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A novel and simple approach for the synthesis of copper oxide (CuO) nanorods, without any surfactant or template, is presented. This synthetic method is used for large-scale and controllable production of copper oxide nanorods, with various morphologies and crystallographic structures in large scales.

Issues concerning the examination of 2-(2'-pyridyl)indole and its compounds and the structural changes which occur when it is interacted with protic solvents are discussed. The formation of syn and anti rotameric versions are possible and their relative stabilities in alcohol and aprotic solvents are presented.

TheCu/MgO interface plays a crucial role in applications. Face-centered-cubic(fcc) Cu has been reported to grow on MgO substrate (rock salt structure).However, no body-centered-cubic/tetragonal (bcc(t)) Cu has been stabilizedon MgO. The special atomic structure of the bcc(t)/rock salt interfacecontributes to superior thermal, mechanical, and electrical properties.We report, for the first time, the epitaxial growth of bcc(t) andfcc Cu on Si(100) and Si(111) substrates using MgO(100)/TiN(100) andMgO(111)/TiN(111) buffer layers by pulsed laser deposition. We findthat the deposition temperature determines the structure of Cu. Athigh temperature, only fcc Cu grows on both MgO/TiN(100) and MgO/TiN(111)templates. At room temperature, an epitaxial layer of bcc(t) Cu growspseudomorphically on a MgO(100) template up to the critical thickness,while on a MgO/TiN(111) template, the majority of Cu is fcc, and bcc(t)Cu exists occasionally in a three-dimensional island shape. The growthof these heterostructures involves epitaxy across the misfit scaleby matching MgO{200} planes with bcc(t) Cu{110} planes. The integrationof Cu/MgO on the technologically important Si substrate holds tremendouspromise, because the novel bcc(t) Cu/MgO structure can be integratedwith present-day microelectronic or nanoelectronic devices. [ABSTRACT FROM AUTHOR]

A stopped-flow technique and three-dimensional excitation emission (Ex/Em) fluorescence spectrophotometer were used to detect the full fluorescence spectral kinetic changes that occurred during the complexation between fulvic acid (FA) and several metals [Cu(II), Ni(II), Co(II), Cd(II) and Ca(II)]. The study was carried out with a fulvic acid isolated from Cavan Bog, Canada. At pH 7, the FA reacted rapidly with all metals studied. Two major kinetically distinguishable binding sites on FA ("fast" and "slow"), having reaction half-lives of 1.3-3.9 and 34.7- 69.3 s, respectively, were identified using pseudo-first-order kinetic plots. Kinetic changes of Ex and Em wave-lengths of the fluorescence maximums also indicate two major binding sites. For the fast-reacting binding site, the rate constant and the site relative contribution were as follows, Cu[SUP2+]> Ni[SUP2+]> Co[SUP2+]> Cd[SUP2+] > Ca[SUP2+], which agrees with the Irving-Williams series, indicating that complexation kinetics are affinity dependent. Within each kinetic phase, both Ex and Em wavelengths of fluorescence maximums increased with time, indicating the occurrence of structural changes during the binding process. Based on the results obtained, the use of full fluorescence spectra appears to be a promising tool for further under-standing metal-FA complexation mechanisms. [ABSTRACT FROM AUTHOR]

We report a high-resolution crossed molecular beam experiment investigating the reaction dynamics of the F + CH 4 → HF + CH 3 reaction across a broad range of collision energies (3.1-13.8 kcal/mol). By using time-sliced velocity map imaging within the crossed molecular beam apparatus, we obtain correlated angular distributions and branching ratios for various product pairs (CH 3 (ν), HF(ν')). The resolved reactive rainbow-like features that display a distinct bulge in the angular distribution in different channels reveal the formation of vibrationally ground and excited states of the methyl radical accompanied by different rovibrationally excited HF products. These findings suggest distinct reaction dynamics for channels leading to vibrationally excited methyl radicals compared to those forming ground-state methyl radicals.

Human milk oligosaccharides could prevent pathogenic bacterial infections in neonates; however, direct in vivo anti-infection evidence was still lacking. Here, we systematically evaluated the effects of 2'-fucosyllactose (2'-FL) and 3'-sialyllactose (3'-SL) on the structural development and functional maturation in neonates and their defense against enteroaggregative Escherichia coli infection. It was found that supplementation with 2'-FL and 3'-SL improved the resistance of weaned mice to enteroaggregative E. coli . The mechanism related to the promotion of 2'-FL and 3'-SL in the maturation of intestinal mucosal immunity by promoting stem cell differentiation, mucus layer integrity, and tight junction formation. 2'-FL and 3'-SL significantly increased the ratio of Th1 and Treg cells in the lamina propria, contents of short-chain fatty acids, as well as the serum content of IgA. This study lays a theoretical basis for the application of 2'-FL and 3'-SL in infant formula, as well as the development of intestinal health products.

High-frequency, high-power, and high-speed telecommunication in a complex environment promotes the development of dielectric materials toward a low dielectric constant, low dielectric loss, good thermal properties, and long-term reliability. Here, polyimide/polytetrafluoroethylene (PI/PTFE) nanofiber membranes with an inherent super hydrophobicity, excellent dielectric properties, good thermal stability, and enhanced tensile strength were prepared via a simple electrospinning strategy and an imidization reaction. The obtained PI/PTFE membranes demonstrate a superlow average dielectric constant of 1.22-1.27 and a dielectric loss of 0.032-0.048 in high frequency, together with an enhanced tensile strength, benefiting from the special nanofiber-bead structure formed in the composite membrane. The mixing of polyamic acid (PAA) and PTFE in the electrospinning solution endows the obtained PI/PTFE nanofiber membrane with a uniform distribution of PTFE and thus an inherent superhydrophobicity with a water contact angle of 156.1 and 159.2° for PI/PTFE-30% and PI/PTFE-40%, respectively. Besides, the hydrophobicity could be kept even after standing more than 10,000 water drops, and the thermal properties exhibited promising results with T max = 587 °C and T d5% = 423 °C, rendering these PI/PTFE membranes favorable alternatives for prospective telecommunication.

