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Authors set out to develop a statistical model for estimating the concentration of Hg in fish tissue. Important factors for the estimation include the species, the location, fish weight, and water body pH. In the southeast United States, it was found that southeast Mississippi and central Arkansas have fish with high Hg concentrations.

The nutrient enrichment of the Neuse River Estuary in North Carolina is believed to have declined in recent years because of algal blooms, fish kills, and toxic microorganisms. Research taking a local regression analysis (STL) approach to seasonal trend decomposition analysis of long-term and seasonal trends in nutrient concentrations indicates that upstream, phosphorus concentrations have decreased markedly, but remain downstream. This has resulted in the nitrogen to phosphorus concentrations rising considerably. A comparison of the ambient nutrient rations with the Redfield value indicates that phytophankton growth may be changing from nitrogen to phosphorous limitation during the better part of the year. This, in turn, may be precipitating a change in the biotic community.

Three pesticide and five herbicide concentrations in the Willamette River Basin, Oregon, are examined using tree-based models for factors contributing to different levels of their concentration.

A shock tube experiment was used to examine the laser photolytic generation of NH2 radicals in the temperature range of 1340 and 1670 K. Results showed that this photolytically initiated radical chain process in NH3/NO/Ar mixtures was exclusively controlled by the branching ratio of two reactions. Shock tube measurements of this chain process permitted a determination of the branching ratio alpha through the computation of the formula alpha = kla/(kla +klb). Alpha was found to increase from 0.42 at 1340 k to 0.53 at 1670 K. Analysis permitted the computation of uncertainty for alpha values.

Two Bayesian models demonstrate that very few individuals of the five species of fish from Lake Michigan could fall into the category in which their consumption is unrestricted because of their high polychlorinated biphenyls (PCBs) content. Five salmonid species were the subject of a fish consumption advisory that was issued by the state of Wisconsin. Results have revealed that brown trout have the highest PCB concentration among smaller fish. Lake trout, on the other hand, have the highest PCB concentration among larger fish.

We discuss the uncertainty associated with a commonly used method for measuring the concentration of microcystin, a group of toxins associated with cyanobacterial blooms. Such uncertainty is rarely reported and accounted for in important drinking water management decisions. Using monitoring data from Ohio Environmental Protection Agency and from City of Toledo, we document the sources of measurement uncertainty and recommend a Bayesian hierarchical modeling approach for reducing the measurement uncertainty. Our analysis suggests that (1) much of the uncertainty is a result of the highly uncertain "standard curve" developed during each test and (2) the uncertainty can be reduced by pooling raw test data from multiple tests. Based on these results, we suggest that estimation uncertainty can be effectively reduced through the effort of either (1) regional regulatory agencies by sharing and combining raw test data from regularly scheduled microcystin monitoring program or (2) the manufacturer of the testing kit by conducting additional tests as part of an effort to improve the testing kit. [ABSTRACT FROM AUTHOR]

The implications of Stein's paradox stirred considerable debate in statistical circles when the concept was first introduced in the 1950s. The paradox arises when we are interested in estimating the means of several variables simultaneously. In this situation, the best estimator for an individual mean, the sample average, is no longer the best. Rather, a shrinkage estimator, which shrinks individual sample averages toward the overall average is shown to have improved overall accuracy. Although controversial at the time, the concept of shrinking toward overall average is now widely accepted as a good practice for improving statistical stability and reducing error, not only in simple estimation problems, but also in complicated modeling problems. However, the utility of Stein's insights are not widely recognized in the environmental management community, where mean pollutant concentrations of multiple waters are routinely estimated for management decision-making. In this essay, we introduce Stein's paradox and its modern generalization, the Bayesian hierarchical model, in the context of environmental standard compliance assessment. Using simulated data and nutrient monitoring data from wadeable streams around the Great Lakes, we show that a Bayesian hierarchical model can improve overall estimation accuracy, thereby improving our confidence in the assessment results, especially for standard compliance assessment of waters with small sample sizes. [ABSTRACT FROM AUTHOR]

Characterizing contaminant occurrences in China's centralized source waters can provide an understanding of source water quality for stakeholders. The single-factor (i.e., worst contaminant) water-quality assessment method, commonly used in Chinese official analysis and publications, provides a qualitative summary of the country's water-quality status but does not specify the extent and degree of specific contaminant occurrences at the national level. Such information is needed for developing scientifically sound management strategies. This article presents a Bayesian hierarchical modeling approach for estimating contaminant concentration distributions in China's centralized source waters using arsenic and fluoride as examples. The data used are from the most recent national census of centralized source waters in 2006. The article uses three commonly used source water stratification methods to establish alternative hierarchical structures reflecting alternative model assumptions as well as competing management needs in characterizing pollutant occurrences. The results indicate that the probability of arsenic exceeding the standard of 0.05 mg/L is about 0.96-1.68% and the probability of fluoride exceeding 1 mg/L is about 9.56-9.96% nationally, both with strong spatial patterns. The article also discusses the use of the Bayesian approach for establishing a source water-quality information management system as well as other applications of our methods. [ABSTRACT FROM AUTHOR]

