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Because of the complex structure and inherent inert chemical activity of lignin, it is still challenging to depolymerize lignin to obtain valuable chemicals efficiently. Here, we present an FeCl 3 -promoted photocatalytic depolymerization strategy to realize the C α -C β oxidative cleavage of lignin model compounds at room temperature. The method generates benzoic acid and phenol compounds in high yields. In addition, the method is effective for the depolymerization of organosolv lignin by cleavage of the products of C α -C β bonds and affords the corresponding products. This strategy provides a method of using an economical photocatalyst to depolymerize lignin and provides a reference for the industrial depolymerization of lignin.

In this contribution, we report on the visualization of 12-crown-4 molecular diffusion behavior within a single-crystal particle of covalent organic framework-300 (COF-300) using operando dark-field optical microscopy. The diffusion area and front of 12-crown-4 are directly tracked in real time, offering key information for quantifying the diffusion coefficient ( D ). The direction of the diffusion and variation of D reveal intraparticle and interparticle heterogeneity. Notably, an unexpected hydration-accelerated diffusion process of 12-crown-4 within the pore channels of COF-300 is captured, in which a relatively low concentration of 12-crown-4 aqueous solution induces a fast diffusion, whereas the pure 12-crown-4 liquid cannot access the framework. The observed acceleration diffusion is demonstrated to arise from the hydrogen-bonding interactions between surface water molecules of hydrated 12-crown-4 and the imine groups of COF-300. These findings expand the mechanistic understanding of the noncovalent interactions between COFs and crown ethers (CEs), which will help to design and prepare CE-based COFs with improved performance.

Biobased chemicals, crucial for the net-zero chemical industry, rely on lignocellulose residues as a major feedstock. However, its availability and environmental impacts vary greatly across regions. By 2050, we estimate that 3.0-5.2 Gt of these residues will be available from the global forest and agricultural sectors, with key contributions from Brazil, China, India, and the United States. This supply satisfies the growing global feedstock demands for plastics when used efficiently. Forest residues have 84% lower climate change impacts than agricultural residues on average globally but double the land-use-related biodiversity loss. Biobased plastics may reduce climate change impacts relative to fossil-based alternatives but are insufficient to fulfill net-zero targets. In addition, they pose greater challenges in terms of biodiversity loss and water stress. Avoiding feedstock sourcing from biodiversity-rich areas could halve lignocellulose residues-related biodiversity loss without significantly compromising availability. Improvements in region-specific feedstock sourcing, agricultural management and biomass utilization technologies are warranted for transitioning toward a sustainable chemical industry.

Recently, Cr 3+ -activated near-infrared (NIR) phosphors have received much more attention due to their excellent photoluminescence (PL) properties. However, most of them suffer from poor thermal stability which limits further application. Herein, a novel Lu 2 CaGa 4 SnO 12 :Cr 3+ phosphor with broadband NIR emission (λ em = 750 nm) is synthesized successfully. Despite the good luminescence property, its PL intensity decreases obviously with temperature ( I 425 K = 79%). To improve the thermal stability, a series of Lu 2+ x Ca 1- x Ga 4+ x Sn 1- x O 12 :Cr 3+ ( x = 0-1.0) solid solutions with tunable thermal quenching performance have been designed. It is found that the fluorescence intensity ratio (FIR) of 4 T 2 → 4 A 2 to 2 E → 4 A 2 [ I ( 4 T 2 )/ I ( 2 E)] transitions (i.e. electron occupation) decreases monotonously with increasing [Lu 3+ -Ga 3+ ] co-substitution, resulting from a strengthened crystal field strength and increased energy difference between 4 T 2 and 2 E energy levels. Benefiting from the various thermal population and energy difference Δ', the PL thermal quenching behavior of Lu 2+ x Ca 1- x Ga 4+ x Sn 1- x O 12 :Cr 3+ can be adjusted easily, and the corresponding mechanism is explored in detail. Most notably, the emission intensity of Lu 2+ x Ca 1- x Ga 4+ x Sn 1- x O 12 :Cr 3+ at 425 K can reach up to 142% compared with that at 300 K, which may be the best for Cr 3+ -activated NIR phosphors. This work may provide an alternative path for the development of thermally stable broadband NIR phosphors.

High-efficiency generation of spin-triplet states in organic molecules is of great interest in diverse areas such as photocatalysis, photodynamic therapy, and upconversion photonics. Recent studies have introduced colloidal semiconductor nanocrystals as a new class of photosensitizers that can efficiently transfer their photoexcitation energy to molecular triplets. Here, we demonstrate that metallic Ag nanoparticles can also assist in the generation of molecular triplets in polycyclic aromatic hydrocarbons (PAHs), but not through a conventional sensitization mechanism. Instead, the triplet formation is mediated by charge-separated states resulting from hole transfer from photoexcited PAHs (anthracene and pyrene) to Ag nanoparticles, which is established through the rapid formation and subsequent decay of molecular anions revealed in our transient absorption measurements. The dominance of hole transfer over electron transfer, while both are energetically allowed, could be attributed to a Marcus inverted region of charge transfer. Owing to the rapid charge separation and the rapid spin-flip in metals, the triplet formation yields are remarkably high, as confirmed by their engagement in production of singlet oxygen with a quantum efficiency reaching 58.5%. This study not only uncovers the fundamental interaction mechanisms between metallic nanoparticles and organic molecules in both charge and spin degrees of freedom but also greatly expands the scope of triplet "sensitization" using inorganic nanomaterials for a variety of emerging applications.

g-C 3 N 4 /Ag-ZnO (CAZ) composite photocatalysts were synthesized successfully by the hydrothermal method. The photocatalytic performance of photocatalysts was assessed through experiments measuring both hydrogen (H 2 ) production and the degradation of methylene blue (MB). The H 2 production rate of 60% CAZ reached 2.450 mmol·g -1 ·h -1 , which was 8.5 times that of g-C 3 N 4 . 25% CAZ degraded 99.14% of MB dye within 40 min, and its degradation rate constant was 12.4 times that of g-C 3 N 4 . CAZ composite photocatalysts have good synergistic properties in degradation and hydrogen production and exhibit better photocatalytic performance. A Z-scheme photocatalytic system mechanism of CAZ has been proposed for the enhanced H 2 production and photocatalytic degradation rate.

Infection and aseptic loosening caused by bacteria and poor osseointegration remain serious challenges for orthopedic implants. The advanced surface modification of implants is an effective strategy for addressing these challenges. This study presents a "pneumatic nanocannon" coating for titanium orthopedic implants to achieve on-demand release of antibacterial and sustained release of osteogenic agents. SrTiO 3 nanotubes (SrNT) were constructed on the surface of Ti implants as "cannon barrel," the "cannonball" (antibiotic) and "propellant" (NH 4 HCO 3 ) were codeposited into SrNT with assistance of mussel-inspired copolymerization of dopamine and subsequently sealed by a layer of polydopamine. The encapsulated NH 4 HCO 3 within the nanotubes could be thermally decomposed into gases under near-infrared irradiation, propelling the on-demand delivery of antibiotics. This coating demonstrated significant efficacy in eliminating typical pathogenic bacteria both in planktonic and biofilm forms. Additionally, this coating exhibited a continuous release of strontium ions, which significantly enhanced the osteogenic differentiation of preosteoblasts. In an implant-associated infection rat model, this coating demonstrated substantial antibacterial efficiency (>99%) and significant promotion of osseointegration, along with alleviated postoperative inflammation. This pneumatic nanocannon coating presents a promising approach to achieving on-demand infection inhibition and sustained osseointegration enhancement for titanium orthopedic implants.

