Light-induced degradation of dimethylmercury in different natural waters.

Photo-induced degradation of dimethylmercury (DMHg) is considered to be an important source for the generation of methylmercury (MMHg). However, studies on DMHg photodegradation are scarce, and it is even debatable about whether DMHg can be degraded in natural waters. Herein, we found that both DMHg and MMHg could be photodegraded in three natural waters collected from the Yellow River Delta, while in pure water only DMHg photodegradation occurred under visible light irradiation. The effects of different environmental factors on DMHg photodegradation were investigated, and the underlying mechanisms were elucidated by density functional theory calculations and a series of control experiments. Our findings revealed that the DMHg degradation rate was higher in the tidal creek water compared to Yellow River, Yan Lake, and purified water. NO3-, NO2-, and DOM could promote the photodegradation with DOM and NO3- showing particularly strong positive effects. Different light sources were employed, and UV light was found to be more effective in DMHg photodegradation. Moreover, MMHg was detected during the photodegradation of DMHg, confirming that the photochemical demethylation of DMHg is a source of MMHg in sunlit water. This work may provide a novel mechanistic insight into the DMHg photodegradation in natural waters and enrich the study of the global biogeochemical cycle of Hg.

Incorporation of Shewanella oneidensis MR-1 and goethite stimulates anaerobic Sb(III) oxidation by the generation of labile Fe(III) intermediate.

Dissimilatory iron-reducing bacteria (DIRB) affect the geochemical cycling of redox-sensitive pollutants in anaerobic environments by controlling the transformation of Fe morphology. The anaerobic oxidation of antimonite (Sb(III)) driven by DIRB and Fe(III) oxyhydroxides interactions has been previously reported. However, the oxidative species and mechanisms involved remain unclear. In this study, both biotic phenomenon and abiotic verification experiments were conducted to explore the formed oxidative intermediates and related processes that lead to anaerobic Sb(III) oxidation accompanied during dissimilatory iron reduction. Sb(V) up to 2.59 µmol L-1 combined with total Fe(II) increased to 188.79 µmol L-1 when both Shewanella oneidensis MR-1 and goethite were present. In contrast, no Sb(III) oxidation or Fe(III) reduction occurred in the presence of MR-1 or goethite alone. Negative open circuit potential (OCP) shifts further demonstrated the generation of interfacial electron transfer (ET) between biogenic Fe(II) and goethite. Based on spectrophotometry, electron spin resonance (ESR) test and quenching experiments, the active ET production labile Fe(III) was confirmed to oxidize 94.12% of the Sb(III), while the contribution of other radicals was elucidated. Accordingly, we proposed that labile Fe(III) was the main oxidative species during anaerobic Sb(III) oxidation in the presence of DIRB and that the toxicity of antimony (Sb) in the environment was reduced. Considering the prevalence of DIRB and Fe(III) oxyhydroxides in natural environments, our findings provide a new perspective on the transformation of redox sensitive substances and build an eco-friendly bioremediation strategy for treating toxic metalloid pollution.

BRD4L cooperates with MYC to block local tumor invasion via suppression of S100A10.

Targeted therapy based on BRD4 and MYC shows promise due to their well-researched oncogenic functions in cancer, but their tumor-suppressive roles are less understood. In this study, we employ a systematic approach to delete exons that encode the low-complexity domain (LCD) of BRD4L in cells by using CRISPR-Cas9. In particular, the deletion of exon 14 (BRD4-E14) results in cellular morphological changes towards spindle-shaped and loosely packed. BRD4-E14 deficient cells show increased cell migration and reduced cell adhesion. The expression of S100A10 was significantly increased in cells lacking E14. BRD4L binds with MYC via the E14-encoded region of the LCD to inhibit the expression of S100A10. In cancer tissues, there is a positive correlation between BRD4 and MYC, while both of these proteins are negatively associated with S100A10 expression. Finally, knocking out the BRD4-E14 region or MYC promotes tumor growth in vivo. Together, these data support a tumor-suppressive role of BRD4L and MYC in some contexts. This discovery emphasizes the significance of a discreetly design and precise patient recruitment in clinical trials that testing cancer therapy based BRD4 and MYC.

