Construction of a Dual-Function Mo-ZIS@Ti for Photocatalytic Benzyl Alcohol Oxidation and Hydrogen Evolution Performance.

The photocatalytic oxidation of benzyl alcohol and the simultaneous evolution of hydrogen from water are efficient dual-optimal routes. It is important to develop composite catalysts that combine redox properties and facilitate electron-hole separation and transport. Herein, the bimetallic-doped Mo-ZIS@Ti photocatalyst was designed and synthesized, and the selective oxidation of benzyl alcohol and hydrogen evolution by water splitting was realized at the same time. Under visible light irradiation, benzyl alcohol was completely converted with more than 99% selectivity for benzaldehyde, and the H2 production rate was 5.6 times higher than the initial ZIS. The exceptional catalytic performance was ascribed to utilizing Ti-MIL-125 as a precursor, wherein slowly releasing-doped Ti formed robust Ti-S bonds that quickly transfer electrons and reduce sites. Meanwhile, doping Mo effectively captures photogenerated holes and acts as active sites for oxidation reactions. Both experimental characterization and work function calculations demonstrate that the bimetallic synergism effectively modulates the electronic structure of ZIS, promotes the directional separation of electrons and holes, and significantly improves the photoactivity and stability of ZIS. This work contributes a route to obtain benzaldehyde and green hydrogen at the same time and also gives new insights for the construction and mechanism study of bimetallic-doping catalysts.

Construction of one-dimensional ZnCdS(EDA)/Ni@NiO for photocatalytic hydrogen evolution.

The development of photocatalysts plays a pivotal role in facilitating the production of green hydrogen energy through water splitting. In this study, one-dimensional (1D) organic-inorganic ZnCdS(EDA)/Ni@NiO (EDA: ethylenediamine) nanorods were prepared by combining organic molecules of EDA into ZnCdS. The EDA molecule possesses two amino functional groups with strong electron-donating capacity, thereby facilitating electron transfer to ZnCdS(EDA)/Ni@NiO and enabling efficient hydrogen evolution through photocatalytic water splitting. The H2 evolution rate of ZnCdS(EDA)/Ni@NiO was 159 µmol g-1 h-1 in the absence of sacrificial agents, and its H2 evolution rate in the system with EDA as the sacrificial agent can reach 5760 µmol g-1 h-1. The combination of EDA, a S vacancy, and heterojunction was proved to be the main factor for improving the separation and transfer rate of photogenerated carriers. The incorporation of ZnCdS(EDA)/Ni@NiO enhances the participation of photogenerated electrons in the photocatalytic hydrogen evolution reaction, thereby improving the overall photocatalytic activity. The synthesis of this one-dimensional composite catalyst holds great potential for advancing the development of efficient photocatalytic materials.

BST2 promotes gastric cancer metastasis under the regulation of HOXD9 and PABPC1.

Gastric cancer (GC) constitutes substantial cancer mortality worldwide. Several cancer types aberrantly express bone marrow stromal cell antigen 2 (BST2), yet its functional and underlying mechanisms in GC progression remain unknown. In our study, RNA sequencing data revealed that BST2 was transcriptionally activated by homeobox D9 (HOXD9). BST2 was significantly upregulated in GC tissues and promoted epithelial-mesenchymal transition and metastasis of GC. BST2 knockdown reversed HOXD9's oncogenic effect on GC metastasis. Moreover, BST2 messenger RNA stability could be enhanced by poly(A) binding protein cytoplasmic 1 (PABPC1) through the interaction between BST2 3'-UTR and PABPC1 in GC cells. PABPC1 promoted GC metastasis, which BST2 silencing attenuated in vitro and in vivo. In addition, positive correlations among HOXD9, BST2, and PABPC1 were established in clinical samples. Taken together, increased expression of BST2 induced by HOXD9 synergizing with PABPC1 promoted GC cell migration and invasion capacity.

Constructing a novel type-â ¡ ZnO/BiOCOOH heterojunction microspheres for the degradation of tetracycline and bacterial inactivation.

