Multifunctional Roles of Zinc in Cadmium Transport in Soil-Rice Systems: Novel Insights from Stable Isotope Fractionation and Gene Expression.

The effect of Zn on Cd accumulation in rice varies under flooding and drainage conditions, and the underlying mechanism during uptake and transport from the soil to grains remains unclear. Isotope fractionation and gene expression were investigated using pot experiments under distinct water regimes and with Zn addition to gain a deeper understanding of the molecular effects of Zn on Cd uptake and transport in rice. The higher OsHMA2 expression but constitutively lower expression of zinc-regulated, iron-regulated transporter-like protein (ZIP) family genes in roots under the drainage regime than the flooding regime caused the enrichment of nonheavy Zn isotopes in the shoots relative to roots but minimally affected Cd isotopic fractionation. Drainage regime seem to exert a striking effect on the root-to-shoot translocation of Zn rather than Cd, and increased Zn transport via OsHMA2. The changes in expression patterns in response to Zn addition were similar to those observed upon switching from the flooding to drainage regime, except for OsNRAMP1 and OsNRAMP5. However, soil solution-to-rice plants and root-to-shoot fractionation toward light Zn isotopes with Zn addition (Δ66Znrice plant-soil solution = -0.49 to -0.40‰, Δ66Znshoot-root = -0.36 to -0.27‰) indicated that Zn transport occurred via nonspecific uptake pathways and OsHMA2, respectively. Accordingly, the less pronounced and minimally varied Cd isotope fractionation suggested that OsNRAMP5 and OsHMA2 are crucial for Cd uptake and root-to-shoot transport, respectively, facilitating Cd accumulation in grains. This study demonstrated that a high Zn supply promotes Cd uptake and root-to-shoot transport in rice by sharing distinct pathways, and by utilizing a non-Zn-sensitive pathway with a high affinity for Cd.

Synergistic effects of warming and humic substances on driving arsenic reduction and methanogenesis in flooded paddy soil.

Microbially-driven arsenic reduction and methane emissions in anaerobic soils are regulated by widespread humic substances (HS), while how this effect responds to climate change remains unknown. We investigated potential synergistic effects of HS in response to temperature changes in arsenic-contaminated paddy soils treated with humic acid (HA) and fulvic acid (FA) at temperatures ranging from 15 to 45 °C. Our results reveal a significant increase in arsenic reduction (5.6 times) and methane emissions (178 times) driven by HS, which can be exponentially stimulated at 45 °C. Acting as a electron shuttle, HS determines microbial arsenic reduction, further stimulated by warming. The top three sensitive genera are Geobacter, Anaeromyxobacter, and Gaiella which are responsible for enhanced arsenic reduction, as well as for the reduction of iron and HS with their functional genes; arrA and Geobacter spp. The top three sensitive methanogens are Methanosarsina, Methanocella, and Methanoculleus. Our study suggests notable synergistic effects between HS and warming in stimulating arsenic reduction and methanogenesis in paddy soils. Overall, the findings of this work highlight the high sensitivity of HS-mediated microbial arsenic transformation and methanogenesis in response to warming, which add potential value in predicting the biogeochemical cycling of arsenic and methane in soil under the context of climate change.

Microbial arsenic methylation in soil-water systems and its environmental significance.

In this review, we have summarized the current knowledge about the environmental importance, relevance, and consequences of microbial arsenic (As) methylation in various ecosystems. In this regard, we have presented As biomethylation in terrestrial and aquatic ecosystems particularly in rice paddy soils and wetlands. The functions of As biomethylation by microbial consortia in anaerobic and aerobic conditions are extensively discussed. In addition, we have tried to explain the interconnections between As transformation and carbon (C), such as microbial degradation of organic compounds and methane (CH4) emission. These processes can cause As release because of the reduction of arsenate (As(V)) to the more mobile arsenite (As(III)) as well as As methylation and the formation of toxic trivalent methylated As species in anaerobic conditions. Furthermore, the sulfur (S) transformation can form highly toxic thiolated As species owing to its interference with As biomethylation. Besides, we have focused on many other mutual interlinks that remain elusive between As and C, including As biomethylation, thiolation, and CH4 emission, in the soil-water systems. Recent developments have clarified the significant and complex interactions between the coupled microbial process in anoxic and submerged soils. These processes, performed by little-known/unknown microbial taxa or well-known members of microbial communities with unrecognized metabolic pathways, conducted several concurrent reactions that contributed to global warming on our planet and have unfavorable impacts on water quality and human food resources. Finally, some environmental implications in rice production and arsenic removal from soil-water systems are discussed. Generally, our understanding of the ecological and metabolic evidence for the coupling and synchronous processes of As, C, and S are involved in environmental contamination-caused toxicity in human food, including high As content in rice grain, water resources, and global warming through methanogenesis elucidate combating global rice safety, drinking water, and climate changes.