Lithium (Li) metal batteries face challenges, such as dendrite growth and electrolyte interface instability. Artificial interface layers alleviate these issues. Here, cellulose nanocrystal (CNC) nanomembranes, with excellent mechanical properties and high specific surface areas, combine with polyvinylidene-hexafluoropropylene (PVDF-HFP) porous membranes to form an artificial solid electrolyte interphase (SEI) layer. The porous structure of PVDF-HFP equalizes the electric field near metallic lithium surfaces. The high mechanical modulus of CNC (6.2 GPa) effectively inhibits dendrite growth, ensures the uniform flow of lithium ions to the lithium metal electrode, and inhibits the growth of lithium dendrites during cycling. The synergy of high polarity β-phase poly(vinylidene fluoride) (PVDF) and CNC provides over 1000 h of stability for Li//Li batteries. Moreover, Li//LiFePO 4 (LFP) full cells with this artificial protective layer perform well at 5 C, showcasing the potential of this film in lithium metal batteries.

Net primary productivity (NPP) is highly sensitive to multiple stressors under progressive and intensifying climate change and anthropogenic impacts. The importance of understanding spatiotemporal distribution patterns and the associated driving factors that govern estuary NPP is paramount for regional carbon (C) budget assessments. Using a combined remote sensing and machine learning (ML) approach, the average NPP of the Yangtze Estuarine-offshore continuum (YEOC) was measured at 273.19 ± 21.26 mgC m -2 day -1 over the past two decades. Temporally, NPP exhibited a significant downward trend between 2002 and 2022. Climate factors (climate fluctuations, sea level rise, and discharge) drove phytoplankton biomass (Chl- a ) while light conditions (PAR and K d490 ) affected photosynthesis rates. Together, they can explain 65% of the NPP variation. Anthropogenic disturbances (i.e., damming and nutrient emissions) were not significant. Additionally, changes in NPP decreased phytoplankton C sequestration rates from 11.9 to 10.4 Tg C year -1 , reducing the estuary's C sink capacity, which relies on biological C fixation. This study highlights the climate's influence on the spatiotemporal transformation of YEOC NPP while enhancing our understanding of the response of EOC C budgets to climate change and anthropogenic activities.

The presence of an oily odor in rice-made Baijiu is a unique characteristic that has not been thoroughly studied. This study qualitatively and quantitatively identified important aroma-active compounds in samples with typical and atypical oily odors using aroma extract dilution analysis (AEDA). By comparing the differences between flavor dilution (FD) and odor activity values (OAVs), nine compounds showing significant differences were selected. By combining normal-phase silica gel column and sensory analysis, these nine potential oily odor compounds were isolated from the typical oily odor sample. Addition and omission experiments confirmed that hexanal, trans -2-heptenal, trans , trans -2,4-nonadienal, (2 E )-2-decenal, trans , trans -2,4-decadienal, and γ-nonanolide are key contributors to the oily odor.

Demystifying the molecular mechanism of growth is vital for the rational design, synthesis, and optimization of functional nanomaterials. Despite the promising perspectives and extensive efforts, the growth mechanism of atomically thin TiO 2 (B) nanosheets remains unclear, hence it is difficult to tune their band and surface structures. Herein, we report an oriented attachment-based crystallization mechanism of TiO 2 (B) nanosheets from a 1D titanium glycolate coordination polymer through hydrolysis and condensation. With time-tracking experiments, this 1D coordination polymer is found to be an intermediate in the synthesis of TiO 2 (B) nanosheets by using Ti alkoxides and chlorides as precursors, suggesting the universality of the 1D-to-2D growth mechanism. Such a side-to-side attachment pathway bridges the classical and nonclassical interpretations of crystallization, and meanwhile hints at the possibility of other 1D complexes as potential precursors for 2D materials.

Photoresponsive multicolor luminescent systems offer interesting functions, which have led to applications in anticounterfeiting and biological imaging. However, expanding the color range of these materials remains a challenging task. Herein, a carbazole-modified dithienylethene derivative ( DTE-CZ ) that exhibits modulated fluorescence color changes through the photocyclization reaction and photolysis reaction is synthesized. DTE-CZ emits orange fluorescence, and it can release a fluorophore which emits blue fluorescence by the photolysis reaction, resulting in the color change. Upon complexation of DTE-CZ with cucurbit[10]uril (CB[10]), the fluorescence wavelength will have a blue shift and the photolysis reaction will be inhibited. Benefiting from the influence of CB[10] and the photolysis reaction of free guests, the color range of the photoresponsive system which is composed of free guests and host-guest complexes is further extended. White light emission along with a color shift from yellow-green to blue was achieved by adjusting the ratio of free guests to host-guest complexes. Finally, the photoresponsive multicolor systems are utilized to construct a photostimulated PVA film and an information encryption system. This work provides an alternative strategy for the preparing of photoresponsive multicolor luminescent system and modulation of its color range.

The demands for highly miniaturized and multifunctional electronics are rapidly increasing. As scaling-down processes of transistors are restricted by physical limits, reconfigurable electronics with switchable operation functions for different tasks are developed for higher function integration based on split- or vertical-dual-gate structures. To promote the present reconfigurable electronics and exceed the function integration limit, the critical issue is to integrate complex operations into simple circuit forms by establishing more control dimensions. This work proposes a multibarrier collaborative (MBC) modulation architecture to increase the control dimension by multiple forms of potential barriers and achieves combinational and reconfigurable logic operations by a single MBC device. The MBC architecture exhibits ultrahigh logic operation density, including 58.8% area reduction for multiplexer operations and 71.4% area reduction for 4-logic reconfigurable operations. Besides, a hardware security module composed of 4 MBC devices implementing 8 types of logic operations is demonstrated. This work reveals an effective design of function integration for next-generation electronics.