A novel ZnO/BiOCOOH microsphere photocatalyst with a type-Ⅱ mechanism was developed for the first time. This strategy was accomplished by immobilizing ZnO onto 3D BiOCOOH microspheres via a single-step hydrothermal synthesis method. The ability to degrade tetracycline (TC) in water under visible light and inactivate bacteria of as-catalyst were analyzed. Among the prepared samples, the ZnO/BiOCOOH composite, with a mass ratio of 40%(Zn/Bi), exhibited the highest photocatalytic activity, which was able to degrade 98.22% of TC in just 90 min and completely eradicated Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) in 48 h, and had potential application in solving water resource environmental pollution. The photoelectric characteristics of the photocatalysts were examined by means of electrochemical impedance spectroscopy (EIS) and photoluminescence (PL) spectroscopy. The findings indicated that the superior photocatalytic performance could be credited to the dissociation of electrons (e-) and holes (h+) in heterojunction composites. Finally, electron paramagnetic resonance (EPR) and capture experiments were conducted to confirm the photocatalytic mechanism of the type-Ⅱ heterojunction. This work provides a new Bi-base photocatalyst for aqueous environmental control.

Construction of ZnxCdyS with a 3D Hierarchical Structure for Enhanced Photocatalytic Hydrogen Production from Water Splitting.

The ZnxCdyS has been proven to have unique photoelectric properties, but its synthesis method and photocatalytic water cracking performance need to be further improved. In this paper, Cd-MOF@ZIF-8 with a MOF-on-MOF (MOF = metal-organic framework) structure was prepared by a simple ion adsorption method. Then, a CdS/ZnxCdyS heterojunction with a 3D hierarchical structure was formed by solvothermal sulfidation. The prepared catalysts with different Zn/Cd ratios show an improved hydrogen production performance for photocatalytic water splitting, and the hydrogen evolution rate of Zn1Cd1S can reach up to 29.2 mmol·g-1·h-1. The excellent photocatalytic activity not only benefits from ZnxCdyS strong light conversion ability but also is closely related to the hierarchical structure and large specific surface area. A type II heterojunction also plays an important role in the spatial separation of photogenerated carriers. This paper provides a simple and feasible idea for the synthesis of a photocatalyst with a large specific surface area using a MOF-on-MOF synthesis strategy.

The VAX2-LINC01189-hnRNPF signaling axis regulates cell invasion and migration in gastric cancer.

Transcription factors (TFs) and long noncoding RNAs (lncRNAs) contribute to gastric cancer (GC). However, the roles of TFs and lncRNAs in the invasion and metastasis of GC remain largely unknown. Here, we observed that the transcription factor VAX2 is significantly upregulated in GC cells and tissues and acts as an oncogene. Moreover, high VAX2 expression is associated with the advancement of tumors in GC. In terms of functionality, the enforced expression of VAX2 promotes the proliferation and metastasis of GC cells. Mechanistically, VAX2 specifically interacts with the LINC01189 promoter and represses LINC01189 transcription. Furthermore, LINC01189 exhibits significant downregulation in GC and functions as a suppressor gene. Functionally, it inhibits migratory and invasive abilities in GC cells. In the context of GC metastasis, VAX2 plays a role in modulating it by trans-repressing the expression of LINC01189. Additionally, LINC01189 binds to hnRNPF to enhance hnRNPF degradation through ubiquitination. The cooperation between LINC01189 and hnRNPF regulates GC cell invasion and migration. In addition, both VAX2 and hnRNPF are highly expressed, while LINC01189 is expressed in at low levels in GC tissues compared to normal gastric tissues. Our study suggests that VAX2 expression facilitates, while LINC01189 expression suppresses, metastasis and that the VAX2-LINC01189-hnRNPF axis plays a contributory role in GC development.

The ATF2/miR-3913-5p/CREB5 axis is involved in the cell proliferation and metastasis of colorectal cancer.