A Bayesian approach is used to update and improve water quality model predictions with monitoring data. The objective of this work is to facilitate adaptive management by providing a framework for sequentially updating the assessment of water quality status, to evaluate compliance with water quality standards, and to indicate if modification of management strategies is needed. Currently, most water quality or watershed models are calibrated using historical data that typically reflect conditions different from those being forecast. In part because of this, predictions are often subject to large errors. Fortunately, in many instances, postmanagement implementation monitoring data are available, although often with limited spatiotemporal coverage. These monitoring data support an alternative to the one-time prediction: pool the information from both the initial model prediction and postimplementation monitoring data. To illustrate this approach, a watershed nutrient loading model and a nitrogen-chlorophyll a model for the Neuse River Estuary were applied to develop a nitrogen total maximum daily load program for compliance with the chlorophyll a standard. Once management practices were implemented, monitoring data were collected and combined with the model forecast on an annual basis using Bayes Theorem. Ultimately, the updated posterior distribution of chlorophyll a concentration indicated that the Neuse River Estuary achieved compliance with North Carolina's standard. [ABSTRACT FROM AUTHOR]

We model the response of chlorophyll a—a surrogate for the phytoplankton community volume—to variations in lake total phosphorus (TP) and total nitrogen (TN) concentrations. The model is fitted to a large cross-sectional data set from the Finnish Lake monitoring network. The objective is to support the Finnish Government in identifying management actions to achieve compliance of the chlorophyll a concentration standard with a given confidence level and to provide tools for the estimation of critical (target) loads for nutrients in monitored lakes. We develop a Bayesian hierarchical linear model which combines advantages of both the currently preferred non-hierarchical lake-type-specific linear model and lake-specific linear model fitted separately using data from a single lake. The hierarchical model is less biased at lake-level compared to the lake type model. In contrast to the lake model, it predicts the lake specific chlorophyll a response to nutrients outside the lake specific observational range. The hierarchical model is used to calculate probabilities of chlorophyll a concentration exceeding the standard under different nitrogen and phosphorus concentration combinations. These probabilities can be used to estimate acceptable nitrogen-phosphorus concentration combinations by a lake manager. We discuss how our study can be useful in implementing the European Water Framework Directive. [ABSTRACT FROM AUTHOR]

We present a Bayesian approach for characterizing background contaminant concentration distributions using data from sites that may have been contaminated. Our method, focused on estimation, resolves several technical problems of the existing methods sanctioned by the U.S. Environmental Protection Agency (USEPA) (a hypothesis testing based method), resulting in a simple and quick procedure for estimating background contaminant concentrations. The proposed Bayesian method is applied to two data sets from a federal facility regulated under the Resource Conservation and Restoration Act. The results are compared to background distributions identified using existing methods recommended by the USEPA. The two data sets represent low and moderate levels of censorship in the data. Although an unbiased estimator is elusive, we show that the proposed Bayesian estimation method will have a smaller bias than the EPA recommended method. [ABSTRACT FROM AUTHOR]

The northwestern Gulf of Mexico shelf has been nicknamed "The Dead Zone" due to annual summertime (May-September) bottom-water hypoxia (dissolved oxygen ⩽ 2 mg L-1) that can be extensive (> 20 000 km²) last for several months. Hypoxia has been attributed to eutrophication caused by increasing nitrogen loads, although directly linking hypoxia to nitrogen is difficult. While the areal extent of hypoxia has been shown to increases with Mississippi River flow, it is nuclear whether this is increase results from enhanced vertical water-column stratification or from eutrophication caused by river-borne nutrients. Disentangling the relative contributions of eutrophication versus stratification has important management consequences. Our analysis indicates that the top:bottom salinity difference is an important predictor of hypoxia, exhibiting a threshold, where the probability of hypoxia increases rapidly, at approximately 4.1 ppt. Using a Bayesian change-point model, we show that this stratification threshold decreased from 1982 to 2002, indicating the degree of stratification needed to induce hypoxia and nitrogen, it does implicate a long-term factor transcending yearly flow-induced stratification differences,. Concurrently, we show that surface temperature increased, while surface dissolved oxygen decreased, suggesting that factors in addition to nitrogen may be influencing the incidence of hypoxia in the bottom water. [ABSTRACT FROM AUTHOR]

Water quality studies often include the analytical challenge of incorporating censored data and quantifying error of estimation. Many analytical methods exist for estimating distribution parameters when censored data are present. This paper presents a Bayesian-based hierarchical model for estimating the national distribution of the mean concentrations of chemicals occurring in U.S. public drinking water systems using fluoride and thallium as examples. The data used are Safe Drinking Water Act compliance monitoring data (with a significant proportion of left-censored data). The model, which assumes log- normality, was evaluated using simulated data sets generated from a series of Weibull distributions to illustrate the robustness of the model. The hierarchical model is easily implemented using the Markov chain Monte Carlo simulation method. In addition, the Bayesian method is able to quantify the uncertainty in the estimated cumulative density function. The estimated fluoride and thallium national distributions are presented. Results from this study can be used to develop prior distributions for future U.S. drinking water regulatory studies of contaminant occurrence. [ABSTRACT FROM AUTHOR]

Reports on a statistical analysis of the phosphorus assimilative capacity of freshwater wetlands in North America. Development of a mass loading model; Use of the model to separate P assimilative capacity; Amount of nutrients found in North American wetlands; Absence of significant changes in ecosystem structure and function.

This letter to the editor is provided in defense of research recommending a higher threshold for water column total phosphorus (TP) concentration in the Florida Everglades wetlands.

