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Chiral γ-amino alcohols are prevalent structural motifs in natural products and bioactive compounds. Nevertheless, efficient and atom-economical synthetic methods toward enantiomerically enriched γ-amino alcohols are still lacking. In this study, a highly enantioselective rhodium-catalyzed reductive hydroformylation of readily available α-substituted enamides is developed, providing a series of pharmaceutically valuable chiral 1,3-amino alcohols in good yields and excellent enantioselectivities in a single step. The development of the 4,4'-bisarylamino-substituted BIBOP ligand is crucial for the success of this transformation. DFT calculations and experimental data have revealed the importance of hydrogen bonding between the N-H group in the structure of TFPNH-BIBOP and the enamide carbonyl group in promoting both high enantioselectivity and reactivity. This method has enabled the concise synthesis of several chiral pharmaceutical intermediates including a single-step synthesis of the key chiral intermediate of maraviroc.

In all-solid-state batteries (ASSBs), silicon-based negative electrodes have the advantages of high theoretical specific capacity, low lithiation potential, and lower susceptibility to lithium dendrites. However, their significant volume variation presents persistent interfacial challenges. A promising solution lies in finding a material that combines ionic-electronic conductivity, stable physicochemical properties, and adhesive characteristics. Poly(acrylic acid) (PAA) is widely used in liquid-state batteries due to its superior properties compared to polyvinylidene fluoride (PVDF). In this study, silicon particles were coated with varying concentrations of PAA and LiPAA using an in situ liquid-phase coating method to form electrode sheets. The experimental and analytical results revealed significant trends in the impact of different additive concentrations on the electrochemical performance, with 1.0 wt % LiPAA showing notable improvements in Coulombic efficiency, rate capability, and long-term cycling stability. The assembled all-solid-state batteries exhibited a high initial discharge capacity of 3200 mAh/g, with a capacity retention of 81.9% after 300 cycles at 0.3 C, and a stable discharge capacity of 1300 mAh/g at a 2 C rate. A rapid and efficient in situ liquid-phase coating method for LiPAA was developed and confirmed through FTIR, XRD, and TEM characterization. SEM and XPS analyses demonstrated that LiPAA encapsulation effectively alleviates interfacial issues. This study demonstrated for the first time that an appropriate amount of LiPAA coating on silicon particles can mitigate the interfacial challenges caused by the volume expansion of silicon-based negative electrodes. These findings improve electrochemical performance and promote the application of silicon-based negative electrodes in all-solid-state batteries.

Psoriasis is a complex and chronic inflammatory disease. Current drugs help control the symptoms of psoriasis but make no cure, urging discovery of novel drugs. We report in this paper the discovery of new phosphodiesterase 4 (PDE4) inhibitors for treatment of psoriasis. We designed and synthesized 45 new compounds, among which 14h exhibited IC 50 of 0.57 nM for PDE4D and >4100-fold selectivity over other PDE families. Compound 14h inhibited release of inflammatory cytokines of TNF-α (IC 50 = 34.2 μM) and IL-6 (IC 50 = 40.9 μM) in Raw264.7 cells and reduced the expression of IL-1β and IL-17A in the skin of psoriasis mice. In addition, 14h alleviated IMQ-induced psoriasis in the mouse model and reduced the erythema level, scales, and thickness of the back skin of the mice. In short, our results suggested that PDE4 inhibitor 14h is a strong candidate for the topical treatment of psoriasis.

Nociceptors, crucial sensory receptors within biological systems, are essential for survival in diverse and potentially hazardous environments. Efforts to replicate nociceptors through advanced electronic devices, such as memristors and neuromorphic transistors, have achieved limited success, capturing basic nociceptive functions while more advanced characteristics like various forms of central sensitization and analgesic effect remain out of reach. Here, we introduce a vertical multigate, multichannel electrolyte-gated transistor (Vm-EGT), designed to mimic nociceptors. Utilizing the hybrid mechanism combining electric-double-layer (EDL) with ion intercalation/deintercalation in EGTs, our approach successfully replicates peripheral sensitization and desensitization characteristics of nociceptors. The intricate multigate and multichannel design of the Vm-EGT enables the emulation of more advanced nociceptive functionalities, including central sensitization and analgesic effect. Furthermore, we demonstrate that by exploiting the inherent current-voltage relationship, the Vm-EGT can simulate these advanced nociceptive features and seamlessly transition between them. Integrating a Vm-EGT with a thermistor and a heating plate, we have developed an artificial thermal nociceptor that closely mirrors the sensory attributes of its biological counterpart. Our approach significantly advances the emulation of nociceptors, providing a basis for the development of sophisticated artificial sensory systems and intelligent robotics.

Solvent-free oxidative desulfurization can avoid environmental pollution caused by organic solvents as well as prevent loss of fuel during the oil-water separation process. In this work, first, hydrophilic ionic liquid gel microspheres with [BMIM]BF 4 and PHEMA as the dispersion medium and gel network, respectively, were successfully prepared by using mesoporous silica microspheres as a supporting skeleton capable of stabilizing the gel through an anchoring effect, and then the catalyst [BMIM]PW and oxidant H 2 O 2 were incorporated into the gel microspheres to construct a liquid compartment microreactor for deep desulfurization. The prepared microreactor (SiO 2 @[BMIM]PW/ILG-microspheres) has excellent extraction-catalytic capacity and exhibited ∼100% desulfurization ratio for a model oil of n -heptane with 500 ppm of DBT at 60 °C for 3 h without solvents. Additionally, the prepared microreactor can absorb hydrophilic desulfurization products after the reaction and has advantages of reusability and simple recovery without polluting the fuel oil, which is beneficial for potential petroleum industrial application.

The experimental exploration of the chemical space of crystalline materials, especially metal-organic frameworks (MOFs), requires multiparameter control of a large set of reactions, which is unavoidably time-consuming and labor-intensive when performed manually. To accelerate the rate of material discovery while maintaining high reproducibility, we developed a machine learning algorithm integrated with a robotic synthesis platform for closed-loop exploration of the chemical space for polyoxometalate-scaffolding metal-organic frameworks (POMOFs). The eXtreme Gradient Boosting (XGBoost) model was optimized by using updating data obtained from the uncertainty feedback experiments and a multiclass classification extension based on the POMOF classification from their chemical constitution. The digital signatures for the robotic synthesis of POMOFs were represented by the universal chemical description language (χDL) to precisely record the synthetic steps and enhance the reproducibility. Nine novel POMOFs including one with mixed ligands derived from individual ligands through the imidization reaction of POM amine derivatives with various aldehydes have been discovered with a good repeatability. In addition, chemical space maps were plotted based on the XGBoost models whose F1 scores are above 0.8. Furthermore, the electrochemical properties of the synthesized POMOFs indicate superior electron transfer compared to the molecular POMs and the direct effect of the ratio of Zn, the type of ligands used, and the topology structures in POMOFs for modulating electron transfer abilities.