Various miRNAs have been shown to participate in the tumor progression and development of colorectal cancer (CRC). However, the role of miR-3913-5p in CRC are yet to be clearly defined. In the present study, we determine that miR-3913-5p is downregulated in CRC cell lines and CRC tissues. Exogenous miR-3913-5p expression weakens the CRC cells growth, migration and invasion. Mechanistically, miR-3913-5p directly targets the 3'UTR of CREB5. Overexpression of CREB5 reverses the suppression of CRC cells proliferation, migration and invasion induced by miR-3913-5p. Furthermore, ATF2 negatively regulates the transcription of miR-3913-5p by binding to its promoter. CREB5 can cooperate with ATF2. CREB5 is required for ATF2 in regulating miR-3913-5p. Finally, inverse correlations can be found between the expressions of miR-3913-5p and CREB5 or ATF2 in CRC tissues. Thus, a plausible mechanism of ATF2/miR-3913-5p/CREB5 axis regulating CRC progression is elucidated. Our findings suggest that miR-3913-5p functions as a tumor suppressor in CRC. ATF2/miR-3913-5p/CREB5 axis might be a potential therapeutic target against CRC progression.

Desorption of sulfamethoxazole from polyamide 6 microplastics: Environmental factors, simulated gastrointestinal fluids, and desorption mechanisms.

Microplastics (MPs) can enrich pollutants after being released into the environment, and the contaminants-loaded MPs are usually ingested by organisms, resulting in a potential dual biotoxic effect. In this paper, the adsorption behavior of Sulfamethoxazole (SMX) on Polyamide 6 (PA6) MPs was systematically investigated and simulated by the kinetic and isotherm models. The effect of environmental conditions (pH, salinity) on the adsorption process was studied, and the desorption behavior of SMX-loaded PA6 MPs was focused on simulating the seawater, ultrapure water, gastric and intestinal fluids. We found that lower pH and solubilization of SMX by gastrointestinal components (bovine serum albumin (BSA), sodium taurocholate (NaT), and pepsin) can reduce the electrostatic interaction between the surface charge of PA6 MPs and SMX. The result will lead to an increase in the desorption capacity of SMX-loaded PA6 MPs in gastrointestinal fluids and therefore will provide a reasonable mechanism for the desorption of SMX-loaded PA6 MPs in the gastrointestinal fluids. This study will provide a theoretical reference for studying the desorption behavior of SMX-loaded PA6 MPs under gastrointestinal conditions.

Adsorption Behavior of Diclofenac on Polystyrene and Poly(butylene adipate-co-terephthalate) Microplastics: Influencing Factors and Adsorption Mechanism.

To unveil the intricacies surrounding the interaction between microplastics (MPs) and pollutants, diligent investigation is warranted to mitigate the environmental perils they pose. This exposition delves into the sorption behavior and mechanism of diclofenac sodium (DCF), a contaminant, upon two distinct materials: polystyrene (PS) and poly(butylene adipate-co-terephthalate) (PBAT). Experimental adsorption endeavors solidify the observation that the adsorption capacity of DCF onto the designated MPs amounts to Q(PBAT) = 9.26 mg g-1 and Q(PS) = 9.03 mg g-1, respectively. An exploration of the factors governing these discrepant adsorption phenomena elucidates the influence of MPs and DCF properties, environmental factors, as well as surfactants. Fitting procedures underscore the suitability of the pseudo-second-order kinetic and Freundlich models in capturing the intricacies of the DCF adsorption process onto MPs, corroborating the notion that the mentioned process is characterized by non-homogeneous chemisorption. Moreover, this inquiry unveils that the primary adsorption mechanisms of DCF upon MPs encompass electrostatic interaction, hydrogen bonding, and halo hydrogen bonding. An additional investigation concerns the impact of commonly encountered surfactants in aqueous environments on the adsorption of DCF onto MPs. The presence of surfactants elicits modifications in the surface charge properties of MPs, consequently influencing their adsorption efficacy vis-à-vis DCF.

Comparing the adsorption of methyl orange and malachite green on similar yet distinct polyamide microplastics: Uncovering hydrogen bond interactions.