Nanoconfined Fe(II) releaser for long-term arsenic immobilization and its sustainability assessment.

Ferrous (Fe(II))-based oxygen activation for pollutant abatements in soil and groundwater has attracted great attention, while the low utilization and insufficient longevity of electron donors are the primary challenges to hinder its practical applications. Herein, we propose a nanoconfined Fe(II) releasing strategy that enables stable long-term electron donation for oxygen activation and efficient arsenic (As) immobilization under oxic conditions, by encapsulating zero-valent iron in biomass-derived carbon shell (ZVI@porous carbon composites; ZVI@PC). This strategy effectively enhances the generation of reactive oxygen species, enabling efficient oxidation and subsequent immobilization of As(III) in soils. Importantly, this Fe(II) releaser exhibits strong anti-interference capability against complex soil matrices, and the accompanying generation of Fe(III) enables As immobilization in soils, effectively lowering soil As bioavailability. Soil fixed-bed column experiments demonstrate a 79.5 % reduction of the total As in effluent with a simulated rainfall input for 10 years, indicating the excellent long-term stability for As immobilization in soil. Life cycle assessment results show that this Fe(II) releaser can substantially mitigate the negative environmental impacts. This work offers new insights into developing green and sustainable technologies for environmental remediation.

Residue changes, degradation, processing factors and their relation between physicochemical properties of pesticides in peanuts during multiproduct processing.

This study systematically investigates the residue changes, processing factors (PFs), and relation between the physicochemical properties of pesticides during peanut processing. Results revealed that peeling, washing, and boiling treatments removed partial or substantial pesticide residues from peanuts with PFs of 0.29-1.10 (most <1). By contrast, pesticides appeared to be partially concentrated during roasting, stir-frying, and deep-frying peanuts with PFs of 0.16-1.25. During oil pressing, 13 of the 28 pesticides were concentrated in the peanut oil (PF range: 1.06-2.01) and 25 of the pesticides were concentrated in the peanut meal (1.07-1.46). Physicochemical parameters such as octanol-water partition coefficient, degradation point, molecular weight, and melting point showed significant correlations with PFs during processing. Notably, log Kow exhibited strong positive correlations with the PFs of boiling, roasting, and oil pressing. Overall, this study describes the fate of pesticides during multiproduct processing, providing guidance to promote the healthy consumption of peanuts for human health.

Ubiquitin-specific protease 7 inhibitors reveal a differentiated mechanism of p53-driven anti-cancer activity.

The USP7 deubiquitinase regulates proteins involved in the cell cycle, DNA repair, and epigenetics and has been implicated in cancer progression. USP7 inhibition has been pursued for the development of anti-cancer therapies. Here, we describe the discovery of potent and specific USP7 inhibitors exemplified by FX1-5303. FX1-5303 was used as a chemical probe to study the USP7-mediated regulation of p53 signaling in cells. It demonstrates mechanistic differences compared to MDM2 antagonists, a related class of anti-tumor agents that act along the same pathway. FX1-5303 synergizes with the clinically approved BCL2 inhibitor venetoclax in acute myeloid leukemia (AML) cell lines and ex vivo patient samples and leads to strong tumor growth inhibition in in vivo mouse xenograft models of multiple myeloma and AML. This work introduces new USP7 inhibitors, differentiates their mechanism of action from MDM2 inhibition, and identifies specific opportunities for their use in the treatment of AML.

