate reduction reaction (NO 3 - RR) is a promising low-carbon and environmentally friendly approach for the production of ammonia (NH 3 ). Herein, we develop a high-temperature quenched copper (Cu) catalyst with the aim of inducing nonequilibrium phase transformation, revealing the multiple defects (distortion, dislocations, vacancies, etc.) presented in Cu, which lead to low overpotential for NO 3 - RR and high efficiency for NH 3 production. Further loading a low content of iridium (Ir) species on the Cu surface improves the reactivity and ammonia selectivity. The resultant CuIr electrode exhibits a Faradaic efficiency of 93% and a record yield of 6.01 mmol h -1 cm -2 at -0.22 V RHE exceeding those of state-of-the-art NO 3 - RR catalysts. Detailed investigations have demonstrated that the synergistic effect between multiple defects and Ir decoration effectively regulate the d-band center of copper, change the adsorption state of the catalyst surface, and promote the adsorption and reduction of intermediates and reactants. The strong H* adsorption ability of the Ir element provides more active hydrogen for the generation of ammonia, promoting the reduction of nitrate to NH 3 .

The pursuit of two-dimensional (2D) magnetism is promising for energy-efficient electronic devices, including magnetoelectric random access memory and radio frequency/microwave magnonics, and it is gaining fundamental insights into quantum sensing technology. The key challenge resides in overseeing magnetic exchange interactions through a precise chemical reduction process, wherein manipulation of the arrangement of atoms and electrons is essential for achieving room-temperature 2D magnetism tailoring in a manner compatible with device architectures. Here, we report an electrochemically crafted CrI 3 layered magnet─a van der Waals material─with precisely tailored lithiation and delithiation degrees. The crystalline and packing structure within the intralayer are preserved during the lithium intercalation within the interlayer, owing to weak interlayer coupling. Intrinsic ferromagnetism featuring a Curie temperature reaching 420 K has been unequivocally demonstrated, showcasing a coercivity of 1120 Oe at room temperature. The degree of lithiation through the reduction from Cr 3+ to Cr 2+ plays a crucial role in determining a 28.5% change in magnetization and a 0.29 eV shift in the bandgap. Room temperature ferromagnetism and magnetoelectricity are critical for noncontact, specifically photon-driven, dynamic magnetism control of 2D magnet-based magnonics devices.

Alcohols are promising fuels for direct alcohol fuel cells and are common scavengers to identify reactive oxygen species (ROS) in electro-Fenton (EF) systems. However, the side impacts of alcohols on oxygen reduction reactions and ROS generation are controversial due to the complex interactions between electrodes and alcohol-containing electrolytes. Herein, we employed synchrotron-Fourier-transform infrared spectroscopy and electron paramagnetic resonance technologies to directly observe the changes of chemical species and electrochemical properties on the electrode surface. Our studies suggested that alcohols exhibited different limiting degrees on proton (H + ) mass transfer toward the catalytic surface, following an order of methanol < ethanol < isopropanol < tert -butyl alcohol (TBA). In addition, the formation of hydrophobic TBA clusters at high concentrations (>400 mM) resulted in a significant reduction in ionic conductivity and an elevation in charge transfer resistance, which impedes H + mass transfer and raises the energy barrier for 2e - oxygen reduction reaction processes. Moreover, the organic radical • CH 2 (CH 3 ) 2 CH 2 OH produced by the interaction of Fe 3+ and • OH with the alcohol in the EF system serves as a crucial intermediate in facilitating H 2 O 2 regeneration, which complicates the quenching effect of alcohols on • OH identification. Therefore, it is recommended that methanol should be used as the scavenger instead of TBA and the concentration should be less than 400 mM in EF systems.

Asperalins represent a novel class of viridicatin natural products with potent inhibitory activities against fish pathogens. In this study, we elucidated the biosynthesis of asperalins in the Aspergillus oryzae NSAR1 heterologous host and identified the FAD-dependent monooxygenase AplB stereoselectively hydroxylates viridicatin to yield a unique 3 R ,4 S configuration. The monomodular NRPS AplJ catalyzes a rare intramolecular ester bond formation reaction using dihydroquinoline as a nucleophile. Subsequent modifications by cytochrome P450 AplF, chlorinase AplN, and prenyltransferase AplE tailor the anthranilic acid portion, leading to the formation of asperalins. Additionally, we explored the potential of AplB for the hydroxylation of viridicatin analogs, demonstrating its relaxed substrate specificity. This finding suggests that AplB could be developed as a biocatalyst for the synthesis of viridicatin derivatives.

The electrochemical nitrate reduction reaction (NO 3 RR) is considered a sustainable technology to convert the nitrate pollutants to ammonia. However, developing highly efficient electrocatalysts is necessary and challenging given the slow kinetics of the NO 3 RR with an eight-electron transfer process. Here, a Cu 1.5 Mn 1.5 O 4 (CMO)/CeO 2 heterostructure with rich interfaces is designed and fabricated through an electrospinning and postprocessing technique. Benefiting from the strong coupling between CMO and CeO 2 , the optimized CMO/CeO 2 -2 catalyst presents excellent NO 3 RR performance, with NH 3 Faraday efficiency (FE) up to 93.07 ± 1.45% at -0.481 V vs reversible hydrogen electrode (RHE) and NH 3 yield rate up to 48.06 ± 1.32 mg cm -2 h -1 at -0.681 V vs RHE. Theoretical calculations demonstrate that the integration of CeO 2 with CMO modulates the adsorption/desorption process of the reactants and intermediates, showing a reduced energy barrier in the rate determination step of NO* to N* and achieving an outstanding NO 3 RR performance.

Herein, we present an efficient and practical kinetic resolution (KR) of racemic allylic pyrazoles utilizing photoexcited chiral-copper-complex-mediated alkene E → Z isomerization. This method enables the synthesis of both enantioenriched E - and Z -allylic pyrazoles, achieving enantiomeric excesses (e.e.) of up to 97% and selectivity factors ( S factors) as high as 217. Remarkably, the method's ability to furnish allylic pyrazoles with the Z -configuration, which is notably arduous to obtain under thermodynamic control, underscores the transformative potential of this synthetic protocol.