Electrolysis of infinite seawater is a promising and sustainable approach for clean hydrogen production. However, it remains a big challenge to accomplish corrosion-resistant and chlorine-free seawater electrolysis at low power input. Herein, the bimetallic nickel-iron sulfide-based electrocatalytic nanoarrays are constructed by a facile hydrothermal sulfidation of redox-etched iron foam (IF), which manifests an effective and reliable strategy for the sulfion oxidation reaction (SOR) to assist alkaline seawater electrolysis for the achievement of energy-saving hydrogen production and value-added sulfion upcycling. The resulting NiFeS x /FeNi 3 /IF required 0.353 and 0.415 V vs RHE for SOR at current densities of 50 and 100 mA cm -2 , which are considerably lower than the theoretical potential of the oxygen evolution reaction (OER, 1.23 V vs RHE). In situ spectroscopy analysis demonstrated efficient sulfion oxidation on the surface of NiFeS x /FeNi 3 /IF. Furthermore, the NiFeS x /FeNi 3 /IF-assembled electrolyzer delivered a greatly reduced cell voltage of 0.92 V at 50 mA cm -2 and maintains excellent durability for 30 h, achieving high Faradaic efficiency for both hydrogen production and sulfion degradation. In addition, under natural sunlight (660.4 W m -2 ), only a 0.947 V voltage of the solar panel smoothly powers the SOR-coupled seawater electrolysis for green hydrogen production and economic sulfur recovery.

ConspectusLate-stage halogenation, targeting specific positions in complex substrates, has gained significant attention due to its potential for diversifying and functionalizing complex molecules such as natural products and pharmaceutical intermediates. Utilizing readily available halogenating reagents, such as hydrogen halides (HX), N-halosuccinimides (NXS), and dichloroethane (DCE) reagents for late-stage halogenation shows great promise for expanding the toolbox of synthetic chemists. However, the reactivity of haleniums (X + , X = Cl, Br, I) can be significantly hindered by the presence of various functional groups such as hydroxyl, amine, amide, or carboxylic acid groups. The developed methods of late-stage halogenation often rely on specialized activating reagents and conditions. Recently, our group (among others) has put great efforts into addressing these challenges and unlocking the potential of these readily available HX, NXS, and DCE reagents in complex molecule halogenation. Developing new methodologies, catalyst systems, and reaction conditions further enhanced their utility, enabling the efficient and selective halogenation of intricate substrates.With the long-term goal of achieving selective halogenation of complex molecules, we summarize herein three complementary research topics in our group: (1) Efficient oxidative halogenations: Taking inspiration from naturally occurring enzyme-catalyzed oxidative halogenation reactions, we focused on developing cost-effective oxidative halogenation reactions. We found the combination of dimethyl sulfoxide (DMSO) and HX (X = Cl, Br, I) efficient for the oxidative halogenation of aromatic compounds and alkenes. Additionally, we developed electrochemical oxidative halogenation using DCE as a practical chlorinating reagent for chlorination of (hetero)arenes. (2) Halenium reagent activation: Direct electrophilic halogenation using halenium reagents is a reliable method for obtaining organohalides. However, compared to highly reactive reagents, the common and readily available NXS and dihalodimethylhydantoin (DXDMH) demonstrate relatively lower reactivity. Therefore, we focused on developing oxygen-centered Lewis base catalysts such as DMSO, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and nitromethane to activate NXS or DXDMH, enabling selective halogenation of bioactive substrates. (3) Halogenation of inert substrates: Some substrates, such as electron-poor arenes and pyridines, are inert toward electrophilic functionalization reactions. We devised several strategies to enhance the reactivity of these molecules. These strategies, characterized by mild reaction conditions, the ready availability and stability of catalysts and reagents, and excellent tolerance for various functional groups, have emerged as versatile protocols for the late-stage aromatic halogenation of drugs, natural products, and peptides. By harnessing the versatility and selectivity of these catalysts and methodologies, synthetic chemists can unlock new possibilities in the synthesis of halogenated compounds, paving the way for the development of novel functional materials and biologically active molecules.

This study presents the synthesis of novel naphthofurano-iminosugars ( 4 ) using 2,3- O -isopropylidene D-ribose tosylate ( 1a ), anilines ( 2 ), and 1,4-benzoquinone ( 3a ) as starting materials through key iminium ion/enamine intermediates via [3 + 2] cyclization reactions at room temperature. The reaction has unique regioselectivity and stereoselectivity with moderate to excellent yields. The adaptability of this method has been demonstrated using various substituted anilines, on which both electron-donating and electron-withdrawing groups were well employed in the reactions. Notably, the treatment of the fused multicyclic iminosugar 4 with TFA efficiently leads to an interesting unexpected pyridinium salt ( 8 ), possible via four sequential steps: deprotection of the 2,3- O -isopropylidene group, furan ring opening, dehydration condensation of the OH groups, and elimination of water.

An efficient reagent-free method for the synthesis of polysubstituted 4-quinolone from 2-substituted alkynoyl aryl-sulfonamide was developed. This developed method tolerates various functional groups and gives the corresponding 4-quinolones. We have successfully extended this method to the synthesis of dihydro-4-quinolones from 2-alkenoyl aryl sulfonamide derivatives.

Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis and exploring atomic-level behaviors. However, their potential as greener, efficient catalysts for challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu 13 (Nap) 3 (PPh 3 ) 7 H 10 (hereafter Cu 13 Nap), protected by 1-naphthalene thiolate (Nap), which performs well in decarboxylative oxidation (90% yield) under photochemical conditions. In comparison, the isostructural Cu 13 (DCBT) 3 (PPh 3 ) 7 H 10 (hereafter Cu 13 DCBT), stabilized by 2,4-dichlorobenzenethiolate (DCBT), yields only 28%, and other previously reported Cu NCs (Cu 28 , Cu 29 , Cu 45 , Cu 57 , and Cu 61 ) yield in the range of 6-18%. The introduction of naphthalene thiolate to the surface of Cu 13 NCs influences their electronic structure and charge transfer in the ligand shell, enhancing visible light absorption and catalytic performance. Density functional theory (DFT) and experimental evidence suggest that the reaction proceeds primarily through an energy transfer mechanism. The energy transfer pathway is uncommon in the context of previous reports for decarboxylative oxidation reactions. Our findings suggest that strategically manipulating ligands holds significant potential for creating composite active sites on atomically precise copper NCs, resulting in enhanced catalytic efficacy and selectivity across various challenging reactions.