Residue levels, processing factors and risk assessment of pesticides in ginger from market to table.

Ginger is consumed as a spice and medicine globally. However, pesticide residues in ginger and their residue changes during processing remain poorly understood. Our results demonstrate that clothianidin, carbendazim and imidacloprid were the top detected pesticides in 152 ginger samples with detection rates of 17.11-27.63%, and these pesticides had higher average residues of 44.07-97.63 µg/kg. Although most samples contained low levels of pesticides, 66.45% of the samples were detected with pesticides, and 38.82% were contaminated with 2-5 pesticides. Peeling, washing, boiling and pickling removed different amounts of pesticides from ginger (processing factor range: 0.06-1.56, most <1). By contrast, pesticide residues were concentrated by stir-frying and drying (0.50-6.45, most >1). Pesticide residues were influenced by pesticide physico-chemical parameters involving molecular weight, melting point, degradation point and octanol-water partition coefficient by different ginger processing methods. Chronic and acute dietary risk assessments suggest that dietary exposure to pesticides from ginger consumption was within acceptable levels for the general population. This study sheds light on pesticide residues in ginger from market to processing and is of theoretical and practical value for ensuring ginger quality and safety.

Greenhouse cultivation enhances pesticide bioaccumulation in cowpeas following repeated spraying.

Understanding pesticide residue patterns in crops is important for ensuring human health. However, data on residue accumulation and distribution in cowpeas grown in the greenhouse and open field are lacking. Our results suggest that acetamiprid, chlorantraniliprole, cyromazine, and thiamethoxam residues in greenhouse cowpeas were 1.03-15.32 times higher than those in open field cowpeas. Moreover, repeated spraying contributed to the accumulation of pesticide residues in cowpeas. Clothianidin, a thiamethoxam metabolite, was detected at 1.04-86.00 µg/kg in cowpeas. Pesticide residues in old cowpeas were higher than those in tender cowpeas, and the lower half of the plants had higher pesticide residues than did the upper half. Moreover, pesticide residues differed between the upper and lower halves of the same cowpea pod. Chronic and acute dietary risk assessments indicated that the human health risk was within acceptable levels of cowpea consumption. Given their high residue levels and potential accumulation, pesticides in cowpeas should be continuously assessed.

Dissipation, accumulation, distribution and risk assessment of fungicides in greenhouse and open-field cowpeas.

Pesticide residues in cowpeas have raised worldwide concern. However, only a few studies have focused on pesticide accumulation and distribution in greenhouse and open-field cowpeas. Field trial results suggest that difenoconazole, dimethomorph, thifluzamide and pyraclostrobin dissipated faster in open fields (mean half-lives, 1.72-1.99 days) than in greenhouses (2.09-3.55 days); moreover, fungicide residues in greenhouse cowpeas were 0.84-8.19 times higher than those in the open-field cowpeas. All fungicides accumulated in the greenhouse and open-field cowpeas after repeated spraying. Fungicide residues in old cowpeas were higher than those in tender cowpeas, and residues in the upper halves of cowpea pods were higher than those in the lower halves. In addition, cowpeas distributed in the lower halves of the plants had higher fungicide residues. Our findings suggest that greenhouse cultivation contributed to the pesticide residues in cowpeas after repeated spraying, although the levels of dietary health risks remained acceptable under both cultivation scenarios.

Multitask Deep Learning Enabling a Synergy for Cadmium and Methane Mitigation with Biochar Amendments in Paddy Soils.

Biochar has demonstrated significant promise in addressing heavy metal contamination and methane (CH4) emissions in paddy soils; however, achieving a synergy between these two goals is challenging due to various variables, including the characteristics of biochar and soil properties that influence biochar's performance. Here, we successfully developed an interpretable multitask deep learning (MTDL) model by employing a tensor tracking paradigm to facilitate parameter sharing between two separate data sets, enabling a synergy between Cd and CH4 mitigation with biochar amendments. The characteristics of biochar contribute similar weightings of 67.9% and 62.5% to Cd and CH4 mitigation, respectively, but their relative importance in determining biochar's performance varies significantly. Notably, this MTDL model excels in custom-tailoring biochar to synergistically mitigate Cd and CH4 in paddy soils across a wide geographic range, surpassing traditional machine learning models. Our findings deepen our understanding of the interactive effects of Cd and CH4 mitigation with biochar amendments in paddy soils, and they also potentially extend the application of artificial intelligence in sustainable environmental remediation, especially when dealing with multiple objectives.