Parkinson's disease (PD) is a neurodegenerative disease characterized by the progressive loss of dopaminergic neurons in the substantia nigra, the etiology of which remains unclear. Studies have shown that neuroinflammation and oxidative stress (OS) play an important role in neuronal damage in patients with PD. Disturbances in the gut microbiota influence neuroinflammation and OS through the microbiota-gut-brain axis. Ginkgolide C (GC), a traditional Chinese medicine extracted from the leaves of Ginkgo biloba , has been reported to exhibit anti-inflammatory effects and the ability to modulate intestinal microbial composition. However, the potential of GC to positively impact PD by modulating the gut microbiota remains unexplored. This study aimed to explore the effects of GC on 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)-induced PD in mice and elucidate its underlying mechanisms. Our findings elucidated that GC treatment significantly ameliorates behavioral deficits as well as pathological damage via restoring gut microbial homeostasis to downgrade OS and neuroinflammation in MPTP-induced PD mice. Mechanistically, GC treatment exerts antioxidant effects via activating the AKT/Nrf2/HO-1 pathway in MPP + -exposed SN4741 neuronal cells and significantly downregulates the expression of inflammatory mediators via regulating NF-κB and MAPK signaling in lipopolysaccharide (LPS)-stimulated BV2 microglial cells. Overall, our study demonstrates that GC administration alleviates MPTP-induced neurodegeneration via rebuilding gut microbial homeostasis to inhibit OS and neuroinflammation in mice, indicating that GC might serve as a promising candidate medicine for PD.

Mastitis is a common mammalian disease occurring in the mammary tissue and poses a major threat to agriculture and the dairy industry. Hordenine (HOR), a phenylethylamine alkaloid naturally extracted from malt, has various pharmacological effects, but its role in mastitis is unknown. The aim of this study was to investigate the role of HOR and its underlying mechanism in a lipopolysaccharide (LPS)-induced inflammatory response model of mouse mammary epithelial cells (EpH4-Ev) and mouse mastitis model. The experimental results showed that HOR attenuated LPS-induced mammary tissue damage (from 3.75 ± 0.25 to 1.75 ± 0.25) and restored the integrity of the blood-milk barrier. Further mechanistic studies revealed that HOR inhibited LPS-induced overactivation of the TLR4-MAPK/NF-κB signaling pathway and activated the AMPK/Nrf2/HO-1 signaling pathway. Additionally, HOR altered the composition of the intestinal microbiota in mice, ultimately reducing the extent of inflammatory injury (from 3.33 ± 0.33 to 0.67 ± 0.33) and upregulating the expression of tight junction proteins (ZO-1, occludin, and claudin-3). The findings of this study provide a theoretical basis in the rational use of HOR for the prevention and treatment of mastitis and the maintenance of mammalian mammary gland health.

Integrating biomechanical and biomolecular sensing mechanisms into wearable devices is a formidable challenge and key to acquiring personalized health management. To address this, we have developed an innovative multifunctional sensor enabled by plasma functionalized silk fabric, which possesses multimodal sensing capabilities for biomechanics and biomolecules. A seed-mediated in situ growth method was employed to coat silver nanoparticles (AgNPs) onto silk fibers, resulting in silk fibers functionalized with AgNPs (SFs@Ag) that exhibit both piezoresistive response and localized surface plasmon resonance effects. The SFs@Ag membrane enables accurate detection of mechanical pressure and specific biomolecules during wearable sensing, offering a versatile solution for comprehensive personalized health monitoring. Additionally, a machine learning algorithm has been established to specifically recognize muscle strain signals, potentially extending to the diagnosis and monitoring of neuromuscular disorders such as amyotrophic lateral sclerosis (ALS). Unlike electromyography, which detects large muscles in clinical medicine, sensing data for tiny muscles enhance our understanding of muscle coordination using the SFs@Ag sensor. This detection model provides feasibility for the early detection and prevention of neuromuscular diseases. Beyond muscle stress and strain sensing, biomolecular detection is a critical addition to achieving effective health management. In this study, we developed highly sensitive surface-enhanced Raman scattering (SERS) detection for wearable health monitoring. Finite-difference time-domain numerical simulations ware utilized to analyze the efficacy of the SFs@Ag sensor for wearable SERS sensing of biomolecules. Based on the specific SERS spectra, automatic extraction of signals of sweat molecules was also achieved. In summary, the SFs@Ag sensor bridges the gap between biomechanical and biomolecular sensing in wearable applications, providing significant value for personalized health management.

Herein, composites of nanosheets with van der Waals contacts are employed to disclose how the interlayer-microenvironment affects the product selectivity of carbon dioxide (CO 2 ) photoreduction. The concept of composites of nanosheets with dual active sites is introduced to manipulate the bonding configuration and promote the thermodynamic formation of methanol (CH 3 OH). As a prototype, the CoNi 2 S 4 -In 2 O 3 composites of nanosheets are prepared, in which high-resolution transmission electron microscopy imaging, X-ray photoelectron spectroscopy spectra, and zeta potential tests confirm the presence of van der Waals contacts rather than chemical bonding between the In 2 O 3 nanosheets and the CoNi 2 S 4 nanosheets within the composite. The fabricated CoNi 2 S 4 -In 2 O 3 composites of nanosheets exhibit the detection of the key intermediate *CH 3 O during CO 2 photoreduction through in situ Fourier transform infrared spectra, while the In 2 O 3 nanosheets and CoNi 2 S 4 nanosheets alone do not show this capability, further verified by the density functional theory calculations. Accordingly, the CoNi 2 S 4 -In 2 O 3 composites of nanosheets show the ability to produce CH 3 OH, whereas the CoNi 2 S 4 and In 2 O 3 nanosheets solely generate carbon monoxide products from CO 2 photoreduction.

Vibration affects the wetting behavior of droplets, and it is feasible to use vibration to modulate the adhesion characteristics of droplets. In this paper, the effect of vertical sinusoidal vibrations on the wettability of molten aluminum droplets on the substrate surfaces of smooth and with nanopillars is investigated. The increase in the frequency or amplitude of the vibration leads to a rise in the interfacial potential energy between the molten droplets and the substrate, which in turn leads to the occurrence of the Wenzel-Cassie transition. Once the vibration frequency reaches the threshold values, the molten droplets leave from the substrate, that is, dewetting occurs. The molten droplets in the Wenzel state undergo a Wenzel-Cassie transition before dewetting occurs. A phase diagram describing the frequency thresholds at which the molten aluminum droplets undergo dewetting and the Wenzel-Cassie transition at different amplitudes is plotted. For a specific amplitude, the frequency of vibration required for dewetting to occur in molten aluminum droplets in the Young state is lower than that in the Wenzel state. The needed vibrational frequency for dewetting or the Wenzel-Cassie transition decreases with increasing amplitude.

In the preparation process of c-Si solar cells, qualified Si wafers must be processed through mechanical processing during manufacturing. Most of these processes involve mechanical processing, which inevitably results in severe mechanical damage layers and a wafer surface with large roughness. The current industry practice involves etching of the damage layer using an acid/alkali solution, and it is usually followed by deposition of additional passivation layers in the subsequent processes. However, even with these treatments, there still remain non-negligible microscopic saw damage and scratches on the wafer surface, which hinder the urgent development of a higher conversion efficiency of solar cells. Here, we provide a simple method to effectively suppress the impact of this surface damage. UV-OZONE treatment, which involves generation of an oxide layer and subsequent cleaning with hydrofluoric acid, leads to the effective regain of solar cell performance due to the passivation of dangling bonds and removal of sharp microstructures based on the creation of mechanical scratches. In addition, PEDOT:PSS/n-Si solar cells were prepared to exploit their strong surface dependence to investigate the effect of scratches on the overall performance. These results further validate the impact of scratches on solar cells, and a simple and effective method for surface damage suppression is provided.