Te x Se 1- x shortwave infrared (SWIR) photodetectors show promise for monolithic integration with readout integrated circuits (ROIC), making it a potential alternative to conventional expensive SWIR photodetectors. However, challenges such as a high dark current density and insufficient detection performance hinder their application in large-scale monolithic integration. Herein, we develop a ZnO/Te x Se 1- x heterojunction photodiode and synergistically address the interfacial elemental diffusion and dangling bonds via inserting a well-selected 0.3 nm amorphous TeO 2 interfacial layer. The optimized device achieves a reduced dark current density of -3.5 × 10 -5 A cm -2 at -10 mV, a broad response from 300 to 1700 nm, a room-temperature detectivity exceeding 2.03 × 10 11 Jones, and a 3 dB bandwidth of 173 kHz. Furthermore, for the first time, we monolithically integrate the Te x Se 1- x photodiodes on ROIC (64 × 64 pixels) with the largest-scale array among all Te x Se 1- x -based detectors. Finally, we demonstrate its applications in transmission imaging and substance identification.

Unfavorable phenotypes characterized by low immunogenicity and acidity within the tumor microenvironment (TME) contribute to immunosuppression and therapeutic resistance. Herein, we rationally synthesized a multifunctional nanoregulator by encapsulating DOX and erianin into calcium carbonate (CaCO 3 )-based nanoparticles using a modified double emulsion method. The DOX and erianin-loaded CaCO 3 -based nanoparticles, termed DECaNPs, could effectively induce the calcium overload by triggering calcium influx and absorbing CaCO 3 nanoparticles. Additionally, DECaNPs also neutralize the acidic TME by interacting with extracellular protons and limiting lactic acid production, a result of metabolic remodeling in cancer cells. As a result, DECaNPs elicit cellular oxidative stress damage, which mediates the activation of ferroptosis/apoptosis hybrid pathways, and profound immunogenic cell death. Treatment with DECaNPs could inhibit the growth of tumors by promoting oxidative stress, acid neutralization, metabolic remodeling, and protective antitumor immunity in vivo . In addition, DECaNPs could synergistically amplify the antitumor effects of αPD-L1 in a bilateral tumor model by eliciting systemic immune responses. In all, our work presents the preparation of CaCO 3 -based nanoregulators designed to reverse the unfavorable TME and enhance αPD-L1 immunotherapy through multiple mechanisms.

S-redox involving solvated polysulfides is accompanied by volumetric change and structural decay of the S-based cathodes. Here, we propose a synchronous construction strategy for consolidating Li, Se, S, and C elements within a composite cathode via a paradigm reaction of 8Li+2Se+CS 2 = 2Li 4 SeS+C. The obtained composite features crystalline Li 4 SeS encapsulated in a carbon nanocage (Li 4 SeS@C), exhibiting ultrahigh electrical conductivity, ultralow activation barrier, and excellent structural integrity, accordingly enabling large specific capacity (615 mAh g -1 ) and high capacity retention (87.3% after 350 cycles) at 10 A g -1 . TOF-SIMS demonstrates its superior volumetric efficiency to a similar derivative SeS@C (2Se+CS 2 = 2SeS+C), and DFT reveals its lower activation barrier than Li 2 S@C and Li 2 Se@C. This consolidation design significantly improves the electrochemical performance of S-based cathodes, and the paradigm reaction guarantees structural diversity and flexibility. Moreover, employing a synchronous construction mechanism to maximize the synergistic effect between element consolidation and carbon encapsulation opens up a new approach for developing robust S or chalcogenide cathodes.

A smart window that dynamically regulates light transmittance is crucial for modern life end-users and promising for on-demand optical devices. The advent of three-dimensional (3D) photonic crystal microspheres has enriched the functions of a smart window. However, the smart window formed by polymer microspheres encounters poor mechanical strength and microstructural defects. Herein, to solve this limitation, we report the microsphere-based smart window composed of tightly packed cross-linked polymer microspheres (as a precursor) containing organic photochromic dyes, followed by compression under a high elastic state. When excited under an ultraviolet supply, our smart window showed a rapid and reversible fluorescent photoluminescence without fatigue (50 cycles). Moreover, the bulk devices with a microsphere cross-linked network structure enable excellent mechanical strength (hardness reached 0.158 GPa) and visible-light transparency. Interestingly, a QR code can be recognized under visible light exposure but not under ultraviolet light exposure because of photoluminescence of the smart window. Our method generally provided a paradigm for various amorphous polymers, which can be regarded as a simple and effective approach to build a versatile strategy to introduce an ideal marketplace with economic and community benefits.

Starting from three ibuprofen-coumarin hit compounds, we designed 18 derivative compounds targeting cyclooxygenase-2 (COX-2) by introducing different substituents onto them by using the computational auto in silico ligand directing evolution (AILDE) method. After synthesizing and testing the activity, we found that 6 representative compounds have micromolar enzyme inhibitory activity against COX-2. Additionally, 16 compounds have shown certain inhibitory activity in cervical cancer cells. Among these compounds, 6c (IC 50 = 0.606 μM, HeLa) and 7g (IC 50 = 0.783 μM, HeLa) have exhibited excellent activity, which is approximately 10 times better than the commercial drug gefitinib. According to molecular simulation results, the halogen atoms of 6c and 7g on the coumarin ring can form halogen bonds with COX-2, which significantly improves their activity compared to their hit compounds 6a and 7a . However, the key interactions were lost in binding with COX-1. The calculation results revealed that the two compounds are selective COX-2 inhibitors, with potential selectivity indexes of 6-fold and 5-fold, respectively. The cell-based activity of compounds 6c and 7g toward HEK293 cells demonstrates that our compounds possess an acceptable safety toward normal cells. The results indicate that 6c and 7g can serve as potential lead compounds for further lucubrate., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The preparation of porous carbon is constrained by the extensive use and detrimental impact of activators and dopants. Therefore, developing green and efficient strategies that leverage the intrinsic properties and pretreatment of the materials to achieve self-activation and self-doping is particularly crucial for porous carbon materials. Herein, potassium histidine was utilized as the molecular salt precursor, attaining the efficient and streamlined preparation of porous carbon through a one-step carbonization process that enables self-activation, self-doping, and self-templating. More interestingly, the carbonization temperature significantly impacts the porous structure of the molecular salt precursors, the properties of the heteroatoms, and electrochemical performance. The designed electrodes exhibit high accessibility to electrolyte ions and effective ion-electron transport channels. Therefore, the optimal carbon material (KHis800) has an excellent mass-specific capacitance of 305.2 F g -1 at 0.2 A g -1 , and a high capacitance retention rate of 115.6% (50,000 cycles at 5 A g -1 ). Notably, KHis800 also shows a maximum energy density of 19.6 Wh kg -1 . This research is dedicated to exploring a more efficient preparation method for porous carbon material via molecular salts, offering insights for the sustainable development of carbon materials.