Integration with carbon capture technology enables a positive carbon balance for sustainable rice paddy remediation with calcium­silicon composites.

In situ stabilization technologies based on lime-derived materials are extensively used for remediating Cd-contaminated paddy soils. However, the environmental impacts and carbon budget associated with these technologies throughout the paddy soil remediation life cycle are gaining increasing attention. Herein, through paddy field trials, two representative lime-derived materials, quicklime and calcium-silicon composite (Ca/Si), are evaluated for their remediation effectiveness and environmental sustainability in the remediation of Cd-contaminated soils. The results demonstrate that both quicklime and Ca/Si can reduce Cd bioavailability and enable the safe use of rice grain. Nevertheless, the life cycle assessment score of the quicklime case is 4.4 times that of the Ca/Si case, indicating that the quicklime case has a greater negative impact on the environment. Furthermore, the net ecosystem carbon budget analysis reveals that both lime-derived materials exhibit outward carbon emissions throughout their life cycle, in which the carbon emission of the quicklime case (-20.2 t CO2-eq/ha) is 20 times that of the Ca/Si case (-1 t CO2-eq/ha). Moreover, the implementation of carbon capture technology results in the Ca/Si case achieving a positive carbon budget and contributing to a carbon neutrality plan. Conversely, the quicklime case falls short, affording only a 24.8 % reduction in carbon emissions. Overall, this study provides valuable insights into the environmental sustainability of different lime-derived materials for paddy soil remediation and carbon mitigation.

Comprehensive next-generation sequencing reveals double primary colorectal carcinoma missed by diagnostic imaging: A case report.

BACKGROUND: Multiple primary colorectal carcinoma (MPCC) is a rare clinical disease, which is challenging to differentiate from metastatic disease using histopathological methods. Next-generation sequencing (NGS) has been employed to identify multiple primary cancers. CASE SUMMARY: This study a rare case of a 63-year-old male patient diagnosed with MPCC by targeted NGS, which was initially missed by radiological evaluation. The patient was found to have two tumors located on the surface of the colorectum which had distinct genomic alterations. Based on wild-type KRAS detected in the unresected tumor, the patient benefited from the epidermal growth factor receptor (EGFR) inhibitor cetuximab treatment, but developed novel mutations including KIF5B-RET fusion, which provides a possible resistance mechanism to anti-EGFR therapy. CONCLUSION: Our case highlights the necessity of using genetic testing for primary tumor diagnosis and the application of serial plasma circulating tumor DNA profiling for dynamic disease monitoring.

Enantioselective Access to Chiral 2,5-Diketopiperazines via Stereogenic-at-Cobalt(III)-Catalyzed Ugi-4CRs/Cyclization Sequences.

An asymmetric synthesis of chiral 2,5-diketopiperazines by the Ugi-4CR/cyclization is exhibited. The employment of catalytic anionic chiral Co(III) complexes delivered α-propiolyl aminoamides in high yields with excellent enantioselectivities (31 examples, up to 95% ee). The following treatment of Ugi-adducts with PPh3 leads to chiral 2,5-DKPs without significant loss of enantioselectivities (26 examples, up to 91% ee).

Near-Infrared Light and Acid/Base Dual-Regulated Polymerization Utilizing Imidazole-Anion-Fused Perylene Diimides as Photocatalysts.

This work presents the first example of acid/base-responsive and near-infrared (NIR)-absorbing photocatalysts based on imidazole-anion-fused perylene diimide chromophores. The photocatalysts were in situ generated by deprotonation of imidazole-fused perylene diimide under an alkaline environment. NIR (λ = 730 nm, 128 mW/cm2) photoinduced atom transfer radical polymerization (ATRP) was implemented, exhibiting high efficiency and excellent livingness under ppm level of photocatalysts (15 ppm relative to monomer) and Cu(II) complex (10 ppm relative to monomer) concentrations. The method showed capabilities to polymerize behind opaque barriers (i.e., paper and pig skin) and under aerobic condition. Notably, this work demonstrated a dual temporal control of polymerization by adding weak base/acid and switching NIR light on/off. The polymerization can even be halted by bubbling CO2 and was then fully recovered by adding triethylamine. The NIR photoATRP of acrylamide monomers in aqueous solution was also performed, which can be regulated by the change of pH.