At present, it is very necessary to select and prepare suitable positive and negative electrode materials to fabricate high-performance asymmetric supercapacitors. Metal-organic frameworks (MOFs) have garnered significant attention in the energy storage field due to their high conductivity. As a branch, the zirconium organic framework (UIO-66) is a promising porous material due to its large specific surface area and abundant Zr centers. Graphene oxide (GO) and MXene are very suitable as substrate materials for conducting an MOF due to their abundant active sites and adjustable interlayer distance. The GO/MXene@NiZrP prepared through an in situ composite of GO and Mxene with the hydrothermal method and calcining method showed excellent electrochemical performance. Compared with the precursor UIO-66, the specific capacitance of the final product GO/MXene@NiZrP increases more than ten times, mainly because of its special layered porous structure, and GO/MXene@NiZrP has a larger specific surface area, pore volume, and surface defects caused by unstable Zr 4+ than those of UIO-66. Using GO/MXene@NiZrP as the positive electrode and biochar (BC) as the negative electrode, an asymmetric supercapacitor, BC//GO/MXene@NiZrP, is assembled. After 10,000 cycles at a current density of 10 A g -1 , the capacitance retention remains at 83.3%, showing excellent cycle stability.

The hypothesis underlying the abiogenic origin of life suggests that the nonenzymatic synthesis of long-chain fatty acids led to the construction of vesicles for compartmentalization in an early stage during the transition from geochemistry to biochemistry. However, evidence for this theory remains elusive as C 5+ carboxylic acids cannot be synthesized using current laboratory simulations. Here, we report the synthesis of long-chain carboxylic acids (C 3 -C 7 ) with a 42 mmol/g Co+Ni yield and 87.7% selectivity from formate (an intermediate of the acetyl-CoA pathway) over a cobalt-nickel alloy under alkaline hydrothermal conditions and the subsequent formation of microdroplets from organics. Density functional theory (DFT) calculations confirmed that the synergistic effect of the bimetal catalyst is key for catalyzing C-C coupling. Investigations by infrared spectroscopy, electron paramagnetic resonance, and isotope-labeled experiments revealed that HCO* serves as a reaction intermediate and is involved in the subsequent elementary steps for synthesizing long-chain carboxylic acids from formate. Taken together, these findings may help explain how the first protocells emerged geochemically and provide support for the hypothesis of the abiogenic origin of life. The hydrothermal system developed may also be applicable for the sustainable synthesis of long-chain carboxylates from one-carbon substrates using nonnoble metal catalysts.

Nonylphenol (NP) is an important fine chemical raw material and intermediate that is widely utilized in industry and may be distributed in aquatic ecosystems. Following its entry into the food and water cycles, it can subsequently enter the human body and potentially harm the human reproductive system. For the purpose of monitoring NP in water, it is thus essential to build a straightforward, affordable, and robust electrochemical sensor. Based on a two-step chemical modification proceeding and an electrostatic self-assembly effect, a double-modified β-cyclodextrin functionalized multiwalled carbon nanotube sensor (HE-β-CD-CTAC/F-MWCNTs) has been successfully constructed. It incorporates the excellent host-guest interaction ability of β-cyclodextrin and the high chemical activity of cetyltrimethylammonium chloride (CTAC), and the carbon nanotubes have an enormous particular surface area and strong electrical conductivity. The electrochemical oxidation reaction of NP with the sensor is controlled by a surface adsorption process of equal numbers of protons and electrons. In accordance with the optimized experimental parameters, the limit of detection (LOD) for the sensor is 0.13 μM, and it responds linearly to NP in the concentration range of 1-200 μM. Meanwhile, the sensor has excellent repeatability, stability, and immunity to interference. For the detection of NP in real water samples, the sensor also showed an excellent recovery rate (92.8%-98.5%) and relative standard deviation (1.16%-3.26%).

Based on the ab initio energy points of both ground and excited states, a neural network fitting method combined with a specific function was successfully used to construct the diabatic potential energy surfaces (PESs) of the SrH 2 + system. The topographical features of the diabatic PESs were examined in detail. The results indicate that the nonadiabatic transition characteristics between ground and excited states are accurately described by the newly constructed diabatic PESs. To verify the validity and applicability of the diabatic PESs, as well as the nonadiabatic effects during the reaction process, the quantum dynamics studies of the Sr + (5s 2 S) + H 2 reaction were performed based on both adiabatic and diabatic PESs. The dynamics results indicate that adiabatic dynamics results are dozens of times larger than those of nonadiabatic. This illustrates the significant effect of nonadiabaticity, indicating that adiabatic dynamics results often overestimate the actual values. The integral cross sections (ICSs) were calculated and compared with the experimental data. The diabatic ICSs are in good agreement with the experimental results. The reasonable dynamics results indicate that the newly constructed diabatic PESs are suitable for the relevant dynamics studies.

It offers bright prospects to develop non-Pt group metal (non-PGM) electrocatalysts in the area of energy storage and conversion. Herein, we reported a simple spatial isolation strategy to synthesize Co-based electrocatalysts, using partially substituted Zn atoms in a ZnCo-ZIF precursor. The "fence" effect that originated from the partially substituted Zn atoms can yield a better isolation of Co atoms, achieving selective loading of Co species on nitrogen-doped porous carbon varying from nanoparticles to single atoms. The low boiling point of Zn enables abundant porous structures to the N-doped carbon substrate after pyrolysis. The best performing single-atom Co catalyst (Co-SAs/N-C) exhibits excellent oxygen reduction reaction activity in alkaline media. As an illustration, the rechargeable liquid Zn-air battery incorporating the Co-SAs/N-C catalyst demonstrates a substantial open circuit voltage of 1.49 V, a high specific capacity of 689.3 mAh g -1 , and remarkable cycling stability over 200 h. This study paves the way for the strategic development of non-PGM electrocatalysts in battery applications.

Sunitinib (SUN) is a first-line drug for the treatment of renal clear carcinoma cells by targeting receptor tyrosine kinases (RTK) on the cell membrane. However, the effective delivery of SUN to the cell membrane remains a significant challenge. In this study, we fabricated precisely structured DNA nanotapes with strong surface SUN adhesion, enabling RTK inhibition of renal clear carcinoma cells. In our design, the precisely assembled linear topological six-helical-bundle DNA origami serves as the framework, and positively charged chitosan is adsorbed onto the DNA origami surface, thereby forming DNA nanotapes. The SUN was efficiently loaded onto the surface of the DNA nanotapes by electrostatic interaction. We found that DNA nanotapes exhibit excellent stability in serum. Importantly, DNA nanotapes carrying SUN can achieve prolonged cell membrane retention and inhibit RTK, thereby enhancing cytotoxicity toward 786-0 cells. Taken together, this study provides a promising candidate platform for the efficient delivery of cell membrane receptor inhibitors in anticancer therapy., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Corneal alkali burns represent a prevalent ophthalmic emergency with the potential to induce blindness. The main contributing mechanisms include excessive inflammation and delayed wound healing. Existing clinical therapies have limitations, promoting the exploration of alternative methods that offer improved efficacy and reduced side effects. Adipose-derived stem cell-exosome (ADSC-Exo) has the potential to sustain immune homeostasis and facilitate tissue regeneration. Nevertheless, natural ADSC-Exo lacks disease specificity and exhibits limited bioavailability on the ocular surface. In this study, we conjugated antitumor necrosis factor-α antibodies (aT) to the surface of ADSC-Exo using matrix metalloproteinase-cleavable peptide chains to create engineered aT-Exo with synergistic effects. In both in vivo and in vitro assessments, aT-Exo demonstrated superior efficacy in mitigating corneal injuries compared to aT alone, unmodified exosomes, or aT simply mixed with exosomes. The cleavable conjugation of aT-Exo notably enhanced wound healing and alleviated inflammation more effectively. Simultaneously, we developed poly(vinyl alcohol) microneedles (MNs) for precise and sustained exosome delivery. The in vivo results showcased the superior therapeutic efficiency of MNs compared with conventional topical administration and subconjunctival injection. Therefore, the bioactive nanodrugs-loaded MNs treatment presents a promising strategy for addressing ocular surface diseases.