The prevalence of foodborne pathogenic bacteria, especially drug-resistant strains, such as Salmonella enterica , poses serious threats to public health, highlighting the requirement for the development of rapid and precise detection methods. Herein, a CRISPR/Cas12a-triggered visible-light-driven photoelectrochemical (PEC) assay (CasPEC) was developed using a SiO 2 -quenched BiVO 4 /MoS 2 p/n-type heterojunction as the photoactive material. The CRISPR/Cas12a recognition endowed the CasPEC assay with high specificity capable of resolving single-nucleotide polymorphisms (SNPs) and identifying SNP-involved drug-resistant bacteria. SiO 2 was linked to the surface of the BiVO 4 /MoS 2 heterojunction by single-stranded DNA (ssDNA), which would be cleaved by target-activated CRISPR/Cas12a. This cleavage of ssDNA resulted in the detachment of SiO 2 , thereby achieving a "signal-on" PEC output. Leveraging the multiple-turnover CRISPR cleavage and the outstanding photoactive performance of PEC signaling, the CasPEC assay for S. enterica showed a detection limit of 103 colony-forming units (CFU)/mL and the ability to detect as few as 0.01% drug-resistant strains. The CasPEC assay can accurately sense the S. enterica contamination in complex food matrices, including beef and milk. These findings demonstrated the great potential of the CasPEC assay for detecting pathogenic bacterial contamination in food, particularly concerning food safety related to SNP-involved drug-resistant bacteria.

The combination of infrared spectroscopy (IR) and ion mobility mass spectrometry (IM-MS) has revealed that protein secondary structures are retained upon transformation from aqueous solution to the gas phase under gentle conditions. Yet the details about where and how these structural elements are embedded in the gas phase remain elusive. In this study, we employ long time scale molecular dynamics (MD) simulations to examine the extent to which proteins retain their solution structures and the impact of protonation state on the stability of secondary structures in the gas phase. Our investigation focuses on two well-studied proteins, myoglobin and β-lactoglobulin, representing typical helical and β-sheet proteins, respectively. Our simulations accurately reproduce the experimental collision cross section (CCS) data measured by IM-MS. Based on accurately reproducing previous experimental collision cross section data and dominant secondary structural species obtained from IM-MS and IR, we confirm that both proteins largely retain their native secondary structural components upon passing from aqueous solution to the gas phase. However, we observe significant reductions in secondary structure contents (19.2 ± 1.2% for myoglobin and 7.3 ± 0.6% for β-lactoglobulin) in specific regions predominantly composed of ionizable residues. Further mechanistic analysis suggests that alterations in protonation states of these residues after phase transition induce changes in their local interaction networks and backbone dihedral angles, which potentially promote the unfolding of secondary structures in the gas phase. We anticipate that similar protonation state induced unfolding may be observed in other proteins possessing distinct secondary structures. Further studies on a broader array of proteins will be essential to refine our understanding of protein structural behavior during the transition to the gas phase.

Transketolase (TKL; EC 2.2.1.1) is a highly promising potential target for herbicidal applications. To identify novel TKL inhibitors, we designed and synthesized a series of 3-oxopropionamide-1-methylpyrazole carboxylate analogues and assessed their herbicidal activities. Ethyl 3-((1-((2,4-dichlorophenyl)amino)-1-oxopropan-2-yl)oxy)-1-methyl-1 H -pyrazole-5-carboxylate ( D15 ) and ethyl 1-methyl-3-((1-oxo-1-((thiophen-2-ylmethyl)amino)propan-2-yl)oxy)-1 H -pyrazole-5-carboxylate ( D20 ) exhibited superior growth inhibition activities against both the root and stem of Amaranthus retroflexus ( A. retroflexus ) compared to nicosulfuron and mesotrione. Additionally, D15 achieved an inhibition rate of more than 90% against the roots and stems of Digitaria sanguinalis ( D. sanguinalis ), outperforming the four control agents at a concentration of 200 mg/L using the small cup method. In the pre-emergence herbicidal activity test, D15 effectively inhibited D. sanguinalis by more than 90% at 150 g ai/ha, surpassing the efficacy of the control, mesotrione. Conversely, in the postemergence herbicidal activity test, D20 exhibited efficient inhibition of A. retroflexus by more than 90% at 150 g ai/ha, outperforming the control agents nicosulfuron, mesotrione, and metamifop. The results of the TKL enzyme activity test showed that the IC 50 values of compounds D15 and D20 were 0.384 and 0.655 mg/L, respectively, which were close to those of the control agents. Furthermore, molecular docking and molecular dynamics simulation studies revealed that D15 and D20 interacted favorably with the TKL of Setaria viridis . Such findings highlight the promising potential of D15 and D20 as lead TKL inhibitors for the optimization of new herbicides.

