Transformation of ZIF-67 Nanocubes to ZIF-L Nanoframes.

Investigating the process of crystalline transformation in metal-organic frameworks (MOFs) has significant implications in advancing our understanding of the growth mechanisms and design of innovative materials. This study achieves a theoretically impossible transformation direction from three-dimensional (3D) zeolitic imidazolate nanocubes (ZIF) to two-dimensional (2D) ZIF nanoframes through the Marangoni effect in droplets. This transformation challenges the established belief that only a transition from 2D ZIF-L to 3D ZIF-67 is possible, which neglects the reverse process. Finite element analysis indicates that the conversion from 3D ZIF to 2D ZIF is feasible when uniform mass distribution and heat transport are guaranteed under Marangoni flow. This research not only demonstrates an alternative pathway for MOF crystalline transformation but also provides a fresh perspective on the construction of MOF nanoframes.

Constructing Directional Electrostatic Potential Difference via Gradient Nitrogen Doping for Efficient Oxygen Reduction Reaction.

Nitrogen doping has been recognized as an important strategy to enhance the oxygen reduction reaction (ORR) activity of carbon-encapsulated transition metal catalysts (TM@C). However, previous reports on nitrogen doping have tended to result in a random distribution of nitrogen atoms, which leads to disordered electrostatic potential differences on the surface of carbon layers, limiting further control over the materials' electronic structure. Herein, a gradient nitrogen doping strategy to prepare nitrogen-deficient graphene and nitrogen-rich carbon nanotubes encapsulated cobalt nanoparticles catalysts (Co@CNTs@NG) is proposed. The unique gradient nitrogen doping leads to a gradual increase in the electrostatic potential of the carbon layer from the nitrogen-rich region to the nitrogen-deficient region, facilitating the directed electron transfer within these layers and ultimately optimizing the charge distribution of the material. Therefore, this strategy effectively regulates the density of state and work function of the material, further optimizing the adsorption of oxygen-containing intermediates and enhancing ORR activity. Theoretical and experimental results show that under controlled gradient nitrogen doping, Co@CNTs@NG exhibits significantly ORR performance (Eonset = 0.96 V, E1/2 = 0.86 V). At the same time, Co@CNTs@NG also displays excellent performance as a cathode material for Zn-air batteries, with peak power density of 132.65 mA cm-2 and open-circuit voltage (OCV) of 1.51 V. This work provides an effective gradient nitrogen doping strategy to optimize the ORR performance.

Fence-type Molecular Electrocatalysts for High-Performance Lithium-Sulfur Batteries.

Improving the slow redox kinetics of sulfur species and shuttling issues of soluble intermediates induced from the multiphase sulfur redox reactions are crucial factors for developing the next-generation high-energy-density lithium-sulfur (Li-S) batteries. In this study, we successfully constructed a novel molecular electrocatalyst through in situ polymerization of bis(3,4-dibromobenzene)-18-crown-6 (BD18C6) with polysulfide anions on the cathode interface. The crown ether (CE)-based polymer acts as a spatial "fence" to precisely control the unique redox characteristics of sulfur species, which could confine sulfur substance within its interior and interact with lithium polysulfides (LiPSs) to optimize the reaction barrier of sulfur species. The "fence" structure and the double-sided Li+ penetrability of the CE molecule may also prevent the CE catalytic sites from being covered by sulfur during cycling. This new fence-type electrocatalyst mitigates the "shuttle effect", enhances the redox activity of sulfur species, and promotes the formation of three-dimensional stacked lithium sulfide (Li2S) simultaneously. It thus enables lithium-sulfur batteries to exhibit superior rate performance and cycle stability, which may also inspire development facing analogous multiphase electrochemical energy-efficient conversion process.

Phosphate enhanced Cu(II)/peracetic acid process for diclofenac removal: Performance and mechanism.