A photoredox-promoted decarboxylative C-H glycosylation for the synthesis of nonclassical heteroaryl C-glycosides is reported. This methodology is characterized by an exceedingly simple reaction system, high diastereoselectivity, and good functional group tolerance. Moreover, the operational procedure is simple, and the gram-scale reaction highlights the practical applicability of this protocol.

Solar-driven plastics conversion into valuable fuels has attracted broad attention in recent years, which has enormous potential for plastics recycling in the future. However, it usually encounters low conversion efficiency, where one of the reasons is attributed to the poor carrier dynamics in the photocatalytic process. In this Perspective, we critically review the developed strategies, involving defect engineering, doping engineering, heterojunction engineering, and composite construction, for boosted carrier separation efficiency. In addition, we provide an outlook for more potential strategies to engineer catalysts for promoted carrier dynamics. Finally, we also propose prospects for the future research direction of plastics photoconversion into fuels.

The ongoing transition toward electric vehicles (EVs) is changing materials used for vehicle production, of which the consequences for the environmental performance of EVs are not well understood and managed. We demonstrate that electrification coupled with lightweighting of automobiles will lead to significant changes in the industry's demand not only for battery materials but also for other materials used throughout the entire vehicle. Given the automotive industry's substantial consumption of raw materials, changes in its material demands are expected to trigger volatilities in material prices, consequently impacting the material composition and attractiveness of EVs. In addition, the materials recovered during end-of-life recycling of EVs as the vehicle fleet turns over will impact recycled material supplies both positively and negatively, impacting material availabilities and the economic incentive to engage in recycling. These supply chain impacts will influence material usage and the associated environmental performance of not only the automotive sector but also other metal-heavy industries such as construction. In light of these challenges, we propose the need for new research to understand the dynamic materials impacts of the EV transition that encompasses its implications on EV adoption and fleet life cycle environmental performance. Effectively coordinating the coevolution of material supply chains is crucial for making the sustainable transition to EVs a reality.

Postconsumer plastics are generally perceived as valueless with only a small portion of plastic waste being closed-loop recycled into similar products while most of them are discarded in landfills. Depositing plastic waste in landfills not only harms the environment but also signifies a substantial economic loss. Alternatively, constructing value-added chemical feedstocks via mining the waste-derived intermediate species as a carbon (C) source under mild electrochemical conditions is a sustainable strategy to realize the circular economy. This proof-of-concept work provides an attractive "turning trash to treasure" strategy by integrating electrocatalytic polyethylene terephthalate (PET) plastic upcycling with a chemical C-S coupling reaction to synthesize organosulfur compounds, hydroxymethanesulfonate (HMS). HMS can be produced efficiently (Faradaic efficiency, FE of ∼70%) via deliberately capturing electrophilic intermediates generated in the PET monomer (ethylene glycol, EG) upcycling process, followed by coupling them with nucleophilic sulfur (S) species (i.e., SO 3 2- and HSO 3 - ). Unlike many previous studies conducted under alkaline conditions, PET upcycling was performed over an amorphous MnO 2 catalyst under near-neutral conditions, allowing for the stabilization of electrophilic intermediates. The compatibility of this strategy was further investigated by employing biomass-derived compounds as substrates. Moreover, comparable HMS yields can be achieved with real-world PET plastics, showing its enormous potential in practical application. Lastly, Density function theory (DFT) calculation reveals that the C-C cleavage step of EG is the rate-determining step (RDS), and amorphous MnO 2 significantly decreases the energy barriers for both RDS and C-S coupling when compared to the crystalline counterpart.

Thousands of mass peaks emerge during molecular characterization of natural dissolved organic matter (DOM) using ultrahigh-resolution mass spectrometry. While mass peaks assigned to certain molecular formulas have been extensively studied, the uncharacterized mass peaks that represent a significant fraction of organic matter and convey biogenic elements and energy have been previously ignored. In this study, we introduce the term dark DOM (DDOM) for unassigned mass peaks and have explored its characteristics and environmental behaviors using a data set of 38 DOM extracts covering the Yangtze River-to-ocean continuum. We identified a total of 9141 DDOM molecules, which exhibited higher molecular weight and greater diversity than the DOM subset with assigned DOM formulas. Although DDOM contributed a smaller fraction of relative abundance, it significantly impacted the molecular weight and molecular composition of bulk DOM. A portion of DDOM with higher molecular weight was found to increase molecular abundance across the river-to-ocean continuum. These compounds could contain halogenated organic molecules and might have a high potential to contribute to the refractory organic carbon pool. With this study, we underline the contribution of dark matter to the total DOM pool and emphasize that more DDOM research is needed to understand its contribution to global biogeochemical cycles and carbon sequestration.

NIR-II imaging-guided phototherapy is an attractive, yet challenging, tumor treatment strategy. By monitoring the accumulation of phototherapy reagents at the tumor site through imaging and determining the appropriate therapy window, the therapeutic effect could be significantly improved. Probes with NIR-II (1000-1700 nm) fluorescence emission and a large Stokes shift hold great promise for fluorescence imaging with deep penetration, minimized self-quenching, and high spatiotemporal resolution. However, due to the lack of a suitable molecular framework, the design of a simple small-molecule dye with a large Stokes shift and NIR-II fluorescence emission has rarely been reported. Herein, we prepare an asymmetric D-π-A type NIR-II fluorescence probe (TBy). The probe is incapsulated in an amphiphilic polymer and modified with a fibronectin targeting peptide CREKA, which could recognize the fibrin-fibronectin complex overexpressed in multiple malignant tumors. The nanoparticles thus constructed (TByC-NPs) have maximum fluorescence emission at 1037 nm with a large Stokes shift of 426 nm, which is the largest Stokes shift among organic NIR-II fluorescent dyes reported in the literature. The TByC-NPs exhibit a good NIR-II imaging performance, active tumor targeting, and good photothermal and photodynamic capabilities. In vitro and in vivo studies verify that the TByC nanoplatform shows outstanding biocompatibility for NIR-II imaging-guided phototherapy and provides an excellent antitumor effect.