In recent years, driven by ever-increasing application of energetic materials in deep-seated mineral resource exploitation and aerospace engineering, the mining of advanced safe energetic materials with significant thermal stability has drawn widespread publicity. Here, a tricyclic bridged energetic compound 2-amino-4,6-bis(3,5-diamino-4-nitropyrazol-1-yl)-1,3,5-triazine ( NPX-03 ) was prepared using simple synthetic route. Furthermore, an interesting highly thermostable nitrogen-rich perchlorate, NPX-03·2HClO 4 , was prepared by the self-assembly reaction of NPX-03 and HClO 4 , displaying a thermal decomposition peak temperature of 375.9 °C. Moreover, NPX-03·2HClO = 8187 m s 4 exhibits good detonation velocity ( D = 8187 m s -1 ) and insensitivity (IS = 50 J, FS > 360 N), thereby being promising candidates for advanced insensitive high-energy materials.

Effects of thermal cycling on the microstructure and thermoelectric properties are studied for the undoped and Na-doped SnSe samples using X-ray computed tomography and property measurements. It is observed that thermal cycling causes significant cracks to develop, which decrease both the electrical and lattice thermal conductivities but do not affect the thermopower. The zT values are drastically reduced after the repeated heat treatment. It is important to account for density changes during cycling to obtain accurate values of the thermal conductivity. Even before thermal cycling, the spark-plasma sintered (SPS) samples have a significant number of microcracks. The orientation of cracks within the SPS pellets and their effect on the microstructure are influenced by the presence of a Na-rich impurity. The SnSe and Sn 0.995 Na 0.005 Se samples without the impurity develop cracks and exhibit grain growth parallel to the pellet surface, which is also the plane of the 2D SnSe layers. The Sn 0.97 Na 0.03 Se sample containing the impurity develops cracks that are orthogonal to the pellet surface. Such an orientation of cracks in Sn 0.97 Na 0.03 Se inhibits grain growth. All samples appear mechanically unstable after thermal cycling.

Fibroblast activation protein (FAP) has recently gained significant attention as a promising tumor biomarker for both diagnosis and therapeutic applications. A series of radiopharmaceuticals based on fibroblast activation protein inhibitors (FAPIs) have been developed and translated into the clinic. Though some of them such as radiolabeled FAPI-04 probes have achieved favorable in vivo imaging performance, further improvement is still highly desired for obtaining radiopharmaceuticals with a high theranostics potential. In this study, we innovatively designed an FAPI ligand SMIC-3002 by changing the core quinoline motif of FAPI-04 to the quinolinium scaffold. The engineered molecule was further radiolabeled with 68 Ga to generate a positron emission tomography (PET) probe, [ 68 Ga]Ga-SMIC-3002, which was then evaluated in vitro and in vivo. [ 68 Ga]Ga-SMIC-3002 demonstrated high in vitro stability, nanomolar affinity for FAP (8 nM for protein, 23 nM for U87MG cells), and specific uptake in FAP-expressing tumors, with a tumor/muscle ratio of 19.1 and a tumor uptake of 1.48 ± 0.03 ID/g% at 0.5 h in U87MG tumor-bearing mice. In summary, the quinolinium scaffold can be successfully used for the development of the FAP-targeted tracer. [ 68 Ga]Ga-SMIC-3002 not only shows high potential for clinical translation but also offers insights into designing a new generation of FAPI tracers.

The design and preparation of anode materials with structural stability, fast ion transmission, and low open-circuit voltage are critical to the development of magnesium ion batteries (MIBs). The feasibility of the unique phase Haeckelite MoS 2 (Hae-MoS 2 ) monolayer with Haeckelite structure as a potential anode material for MIBs was investigated using density functional theory (DFT) calculations. The Hae-MoS 2 monolayer exhibits excellent structural stability and semimetallic characteristics with a Dirac cone located at the Gamma point of band structure. Mg ion is easily adsorbed on the Hae-MoS 2 monolayer surface with an adsorption energy of -2.06 eV and can diffuse rapidly with a low diffusion energy barrier (0.3 eV), indicating excellent charge and discharge rates. Most importantly, the Hae-MoS 2 monolayer exhibits a suitable open-circuit voltage, which falls within the desired voltage range and ensures the safety of battery performance. These exceptional properties indicate that the Hae-MoS 2 monolayer can be proposed as a candidate for anode material for MIBs.

Characterized by progressive and irreversible degeneration of the articular cartilage (AC), osteoarthritis (OA) is the most common chronic joint disease, and there is no cure for OA at present. Recent studies suggest that enhancing the recruitment of endogenous mesenchymal stem cells (MSCs) to damaged cartilage is a promising therapeutic strategy for cartilage repair. Tetrahedral framework nucleic acid (tFNA) is a novel DNA nanomaterial and has shown great potential in the field of biomedical science. Transforming growth factor-beta 3 (TGF-β3), a vital member of the highly conserved TGF-β superfamily, is considered to induce chondrogenesis. A 66-base DNA aptamer named HM69 is reported to identify and recruit MSCs. In this study, aptamer HM69-modified tFNAs were successfully self-assembled and used to load TGF-β3 when the disulfide bonds combined. We confirmed the successful synthesis of the final composition, HM69-tFNA@TGF-β3 (HTT), by PAGE, dynamic light scattering, and atomic force microscopy. The results of in vitro experiments showed that HTT effectively induced MSC proliferation, migration, and chondrogenic differentiation. In addition, HTT-treated MSCs were shown to protect the OA chondrocytes. In DMM mice, the injection of HTT improved the therapeutic outcome of mouse pain symptoms and AC degeneration. In conclusion, this study innovatively used the disulfide bonds combined with TGF-β3 and tFNA, and an additional sequence HM69 was loaded on tFNA for the better-targeted recruitment of MSCs. HTT demonstrated its role in promoting the chondrogenesis of MSCs and cartilage protection, indicating that it might be promising for OA therapy.