The hidden diet: Synthetic antioxidants in packaged food and their impact on human exposure and health.

Synthetic antioxidants (AOs) are commonly used in everyday items and industrial products to inhibit oxidative deterioration. However, the presence of AOs in food packaging and packaged foods has not been thoroughly documented. Moreover, studies on human exposure to AOs through skin contact with packaging or ingesting packaged foods are limited. In this study, we analyzed twenty-three AOs-including synthetic phenolic antioxidants (SPAs) and organophosphite antioxidants (OPAs)-along with six transformation products in various food samples and their packaging materials. We found AOs in food products at concentrations ranging from 1.30 × 103 to 1.77 × 105 ng/g, which exceeded the levels in both outer packaging (6.05 × 102-3.07 × 104 ng/g) and inner packaging (2.27 × 102-1.09 × 105 ng/g). The most common AOs detected in foodstuffs were tris(2,4-di-tert-butylphenyl) phosphate (AO168O), butylated hydroxytoluene (BHT), and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO1076), together constituting 95.7 % of the total AOs found. Our preliminary exposure assessment revealed that dietary exposure-estimated at a median of 2.55 × 104 ng/kg body weight/day for children and 1.24 × 104 ng/kg body weight/day for adults-is a more significant exposure route than dermal contact with packaging. Notably, four AOs were identified in food for the first time, with BHT making up 76.8 % and 67.6 % of the total BHT intake for children and adults, respectively. These findings suggest that food consumption is a significant source of BHT exposure. The estimated daily intakes of AOs via consumption of foodstuffs were compared with the recommended acceptable daily intake to assess the risks. This systematic investigation into AOs contributes to understanding potential exposure and health risks associated with AOs in packaged foods. It emphasizes the need for further evaluation of human exposure to these substances.

Confounding effects of seasonality and anthropogenic river regulation on suspended particulate matter-driven mercury transport to coastal seas.

Riverine mercury (Hg) is mainly transported to coastal areas in suspended particulate matter (SPM)-bound form, posing a potential threat to human health. Water discharge and SPM characteristics in rivers vary naturally with seasonality and can also be arbitrarily disrupted by anthropogenic regulation events, but their effects on Hg transport remain unresolved. Aiming to understand the confounding effects of seasonality and anthropogenic river regulation on Hg and SPM transport, this study selected the highly sediment-laden Yellow River as a representative conduit. Significant variations in SPM concentrations (108 - 7097 mg/L) resulted in fluctuations in total mercury (THg, 3.79 - 111 ng/L) in river water corresponding to seasonality and anthropogenic water/sediment regulation. Principal component analysis and structural equation model revealed that SPM was the essential factor controlling THg and particulate Hg (PHg) in river water. While SPM exhibited equilibrium state in the dry season, a net resuspension during the anthropogenic regulation and net deposition in the wet season demonstrated the impact of SPM dynamics on Hg distribution and transport to coastal regions. Combining water discharge, SPM, and Hg concentrations, a modified model was developed to quantify Hg flux (2256 kg), over 98% of which was in particulate phase.

Apoptotic extracellular vesicles restore homeostasis of the articular microenvironment for the treatment of rheumatoid arthritis.

Rheumatoid arthritis (RA) is a severe autoimmune disease with symptoms including synovial inflammation, cartilage erosion, and bone loss in RA lesions, which eventually lead to joint deformity and function loss. Most current treatments fail to achieve satisfying therapeutic outcomes with some adverse effects. Extracellular vesicles derived from apoptotic cells (apoEVs) have emerged as important mediators in intercellular communication regulating diverse physiological and pathological processes. In this study, we investigated the therapeutic efficacy of macrophage-derived and osteoclast-derived apoEVs (Mφ-apoEVs and OC-apoEVs) on RA. The in vitro results showed that both Mφ-apoEVs and OC-apoEVs induced macrophage repolarization toward the anti-inflammatory M2 phenotype, promoted chondrocyte functions and chondrogenesis, and inhibited osteoclast formation and maturation. In addition, OC-apoEVs promoted osteogenic differentiation. The in vivo study on the CIA mouse model further demonstrated that apoEVs could couple various functions and exert synergistic effects on the joint with RA, as evidenced by the regression of synovial inflammation, the reversal of cartilage damage and bone erosion, and the preservation of joint structure. These findings demonstrated that Mφ-apoEVs and OC-apoEVs contributed to restoring the homeostasis of the overall microenvironment in the RA joint and highlighted their potential application as a promising alternative to treat RA.