Broadband near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) hold promising potential as next-generation compact, portable, and intelligent NIR light sources. Nonetheless, the lack of high-performance broadband NIR phosphors with an emission peak beyond 900 nm has severely hindered the development and widespread application of NIR pc-LEDs. This study presents a strategy for precise control of energy-state coupling in spinel solid solutions composed of Mg x Zn 1- x Ga 2 O 4 to tune the NIR emissions of Cr 3+ activators. By combining crystal field engineering and heavy doping, the Cr 3+ -Cr 3+ ion pair emission from the 4 T 2 state is unlocked, giving rise to unusual broadband NIR emission spanning 650 and 1400 nm with an emission maximum of 913 nm and a full width at half-maximum (fwhm) of 213 nm. Under an optimal Mg/Zn ratio of 4:1, the sample achieves record-breaking performance, including high internal and external quantum efficiency (IQE = 83.9% and EQE = 35.7%) and excellent thermal stability ( I 423 K / I 298 K = 75.8%). Encapsulating the as-obtained phosphors into prototype pc-LEDs yields an overwhelming NIR output power of 124.2 mW at a driving current of 840 mA and a photoelectric conversion efficiency (PCE) of 10.5% at 30 mA, rendering high performance in NIR imaging applications.

To discover novel transketolase (TKL, EC 2.2.1.1) inhibitors with potential herbicidal applications, a series of pyrazole acyl thiourea derivatives were designed based on a previously obtained pyrazolamide acyl lead compound, employing a scaffold hopping strategy. The compounds were synthesized, their structures were characterized, and they were evaluated for herbicidal activities. The results indicate that 7a exhibited exceptional herbicidal activity against Digitaria sanguinalis and Amaranthus retroflexus at a dosage of 90 g ai/ha, using the foliar spray method in a greenhouse. This performance is comparable to that of commercial products, such as nicosulfuron and mesotrione. Moreover, 7a showed moderate growth inhibitory activity against the young root and stem of A. retroflexus at 200 mg/L in the small cup method, similar to that of nicosulfuron and mesotrione. Subsequent mode-of-action verification experiments revealed that 7a and 7e inhibited Setaria viridis TKL ( Sv TKL) enzyme activity, with IC 50 values of 0.740 and 0.474 mg/L, respectively. Furthermore, they exhibited inhibitory effects on the Brassica napus acetohydroxyacid synthase enzyme activity. Molecular docking predicted potential interactions between these ( 7a and 7e ) and Sv TKL. A greenhouse experiment demonstrated that 7a exhibited favorable crop safety at 150 g ai/ha. Therefore, 7a is a promising herbicidal candidate that is worthy of further development.

The design and synthesis of new herbicidal active compounds based on a new target are of great significance for the development of new herbicides. Transketolase (TK) plays a key role in the Calvin cycle of plant photosynthesis and has been confirmed as a potential candidate target to develop and discover new herbicides. To obtain compounds with ultraefficient targeting of TK, a series of pyrazole amide derivatives were designed and synthesized through structural optimization for lead compound 4u based on TK as the new target. The bioassay results showed that compounds 6ba and 6bj displayed a highly inhibitory effect with the root inhibition of about 90% against Digitaria sanguinalis ( DS ) and 80% against Amaranthus retroflexus ( AR ) and Setaria viridis ( SV ) by the small cup method, which was better than the positive control mesotrione and nicosulfuron. Furthermore, compounds 6ba and 6bj exhibited an excellent inhibitory effect with the inhibition of about 80% (against DS ) and over 80% (against SV ) at the dosage of 150 g of active ingredient/ha by the foliar spray method. The TK enzyme activity inhibition test showed that the inhibition effect of target compounds against TK was consistent with the results of herbicidal activities. Also, molecular docking analysis showed that compounds 6ba and 6bj went deep into the active cavity of TK, bound to TK by a strong interaction, and might act on the enzyme TK. Above of all, compounds 6ba and 6bj are promising herbicide lead compounds targeting TK. Hence, they could be developed into more efficient herbicides by further structural optimization.

G-quadruplex (G4) selective stabilizing ligands can regulate c- MYC gene expression, but the kinetic basis remains unclear. Determining the effects of ligands on c- MYC promoter G4s' folding/unfolding kinetics is challenging due to the polymorphic nature of G4s and the high energy barrier to unfold c- MYC promoter G4s. Here, we used single-molecule magnetic tweezers to manipulate a duplex hairpin containing a c- MYC promoter sequence to mimic the transiently denatured duplex during transcription. We measured the effects of six commonly used G4s binding ligands on the competition between quadruplex and duplex structures, as well as the folding/unfolding kinetics of G4s. Our results revealed two distinct roles for G4s selective stabilization: CX-5461 is mainly acting as c- MYC G4s stabilizer, reducing the unfolding rate ( k u ) of c- MYC G4s, whereas PDS and 360A also act as G4s chaperone, accelerating the folding rates ( k f ) of c- MYC G4s. qRT-PCR results obtained from CA46 and Raji cell lines demonstrated that G4s stabilizing ligands can downregulate c- MYC expression, while G4s stabilizer CX-5461 exhibited the strongest c- MYC gene suppression. These results shed light on the potential of manipulating G4s' folding/unfolding kinetics by ligands for precise regulation of promoter G4-associated biological activities.

Endotoxemia is a life-threatening multiple organ failure disease caused by bacterial endotoxin infection. Unfortunately, current single-target therapy strategies have failed to prevent the progression of endotoxemia. Here, we reported that alanine fullerene redox modulator (AFRM) remodeled the intestinal microenvironment for multiple targets endotoxemia mitigation by suppressing inflammatory macrophages, inhibiting macrophage pyroptosis, and repairing epithelial cell barrier integrity. Specifically, AFRM exhibited broad-spectrum and self-cascade redox regulation properties with superoxide dismutase (SOD)-like enzyme, peroxidase (POD)-like enzyme activity, and hydroxyl radical (•OH) scavenging ability. Guided by proteomics, we demonstrated that AFRM regulated macrophage redox homeostasis and down-regulated LPS/TLR4/NF-κB and MAPK/ERK signaling pathways to suppress inflammatory hyperactivation. Of note, AFRM could attenuate inflammation-induced macrophage pyroptosis via inhibiting the activation of gasdermin D (GSDMD). In addition, our results revealed that AFRM could restore extracellular matrix and cell-tight junction proteins and protect the epithelial cell barrier integrity by regulating extracellular redox homeostasis. Consequently, AFRM inhibited systemic inflammation and potentiated intestinal epithelial barrier damage repair during endotoxemia in mice. Together, our work suggested that fullerene based self-cascade redox modulator has the potential in the management of endotoxemia through synergistically remodeling the inflammation and epithelial barriers in the intestinal microenvironment.