A three-dimensional (3D) hierarchical microfiber bundle-based scaffold integrated with silver nanowires (AgNWs) and porous polyurethane (PU) was designed for the Joule heater via a facile dip-coating method. The interconnected micrometer-sized voids and unique hierarchical structure benefit uniform AgNWs anchored and the formation of a high-efficiency 3D conductive network. As expected, this composite exhibits a superior electrical conductivity of 1586.4 S/m and the best electrothermal conversion performance of 118.6 °C at 2.0 V compared to reported wearable Joule heaters to date. Moreover, the durable microfiber bundle-PU network provides strong mechanical properties, allowing for the stable and durable electrothermal performance of such a composite to resist twisting, bending, abrasion, and washing. Application studies show that this kind of Joule heater is suitable for a wide range of applications, such as seat heating, a heating jacket, personal thermal management, etc.

The development of a photosensitizer (PS) that induces pyroptosis could be a star for photodynamic therapy (PDT), particularly with type-I PSs that produce reactive oxygen species (ROS) in a hypoxic tumor microenvironment. Since pyroptosis is a recently characterized cell death pathway, it holds promise for advancing PDT in oncology, with PSs playing a critical role. Herein, we develop a PS named Th-M with aggregation-induced emission (AIE) characteristics for type-I PDT against tongue squamous cell carcinoma (TSCC). Th-M stands out for its exceptional mitochondrial-targeting ability, which triggers mitochondrial dysfunction and leads to Caspase-3 and Gasdermin E (GSDME) cleavage under white light irradiation, inducing pyroptosis in TSCC cells. Our studies verify the effectiveness of Th-M in destroying cancer cells in vitro and suppressing tumor growth in vivo while also demonstrating a favorable biosafety profile. This work pioneers the application of Th-M as a mitochondria-targeted, type-I PS that leverages the mechanism of pyroptosis, offering a potent approach for the treatment of TSSC with promising implications for future PDT of cancers.

Compared to other protein therapeutics, there is currently limited knowledge about the residual host cell proteins (HCPs) in adeno-associated virus (AAV)-based gene therapy products. This is primarily due to the lack of a robust and sensitive mass spectrometry-based method for HCP analysis in AAV samples. Existing liquid chromatography-mass spectrometry methods used for analyzing HCPs in therapeutic monoclonal antibodies (mAbs) often cannot be directly applied to AAVs, due to some unique characteristics of AAV samples encountered during their development such as limited sample availability/protein concentration and the presence of surfactants. In this study, we have developed a novel workflow for robust and in-depth HCP analysis of AAV samples by combining wide-window data-dependent acquisition for improved low-abundance HCP detection with single-pot, solid-phase-enhanced sample preparation (SP3) for low-input sample preparation. Using this newly developed method, we were able to detect more than 650 HCPs in a commercial AAV1 sample with a high quantitative reproducibility. This represents a greater than 5-fold increase in HCP protein identification compared to an in-solution digestion method followed by traditional data-dependent acquisition. Similar benefits can also be achieved for other AAV serotypes that were produced internally and purified through different processes. The detection limit of this method is as low as 0.06 ng/mL, enabling more comprehensive HCP coverage in AAV samples. Moreover, for the first time, we have identified several process-related viral proteins, such as Rep 78 and E4. These proteins need to be closely monitored during AAV process development as they may present a greater risk for immunogenicity compared to HCPs that are derived from human HEK293 cells.

Biomimetic engineering surfaces featuring heterogeneous wettability are vital for atmospheric water harvesting applications. Existing research predominantly focuses on the coordinated regulation of surface wettability through structural and chemical modifications, often overlooking the prevalent triboelectric charge effect at the liquid-solid interface. In this work, we designed a heterogeneous wettability surface by strategic masking and activated its latent triboelectric charge using triboelectric brushes, thereby enhancing the removal and renewal of surface droplets. By examining the dynamic evolution of droplets, the mechanism of triboelectric enhancement in the water collection efficiency is elucidated. Leveraging this inherent triboelectric charge interaction, fog collection capacity can be augmented by 29% by activating the system for 5 s every 60 s. Consequently, the advancement of triboelectric charge-enhanced fog collection technology holds both theoretical and practical significance for overcoming the limitations of traditional surface wettability regulation.

Electrocatalytic water splitting is a crucial strategy for advancing hydrogen energy and addressing the global energy crisis. Despite its significance, the need for a straightforward and swift method to synthesize electrocatalysts with exceptional performance remains pressing. In this study, we demonstrate a novel approach for the preparation of multimetal-based electrocatalysts in a continuous flow reactor, enabling the quick synthesis of a large number of products through a streamlined process. The resultant NiFe-LDH comprises nanoflakes with a high specific surface area and requires only 255.4 mV overpotential to achieve a current density of 10 mA·cm -2 in 1 M KOH, surpassing samples fabricated by conventional hydrothermal methods. Our method can also be applied to craft a spectrum of other multimetal-based electrocatalysts, including CoFe-LDH, CoAl-LDH, NiMn-LDH, and NiCoFe-LDH. Additionally, the NiFe-LDH electrocatalyst is further applied to anodic methanol electrooxidation coupled with cathodic hydrogen evolution. Moreover, the simplicity and generality of our fabrication method render it applicable for the facile preparation of various multimetal-based electrocatalysts, offering a scalable solution to the quest for high-performance catalysts in advancing sustainable energy technologies.