Microplastics (MPs) and dye pollutants are widespread in aquatic environments. Here, the adsorption characteristics of anionic dye methyl orange (MO) and cationic dye malachite green (MG) on polyamide 6 (PA6) and polyamide 66 (PA66) MPs were investigated, including kinetics, isotherm equilibrium and thermodynamics. The co-adsorption of MO and MG under different pH was also evaluated. The results reveal that the adsorption process of MO and MG is suitably expounded by a pseudo-second-order kinetic model. The process can be characterized by two stages: internal diffusion and external diffusion. The isothermal adsorption equilibrium of MO and MG can be effectively described using the Langmuir model, signifying monolayer adsorption. Furthermore, the thermodynamic results indicated that the adsorption was spontaneous with exothermic and endothermic properties, respectively. The results of binary systems reveal that MO dominates the adsorption at low pH (2-5), while MG dominates at high pH (8-10). Strong competitive adsorption was observed between MO and MG in neutral conditions (pH 6-8). The desorption experiments confirm that PA6 and PA66 could serve as potential carriers of MO and MG. The interaction between dyes and polyamide MPs is primarily mediated through hydrogen bonds and electrostatic attraction. The results reveal that PA6 formed more hydrogen bonds with the dyes, resulting in higher adsorption capacity than that of PA66. This difference can be attributed to the disparities in the synthesis process and polymerization method. Our study uncovered the adsorption mechanism of dye pollutants on PA6 and PA66, and provided a more comprehensive theoretical basis for the risk assessment concerning different types of polyamide MPs in aquatic environments.

Excited-State Dynamics in All-Polymer Blends with Polymerized Small-Molecule Acceptors.

Polymerizing small-molecular acceptors (SMAs) is a promising route to construct high performance polymer acceptors of all-polymer solar cells (all-PSCs). After SMA polymerization, the microstructure of molecular packing is largely modified, which is essential in regulating the excited-state dynamics during the photon-to-current conversion. Nevertheless, the relationship between the molecular packing and excited-state dynamics in polymerized SMAs (PSMAs) remains poorly understood. Herein, the excited-state dynamics and molecular packing are investigated in the corresponding PSMA and SMA utilizing a combination of experimental and theoretical methods. This study finds that the charge separation from intra-moiety delocalized states (i-DEs) is much faster in blends with PSMAs, but the loosed π-π molecular packing suppresses the excitation conversion from the local excitation (LE) to the i-DE, leading to additional radiative losses from LEs. Moreover, the increased aggregations of PSMA in the blends decrease donor: acceptor interfaces, which reduces triplet losses from the bimolecular charge recombination. These findings suggest that excited-state dynamics may be manipulated by the molecular packing in blends with PSMAs to further optimize the performance of all-PSCs.

The HOXD9-mediated PAXIP1-AS1 regulates gastric cancer progression through PABPC1/PAK1 modulation.

Long non-coding RNAs (lncRNAs) have been functionally characterised in various diseases. LncRNA PAX-interacting protein 1-antisense RNA 1 (PAXIP1-AS1) has reportedly been associated with cancer development. However, its role in gastric cancer (GC) remains poorly understood. Here, we showed that PAXIP1-AS1 was transcriptionally repressed by homeobox D9 (HOXD9) and was significantly downregulated in GC tissues and cells. Decreased expression of PAXIP1-AS1 was positively correlated with tumour progression, while PAXIP1-AS1 overexpression inhibited cell growth and metastasis both in vitro and in vivo. PAXIP1-AS1 overexpression significantly attenuated HOXD9-enhanced epithelial-to-mesenchymal transition (EMT), invasion and metastasis in GC cells. Poly(A)-binding protein cytoplasmic 1 (PABPC1), an RNA-binding protein, was found to enhance the stability of PAK1 mRNA, leading to EMT progress and GC metastasis. PAXIP1-AS1 was found to directly bind to and destabilise PABPC1, thereby regulating EMT and metastasis of GC cells. In summary, PAXIP1-AS1 suppressed metastasis, and the HOXD9/PAXIP1-AS1/PABPC1/PAK1 signalling axis may be involved in the progression of GC.

The LINC00501-HSP90B1-STAT3 positive feedback loop promotes malignant behavior in gastric cancer cells.

