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In this study, the induction period (tind) of l-arginine trifluoroacetate (LATF) at different levels of supersaturation have been examined at 298.15 K for both spontaneous and seeded growth systems. From the dependence of tind on supersaturation, it was possible to distinguish between the mechanisms of homogeneous and heterogeneous nucleation. On the basis of the experimental data pertaining to the homogeneous nucleation, the solid−liquid interfacial energy can be evaluated. Additionally, in the process of ascertaining the growth mechanism of LATF as two-dimensional (2D) nucleation-mediated growth using by theoretical expressions, a combined analysis of results in both experiments provides information about the growth and nucleation rate constants. Eventually, analysis of atomic force microscopy investigations on the facets of LATF crystals corroborates the 2D nucleation-mediated growth mechanism. The induction time for homogeneous and heterogeneous nucleation of l-arginine trifluoroacetate (LATF) crystals at different levels of supersaturation at room temperature have been investigated. Using the combined results from the spontaneous and seeded crystal growth experiments, estimations of the rate constants for growth and nucleation were made. Ex situ atomic force microscopy analysis validates that two-dimensional nucleation growth mechanism dominates in LATF crystallization. [ABSTRACT FROM AUTHOR]

Circularly polarized luminescent (CPL) materials have garnered considerable interest for a variety of advanced optical applications including 3D imaging, data encryption, and asymmetric catalysis. However, the development of high-performance CPL has been hindered by the absence of simple synthetic methods for chiral luminescent emitters that exhibit both high quantum yields and dissymmetry factors. In this study, we present an innovative approach for the synthesis of macro-chiral liquid crystal quantum dots (Ch-QDs/LC) and their CPL performance enhancement through doping with 4-cyano-4'-pentylbiphenyl (5CB), thus yielding a CPL-emitting generator (CEG). The Ch-QDs/LCs were synthesized, and their surfaces functionalized with a chiral mesogenic ligand, specifically cholesteryl benzoate, anchored via a lipoic acid linker. Under the regulation of chiral 2S-Zn 2+ coordination complexes, the chiral LC encapsulation process promotes coordinated ligand substitution, resulting in an exceptional quantum yield of 56.3%. This is accompanied by high absorption dissymmetry factor ( g abs ) and luminescence dissymmetry factor ( g lum ) values ranging from 10 -3 to 10 -2 , surpassing most reported dissymmetry factors by at least an order of magnitude. The modular Ch-QDs/LCs demonstrate the ability to transfer chirality to the surrounding medium efficiently and manifest macro-chiral characteristics within a nematic LC matrix. Utilizing Ch-QDs/LC as an effective CPL emitter within achiral 5CB matrices enabled the system to achieve a maximum g lum value of 0.35. The resultant CEG device acted as a direct CPL source, initiating enantioselective photopolymerization.

Cane molasses, a sugar-rich agro-industrial byproduct, was used to enhance the production of ε-poly-l-lysine (ε-PL) in Streptomyces albulus PD-1 as a cost-effective carbon source. The sucrose metabolism pathway was engineered by heterologously expressing sucrose-6-phosphate hydrolase from Escherichia coli W. The optimization of various promoters identified the SP44 promoter, increasing the total sugar utilization rate by 2.76-fold compared with the ermEp* promoter. Additionally, adaptive laboratory evolution improved the total sugar utilization rate. The evolved strain achieved an ε-PL titer of 2.65 ± 0.15 g/L in flask experiments, increasing the ε-PL titer by 7.16-fold compared with the unevolved strain. Comparative transcriptomic analyses revealed that the enhanced tolerance of the evolved strain to high concentrations of cane molasses was primarily due to modifications in the sucrose metabolism pathways, microbial metabolism in heavy metals and phenols, and the amino acids transport and metabolic pathways. These changes enabled more efficient ε-PL production. During fed-batch fermentation in a 5-L fermentor using a concentration of 50 g/L cane molasses, the ε-PL titer reached 36.88 ± 0.62 g/L, and dry cell weight was 41.1 ± 1.0 g/L. This study illustrates that cane molasses is an economical carbon source for producing ε-PL on an industrial scale.

Urban greening (UG) affects local climate by altering surface energy balance, while long-term UG cooling potential, patterns, and contribution to curbing urban warming remain unclear. Here, we designed an novel statistical model to evaluate the cooling potential of UG (CPUG) and created the first CPUG map for China. By exploring the trends in observed and simulated urban surface temperatures (UST), we quantified the CPUG of 0.20 K over the past two decades, which slowed down the warming trend by 14.17% in Chinese cities. We found that the CPUG varied significantly between the urban core and sprawl areas. Specifically, the CPUG in the urban core was approximately 1.01 K, and it contributed to curbing urban warming by 56.08%, which was more than 7.2 times higher than in the sprawl areas, where the CPUG was only 0.14 K and contributed to curbing urban warming by 9.93%. We further revealed that urbanization and major ecological restoration projects are the key factors influencing CPUG, emphasizing the need for anthropogenic vegetation management to curb urban warming. The proposed model in this study provides a powerful tool for quantitatively assessing the impact of long-term UG trends on urban warming. The results of the study are an important reference for building climate-adaptive cities.

Aryl ketones are often used as photosensitizers and photoinitiators. Free radical intermediates have been suggested, but not confirmed, to be generated after photoirradiation. Here we found, unexpectedly, that a persistent radical was produced from di-2-pyridyl ketone after UV irradiation, which was detected by the direct ESR method. Interestingly, the persistent radical was very sensitive to oxygen and the pH of the reaction medium. A similar persistent radical was also observed from phenyl-2-pyridyl ketone, but not from 3-benzoylpyridine, 4-benzoylpyridine, and benzophenone, suggesting that the presence of a carbonyl group connected to the ortho -position of the pyridine ring is critical for such radical production. By complementary applications of ESR, HPLC, and ESI-Q-TOF-MS, the possible chemical structures of the persistent radical and final product were identified, and the possible underlying reaction mechanism was proposed. This represents the first report on UV-induced persistent radical generation from 2-pyridyl ketones, which should be of great significance for future studies.