Programmed cell death protein 1 (PD-1) inhibitors are the most common immune-checkpoint inhibitors and considered promising drugs for hepatocellular carcinoma (HCC). However, in clinical settings, they have a low objective response rate (15%-20%) for patients with HCC; this is because of the insufficient level and activity of tumor-infiltrating T lymphocytes (TILs). The combined administration of oxymatrine (Om) and astragaloside IV (As) can increase the levels of TILs by inhibiting the activation of cancer-associated fibroblasts (CAFs) and improve the activity of TILs by enhancing their mitochondrial function. In the present study, we constructed a magnetic metal-organic framework (MOF)-based nanoplatform with platelet membrane (Pm) coating (PmMN@Om&As) to simultaneously deliver Om and As into the HCC microenvironment. We observed that PmMN@Om&As exhibited a high total drug-loading capacity (33.77 wt %) and good immune escape. Furthermore, it can target HCC tissues in a magnetic field and exert long-lasting effects. The HCC microenvironment accelerated the disintegration of PmMN@Om&As and the release of Om&As, thereby increasing the level and activity of TILs by regulating CAFs and the mitochondrial function of TILs. In addition, the carrier could synergize with Om&As by enhancing the oxygen consumption rate and proton efflux rate of TILs, thereby upregulating the mitochondrial function of TILs. Combination therapy with PmMN@Om&As and α-PD-1 resulted in a tumor suppression rate of 84.15% and prolonged the survival time of mice. Our study provides a promising approach to improving the antitumor effect of immunotherapy in HCC.

Herein, we achieved the asymmetric synthesis of (+)-vellosimine in 13 steps (longest linear sequences, LLS). This synthesis featured a sequential nucleophilic addition/cyclization process, which provided an efficient protocol for synthesizing a range of indole fused azabicyclo[3.3.1]nonane. Additionally, a SmI 2 -mediated reductive cyclization of ketone with an attached α,β-unsaturated ester for constructing the strained quinuclidine moiety was also highlighted.

Graphene is widely used in heat dissipation, owing to its inherently high in-plane thermal conductivity and excellent mechanical properties. However, its poor cross-plane thermal conductivity limits its use in some electronic applications. The electron distribution of graphene and the interaction with the base material can be greatly altered by introducing F, the most electronegative element, giving fluorinated graphene oxide (FG) with a high thermal conductivity. Herein, FG is prepared by grafting F atoms onto the surface of graphene oxide in a low-temperature solid-phase reaction with poly(vinylidene fluoride) as a fluorine source. This method can effectively avoid the use of dangerous substances such as HF and F 2 . The FG dispersion and aqueous poly(vinyl alcohol) (PVA) solution are sequentially vacuum-filtered to obtain the FG/PVA composite film. After natural drying and hot-pressing, the thermal conductivity of the N-FG/PVA film is enhanced by the hydrogen bond between F of FG and the hydroxyl group of PVA. The in-plane and cross-plane thermal conductivity of an N-FG/PVA film containing 10.4 wt % FG are 7.13 and 1.42 W m -1 k -1 , respectively. The film has a tensile strength of 60 MPa and an elongation at a break of 28%, which is promising for the thermal management of flexible electronic devices.

A catalytic asymmetric nucleophilic reverse prenylation of indol-2-ones in situ generated from 3-bromooxindoles with prenyltributylstannane promoted by Ni(II)/chiral N,N' -dioxide was developed. This reaction provides facile access to C3 reverse-prenylated oxindoles in good to excellent enantioselectivities, which enabled the asymmetric synthesis of debromoflustramine A in five steps.

Producing sulfur from a sulfide oxidation reaction (SOR)-based technique using sulfide aqueous solution has attracted considerable attention due to its ecofriendliness. This study demonstrates that NiS-doped cobalt sulfide NiS-CoS-supported NiCo alloy foam can deliver the SOR with superior electrocatalytic activity and robust stability compared to reported non-noble metal-based catalysts. Only 0.34 V vs RHE is required to drive a current density of 100 mA cm -2 for the SOR. According to the experiment, the catalyst exhibits a unique sulfurophobicity feature because of the weak interaction between sulfur and the transition metal sulfide (low affinity for elemental sulfur), preventing electrode corrosion during the SOR process. More impressively, the chain-growth mechanism of the SOR from short- to long-chain polysulfides was revealed by combining electrochemical and spectroscopic in situ methods, such as in situ ultraviolet-visible and Raman. It is also demonstrated that electrons can transfer straight from the sulfion (S 2- ) to the active site on the anode surface during the low-energy-consumption SOR process. This work provides new insight into simultaneous energy-saving hydrogen production and high-value-added S recovery from sulfide-containing wastewater.

The characteristics of high burning rate, high energy output, and low pressure exponent have always been the focus of development in the field of composite solid rocket propellants. In this paper, a metal-organic framework (MOF-199) compound is introduced to prepare micro-nanospherical CL-20@MOF-199 composites via the spray-drying self-assembly technique to reach the above goals. MOF-199, which acts as an attractive combustion catalyst and a safety regulator, is uniformly coated on the surface of CL-20 with close interface contact between particles, effectively accelerating the thermal decomposition of CL-20 and ensuring safety performance. The average noncovalent interaction (aNCI) analysis illustrates that there are strong C-H···O hydrogen bonds and van der Waals interaction between CL-20 and MOF-199 molecules, greatly enhancing the effect of interparticle assembly. The effects of different contents of MOF-199 on the thermal, safety, and energy properties of CL-20 were discussed. The thermal analysis demonstrates that MOF-199 has a significant thermal catalytic effect on CL-20, with an advanced peak temperature of thermal decomposition of 14.2 °C and a reduced activation energy barrier of 34.2 kJ·mol -1 , mainly benefitting from more exposed catalytic active sites and close interface contact. In addition, CL-20@MOF-199 composites exhibit decreased mechanical sensitivity (IS: 21-40 cm, FS: 80-240 N) and excellent energy performance. This work clearly demonstrates that MOF-199 is both a superior combustion catalyst and a good safety buffer for CL-20, and it opens new potential for further applications of CL-20 in composite solid propellants.

Water molecules and the associated proton transfer (PT) are prevalent in chemical and biological systems and have been a hot research topic. Spectroscopic characterization and ab initio molecular dynamics (AIMD) simulations have previously revealed insights into acidic and basic liquids. Presumably, the situation in the acidic/basic solution is not necessarily the same as in pure water; in addition, the autoionization constant for water is only 10 -14 under ambient conditions, making the study of PT in pure water challenging. To overcome this issue, we modeled periodic water box systems containing 1000 molecules for tens of nanoseconds based on a neural network potential (NNP) with quantum mechanical accuracy. The NNP was generated by training a dataset containing the energies and atomic forces of 17 075 configurations of periodic water box systems, and these data points were calculated at the MP2 level that considers electron correlation effects. We found that the size of the system and the duration of the simulation have a significant impact on the convergence of the results. With these factors considered, our simulations showed that hydronium (H 3 O + ) and hydroxide (OH - ) ions in water have distinct hydration structures, thermodynamic and kinetic properties, e.g., the longer-lasting and more stable hydrated structure of OH - ions than that of H 3 O + , as well as a significantly higher free energy barrier for the OH - -associated PT than that of H 3 O + , leading the two to exhibit completely different PT behaviors. Given these characteristics, we further found that PT via OH - ions tends not to occur multiple times or between many molecules. In contrast, PT via H 3 O + can synergistically occur among multiple molecules and prefers to adopt a cyclic pattern among three water molecules, while it occurs mostly in a chain pattern when more water molecules are involved. Therefore, our studies provide a detailed and solid microscopic explanation for the PT process in pure water.