Since limitedly existing researches suggested Cu(II) had deficiently catalytic ability to PAA, in this work, we tested the oxidation performance of Cu(II)/PAA system on diclofenac (DCF) degradation under neutral conditions. It was found that overwhelming DCF removal could be obtained in Cu(II)/PAA system at pH 7.4 using phosphate buffer solution (PBS) compared to poor loss of DCF without PBS, and the apparent rate constant of DCF removal in PBS/Cu(II)/PAA system was 0.0359 min-1, 6.53 times of that in Cu(II)/PAA system. Organic radicals (i.e., CH3C(O)O• and CH3C(O)OO•) were evidenced as the dominant contributors to DCF destruction in PBS/Cu(II)/PAA system. PBS motivated the reduction of Cu(II) to Cu(I) through chelation effect, and then the activation of PAA by Cu(I) was facilitated. Besides, due to the steric hindrance of Cu(II)-PBS complex (CuHPO4), PAA activation was mediated from non-radical-generating pathway to radical-generating pathway, leading to desirably effective DCF removal by radicals. The transformation of DCF mainly experienced hydroxylation, decarboxylation, formylation and dehydrogenation in PBS/Cu(II)/PAA system. This work proposes the potential of coupling of phosphate and Cu(II) in optimizing PAA activation for organic pollutants elimination.

Progress of NiO-Based Anodes for High-Performance Li-Ion Batteries.

Rechargeable lithium-ion batteries (LIBs) are of great significance to the development of renewable energy. The traditional graphite anode is gradually unable to meet increasing demands for high energy density and power density due to its low theoretical capacity. NiO has gained considerable attention because of its high theoretical capacity, low toxicity, and stable chemical properties. This review summarizes the research progress of NiO-based nanomaterials in LIBs and centers on the electrochemical reaction mechanism, synthesis methods, and strategies for improving the electrochemical properties of NiO anodes. The results demonstrate that the electrochemical characteristics highly depend on the synthesis method, morphology, surface area, conductive substrate, etc. Compared with pure NiO, NiO-based composites including NiO/carbon-based materials and NiO/metal oxide often present higher capacity and cycle stability. Furthermore, challenges and future perspectives of NiO-based anodes are also discussed.

Hierarchically Structured Two-Dimensional Bimetallic CoNi-Hexaaminobenzene Coordination Polymers Derived from Co(OH)2 for Enhanced Oxygen Evolution Catalysis.

Conjugated coordination polymers (CPs) with designable and predictable structures have drawn tremendous attention in recent years. However, the poor electrical conductivity and low structural stability seriously restrict their practical applications in electronic devices. Herein, the rational design and synthesis of a hierarchically structured 2D bimetallic CoNi-hexaaminobenzene CPs derived from Co(OH)2 are reported as an efficient oxygen evolution reaction (OER) self-supported electrode. The as-obtained electrode possesses high electrochemical surface area and intrinsic activity, exhibiting high electrochemical catalytic activity, favorable reaction kinetics performance, and strong durability compared with those of the powder catalysts. As a result, the electrode delivers low overpotential of 219 mV @ 10 mA cm-2 and Tafel slope of 42 mV dec-1 as well as 91.3% retention of current density after 24 h of reaction time. The results of density functional theory computations reveal that the synergistic effect of Co and Ni plays an important role in OER. This work not only presents a strategy to fabricate advanced self-supported electrodes with abundant and dense active sites, but also promotes the development of conjugated CPs for electrocatalysis.

Merging Single-Atom-Dispersed Iron and Graphitic Carbon Nitride to a Joint Electronic System for High-Efficiency Photocatalytic Hydrogen Evolution.