Nano-pesticides have attracted much attention in the field of agriculture, due to existing problems such as decreased bactericidal effect and poor adhesion. An environmentally friendly metal porphyrin (Cu-TCPP)-based nanocarrier pesticide release of diniconazole (DIN) was designed to enhance bactericidal efficacy and modulate its bioavailability in a multidimensional manner by constructing a metal phenolic network (MPN) encapsulation. The introduction of the MPN prevents the DIN from prematurely escaping from the Cu-TCPP@DIN@MPN in the environment and gives it strong interfacial adhesion to resist rain washing. The resulting Cu-TCPP@DIN@MPN nanoparticles (NPs) showed a lamellar stacked embedded structure, which improved the inhibition of Fusarium oxysporum (90.9%) and photostability (67.2%), while they do not affect healthy plant growth and meet the relevant food safety requirements for DIN residues. This work provides new ideas for the development of superior photostable, adhesive, rainwater erosion-resistant, and sustainable nanocarrier pesticides.

Disialoganglioside (GD2) is one of the most popular overexpressed antigens for tumor cell targeting. However, GD2-specific antibodies often show unintended targeting to GD2-expressing health-maintaining cells due to the comparable binding affinities both at physiological pH and in a slightly acidic tumor microenvironment (TME). In this work, an affinity-switchable zwitterionic PAMAM G5 dendrimer (G5-3S) is developed for selective binding to GD2 only in a slightly acidic TME. It has 3 sulfonic groups, 128 carboxylic groups, and 125 amino groups on the surface. This affinity switch is realized by multiple hydrogen bond (H-bond) formation between protonated carboxylic groups surrounding a sulfonic group and overexpressed GD2 clusters on the tumor cell membrane in the slightly acidic TME, whereas there is no stable H-bond formation at physiological pH. Thus, G5-3S shows superior selectivity to GD2-overexpressed tumor cells over anti-GD2 antibodies by avoiding targeting GD2-expressing health-maintaining cells at physiological pH. This suggests that G5-3S is a promising candidate for GD2-overexpressed cancer treatment.

Supramolecular polymers hold promise in thermal management applications due to their multistability, high responsiveness, and cost-effectiveness. In this work, we successfully regulate phonon transport at the molecular level in supramolecular polymers by adjusting the strength of intermolecular hydrogen bonding. We synthesized three supramolecular polymer fibers with thermal conductivity differences of up to 289% based on melamine (M) and three simple positional isomers of hydroxybenzoic acid. Differential Scanning Calorimetry (DSC) measurement revealed discrepancies in thermal stability of the polymers, where structures with higher stability exhibited enhanced thermal conductivity. Fourier Transform Infrared Spectroscopy (FTIR) measurement and Density Functional Theory (DFT) calculations indicate that these differences arise from variations in hydrogen-bonding strengths at different bonding sites. Higher hydrogen-bonding strength leads to more stable thermal pathways, reduces phonon scattering, and increases thermal conductivity. Our findings provide valuable insights into controlling the thermal conductivity of polymer fibers, paving the way for applications in phonon-based thermal devices.

Manganese(II) halides have been a new generation of optoelectronic materials due to their fascinating luminescent properties, however, lacking specific solvent-responsive analogues with high quantum efficiency. Herein, we prepared three single crystals, [Pr(MIm) 2 ][MnBr 4 ] ([Pr(MIm) 2 ] 2+ = 1,3-di(methylimidazolium)-propane, Compound 1 ), [Pr(EIm) 2 ][MnBr 4 ] ([Pr(EIm) 2 ] 2+ = 1,3-di(ethylimidazolium)-propane, Compound 2 ), and [Bu(MIm) 2 ][MnBr 4 ] ([Bu(MIm) 2 ] 2+ = 1,4-di(methylimidazolium)-butane, Compound 3 ), where different Bola-type cations were chosen as organic components to separate [MnBr 4 ] 2- tetrahedrons. All three compounds emitted bright green light with excellent quantum yields of 95.3, 80.0, and 96.2%, benefiting from the large Mn···Mn distance. More interestingly, Compound 3 showed a highly selective response to methanol in a series of tested organic solvents, with a rapid and reversible change in emission color from green to red. The single crystal of [Bu(MIm) 2 ][MnBr 4 ]·CH 3 OH with red emission proved that the luminescence switching was attributed to the adsorption of CH 3 OH molecules into the lattice space in the form of the O-H···Br hydrogen bonds. To our knowledge, for tetrahedrally coordinated Mn(II) species, the reversible emission color switching between green and red triggered by a solvent without the change of coordination number is achieved for the first time, providing promising applications for the specific detection of methanol.

Nanomedicines have been widely used in colorectal cancer treatment, but their suboptimal targeting and deficient penetration capabilities remain obstacles in the delivery of therapeutics. In this study, inspired by the natural tumor tropism and intestinal invasion of Salmonella , we engineered highly biomimetic nanoparticles (SM-AuNRs) utilizing a Salmonella membrane to coat bacilliform Au nanorods. The engineered SM-AuNRs were able to mimic the germ's morphology and biological surface. SM-AuNRs containing the specific proteins inherited from the Salmonella membrane facilitated specific targeting and internalization into tumor cells. Meanwhile, SM-AuNRs with the rod-shaped morphology effectively traversed mucus barriers and tumor stroma. Due to the superior biological barrier penetrating and tumor targeting capabilities, doxorubicin-loaded SM-AuNRs with near-infrared laser irradiation displayed remarkable photothermal-chemotherapeutic antitumor effects in mouse orthotopic colorectal cancer models. Our findings pave the way for the design of bacteria-mimicking nanoparticles, presenting a promising avenue for the targeting and efficient treatment of colorectal cancer.