Two-dimensional materials hold great potentials for beyond-CMOS (complementary metal-oxide-semiconductor) electronical and optoelectrical applications, and the development of field effect transistors (FET) with excellent performance using such materials is of particular interest. How to improve the performance of devices thus becomes an urgent issue. The performance of FETs depends greatly on the intrinsic electrical properties of the channel materials, meanwhile the device interface quality, such as extrinsic scattering of charged impurities, charge traps, and substrate surface roughness have a great influence on the performance. In this paper, the impact of the interface quality on the carrier diffusion behaviors of monolayer (ML) MoSe 2 has been investigated by using an in situ ultrafast laser technique to avoid the surface contamination during device fabrication process. Two types of self-assembled monolayers (SAMs) are introduced to modify the gate dielectric surface through an interface engineering approach to obtain chemical-stable interfaces. The results showed that the transport properties of ML MoSe 2 were enhanced after interface engineering, for example, the carrier mobility of ML MoSe 2 was improved from ∼59.4 to ∼166.5 cm 2 V -1 s -1 after the SAM modification. Meanwhile, the photocarrier dynamics of ML MoSe 2 before and after interfacial engineering were also carefully studied. Our studies provide a feasible method for improving the carrier diffusion behaviors of such materials, and making them suited for application in future integrated circuit.

Ameliorating microglia-mediated neuroinflammation is a crucial strategy in developing new drugs for neurodegenerative diseases. Plant compounds are an important screening target for the discovery of drugs for the treatment of neurodegenerative diseases. However, due to the spatial complexity of phytochemicals, it becomes particularly important to evaluate the effectiveness of compounds while avoiding the mixing of cytotoxic substances in the early stages of compound screening. Traditional high-throughput screening methods suffer from high cost and low efficiency. A computational model based on machine learning provides a novel avenue for cytotoxicity determination. In this study, a microglia cytotoxicity classifier was developed using a machine learning approach. First, we proposed a data splitting strategy based on the molecule murcko generic scaffold, under this condition, three machine learning approaches were coupled with three kinds of molecular representation methods to construct microglia cytotoxicity classifier, which were then compared and assessed by the predictive accuracy, balanced accuracy, F 1 -score, and Matthews Correlation Coefficient. Then, the recursive feature elimination integrated with support vector machine (RFE-SVC) dimension reduction method was introduced to molecular fingerprints with high dimensions to further improve the model performance. Among all the microglial cytotoxicity classifiers, the SVM coupled with ECFP4 fingerprint after feature selection (ECFP4-RFE-SVM) obtained the most accurate classification for the test set (ACC of 0.99, BA of 0.99, F 1 -score of 0.99, MCC of 0.97). Finally, the Shapley additive explanations (SHAP) method was used in interpreting the microglia cytotoxicity classifier and key substructure smart identified as structural alerts. Experimental results show that ECFP4-RFE-SVM have reliable classification capability for microglia cytotoxicity, and SHAP can not only provide a rational explanation for microglia cytotoxicity predictions, but also offer a guideline for subsequent molecular cytotoxicity modifications.

Nowadays, plastic waste threatens public health and the natural ecosystems of our lives. It is highly beneficial to recycle plastic waste in order to maximize the reuse of its contained carbon sources for the development of other valuable products. Unfortunately, traditional techniques usually require significant energy consumption and result in the generation of hazardous waste. Herein, the up-to-date developments on the "green" strategies under mild conditions including electrocatalysis, photocatalysis, and photoelectrocatalysis of plastic wastes are presented. During the oxidation of plastics in these "green" strategies, corresponding reduction reactions usually exist, which affect the property of catalytic plastics conversion. Particularly, we mainly focus on how to design the corresponding half reactions, such as the water reduction, carbon dioxide reduction, and nitrate reduction. Finally, we provide forward-looking insight into the enhancement of these "green" strategies, the extension of more half reactions into other organic catalysis, a comprehensive exploration of the underlying mechanisms through in situ studies and theoretical analysis and the problems for practical applications that needs to be solved.

Metal-organic polyhedra (MOPs) can exhibit tunable porosity and functionality, suggesting potential for applications such as molecular separations. MOPs are typically constructed by the bottom-up multicomponent self-assembly of organic ligands and metal ions, and the final functionality can be hard to program. Here, we used trianglsalen macrocycles as preorganized building blocks to assemble octahedral-shaped MOPs. The resultant MOPs inherit most of the preorganized properties of the macrocyclic ligands, including their well-defined cavities and chirality. As a result, the porosity in the MOPs could be tuned by modifying the structure of the macrocycle building blocks. Using this strategy, we could systematically enlarge the size of the MOPs from 26.3 to 32.1 Å by increasing the macrocycle size. The family of MOPs shows experimental surface areas of up to 820 m 2 /g, and they are stable in water. One of these MOPs can efficiently separate the rare gases Xe from Kr because the prefabricated macrocyclic windows of MOPs can be modified to sit at the Xe/Kr size cutoff range.

This study aims to enhance the performance of perovskite solar cells (PSCs) by optimizing the interface between the perovskite and electron transport layers (ETLs). Additionally, we plan to protect the absorber layer from ultraviolet (UV) degradation using a ternary oxide system comprising SnO 2 , strontium stannate (SrSnO 3 ), and strontium oxide (SrO). In this structure, the SnO 2 layer functions as an electron transport layer, SrSnO 3 acts as a layer for UV filtration, and SrO is employed to passivate the interface. SrSnO 3 is characterized by its chemical stability, electrical conductivity, extensive wide band gap energy, and efficient absorption of UV radiation, all of which significantly enhance the photostability of PSCs against UV radiation. Furthermore, incorporating SrSnO 3 into the ETL improves its electronic properties, potentially raising the energy level and improving alignment, thereby enhancing the electron transfer from the perovskite layer to the external circuit. Integrating SrO at the interface between the ETL and perovskite layer reduces interface defects, thereby reducing charge recombination and improving electron transfer. This improvement results in higher solar cell efficiency, reduced hysteresis, and extended device longevity. The benefits of this method are evident in the observed improvements: a noticeable increase in open-circuit voltage ( V oc ) from 1.12 to 1.16 V, an enhancement in the fill factor from 79.4 to 82.66%, a rise in the short-circuit current density ( J sc ) from 24.5 to 24.9 mA/cm 2 and notably, a marked improvement in the power conversion efficiency (PCE) of PSCs, from 21.79 to 24.06%. Notably, the treated PSCs showed only a slight decline in PCE, reducing from 24.15 to 22.50% over nearly 2000 h. In contrast, untreated SnO 2 perovskite devices experienced a greater decline, with efficiency decreasing from 21.79 to 17.83% in just 580 h.

Triclocarban (TCC), as a widely used antimicrobial agent, is accumulated in waste activated sludge at a high level and inhibits the subsequent anaerobic digestion of sludge. This study, for the first time, investigated the effectiveness of microbial electrolysis cell-assisted anaerobic digestion (MEC-AD) in mitigating the inhibition of TCC to methane production. Experimental results showed that 20 mg/L TCC inhibited sludge disintegration, hydrolysis, acidogenesis, and methanogenesis processes and finally reduced methane production from traditional sludge anaerobic digestion by 19.1%. Molecular docking revealed the potential inactivation of binding of TCC to key enzymes in these processes. However, MEC-AD with 0.6 and 0.8 V external voltages achieved much higher methane production and controlled the TCC inhibition to less than 5.8%. TCC in the MEC-AD systems was adsorbed by humic substances and degraded to dichlorocarbanilide, leading to a certain detoxification effect. Methanogenic activities were increased in MEC-AD systems, accompanied by complete VFA consumption. Moreover, the applied voltage promoted cell apoptosis and sludge disintegration to release biodegradable organics. Metagenomic analysis revealed that the applied voltage increased the resistance of electrode biofilms to TCC by enriching functional microorganisms (syntrophic VFA-oxidizing and electroactive bacteria and hydrogenotrophic methanogens), acidification and methanogenesis pathways, multidrug efflux pumps, and SOS response.