Noncovalent interactions involving aromatic rings, such as π-stacking and π-ion interactions, play an essential role in molecular recognition, assembly, catalysis, and electronics. However, the inherently weak and complex nature of these interactions has made it challenging to study them experimentally, especially with regard to elucidating their properties in solution. Herein, the noncovalent interactions between π and π-hole, π and cation, and π-hole and anion in molecular complexes in nonpolar solution are investigated in situ through single-molecule electrical measurements in combination with theoretical calculations. Specifically, phenyl and pentafluorobenzyl groups serve as π and π-hole sites, respectively, while Li + and Cl - are employed as the cation and anion. Our findings reveal that, in comparison with homogeneous π···π interactions, heterogeneous π···π-hole and π···cation interactions exhibit greater binding energies, resulting in a longer binding lifetime of the molecular junctions. Meanwhile, π···Li + and π-hole···Cl - interactions present significantly distinct binding characteristics, with the former being stronger but more flexible than the latter. Furthermore, by changing the molecular components, similar conductivity can be achieved in both molecular dimers or sandwich complexes. These results provide new insights into π- and π-hole-involved noncovalent interactions, offering novel strategies for precise manipulation of molecular assembly, recognition, and molecular device.

Achieving robust electrical contacts is crucial for realizing the promise of monolayer 2D semiconductors such as semiconducting transition metal dichalcogenides (s-TMDs) in electronics. Despite recent breakthroughs, a gap remains between the experimental and theoretical understanding of metal-s-TMDs contacts. This study explores bismuth semimetal contacts to monolayer MoSe 2 , using a platform that minimizes experimental sources of uncertainty; we combine contact-front and contact-end measurements to measure key parameters like specific resistivity (ρ c ) and transfer length ( L t ). We find that the resistivity of MoSe 2 under the contacts is enhanced due to charge transfer that can be modeled using a self-consistent approach. In contrast, ab initio calculations of the interlayer charge transfer rate are inconsistent with the measured value of ρ c , highlighting the need for new theoretical approaches.

Pesticides play a crucial role in ensuring food production and food security. Conventional pesticide formulations can not meet the current needs of social and economic development, and they also can not meet the requirements of green agriculture. Therefore, there is an urgent need to develop efficient, stable, safe, and environmentally friendly pesticide formulations to gradually replace old formulations which have high pollution and low efficacy. The rise of nanotechnology provides new possibilities for innovation in pesticide formulations. Through reasonable design and construction of an environmentally friendly pesticide delivery system (PDS) based on multifunctional nanocarriers, the drawbacks of conventional pesticides can be effectively solved, realizing a water-based, nanosized, targeted, efficient, and safe pesticide system. In the past five years, researchers in chemistry, materials science, botany, entomology, plant protection, and other fields are paying close attention to the research of nanomaterials based PDSs and nanopesticide formulations and have made certain research achievements. These explorations provide useful references for promoting the innovation of nanopesticides and developing a new generation of green and environmentally friendly pesticide formulations. This Perspective summarizes the recent advances of nanomaterials in PDSs and nanopesticide innovation, aiming to provide useful guidance for carrier selection, surface engineering, controlled release conditions, and application in agriculture.

Poly(methyl methacrylate) (PMMA) bone cements have been widely used in orthopedics; thanks to their excellent mechanical properties, biocompatibility, and chemical stability. Barium sulfate and zirconia are usually added into PMMA bone cement to enhance the X-ray radiopacity, while the mechanical strength, radiopacity, and biocompatibility are not well improved. In this study, an insoluble and corrosion-resistant ceramic, tantalum carbide (TaC), was added into the PMMA bone cement as radiopacifies, significantly improving the mechanical, radiopaque, biocompatibility, and osteogenic performance of bone cement. The TaC-PMMA bone cement with varied TaC contents exhibits compressive strength over 100 MPa, higher than that of the commercial 30% BaSO 4 -PMMA bone cement. Intriguingly, when the TaC content reaches 20%, the radiopacity is equivalent to the commercial bone cement with 30% of BaSO 4 in PMMA. The cytotoxicity and osteogenic performance indicate that the incorporation of TaC not only enhances the osteogenic properties of PMMA but also does not reduce cell viability. This study suggests that TaC could be a superior and multifunctional radio-pacifier for PMMA bone cement, offering a promising avenue for improving patient outcomes in orthopedic applications.

Biomolecular condensates are dynamic liquid droplets through intracellular liquid-liquid phase separation that function as membraneless organelles, which are highly involved in various complex cellular processes and functions. Artificial analogs formed via similar pathways that can be integrated with biological complexity and advanced functions have received tremendous research interest in the field of synthetic biology. The coacervate droplet-based compartments can partition and concentrate a wide range of solutes, which are regarded as attractive candidates for mimicking phase-separation behaviors and biophysical features of biomolecular condensates. The use of peptide-based materials as phase-separating components has advantages such as the diversity of amino acid residues and customized sequence design, which allows for programming their phase-separation behaviors and the physicochemical properties of the resulting compartments. In this Perspective, we highlight the recent advancements in the design and construction of biomimicry condensates from synthetic peptides relevant to intracellular phase-separating protein, with specific reference to their molecular design, self-assembly via phase separation, and biorelated applications, to envisage the use of peptide-based droplets as emerging biomedical delivery vehicles.