Roles of Chloride and Sulfate Ions in Controlling Cadmium Transport in a Soil-Rice System as Evidenced by the Cd Isotope Fingerprint.

Anions accompanying inorganic fertilizers, such as chloride and sulfate ions, potentially affect the solubility, uptake, and transport of Cd to rice grains. However, the role of anions in controlling Cd transport in the soil-soil solution-Fe plaque-rice plant continuum remains poorly understood. Cd isotope ratios were applied to Cd-contaminated soil pots, hydroponic rice, and adsorption experiments with or without KCl and K2SO4 treatments to decipher transport processes in the complex soil-rice system. The chloride and sulfate ions increased the Cd concentrations in the soil solution, Fe plaque, and rice plants. Accordingly, the magnitude of positive fractionation from soil to the soil solution was less pronounced, but that between soil and Fe plaque or rice plant is barely varied. The similar isotope composition of Fe plaque and soil, and the similar fractionation magnitude between Fe plaque and the solution and between goethite and the solution, suggested that desorption-sorption between iron oxides and the solution could be important at the soil-soil solution-Fe plaque continuum. This study reveals the roles of chloride and sulfate ions: (i) induce the mobility of light Cd isotopes from soil to the soil solution, (ii) chloro-Cd and sulfato-Cd complexes contribute to Cd immobilization in the Fe plaque and uptake into roots, and (iii) facilitate second leaves/node II-to-grain Cd transport within shoots. These results provide insights into the anion-induced Cd isotope effect in the soil-rice system and the roles of anions in facilitating Cd migration and transformation.

Surface functional groups and biofilm formation on microplastics: Environmental implications.

Microplastics (MPs) contamination is becoming a significant environmental issue, as the widespread omnipresence of MPs can cause many adverse consequences for both ecological systems and humans. Contrary to what is commonly thought, the toxicity-inducing MPs are not the original pristine plastics; rather, they are completely transformed through various surface functional groups and aggressive biofilm formation on MPs via aging or weathering processes. Therefore, understanding the impacts of MPs' surface functional groups and biofilm formation on biogeochemical processes, such as environmental fate, transport, and toxicity, is crucial. In this review, we present a comprehensive summary of the distinctive impact that surface functional groups and biofilm formation of MPs have on their significant biogeochemical behavior in various environmental media, as well as their toxicity and biological effects. We place emphasis on the role of surface functional groups and biofilm formation as a means of influencing the biogeochemical processes of MPs. This includes their effects on pollutant fate and element cycling, which in turn impacts the aggregation, transport, and toxicity of MPs. Ultimately, future research studies and tactics are needed to improve our understanding of the biogeochemical processes that are influenced by the surface functional groups and biofilm formation of MPs.

Facet-dependent electron transfer induces distinct arsenic reallocations on hematite.

The interfacial electron transfer (ET) between electron shuttling compounds and iron (Fe) oxyhydroxides plays a crucial role in the reductive dissolution of Fe minerals and the fate of surface-bound arsenic (As). However, the impact of exposed facets of highly crystalline hematite on reductive dissolution and As immobilization is poorly understood. In this study, we systematically investigated the interfacial processes of the electron shuttling compound cysteine (Cys) on various facets of hematite and the reallocations of surface-bound As(III) or As(V) on the respective surfaces. Our results demonstrate that the ET process between Cys and hematite generates Fe(II) and leads to reductive dissolution, with more Fe(II) generated on {001} facets of exposed hematite nanoplates (HNPs). Reductive dissolution of hematite leads to significantly enhanced As(V) reallocations on hematite. Nevertheless, upon the addition of Cys, a raipd release of As(III) can be halted by its prompt re-adsorption, leaving the extent of As(III) immobilization on hematite unchanged throughout the course of reductive dissolution. This is due to that Fe(II) can form new precipitates with As(V), a process that is facet-dependent and influenced by water chemistry. Electrochemical analysis reveals that HNPs exhibit higher conductivity and ET ability, which is beneficial for reductive dissolution and As reallocations on hematite. These findings highlight the facet-dependent reallocations of As(III) and As(V) facilitated by electron shuttling compounds and have implications for the biogeochemical processes of As in soil and subsurface environments.