Two-dimensional materials with a unique layered structure have attracted intense attention all around the world due to their extraordinary physical properties. Most importantly, the internal Coulomb coupling can be regulated, and thus electronic transition can be realized by manipulating the interlayer interaction effectively through adding external fields. At present, the properties of two-dimensional materials can be tuned through a variety of methods, such as adding pressure, strain, and electromagnetic fields. For optoelectronic applications, the lifetime of the photogenerated carriers is one of the most crucial parameters for the materials. Here, we demonstrate effective modulation of the optical band gap structure and photocarrier dynamics in CuS nanoflakes by applying hydrostatic pressure via a diamond anvil cell. The peak differential reflection signal shows a linear blueshift with the pressure, suggesting effective tuning of interlayer interaction inside CuS by pressure engineering. The results of transient absorption show that the photocarrier lifetime decreases significantly with pressure, suggesting that the dissociation process of the photogenerated carriers accelerates. It could be contributed to the phase transition or the decrease of the phonon vibration frequency caused by the pressure. Further, Raman spectra reveal the change of Cu-S and S-S bonds after adding pressure, indicating the possible occurrence of structural phase transition. Interestingly, all of the variation modes are reversible after releasing pressure. This work has provided an excellent sight to show the regulation of pressure on the photoelectric properties of CuS, exploring CuS to wider applications that can lead toward the realization of future excitonic and photoelectric devices modulated by high pressure., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In this work, thermo-oxidative behavior, kinetic triplet, and free radical mechanism of ultraheavy oil during an in situ combustion (ISC) process were systematically surveyed via multiple thermal analysis techniques (TG/DTG/DSC/PDSC), model-free methods, and related mathematical simulation. First, specific mass loss, exothermic intensity, and corresponding temperature intervals were respectively determined in low-/high-temperature oxidation (LTO/HTO) regions. In addition, the comparison of atmospheric/pressurized differential scanning calorimetry (DSC/PDSC) experiments indicated that the pressurized conditions could obviously strengthen the oxidation progress with more heat emission. Then two model-free methods were contrastively employed for PDSC data to calculate LTO and HTO activation energy variations with the conversion rate. Moreover, the acceleratory rate model for LTO and the Sestak-Berggren model for HTO were accordingly picked as the most probable mechanism functions, which were later used to determine the simulated curves. Then, the simulations of α- T and dα/d T - T curves were respectively attained using Friedman equation in MATLAB software and contrasted with experimental data to validate the accuracy of the yielded kinetic triplet and forecast the combustion behavior. Further, the evolution pathways of the underlying oxidation mechanism was illustrated. This study updates the understanding of the nonisothermal combustion process, contributing to the subsequent numerical simulation and feasible investigation for in situ combustion implementation to enhance heavy oil recovery., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Passion fruit ( Passiflora spp.) is an important fruit tree in the family Passifloraceae. The color of the fruit skin, a significant agricultural trait, is determined by the content of anthocyanin in passion fruit. However, the regulatory mechanisms behind the accumulation of anthocyanin in different passion fruit skin colors remain unclear. In the study, we identified and characterized a R2R3-MYB transcription factor, PeMYB114 , which functions as a transcriptional activator in anthocyanin biosynthesis. Yeast one-hybrid system and dual-luciferase analysis showed that PeMYB114 could directly activate the expression of anthocyanin structural genes ( PeCHS and PeDFR ). Furthermore, a natural variation in the promoter region of PeMYB114 alters its expression. PeMYB114 purple accessions with the 224-bp insertion have a higher anthocyanin level than PeMYB114 yellow accessions with the 224-bp deletion. The findings enhance our understanding of anthocyanin accumulation in fruits and provide genetic resources for genome design for improving passion fruit quality.

Magnetic molecules adsorbed on two-dimensional (2D) substrates have attracted broad attention because of their potential applications in quantum device applications. Experimental observations have demonstrated substantial alteration in the spin excitation energy of iron phthalocyanine (FePc) molecules when adsorbed on nitrogen-doped graphene substrates. However, the underlying mechanism responsible for this notable change remains unclear. To shed light on this, we employ an embedding method and ab initio quantum chemistry calculations to investigate the effects of surface doping on molecular properties. Our study unveils an unconventional chemical bonding at the interface between the FePc molecule and the N-doped graphene. This bonding interaction, stronger than non-covalent interactions, significantly modifies the magnetic anisotropy energy of the adsorbed molecule, consistent with experimental observations. These findings provide valuable insights into the electronic and magnetic properties of molecules on 2D substrates, offering a promising pathway for precise manipulation of molecular spin states.

The intricate protonation process in carbon dioxide reduction usually makes the product unpredictable. Thus, it is significant to control the reactive intermediates to manipulate the reaction steps. Here, we propose that the synergistic La-Ti active sites in the N-La 2 Ti 2 O 7 nanosheets enable the highly selective carbon dioxide photoreduction into methane. In the photoreduction of CO 2 over N-La 2 Ti 2 O 7 nanosheets, in situ Fourier transform infrared spectra are utilized to monitor the *CH 3 O intermediate, pivotal for methane production, whereas such monitoring is not conducted for La 2 Ti 2 O 7 nanosheets. Also, theoretical calculations testify to the increased charge densities on the Ti and La atoms and the regulated formation energy barrier of *CO and *CH 3 O intermediates by the constructed synergistic active sites. Accordingly, the methane formation rate of 7.97 μL h -1 exhibited by the N-La 2 Ti 2 O 7 nanosheets, along with an electron selectivity of 96.6%, exceeds that of most previously reported catalysts under similar conditions.

Traditional metal materials used in electronic devices are often problematic due to issues like bending resistance, oxidation leading to failure, and environmental pollution. To address these challenges, microwave electronic devices are constantly casting around for metal substitute materials with additional characteristics such as flexibility, anticorrosive, and eco-friendly. However, finding suitable materials that are accessible for radiofrequency (RF) applications is a difficult yet promising task. Consequently, a high-performance metasurface antenna based on highly conductive graphene films for satellite communications is developed in this paper. The proposed graphene assembled films (GAFs) have a conductivity of up to 1.13 × 10 6 S/m. Simulation and measurement results confirm the excellent performance of the designed antenna. Comparative experiments are also conducted on salt spray and mechanical bending between GAF antenna patterns and copper foil counterparts, further demonstrating the outstanding flexible property and corrosion resistance performance of prepared GAFs.

