The development of nanoscale pesticide delivery systems has significantly enhanced pesticide bioactivity while reducing the associated toxicological risks. However, the variability in efficacy across different sustained-release formulations highlights the need for precise regulatory oversight. This study focuses on balancing the toxicity, bioactivity, and dissipation of residual levels of pesticides across various formulation sizes to optimize their agricultural applications. Three difenoconazole formulations with distinct particle architectures were created using established methodologies: a conventional 10% suspension concentrate (SC) created through wet milling, a 10% microemulsion (ME) employing emulsifiable oil technology, and a 5% nanocapsule suspension (NCS) synthesized via interfacial polymerization. Systematic evaluation revealed that the nanoscale formulations (ME and NCS) demonstrated enhanced bioactivity against Rhizoctonia solani, the soil-borne phytopathogen responsible for rice sheath blight, compared to micron-scale SC. Similarly, ME and NCS displayed superior toxicological safety compared to SC when tested in zebrafish. Notably, the environmental dissipation kinetics in paddy ecosystems varied across formulations. The NCS displayed accelerated degradation (DT50 = 3.2 d), while the ME exhibited prolonged residual persistence (DT50 = 7.8 d), which was attributed to its optimized oil-water interfacial stabilization. These patterns significantly deviated from the dissipation rate of the technical-grade active ingredient (DT50 = 5.1 d). These findings provide novel insights into the structure-activity relationships of nano-enabled agrochemicals, offering critical design principles for next-generation pesticide delivery systems that optimize field efficacy and minimize environmental impact.

Noble metals and metal-organic frameworks (MOFs) composite serve as prospective substrate for surface-enhanced Raman scattering (SERS) technology. Herein, an Ag aerogel/ZIF-8 nanocomposite was synthesized and exploited as an ultrasensitive SERS substrate. The as-designed Ag aerogel/ZIF-8 nanocomposite exhibited superior SERS performance, enabling the detection of 4-mercaptobenzoic acid (4-MBA) probe molecules at an ultra-low concentration of 10-10 M. The Ag aerogel/ZIF-8 nanocomposite demonstrated a remarkably high SERS enhancement factor (EF) of 3.73 × 106. The SERS performance resulted from the combined contribution of electromagnetic field enhancement and charge-transfer process. Furthermore, the Ag aerogel/ZIF-8 nanocomposite exhibited good reproducibility, with the SERS signals showing minimal standard deviation in repeated measurements. The Ag aerogel/ZIF-8 nanocomposite further enabled SERS-based detection of gaseous benzaldehyde, demonstrating its potential for monitoring volatile organic compounds (VOCs) in air samples. Compared with conventional MOF- or aerogel-based SERS substrates, the as-prepared Ag aerogel/ZIF-8 nanocomposite combines excellent SERS activity with high porosity, large surface area, and strong adsorption ability. This unique hybrid structure significantly improves sensitivity, selectivity, and stability, showing high novelty and advancement for SERS detection, and can be applied to food safety, disease diagnosis and environmental monitoring.

Bacterial flavohemoglobins are well-characterized as versatile proteins that significantly augment the biosynthesis yields of diverse value-added compounds in engineered microbial platforms. Our previous studies revealed marked upregulation of a flavohemoglobin-encoding gene in Ensifer adhaerens under oxygen-limiting conditions, with potential associations to vitamin B12 production. In this study, a novel flavohemoglobin (FHP, encoded by b12fla gene) from Ensifer adhaerens were characterized. FHP exhibited high sequence and structural similarity to HMP (the flavohaemoglobin from Halalkalibacterium halodurans), yet demonstrating 3-fold higher NADH oxidase activity. Heterologous expression of FHP in Escherichia coli positively influences cell growth, biomass yield on carbon and nitrogen sources, increased OD600 and Oxygen Uptake Rate (OUR) in 50-L fermenter of FHP-expressing strain EcFHP (12