While Catellani reactions have become increasingly important for arene functionalizations, they have been solely catalyzed by palladium. Here we report the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies reveal a surprising outer-sphere concerted metalation/deprotonation pathway during the formation of the nickelacycle, as well as the essential roles of the base and the triflate anion. The reaction shows a broad functional group tolerance and enhanced regioselectivity compared to the corresponding palladium catalysis.

A narrow-band red-light component is critical to establish high color rendition and a wide color gamut of phosphor-converted white-light-emitting diodes (pc-WLEDs). In this sense, Mn 4+ -doped K 2 SiF 6 fluoride is the most successful material that has been commercialized. As with K 2 SiF 6 :Mn 4+ phosphors, Mn 4+ -doped tantalum heptafluoride (K 2 TaF 7 :Mn 4+ ) fulfills a similar luminescence behavior and has been brought in a promising narrow-band red phosphor. But the limited brightness and low moisture-resistant performances have inevitably blocked its practical application. Herein, we employed the density functional theory (DFT)-based ab initio estimation approach to quickly identify the proper sensitizer by systematically investigating the electronic-band coupling between the several possible sensitizers (Rb, Hf, Zr, Sn, Nb, and Mo) and the luminescent center (Mn). Combined with experimental results, Mo was demonstrated to be the optimal sensitizer, which resulted in a 60% enhancement of the emission. On the side, the moisture sensitivity has been effectively improved via grafting the hydrophobic octadecyltrimethoxysilane (ODTMS) layer on the phosphor surface. Through employing the K 2 TaF 7 :Mn 4+ ,Mo 6+ @ODTMS composite as a red component, warm WLEDs with good performance were achieved with a correlated color temperature (CCT) of 4352 K, a luminous efficacy (LE) of 90.1 lm/W, and a color rendering index (Ra) of 83.4. In addition, a wide color gamut reaching up to 102.8% of the NTSC 1953 value could be realized. Aging tests at 85 °C and 85% humidity for 120 h on this device manifested that the ODTMS-modified phosphor had much better moisture stability than that of the unmodified one. These studies provided viable tools for optimizing Mn 4+ luminescence in fluoride hosts.

2-Arylindoles are privileged structures widely present in biologically active molecules. New sustainable synthetic routes toward their synthesis are, therefore, in high demand. Herein, a mixed base-promoted benzylic C-H deprotonation of commercially available ortho -anisoles, addition of the resulting anion to benzonitriles, and S N Ar to displace the methoxy group provide indoles. A diverse array of 2-arylindoles is prepared with good yields (>30 examples, yields up to 99%) without added transition metal catalysts.

Reactive oxygen species (ROS) produced by noble metallic nanoparticles under visible light is an effective way to combat drug-resistant bacteria colonized on the wound. However, the photocatalytic efficiency of noble metallic nanoparticles is limited by its self-aggregation in water media. Moreover, the fast release of noble metallic ions from nanoparticles might engender cellular toxicity and hazardous environmental issues. Herein, we chose AgNPs, the most common plasmonic noble metallic nanoparticles, as an example, modifying the surface of AgNPs with oleic acid and n -butylamine and imbedded them into calcium alginate (CA) hydrogel that holds tissue adhesion, rapid hemostatic, sunlight-sensitive antibacterial and anti-inflammatory abilities, and thus effectively promotes the healing of wounds. Unlike conventional AgNP-based materials, the constrain of colloids and hydrogel networks hinders the leach of Ag + . Nonetheless, the CA/Ag hydrogels exhibit on-demand photodynamic antibacterial efficacy due to the generation of ROS under visible light. In addition, the CA/Ag hydrogel can effectively stop the hemorrhage in a mouse liver bleeding model due to their skin-adaptive flexibility and tissue adhesiveness. The potent sunlight-responsive antibacterial activity of the CA/Ag hydrogel can effectively kill multidrug-resistant bacteria both in vitro (>99.999%) and in vivo (>99.9%), while the diminished Ag + release guarantees its biocompatibility. The CA/Ag hydrogel significantly promotes the wound healing process by the downregulation of proinflammatory cytokines (TNF-α and IL-6) in a rodent full-thickness cutaneous wound model. Overall, the proposed multifunctional CA/Ag nanocomposite hydrogel has excellent prospects as an advanced wound dressing.

4-Hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27; HPPD) represents a potential target for novel herbicide development. To discover the more promising HPPD inhibitor, we designed and synthesized a series of bis-5-cyclopropylisoxazole-4-carboxamides with different linkers using a multitarget pesticide design strategy. Among them, compounds b9 and b10 displayed excellent herbicidal activities versus Digitaria sanguinalis ( DS ) and Amaranthus retroflexus ( AR ) with the inhibition of about 90% at the concentration of 100 mg/L in vitro, which was better than that of isoxaflutole (IFT). Furthermore, compounds b9 and b10 displayed the best inhibitory effect versus DS and AR with the inhibition of about 90 and 85% at 90 g (ai)/ha in the greenhouse, respectively. The structure-activity relationship study showed that the flexible linker (6 carbon atoms) is responsible for increasing their herbicidal activity. The molecular docking analyses showed that compounds b9 and b10 could more closely bind to the active site of HPPD and thus exhibited a better inhibitory effect. Altogether, these results indicated that compounds b9 and b10 could be used as potential herbicide candidates targeting HPPD.

Fabricating perovskite solar cells (PSCs) in ambient air condition is beneficial for lowering the processing cost and boosting the commercialization. Formamidinium lead iodide (FAPbI 3 ) is an attractive candidate for efficient PSCs; however, it easily suffers from degradation and phase transition in the presence of ambient moisture. Methylammonium (MA) cation is commonly incorporated to stabilize FAPbI 3 , whereas the residual MA tends to deteriorate the thermal and operational stability. Herein, we report a MA-free strategy to fabricate high-quality α-FAPbI 3 films and inverted PSCs under open air conditions with a relative humidity (RH) of 60 ± 10%. The incorporation of phenylethylammonium iodide (PEAI) effectively inhibits the decomposition and phase transition of FAPbI 3 during its crystallization in humid air. Accordingly, phase-pure α-FAPbI 3 perovskite films with significantly reduced δ-FAPbI 3 and PbI 2 content are successfully obtained. In addition, introducing PEAI strongly enhances the crystallinity of FAPbI 3 perovskite films, thereby yielding enlarged grain sizes and reduced grain boundaries. Defects at the grain boundaries and surface are further passivated by PEAI addition, so that the trap state density is significantly decreased. As a result, the non-radiative recombination is effectively suppressed and the charge carrier transport is promoted. The inverted device optimized with a suitable PEAI concentration exhibits an enhanced power conversion efficiency (PCE) of 17.83%, which significantly surpasses the control device (12.29% PCE). Moreover, the PEAI optimized FAPbI 3 PSCs demonstrate strongly improved long-term stability, with nearly 97% PCE maintained after 27-day storage under ambient conditions. This work provides a feasible way to fabricate PSCs in ambient air for promoting their wide range of applications.