Dissipation, Metabolism, Accumulation, Processing and Risk Assessment of Fluopyram and Trifloxystrobin in Cucumbers and Cowpeas from Cultivation to Consumption.

Fluopyram and trifloxystrobin are widely used for controlling various plant diseases in cucumbers and cowpeas. However, data on residue behaviors in plant cultivation and food processing are currently lacking. Our results showed that cowpeas had higher fluopyram and trifloxystrobin residues (16.48-247.65 µg/kg) than cucumbers (877.37-3576.15 µg/kg). Moreover, fluopyram and trifloxystrobin dissipated faster in cucumbers (half-life range, 2.60-10.66 d) than in cowpeas (10.83-22.36 d). Fluopyram and trifloxystrobin were the main compounds found in field samples, and their metabolites, fluopyram benzamide and trifloxystrobin acid, fluctuated at low residue levels (≤76.17 µg/kg). Repeated spraying resulted in the accumulation of fluopyram, trifloxystrobin, fluopyram benzamide and trifloxystrobin acid in cucumbers and cowpeas. Peeling, washing, stir-frying, boiling and pickling were able to partially or substantially remove fluopyram and trifloxystrobin residues from raw cucumbers and cowpeas (processing factor range, 0.12-0.97); on the contrary, trifloxystrobin acid residues appeared to be concentrated in pickled cucumbers and cowpeas (processing factor range, 1.35-5.41). Chronic and acute risk assessments suggest that the levels of fluopyram and trifloxystrobin in cucumbers and cowpeas were within a safe range based on the field residue data of the present study. The potential hazards of fluopyram and trifloxystrobin should be continuously assessed for their high residue concentrations and potential accumulation effects.

Dissipation, metabolism, accumulation, processing and risk assessment of fluxapyroxad in cucumber and cowpea vegetables from field to table.

Understanding the residue fate of fluxapyroxad is critical for food safety and human health. The present study profiled the dissipation, metabolism, accumulation, removal and risk assessment of fluxapyroxad in cucumbers and cowpeas from field to table. Greenhouse-field trials suggested that fluxapyroxad dissipated faster in cucumbers than in cowpeas, and M700F008 was the only detected metabolite at

A MD Simulation Prediction for Regulation of N-Terminal Modification on Binding of CD47 to CD172a in a Force-Dependent Manner.

Cancer cells can evade immune surveillance through binding of its transmembrane receptor CD47 to CD172a on myeloid cells. CD47 is recognized as a promising immune checkpoint for cancer immunotherapy inhibiting macrophage phagocytosis. N-terminal post-translated modification (PTM) via glutaminyl cyclase is a landmark event in CD47 function maturation, but the molecular mechanism underlying the mechano-chemical regulation of the modification on CD47/CD172a remains unclear. Here, we performed so-called "ramp-clamp" steered molecular dynamics (SMD) simulations, and found that the N-terminal PTM enhanced interaction of CD172a with CD47 by inducing a dynamics-driven contraction of the binding pocket of the bound CD172a, an additional constraint on CYS15 on CD47 significantly improved the tensile strength of the complex with or without PTM, and a catch bond phenomenon would occur in complex dissociation under tensile force of 25 pN in a PTM-independent manner too. The residues GLN52 and SER66 on CD172a reinforced the H-bonding with their partners on CD47 in responding to PTM, while ARG69 on CD172 with its partner on CD47 might be crucial in the structural stability of the complex. This work might serve as molecular basis for the PTM-induced function improvement of CD47, should be helpful for deeply understanding CD47-relevant immune response and cancer development, and provides a novel insight in developing of new strategies of immunotherapy targeting this molecule interaction.