Microstructure construction is a common strategy for enhancing the sensitivity of flexible pressure sensors, but it typically requires complex manufacturing techniques. In this study, we develop a flexible iontronic pressure sensor (FIPS) by embedding an isolated three-dimensional network spacer (3DNS) between an ionic gel and a flexible Ti 3 C 2 T x MXene electrode, thereby avoiding complex microstructure construction techniques. By leveraging substantial deformation of the 3DNS and the high capacitance density resulting from the electrical double layer effect, the sensor exhibits high sensitivity (87.4 kPa -1 ) over a broad high-pressure range (400-1000 kPa) while maintaining linearity ( R 2 = 0.998). Additionally, the FIPS demonstrates a rapid response time of 46 ms, a low limit of detection at 50 Pa, and excellent stability over 10 000 cycles under a high pressure of 600 kPa. As practical demonstrations, the FIPS can effectively monitor human motion such as elbow bending and assist a robotic gripper in accurately sensing gripping tasks. Moreover, a real-time, adaptive 7 × 7 sensing array system is built and can recognize both numeric and alphabetic characters. Our design philosophy can be extended for fabricating pressure sensors with high sensing performance without involving complex techniques, facilitating the applications of flexible sensors in human motion monitoring, robotic tactile sensing, and human-machine interaction.

The granule-based anammox process has been reported to be more resistant to the stress of antibiotics; however, the underlying resistance mechanism is still not fully understood. In this study, we found that more microbubbles stably adhered to the surface layer of anammox granular sludge (AnGS, Gs) operating under long-term sulfamethoxazole (SMZ) stress of 2 mg/L, compared to that in the control reactor (Gc). The difference in covering content can be up to over three times (1.0 ± 0.1% vs 0.3 ± 0.0%). Batch tests showed that the coverage ratio of microbubbles on Gs reached approximately 32.5%, which significantly reduced SMZ transfer into AnGS due to the adsorption of SMZ by bubbles, thus alleviating the inhibition of anammox bacterial activity by 36.5%. The adhesion force between the microbubbles and the surface layer of Gs was found to be largely enhanced by 75.0% compared to that of Gc. The increased hydrophobicity of surface layer due to the increased extracellular polymer substance (EPS, mainly proteins) content, and the larger capillary force of surface layer, owing to the unique micronano structure, were identified as key factors responsible for the stable adhesion of microbubbles on the Gs. Consequently, this study demonstrated the vital roles of the surface-adhered microbubbles in resisting the stress of SMZ and shed light on the regulation and development of robust granule-based anammox processes.

Thermal resistance at interfaces/contacts stands as a persistent and increasingly critical issue, which hinders ultimate scaling and the performance of electronic devices. Compared to the extensive research on contact electrical resistance, contact thermal resistance and its mitigation strategies have received relatively less attention. Here, we report on an effective, in situ, and energy-efficient approach for enhancing thermal transport through the contact between semiconducting nanoribbons. By applying microampere-level electrical currents to the contact between Bi 2 Se 3 nanoribbons, we demonstrate that the contact thermal resistance between two nanoribbon segments is reduced dramatically by a factor of 4, rendering the total thermal resistance of two ribbon segments with a contact approximately the same as that of the corresponding single continuous nanoribbon of the same length. Analysis suggests that the ultralow contact thermal resistance is due to enhanced phonon transmission as a result of enhanced adhesion energy at the contact, with marginal contributions from direct electron-phonon coupling, even for ohmic contacts. Our work introduces a broadly applicable electrical treatment approach to various contacts between conducting and semiconducting materials, which has important implications for the design and operation of nanoelectronic devices and energy converters.

The development of a highly active and stable oxygen evolution reaction (OER) electrocatalyst is desirable for sustainable and efficient hydrogen production via proton exchange membrane water electrolysis (PEMWE) powered by renewable electricity yet challenging. Herein, we report a robust Pt/Ru-codoped spinel cobalt oxide (PtRu-Co 3 O 4 ) electrocatalyst with an ultralow precious metal loading for acidic overall water splitting. PtRu-Co 3 O 4 exhibits excellent catalytic activity (1.63 V at 100 mA cm -2 ) and outstanding stability without significant performance degradation for 100 h operation. Experimental analysis and theoretical calculations indicate that Pt doping can induce electron transfer to Ru-doped Co 3 O 4 , optimize the absorption energy of oxygen intermediates, and stabilize metal-oxygen bonds, thus enhancing the catalytic performance through an adsorbate-evolving mechanism. As a consequence, the PEM electrolyzer featuring PtRu-Co 3 O 4 catalyst with low precious metal mass loading of 0.23 mg cm -2 can drive a current density of 1.0 A cm -2 at 1.83 V, revealing great promise for the application of noniridium-based catalysts with low contents of precious metal for hydrogen production.