Associations between ultrafine particles (UFPs) and hourly onset of acute myocardial infarction (AMI) have rarely been investigated. We aimed to evaluate the impacts of UFPs on AMI onset and the lag patterns. A time-stratified case-crossover study was performed among 20,867 AMI patients from 46 hospitals in Shanghai, China, between January 2015 and December 2020. Hourly data of AMI onset and number concentrations of nanoparticles of multiple size ranges below 0.10 μm (0.01-0.10, UFP/PNC 0.01-0.10 ; 0.01-0.03, PNC 0.01-0.03 ; 0.03-0.05, PNC 0.03-0.05 ; and 0.05-0.10 μm, PNC 0.05-0.10 ) were collected. Conditional logistic regressions were applied. Transient exposures to these nanoparticles were significantly associated with AMI onset, with almost linear exposure-response curves. These associations occurred immediately after exposure, lasted for approximately 6 h, and attenuated to be null thereafter. Each interquartile range increase in concentrations of total UFPs, PNC 0.01-0.03 , PNC 0.03-0.05 , and PNC 0.05-0.10 during the preceding 0-6 h was associated with increments of 3.29, 2.08, 2.47, and 2.93% in AMI onset risk, respectively. The associations were stronger during warm season and at high temperatures and were robust after adjusting for criteria air pollutants. Our findings provide novel evidence that hourly UFP exposure is associated with immediate increase in AMI onset risk.

Switchable multicomponent reactions have been attractive tools for the construction of compound libraries with skeleton diversity and complexity by slightly changing the reaction conditions. Described herein is a regioselectivity-switchable formal [1 + 2 + 2] cycloaddition reaction from difluoroalkyl compounds, enaminones, and RNHNH 2 , ultimately using 1-methylindazol-3-amine as a traceless mediator to switch the inherent regioselectivity of 1,3,4-trisubstituted pyrazole formation to 1,4,5-trisubstituted pyrazoles. Remarkable features of this work include mild conditions, simple operation, and broad scopes.

This study investigated the effects of sesamolin on kidney injury, intestinal barrier dysfunction, and gut microbiota imbalance in high-fat and high-fructose (HF-HF) diet-fed mice and explored the underlying correlations among them. The results indicated that sesamolin suppressed metabolic disorders and increased renal function parameters. Histological evaluation showed that sesamolin mitigated renal epithelial cell degeneration and brush border damage. Meanwhile, sesamolin inhibited the endotoxin-mediated induction of the Toll-like receptor 4-related IKKα/NF-κB p65 pathway activation. Additionally, sesamolin mitigated intestinal barrier dysfunction and improved the composition of gut microbiota. The correlation results further indicated that changes in the dominant phyla, including Firmicutes , Deferribacterota , Desulfobacterota , and Bacteroidota , were more highly correlated with a reduction in endotoxemia and metabolic disorders, as well as decreases in intestinal proinflammatory response and related renal risk biomarkers. The results of this study suggest that sesamolin attenuates kidney injuries, which might be associated with its effects on the reduction of endotoxemia and related metabolic disorders through the restoration of the intestinal barrier and the modulation of gut microbiota. Thus, sesamolin may be a potential dietary supplement for protection against obesity-associated kidney injury.

The lack of antimicrobial and osteoconductive activities of titanium (Ti) for orthopedic implants has led to problems such as infection and structural looseness, which bring physical and psychological sufferings to patients as well as economic burden on the healthcare system. To endow Ti implants with anti-infective function and bioactivity, in this study, we successfully constructed TiO 2 nanospike (TNS) structure on the surface of Ti followed by assembling metal-polyphenol networks (MPNs) and depositing antimicrobial peptides (AMPs). The TNSs' structure can disrupt the bacteria by physical puncture, and it was also proved to have excellent photothermal conversion performance upon near-infrared light irradiation. Furthermore, with the assistance of contact-active chemo bactericidal efficacy of AMPs, TNS-MPN-AMP nanocoating achieved physical/photothermal/chemo triple-synergistic therapy against pathogenic bacteria. The anti-infective efficiency of this multimodal treatment was obviously improved, with an antibacterial ratio of >99.99% in vitro and 95.03% in vivo. Moreover, the spike-like nanostructure of TNSs and the bioactive groups from MPNs and AMPs not only demonstrated desirable biocompatibility but also promoted the surface hydroxyapatite formation in simulated body fluid for further osseointegration enhancement. Altogether, this multifaceted TNS-MPN-AMP nanocoating endowed Ti implants with enhanced antibacterial activity, excellent cytocompatibility, and desirable osteoconductive ability.

Field-effect transistor (FET) devices with multi-gate coupled structures usually exhibit special electrical properties and are suitable for fabricating multifunctional devices. Among them, the 1D nanowire gate configuration has become a promising gate design to tailor 2D FET performances. However, due to possible short circuiting induced by nanowire contact and the high requirement for precision manipulation, the integration of multi-nanowires as gates in a single 2D electronic system remains a grand challenge. Herein, local laser--thinned multiple core-shell SiC@SiO 2 nanowires are successfully integrated into MoS 2 transistors as multi-gates for active control of extendable logic applications. Nanowire gates (NGs) locally enhance the carrier transportation, and the use of multiple NGs can achieve designed band structures to tune the performance of the device. For core-shell structures, a semiconducting core is used to introduce a gate bias, and the insulating shell provides protection against short circuiting between NGs, facilitating nanowire assembly. Furthermore, a global control gate is introduced to co-tune the overall electrical characteristics, while active control of logic devices and extendable inputs are achieved based on this model. This work proposes a novel nanowire multi-gate configuration, which provides possibilities for localized, precise control of band structures and the fabrication of highly integrated, multifunctional, and controllable nano-devices.

Artificial neurons as the basic units of spiking neural network (SNN) have attracted increasing interest in energy-efficient neuromorphic computing. 2D transition metal dichalcogenide (TMD)-based devices have great potential for high-performance and low-power artificial neural devices, owing to their unique ion motion, interface engineering, and resistive switching behaviors. Although there are widespread applications of TMD-based artificial synapses in neural networks, TMD-based neurons are seldom reported due to the lack of bio-plausible multi-mechanisms to mimic leaking, integrating, and firing biological behaviors without external assistance. In this work, for the first time, a methodology is developed by introducing the hybrid effect of charge trapping (CT) and Schottky barrier (SB) in MoS 2 FETs for barristor memory and one-transistor (1T) compact artificial neuron realization. By correlating the CT and SB processes, quasi-volatile and resistive switching behaviors are realized on the fabricated MoS 2 FET and utilized to mimic the accumulating, leaking, and firing biological behaviors of neurons. Therefore, based on a single quasi-volatile CT-SB MoS 2 barristor memory, a 1T compact neuron of the basic leaky-integral-and-fire (LIF) function is demonstrated without a peripheral circuit. Furthermore, a spiking neural network (SNN) based on the CT-SB MoS 2 barristor neurons is simulated and implemented in pattern classification with high accuracy approaching 95.82%. This work provides a highly integrated and inherently low-energy implementation for neural networks.

Herein, we describe a catalytic asymmetric intramolecular vinylogous aldol reaction by taking advantage of dual organocatalysts, which enables convergent synthesis of ortho -fused tricyclic diketones in excellent enantioselectivities and diastereoselectivities. Noteworthy is that the reaction stereoselectively forges three consecutive stereogenic carbon centers including a quaternary one. Density functional theory calculations reveal that the enantioselectivity was facilitated by a transannular hydrogen bonding between the protonated quinuclidine moiety of the chiral aminocatalyst and the diketone fragment of the substrate.