High concentrations of microplastics (MPs) have been documented in the deep-sea surface sediments of the Arctic Ocean. However, studies investigating their high-resolution vertical distribution in sediments from the European waters to the Arctic remain limited. This study examines MPs in five sediment cores from the Norwegian Coastal Current (NCC), encompassing the water-sediment interface and sediment layers up to 19 cm depth. Advanced analytical methods for MP identification down to 11 μm in size were combined with radiometric dating and lithology observations. MPs were present across all sediment cores, including layers predating the introduction of plastics, with concentrations exhibiting significant variation (54-12,491 MP kg -1 ). The smallest size class (11 μm) predominated in most sediment layers (34-100%). A total of 18 different polymer types were identified across all sediment layers, with polymer diversity and depth correlations varying widely between stations. Our findings suggest that differences in seafloor topography and the impact of anthropogenic activities (e.g., fishing) lead to varying environmental conditions at the sampling sites, influencing the vertical distribution of MPs. This challenges the reliability of using environmental parameters to predict MP accumulation zones and questions the use of MPs in sediment cores as indicators of the Anthropocene.

Ecological integrity assessment and degradation diagnosis are used globally to evaluate the health of water bodies and pinpoint critical stressors. However, current studies mainly focus on separate evaluation or diagnosis, leading to an inadequate exploration of the relationship between stressors and responses. Here, based on multiple data sets in an urban lake system, a synchronous evaluation-diagnosis model with quantitative stressor-response analysis was advanced, aiming to improve the accuracy of evaluation and diagnosis. The weights for key physicochemical stressors were quantitatively determined in the sequence of NDAVI adj > COD Mn > TP > NH 4 + -N by the combination of generalized additive model and structural equation modeling, clarifying the most significant effects of aquatic vegetation on the degradation of fish assemblages. Then, sensitive biological metrics were screened by considering the distinct contributions of four key stressors to alleviate the possible deviation caused by common methods. Finally, ecological integrity was evaluated by summing the key physicochemical stressors and sensitive biological metrics according to the model-deduced weights instead of empirical weights. Our system's diagnosis and evaluation results achieved an accuracy of over 80% when predicting anthropogenic stress and biological status, which highlights the great potential of our multiple-level system for ecosystem management.

Alveolar bone defect reconstruction is a common challenge in stomatology. To address this, a thermosensitive/photosensitive gelatin methacrylate (GelMA) gel was developed based on various air solubilities and light-curing technologies. The gel was synthesized by using a freeze-ultraviolet (FUV) method to form a porous and quickly (within 15 min) solidifying modified network structure. Unlike other gel scaffolds limited by complex preparation procedures and residual products, this FUV-GelMA gel shows favorable manufacturing ability, promising biocompatibility, and adjustable macroporous structures. The results from a rat model suggested that this gel scaffold creates a conducive microenvironment for mandible reconstruction and vascularization. In vitro experiments further confirmed that the FUV-GelMA gel promotes osteogenic differentiation of human bone marrow mesenchymal stem cells and angiogenesis of human umbilical vein endothelial cells. Investigation of the underlying mechanism focused on the p38 mitogen-activated protein kinase (MAPK) pathway. We found that SB203580, a specific inhibitor of p38 MAPK, abolished the therapeutic effects of the FUV-GelMA gel on osteogenesis and angiogenesis, both in vitro and in vivo. These findings introduced a novel approach for scaffold-based tissue regeneration in future clinical applications.

This study investigated the uptake pathways, acropetal translocation, subcellular distribution, and biotransformation of OPEs by rice ( Oryza sativa L.) after Cu exposure. The symplastic pathway was noted as the major pathway for the uptake of organophosphate triesters (tri-OPEs) and diesters (di-OPEs) by rice roots. Cu exposure enhanced the accumulation of tri-OPEs in rice roots, and such enhancement was positively correlated with Cu concentrations, attributing to the Cu-induced root damage. The hydrophilic Cl-OPEs in the cell-soluble fraction of rice tissues were enhanced after Cu exposure, while the subcellular distributions of alkyl- and aryl-OPEs were not affected by Cu exposure. Significantly higher biotransformation rates of tri-OPEs to di-OPEs occurred in leaves, followed by those in stems and roots. Our study reveals the mechanisms associated with the uptake, translocation, and biotransformation of various OPEs in rice after Cu exposure, which provides new insights regarding the phytoremediation of soils cocontaminated with heavy metal and OPEs.

Identifying causative toxicants in mixtures is critical, but this task is challenging when mixtures contain multiple chemical classes. Effect-based methods are used to complement chemical analyses to identify toxicants, yet conventional bioassays typically rely on an apical and/or single endpoint, providing limited diagnostic potential to guide chemical prioritization. We proposed an event-driven taxonomy framework for mixture risk assessment that relied on high-throughput screening bioassays and toxicant identification integrated by deep learning. In this work, the framework was evaluated using chemical mixtures in sediments eliciting aryl-hydrocarbon receptor activation and oxidative stress response. Mixture prediction using target analysis explained <10% of observed sediment bioactivity. To identify additional contaminants, two deep learning models were developed to predict fingerprints of a pool of bioactive substances (event driver fingerprint, EDFP) and convert these candidates to MS-readable information (event driver ion, EDION) for nontarget analysis. Two libraries with 121 and 118 fingerprints were established, and 247 bioactive compounds were identified at confidence level 2 or 3 in sediment extract using GC-qToF-MS. Among them, 12 toxicants were analytically confirmed using reference standards. Collectively, we present a "bioactivity-signature-toxicant" strategy to deconvolute mixtures and to connect patchy data sets and guide nontarget analysis for diverse chemicals that elicit the same bioactivity.