Objectives: The aim of this study was to investigate the ameliorative effect of platycodin D (PD) on cognitive dysfunction in type 2 diabetes mellitus (T2DM) and its potential molecular mechanisms of action in vivo and in vitro. Materials and methods: An animal model of cognitive impairment in T2DM was established using a single intraperitoneal injection of streptozotocin (100 mg/kg) after 8 weeks of feeding a high-fat diet to C57BL/6 mice. In vitro, immunofluorescence staining and Western blot were employed to analyze the effects of PD on glucose-induced neurotoxicity in mouse hippocampal neuronal cells (HT22). Results: PD (2.5 mg/kg) treatment for 4 weeks significantly suppressed the rise in fasting blood glucose in T2DM mice, improved insulin secretion deficiency, and reversed abnormalities in serum triglyceride, cholesterol, low-density lipoprotein, and high-density lipoprotein levels. Meanwhile, PD ameliorated choline dysfunction in T2DM mice and inhibited the production of oxidative stress and apoptosis-related proteins of the caspase family. Notably, PD dose-dependently prevents the loss of mitochondrial membrane potential, promotes phosphorylation of phosphatidylinositol 3 kinase and protein kinase B (Akt) in vitro, activates glycogen synthase kinase 3β (GSK3β) expression at the Ser9 site, and inhibits Tau protein hyperphosphorylation. Conclusions: These findings clearly indicated that PD could alleviate the neurological damage caused by T2DM, and the phosphorylation of Akt at Ser473 may be the key to its effect.

The purpose of this study was to identify ovalbumin-derived immunomodulatory peptides by in vitro cell experiments, de novo sequencing, and molecular docking. Ovalbumin hydrolysates were prepared by two enzymes (alkaline protease and papain) individually, sequentially, or simultaneously, respectively. The simultaneous enzymatic hydrolysate (OVAH) had a high degree of hydrolysis (38.12 ± 0.48%) and exhibited immune-enhancing and anti-inflammatory activities. A total of 160 peptides were identified by LC-MS/MS in OVAH. Three novel peptides NVMEERKIK, ADQARELINS, and WEKAFKDE bound to TLR4-MD2 through hydrogen bonds and hydrophobic interactions with high binding affinity and binding energies of -181.40, -178.03, and -168.12 kcal/mol, respectively. These three peptides were synthesized and validated for two-way immunomodulatory activity. NVMEERKIK exhibiting the strongest immunomodulatory activity, increased NO and TNF-α levels by 128.69 and 38.01%, respectively, in normal RAW264.7 cells and reduced NO and TNF-α levels by 27.31 and 39.13%, respectively, in lipopolysaccharide-induced inflammatory RAW264.7 cells. Overall, this study first revealed that ovalbumin could be used as an immunomodulatory source for controlling inflammatory factor secretion.

Alloying-type anode materials provide high capacity for lithium-ion batteries; however, they suffer pulverization problems resulting from the volume change during cycling. Realizing the cycling reversibility of these anodes is therefore critical for sustaining their electrochemical performance. Here, we investigate the structural reversibility of Sn NPs during cycling at atomic-level resolution utilizing in situ high-resolution TEM. We observed a surprisingly near-perfect structural reversibility after a complete cycle. A three-step phase transition happens during lithiation, accompanied by the generation of a significant number of defects, grain boundaries, and up to 202% volume expansion. In subsequent delithiation, the volume, morphology, and crystallinity of the Sn NPs were restored to their initial state. Theoretical calculations show that compressive stress drives the removal of vacancies generated within the NPs during delithiation, therefore maintaining their intact morphology. This work demonstrates that removing vacancies during cycling can efficiently improve the structural reversibility of high-capacity anode materials.

In this study, we explore the impact of monovalent (NaCl) and divalent (CaCl 2 ) brines, coupled with sodium dodecyl sulfate (SDS) surfactant at varying low concentrations, on the detachment and displacement of oil from sandstone rock surfaces. Employing the sessile drop method and molecular dynamics simulations, we scrutinize the behavior of the brine solutions. Our findings reveal that both low salinity and low-salinity surfactant solutions induce a gradual shift in rock wettability toward a more water-wet state. This wettability transformation is not instantaneous but evolves over time, as observed through meticulous molecular motion analyses. Through contact angle measurements and molecular dynamics simulations, we delve into the molecular motion at subpore and micropore scales on sandstone/quartz surfaces. The adsorption of surface-active agents from the oil to the oil-brine interface results in a reduced interfacial tension, significantly contributing to oil displacement. Notably, low salinity concentrations ranging from 1000 to 10,000 ppm exhibit the lowest contact angles within 30 min across all solutions. However, higher concentrations deviate from this declining trend, especially with divalent ions like Ca 2+ , which bridge polar molecules onto the rock surface, resulting in an increased oil-wetting state. This research unveils the intricate molecular motions involved in employing low-salinity surfactant solutions for oil detachment from surfaces. Furthermore, it provides valuable insights into the underlying forces driving oil detachment and wettability alteration., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Patients with arterial embolic disease have benefited greatly from antiplatelet therapy. However, hemorrhage risk of antiplatelet agents cannot be ignored. Herein, we describe the discovery of 2,3-dihydro[1,4]dioxino[2,3- g ]benzofuran compounds as novel PAR4 antagonists. Notably, the isomers 36 and 37 with the chemotype of phenoxyl methylene substituted on the 2,3-dihydro-1,4-dioxine ring exhibited potent in vitro antiplatelet activity (IC 50 = 26.13 nM for 36 and 14.26 nM for 37 ) and significantly improved metabolic stability in human liver microsomes ( T 1/2 = 97.6 min for 36 and 11.1 min for BMS-986120). 36 also displayed good oral PK profiles (mice: T 1/2 = 7.32 h and F = 45.11%). Both of them showed overall potent ex vivo antiplatelet activity at concentrations of 6 and 12 mg/kg, with no impact on the coagulation system and low bleeding liability. Our work will facilitate development of novel PAR4 antagonists as a safer therapeutic option for arterial embolism.