Long non-coding RNAs (lncRNAs) have been implicated in gastric cancer (GC) carcinogenesis and progression. However, the role of LINC00501 in GC growth and metastasis remains unclear. In this study, we found that LINC00501 was frequently upregulated in GC cells and tissues and was closely related to adverse GC clinicopathological features. Aberrant overexpression of LINC00501 promoted GC cell proliferation, invasion, and metastasis both in vitro and in vivo. Mechanistically, LINC00501 stabilized client protein STAT3 from deubiquitylation by directly interacting with cancer chaperone protein HSP90B1. Furthermore, the LINC00501-STAT3 axis modulated GC cell proliferation and metastasis. In turn, STAT3 bound directly to the LINC00501 promoter and positively activated LINC00501 expression, thus forming a positive feedback loop, thereby accelerating tumor growth, invasiveness, and metastasis. In addition, LINC00501 expression was positively correlated with STAT3 and p-STAT3 protein expression levels in gastric clinical samples. Our results reveal that LINC00501 acts as an oncogenic lncRNA and that the LINC00501-HSP90B1-STAT3 positive feedback loop contributes to GC development and progression, suggesting that LINC00501 may be a novel potential biomarker and treatment target for GC.

Dicyandiamide-assisted synthesis of N-doped porous CoMn-Nx@N-C carbon nanotube composites via MOFs as efficient trifunctional electrocatalysts in the same electrolyte.

The development of low-cost, long-term stability, and good oxygen reversible catalytic reaction (ORR/OER) and hydrogen evolution (HER) activity under the same electrolyte concentration of electrocatalytic materials has an important role in the construction of large-scale applications and more valuable sustainable energy systems. Among them, the representative CoMn-Nx@N-C-900-0.2 showed good ORR/OER/HER catalytic activity in 0.1 M KOH alkaline electrolyte, specifically manifested by its half-wave potential E = 0.84 V in the ORR test, which was better than that of commercial Pt/C. The total oxygen electrode activity index of OER/ORR was E = 0.79 V, and it also showed good HER performance. When the current density was 10 mA cm-2, the operating potential was E = -0.266 V. The synergistic effects of the CoMn bimetallic alloy, tubular layered porous structure, which exposed more active area and various nitrogen species such as CoMn-Nx, were the main reasons for the improvement of the trifunctional catalytic performance of electrocatalytic materials. The synthesis strategy and analysis of the electrocatalyst performance provide a new reference for the development of multifunctional materials with high catalytic performance.

Adsorption behavior of UV aged microplastics on the heavy metals Pb(II) and Cu(II) in aqueous solutions.

As the "vector" of heavy metals in the aquatic environment, microplastics (MPs) have a great influence on the migration and transformation of heavy metals. In this study, the adsorption of polypropylene (PP), polyethylene (PE) and polystyrene (PS) on two models of heavy metals after UV aging and environmental variables (ionic coexistence, pH, salinity, and fulvic acid) were comprehensively explored on adsorption. The results show that new oxidation functional groups are formed and their hydrophilicity is enhanced after MPs aging. As a result, the adsorption experiments showed that the adsorption of contaminants by UV aged MPs exceeds that of pristine MPs. The adsorption amounts of Pb(II) and Cu(II) by PP, PE and PS increased by 1.45, 1.46, 1.25 and 1.63, 1.39, 1.22 times, respectively. Adsorption kinetic data were more consistent with the pseudo-second-order kinetic model, proving chemisorption to be the mechanism governing the interaction between metal ions and MPs. The Freundlich model could accurately predict the heavy metal adsorption isotherms on MPs, showing that non-homogeneous multilayer adsorption dominates the process. In Pb(II)-Cu(II) binary composite system, metal ion adsorption capacity on MPs is less than that of the single system adsorption capacity, which proves that there is a specific inhibitory effect between coexisting ions. Additionally, external factors like pH, salinity, and fulvic acid content have a big impact on adsorption behavior. According to mechanism analysis, the adsorption process mainly relies on electrostatic interaction, surface complexation, and van der Waals force.

UV and chemical aging alter the adsorption behavior of microplastics for tetracycline.