The strategy to enhance phosphor stability against thermal quenching and moisture conditions will contribute to controlling the feature of phosphor-converted white-light-emitting diodes (pc-WLEDs). Herein, an effective strategy is achieved with the incorporation of Sm 3+ ions, and a robust reddish-orange emission (no thermal quenching up to 498 K) is obtained based on Ba 3 LaNb 3 O 12 as a host. In light of excitation by near-ultraviolet irradiation at 408 nm, Ba 3 LaNb 3 O 12 :Sm 3+ gives rise to a typical signal ascribed to the 4 G 5/2 → 6 H J /2 ( J = 5, 7, 9, and 11) transitions of Sm 3+ ions. The concentration quenching effect is observed when the Sm 3+ content exceeds 10%, and the quenching mechanism is caused by electronic dipole-dipole interactions. Based on the narrow emission curves, a very high color purity (92.4%) could be recorded. The Sm 3+ substitution at the Ba 2+ /La 3+ site leads to a rigid structural lattice and abundant electron-trapping centers for the Sm 3+ ions, which will be responsible for the zero-thermal-quenching phenomenon. In addition, oleic acid (OA) is selected to form a hydrophobic covering surface structure to protect Ba 3 LaNb 3 O 12 :Sm 3+ , which can assist in improving the moisture resistance. The most favorable parameters concerning the warm-light emission (a high general color rendering index, Ra, of 85.7 and a low correlated color temperature, CCT, of 4965 K) can be achieved in pc-WLEDs containing an OA-modified sample. Moreover, its luminous efficiency, LE, can maintain 82.9% of its initial value after 120 h under controlled environmental conditions of 85 °C and 85% humidity. These results pave a new way to optimize the sample as a potential candidate for red-emitting materials.

The occurrence of energy transfer (ET) would enhance the luminescence of the activator but sacrifice that of the sensitizer. However, the novel Sm 3+ -doped Ca 2 TbSn 2 Al 3 O 12 (CTSAO) phosphor reported here seems to be an exception. In the series of CTSAO: x Sm 3+ phosphors investigated, something unexpected occurs; the activator, Sm 3+ , did not gain any energy compensation from the sensitizer, Tb 3+ , when temperature increases. Instead, when the loss of Sm 3+ luminescence accelerates, simultaneously, the loss of Tb 3+ luminescence accordingly alleviates. By careful calculations on the ET efficiency of the CTSAO:0.06Sm 3+ phosphor at different temperatures, it is surprisingly found that the efficiency keeps decreasing as temperature increases. It means that the Tb 3+ -Sm 3+ energy transfer is capable of being interrupted by an increasing temperature. By simulation, it is found that the occurrence of thermal interruption of energy transfer benefits the achievement of a higher temperature sensing sensitivity. In this sense, making use of the thermal interruption of energy transfer could become a novel route for further design of the fluorescence intensity ratio-type luminescence thermometers.

Transketolase (TK) was identified as a new target for the development of novel herbicides. In this study, a series of naphthalimide-aroyl hybrids were designed and prepared based on TK as a new target and tested for their herbicidal activities. In vitro bioassay showed that compounds 4c and 4w exhibited stronger inhibitory effects against Digitaria sanguinalis ( DS ) and Amaranthus retroflexus ( AR ) with the inhibition over 90% at 200 mg/L and around 80% at 100 mg/L. Also, compounds 4c and 4w exhibited excellent postemergence herbicidal activity against DS and AR with the inhibition around 90% at 90 g [active ingredient (ai)]/ha and 80% at 50 g (ai)/ha in the greenhouse, which was comparable with the activity of mesotrione. The fluorescent quenching experiments of At TK revealed the occurrence of electron transfer from compound 4w to At TK and the formation of a strong exciplex between them. Molecular docking analyses further showed that compounds 4w exhibited profound affinity with At TK through the interaction with the amino acids in the active site, which results in its strong inhibitory activities against TK. These findings demonstrated that compound 4w is potentially a lead candidate for novel herbicides targeting TK.

Chiral drugs are of great significance in drug development and life science because one pair of enantiomers has a different combination mode with target biological active sites, leading to a vast difference in physical activity. Metal-organic framework (MOF)-based chiral hybrid materials with specific chiral sites have excellent applications in the highly effective sensing of drug enantiomers. Sitagliptin and clonidine are effective curing drugs for controlling diabetes and hypertension, while insulin and norepinephrine are the biomarkers of these two diseases. Excessive use of sitagliptin and clonidine can cause side effects such as stomach pain, nausea, and headaches. Herein, through post-synthetic strategy, MOF-based chiral hybrid material Eu-BTB@ d -carnitine (H 3 BTB = 1,3,5-benzenetrisbenzoic acid) was synthesized. Eu-BTB@ d -carnitine has dual emission peaks at 417 and 616 nm when excited at 330 nm. Eu-BTB@ d -carnitine can be applied in luminescent recognition toward sitagliptin and clonidine with high sensitivity and low detection limit (for sitagliptin detection, K sv is 7.43 × 10 6 [M -1 ]; for clonidine detection, K sv is 9.09 × 10 6 [M -1 ]; limit of detection (LOD) for sitagliptin is 10.21 nM, and LOD of clonidine is 8.34 nM). In addition, Eu-BTB@ d -carnitine can further realize highly sensitive detection of insulin in human fluids with a high K sv (2.08 × 10 6 [M -1 ]) and a low LOD (15.48 nM). On the other hand, norepinephrine also can be successfully discriminated by the hybrid luminescent platform of Eu-BTB@ d -carnitine and clonidine with a high K sv value of 4.79 × 10 6 [M -1 ] and a low LOD of 8.37 nM. As a result, the chiral hybrid material Eu-BTB@ d -carnitine can be successfully applied in the highly effective ratiometric sensing of curing drugs and biomarkers for diabetes and hypertension.

In contrast to molecular-dipole polymers, such as PVDF, ferroelectrets are a new class of flexible spatially heterogeneous piezoelectric polymers with closed or open voids that act as deformable macro-dipoles after charging. With a spectrum of manufacturing processes being developed to engineer the heterogeneous structures, ferroelectrets are made with attractive piezoelectric properties well-suited for applications, such as pressure sensors, acoustic transducers, etc. However, the sources of the macro-dipole charges have usually been the same, microscopic dielectric barrier discharges within the voids, induced when the ferroelectrets are poled under a large electric field typically via a so-called corona poling, resulting in the separation and trapping of opposite charges into the interior walls of the voids. Such a process is inherently self-limiting, as the reverse internal field from the macro-dipoles eventually extinguishes the microdischarges, resulting in limited density of ions and not too high overall piezoelectric performance. Here, a new method to form ferroelectrets with gigantic electroactivity is proposed and demonstrated with the aid of an external ion booster. A laminate consisting of expanded polytetrafluoroethylene (ePTFE) and fluorinated-ethylene-propylene (FEP) was prefilled with bipolar ions produced externally by an ionizer and sequentially poled to force the separation of positive and negative ions into the open fibrous structure, rendering an impressive piezoelectric d 33 coefficient of 1600 pC/N─an improvement by a factor of 4 in comparison with the d 33 of a similar sandwich poled with nonenhanced corona poling. The (pre)filling clearly increases the ion density in the open voids significantly. The charges stored in the open-cell structure stays at a high level for at least 4 months. In addition, an all-organic nanogenerator was made from an ePTFE-based ferroelectret, with conducting poly(3,4-ethylene dioxythiophene): poly(styrenesulfonate) (PEDOT: PSS) coated fabric electrodes. When poled with this ion-boosting process, it yielded an output power twice that of a similar sample poled in a conventional corona-only process. The doubling in output power is mainly brought about by the significantly higher charge density achieved with the aid of external booster. Furthermore, aside from the bipolar ions, extra monopolar ions can during the corona poling be blown into the open pores by using for instance a negative ionic hair dryer to produce a unipolar ePTFE-based ferroelectret with its d 33 coefficient enhanced by a factor of 3. Ion-boosting poling thus unleashes a new route to produce bipolar or unipolar open-cell ferroelectrets with highly enhanced piezoelectric response.