The use of disinfectants containing benzalkonium chloride (BAC) has become increasingly widespread in response to triclosan (TCS) restrictions and the COVID-19 pandemic, leading to the increasing presence of BAC in aquatic ecosystems. However, the potential environmental health impacts of BAC on fish remain poorly explored. In this study, we show that BAC and TCS can induce the gut dysbiosis in zebrafish ( Danio rerio ), with substantial effects on health. Breeding pairs of adult zebrafish were exposed to environmentally relevant concentrations of BAC and TCS (0.4-40 μg/L) for 42 days. Both BAC and TCS exposure perturbed the gut microbiota, triggering the classical NF-κB signaling pathway and resulting in downstream pathological toxicity associated with inflammatory responses, histological damage, inhibited ingestion, and decreased survival. These effects were dose-dependent and sex-specific, as female zebrafish were more susceptible than male zebrafish. Furthermore, we found that BAC induced toxicity to a greater extent than the restricted TCS at environmentally relevant concentrations, which is particularly concerning. Our results suggest that environmental exposure to antimicrobial chemicals can have ecological consequences by perturbing the gut microbiota, a previously underappreciated target of such chemicals. Rigorous ecological analysis should be conducted before widely introducing replacement antimicrobial compounds into disinfecting products.

A multiscale complex fracture and matrix damage coupled productivity prediction model under cyclic percussion of horizontal wells is established, according to the evolution of matrix permeability and the characteristics of complex fracture seepage after cyclic conflagration compression fracturing. The effects of the conflagration loading rate, cyclic percussion times, horizontal in situ stress difference, seepage interference, and wellbore pressure drop on horizontal well productivity are analyzed. The results show that the loading rate and percussion times are positively correlated with the production growth rate, but the growth through percussion has a threshold. Besides that, the length of the branch fracture is closer to that of the main fracture when there is a small stress difference, which results in a higher initial productivity and recovery degree of the gas well. Additionally, section spacing can affect the distribution of the pressure field and flow field around the well. An excessive spacing can lead to bending of flow field around the well, while a too small value is able to aggravate interjoint interference. Therefore, the critical section spacing, which can establish pressure communication between sections, is taken as the optimal section spacing. According to our work, when the fracture half-length is 5, 7, and 9 m, the optimum section spacing is 15, 25, and 30 m, respectively. Under this condition, when the horizontal length exceeds 800, 700, and 500 m, the influence of the wellbore pressure drop on the productivity of horizontal wells should be considered., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

We report an efficient perfluoroalkoxylation reaction of alkyl halides catalyzed by copper(I) iodide (CuI), which facilitates the simultaneous activation of both perfluoroalkoxide and alkyl halides. This methodology is tolerant of a wide range of functional groups and eliminates the need for costly metal reagents. The reaction is conducted in a single step under mildly practical conditions.

Efficient electrochemical energy conversion technologies, such as fuel cells and water electrolyzers, require high current densities to lower the capital cost for large-scale commercialization but are often limited by mass transport. In this study, we demonstrated exceptional electrochemical performances in proton electrolyte membrane water electrolyzers (PEMWEs) creating micropatterned pore channels in the porous transport layer (MPC PTL) using a picosecond laser. This approach yielded an impressive performance of 1.82 V @ 2 A·cm -2 , which is better than commercial PTL of 1.90 V @ 2 A cm -2 . The significant performance enhancement is attributed to the micropatterned porous channel structure, facilitating the efficient expulsion of oxygen bubbles and input of reactant water. This work provides valuable insights for the design of PTL responsible for biphasic transport in electrochemical energy conversion technologies.

Stabilizing the crystalline structure and surface chemistry of Ni-rich layered oxides is critical for enhancing their capacity output and cycle life at a high cutoff voltage. Herein, we adopted a simple one-step solid-state method by directly sintering the Ni 0.9 Co 0.1 (OH) 2 precursor with LiOH and Ta 2 O 5 , to simultaneously achieve the bulk material synthesis of LiNi 0.9 Co 0.1 O 2 and in situ construction of a rock-salt Ta-doped interphase and an amorphous LiTaO 3 outer layer, forming a chemically bonded surface biphase coating on LiNi 0.9 Co 0.1 O 2 . Such a cathode architectural design has been demonstrated with superior advantages: (1) eliminating surface residual alkali, (2) strengthening the layered oxygen lattice, (3) suppressing bulk-phase transformation, and (4) facilitating Li-ion transport. The obtained cathode exhibits excellent electrochemical performance, including a high initial reversible capacity of 180.3 mAh g -1 at 1.0 C with 85.5% retention after 300 cycles (2.8-4.35 V) and a high initial reversible capacity of 182.5 mAh g -1 at 0.2 C with 87.6% retention after 100 cycles (2.8-4.5 V). Notably, this facile and scalable electrode engineering makes Ni-rich layered oxides promising for practical applications.