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields including sensing, photoelectronics, and photonic applications. While significant progress has been made in solid-state NLO switching materials, these materials typically showcase their highest NLO performance near room temperature. However, this performance drastically deteriorates upon heating, primarily due to the phase transition undergone by the materials from noncentrosymmetric to centrosymmetric phase. Here, we introduce a new class of NLO switching materials, solid-state supramolecular compounds 18-Crown-6 ether@Cu 2 Cl 4 ·4H 2 O ( 1·4H 2 O ), exhibiting reversible and stable NLO switching when subjected to near-infrared (NIR) photoexcitation and/or thermal stimuli. The reversible crystal structure in response to external stimuli is attributed to the presence of a weakly coordinated bridging water molecule facilitated by hydrogen bonding/chelation interactions between the metal halide and crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110 °C. In addition, the bridging water molecules within the complex can be released and recaptured in a fully reversible manner, all without requiring excessive energy input. This feature allows for precise control of SHG signal activation and deactivation through structural transformations, resulting in a high-contrast off/on ratio, reaching values in the million-fold range.

A multisignal method for the sensitive detection of norovirus based on Mn paramagnetic relaxation and nanocatalysis was developed. This dual-modality sensing platform was based on the strong relaxation generated by cracked Au@MnO 2 nanoparticles (NPs) and their intrinsic enzyme-like activity. Ascorbic acid rapidly cracked the MnO 2 layer of Au@MnO 2 NPs to release Mn(II), resulting in the relaxation modality being in a "switch-on" state. Under the optimal conditions, the relaxation modality exhibited a wide working range (6.02 × 10 3 -3.01 × 10 7 copies/μL) and a limit of detection (LOD) of 2.29 × 10 3 copies/μL. Using 4,4',4″,4″'-(porphine-5,10,15,20-tetrayl) tetrakis (benzenesulfonic acid) (tpps)-β-cyclodextrin (tpps-β-CD) as a T 1 relaxation signal amplification reagent, a lower LOD was obtained. The colorimetric modality exploited the "peroxidase/oxidase-like" activity of Au@MnO 2 NPs, which catalyzed the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB, which exhibited a working range (6.02 × 10 4 -6.02 × 10 6 copies/μL) and an LOD of 2.6 × 10 4 copies/μL. In addition, the rapid amplification reaction of recombinase polymerase enabled the detection of low norovirus levels in food samples and obtained a working range of 10 1 -10 6 copies/mL and LOD of 10 1 copies/mL (relaxation modality). The accuracy of the sensor in the analysis of spiked samples was consistent with that of the real-time quantitative reverse transcription polymerase chain reaction, demonstrating the high accuracy and practical utility of the sensor.

Glycoproteins account for numerous biological processes including those associated with diseases and infections. The advancement of glycopeptides has emerged as a promising strategy for unraveling biological pathways and discovering novel medicines. In this arena, a key challenge arises from the absence of efficient synthetic strategies to access glycopeptides and glycoproteins. Here, we present a highly concise approach to bridging saccharides with amino acids and peptides through an amide linkage. Our amide-linked C -glycosyl amino acids and peptides are synthesized through cooperative Ni-catalyzed and photoredox processes. The catalytic process generates a glycosyl radical and an amide carbonyl radical, which subsequently combine to yield the C -glycosyl products. The saccharide reaction partners encompass mono-, di-, and trisaccharides. All 20 natural amino acids, peptides, and their derivatives can efficiently undergo glycosylations with yields ranging from acceptable to high, demonstrating excellent stereoselectivities. As a substantial expansion of applications, we have shown that simple C -glycosyl amino acids can function as versatile building units for constructing C -glycopeptides with intricate spatial complexities.

Hybrid piezoelectric/triboelectric nanogenerators combine the merits of piezoelectric nanogenerators (PENGs) and triboelectric nanogenerators (TENGs), possessing enhanced electrical output and sensitivity. However, the structures of the majority of hybrid nanogenerators are rather complex in integrating both functions, limiting their practical application in wearable electronics. Herein, we propose to construct a piezoelectric/triboelectric hybrid nanogenerator (PT-NG) with a simple structure based on a composite film to simultaneously achieve the coupling of piezoelectric charge generation and triboelectrification with improved energy conversion efficiency. The composite film consists of electrospun PVDF nanofibers embedded in the surface of the PDMS film, which not only forms a rough nanomorphology on the surface of PDMS but also provides structural protection to the PVDF nanofibers by PDMS during compressive deformation. The results have shown that the PT-NG can generate much higher electrical outputs than individual TENG and PENG devices. The PT-NG devices exhibit a high level of mechanical-to-electrical energy conversion efficiency with superior performance in charging capacitors and functioning as self-powered wearable sensors for the detection of different signals from finger movement, the recognition of various gestures, and the monitoring of respiration. More importantly, the composite device possesses an impressive structure durability, maintaining its layered structure over 5000 testing cycles without noticing any obvious damage on the nanofibers or detachment between the layers. Our results have demonstrated that the combining of piezoelectric nanofibers and triboelectric substrate is an efficient way to fabricate highly efficient energy harvesting devices for intelligent identification and health monitoring.