With the ongoing growth in global demand for natural gas, gas hydrates have great potential as efficient and safe media for gas storage and transportation. Nevertheless, the slow kinetics of hydrate formation constitute a critical bottleneck that restricts the large‑scale industrial application of this technology. Conventional chemical promoters are toxic and tend to generate foam during gas recovery, which adversely affects the environment, reduces gas recovery efficiency, and increases operational costs. Naturally occurring natural gas hydrates mainly form in deep‑sea sediments, among which carbonates are one of the primary components of marine sediments. Therefore, the formation kinetics of methane hydrate in systems composed of hydrophobic amino acids (L‑leucine, L‑methionine, and L‑phenylalanine) and 60nm CaCO3 particles was investigated under static conditions at 6MPa and 273.15K. The dispersion stability of CaCO3 nanofluids was characterized via static sedimentation tests and turbidity measurements. The results reveal that 0.3wt.% phenylalanine exhibits the strongest promotion effect on methane hydrate formation, with a gas uptake capacity of 90.76 (mmol/mol), which is superior to that of the pure water‑CaCO3 system under stirring at 400 RPM. After three cycles of gas storage and release, the methane hydrate gas uptake capacity decreases by 48.7%, and the induction time increases by 50.3% in the fourth cycle. When amino acids are used as dispersants for nano‑CaCO3, the dispersion stability of nanofluids declines with increasing amino acid concentration. Morphological observations indicate that in the 0.3wt.% phenylalanine solution, methane hydrates grow upward and downward along the vessel wall centered at the gas‑liquid interface.

Under the global carbon neutrality target, CO2 hydrate storage in submarine clay sediments exhibits remarkable application potential owing to its high storage capacity and low leakage risk, yet it faces core bottlenecks: sluggish hydrate formation kinetics, insufficient long-term stability, and poor environmental compatibility of conventional promoters. To address these challenges, this study selected environmentally friendly sodium lignosulfonate (SL) as a promoter, and systematically explored its regulatory effects on CO2 hydrate formation kinetics, phase distribution, and occurrence stability in static montmorillonite (MMT) systems with varying clay contents. The results demonstrate that SL’s promotion effect on CO2 hydrate formation is strongly concentration-dependent, with optimal performance at 1.5 wt% SL, where hydrate gas uptake increases by approximately 200% compared with the pure water system. SL exerts a dual promotion-inhibition effect in MMT systems: in low-concentration MMT (0.1–5.0 wt%), SL enhances apparent CO2 retention and hydrate yield, significantly accelerating hydrate growth kinetics; in high-concentration MMT (10.0–30.0 wt%), however, hydrate formation kinetics gradually declines with pronounced inhibition, which cannot be effectively mitigated even by further elevating SL concentration. Furthermore, SL reduces hydrate dissociation rate and effectively improves hydrate occurrence stability in clay layers. This study first quantifies the critical effects of SL on hydrate formation kinetics and stability in static clay systems, confirming SL as an efficient, eco-friendly and low-cost promoter, offering new insights to resolve the core bottlenecks of CO2 hydrate storage in submarine clay sediments.

RNA interference (RNAi) has led to multiple FDA-approved therapeutics and boasts a robust clinical pipeline. However, its transformation for kidney disease remains hindered by the absence of effective delivery vehicles, which are constrained by low delivery efficiency and non-target organ release. Herein, six novel modules of 2-(2-nitro-1H-imidazol-1-yl)ethanamine (IEN) with different carbon-chain linkers were designed and synthesized, then subsequently grafted onto chitosan (CS-Linker-IEN) to enable efficient delivery of RNAi in renal tissues. The CS-Linker-IEN self-assembles with siRNA into spherical nanoparticles (CS-Linker-IEN/siRNA) primarily through electrostatic, hydrogen-bond, and tunable hydrophobic interactions. This assembly enables the screening of an optimal size driven by tunable hydrophobicity and achieves efficient delivery to renal proximal tubule epithelial cells, with the smallest-sized CS-Hex-IEN/siRNA nanoparticles exhibiting the highest renal accumulation. Under hypoxic conditions characteristic of specific kidney diseases, the IEN moiety undergoes a structural transformation into 2-(2-amino-1H-imidazol-1-yl)ethanamine (AIE). This transformation reverses the hydrophobic-hydrophilic interactions, thereby enabling kidney-specific siRNA release. In a murine model of IRI-induced acute kidney injury (AKI), CS-Linker-IEN demonstrated targeted release of siCD36 to renal tubular epithelial cells, effectively mediating CD36 interference. This intervention conferred renoprotective effects through restoration of lipid metabolism, attenuation of oxidative stress, and suppression of the NF-κB signaling pathway. Given a plethora of kidney diseases that could benefit from RNAi, it is anticipated that this finding will expand the preclinical landscape of renal therapeutics.