Scalable and sustainable solar hydrogen production via photocatalytic water splitting requires extremely active and stable light-harvesting semiconductors to fulfill the stringent requirements of suitable energy band position and rapid interfacial charge transfer process. Motivated by this point, increasing attention has been given to the development of photocatalysts comprising intimately interfaced photoabsorbers and cocatalysts. Herein, a simple one-step approach is reported to fabricate a high-efficiency photocatalytic system, in which single-site dispersed iron atoms are rationally integrated on the intrinsic structure of the porous crimped graphitic carbon nitride (g-C3 N4 ) polymer. A detailed analysis of the formation process shows that a stable complex is generated by spontaneously coordinating dicyandiamidine nitrate with iron ions in isopropanol, thus leading to a relatively complicated polycondensation reaction upon thermal treatment. The correlation of experimental and computational results confirms that optimized electronic structures of Fe@g-C3 N4 with an appropriate d-band position and negatively shifting Fermi level can be achieved, which effectively gains the reducibility of electrons and creates more active sites for the photocatalytic reactions. As a result, the Fe@g-C3 N4 exhibits a highlighted intramolecular synergistic effect, performing greatly enhanced solar-photon-driven activities, including excellent photocatalytic hydrogen evolution rate (3390 µmol h-1 g-1 , λ > 420 nm) and a reliable apparent quantum efficiency value of 6.89% at 420 nm.

Synthesis of Rice-Husk-Carbon-Supported Nickel Ferrite Catalyst for Reduction of Nitrophenols.

In this paper, magnetic NiFe2O4-RHC (rice husk carbon) catalysts with different NiFe2O4 contents are prepared through a one-step hydrothermal method and employed as a catalyst for the reduction of nitrophenols. The resulting catalysts are characterized using various techniques. It is indicated that the NiFe2O4 nanoparticles are well dispersed on the RHC with the average size of 9.97 nm and 224.13 m²·g-1 BET surface area. NiFe2O4-RHC (0.75) has the highest activity for the reduction of nitrophenols (k = 0°8872 min-1). The combination of NiFe2O4 nanoparticles with RHC results in a dramatic conversion of the inert NiFe2O4 into a highly active catalyst for the reduction of nitrophenols at 25 °C employing NaBH4 as the reducing agent in aqueous medium. The excellent catalytic performance of NiFe2O4-RHC (0.75) may be attributed to the specific characteristics of the nanostructure and the synergistic effect between NiFe2O4 and RHC. The effect of the substituent and temperature are also investigated. The activation energy was reduced to 15.342 kJ mol-1, facilitating the reaction at lower temperature. Furthermore, the catalyst NiFe2O4-RHC (0.75) is very cheap when RHC is introduced as the support compared to other carbon materials. The catalyst also exhibits magnetic performance and good stability; it can be used for 10 successive experiments with a conversion of 96%.

ZnGaNO Photocatalyst Particles Prepared from Methane-Based Nitridation Using Zn/Ga/CO3 LDH as Precursor.

Methane-based nitridation was employed to produce wurtzite zinc-gallium oxynitride (ZnGaNO) photocatalyst particles using Zn/Ga/CO3 layered double hydroxides (LDHs) as precursor. Introduction of methane to nitridation would promote the formation of Zn-O bonding and suppress shallow acceptor complexes such as V(Zn)-Ga(Zn) and Ga-Oi in ZnGaNO particles. On the other hand, high flow rate of methane would induce breaking of Ga-N bonding and enhance surface deposition of metallic Ga atoms. After loading with Rh and RuO2, ZnGaNO particles had free electron density in an order of S50 > S20 > S90 > S0, which correlated well with their photocatalytic performance upon visible-light irradiation. The best performance of the loaded S50 was ascribed to the relatively flat surface band bending of the particle. Methane-based nitridation of Zn/Ga/CO3 LDHs would provide a new route to tune the surface chemistry of ZnGaNO and enhance the photocatalytic performance to its full potential.

Alcohol Dehydrogenases and Acetaldehyde Dehydrogenases are Beneficial for Decidual Stromal Cells to Resist the Damage from Alcohol.