Edges and surfaces play indispensable roles in affecting the chemical-physical properties of materials, particularly in two-dimensional transition metal dichalcogenides (TMDCs) with reduced dimensionality. Herein, we report a novel edge/surface structure in multilayer 1T-TiSe 2 , i.e., the orthogonal (1 × 1) reconstruction, induced by the self-intercalation of Ti atoms into interlayer octahedral sites of the host TiSe 2 at elevated temperature. Formation dynamics of the reconstructed edge/surface are captured at the atomic level by in situ scanning transmission electron microscopy (STEM) and further validated by density functional theory (DFT), which enables the proposal of the nucleation mechanism and two growth routes (zigzag and armchair). Via STEM-electron energy loss spectroscopy (STEM-EELS), a chemical shift of 0.6 eV in Ti L 3,2 is observed in the reconstructed edge/surface, which is attributed to the change of the coordination number and lattice distortion. The present work provides insights to tailor the atomic/electronic structures and properties of 2D TMDC materials.

The removal of antibiotic-resistant bacteria (ARB) and antibiotic-resistance genes (ARGs) using sulfate anion radical (SO 4 •- )-based advanced oxidation processes has gained considerable attention recently. However, immense uncertainties persist in technology transfer. Particularly, the impact of dichlorine radical (Cl 2 •- ) generation during SO 4 •- -mediated disinfection on ARB/ARGs removal remains unclear, despite the Cl 2 •- concentration reaching levels notably higher than those of SO 4 •- in certain SO 4 •- -based procedures applied to secondary effluents, hospital wastewaters, and marine waters. The experimental results of this study reveal a detrimental effect on the disinfection efficiency of tetracycline-resistant Escherichia coli (Tc-ARB) during SO 4 •- -mediated treatment owing to Cl 2 •- generation. Through a comparative investigation of the distinct inactivation mechanisms of Tc-ARB in the Cl 2 •- - and SO 4 •- -mediated disinfection processes, encompassing various perspectives, we confirm that Cl 2 •- is less effective in inducing cellular structural damage, perturbing cellular metabolic activity, disrupting antioxidant enzyme system, damaging genetic material, and inducing the viable but nonculturable state. Consequently, this diminishes the disinfection efficiency of SO 4 •- -mediated treatment owing to Cl 2 •- generation. Importantly, the results indicate that Cl 2 •- generation increases the potential risk associated with the dark reactivation of Tc-ARB and the vertical gene transfer process of tetracycline-resistant genes following SO 4 •- -mediated disinfection. This study underscores the undesired role of Cl 2 •- for ARB/ARGs removal during the SO 4 •- -mediated disinfection process.

Upcycling plastic wastes into value-added chemicals is a promising approach to put end-of-life plastic wastes back into their ecocycle. As one of the polyesters that is used daily, polyethylene terephthalate (PET) plastic waste is employed here as the model substrate. Herein, a nickel (Ni)-based catalyst was prepared via electrochemically depositing copper (Cu) species on Ni foam (NiCu/NF). The NiCu/NF formed Cu/CuO and Ni/NiO/Ni(OH) 2 core-shell structures before electrolysis and reconstructed into NiOOH and CuOOH/Cu(OH) 2 active species during the ethylene glycol (EG) oxidation. After oxidation, the Cu and Ni species evolved into more reduced species. An indirect mechanism was identified as the main EG oxidation (EGOR) mechanism. In EGOR, NiCu 60s /NF catalyst exhibited an optimal Faradaic efficiency (FE, 95.8%) and yield rate (0.70 mmol cm -2 h -1 ) for formate production. Also, over 80% FE of formate was achieved when a commercial PET plastic powder hydrolysate was applied. Furthermore, commercial PET plastic water bottle waste was employed as a substrate for electrocatalytic upcycling, and pure terephthalic acid (TPA) was recovered only after 1 h electrolysis. Lastly, density functional theory (DFT) calculation revealed that the key role of Cu was significantly reducing the Gibbs free-energy barrier (Δ G ) of EGOR's rate-determining step (RDS), promoting catalysts' dynamic evolution, and facilitating the C-C bond cleavage., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Exploring accurate, noninvasive, and inexpensive disease diagnostic sensors is a critical task in the fields of chemistry, biology, and medicine. The complexity of biological systems and the explosive growth of biomarker data have driven machine learning to become a powerful tool for mining and processing big data from disease diagnosis sensors. With the development of bioinformatics and artificial intelligence (AI), machine learning models formed by data mining have been able to guide more sensitive and accurate molecular computing. This review presents an overview of big data collection approaches and fundamental machine learning algorithms and discusses recent advances in machine learning and molecular computational disease diagnostic sensors. More specifically, we highlight existing modular workflows and key opportunities and challenges for machine learning to achieve disease diagnosis through big data mining.

We applied solid- and solution-state nuclear magnetic resonance spectroscopy to examine the structure of multidomain peptides composed of self-assembling β-sheet domains linked to bioactive domains. Bioactive domains can be selected to stimulate specific biological responses ( e.g ., via receptor binding), while the β-sheets provide the desirable nanoscale properties. Although previous work has established the efficacy of multidomain peptides, molecular-level characterization is lacking. The bioactive domains are intended to remain solvent-accessible without being incorporated into the β-sheet structure. We tested for three possible anticipated molecular-level consequences of introducing bioactive domains to β-sheet-forming peptides: (1) the bioactive domain has no effect on the self-assembling peptide structure; (2) the bioactive domain is incorporated into the β-sheet nanofiber; and (3) the bioactive domain interferes with self-assembly such that nanofibers are not formed. The peptides involved in this study incorporated self-assembling domains based on the (SL) 6 motif and bioactive domains including a VEGF-A mimic (QK), an IGF-mimic (IGF-1c), and a de novo SARS-CoV-2 binding peptide (SBP3). We observed all three of the anticipated outcomes from our examination of peptides, illustrating the unintended structural effects that could adversely affect the desired biofunctionality and biomaterial properties of the resulting peptide hydrogel. This work is the first attempt to evaluate the structural effects of incorporating bioactive domains into a set of peptides unified by a similar self-assembling peptide domain. These structural insights reveal unmet challenges in the design of highly tunable bioactive self-assembling peptide hydrogels.

Vanadium-based oxides have garnered significant attention as cathode materials for aqueous zinc-ion batteries (AZIBs) because of their high theoretical capacity and low cost. However, the limited reaction kinetics and poor long-term cycle stability hinder their widespread application. In this paper, we propose a novel approach by coinserting Ni 2+ and NH 4 + ions into V 2 O 5 ·3H 2 O, i.e., NNVO. Structural characterization shows that the coinsertion of Ni 2+ and NH 4 + not only extends the interlayer spacing of V 2 O 5 ·3H 2 O but also significantly promotes the transport kinetics of Zn 2+ because of the synergistic "pillar" effect of Ni 2+ and NH 4 + , as well as the increased oxygen vacancies that effectively lower the energy barrier for Zn 2+ insertion. As a result, the AZIBs with an NNVO electrode exhibit a high capacity of 398.1 mAh g -1 (at 1.0 A g -1 ) and good cycle stability with 89.1% capacity retention even after 2000 cycles at 5.0 A g -1 . At the same time, a highly competitive energy density of 262.9 Wh kg -1 is delivered at 382.9 W kg -1 . Considering the simple scheme and the resultant high performance, this study may provide a positive attempt to develop high-performance AZIBs.