Previous studies have detected microplastics (MPs) in human biological samples, such as lungs, alveolar lavage fluid, and thrombus. However, whether MPs induce health effects after inhalation are unclear. In this study, fluorescent polystyrene microplastics (PS-MPs) were found in the thymus, spleen, testes, liver, kidneys, and brain on day 1 or day 3 after one intratracheal instillation. Furthermore, mice showed inflammation in multiple organs, manifested as obvious infiltration of neutrophils and macrophages, increased Toll-like receptors (TLRs), myeloid differentiation primary response protein 88 (MyD88) and nuclear factor-κB (NF-κB), as well as proinflammatory cytokines (tumor necrosis factor (TNF)-α and interleukin (IL)-1β) in the lungs, thymus, spleen, liver, and kidneys after four intratracheal instillations of PS-MPs at once every 2 weeks. Hepatic and renal function indexes were also increased. Subsequently, the inflammatory response in multiple murine organs was significantly alleviated by TLR2 and TLR4 inhibitors. Unexpectedly, we did not find any elevated secretion of monocyte chemotactic protein (MCP)-1 or TNF-α by RAW264.7 macrophages in vitro. Thus, PS-MPs induced inflammatory injuries in multiple murine organs via the TLRs/MyD88/NF-κB pathway in vivo, but not macrophages in vitro. These results may provide theoretical support for healthy protection against PS-MPs and their environmental risk assessment.

The escalating concern of perfluoroalkyl and polyfluoroalkyl substances (PFAS), particularly at contaminated sites, has prompted extensive investigations. In this study, samples of multimedia including air, rhizosphere soil, and tissues of wheat at various growing stages were collected near a mega fluorochemical industrial park in China. Perfluorooctanoic acid (PFOA) was predominant in both air and soil with a strong correlation, highlighting air deposition as an important source in the terrestrial system. PFAS concentrations in wheat decreased in the stem and ear but increased in the leaves as wheat matured. Specifically, perfluorobutanoic acid (PFBA) dominated in the aboveground tissues in the full-life-cycle, except that PFOA surpassed and became predominant in leaves during the filling and maturing stages, hinting at an airborne source. For all PFAS, both bioaccumulation factors and translocation factors (TFs) were inversely correlated with the carbon chain length during the full-life-cycle. The obtained TF values were considerably higher than those obtained from ambient sites reported previously, further suggesting an unneglectable foliar uptake from air, which was estimated to be 25% for PFOA. Moreover, spray irrigation remarkably enhanced the absorption of PFAS in wheat via foliar uptake relative to flood irrigation. The estimated daily intake of PFBA via wheat consumption and air inhalation was 0.50 μg/kg/day for local residents, at least one magnitude higher than the corresponding threshold, suggesting an alarmingly high exposure risk.

Molecular property prediction (MPP) techniques are pivotal in reducing drug development costs by preemptively predicting bioactivity and ADMET properties. Despite the application of numerous deep learning approaches, enhancing the representational capacity of these models remains a significant challenge. This paper presents a novel knowledge-based Transformer framework, KnoMol, designed to improve the understanding of molecular structures. KnoMol integrates expert chemical knowledge into the Transformer, emulating the analytical methods of medicinal chemists. Additionally, the multiperspective attention mechanism provides a more precise way to represent ring systems. In the evaluation experiments, KnoMol achieved state-of-the-art performance on both MoleculeNet and small-scale data sets, surpassing existing models in terms of accuracy and generalization. Further research indicated that the incorporation of knowledge significantly reduces KnoMol's reliance on data volumes, offering a solution to the challenge of data scarcity. Moreover, KnoMol identified several new inhibitors of HER2 in a case study, demonstrating its value in real-world applications. Overall, this research not only provides a powerful tool for MPP but also serves as a successful precedent for embedding knowledge into Transformers, with positive implications for computer-aided drug discovery and the development of MPP algorithms.

Long-range allosteric communication between distant sites and active sites in proteins is central to biological regulation but still poorly characterized, limiting the development of protein engineering and drug design. Addressing this gap, NRIMD is an open-access web server for analyzing long-range interactions in proteins from molecular dynamics (MD) simulations, such as the effect of mutations at distal sites or allosteric ligand binding at allosteric sites on the active center. Based on our recent works on neural relational inference using graph neural networks, this cloud-based web server accepts MD simulation data on any length of residues in the alpha-carbon skeleton format from mainstream MD software. The input trajectory data are validated at the frontend deployed on the cloud and then processed on the backend deployed on a high-performance computer system with a collection of complementary tools. The web server provides a one-stop-shop MD analysis platform to predict long-range interactions and their paths between distant sites and active sites. It provides a user-friendly interface for detailed analysis and visualization. To the best of our knowledge, NRIMD is the first-of-its-kind online service to provide comprehensive long-range interaction analysis on MD simulations, which significantly lowers the barrier of predictions on protein long-range interactions using deep learning. The NRIMD web server is publicly available at https://nrimd.luddy.indianapolis.iu.edu/.

Idiopathic pulmonary fibrosis, an idiopathic interstitial lung disease with high mortality, remains challenging to treat due to the lack of clinically approved lung-targeting drugs. Herein, we present PDIC-DPC, a perylenediimide derivative that exhibits superior lung-selective enrichment. PDIC-DPC forms nanocomposites with plasma proteins, including fibrinogen beta chain and vitronectin, which bind to pulmonary endothelial receptors for lung-specific accumulation. Moreover, PDIC-DPC significantly suppresses transforming growth factor beta1 and activates adenosine monophosphate-activated protein kinase. As a result, compared to existing therapeutic drugs, PDIC-DPC achieves superior therapeutic outcomes, evidenced by the lowest Ashcroft score, significantly improved pulmonary function, and an extended survival rate in a bleomycin-induced pulmonary fibrosis model. This study elucidates the lung-selective enrichment of assembled prodrug from biological perspectives and affords a platform enabling therapeutic efficiency on idiopathic pulmonary fibrosis.