Inspired by advances in cryopreservation techniques, which are essential for modern biomedical applications, there is a special interest in the ice recrystallization inhibition (IRI) of the antifreeze protein (AFPs) mimics. There are in-depth studies on synthetic materials mimicking AFPs, from simple molecular structure levels to complex self-assemblies. Herein, we report the valence-dependent IRI activity of colloidal organic molecules (CMs). The CMs were prepared through polymerization-induced particle-assembly (PIPA) of the ABC-type triblock terpolymer of poly(acryloxyethyl trimethylammonium chloride)- b -poly(benzyl acrylate)- b -poly(diacetone acrylamide) (PATAC- b -PBzA- b -PDAAM) at high monomer conversions. Stabilized by the cationic block of PATAC, the strong intermolecular H-bonding and incompatibility of the PDAAM block with PBzA contributed to the in situ formation of Janus particles (AX 1 ) beyond the initial spherical seed particles (AX 0 ), as well as the high valency clusters of linear AX 2 and trigonal AX 3 . Their distribution was controlled mainly by the polymerization degrees (DPs) of PATAC and PDAAM blocks. IRI activity results of the CMs suggest that the higher fraction of AX 1 results in the better IRI activity. Increasing the fraction of AX 1 from 27% to 65% led to a decrease of the mean grain size from 39.8% to 10.9% and a depressed growth rate of ice crystals by 58%. Moreover, by replacing the PDAAM block with the temperature-responsive one of poly( N -isopropylacrylamide) (PNIPAM), temperature-adjustable IRI activity was observed, which is well related to the reversible transition of AX 0 to AX 1 , providing a new idea for the molecular design of amphiphilic polymer nanoparticle-based IRI activity materials.

The matching of poly(ethylene oxide) (PEO)-based electrolytes with ultrahigh-nickel cathode materials is crucial for designing new-generation high-energy-density solid-state lithium metal batteries (SLMBs), but it is limited by serious interfacial side reactions between PEO and ultrahigh-nickel materials. Here, a high-concentration electrolyte (HCE) interface with a customized Li + solvation sheath is constructed between the cathode and the electrolyte. It induces the formation of an anion-regulated robust cathode/electrolyte interface (CEI), reduces the unstable free-state solvent, and finally achieves the compatibility of PEO-based electrolytes with ultrahigh-nickel cathode materials. Meanwhile, the corrosion of the Al current collector caused by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) ions is prevented by lithium difluoro(oxalato)borate (LiDFOB) ions. The synergistic effect of the double lithium salt is achieved by a well-tailored ratio of TFSI - and DFOB - in the first solvation sheath of Li + . Compared with reported PEO-based SLMBs matched with ultrahigh-nickel (Ni ≥ 90%) cathodes, the SLMB in this work delivers a high discharge specific capacity of 216.4 mAh g -1 (0.1C) even at room temperature. This work points out a direction to optimize the cathode/electrolyte interface.

Stable and simplest expanded porphyrins, π-ring-fused porphyrin(2.1.1.1)s and Rh(I) complexes, have been obtained for the first time. Two free bases show chair-shaped molecular conformations, as if reassembled by the halves of porphyrin(1.1.1.1) and porphyrin(2.1.2.1). The insertion of Rh(CO) 2 groups induced more twisted molecular conformations. The NMR spectra, X-ray structure, NICS, and ACID of obtained molecules all support their nonaromaticity due to chair-shaped molecular conformations. The protonated and Rh(I) coordination of porphyrin(2.1.1.1)s process red-shifted absorptions in the NIR region.

Photoactivation is a phenomenon that could enhance the photoluminescence (PL) and photostability upon UV/vis light exposure, which is usually observed in CdSe/ZnS quantum dots (QDs). However, the photoactivation phenomenon has been scarcely reported in fluorescent carbon quantum dots (CQDs). Herein, the nitrogen-doped carbon quantum dots (N-CQDs) were prepared through a facile solvothermal approach with naphthalenetracarboxylic dianhydride and serine as precursors. Upon simple UV light irradiation for 10 min, the fluorescence quantum yield (QY) of N-CQDs could increase up to 10-fold. Based on this phenomenon, the N-CQDs were explored as an ultraviolet (UV) light sensor to assess the intensity of ultraviolet radiation in sunlight and indirectly evaluate the UV-blocking efficiency of various sunscreen products. Thus, this contribution not only provided an insight into developing a low-cost UV detector but also opened a door for the development of carbon quantum dots with converse-photobleaching properties.

The authentication of the entomological origin of honey is a widespread concern, necessitating the prompt establishment of an effective approach for distinguishing between Apis cerana cerana honey (ACH) and Apis mellifera ligustica honey (AMH). Hydroxy fatty acids (HFAs) found in honey are bee-derived components synthesized by the mandibular glands of worker bees. We previously discovered significant variations in the hydroxy fatty acid composition between ACH and AMH, suggesting their potential as indicators for identifying the authenticity of the entomological origin of honey. Herein, we identified differentially expressed genes associated with HFA synthesis by conducting transcriptome sequencing of the mandibular glands of AC and AM honeybees. Subsequently, we proposed a method for the relative quantitative analysis of bee-derived RNA components using real-time fluorescence quantitative polymerase chain reaction, which was supplemented by multivariate statistical analysis to further discern differences in HFA synthesis-related mRNA between ACH and AMH. The results showed that the mRNAs of FAXDC2 (fatty acid hydroxylase domain-containing protein 2) and FAS (fatty acid synthase) may serve as indicators to discern the entomological origin of honey. This study presents two novel biomarkers for detecting mislabeling of the entomological origin in ACH and AMH based on variations in bee-derived components.

The massive production and application of nanomaterials (NMs) have raised concerns about the potential adverse effects of NMs on human health and the environment. Evaluating the adverse effects of NMs by laboratory methods is expensive, time-consuming, and often fails to keep pace with the invention of new materials. Therefore, in silico methods that utilize machine learning techniques to predict the toxicity potentials of NMs are a promising alternative approach if regulatory confidence in them can be enhanced. Previous reviews and regulatory OECD guidance documents have discussed in detail how to build an in silico predictive model for NMs. Nevertheless, there is still room for improvement in addressing the ways to enhance the model representativeness and performance from different angles, such as data set curation, descriptor selection, task type (classification/regression), algorithm choice, and model evaluation (internal and external validation, applicability domain, and mechanistic interpretation, which is key to ensuring stakeholder confidence). This review explores how to build better predictive models; the current state of the art is analyzed via a statistical evaluation of literature, while the challenges faced and future perspectives are summarized. Moreover, a recommended workflow and best practices are provided to help in developing more predictive, reliable, and interpretable models that can assist risk assessment as well as safe-by-design development of NMs.