Aims: The aim of this study was to examine the effect of alcohol on the decidualization of human endometrial stromal cells during early pregnancy. Methods: During in vitro decidualization, human endometrial stromal cells were treated with alcohol, 4-methylpyrazole hydrochloride (FPZ), the inhibitor of alcohol dehydrogenases (ADHs), and tetraethylthiuram disulfide (DSF), the inhibitor of acetaldehyde dehydrogenases (ALDHs), respectively. Cell viability and decidualization were examined. Apoptosis and proliferation were also evaluated. Results: The findings showed that ADHs and ALDHs were up-regulated during decidualization. After alcohol treatment, the cell viability of decidual stromal cells was significantly higher than control, which was abrogated by FPZ or DSF. When cells were treated with alcohol, proliferation-related signal pathways were up-regulated in decidualized cells. Additionally, FOXO1 transcriptionally up-regulates ADH1B. Conclusion: Our study provided an evidence that highly expressed ADHs and ALDHs endow decidual stromal cells an ability to alleviate the harm from alcohol.

Identification of gene expression changes in rabbit uterus during embryo implantation.

Embryo implantation in the rabbit is unique in that a typical fusion type of implantation is employed, in which trophoblast cells adhere and fuse to the apical surface of uterine epithelial cells. In the present study, we analyzed global gene expression changes in the rabbit uterus during embryo implantation by using RNA-seq. We identified a total of 536 differentially expressed genes (fold change >2 and adjusted p-value <0.01), of which 266 genes were down-regulated and 270 genes were up-regulated at the implantation site compared to the inter-implantation site. Functional clustering revealed that cell adhesion is among top ranked enriched terms from both gene ontology and pathway analysis, highlighting the importance of cell adhesion during embryo implantation in rabbits. Through gene network analysis, we prioritized 9 genes using the hub gene method. Our study provides a valuable resource for in-depth understanding of the mechanism underlying embryo implantation in rabbits.

Efficient prediction of progesterone receptor interactome using a support vector machine model.

Protein-protein interaction (PPI) is essential for almost all cellular processes and identification of PPI is a crucial task for biomedical researchers. So far, most computational studies of PPI are intended for pair-wise prediction. Theoretically, predicting protein partners for a single protein is likely a simpler problem. Given enough data for a particular protein, the results can be more accurate than general PPI predictors. In the present study, we assessed the potential of using the support vector machine (SVM) model with selected features centered on a particular protein for PPI prediction. As a proof-of-concept study, we applied this method to identify the interactome of progesterone receptor (PR), a protein which is essential for coordinating female reproduction in mammals by mediating the actions of ovarian progesterone. We achieved an accuracy of 91.9%, sensitivity of 92.8% and specificity of 91.2%. Our method is generally applicable to any other proteins and therefore may be of help in guiding biomedical experiments.

A Transcriptomic Study of Maternal Thyroid Adaptation to Pregnancy in Rats.

Thyroid disorders are relatively frequently observed in pregnant women. However, the impact of pregnancy on maternal thyroid has not been systematically evaluated. In the present study, using the rat as an animal model, we observed that the weight of maternal thyroid increased by about 18% in late pregnancy. To gain an insight into the molecular mechanisms, we took advantage of RNA-seq approaches to investigate global gene expression changes in the maternal thyroid. We identified a total of 615 differentially expressed genes, most of which (558 genes or 90.7%) were up-regulated in late pregnancy compared to the non-pregnant control. Gene ontology analysis showed that genes involved in cell cycle and metabolism were significantly enriched among up-regulated genes. Unexpectedly, pathway analysis revealed that expression levels for key components of the thyroid hormone synthesis pathway were not significantly altered. In addition, by examining of the promoter regions of up-regulated genes, we identified MAZ (MYC-associated zinc finger protein) and TFCP2 (transcription factor CP2) as two causal transcription factors. Our study contributes to an increase in the knowledge on the maternal thyroid adaptation to pregnancy.

Super-twisting sliding mode control for neutral point voltage of three-phase four-wire inverter based on SiC/Si hybrid switch.