Occurrence, potential sources, and ecological risks of traditional and novel organophosphate esters in facility agriculture soils: A case study in Beijing, China.

Although traditional organophosphate esters (OPEs) in soils have attracted widespread interest, there is little information on novel OPEs (NOPEs), especially in facility agriculture soils. In this work, we surveyed 11 traditional OPEs, four NOPEs, and four corresponding organophosphite antioxidant precursors (OPAs) for the NOPEs in soil samples collected from facility greenhouses and open fields. The median summed concentrations of traditional OPEs and NOPEs were 14.1 µg/kg (range: 5.38-115 µg/kg) and 702 µg/kg (range: 348-1952 µg/kg), respectively, in film-mulched soils from greenhouses. These concentrations were much higher than those in soils without mulch films, which suggests that OPEs in soils are associated with plastic mulch films. Tris(2,4-di-tert-butylphenyl) phosphate, which is a NOPE produced by oxidation of (2,4-di-tert-butylphenyl) phosphite, was the predominant congener in farmland soils, with concentrations several orders of magnitude greater than those of traditional OPEs. Comparisons of OPEs in different mulch films and the corresponding mulched soils revealed that degradable and black films caused more severe pollution than polyethylene and white films. Traditional OPEs, including tris(2-ethylhexyl) phosphate and tricresyl phosphate, exhibited moderate risks in farmland soils, especially in film-mulched soils. NOPEs, including trisnonylphenol phosphate, posed high ecological risks to the terrestrial ecosystem. Risk evaluations should be conducted for a broad range of NOPEs in the environment.

Transcriptional control of CCAAT/enhancer binding protein zeta gene in chicken adipose tissue.

CCAAT/enhancer binding protein zeta (C/EBPZ) was differentially expressed in abdominal adipose tissues of fat and lean broilers and regulated adipogenesis in chicken. The objective of this study was to elucidate the transcriptional regulation of C/EBPZ gene in chicken adipose tissue. A 2,031-base pair (bp) chicken C/EBPZ sequence (2,025 nucleotides upstream to 6 nucleotides downstream from the initiator codon, -2,025/+6) was studied. The sequence exhibited a significant promoter activity (P < 0.05) and had some cis-acting elements, notably, a core promoter was identified in nucleotides -94 to +6. Additionally, DNA pull-down assay showed that proteins interacted with chicken C/EBPZ promoter (-173/+6) in preadipocytes were implicated in transcription, post-transcriptional regulation and translation. In addition, KLF2 facilitated the activities of chicken C/EBPZ promoter (-2,025/+6, -1,409/+6, -793/+6, -485/+6, -173/+6, and -94/+6) in preadipocytes (P < 0.05). The expression levels of KLF2 and C/EBPZ in chicken abdominal adipose tissue were substantially associated (r = 0.5978278, P < 0.0001), and KLF2 increased C/EBPZ expression in vitro (P < 0.05). Additionally, chromatin immunoprecipitation (ChIP)-PCR analysis revealed that KLF2 has the ability to interact with the chicken C/EBPZ promoter regions at least at the positions -1,245/-1,048 and -571/-397. Mutation analysis showed that the CGCAGCGCCCG motif located in the chicken C/EBPZ promoter at positions -45 to -35 is involved in regulating transcription and facilitates trans activation by KLF2. These results provided some information of transcription control of C/EBPZ in chicken adipose tissue.

Spatial and temporal variations in the pollution status and sources of mercury in the Jiaozhou bay.