Colloidal semiconductor quantum dots (QDs) have garnered significant attention as promising photocatalysts for the hydrogen evolution reaction, but their performance is still unsatisfactory owing to the inherent limitations in carrier separation and transport dynamics within QD systems. Herein, the "giant" CdSe/CdS core/shell QDs (GQDs) were employed for photocatalytic hydrogen evolution applications. Notably, it exhibits a significantly enhanced activity (4.26-fold) compared to the conventional CdSe/CdS core/shell QDs under visible light illumination. Further investigations reveal that the shell-thickness-dependent lifetime and separation efficiency of charge carriers are responsible for the enhancement. The results are expected to provide insights and theoretical foundations for the rational design of QD-based photocatalysts.

Background:Xylazine has been increasingly linked to human overdose deaths. No antidote has been identified and naloxone cannot reverse the effect of xylazine. Xylazine withdrawal is not alleviated by opioids. It is imperative to detect xylazine when treating overdoses. No screening method for xylazine has been approved by FDA. We aim to develop a rapid and high sensitivity xylazine test for clinical urine testing. Methods:Monoclonal antibodies with high sensitivity and specificity against xylazine were developed. The leading clone was used to develop a competitive lateral flow immunoassay. The analytical cutoff, specificity and clinical performance of this test was characterized using standards in drug-free urine and clinical urine samples. Results:The rapid xylazine dipstick test has a test time of 5 minutes, and a cutoff of 10 ng/mL xylazine in drug-free urine. No cross reactivity with other commonly used drugs or endogenous metabolites were observed, except for 3% cross reactivity with clonidine. In 181 mass spectrometry confirmed clinical urine samples with xylazine concentrations > 10 ng/mL and 120 urine samples with xylazine concentrations <10 ng/mL, the dipstick demonstrated a clinical sensitivity of 100% and a clinical specificity of 97%. All 4 false positives had combined xylazine and 4-hydroxy-xylazine concentrations in the 5-10 ng/mL range, with additional xylazine metabolites detected by mass spectrometry. Conclusions:When used with 10 ng/mL cutoff, the rapid xylazine dipstick demonstrates high clinical sensitivity and clinical specificity in urine samples, compared to gold standard mass spectrometry methods. This novel test has the potential to enable informed clinical decisions in suspected xylazine overdoses.

Since March 2013, the H7N9 subtype of avian influenza virus (AIV) has become an important zoonotic infectious disease, garnering significant global attention because of its potential to affect human health. Establishing a rapid, effective, and sensitive method to detect H7 subtype AIVs is crucial for disease control. In this study, we developed a graphene oxide multilayer quantum dot-based immunochromatographic strip for the ultrasensitive detection of H7 subtype AIVs. The method demonstrated excellent sensitivity, with a limit of detection of 0.063 hemagglutinin units and 0.016 ng/ml for the hemagglutinin protein. The method exhibited remarkable specificity, with no reaction with other subtypes of influenza A virus andno cross-reactivity with other types of avian virus. Additionally, this method exhibited excellent reproducibility, with both inter-group and intra-group variations remaining below 10 %. Preliminary testing on avian clinical samples showed impressive consistency, underscoring the method's reliability. These initial results suggest that this detection approach has significant potential for widespread use in analyzing avian clinical samples, indicating substantial promise for its future application in various diagnostic settings.