The three-phase four-wire voltage source inverter (3P4W VSI) is widely used in applications like uninterrupted power supply (UPS) and bidirectional onboard charger. The increasing power density demand requires higher switching frequency and lower switching loss. To fulfill the conflicting objectives, two-fold methodology is proposed in this paper: 1) SiC/Si hybrid switches (HyS) together with recently reported gate trigger are reported for the first time in the 3P4W VSI; 2) the natural point voltage is controlled to track a sinusoidal voltage with the frequency equal to 3 times of fundamental frequency in order to achieve higher DC-bus voltage utilization rate, and further reduce the switching loss. The traditional PI controller is very hard to achieve desired performance due to both the nonlinearity and the variant reference of the natural point voltage control system. Thereby, the super-twisting sliding mode control (ST-SMC) is proposed in this paper to achieve desired tracking performance and fast dynamic response. The effectiveness and superiority of the system are verified by both simulation and experiment comparison with the existing methods using a 5 kW prototype.

Bimetallic metal-organic framework as a high-performance peracetic acid activator for sulfamethoxazole degradation.

A novel 3D bimetallic metal-organic framework (MOF(Fe-Co)) was successfully prepared and its performance on sulfamethoxazole (SMX) removal in advanced oxidation process (AOP) based on peracetic acid (PAA) was evaluated. MOF(Fe-Co) exhibited an efficient catalytic performance on PAA activation for SMX degradation under neutral condition. Increasing PAA concentration could enhance SMX removal, while the variation of MOF(Fe-Co) dosage from 0.05 to 0.2 g/L had an inappreciable effect on SMX removal. According to the results of inductively coupled plasma mass spectrometry analyses and X-ray photoelectron spectroscopy, catalytic reactions mainly occurred on the surface of MOF(Fe-Co). Organic radicals (i.e., CH3C(O)OO• and CH3C(O)O•) were demonstrated to be the predominant reactive radicals for SMX degradation by MOF(Fe-Co)/PAA through radical quenching experiments. The presence of Cl- could enhance the degradation of SMX by MOF(Fe-Co)/PAA, while HCO3- and natural organic matter inhibited SMX degradation severely. Five identified degradation products were detected in this system and four possible SMX transformation pathways were proposed, including amino oxidation, S-N bond cleavage, coupling reaction and hydroxylation.

Aldehyde group pendant-grafted pectin-based injectable hydrogel.

Periodate oxidation has been the widely accepted route for obtaining aldehyde group-functionalized polysaccharides but significantly influenced the various physicochemical properties due to the ring opening of the backbone of polysaccharides. The present study, for the first time, presents a novel method for the preparation of aldehyde group-functionalized polysaccharides that could retain the ring structure and the consequent rigidity of the backbone. Pectin was collected as the representative of polysaccharides and modified with cyclopropyl formaldehyde to obtain pectin aldehyde (AP), which was further crosslinked by DL-lysine (LYS) via the Schiff base reaction to prepare injectable hydrogel. The feasibility of the functionalization was proved by FT-IR and 1H NMR techniques. The obtained hydrogel showed acceptable mechanical properties, self-healing ability, syringeability, and sustained-release performance. Also, as-prepared injectable hydrogel presented great biocompatibility with a cell proliferation rate of 96 %, and the drug-loaded hydrogel exhibited clear inhibition of cancer cell proliferation. Overall, the present study showed a new method for the preparation of aldehyde group-functionalized polysaccharides, and the drug-loaded hydrogel has potential in drug release applications.

Heat-activated peracetic acid for degradation of diclofenac: kinetics, influencing factors and mechanism.