To discover protoporphyrinogen oxidase (PPO) inhibitors with robust herbicidal activity and crop safety, three types of substituted 3-(pyridin-2-yl)phenylamino derivatives bearing amide, urea, or thiourea as side chain were designed via structure splicing strategy. Postemergence herbicidal activity assessment of 33 newly prepared compounds revealed that many of our compounds such as 6a , 7b , and 8d exhibited superior herbicidal activities against broadleaf and monocotyledon weeds to commercial acifluorfen. In particular, compound 8d exhibited excellent herbicidal activities and high crop safety at a dosage range of 37.5-150 g ai/ha. PPO inhibitory studies supported our compounds as typical PPO inhibitors. Molecular docking studies revealed that compound 8d provided effective interactions with Nicotiana tabacum PPO ( Nt PPO) via diverse interaction models, such as π-π stacking and hydrogen bonds. Molecular dynamics (MD) simulation studies and degradation studies were also conducted to gain insight into the inhibitory mechanism. Our study indicates that compound 8d may be a candidate molecule for the development of novel herbicides.

Operation of rechargeable batteries at ultralow temperature is a significant practical problem because of poor kinetics of the electrode. Here, we report for the first time stabilized multiphase conversions for fast kinetics and long-term durability in ultralow-temperature, organic-sodium batteries. We establish that disodium rhodizonate organic electrode in conjunction with single-layer graphene oxide obviates consumption of organic radical intermediates, and demonstrate as a result that the newly designed organic electrode exhibits excellent electrochemical performance of a highly significant capacity of 130 mAh g -1 at -50 °C. We evidence that the full-cell configuration coupled with Prussian blue analogues exhibits exceptional cycling stability of >7000 cycles at -40 °C while maintaining a discharge capacity of 101 mAh g -1 at a high current density 300 mA g -1 . We show this is among the best reported ultralow-temperature performance for nonaqueous batteries, and importantly, the pouch cell exhibits a continuous power supply despite conditions of -50 °C. This work sheds light on the distinct energy storage characteristics of organic electrode and opens up new avenues for the development of reliable and sustainable ultralow-temperature batteries.

Understanding the mechanism of adipogenesis is an important basis for improving meat quality traits of livestock. Alternative polyadenylation (APA) is a vital mechanism to regulate the expression of eukaryotic genes. However, how the individual APA functions in adipogenesis remains elusive. This study was intended to investigate the effect of malic enzyme 1 (ME1) APA on adipogenesis. Here, intracellular lipid droplets were stained using Oil red O. 3' RACE was used to verify APA events of the ME1 gene. Interactions between ME1 3' untranslated region (3' UTR)-APA isoforms and miRNAs, as well as differential expression of isoforms, were examined using dual-luciferase reporter and molecular experiments. The mechanism of ME1 APA on adipogenesis was explored by gain and loss of function assays. In this study, two ME1 isoforms with different 3' UTR lengths were detected during adipogenesis. Moreover, the ME1 isoform with a short 3' UTR was significantly upregulated compared with the one with a long 3' UTR. Mechanistically, only the long ME1 isoform was targeted by miR-153-3p to attenuate adipogenesis, while the short one escaped the regulation of miR-153-3p to accelerate adipogenesis. Our results reveal a novel mechanism of ME1 APA in regulating adipogenesis.

Spinal tumors often lead to more complex complications than other bone tumors. Nerve injuries, dura mater defect, and subsequent cerebrospinal fluid (CSF) leakage generally appear in spinal tumor surgeries and are followed by serious adverse outcomes such as infections and even death. The use of suitable dura mater replacements to achieve multifunctionality in fluid leakage plugging, preventing adhesions, and dural reconstruction is a promising therapeutic approach. Although there have been innovative endeavors to manage dura mater defects, only a handful of materials have realized the targeted multifunctionality. Here, we review recent advances in dura repair materials and techniques and discuss the relative merits in both preclinical and clinical trials as well as future therapeutic options. With these advances, spinal tumor patients with dura mater defects may be able to benefit from novel treatments.

Photoelectrochemical (PEC) water splitting is an attractive strategy to convert solar energy to hydrogen. However, the lifetime of PEC devices is restricted by the photocorrosion of semiconductors and the instability of co-catalysts. Herein, we report a feasible in situ inherent cross-linking method for stabilizing semiconductors that uses a CoFe-dispersed polyacrylamide (PAM) hydrogel as a transparent protector. The CoFe-PAM hydrogel protected BiVO 4 (BVO) photoanode reached a photocurrent density of 5.7 mA cm -2 at 1.23 V RHE under AM 1.5G illumination with good stability. The PAM hydrogel network improved the loading of Fe sites while enabling the retention of more CoFe co-catalysts and increasing the electron density of the reaction active sites, further improving the PEC performance and stability. More importantly, by tuning the polymerization network, we pioneer the use of quasi-solid-state electrolytes in photoelectrochemistry, where the high concentration of ionic solvent in the PAM hydrogel ensures effective charge transport and good water storage owing to the hydrophilic and porous structure of the hydrogel. This work expands the scope of PEC research by providing a class of three-dimensional hydrogel electrocatalysts and quasi-solid-state electrolytes with huge extension potential, and the versatility of these quasi-solid-state electrolytes can be employed for other semiconductors.

The extraction of potassium from polyhalite ore (K 2 SO 4 ·MgSO 4 ·2CaSO 4 ·2H 2 O) can help alleviate potassium resource shortages in China. In this study, the leaching behavior of potassium extracted from polyhalite ore in water was investigated using leaching experiments and kinetic analysis. The effects of various factors, such as liquid-to-solid ratio, leaching temperature, leaching time, and polyhalite ore particle size were comprehensively studied. It was found that high temperatures improved the reaction rate and efficiency at the beginning (1-15 min) but reduced the final leaching efficiency of potassium. And this phenomenon is discussed from the aspects of the dissolution-reprecipitation of potassium, newly formed solid products during the leaching process, and leaching thermodynamics. The leaching of potassium followed the Avrami model, with an apparent activation energy of 26.29 kJ/mol. Additionally, it was determined that the mixed controlled step (surface chemical reaction and diffusion) was the controlling step during potassium leaching. This study clarified the leaching mechanism of the polyhalite in water, and the causes of hindering the leaching of potassium were analyzed. The research results can provide theoretical reference and solutions for parameter design for the enhanced leaching process and selection of leaching agents in the future., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