The selection of adsorption materials is a key factor affecting the adsorption of toluene. The zeolite imidazolium ester skeleton (ZIF-67) was grown in situ onto the surface of biomass fibers and deposited with methyltrichlorosilane (MTCS) to construct a hydrophobic adsorption material for volatile organic compounds (VOCs). The specific surface area of the prepared adsorbent was as high as 350.05 m 2 & sdot; g- 1 , which decreased after the depo degrees degrees sition of MTCS. The water contact angle of the material increased from 0 to 119.8 . The static adsorption of toluene on the composite paper was 92-120 mg & sdot;g-1, and the dynamic adsorption of toluene was 52-69 mg & sdot;g- 1 , and the hydrophobically modified samples had better adsorption effects in humid environments. The interactions between ZIF-67 and toluene were analyzed by electrostatic potential (ESP) and independent gradient model (IGM) based on density flooding theory (DFT), which provided some theoretical support for this study.

Simultaneous promotion of charge and mass transportation between catalytic centers and reactants is crucial for photocatalysis but remains a substantial challenge on account of the widespread use of homogeneous or heterogeneous photocatalysts that suffer from sluggish reactant-diffusion kinetics or interfacial electron-transport resistance, respectively. Herein, we demonstrate the construction of conjugated microporous polymer aerogels as available quasi-homogeneous photocatalysts by integrating structural designability, which allows for the incorporation of electron-acceptor building blocks featuring ultralong-lived excitons as high-concentration local catalytic centers, and hierarchically porous gel networks that wrap solvent and reactants to provide a "single" reaction phase without interfacial resistance. A total of 18 samples of C─H functionalization reactions underpinned by four different mechanisms were screened to showcase the general applicability of the obtained aerogel photocatalysts, which achieved remarkable conversion efficiencies, gram-scale productivities, and recyclability. By combining a designable structure for photophysical properties with hierarchical porosities for optimal charge/mass transfer, we believe microporous polymer aerogels can serve as a versatile design platform for quasi-homogeneously photocatalyzing challenging reactions.

Electrocatalytic hydrogen production is an effective method to solve environmental issues and energy crisis. However, cheap and high performance electrocatalysts are still very scarce. In this work, the hydrogen evolution reaction performance of holey graphdiyne supported transition metals single-atom catalysts (TM-SAC-HGY) were investigated by first-principles study. It is found that TM atoms are stably anchored on monolayer HGY by forming TM-C bonds. Meanwhile, TM atoms transfer electrons to both HGY and H atom. More importantly, the H adsorption free energy (Delta GH) of Cu-SAC-HGY is 0.028 eV, which is very close to 0 eV. Therefore, Cu-SAC-HGY has excellent HER activity. By analyzing the results of partial density of states, it can be concluded that the orbital hybridization strength of TM and H plays a decisive role in affecting HER activity. This work could contribute to the development of more efficient HER electrocatalysts.

The metal-nitrogen chelated species, MN4, have shown promise as efficient electrocatalysts for nitrate reduction, yet the symmetric arrangement of N atoms results in suboptimal adsorption affinity toward reaction substrates and intermediates. The current approaches to breaking the symmetry of MN4 suffer from inaccuracy and inhomogeneity because of the lack of strategies stemming from molecular design aspects. Herein, we report the construction of symmetry-broken MN2O2 sites in coordination polymers via sequential coordination-covalent control in a one-pot reaction. The dehydrogenating coordination preferentially occurs prior to the covalent imide-formation reaction, allowing the two reactions to be completely separated to afford molecularly precise polymer electrocatalysts that feature near-unity coordination degree and monodispersed atomic MN2O2 species with lowered symmetry, facilitating efficient nitrate reduction. Our study provides a design rationale to integrate diverse coordination and covalent chemistries into coordination polymers for electrocatalysis.