A rational molecular design approach was developed in our laboratory to guide the discovery of novel sterol biosynthesis inhibitors. Based on the application of bioactivities of heterocyclic rings and molecular docking targeting the sterol biosynthesis 14α-demethylase, a series of 4-chloropyrazole-based pyridine derivatives were rationally designed, synthesized, and characterized and their fungicidal activities were also evaluated. Bioassay results showed that 7e , 7f , and 7m exhibited commendable, diverse antifungal actions that are comparable to those of the positive controls imazalil and triadimefon. The active compounds' mode of action was further studied by microscopy observations, Q-PCR, and enzyme inhibition assay and discovered that target compounds affect fungal sterol biosynthesis via disturbing Rc CYP51 enzyme system. These findings support that their fungicidal mode of action still targets the cytochrome P450-dependent 14α-demethylase as the molecular design did at first. The above results strongly suggest that our rational molecular design protocol is not only practical but also efficient.

In this study, a superhydrophobic coating on glass has been prepared through a single-step aerosol-assisted chemical vapor deposition (AACVD) process. During the process, an aerosolized precursor containing polydimethylsiloxane, epoxy resin, and stearic acid functionalized Al-doped ZnO nanoparticles was deposited onto the glass at 350 °C. X-ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy showed that the precursor was successfully coated and formed a nano/microstructure (surface roughness: 378.0 ± 46.1 nm) on the glass surface. The coated surface had a water contact angle of 159.1 ± 1.2°, contact angle hysteresis of 2.2 ± 1.7°, and rolling off-angle of 1°, indicating that it was superhydrophobic. In the self-cleaning test of the coated surface at a tilted angle of 20°, it was shown that water droplets rolled and washed out dirt on the surface. The stability tests showed that the surface remained superhydrophobic after 120 h of exposure to ultraviolet (UV) irradiation and even after heat exposure at 350 °C. In addition, the surface was highly repellent to water solutions of pH 1-13. The results showed that the addition of the functionalized nanoparticles into the precursor allowed for the control of surface roughness and provided a simplified single-step fabrication process of the superhydrophobic surface. This provides valuable information for developing the manufacturing process for superhydrophobic surfaces.

Indole is a popular and functional scaffold existing widely in the fields of medicine, pesticides, spices, food and feed additives, dyes, and many others. Among indoles, 2-arylindole represents a particular and interesting subset but has attracted less attention for drug discovery. In this study, we report a general, practical one-pot assembly of a variety of 2-arylindole derivatives. To develop novel fungicide scaffolds, their fungicide activity was also evaluated. The bioassay results showed that many of the synthesized 2-arylindoles exhibited considerable fungicidal activities especially toward Rhizoctonia cerealis , and several demonstrated an inhibition rate of more than 90%. Notably, 4-fluoro-2-phenyl-1 H -indole 6e was obtained with a broad spectrum of fungicidal activities, which showed excellent growth inhibition activities against R. cerealis , Rhizoctonia solani , Botrytis cinerea , Magnaporthe oryza , and Sclerotinia sclerotiorum with EC 50 values of 2.31, 4.98, 6.78, 10.57, and 17.80 μg/mL, respectively. Preliminary fungicidal mode of action of 6e showed a significant inhibition effect on mycelial growth and spore germination. These results indicated that 2-arylindoles as privileged scaffolds exhibited potential fungicidal activities that deserve further study.

Superhydrophobic surfaces have aroused increasing attentions in the fields of self-cleaning, anti-fouling, heat transfer, etc. However, one of the major problems of the artificial superhydrophobic surface in practical applications is the poor durability. Inspired by the self-healing property of nature organism, we developed a sunlight-driven recoverable superhydrophobic surface by femtosecond laser constructing micropillar array on the surface of the photo-responsive shape-memory polymer (SMP). The photo-responsive SMP composite was prepared by adding reduced graphene oxide (RGO) into thermal-responsive SMP matrix. Due to the excellent sunlight-to-heat transformation property of RGO, the temperature of the as-fabricated RGO-SMP composite could be rapidly increased above the shape transformation temperature of the RGO-SMP under one sunlight irradiation. Once the micropillar array of the RGO-SMP composite was deformed by pressing or stretching treatments, the surface would lose superhydrophobicity. Upon sunlight irradiation, the surface morphology and the wettability of the RGO-SMP micropillars could completely recover to the original states. Meanwhile, this reversible morphology and wettability transformation process could be repeated multiple times. We envision that such a sunlight-recoverable superhydrophobic surface will have great applications in the future.

Alternating magnetic fields (AMFs) are recently demonstrated as a promising strategy to promote the electrochemical catalytic reactions. However, the underlying mechanisms are still an open question. In this work, we systematically investigated the influence of AMFs on the hydrogen evolution reaction (HER) by using a Fe-Co-Ni-P-B magnetic catalyst. The HER catalytic efficiency is boosted significantly by AMFs, with 27% increase in current density at 20 mT. This is attributed to the enhancement of charge-transfer efficiency by Lorentz interaction with a minor contribution from the heating effect. The high magnetic permeability and skin effect of electromagnetic eddy current for the Fe-Co-Ni-P-B electrode can magnify the Lorentz effect. These findings clarify the mechanism of AMF-enhanced HER catalytic activities and open a door for designing a high-efficiency electrocatalysis system.

A rational molecule design strategy based on scaffold hopping was applied to discover novel leads, and then a series of novel pyrazole amide derivatives were designed, synthesized, characterized, and evaluated for their antifungal activities. Bioassay results indicated that some target compounds such as S3 , S12 , and S26 showed good in vivo antifungal activities; among them, S26 exhibited commendable in vivo protective activity with an 89% inhibition rate against Botrytis cinerea on cucumber at 100 μg/mL that is comparable to positive controls boscalid, isopyrazam, and fluxapyroxad. Microscopy observations suggested that S26 affects the normal fungal growth. Fluorescence quenching analysis and SDH (succinate dehydrogenase) enzymatic inhibition studies validated that S26 may not be an SDH inhibitor. Based on induction of plant defense responses testing, S26 enhanced the accumulation of RBOH, WRKY6 , WRKY30 , PR1 , and PAL defense-related genes expression and the defense-associated enzyme phenylalanine ammonia lyase (PAL) expression on cucumber. These findings support that S26 not only displayed direct fungicidal activity but also exhibited plant innate immunity stimulation activity, and it could be used as a promising plant defense-related fungicide candidate.