In the past few decades, mercury (Hg) discharged into the coastal bays of China has significantly increased; however, long-term trends regarding the pollution status and sources of Hg in these bays have yet to be clear. Focusing on this issue, surface sediments and core sediments were collected in the Jiaozhou Bay (JZB), a typical bay highly affected by human activities in China, to analyze the concentrations and stable isotopic composition of Hg. Total mercury (THg) concentrations in surface sediment varied from 7 to 163 ng/g, with higher levels located in the eastern JZB, possibly attributed to intensive industrial and population density. THg in sediment cores 14 and 20 displayed fluctuating increasing trends from 1936 to 2019, reflecting the deterioration of Hg pollution. In contrast, THg in sediment core 28 near the river mouth exhibited a declining trend, possibly due to the river dam construction. Using a stable isotope mixing model, contributions of various sources (atmospheric, riverine, and industrial emissions) to Hg in the JZB were estimated. The results showed that industrial emissions were the main source (over 50%) of mercury in the JZB in 2019. Sediment cores recorded an increase in industrial Hg due to early industrialization and Reform and Opening-up before 2000. In addition, sediment core 20 demonstrated a rise in the percentage of riverine Hg due to land reclamation at the bay's mouth during 2000-2007.

Bioactive mesoporous silica nanoparticle-functionalized titanium implants with controllable antimicrobial peptide release potentiate the regulation of inflammation and osseointegration.

Bacterial infection and delayed osseointegration are two major challenges for titanium-based orthopedic implants. In the present study, we developed a functionalized titanium implant Ti-M@A by immobilizing antimicrobial peptide (AMP) HHC36-loaded diselenide-bridged mesoporous silica nanoparticles (MSNs) on the surface, which showed good long-term and mechanical stability. The functionalized implants can realize the sustained release of AMP over 30 days and exhibit over 95.71 % antimicrobial activity against four types of clinical bacteria (S. aureus, E. coli, P. aeruginosa and MRSA), which arose from the capability to destroy the bacterial membranes. Moreover, Ti-M@A can efficiently inhibit the biofilm formation of the bacteria. The functionalized implants can also significantly promote the osteogenic differentiation of mouse bone marrow-derived mesenchymal stem cells (mBMSCs) because of the Se in MSNs. Notably, it can trigger macrophages toward M2 polarization in vitro by scavenging ROS in LPS-activated macrophages. Consequently, in vivo assays with infection and non-infection bone defect models demonstrated that such bioactive implants can not only kill over 98.82 % of S. aureus, but also promote osseointegration. Hence, this study provides a combined strategy to resolve bacterial infection and delayed osseointegration for titanium implants.

Restricted reaction of layered double hydroxide nanoparticles with phosphate in a confined microsphere space.

Over the past decades, considerable efforts have been made to find useful solutions for phosphate pollution control. The state transition of nanomaterials from freely dispersed to encapsulated provides a realizable route for their application in phosphate elimination. The separation convenience offered by encapsulation has been widely recognized, however, the unique binding mode of nanostructures and phosphate in the confined space remains unclear, limiting its further development. Here, carboxymethyl cellulose (CMC) microspheres were used as hosts to deploy layered double hydroxide (LDH) nanoparticles. On this basis, we described an attempt to explore the adsorption behavior of LDH and phosphate in the microsphere space. Compared to their freely dispersed analogues, LDH particles exhibited higher structural stability, wider pH adaptability, and better phosphate selectivity when spatially confined in the CMC microsphere. Nevertheless, the kinetic process was severely inhibited by three orders of magnitude. Besides, the saturated phosphate adsorption capacity was also reduced to 74.6 % of the freely dispersed system. A combinative characterization revealed that the highly electronegative CMC host not only causes electrostatic repulsion to phosphate, but also extracts the electron density of the metal center of LDH, weakening its ability to act as a Lewis acid site for phosphate binding. Meanwhile, the microsphere encapsulation also hinders the ion exchange function of interlayer anions and phosphate. This study offers an objective insight into the reaction of LDH and phosphate in the confined microsphere space, which may contribute to the advanced design of encapsulation strategies for nanoparticles.

Study on the preparation and n-heptane isomerization performance of MoOx-Pd/Ce-MCM-48 catalyst.