Selective electrocatalytic transformation of alcohols to aldehydes offers an efficient and environmentally friendly platform for the simultaneous production of fine chemicals and pure hydrogen gas. However, traditional alcohol oxidation reactions (AORs) in aqueous electrolyte unavoidably face competitive reactions (e.g., water oxidation and overoxidations reactions) for the presence of active oxygen species from water oxidation, causing an unwanted decrease in final efficiency and selectivity. Here, we developed an integrated all-solid proton generator-transfer electrolyzer to trigger the pure alcohol splitting reaction (ASR). In this splitting process, only O-H and C-H bonds can be cleaved at the proton generator (Pt nanoparticles), thereby completely avoiding all competitive reactions involving oxygen active species to give a > 99% selectivity to aldehydes. The as-generated protons are transported to the cathode by a three-dimensional (3D) conducting network (assemblies of ionomers and carbon spheres) for efficient hydrogen production. Unlike the poor selectivity (<22%) and durability (<3 h) of a conventional AOR electrolyzer, this ASR electrolyzer could be continuously operated at a low cell voltage of 1.2 V for at least 10 days to give a high Faradaic efficiency of 80-93% for aldehyde production.

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.

Fluorescent nanodiamonds (FNDs) with nitrogen-vacancy centers are pivotal for advancing quantum photonics and imaging through deterministic quantum state manipulation. However, deterministic integration of quantum emitters into photonic devices remains a challenge due to the need for high coupling efficiency and Purcell enhancement. We report a deterministic FND-integrated nanofocusing device achieved by assembling FNDs at a plasmonic waveguide tip through plasmonic-enhanced optical trapping. This technique not only increases the emission rate by 58.6 times compared to isolated FNDs but also preferentially directs radiation into the waveguide at a rate 5.3 times higher than that into free space, achieving an exceptional figure-of-merit of ∼3000 for efficient energy transfer. Our findings represent a significant step toward deterministic integration in quantum imaging and communication, opening new avenues for quantum technology advancements.

Sulfur-containing compounds have diverse biological functions and are crucial in crop protection chemistry. In this study, a series of novel 1-methyl-1 H -pyrazol-5-amine derivatives incorporating disulfide moieties were synthesized and evaluated for their antimicrobial properties. In vitro bioassays demonstrated that compound 7f displayed potent antifungal activity against Valsa mali , with an EC 50 value of 0.64 mg/L, outperforming allicin (EC 50 = 26.0 mg/L) but lower than tebuconazole (EC 50 = 0.33 mg/L). In vivo experiments confirmed that compound 7f could effectively inhibit V. mali infection on apples at a concentration of 100 mg/L, similar to the positive control tebuconazole. Mechanistic studies revealed that compound 7f could induce hyphal shrinkage and collapse, trigger intracellular reactive oxygen species accumulation, modulate antioxidant enzyme activities, initiate lipid peroxidation, and ultimately cause irreversible oxidative damage to the cells of V. mali . Additionally, compound 7b exhibited notable antibacterial activity, particularly against Pseudomonas syringae pv. actinidiae , with a MIC 90 value of 1.56 mg/L, surpassing the positive controls allicin, bismerthiazol, and streptomycin sulfate. These findings suggest that 1-methyl-1 H -pyrazol-5-amine derivatives containing disulfide moieties hold promise as potent candidates for the development of novel antimicrobial agents.

An efficient pyridine-catalyzed chemoselective four-component cascade reaction of aromatic aldehydes, malononitrile/cyanoacetates, Morita-Baylis-Hillman (MBH) carbonates, and alcohols has been established. This one-pot reaction progressed in an unusual reaction with solvent participation via a Knoevenagel condensation/oxa-Michael addition/S N 2' substitution sequence. This method allowed for facile access to an array of functionalized chain alkylbenzenes and dihydroquinolinones bearing one all-carbon quaternary center in moderate to excellent yields. It is worth noting that the configuration of the all-carbon quaternary center could be modulated by changing only the electron-withdrawing groups via a tandem reduction/cyclization reaction.

Bradyarrhythmia poses a serious threat to human health, with chronic progression causing heart failure and acute onset leading to sudden death. In this study, we develop a scalable drug-mimicking nanoplasmonic therapeutic strategy by introducing gold nanorod (Au NR) mediated near-infrared (NIR) photothermal effects. An integrated sensing and regulation platform is established for in situ synchronized NIR laser regulation and electrophysiological property recording. The Au NR plasmonic regulation enables the restoration of normal cardiomyocyte rhythm from the bradyarrhythmia. By regulating the aspect ratio and concentration of Au NRs, as well as the intensity and time of NIR irradiation, we precisely optimized the plasmonic photothermal effect to explore effective therapeutic strategies. Furthermore, mRNA sequencing revealed a significant increase in the number of differentially expressed genes (DEGs) involved in the electrophysiological activities of cardiomyocytes following photothermal therapy. Au NR-mediated plasmonic photothermal therapy, as an efficient and noninvasive approach to bradyarrhythmia, holds profound implications for cardiology research.

The origin of life on Earth is believed to be from the ocean, which offers abundant resources in its depths. However, deep-sea operations are limited due to the lack of underwater robots and rigid grippers with sensitive force sensors. Therefore, it is crucial for deep-sea pressure sensors to be integrated with mechanical hands for manipulation. Here, a flexible stress sensor is presented that can function effectively under high water pressure in the deep ocean. Inspired by biological structures found in the abyssal zone, our sensor is designed with an internal and external pressure balance structure (hollow interlocking spherical structure). The digital light processing (DLP) three-dimensional (3D) printing technology is utilized to construct this complex structure after obtaining optimized structural parameters using finite element simulation. The sensor exhibits linear sensitivity of 0.114 kPa -1 within the range of 0-15 kPa and has an extremely short response time of 32 ms, good dynamic-static load response capability, and excellent resistance cycling stability. It shows high sensitivity of 1.74 kPa -1 even under 30 MPa static water pressures and the theoretical working pressure can exceed 110 MPa, which provides a new solution for deep-sea robots.