Surface enhanced Raman scattering (SERS) is a suited detection technique for trace and ultrasensitive detection that extends even to single molecule levels. However, SERS application is currently limited by three main factors: 1) how to create more hotspots to enhance the sensitivity of SERS; 2) how to enrich trace target molecules in SERS hotspots; and 3) how to maintain the stability and reproducibility of SERS detection under environmental interference. In this study, mesoporous Cu2O coated Au/Ag plasmonic nanocomposites (NCs) were designed and prepared as SERS substrates. The tightly packed Au/Ag nanoaggregates (NAs) create more hotspots, oxygen vacancies in Cu2O can also enhances Raman signal by photoinduced charge transferring. Meanwhile, mesoporous Cu2O coating is beneficial for enriching more target molecules, so the as-prepared Au/Ag@Cu2O NCs showed excellent SERS sensitivity. When the target molecules 4-mercaptobenzoic acid (4-MBA) was detected on the Au/Ag@Cu2O substrate, the substrate showed high SERS activity. The enhancement factor reached as high as 3.78 × 106, and the detection limit was as low as 10-11 M. Meanwhile, the SERS spectra demonstrate excellent selectivity and reproducibility. In addition, the Au/Ag@Cu2O NCs substrate was applied to detect volatile organic compounds (VOC) pyridine molecules in the air, and when it was naturally adsorbed in air for 20 min, it showed an obvious SERS signal of pyridine. Therefore, these Au/Ag@Cu2O NCs with high SERS detection performance have important practical value in applications of volatile organic gas molecule.

Drug-resistant bacterial infections, exacerbated by antibiotic resistance and biofilm resilience, disrupt tissue repair through dysregulated inflammation and impaired regeneration. Neutrophil extracellular traps (NETs) play a crucial role in endogenous immunity by entrapping and eliminating pathogens, inspiring the development of synthetic biomaterials that replicate this function. However, current synthetic NETs face challenges in complexity, biocompatibility, structural integrity and effectiveness. Here, we present a NETs-mimicking hydrogel composed of reversible lysozyme amyloid flexible nanofibrils (FFs) enabling pathogen elimination and tissue regeneration. The FFs therein self-assemble from natural egg-white lysozyme endowing these nanoNETs with bioactivity against pathogens, and when duly labeled to respond to near-infrared irradiation, they disassemble into unfolded lysozyme monomers with antimicrobial activity. Notably, the hydrogel disassembly is followed by the controlled release of pre-dissolved Mg²⁺ ions, reprogramming macrophages toward a pro-regenerative phenotype and mitigating inflammation. In both murine and porcine models, these biocompatible nanoNETs demonstrate excellent antibacterial performance, accelerating healing of wounds infected by methicillin-resistant Staphylococcus aureus (MRSA). Moreover, these nanoNETs boost in-vivo healing of MRSA-infected periprosthetic joints, preserving osteogenic and regenerative microenvironments. These results build on the reversible nature of flexible amyloids to introduce stimuli-responsive biocompatible nanoNETs with significant potential for antimicrobial and regenerative therapies in bacterial-resistant infections.

alpha-Fe2O3 is a promising photoanode material, but its photoelectrochemical (PEC) properties are severely limited by harmful surface states and unclear interfacial structure-activity relationships with cocatalysts. In this work, we innovatively introduces gallic acid (GA) as a coordinating agent and successfully encapsulates the tannin Co (TACo) complex onto Ti-Fe2O3 in a conformal manner. Specifically, through surface photovoltage systems, transient absorption spectroscopy (TAS) analysis, and self-designed transient photocurrent in-situ testing (TPC), we have confirmed that gallic acid not only acts as a bridge between Ti-Fe2O3 and TACo, but also actively regulates the surface state of Ti-Fe2O3. In addition, the coordination effect of GA constructs an efficient charge transfer channel, significantly promoting the water oxidation reaction process involving holes. The photocurrent density of the synthesized Ti-Fe2O3/GA/TACo reached 3.3 mA/cm2 at 1.23 V vs. RHE, which is 1.68 and 10 times higher than Ti-Fe2O3/TACo and Ti-Fe2O3, respectively. The bridging effect of small molecules in this study provides a clear interface for the study of charge transfer and structure-activity relationships.