To use resources rationally, the recovery and recycling of rare earth (RE) from industrial sewage have attracted a lot of attention. Herein, a polymer adsorbent CMC/PAM/Fe 3 O 4 (CPF) was synthesized from renewable carboxymethyl cellulose (CMC), polyacrylamide (PAM), and Fe 3 O 4 by the template of La 3+ using ion imprinting technology. The CPF was characterized with X-ray diffraction (XRD), IR, X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM), and results show that PAM and CMC can crosslink with each other and form copolymers with Fe 3 O 4 particles dispersing in it. The adsorption properties for the template ions La 3+ were fully studied. It is found that CPF exhibited good adsorption performance with an adsorption capacity of 34.6 mg·g -1 . Cycling experiments show that CPF still has high efficiency even after 5 cycles. Meanwhile, the desorption rate can reach more than 98%. The low wastage and high adsorption/desorption efficiency would enable CPF to be a good candidate adsorbent for removal/recovery of La 3+ from industrial sewage., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

We present a net-shaped DNA nanostructure (called "DNA Net" herein) design strategy for selective recognition and high-affinity capture of intact SARS-CoV-2 virions through spatial pattern-matching and multivalent interactions between the aptamers (targeting wild-type spike-RBD) positioned on the DNA Net and the trimeric spike glycoproteins displayed on the viral outer surface. Carrying a designer nanoswitch, the DNA Net-aptamers release fluorescence signals upon virus binding that are easily read with a handheld fluorimeter for a rapid (in 10 min), simple (mix-and-read), sensitive (PCR equivalent), room temperature compatible, and inexpensive (∼$1.26/test) COVID-19 test assay. The DNA Net-aptamers also impede authentic wild-type SARS-CoV-2 infection in cell culture with a near 1 × 10 3 -fold enhancement of the monomeric aptamer. Furthermore, our DNA Net design principle and strategy can be customized to tackle other life-threatening and economically influential viruses like influenza and HIV, whose surfaces carry class-I viral envelope glycoproteins like the SARS-CoV-2 spikes in trimeric forms.

Based on productivity test data and physical property test results from multiple wells, a classification scheme of Archean metamorphic buried hill reservoirs in the Bohai Sea is established by means of mathematical function fitting. By combining data from cores, casting thin sections, scanning electron microscopy, imaging logging, and high-pressure mercury injection and nitrogen adsorption tests, we clarified the reservoir composition and pore structure characteristics of different types of reservoirs are clarified. Furthermore, taking the BZ19-6 and 13-2 wells in the Archean metamorphic buried hills as an example, the development sites of different types of reservoirs are analyzed and the reservoir development model is established. The results show that the Archean metamorphic buried hill reservoirs in the Bohai Sea can be divided into three categories and six subcategories, including type I reservoirs with porosities greater than 8% or permeabilities greater than 1 × 10 -3 μm 2 and type II reservoirs with porosities of 5-8% or permeabilities in the range of 0.1-1 × 10 -3 μm 2 . Reservoirs with porosities of 2-5% and permeabilities of 0.01-0.1 × 10 -3 μm 2 are type III reservoirs. Each type of reservoir can be further divided into a fracture-pore type and a fracture type according to the relative contribution of the porosity and permeability to the reservoir. From type I to type III, the dissolution degree and fracture development gradually weaken, the pore size gradually decreases, and the pore volume gradually decreases. The distribution of favorable reservoirs is comprehensively controlled by weathering and tectonic transformation. The presence of a weathered glutenite zone, weathered leaching zone, or weathered disintegration zone is favorable for the development of type I reservoirs in the weathering crust. In the inner part of the buried hill, the presence of a fracture zone with a thickness of more than 10 m or a dense fracture zone with a thickness of more than 40 m is favorable for the formation of type I reservoirs., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Glycosylation is an important method of modifying natural products and is usually catalyzed by uridine 5'-diphosphate (UDP)-glycosyltransferase. UDP-β-l-arabinose (UDP-Ara) confers specific functions to natural products such as pentacyclic triterpenoids. However, UDP-arabinosyltransferase with high regioselectivity toward pentacyclic triterpenoids has rarely been reported. In addition, UDP-Ara is mainly biosynthesized from UDP-α-d-glucose (UDP-Glc) through several reaction steps, resulting in the high cost of UDP-Ara. Herein, UGT99D1 was systematically characterized for specifically transferring one moiety of arabinose to the C-3 position of typical pentacyclic triterpenoids. Subsequently, 15 enzymes from plants, mammals, and microorganisms were characterized, and a four-enzyme cascade comprising sucrose synthase, UDP-Glc dehydrogenase, UDP-α-d-glucuronic acid decarboxylase, and UDP-Glc 4-epimerase was constructed to transform sucrose into UDP-Ara with UDP recycling. This system was demonstrated to efficiently produce the arabinosylated derivative (Ara-BA) of typical pentacyclic triterpenoid betulinic acid (BA). Finally, the in vitro cytotoxicity tests indicated that Ara-BA showed much higher anticancer activities than BA. The established arabinosylation platform shows the potential to enhance the pharmacological activity of natural products.

Understanding the biosynthetic pathways of fungal pigments can help elucidate their roles in fungal growth processes. Trichodimerol is a unique cage-like dimeric sorbicillinoids pigment that is commonly isolated from many fungi, however, its biosynthesis is just partially clarified. In this study, we report that a biosynthetic gene cluster encoded major facilitator superfamily transporter (StaE) from the fungus Stagonospora sp. SYSU-MS7888 is involved in the formation of trichodimerol, together with several other dimeric sorbicillinoids. Using Aspergillus oryzae NSARI as a heterologous host, we demonstrated that the formation of dimeric sorbicillinoids required co-expression of the transporter StaE with biosynthetic genes (two PKSs and one monooxygenase) that are responsible for constructing the monomer precursor sorbicillinol. Fluorescence microscopy results showed that eGFP-tagged StaE is localized on the endoplasmic reticulum, suggesting that sorbicillinoid dimerizations might be compartmentalized in this organelle.