The regulation solutions and mechanisms of reducing pesticide phytotoxicity to nontarget plants are not well-defined and detailed. Here, we have proposed a new detoxification strategy to control the toxic effects of herbicide imazethapyr (IM) induced in wheat seedlings from the perspective of the plasma membrane (PM) H + -ATPase. We found that the changes in PM H + -ATPase activity have a regulatory effect on the phytotoxic effects induced by IM in plants. Treatment with PM H + -ATPase activators restored the reduced auxin content and photosynthetic efficiency caused by IM, thereby promoting plant growth. Application of a PM H + -ATPase inhibitor further reduced phosphorus content and significantly increased 2,4-dihydroxy-7-methoxy-2 H ,1,4-benzoxazin-3(4 H )one (DIMBOA) and jasmonic acid levels. These effects indicate that auxin and DIMBOA may regulate plant growth trends and detoxification effects mediated by PM H + -ATPase. This work opens a new strategy for regulating herbicide toxicity to nontarget plants from the PM H + -ATPase.

In recent years, there has been considerable push toward the biomedical applications with active particles, which have great potential to revolutionize disease diagnostics and therapy. The direct penetration of active particles through the cell membrane leads to more efficient intracellular delivery than previously considered endocytosis processes but may cause membrane disruption. Understanding fundamental behaviors of cell membranes in response to such extreme impacts by active particles is crucial to develop active particle-based biomedical technologies and manage health and safety issues in this emerging field. Unfortunately, the physical principles underlying the nonequilibrium behaviors from endocytosis to direct penetration remain elusive, and experiments are challenging. Here, we present a computed dynamic phase diagram for transmembrane transport of active particles and identify four characteristic dynamic phases in endocytosis and direct penetration according to the particle activity and membrane tension. The boundaries dividing these phases are analytically obtained with theoretical models, elucidating the nonequilibrium physics and criteria for the transition between different phases. Furthermore, we numerically and experimentally show three distinct dynamic regimes related to the interplay between necking and wrapping during the endocytosis process of active particles, which strikingly contrast the regimes for passive particles. Overall, these findings could be useful for sharpening the understanding of basic principles underlying biological issues related to the safe and efficient biomedical applications of such emerging matters.

The accidental leakage of hydrogen poses a significant barrier to the widespread adoption and development of hydrogen energy due to the potential risks of fire, explosion, and jet fire hazards. Experimental investigations have been conducted on the process of jet fires formed by igniting hydrogen jet streams after accidental releases in scenarios such as high-pressure hydrogen gas storage tanks and hydrogen transmission pipelines. These experiments utilized a release pipe with a diameter of 10 mm and a length of 0.75 m, along with three pressure sensors, to study the influence of release pressure and ignition position on jet flame overpressure and flame propagation. Extensive tests at 1.5 MPa yielded a hydrogen flammability map containing two nonflammable zones and one flammable zone, along with a graph illustrating the relationship between overpressure and ignition points. Furthermore, experiments conducted at ignition positions of 0.05, 0.5 and 1.0 m under release pressures ranging from 6 to 10 MPa revealed that release pressure had no significant effect, while ignition position notably influenced the waveform and peak of the shockwave. Additionally, a peak shockwave reaching 30 kPa was observed at the downstream of the pipe outlet when ignited at 0.05 m, far exceeding the threshold of 24 kPa associated with fatalities. This research aims to provide valuable insights for safety design and protection distance considerations in scenarios involving hydrogen release and ignition., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Fusarium crown and root rot (FCRR) has emerged as a highly destructive soil-borne disease, posing a significant threat to the safe cultivation of tomatoes in recent years. The pathogen of tomato FCRR is Fusarium oxysporum f. sp. radicis-lycopersici ( Forl ). To explore potential phytotoxins from Forl , eight undescribed diterpenoids namely fusariumic acids A-H ( 1-8 ) were isolated. Their structures were elucidated by using spectroscopic data analyses, quantum chemical calculations, and X-ray crystallography. Fusariumic acids A ( 1 ) and C-H ( 3-8 ) were typical isocassadiene-type diterpenoids, while fusariumic acid B ( 2 ) contained a cage-like structure with an unusual 7,8-seco-isocassadiene skeleton. A biosynthetic pathway of 2 was proposed. Fusariumic acids A ( 1 ) and C-H ( 3-8 ) were further assessed for their phytotoxic effects on tomato seedlings at 200 μg/mL. Among them, fusariumic acid F ( 6 ) exhibited the strongest inhibition against the hypocotyl and root elongation of tomato seedlings, with inhibitory rates of 61.3 and 45.3%, respectively.

Natural products are a valuable resource for the discovery of novel crop protection agents. A series of γ-butyrolactone derivatives, derived from the simplification of podophyllotoxin's structure, were synthesized and assessed for their efficacy against tobacco mosaic virus (TMV). Several derivatives exhibited notable antiviral properties, with compound 3g demonstrating the most potent in vivo anti-TMV activity. At 500 μg/mL, compound 3g achieved an inactivation effect of 87.8%, a protective effect of 71.7%, and a curative effect of 67.7%, surpassing the effectiveness of the commercial plant virucides ningnanmycin and ribavirin . Notably, the syn -diastereomer ( syn - 3g ) exhibited superior antiviral activity compared to the anti -diastereomer ( anti - 3g ). Mechanistic studies revealed that syn - 3g could bind to the TMV coat protein and interfere with the self-assembly process of TMV particles. These findings indicate that compound 3g , with its simple chemical structure, could be a potential candidate for the development of novel antiviral agents for crop protection.