Functionality of amorphous multicomponent systems largely depends upon the miscibility among components, especially in systems such as amorphous drugs and electrolytes. An in-depth understanding of mixing behaviors of various constituents is necessitated. Here, we applied the small- and wide-angle X-ray scattering (SWAXS) technique to monitor the mixing behaviors in three typical glass-forming binary systems imposed by varied heat of mixing. It is found that the Porod invariant ( Q ) determined at the glass transition temperature is remarkably enhanced as the concentration fluctuation becomes intensified. Meanwhile, the deviation of Q from the ideal mixing law is markedly weaken at elevated temperatures. The results unambiguously suggest that the degree of concentration fluctuations in mixing systems can be accurately quantified by the structural property, allowing the link to mixing thermodynamics.

Photodynamic therapy (PDT) can eradicate cancer cells under light irradiation, mainly because of reactive singlet oxygen ( 1 O 2 ) being transformed from intratumoral oxygen. Nonetheless, the consumption of oxygen during PDT results in serious hypoxic conditions and an elevated hypoxia-inducing factor-1α (HIF-1α) level that hamper further photodynamic efficacy and induce tumor metastasis. To address this problem, we developed hypoxia-assisted NP-co-encapsulating Ce6 (photosensitizer) and YC-1 (HIF-1α inhibitor) as a self-rectifiable nanoinhibitor for synergistic antitumor treatment. PDT-aggravated intracellular hypoxic stress facilitated NP dissociation to release the drug (YC-1), which achieved tumor killing and HIF-1α inhibition to further enhance the therapeutic effect of PDT and prevent tumor metastasis. Besides, in vivo studies revealed that the HC/PI@YC-1 NPs afforded synergistic anticancer efficacy with minimal toxicity. Therefore, this study provides a prospective approach against PDT drawbacks and combination cancer therapy.

Transketolase (TK) has been regarded as a new target for the development of novel herbicides. In this study, a series of 2-thioether-5-(thienyl/pyridyl)-1,3,4-oxadiazoles were designed and synthesized based on TK as the new target. The preliminary bioassay results indicated that compounds 4l and 4m displayed the best herbicidal activities against Amaranthus retroflexus ( AR ) and Digitaria sanguinalis ( DS ), with the inhibition exceeding 90% at 100-200 mg/L in vitro . Moreover, they also displayed higher postemergence herbicidal activities (90% control) against AR and DS than all of the positive controls at 45-90 g [active ingredient (ai)]/ha in a greenhouse. Notably, compounds 4l and 4m showed a broad spectrum of weed control at 90 g ai/ha. More significantly, compound 4l exhibited good crop selectivity against maize at 90 g ai/ha. Both fluorescent binding experiments and molecular docking analyses indicated that compounds 4l and 4m exhibited strong TK inhibitory activities with superior binding affinities than the others. Preliminary mechanism studies suggested that they might exert their TK inhibitory effects by occupying the active cavity of At TK and forming more strong interactions with amino acids in the active site. Taken together, these results suggested that compound 4l was a potential herbicide candidate for weed control in maize fields targeting TK.

The ubiquitous mineralization of calcium phosphate (CaP) facilitates biological organisms to produce hierarchically structured minerals. The coordination number and strength of Ca 2+ ions with phosphate species, oxygen-containing additives, and solvent molecules played a crucial role in tuning nucleation processes and the surface stability of CaP under the simulated body fluid (SBF) or aqueous solutions upon the addition of oligomeric lactic acid (LAC n , n = 1, 8) and changing pH values. As revealed by ab initio molecular dynamics (AIMD), density functional theory (DFT), and molecular dynamics (MD) simulations as well as high-throughput experimentation (HTE), the binding of LAC molecules with Ca 2+ ions and phosphate species could stabilize both the pre-nucleation clusters and brushite (DCPD, CaHPO 4 ·2H 2 O) surface through intermolecular electrostatic and hydrogen bonding interactions. When the concentration of Ca 2+ ions ([Ca 2+ ]) is very low, the amount of the formed precipitation decreased with the addition of LAC based on UV-vis spectroscopic analysis due to the reduced chance for the LAC capped Ca 2+ ions to coordinate with phosphates and the increased solubility in the acid solution. With the increasing [Ca 2+ ] concentration, the kinetically stable DCPD precipitation was obtained with high Ca 2+ coordination number and low surface energy. Morphologies of DCPD precipitation are in plate, needle, or rod, depending on the initial pH values that were tuned by adding NH 3 ·H 2 O, HCl, or CH 3 COOH. The prepared samples at pH ≈ 7.4 with different Ca/P ratios exhibited negative zeta potential values, which were correlated with the surface electrostatic potential distributions and potential biological applications.

Owing to their minimal side effects and effective protection from oxidative stress, inflammation, and malignant growth, natural polysaccharides (NPs) are a potential adjuvant therapy for several diseases caused by intestinal barrier injury (IBI). More studies are accumulating on the protective effects of NPs with respect to IBI, but the underlying mechanisms remain unclear. Thus, this review aims to represent current studies that investigate the protective effects of NPs on IBI by directly maintaining intestinal epithelial barrier integrity (inhibiting oxidative stress, regulating inflammatory cytokine expression, and increasing tight junction protein expression) and indirectly regulating intestinal immunity and microbiota. Furthermore, the mechanisms underlying IBI development are briefly introduced, and the structure-activity relationships of polysaccharides with intestinal barrier protection effects are discussed. Potential developments and challenges associated with NPs exhibiting protective effects against IBI have also been highlighted to guide the application of NPs in the treatment of intestinal diseases caused by IBI.

The contamination of pathogenic micro-organisms and heavy metals in drinking water sources poses a serious threat to human health, which raises the demand for efficient water treatments. Herein, multi-functional capacitive deionization (CDI) electrodes were developed for the simultaneous decontamination of bacteria and heavy metal contaminants. Polyhexamethylene guanidine (PHMG), an antibacterial polymer, was deposited on the surface of the activated carbon (AC) electrode with the assistance of mussel-inspired polydopamine (PDA) chemistry. The main characterization results proved successful co-deposition of PDA and PHMG on the AC electrode, forming a hydrophilic coating layer in one step. Electrochemical analyses indicated that the AC-PDA/PHMG electrodes presented satisfactory capacitive behaviors, with outstanding salt adsorption capacity and cycling stability. The modified electrodes also exhibit excellent disinfection performance and heavy metal adsorption performance. The bacterial elimination rate of co-deposited electrodes grew along with the increase in the PHMG content. Particularly, AC-PDA/PHMG 2 electrodes successfully removed and deactivated 99.11% Escherichia coli and 98.67% Pseudomonas aeruginosa (10 4 CFU mL -1 ) in water within 60 min. Furthermore, three flow cells made by AC-PDA/PHMG 2 electrodes connected in series achieved efficient removal of salt, heavy metals such as lead and cadmium, and bacteria simultaneously, which indicated that the adsorption performance is significantly improved compared with pristine AC electrodes. These results denote the enormous potential of this one-step prepared multi-functional electrodes for facile and effective water purification using CDI technology.