This study evaluates the "vector" effects of different microplastics (MPs) on coexisting pollutants. The adsorption of tetracycline was studied on biodegradable plastics poly(butylene adipate-co-terephthalate) (PBAT) and non-biodegradable plastics polystyrene (PS), polypropylene (PP), and polyethylene (PE) after UV aging and chemical aging. The physicochemical properties of PBAT changed more obviously after UV radiation and chemical aging comparing to PS, PP and PE. Pores and cracks appear on the surface of aged PBAT. The crystallinity increased from 29.2% to 52.62%. In adsorption experiments, pristine and aged PBAT had strong vector effects on the adsorption of tetracycline than PS, PP and PE. The adsorption capacity of tetracycline on PBAT was increased from 0.7980 mg g-1 to 1.2669 mg g-1 after chemical aging. The adsorption mechanism indicated that electrostatic interactions and hydrogen bonds contribute to the adsorption process. In addition, for the adsorption of tetracycline on PS, π-π interaction was the main cause, and the adsorption mechanism was not considerably changed by aging. In conclusion, this study demonstrates that biodegradable plastics have substantial vector effect on coexisting pollutants at the end of their life cycle, this contributes to assessment of the risk from microplastic pollution.

Competition adsorption of malachite green and rhodamine B on polyethylene and polyvinyl chloride microplastics in aqueous environment.

Microplastics (MPs) will cause compound pollution by combining with organic pollutants in the aqueous environment. It is important for environmental protection to study the adsorption mechanism of different MPs for pollutants. In this study, the adsorption behaviors of malachite green (MG) and rhodamine B (RhB) on polyethylene (PE) and polyvinyl chloride (PVC) were studied in single systems and binary systems, separately. The results show that in single system, the adsorptions of between MPs for pollutants (MG and RhB) are more consistent with the pseudo-second-order kinetics and Freundlich isotherm model, the adsorption capacity of both MPs for MG is greater than that of RhB. The adsorption capacities of MG and RhB were 7.68 mg/g and 2.83 mg/g for PVC, 4.52 mg/g and 1.27 mg/g for PE. In the binary system, there exist competitive adsorption between MG and RhB on MPs. And the adsorption capacities of PVC for the two dyes are stronger than those of PE. This is attributed to the strong halogen-hydrogen bond between the two dyes and PVC, and the larger specific surface area of PVC. This study revealed the interaction and competitive adsorption mechanism between binary dyes and MPs, which is of great significance for understanding the interactions between dyes and MPs in the multi-component systems.

Precise regulation of defect concentration in MOF and its influence on photocatalytic overall water splitting.

In this work, the defective Cu-BDC with different defect concentration and Cu1+/Cu2+ coordinatively unsaturated sites (CUS) content were designed and synthesized by introducing defective linkers with different pKa values. The low-concentration defects in Metal-organic frameworks (MOFs) structure act as the active sites to enhance their photocatalytic activity. In contrast, the high concentration defects serve as the recombination centers of photogenerated electrons and holes to decrease the transfer efficiency of charge carriers. Cu-BDC-FBA shows an excellent bifunctional photocatalytic performance for overall water splitting due to the suitable defect concentration, which gives an oxygen production rate of 3114 µmol g-1 h-1 and hydrogen production rate of 16 829 µmol g-1 h-1, respectively. It is expected that this study can deepen the understanding of the relationship between defects and photocatalytic activity, and provide a new idea for the design and synthesis of defective MOFs photocatalysts with excellent performance.

Intersystem Crossing in Acceptor-Donor-Acceptor Type Organic Photovoltaic Molecules Promoted by Symmetry Breaking in Polar Environments.

The intramolecular electron push-pulling effect has been widely applied to manipulate the excited states in organic photovoltaic (OPV) molecules toward efficient photocurrent generation in working devices with bias fields. However, the effect of field induced polar environments on the excited-state dynamics remains largely unexplored. Here, we investigate the polar environment effect on excited dynamics in acceptor-donor-acceptor type OPV molecules dissolved in solvents with different polarities. By combining ultrafast transient absorption spectroscopy and quantum chemical computation, we observe the stabilization of excited states induced by symmetry breaking in the polar solvent in the molecules exhibiting strong electron push-pulling effects. The stabilized excited states undergo faster intersystem crossing processes with reduced singlet-triplet energy gaps. The findings suggest that the dynamics of charge generation and recombination may be controlled by manipulating the polar environment and electron push-pulling effect to improve the device performance.