OBJECTIVES:Xylazine has been increasingly identified in human overdose deaths. Detection of xylazine in clinical urine samples has clinical utility when treating overdoses. No screening method for xylazine has been approved by the US Food and Drug Administration (FDA). We aim to develop and validate a rapid and high sensitivity xylazine test for clinical urine testing. METHODS:Monoclonal antibodies with high sensitivity and specificity against xylazine were developed. The leading clone was used to develop a competitive lateral flow immunoassay. The analytical cutoff, specificity, and clinical performance of this test was characterized using standards in drug-free urine and clinical urine samples. RESULTS:The rapid xylazine dipstick test has a test time of 5 minutes and a cutoff of 10 ng/mL xylazine in drug-free urine. No cross reactivity with other commonly used drugs or endogenous metabolites were observed, except for 3% cross reactivity with clonidine. In 190 mass spectrometry confirmed clinical urine samples with xylazine concentrations ≥10 ng/mL and 168 urine samples with xylazine concentrations <10 ng/mL, the dipstick demonstrated a clinical sensitivity of 100% and a clinical specificity of 98%. All 4 false positives had combined xylazine and 4-hydroxy-xylazine concentrations in the 5-10 ng/mL range, with additional xylazine metabolites detected by mass spectrometry. CONCLUSIONS:When used with 10 ng/mL cutoff, the rapid xylazine dipstick demonstrates high clinical sensitivity and clinical specificity in urine samples, compared with gold standard mass spectrometry methods. This novel test has the potential to enable informed clinical decisions in cases with suspected xylazine exposure.

alpha-Fe2O3 is a promising photoanode that is limited by its high surface charge recombination and slow water oxidation kinetics. In this study, we synthesized a TiO2 layer on Ti-Fe2O3 by annealing Ti-MOFs, followed by ZIF-67 as a co-catalyst, to fabricate a ZIF-67/TiO2/Ti-Fe2O3 photoanode for photoelectrochemical (PEC) water splitting. The systematic experimental and theoretical results revealed that the improvement in performance was due to multiple effects of the MOF-derived TiO2. This molecule not only passivates the acceptor surface states of Ti-Fe2O3, thereby reducing the number of surface recombination centers, but also acts as an electron barrier to promote charge separation in the Ti-Fe2O3 bulk. Moreover, MOF-derived TiO2 can dramatically reduce the energy barrier for the OER of Ti-Fe2O3, thus promoting the conversion of the intermediate *OH into *O. The synergistic improvement in the bulk and surface properties effectively enhanced the water oxidation performance of Ti-Fe2O3. The ZIF-67/TiO2/Ti-Fe2O3 photoanode exhibits a photocurrent density of up to 4.04 mA cm-2 at 1.23 V vs. RHE, which is 9.4 times as that of pure Ti-Fe2O3, and has long-term stability. Our work provides a feasible strategy for constructing efficient organic-inorganic hybrid photoelectrodes. Published by Elsevier B.V. All rights reserved.

Oxidative stress affects production performance and meat quality of poultry. 6-gingerol (6-Gin) is the main activity component of ginger, has shown promise in alleviating oxidative stress in broilers, However, the specific protection mechanism of 6-Gin against hepatocytes oxidative damage remains unclear. The primary chicken embryo hepatocytes (CEHs) were damaged and the cell viability was decreased by H2O2, 6-Gin can alleviate the cell injure and oxidative stress. Transcriptomic analysis and further experiments showed that H2O2 significantly suppressed the expression of Nrf2, Keap1, and NQO1, as well as antioxidant enzyme activities, increased inflammatory factors, leading to cell apoptosis. In contrast, 6-Gin effectively reduced these effects by promoting Nrf 2 nuclear translocation and activating the Nrf2 signaling pathway. Furthermore, the protective effects of 6-Gin were eliminated by the Nrf2 inhibitor ML385. In conclusion, 6-Gin exerts antioxidant, anti-inflammatory and anti-apoptotic effects on CEHs through the Nrf2 pathway. This study provides the potential value of 6-Gin for treatment of oxidative stress in broilers.