Organic materials are promising for cation storage in calcium ion batteries (CIBs). However, the high solubility of organic materials in an electrolyte and low electronic conductivity remain the key challenges for high-performance CIBs. Herein, a nitrogen-rich covalent organic framework with multiple carbonyls (TB-COF) is designed as an aqueous anode to address those obstacles. TB-COF demonstrates a high reversible capacity of 253 mAh g -1 at 1.0 A g -1 and long cycle life (0.01% capacity decay per cycle at 5 A g -1 after 3000 cycles). The redox mechanism of Ca 2+ /H + co-intercalated in COF and chelating with C═O and C═N active sites is validated. In addition, a novel C═C active site was identified for Ca 2+ ion storage. Both computational and empirical results reveal that per TB-COF repetitive unit, up to nine Ca 2+ ions are stored after three staggered intercalation steps, involving three distinct Ca 2+ ion storage sites. Finally, the evolution process of radical intermediates further elucidates the C═C reaction mechanism.

Evaluating the volatility of organic compounds based solely on their molecular formulas would avoid tough demands in deriving molecular structures. Here, we deployed an iodide-adduct Long Time-of-Flight Chemical Ionization Mass Spectrometry (LToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO) to investigate molecular formulas and thermograms of organic compounds on ambient particulate samples collected in the summer of 2021 in a suburban site of Shanghai and to estimate saturation vapor pressures of low- and semivolatile components of ambient organic aerosols. Then, a hierarchical cluster analysis and a subsequent classification of obtained clusters by similarity calculation were applied to the measured data set of molecular formulas and saturation vapor pressures of organic aerosols with at least a 2/3 appearance frequency, together with a similar data set collected at a rural site in the Beijing-Tianjin-Hebei region during the winter of 2018 (Ren et al., 2018), to classify all compounds into multiple groups. For each group of compounds, parametrizations between volatility and elemental composition were derived, and then relationships between each group of parameters and the mean O:C were established to achieve a volatility-molecular formula parametrization with the O:C as a key input. Statistical comparison of estimated volatilities of low-volatile organic compounds shows a much better performance of our parametrization than previous molecular formula-based ones.

Three-dimensional covalent organic frameworks (3D COFs) have been of great interest due to their inherent numerous open sites and pore confinement effect. However, it has remained challenging to build 3D frameworks via interdigitation (also known as inclined interpenetration) by generating an entangled network formed by multiple 2D layers inclined with respect to each other. Herein, we report the first case of constructing a 3D COF, termed COF-904, through interdigitating 2D hcb nets, which was formed via [3+2] imine condensation reactions by the use of 1,3,5-triformylbenzene and 2,3,5,6-tetramethyl-1,4-phenylenediamine. The single-crystal structure of COF-904 is solved, and the locations of all non-hydrogen atoms are determined by 3D electron diffraction with a resolution up to 0.8 Å. These results not only broaden the strategy for achieving 3D COFs via interdigitation but also demonstrate that structurally complex extended frameworks can arise from simple molecules.

Pancreatic cancer (PC) is one of the most malignant cancers that develops rapidly and carries a poor prognosis. Synergistic cancer therapy strategy could enhance the clinical efficacy compared to either treatment alone. In this study, gold nanorods (AuNRs) were used as siRNA delivery vehicles to interfere with the oncogenes of KRAS. In addition, AuNRs were one of anisotropic nanomaterials that can absorb near-infrared (NIR) laser and achieve rapid photothermal therapy for malignant cancer cells. Modification of the erythrocyte membrane and antibody Plectin-1 occurred on the surface of the AuNRs, making them a promising target nanocarrier for enhancing antitumor effects. As a result, biomimetic nanoprobes presented advantages in biocompatibility, targeting capability, and drug-loading efficiency. Moreover, excellent antitumor effects have been achieved by synergistic photothermal/gene treatment. Therefore, our study would provide a general strategy to construct a multifunctional biomimetic theranostic multifunctional nanoplatform for preclinical studies of PC.

Thermally insulating aerogels can now be prepared from ceramics, polymers, carbon, and metals and composites between them. However, it is still a great challenge to make aerogels with high strength and excellent deformability. We propose a design concept of hard cores and flexible chains that alternately construct the aerogel skeleton structure. The approach gives the designed SiO 2 aerogel excellent compressive (fracture strain 83.32%), tensile. and shear deformabilities, corresponding to maximum strengths of 22.15, 1.18, and 1.45 MPa, respectively. Also, the SiO 2 aerogel can stably perform 100 load-unload cycles at a 70% large compression strain, demonstrating an excellent resilient compressibility. In addition, the low density of 0.226 g/cm 3 , the high porosity of 88.7%, and the average pore size of 45.36 nm effectively inhibit heat conduction and heat convection, giving the SiO 2 aerogel outstanding thermal insulation properties [0.02845 W/(m·K) at 25 °C and 0.04895 W/(m·K) at 300 °C], and the large number of hydrophobic groups itself also gives it excellent hydrophobicity and hydrophobic stability (hydrophobic angle of 158.4° and saturated mass moisture absorption rate of about 0.327%). The successful practice of this concept has provided different insights into the preparation of high-strength aerogels with high deformability.

Immune activating agents represent a valuable class of therapeutics for the treatment of cancer. An area of active research is expanding the types of these therapeutics that are available to patients via targeting new biological mechanisms. Hematopoietic progenitor kinase 1 (HPK1) is a negative regulator of immune signaling and a target of high interest for the treatment of cancer. Herein, we present the discovery and optimization of novel amino-6-aryl pyrrolopyrimidine inhibitors of HPK1 starting from hits identified via virtual screening. Key components of this discovery effort were structure-based drug design aided by analyses of normalized B -factors and optimization of lipophilic efficiency.