In recent years, optical tweezers have become an effective bioassay tool due to their unique advantages, especially in combination with suspension beads, which can be applied to develop a high-performance analysis platform capable of high-quality imaging and stable signal output. However, the optical tweezer-assisted bead analysis is still at the early stage, and further development of different favorable methods is in need. Herein, we have first developed the optical tweezer-assisted immuno-rolling circle amplification (immuno-RCA) on beads for protein detection. Prostate-specific antigen was selected as the model analyte, and the immunosandwich structure on beads was built by the high affinity of "antibody-antigen". The "protein-nucleic acid" signals were effectively converted through the covalent coupling procedure of antibodies and oligonucleotides, further initiating the RCA reaction to achieve signal amplification. The individual beads with the strong irregular Brownian motion in a fluid environment were eventually trapped by the optical tweezers to acquire the accurate and high-quality signal. Compared with the conventional immunoassay on beads, the sensitivity of the developed strategy was increased by 587 times with a limit of detection of 4.29 pg/mL (0.13 pM), as well as excellent specificity, stability, and reproducibility. This study developed the new optical tweezer-assisted beads imaging strategy for protein targets, which has great potential for being applied to clinical serology research and expands the application of optical tweezers in the bioassays.

The oxygen reduction/evolution reaction (ORR/OER) represents a pivotal process in metal-air batteries; however, it is constrained by the limitations of slow kinetics. Nevertheless, the creation of long-lasting and bifunctional catalysts represents a significant challenge. This study presents a series of hierarchical porous carbon-supported cobalt pyrophosphate (Co 2 P 2 O 7 -N/C- T ) catalysts, prepared through the pyrolysis of porphyrin-based NTU-70 nanosheets with red phosphorus at varying temperatures. The Co 2 P 2 O 7 -N/C-800 not only demonstrates remarkable OER performance with an overpotential of only 290 mV at a current density of 10 mA cm -2 in 1 M KOH, but also exhibits an excellent Δ E of 0.74 V in 0.1 M KOH, which is lower than that of Pt/C + RuO 2 (0.76 V). The utilization of Co 2 P 2 O 7 -N/C-800 as an air cathode in a rechargeable Zn-air battery (ZAB) results in a stable discharge voltage plateau of 1.405 V and a high gravimetric energy density of 801.2 mA h g Zn -1 . This work presents a promising strategy for the design of efficient bifunctional catalysts and demonstrates the critical importance of the interplay between the active center and the supported hierarchical porous carbon.

Two-dimensional (2D) magnets have attracted significant attention in recent years due to their importance in the research on both fundamental physics and spintronic applications. Here, we report the discovery of a new ternary compound FePd 2 Te 2 . It features a layered quasi-2D crystal structure with 1D Fe zigzag chains extending along the b -axis in the cleavage plane. Single crystals of FePd 2 Te 2 with centimeter size could be grown. Density functional theory calculations, mechanical exfoliation, and atomic force microscopy on these crystals reveal that they are 2D materials that can be thinned down to ∼5 nm. Magnetic characterization shows that FePd 2 Te 2 is an easy-plane ferromagnet with T C ∼ 183 K and strong in-plane uniaxial magnetic anisotropy. Magnetoresistance and the anomalous Hall effect demonstrate that ferromagnetism could be maintained in FePd 2 Te 2 flakes with large coercivity. A crystal twinning effect is observed by scanning tunneling microscopy which makes the Fe chains right angle bent in the cleavage plane and creates an intriguing spin texture. Besides, a large electronic specific heat coefficient of up to γ ∼ 32.4 mJ mol -1 K -2 suggests FePd 2 Te 2 is a strongly correlated metal. Our results show that FePd 2 Te 2 is a correlated anisotropic 2D magnet that may attract multidisciplinary research interests.

The diphenyl ether molecular pharmacophore has played a significant role in the development of fungicidal compounds. In this study, a variety of pyrazol-5-yl-phenoxybenzamide derivatives were synthesized and evaluated for their potential to act as succinate dehydrogenase inhibitors (SDHIs). The bioassay results indicate certain compounds to display a remarkable and broad-spectrum in their antifungal activities. Notably, compound 12x exhibited significant in vitro activities against Valsa mali , Gaeumannomyces graminis , and Botrytis cinerea , with EC 50 values of 0.52, 1.46, and 3.42 mg/L, respectively. These values were lower or comparable to those of Fluxapyroxad (EC 50 = 12.5, 1.93, and 8.33 mg/L, respectively). Additionally, compound 12x showed promising antifungal activities against Sclerotinia sclerotiorum (EC 50 = 0.82 mg/L) and Rhizoctonia solani (EC 50 = 1.86 mg/L), albeit lower than Fluxapyroxad (EC 50 = 0.23 and 0.62 mg/L). Further in vivo experiments demonstrated compound 12x to possess effective protective antifungal activities against V. mali and S. sclerotiorum at a concentration of 100 mg/L, with inhibition rates of 66.7 and 89.3%, respectively. In comparison, Fluxapyroxad showed inhibition rates of 29.2 and 96.4% against V. mali and S. sclerotiorum , respectively. Molecular docking analysis revealed that compound 12x interacts with SDH through hydrogen bonding, π-cation, and π-π interactions, providing insights into the probable mechanism of action. Furthermore, compound 12x exhibited greater binding energy and SDH enzyme inhibitory activity than Fluxapyroxad (Δ G cal = -46.8 kcal/mol, IC 50 = 1.22 mg/L, compared to Δ G cal = -41.1 kcal/mol, IC 50 = 8.32 mg/L). Collectively, our results suggest that compound 12x could serve as a promising fungicidal lead compound for the development of more potent SDHIs for crop protection.