A Ce-MCM-48 molecular sieve was prepared by the hydrothermal synthesis method. Using Ce-MCM-48 as the support, a series of MoOx Pd/Ce-M catalysts were prepared by the impregnation method by introducing MoOx and Pd. XRD, N2 adsorption desorption, SEM, TEM, NH3-TPD, Py-IR, FT-IR, and ICP-MS were used to characterize the physicochemical properties. The performance of n-heptane isomerization in a micro fixed bed device was evaluated. The results showed that the synthesized Ce-MCM-48 was mesoporous, with a spherical particle morphology, a long-range ordered pore structure, weakly acidic sites on the surface, and an increase of B and L acids. The 2% MoOx-Pd/Ce-M catalyst was used for the probe reaction of n-heptane hydroisomerization; when the reduction temperature was 400 °C, the reduction time was 2 hours, the reaction temperature was 300 °C, the WHSV was 7.6 h-1, the conversion rate was 58.7%, the selectivity was 91.2%, and the maximum yield was 53.5%. The product distribution of multiple C7 isomers increased the selectivity of multi branched isoheptane. The addition of an appropriate amount of MoOx would improve the performance of n-heptane isomerization.

Double-Network DNA Macroporous Hydrogel Enables Aptamer-Directed Cell Recruitment to Accelerate Bone Healing.

Recruiting endogenous bone marrow mesenchymal stem cells (BMSCs) in vivo to bone defect sites shows great promise in cell therapies for bone tissue engineering, which tackles the shortcomings of delivering exogenous stem cells, including limited sources, low retention, stemness loss, and immunogenicity. However, it remains challenging to efficiently recruit stem cells while simultaneously directing cell differentiation in the dynamic microenvironment and promoting neo-regenerated tissue ingrowth to achieve augmented bone regeneration. Herein, a synthetic macroporous double-network hydrogel presenting nucleic acid aptamer and nano-inducer enhances BMSCs recruitment, and osteogenic differentiation is demonstrated. An air-in-water template enables the rapid construction of highly interconnective macroporous structures, and the physical self-assembly of DNA strands and chemical cross-linking of gelatin chains synergistically generate a resilient double network. The aptamer Apt19S and black phosphorus nanosheets-specific macroporous hydrogel demonstrate highly efficient endogenous BMSCs recruitment, cell differentiation, and extracellular matrix mineralization. Notably, the enhanced calvarial bone healing with promising matrix mineralization and new bone formation is accompanied by adapting this engineered hydrogel to the bone defects. The findings suggest an appealing material approach overcoming the traditional limitations of cell-delivery therapy that can inspire the future design of next-generation hydrogel for enhanced bone tissue regeneration.

Synthetic Antioxidants as Contaminants of Emerging Concern in Indoor Environments: Knowns and Unknowns.

Synthetic antioxidants, including synthetic phenolic antioxidants (SPAs), amine antioxidants (AAs), and organophosphite antioxidants (OPAs), are essential additives for preventing oxidative aging in various industrial and consumer products. Increasing attention has been paid to the environmental contamination caused by these chemicals, but our understanding of synthetic antioxidants is generally limited compared to other emerging contaminants such as plasticizers and flame retardants. Many people spend a significant portion (normally greater than 80%) of their time indoors, meaning that they experience widespread and persistent exposure to indoor contaminants. Thus, this Perspective focuses on the problem of synthetic antioxidants as indoor environmental contaminants. The wide application of antioxidants in commercial products and their demonstrated toxicity make them an important family of indoor contaminants of emerging concern. However, significant knowledge gaps still need to be bridged: novel synthetic antioxidants and their related transformation products need to be identified in indoor environments, different dust sampling strategies should be employed to evaluate human exposure to these contaminants, geographic scope and sampling scope of research on indoor contamination should be broadened, and the partition coefficients of synthetic antioxidants among different media need to be investigated.

Advancing document-level event extraction: Integration across texts and reciprocal feedback.

The primary objective of document-level event extraction is to extract relevant event information from lengthy texts. However, many existing methods for document-level event extraction fail to fully incorporate the contextual information that spans across sentences. To overcome this limitation, the present study proposes a document-level event extraction model called Integration Across Texts and Reciprocal Feedback (IATRF). The proposed model constructs a heterogeneous graph and employs a graph convolutional network to enhance the connection between document and entity information. This approach facilitates the acquisition of semantic information enriched with document-level context. Additionally, a Transformer classifier is introduced to transform multiple event types into a multi-label classification task. To tackle the challenge of event argument recognition, this paper introduces the Reciprocal Feedback Argument Extraction strategy. Experimental results conducted on both our COSM dataset and the publicly available ChFinAnn dataset demonstrate that the proposed model outperforms previous methods in terms of F1 value, thus confirming its effectiveness. The IATRF model effectively solves the problems of long-distance document context-aware representation and cross-sentence argument dispersion.