Shale gas, as a promising alternative energy source, has received considerable attention because of its broad resource base and wide distribution. The establishment of shale models that can accurately describe the composition and structure of shale is essential to perform molecular simulations of gas adsorption in shale reservoirs. This Review provides an overview of shale models, which include organic matter models, inorganic mineral models, and composite shale models. Molecular simulations of gas adsorption performed on these models are also reviewed to provide a more comprehensive understanding of the behaviors and mechanisms of gas adsorption on shales. To accurately understand the gas adsorption behaviors in shale reservoirs, it is necessary to be aware of the pore structure characteristics of shale reservoirs. Thus, we also present experimental studies on shale microstructure analysis, including direct imaging methods and indirect measurements. The advantages, disadvantages, and applications of these methods are also well summarized. This Review is useful for understanding molecular models of gas adsorption in shales and provides guidance for selecting experimental characterization of shale structure and composition., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Tin (Sn)-based perovskite solar cells (PSCs) have attracted extensive attention due to the irlow toxicity and excellent optoelectric properties. Nonetheless, the development of Sn-based PSCs is still hampered by poor film quality due to the fast crystallization and the oxidation from Sn 2+ to Sn 4+ . In this work, we compare and employ three ethylammonium halides, EAX (X = Cl, Br, I) to explore their roles in Sn-based perovskites and solar cells. We find that crystallinity and crystallization orientation of perovskites are optimized with the regulation of EAI. EABr leads to reduced defect density and enhanced crystallinity but also the lowest absorption and the widest band gap owing to the substitution of Br - . Notably, perovskites with EACl exhibit the best crystallinity, lowest defect density, and excellent antioxidant capacity benefiting from the partial substitution of Cl - . Consequently, the EACl-modified device achieves a champion PCE of 12.50% with an improved V oc of 0.79 V. Meanwhile, an unencapsulated EACl device shows excellent shelf stability with negligible efficiency degradation after 5400 h of storage in a N 2 -filled glovebox, and the encapsulated device retains its initial efficiency after continuous light illumination at the maximum power point for 100 h in air.

Overwhelming evidence points to an abnormally active Wnt/β-catenin signaling as a key player in colorectal cancer (CRC) pathogenesis. Ursolic acid (UA) is a pentacyclic triterpenoid that has been found in a broad variety of fruits, spices, and medicinal plants. UA has been shown to have potent bioactivity against a variety of cancers, including CRC, with the action mechanism obscure. Our study tried to learn more about the efficacy of UA on CRC and its functional mechanism amid the Wnt/β-catenin signaling cascade. We determined the efficacy of UA on CRC SW620 cells with respect to the proliferation, migration, clonality, apoptosis, cell cycle, and Wnt/β-catenin signaling cascade, with assessment of the effect of UA on normal colonic NCM460 cells. Also, the effects of UA on the tumor development, apoptosis, cell cycle, and Wnt/β-catenin signaling axis were evaluated after a subcutaneous SW620 xenograft tumor model was established in mice. In this work, we showed that UA drastically suppressed proliferation, migration, and clonality; induced apoptosis; and arrested the cell cycle at the G0/G1 phase of SW620 cells, without the influence on NCM460 cells, accompanied by weakened activity of the Wnt/β-catenin signaling pathway. Besides, UA markedly deterred the growth of the xenograft tumor, ameliorated pathological features, triggered apoptosis, and arrested the cell cycle in xenograft CRC tissue, by lessening the Wnt/β-catenin signaling cascade. Overall, UA may inhibit the malignant phenotype, induce apoptosis, and arrest the cell cycle of CRC, potentially by attenuating the Wnt/β-catenin signaling axis, providing insights into the mechanism for the potency of UA on CRC.

Despite the great achievements of immune checkpoint blockade (ICB) therapy on programmed cell death-1 (PD-1)/programmed cell death-ligand 1 (PD-L1) axis, ICB monotherapy still faces obstacles in eradicating solid tumors due to the lack of tumor-associated antigens or tumor-specific cytotoxicity. Photothermal therapy (PTT) is a potential therapeutic modality because it can noninvasively kill tumor cells by thermal ablation and generate both tumor-specific cytotoxicity and immunogenicity, which holds great feasibility to improve the efficiency of ICB by providing complementary immunomodulation. Except for the PD-1/PD-L1 axis, the cluster of differentiation 47 (CD47)/signal regulatory protein alpha (SIRPα) pathway has been considered as a novel strategy of tumor cells to evade the surveillance of macrophages and inactivate the immune response of PD-L1 blockade therapy. Therefore, it is necessary to synergize the antitumor effect of dual-targeting PD-L1 and CD47. Although promising, the application of PD-L1/CD47 bispecific antibodies, especially in combination with PTT, remains a formidable problem, due to the low objective response, activity loss at relatively high temperature, or nonvisualization. Herein, instead of using antibodies, we use MK-8628 (MK) to down-regulate both PD-L1 and CD47 simultaneously through halting the active transcription of oncogene c-MYC, leading to elicitation of the immune response. The hollow polydopamine (HPDA) nanospheres are introduced as a biocompatible nanoplatform with high loading capacity and magnetic resonance imaging (MRI) ability to deliver MK and induce PTT (HPDA@MK). Compared to preinjection, HPDA@MK exhibits the strongest MRI signal at 6 h postintravenous injection to guide the precise combined treatment time. However, due to the local delivery and controlled release of inhibitors, HPDA@MK down-regulates c-MYC/PD-L1/CD47, promotes the activation and recruitment of cytotoxic T cells, regulates the M2 macrophages polarization in tumor sites, and especially boosts the combined therapeutic efficacy. Collectively, our work presents a simple but distinctive approach for c-MYC/PD-L1/CD47-targeted immunotherapy combined with PTT that may provide a desirable and feasible strategy for the treatment of other clinical solid tumors.