Silver nanowires (NWs) (AgNWs) have emerged as the most promising conductive materials in flexible optoelectronic devices owing to their excellent photoelectric properties and mechanical flexibility. It is widely acknowledged that the practical application of AgNW networks faces challenges, such as high surface roughness, poor substrate adhesion, and limited stability. Encapsulating AgNW networks with graphene has been recognized as a viable strategy to tackle these issues. However, conventional methods like self-assembly reduction-oxidation or chemical vapor deposition often yield graphene protective layers with inherent defects. Here, we propose a novel one-step hot-pressing method containing ethanol solution that combines the spontaneous transfer and encapsulation process of rGO films onto the surface of the AgNWs network, enabling the preparation of flexible rGO/AgNWs/PET (reduced graphene oxide/silver NWs/polyethylene terephthalate) electrodes. The composite electrode exhibits outstanding photoelectric properties ( T ≈ 88%, R ≈ 6 Ω sq -1 ) and possesses a smooth surface, primarily attributed to the capillary force generated by ethanol evaporation, ensuring the integrity of the rGO delamination process on the original substrate. The capillary force simultaneously promotes the tight encapsulation of rGO and AgNWs, as well as the welding of the AgNWs junction, thereby enhancing the mechanical stability (20,000 bending cycles and 100 cycles of taping tests), thermal stability (∼30 °C and ∼25% humidity for 150 days), and environmental adaptability (100 days of chemical attack) of the electrode. The electrode's practical feasibility has been validated by its exceptional flexibility and cycle stability (95 and 98% retention after 5000 bending cycles and 12,000 s long-term cycles) in flexible electrochromic devices.

In this study, a water-soluble quaternary ammonium salt (QAS)-functionalized montmorillonite (MMT) was fabricated using a mechanochemical method as a high-performance water lubrication additive. The intercalation of QAS into the MMT layer expands the layer spacing of MMT, but does not affect the hydrophilicity of MMT. The ultrathin layer QAS-functionalized montmorillonite (QAS-MMT) demonstrated excellent water-stable dispersion and can be used as a water-based lubrication additive. Only 0.1% addition can reduce the friction coefficient by more than 71.4% and the wear volume by about 58.8% when compared to water, demonstrating its excellent friction reduction and antiwear performance. The frictional mechanism indicates that the physical adsorption film, together with the chemical reaction film, endows the QAS-MMT additives with outstanding tribological performance, provides excellent lubrication for the contact of steel/steel pairs, and prevents the steel surface from being further worn.

Chemical equilibrium stands as a fundamental principle governing the dynamics of chemical systems. However, it may become intricate when it refers to nanomaterials because of their unique properties. Here, we invesitigated concave gold nanocubes (CGNs) subjected to an akaline Au 3+ /H 2 O 2 solution, which exhibit both etching and growth in a monotonic solution. When CGNs were subjected to an increasingly alkaline Au 3+ /H 2 O 2 solution, their dimensions increased from 107 to 199 nm and then decreased to 125 nm. Transmission electron microscopy (TEM) demonstrated that their morphology undergoes intricate alternations from concave to mutibranch and finally to concave again. Real-time ultraviolet-visible spectroscopy and time-dependent TEM also demonstrated reduction first and then oxidation in one solution. Among the nanomaterials, the obtained carpenterworm-like gold nanoparticles revealed the best catalytic performance in p -nitrophenol reduction by NaBH 4 , with a chemical rate that continues to increase until the reaction reaches completion. Growth leading to atomic dislocation, distortion, and exposure on nanoparticles and the redox of H 2 O 2 plausibly account for the further etching due to the Ostwald ripening effect. Our study may spur more interest in the tuning of the properties, engineering, investigation, and design of new kinds of nanomaterials.

The transition-metal catalyzed asymmetric hydrogenation of unfunctionalized alkenes is challenging. Herein, we report an efficient iridium-catalyzed asymmetric hydrogenation of unfunctionalized cycloalkenes, delivering chiral 2-aryl tetralins in excellent yields and with moderate to excellent enantioselectivities. The reaction can be performed on a gram-scale with a low catalyst loading (S/C = 1000), and the reduced product was obtained without erosion of the enantioselectivity. Deuterium experiments indicated that the C═C bond in the substrate is hydrogenated directly without isomerization.

Electrocatalytic semihydrogenation of alkynols presents a sustainable alternative to conventional thermal methodologies for the high-value production of alkenols. The design of efficient catalysts with superior catalytic and energy efficiency for semihydrogenation poses a significant challenge. Here, we present the application of an electron-divergent Cu 3 Pd alloy-based heterojunction in promoting the electrocatalytic semihydrogenation of alkynols to alkenols using water as the proton source. The tunable electron divergence of Cu δ- and Pd δ+ , modulated by rectifying contact with nitrogen-rich carbons, enables the concerted binding of active H species from the Volmer step of water dissociation and the C≡C bond of alkynols on Pd δ+ sites. Simultaneously, the pronounced electron divergence of Cu 3 Pd facilitates the universal adsorption of OH species from the Volmer step and alkynols on the Cu δ- sites. The electron-divergent dual-center substantially boosts water dissociation and inhibition of completing hydrogen evolution to give a turnover frequency of 2412 h -1 , outperforming the reported electrocatalysts' value of 7.3. Moreover, the continuous production of alkenols at industrial-related current density (-200 mA cm -2 ) over the efficient and durable Cu 3 Pd-based electrolyzer could achieve a cathodic energy efficiency of 45 mol kW·h -1 , 1.7 times the bench-marked reactors, promising great potential for sustainable industrial synthesis.