An improved method for rapid and safe preparation and measurement of dimethylmercury using gas chromatography-atomic fluorescence spectrometry.

Transformations between dimethylmercury (DMHg) and other mercury (Hg) species have been one of the critical knowledge gaps in the Hg global biogeochemical cycle due to the lack of detailed studies. The preparation and measurement of DMHg are challenging due to the high toxicity and volatility of DMHg. In this work, we invented a new DMHg generator for successfully preparing high-purity DMHg in a highly controllable and safe way. The DMHg could be spontaneously volatilized and diffused from the original preparation solution to the solution to be studied. The parameters for generating DMHg were optimized to be the pH value of 4.0 with a MeCo/Hg2+ molar ratio of 10 at 20 °C. The following measurement method of DMHg in the presence of various species of Hg was also investigated and optimized. Hg0 and DMHg could be separated effectively with the carrier gas flow rate of 15 mL min-1 and the gas chromatography column temperature of 30 °C. The interferences of Hg0, monomethylmercury and other species were excluded by systematic control experiments. A sensitive and reliable approach for quantifying trace DMHg in water was developed. Under the optimal conditions, the limits of detection for Hg0, MMHg and DMHg were 0.03, 0.002 and 0.024 ng L-1, respectively, with the relative standard deviation below 8.2%. The developed method was validated by the determination Hg species of different natural water samples. This work is expected to provide a new and safe strategy for DMHg preparation and a verified method for DMHg measurement.

Marriage of High-Throughput Gradient Surface Generation With Statistical Learning for the Rational Design of Functionalized Biomaterials.

Functional biomaterial is already an important aspect in modern therapeutics; yet, the design of novel multi-functional biomaterial is still a challenging task nowadays. When several biofunctional components are present, the complexity that arises from their combinations and interactions will lead to tedious trial-and-error screening. In this work, a novel strategy of biomaterial rational design through the marriage of gradient surface generation with statistical learning is presented. Not only can parameter combinations be screened in a high-throughput fashion, but also the optimal conditions beyond the experimentally tested range can be extrapolated from the models. The power of the strategy is demonstrated in rationally designing an unprecedented ternary functionalized surface for orthopedic implant, with optimal osteogenic, angiogenic, and neurogenic activities, and its optimality and the best osteointegration promotion are confirmed in vitro and in vivo, respectively. The presented strategy is expected to open up new possibilities in the rational design of biomaterials.

Simultaneous CAS9 editing of cpSRP43, LHCA6, and LHCA7 in Picochlorum celeri lowers chlorophyll levels and improves biomass productivity.

High cellular pigment levels in dense microalgal cultures contribute to excess light absorption. To improve photosynthetic yields in the marine microalga Picochlorum celeri, CAS9 gene editing was used to target the molecular chaperone cpSRP43. Depigmented strains (>50% lower chlorophyll) were generated, with proteomics showing attenuated levels of most light harvesting complex (LHC) proteins. Gene editing generated two types of cpSRP43 transformants with distinct lower pigment phenotypes: (i) a transformant (Δsrp43) with both cpSRP43 diploid alleles modified to encode non-functional polypeptides and (ii) a transformant (STR30309) with a 3 nt in-frame insertion in one allele at the CAS9 cut site (non-functional second allele), leading to expression of a modified cpSRP43. STR30309 has more chlorophyll than Δsrp43 but substantially less than wild type. To further decrease light absorption by photosystem I in STR30309, CAS9 editing was used to stack in disruptions of both LHCA6 and LHCA7 to generate STR30843, which has higher (5-24%) productivities relative to wild type in solar-simulating bioreactors. Maximal productivities required frequent partial harvests throughout the day. For STR30843, exemplary diel bioreactor yields of ~50 g m-2 day-1 were attained. Our results demonstrate diel productivity gains in P. celeri by lowering pigment levels.