Here, we detail how the catalytic behavior of immobilized molecular electrocatalysts for the CO 2 reduction reaction (CO 2 RR) can be impacted by catalyst aggregation. Operando Raman spectroscopy was used to study the CO 2 RR mediated by a layer of cobalt phthalocyanine (CoPc) immobilized on the cathode of an electrochemical flow reactor. We demonstrate that during electrolysis, the oxidation state of CoPc in the catalyst layer is dependent upon the degree of catalyst aggregation. Our data indicate that immobilized molecular catalysts must be dispersed on conductive supports to mitigate the formation of aggregates and produce meaningful performance data. We leveraged insights from this mechanistic study to engineer an improved CO-forming immobilized molecular catalyst─cobalt octaethoxyphthalocyanine (EtO 8 -CoPc)─that exhibited high selectivity (FE CO ≥ 95%), high partial current density ( J CO ≥ 300 mA/cm 2 ), and high durability (ΔFE CO < 0.1%/h at 150 mA/cm 2 ) in a flow cell. This work demonstrates how to accurately identify CO 2 RR active species of molecular catalysts using operando Raman spectroscopy and how to use this information to implement improved molecular electrocatalysts into flow cells. This work also shows that the active site of CoPc during CO 2 RR catalysis in a flow cell is the metal center.

In order to give an answer for the challenges of long wavelength-photocontrolled radical polymerization in aqueous solutions and to address the shortcomings of conventional near-infrared (NIR) photocatalysts (PCs) that are difficult to subject to post-treatment, we designed and synthesized a series of β-tetra-substituted water-soluble zinc phthalocyanines (β-TS-Zns) as the NIR PCs for reversible addition-fragmentation chain transfer (RAFT) polymerization successfully under irradiation with NIR (λ max = 730 nm) light at room temperature. Importantly, the NIR PCs can also be designed as polymerizable monomers and covalently loaded on the polymer chains, which are endowed with permanent NIR photocatalysis of the resultant polymers. Moreover, the polymerization can not only be carried out in water but also in phosphate buffer saline (PBS) solution, yielding polymers with controlled molar mass and narrow dispersities ( Đ = 1.03-1.25). Therefore, this NIR-photocontrolled aqueous RAFT polymerization system may provide a charming strategy for possible applications in tissue engineering biomaterial in situ benefiting from the high penetration ability of NIR light.

Developing a bifunctional electrocatalyst with remarkable performance viable for overall water splitting is increasingly essential for industrial-scale renewable energy conversion. However, the current electrocatalyst still requires a large cell voltage to drive water splitting due to the unsuitable adsorption/desorption capacity of reaction intermediates, which seriously hinders the practical application of water splitting. Herein, a unique SiO x /Ru nanosheet (NS) material was proposed as a high-performance electrocatalyst for overall water splitting. The SiO x /Ru NSs show superior performance in the hydrogen evolution reaction with a low overpotential of 23 mV (@ 10 mA cm -2 ) and excellent stability for nearly 200 h (@ 10 mA cm -2 ) in 1 M KOH. By means of the introduction of SiO x , it is beneficial for balancing the local charge density of the surrounding Ru sites. The suitable electronic coupling between the d-band electrons of Ru and the adsorbed species effectively balances the adsorption and desorption of reaction intermediates on the surface. As a result, the catalyst also exhibits overall water splitting activity with a cell voltage of only 1.496 V to reach the current density of 10 mA cm -2 . The present work opens up a new strategy for designing high-performance electrocatalysts for water splitting.

Promoting the aggregation of nanoprobes at tumor sites and realizing precise imaging and treatment of tumors is still one of the important problems to be solved in the field of nanomedicine. Poly-2-phenylbenzobisthiazole (PB) is a novel conjugated polymer with good biocompatibility, excellent photothermal properties in the second near-infrared region (NIR-II), but poor water dispersibility. Herein, a novel self-assembly/polymerization two-in-one strategy was proposed to prepare a new family of poly-2-phenyl-benzobisthiazole-based nanoparticles. Because the hydrophobic polymer PB was well "camouflaged" in the hydrophilic polyphenol-metal networks, the prepared "Trojan horse-like" nanoparticle TF-PB exhibited good water dispersibility. Besides, TF-PB can play a role as a contrast agent for photoacoustic and magnetic resonance dual-modality imaging. When deferoxamine was artificially applied and interacted with TF-PB, the polyphenol-metal networks disintegrated and the hydrophobic material PB was exposed and started hydrophobic aggregation. Thus, it can be applied for precise enhanced photothermal therapy (PTT) in the NIR-II. Meanwhile, the aggregation process enabled non-invasive, fast, and accurate real-time monitoring by self-enhancing photoacoustic imaging. This work has realized the artificially controllable aggregation of photothermal materials in the tumor site, solved the limitations of traditional PTT, and also has good application prospects in clinical therapy.

Autologous blood-derived protein hydrogels have shown great promise in the field of personalized regenerative medicine. However, the inhospitable regenerative microenvironments, especially the unfavorable immune microenvironment, are closely associated with their limited tissue-healing outcomes. Herein, novel immunomodulatory blood-derived hybrid hydrogels (PnP-iPRF) are rationally designed and constructed for enhanced bone regeneration via multichannel regulation of the osteogenic microenvironment. Such double-network hybrid hydrogels are composed of clinically approved injectable platelet-rich fibrin (i-PRF) and polycaprolactone/hydroxyapatite composite nanofibers by using enriched polydopamine (PDA) as the anchor. The polycaprolactone component in PnP-iPRF provides a reinforced structure to stimulate osteoblast differentiation in a proper biomechanical microenvironment. Most importantly, the versatile PDA component in PnP-iPRF can not only offer high adhesion capacity to the growth factors of i-PRF and create a suitable biochemical microenvironment for sustained osteogenesis but also reprogram the osteoimmune microenvironment via the induction of M2 macrophage polarization to promote bone healing. The present study will provide a new paradigm to realize enhanced osteogenic efficacy by multichannel microenvironment regulations and give new insights into engineering high-efficacy i-PRF hydrogels for regenerative medicine.