Currently, near-infrared (NIR) light-emitting materials have been widely used in many fields, such as night vision, bioimaging, and nondestructive analysis. However, it is difficult to achieve multifunction in certain NIR light emitting phosphor. Herein, we propose a new near-infrared phosphor Mg 3 Ga 2 GeO 8 :Cr 3+ ,Ni 2+ that can be applied to at least three fields, i.e., identification of compounds, temperature sensing, anticounterfeiting, and other applications. The multifunctional material exhibited efficient broadband emission of 650-1650 nm under 420 nm excitation. The emission intensity of Ni 2+ in Mg 3 Ga 2 GeO 8 :Cr 3+ ,Ni 2+ is enhanced by two times compared with that of Ni 2+ in Mg 3 Ga 2 GeO 8 :Ni 2+ due to the energy transfer process. Compared with phosphor single doped with Ni 2+ , Mg 3 Ga 2 GeO 8 :Cr 3+ ,Ni 2+ is more convincing in organic compound recognition because it is based on two emission bands: 600-1100 nm and 1100-1650 nm. As a temperature sensor, Mg 3 Ga 2 GeO 8 :Cr 3+ ,Ni 2+ is an ideal temperature-sensing material. This work not only provides a super broadband NIR emitting phosphor with multiple functions but also presents a practical approach for the development of high-efficiency and multifunctional NIR phosphors.

Inflammatory bowel disease (IBD) is an idiopathic intestinal inflammatory disease, whose etiology is intimately related to the overproduction of hypochlorous acid (HClO). Optical monitoring of HClO in the living body favors real-time diagnosis of inflammatory diseases. However, HClO-activated near-infrared (NIR) fluorescent probes with rapid response and high inflammatory cell uptake are still lacking. Herein, we report an activatable acceptor-π-acceptor (A-π-A)-type NIR fluorescent probe ( Cy-DM ) bearing two d-mannosamine groups for the sensitive detection of HClO in early IBD and stool testing. Once reacted with HClO, nonfluorescent Cy-DM could be turned on within 2 s by generating a donor-π-acceptor (D-π-A) structure due to the enhanced intramolecular charge transfer mechanism, showing intense NIR fluorescence emission at 700 nm and a large Stokes shift of 115 nm. Moreover, it was able to sensitively and selectively image exogenous and endogenous HClO in the lysosomes of living cells with a detection limit of 0.84 μM. More importantly, because of the d-mannosamine modification, Cy-DM was efficiently taken up by inflammatory cells in the intestine after intravenous administration, allowing noninvasive visualization of endogenous HClO in a lipopolysaccharide-induced IBD mouse model with a high fluorescence contrast of 6.8/1. In addition, water-soluble Cy-DM has also been successfully applied in ex vivo optical fecal analysis, exhibiting a 3.4-fold higher fluorescence intensity in the feces excreted by IBD mice. We believe that Cy-DM is promising as an invaluable tool for rapid diagnosis of HClO-related diseases as well as stool testing.

As one of the important devices for large-scale electrochemical energy storage, sodium-ion batteries have received much attention due to the abundant resources of raw materials. However, whether it is a base station power source, an energy storage power station, or a start-stop power supply, long energy cycle life (more than 5000 cycles), high stability, and safety performance are application prerequisites. Regrettably, currently, few sodium-ion batteries can meet this requirement, mainly due to shortcomings in positive electrode performance. We report a sufficiently stable sodium-ion battery cathode material, Na 2 Fe 0.95 P 2 O 7 , that retains 97.5% capacity after 5000 charge/discharge cycles. The use of nonstoichiometry in the lattice enables simultaneous modification of the crystal and electronic structure, promoting Na 2 Fe 0.95 P 2 O 7 to be extremely stable while still being able to achieve a capacity of 92 mAh g -1 and stable cycling at high temperatures up to 60 °C. Our results confirm the positive effect of nonstoichiometric ratios on the performance of Na 2 Fe 0.95 P 2 O 7 and provide a reliable idea to promote the practical application of sodium-ion batteries.

Cr 2 (NCN) 3 is a potentially high-capacity and fast-charge Li-ion anode owing to its abundant and broad tunnels. However, high intrinsic chemical instability severely restricts its capacity output and electrochemical reversibility. Herein we report an effective crystalline engineering method for optimizing its phase and crystallinity. Systematic studies reveal the relevancy between electrochemical performance and crystalline structure; an optimal Cr 2 (NCN) 3 with high phase purity and uniform crystallinity exhibits a high reversible capacity of 590 mAh g -1 and a stable cycling performance of 478 mAh g -1 after 500 cycles. In-operando heating XRD reveals its high thermodynamical stability over 600 °C, and in-operando electrochemical XRD proves its electrochemical Li storage mechanism, consisting of the primary Li-ion intercalation and subsequent conversion reactions. This study introduces a facile and low-cost method for fabricating high-purity Cr 2 (NCN) 3 , and it also confirms that the Li storage of Cr 2 (NCN) 3 can be further improved by tuning its phase and crystallinity.