ABSTRACTHeat-activated peracetic acid (PAA) was used to degrade diclofenac (DCF) in this study. Electron paramagnetic resonance and radical scavenging experiments proved that organic radicals (i.e. CH3C(=O)O• and CH3C(=O)OO•) were the primary active species for DCF removal in the heat/PAA process. The degradation efficiency of DCF increased with the increase of temperature or initial PAA concentration in the heat/PAA process, and the optimal reaction pH for DCF removal was neutral. The presence of NO3- or SO42- insignificantly affected DCF degradation, while Cl- was favourable for DCF removal in this process. In contrast, an obvious inhibition on the removal of DCF was observed with the addition of natural organic matter, which might be responsible for the lower DCF removal in real waters. Finally, dechlorination, formylation, dehydrogenation and hydroxylation were proposed to be four degradation pathways of DCF in the heat/PAA system based on the five detected transformation products.

Construction of the comprehensive evaluation system of waterbody pollution degree and the response of sedimentary microbial community.

This study proposed and established a comprehensive evaluation system for the pollution degree of the waterbody by taking overlying water and sediment as a whole. By dividing different sampling points into three gradients according to the pollution degree, the changes in sedimentary microbes under various pollution gradients were compared. The results showed that microbial diversity, abundance and specific OTUs decreased significantly with the increase in pollution degree. Meanwhile, Firmicutes, Bacteroidota and Caldiseriota increased in the severely polluted group, while Chloroflexi and Acidobacteriota decreased. Spearman correlation analysis and co-occurrence network revealed that COD, pH in overlying water, and Mn, Fe in sediments were the most significant pollution degree evaluation indicators affecting sedimentary microorganisms, which drove the sedimentary microbial communities dominated by Proteobacteria and Firmicutes. FAPROTAX functional prediction indicated that increased pollution levels led to the weakening of functional genes related to nitrogen metabolism and sulfur metabolism and the increase of functional genes related to carbon metabolism in sediment microorganisms. This study not only provided new insights into waterbody pollution evaluation but also verified the feasibility of this evaluation method by the response of sedimentary microbial communities to different pollution degrees.

Tuning the Coordination Environment of Carbon-Based Single-Atom Catalysts via Doping with Multiple Heteroatoms and Their Applications in Electrocatalysis.

Carbon-based single-atom catalysts (SACs) are considered to be a perfect platform for studying the structure-activity relationship of different reactions due to the adjustability of their coordination environment. Multi-heteroatom doping has been demonstrated as an effective strategy for tuning the coordination environment of carbon-based SACs and enhancing catalytic performance in electrochemical reactions. Herein, recently developed strategies for multi-heteroatom doping, focusing on the regulation of single-atom active sites by heteroatoms in different coordination shells, are summarized. In addition, the correlation between the coordination environment and the catalytic activity of carbon-based SACs are investigated through representative experiments and theoretical calculations for various electrochemical reactions. Finally, concerning certain shortcomings of the current strategies of doping multi-heteroatoms, some suggestions are put forward to promote the development of carbon-based SACs in the field of electrocatalysis.

Degradation of organic pollutants through activating bisulfite with lanthanum ferrite-loaded biomass carbon.

The removal of methylene blue (MB) in water is a challenging task due to its toxicity, carcinogenicity and resistance to biodegradation. Accordingly, a novel composite catalyst (BC@LF) was prepared by loading lanthanum ferrite (LaFeO3) on biomass carbon (BC) to activate bisulfite (BS) for methylene MB removal in this study. Characterization via scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) indicated that LaFeO3 was successfully loaded on BC. X-ray photoelectron spectroscopy (XPS) analysis suggested that [triple bond, length as m-dash]Fe(iii) was the main active site for BS activation. It was found that 99.4% MB was removed within 60 min in BC@LF/BS system. Sulfate radical (SO4˙-) and hydroxyl radicals (HO˙) were proved to be responsible for MB removal in the BC@LF/BS system and SO5˙- might also be involved in MB removal. The degradation efficiency of MB in the BC@LF/BS system decreased with increasing pH, while the adsorption efficiency of BC@LF for MB improved with increasing pH. Additionally, BC@LF exhibited good reusability for BS activation in successive uses. The BC@LF/BS system exhibited favorable removal effect for various organic compounds, indicating that it has good applicability in the treatment of organic wastewater.