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm -2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA 100 = 17.3 A·mg Ru -1 vs 1.1 A·mg Pt -1 , Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 V cell ) and high stability at an industrial current density of 1.0 A·cm -2 . Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

Currently, metal-organic frameworks (MOFs) have emerged as viable candidates for enduring electrode materials in nonenzyme glucose sensing. However, given the inherent water susceptibility of MOFs and their complete self-reconstruction during the process of electrochemical oxygen evolution in alkaline conditions, we are motivated to explore the truth of MOFs catalyzing glucose oxidation. In this work, we fabricated a two-dimensional cobalt-based zeolitic imidazolate framework (ZIF-L) as the electrode material for catalyzing glucose oxidation in alkaline conditions. Our explorations revealed that while the initial glucose catalytic response varied among ZIF-L samples with differing thicknesses, the ultimate steady-state catalytic performance remained largely consistent. This phenomenon arose from the transformation of ZIF-L with distinct thicknesses into CoOOH with uniform morphological and structural characteristics during the glucose catalysis process. And in situ Raman spectroscopy elucidated the sustained equilibrium within the glucose catalytic system, wherein the dynamic interconversion between CoOOH and Co(OH) 2 governs the overall process. This study contributes to an enhanced understanding of the glucose catalytic mechanism aspects of nonenzymatic glucose sensor electrode materials, offering insights that serve as inspiration for the development of advanced glucose electrode materials.

Investigation of asphaltene adsorption at rock surfaces plays an important role in enhanced oil recovery (EOR) for the petroleum industry. In this work, the interaction performances of asphaltene adsorption at carbonate dolomite and calcite surfaces are investigated based on experimental and simulation insights. On the one hand, macroscopic interaction performances were investigated by spectroscopy experiments to obtain the Langmuir thermodynamic model and pseudo-second-order (PSO) kinetic model. The results indicated monolayer molecular asphaltene adsorption for both dolomite and calcite, while they showed 'slow adsorption-slow desorption' for dolomite but 'fast adsorption-fast desorption' for calcite. Meanwhile, dolomite showed a higher adsorption capacity with q m(dol 1) = 5.35 mg/g > q m(cal 1) = 1.28 mg/g and a stronger adsorption spontaneity with Δ G m(dol 1) θ = -7.76 kJ/mol < Δ G m(cal 1) θ = -4.76 kJ/mol. On the other hand, microscopic interaction performances were investigated for three asphaltene molecules by molecular dynamics simulation (MDS) with ∼8 Å distance-placing and 500 ps time-running. According to the results, dolomite showed higher system stability than calcite with a lower final energy of Δ E dol-cal = -58 kJ/mol, and archipelago asphaltene showed higher adsorption stability with the smallest equilibrium energy of E arch(dol) = -147 kJ/mol for albite and E arch(cal) = -89 kJ/mol for calcite. The model of molecular orientation and force dominance was proposed as the interaction mechanism for asphaltene adsorption, which "lie sideways" at low concentrations but "stands upright" at high concentrations. This work allows the performance investigation and mechanism illustration of asphaltene adsorption at rock surfaces, which can help gain a fundamental understanding of the EOR during reservoir exploitation.

In this work, the interaction performance of zwitterionic surfactant [dodecyl dimethyl sulfopropyl betaine (DSB-12) and hexadecyl dimethyl sulfopropyl betaine (DSB-16)] at the n -octadecane oil surface is investigated from experimental and simulation insights. For a macroscopic experiment, interfacial interferometry technology was developed for real-time monitor interaction performances and to obtain the quantitative interfacial thickness and mass results. The Langmuir model was characterized by thermodynamic analysis, deducing the aggregation spontaneity of DSB-16 > DSB-12 with Δ G agg(DSB-16) = -5.94 kJ mol -1 < Δ G agg(DSB-12) = 24.08 kJ mol -1 . A three-step dynamic model (adsorption, arrangement, and aggregation) was characterized by kinetic analysis, indicating arrangement process as slow-limiting step with k 2(arr) < k 1(ads) , k 3(agg) . For microscopic simulation, and molecular dynamic (MD) method was utilized to theoretically investigate interaction performances and obtain the interfacial configuration and energy results. The interaction stability and interaction strength were indicated to be DSB-16 > DSB-12 with differences of final energy Δ E fin = 48-88 kcal mol -1 . The interaction mechanism was explained by proposing the model of "response enhancement" and "deposition activity" for DSB-16 interactions, and "response decrease" and "elution activity" for DSB-12 interactions. The different performances can be attributed to the different interaction forms and forces of surfactants. This work provided a platform for performance and mechanism investigation between the surfactant molecule and oil surface, which is of great significance in reservoir exploitation and enhanced oil recovery (EOR).

Odd-electron bonds, i.e., the two-center, three-electron (2c/3e), or one-electron (2c/1e) bonds, have attracted tremendous interest owing to their novel bonding nature and radical properties. Herein, complex [K(THF) 6 ][LSn:···Sn:L] ( 1 ), featuring the first and unsupported 2c/1e Sn···Sn σ-bond with a long distance (3.2155(9) Å), was synthesized by reduction of stannylene [LSn:] (L = N , N -dpp- o -phenylene diamide) with KC 8 . The one-electron Sn-Sn bond in 1 was confirmed by the crystal structure, DFT calculations, EPR spectroscopy, and reactivity studies. This compound can be viewed as a stabilized radical by delocalizing to two metal centers and can readily mediate radical reactions such as C-C coupling of benzaldehyde.

Selectively achieving the photoreduction of carbon dioxide (CO 2 ) to methane (CH 4 ) remains a significant challenge, which primarily arises from the complexity of the protonation process. In this work, we designed metal-vacancy pair sites in defective metal oxide semiconductors, which anchor the reactive intermediates with a bridged linkage for the selective protonation to produce CH 4 . As an example, oxygen-deficient Nb 2 O 5 nanosheets are synthesized, in which the niobium-oxygen vacancy pair sites are demonstrated by X-ray photoelectron spectroscopy and electron paramagnetic resonance spectra. In situ Fourier transform infrared spectroscopy monitors the *CH 3 O intermediate, a key intermediate for CH 4 production, during the CO 2 photoreduction in oxygen-deficient Nb 2 O 5 nanosheets. Importantly, the built metal-vacancy pair sites regulate the *CH 3 O formation step as a spontaneous process, making the reduction of CO 2 to CH 4 the preferred method. Therefore, the oxygen-deficient Nb 2 O 5 nanosheets exhibit a CH 4 formation rate of 19.14 μmol g -1 h -1 , with an electron selectivity of ∼94.1%.

Growth factor (GF) mimicry involves recapitulating the signaling of larger molecules or cells. Although GF mimicry holds considerable promise in tissue engineering and drug design applications, difficulties in targeting the signaling molecule to the site of delivery and dissociation of mimicking peptides from their target receptors continue to limit its clinical application. To address these challenges, we utilized a self-assembling peptide (SAP) platform to generate synthetic insulin-like growth factor (IGF)-signaling, self-assembling GFs. Our peptide hydrogels are biocompatible and bind target IGF receptors in a dose-dependent fashion, activate proangiogenic signaling, and facilitate formation of angiogenic microtubules in vitro. Furthermore, infiltrated hydrogels are stable for weeks to months. We conclude that the enhanced targeting and long-term stability of our SAP/GF mimicry implants may improve the efficacy and safety of future GF mimic therapeutics.