The issue of bacterial infectious diseases remains a significant concern worldwide, particularly due to the misuse of antibiotics, which has caused the emergence of antibiotic-resistant strains. Fortunately, the rapid development of nanomaterials has propelled significant progress in antimicrobial therapy, offering promising solutions. Among them, the utilization of nanoenzyme-based chemodynamic therapy (CDT) has become a highly hopeful approach to combating bacterial infectious diseases. Nevertheless, the application of CDT appears to be facing certain constraints for its low efficiency in the Fenton reaction at the infected site. In this study, we have successfully synthesized a versatile nanozyme, which was a composite of molybdenum sulfide (MoS 2 ) and iron sulfide (FeS 2 ), through the hydrothermal method. The results showed that iron/molybdenum sulfide nanozymes (Fe/Mo SNZs) with desirable peroxidase (POD) mimic activity can generate cytotoxic reactive oxygen species (ROS) by successfully triggering the Fenton reaction. The presence of MoS 2 significantly accelerates the conversion of Fe 2+ /Fe 3+ through a cocatalytic reaction that involves the participation of redox pairs of Mo 4+ /Mo 6+ , thereby enhancing the efficiency of CDT. Additionally, based on the excellent photothermal performance of Fe/Mo SNZs, a near-infrared (NIR) laser was used to induce localized temperature elevation for photothermal therapy (PTT) and enhance the POD-like nanoenzymatic activity. Notably, both in vitro and in vivo results demonstrated that Fe/Mo SNZs with good broad-spectrum antibacterial properties can help eradicate Gram-negative bacteria like Escherichia coli and Gram-positive bacteria like Staphylococcus aureus . The most exciting thing is that the synergistic PTT/CDT exhibited astonishing antibacterial ability and can achieve complete elimination of bacteria, which promoted wound healing after infection. Overall, this study presents a synergistic PTT/CDT strategy to address antibiotic resistance, providing avenues and directions for enhancing the efficacy of wound healing treatments and offering promising prospects for further clinical use in the near future.

Organic dyes with simultaneously boosted near-infrared-II (NIR-II) fluorescence, type I photodynamic therapy (PDT), and photothermal therapy (PTT) in the aggregate state are still elusive due to the unclear structure-function relationship. Herein, electron-withdrawing substituents are introduced at the 5-indolyl positions of BODIPY dyes to form tight J-aggregates for enhanced NIR-II fluorescence and type I PDT/PTT. The introduction of an electron-rich julolidine group at the meso position and an electron-withdrawing substituent (-F) at the indolyl moiety can enhance intermolecular charge transfer and the hydrogen bonding effect, contributing to the efficient generation of superoxide radicals in the aggregate state. The nanoparticles of BDP-F exhibit NIR-II fluorescence at 1000 nm, good superoxide radical generation ability, and a high photothermal conversion efficiency (50.9%), which enabled NIR-II fluorescence-guided vasculature/tumor imaging and additive PDT/PTT. This work provides a strategy for constructing phototheranostic agents with enhanced NIR-II fluorescence and type I PDT/PTT for broad biomedical applications.

Metal selenides show outstanding sodium-ion storage performance when matched with an ether-based electrolyte. However, the intrinsic origin of improvement and deterministic interface characteristics have not been systematically elucidated. Herein, employing FeSe 2 anode as the model system, the electrochemical kinetics of metal selenides in ether and ester-based electrolytes and associated solid electrolyte interphase (SEI) are investigated in detail. Based on the galvanostatic intermittent titration technique and in situ electrochemical impedance spectroscopy, it is found that the ether-based electrolyte can ensure fast Na + transfer and low interface impedance. Additionally, the ether-derived thin and smooth double-layer SEI, which is critical in facilitating ion transport, maintaining structural stability, and inhibiting electrolyte overdecomposition, is concretely visualized by transmission electron microscopy, atomic force microscopy, and depth-profiling X-ray photoelectron spectroscopy. This work provides a deep understanding of the optimization mechanism of electrolytes, which can guide available inspiration for the design of practical electrode materials.

Nanoplastics (NPs), as emerging contaminants, have been shown to cause testicular disorders in mammals. However, whether paternal inheritance effects on offspring health are involved in NP-induced reproductive toxicity remains unclear. In this study, we developed a mouse model where male mice were administered 200 nm polyethylene nanoparticles (PE-NPs) at a concentration of 2 mg/L through daily gavage for 35 days to evaluate the intergenerational effects of PE-NPs in an exclusive male-lineage transmission paradigm. We observed that paternal exposure to PE-NPs significantly affected growth phenotypes and sex hormone levels and induced histological damage in the testicular tissue of both F 0 and F 1 generations. In addition, consistent changes in sperm count, motility, abnormalities, and gene expression related to endoplasmic reticulum stress, sex hormone synthesis, and spermatogenesis were observed across paternal generations. The upregulation of microRNA (miR)-1983 and the downregulation of miR-122-5p, miR-5100, and miR-6240 were observed in both F 0 and F 1 mice, which may have been influenced by reproductive signaling pathways, as indicated by the RNA sequencing of testis tissues and quantitative real-time polymerase chain reaction findings. Furthermore, alterations in the gut microbiota and subsequent Spearman correlation analysis revealed that an increased abundance of Desulfovibrio (C21&#95;c20) and Ruminococcus (gnavus) and a decreased abundance of Allobaculum were positively associated with spermatogenic dysfunction. These findings were validated in a fecal microbiota transplantation trial. Our results demonstrate that changes in miRNAs and the gut microbiota caused by paternal exposure to PE-NPs mediated intergenerational effects, providing deeper insights into mechanisms underlying the impact of paternal inheritance.

Unveiling molecular mechanisms that dominate protein phase dynamics has been a pressing need for deciphering the intricate intracellular modulation machinery. While ions and biomacromolecules have been widely recognized for modulating protein phase separations, effects of small molecules that essentially constitute the cytosolic chemical atmosphere on the protein phase behaviors are rarely understood. Herein, we report that vitamin C (V C ), a key small molecule for maintaining a reductive intracellular atmosphere, drives reentrant phase transitions of myosin II/F-actin (actomyosin) cytoskeletons. The actomyosin bundle condensates dissemble in the low-V C regime and assemble in the high-V C regime in vitro or inside neuronal cells, through a concurrent myosin II protein aggregation-dissociation process with monotonic V C concentration increase. Based on this finding, we employ in situ single-cell and single-vesicle electrochemistry to demonstrate the quantitative modulation of catecholamine transmitter vesicle exocytosis by intracellular V C atmosphere, i.e., exocytotic release amount increases in the low-V C regime and decreases in the high-V C regime. Furthermore, we show how V C regulates cytomembrane-vesicle fusion pore dynamics through counteractive or synergistic effects of actomyosin phase transitions and the intracellular free calcium level on membrane tensions. Our work uncovers the small molecule-based reversive protein phase regulatory mechanism, paving a new way to chemical neuromodulation and therapeutic repertoire expansion.