Limonene, a key volatile chemical product (VCP) commonly found in personal care and cleaning agents, is emerging as a major indoor air pollutant. Recently, elevated levels of reactive chlorine species during bleach cleaning and disinfection have been reported to increase indoor oxidative capacity. However, incomplete knowledge of the indoor transformation of limonene, especially the missing chlorine chemistry, poses a barrier to evaluating the environmental implications associated with the concurrent use of cleaning agents and disinfectants. Here, we investigated the reaction mechanisms of chlorinated limonene peroxy radicals (Cl-lim-RO 2 •), key intermediates in determining the chlorine chemistry of limonene, and toxicity of transformation products (TPs) using quantum chemical calculations and toxicology modeling. The results indicate that Cl-lim-RO 2 • undergoes a concerted autoxidation process modulated by RO 2 • and alkoxy radicals (RO•), particularly emphasizing the importance of RO• isomerization. Following this generalized autoxidation mechanism, Cl-lim-RO 2 • can produce low-volatility precursors of secondary organic aerosols. Toxicological findings further indicate that the majority of TPs exhibit increased respiratory toxicity, mutagenicity, and eye/skin irritation compared to limonene, presenting an occupational hazard for indoor occupants. The proposed near-explicit reaction mechanism of chlorine-initiated limonene significantly enhances our current understanding of both RO 2 • and RO• chemistry while also highlighting the health risks associated with the concurrent use of cleaning agents and disinfectants.

In recent years, nanocarrier-based pesticide delivery systems have provided new possibilities for the efficient utilization of pesticides. In this research, we developed a hydroxypropyl-β-cyclodextrin-modified graphene oxide (GO-HP-β-CD) nanocarrier for pyraclostrobin (Pyr) delivery and studied its application for tobacco target spot disease control. GO-HP-β-CD has excellent pesticide-loading performance for Pyr (adsorption capacity of 1562.5 mg/g) and good water dispersibility and stability. Besides, GO-HP-β-CD shows pH-responsive release performance. In addition, GO-HP-β-CD also has better leaf affinity than Pyr, and it can effectively adhere to the leaf surface after simulated washing. The results of antifungal experiments indicate that GO-HP-β-CD-Pyr has a good preventive effect on tobacco target spot disease, and its EC 50 value is 0.384 mg/L, which is lower than Pyr. Specifically, this nanopesticide formulation does not contain toxic organic solvent or additive, so it has good environmental friendliness. Therefore, we believe that the GO-HP-β-CD-Pyr nanopesticide has brilliant potential in the prevention and control of tobacco diseases.

Magnetic polymer microspheres have been extensively utilized as separable and highly efficient adsorbents in wastewater treatment. In this study, a series of novel magnetic spongy porous carbon skeleton materials (Mag-SPCS) have been designed and synthesized by acetonitrile suspension precipitation polymerization, which combines the advantages of the acetonitrile precipitation method and the suspension polymerization method. It was demonstrated that the transformation of the material morphology from microspheres to a porous sponge was achieved by a gradual decrease in the usage amount of ethylene glycol. After N , N -dimethyloctadecylamine (C18) was grafted onto the Mag-SPCS materials, the C18-Mag-SPCS materials with a superhigh saturation adsorption capacity and superfast adsorption efficiency were used for the removal of BTEX (toluene, benzene, and para -xylene) in wastewater. Subsequently, the adsorption properties of the composites with different morphologies were evaluated, and the effect of the usage amount of C18 on the adsorption properties of the C18-Mag-SPCS was further investigated. The maximum adsorption capacities of C18-Mag-SPCS for benzene, toluene, and para -xylene were 714.84, 564.32, and 394.48 mg/g, respectively. The adsorption process was conducted in accordance with the proposed secondary and Langmuir models. Finally, the FTIR, XPS, and XRD characterization results before and after adsorption demonstrated that the adsorption mechanism of toluene onto C18-Mag-SPCS was primarily hydrogen bonding, π-π stacking, and van der Waals forces. These findings of the study indicate that the composite material exhibits an ultrahigh saturation adsorption capacity and ultrafast adsorption efficiency, thereby confirming its considerable potential for application in wastewater treatment.

Mechanical stress within organoids is a pivotal indicator in disease modeling and pharmacokinetics, yet current tools lack the ability to rapidly and dynamically screen these mechanics. Here, we introduce biocompatible and compressible hollow microlasers that realize all-optical assessment of cellular stress within organoids. The laser spectroscopy yields identification of cellular deformation at the nanometer scale, corresponding to tens of pascals stress sensitivity. The compressibility enables the investigation of the isotropic component, which is the fundamental mechanics of multicellular models. By integrating with a microwell array, we demonstrate the high-throughput screening of mechanical cues in tumoroids, establishing a platform for mechano-responsive drug screening. Furthermore, we showcase the monitoring and mapping of dynamic contractile stress within human embryonic stem cell-derived cardiac organoids, revealing the internal mechanical inhomogeneity within a single organoid. This method eliminates time-consuming scanning and sample damage, providing insights into organoid mechanobiology.

CarH is a protein photoreceptor that uses a form of B 12 , adenosylcobalamin (AdoCbl), to sense light via formation of a metastable excited state. Aside from AdoCbl bound to CarH, methylcobalamin (MeCbl) is the only other example─to date─of photoexcited cobalamins forming metastable excited states with lifetimes of nanoseconds or longer. The UV-visible spectra of the excited states of MeCbl and AdoCbl bound to CarH are similar. We have used transient Co K-edge X-ray absorption and X-ray emission spectroscopies in conjunction with transient absorption spectroscopy in the UV-visible region to characterize the excited states of MeCbl. These data show that the metastable excited state of MeCbl has a slightly expanded corrin ring and increased electron density on the cobalt, but only small changes in the axial bond lengths.