Efficient Homolytic Cleavage of H2O2 on Hydroxyl-Enriched Spinel CuFe2O4 with Dual Lewis Acid Sites.

Traditional H2O2 cleavage mediated by macroscopic electron transfer (MET) not only has low utilization of H2O2, but also sacrifices the stability of catalysts. We present a non-redox hydroxyl-enriched spinel (CuFe2O4) catalyst with dual Lewis acid sites to realize the homolytic cleavage of H2O2. The results of systematic experiments, in situ characterizations, and theoretical calculations confirm that tetrahedral Cu sites with optimal Lewis acidity and strong electron delocalization can synergistically elongate the O-O bonds (1.47 Š→ 1.87 Å) in collaboration with adjacent bridging hydroxyl (another Lewis acid site). As a result, the free energy of H2O2 homolytic cleavage is decreased (1.28 eV → 0.98 eV). H2O2 can be efficiently split into ⋅OH induced by hydroxyl-enriched CuFe2O4 without MET, which greatly improves the catalyst stability and the H2O2 utilization (65.2 %, nearly 2 times than traditional catalysts). The system assembled with hydroxyl-enriched CuFe2O4 and H2O2 affords exceptional performance for organic pollutant elimination. The scale-up experiment using a continuous flow reactor realizes long-term stability (up to 600 mL), confirming the tremendous potential of hydroxyl-enriched CuFe2O4 for practical applications.

Bidirectional Enhancement of Nitrogen Removal by Indigenous Synergetic Microalgal-Bacterial Consortia in Harsh Low-C/N Wastewater.

Conventional microalgal-bacterial consortia have limited capacity to treat low-C/N wastewater due to carbon limitation and single nitrogen (N) removal mode. In this work, indigenous synergetic microalgal-bacterial consortia with high N removal performance and bidirectional interaction were successful in treating rare earth tailing wastewaters with low-C/N. Ammonia removal reached 0.89 mg N L-1 h-1, 1.84-fold more efficient than a common microalgal-bacterial system. Metagenomics-based metabolic reconstruction revealed bidirectional microalgal-bacterial interactions. The presence of microalgae increased the abundance of bacterial N-related genes by 1.5- to 57-fold. Similarly, the presence of bacteria increased the abundance of microalgal N assimilation by 2.5- to 15.8-fold. Furthermore, nine bacterial species were isolated, and the bidirectional promotion of N removal by the microalgal-bacterial system was verified. The mechanism of microalgal N assimilation enhanced by indole-3-acetic acid was revealed. In addition, the bidirectional mode of the system ensured the scavenging of toxic byproducts from nitrate metabolism to maintain the stability of the system. Collectively, the bidirectional enhancement system of synergetic microalgae-bacteria was established as an effective N removal strategy to broaden the stable application of this system for the effective treatment of low C/N ratio wastewater.

Insight into the Alkali Resistance Mechanism of FeMoTiOx Catalysts for NH3 Selective Catalytic Reduction of NO: Self-Defense Effects of MoOx for Alkali Capture.

The deactivation of selective catalytic reduction (SCR) catalysts caused by alkali metal poisoning remains an insurmountable challenge. In this study, we examined the impact of Na poisoning on the performance of Fe and Mo co-doped TiO2 (FeaMobTiOx) catalysts in the SCR reaction and revealed the related alkali resistance mechanism. On the obtained Fe1Mo2.6TiOx catalyst, the synergistic catalytic effect of uniformly dispersed FeOx and MoOx species leads to remarkable catalytic activity, with over 90% NO conversion achieved in a wide temperature range of 210-410 °C. During the Na poisoning process, Na ions predominantly adsorb on the MoOx species, which exhibit stronger alkali resistance, effectively safeguarding the FeOx species. This preferential adsorption minimizes the negative effect of Na poisoning on Fe1Mo2.6TiOx. Moreover, Na poisoning has little influence on the Eley-Rideal reaction pathway involving adsorbed NHx reacting with gaseous NOx. After Na poisoning, the Lewis acid sites were deteriorated, while the abundant Brønsted acid sites ensured sufficient NHx adsorption. As a benefit from the self-defense effects of active MoOx species for alkali capture, FeaMobTiOx exhibits exceptional alkali resistance in the SCR reaction. This research provides valuable insights for the design of highly efficient and alkali-resistant SCR catalysts.

Selective anchoring of Pt NPs on covalent triazine-based frameworks via in situ derived bridging ligands for boosting photocatalytic hydrogen evolution.

The efficient and stable production of hydrogen (H2) through Pt-containing photocatalysts remains a great challenge. Herein, we develop an effective strategy to selectively and uniformly anchor Pt NPs (∼1.2 nm) on a covalent triazine-based framework photocatalyst via in situ derived bridging ligands. Compared to Pt/CTF-1, the obtained Pt/AT-CTF-1 exhibits a considerable photocatalytic H2 evolution rate of 562.9 µmol g-1 h-1 under visible light irradiation. Additionally, the strong interaction between the Pt NPs and in situ derived bridging ligands provides remarkable stability to Pt/AT-CTF-1. Experimental investigations and photo/chemical characterization reveal the synergy of the in situ derived bridging ligands in Pt/AT-CTF-1, which can selectively anchor the Pt NPs with homogeneous sizes and efficiently improve the transmission of charge carriers. This work provides a new perspective toward stabilizing ultrasmall nanoclusters and facilitating electron transfer in photocatalytic H2 evolution materials.

Controllable Pyridine N-Oxidation-Nucleophilic Dechlorination Process for Enhanced Dechlorination of Chloropyridines: The Cooperation of HCO4- and HO2.

Dechlorination of chloropyridines can eliminate their detrimental environmental effects. However, traditional dechlorination technology cannot efficiently break the C-Cl bond of chloropyridines, which is restricted by the uncontrollable nonselective species. Hence, we propose the carbonate species-activated hydrogen peroxide (carbonate species/H2O2) process wherein the selective oxidant (peroxymonocarbonate ion, HCO4-) and selective reductant (hydroperoxide anion, HO2-) controllably coexist by manipulation of reaction pH. Taking 2-chloropyridine (Cl-Py) as an example, HCO4- first induces Cl-Py into pyridine N-oxidation intermediates, which then suffer from the nucleophilic dechlorination by HO2-. The obtained dechlorination efficiencies in the carbonate species/H2O2 process (32.5-84.5%) based on the cooperation of HCO4- and HO2- are significantly higher than those in the HO2--mediated sodium hydroxide/hydrogen peroxide process (0-43.8%). Theoretical calculations confirm that pyridine N-oxidation of Cl-Py can effectively lower the energy barrier of the dechlorination process. Moreover, the carbonate species/H2O2 process exhibits superior anti-interference performance and low electric energy consumption. Furthermore, Cl-Py is completely detoxified via the carbonate species/H2O2 process. More importantly, the carbonate species/H2O2 process is applicable for efficient dehalogenation of halogenated pyridines and pyrazines. This work offers a simple and useful strategy to enhance the dehalogenation efficiency of halogenated organics and sheds new insights into the application of the carbonate species/H2O2 process in practical environmental remediation.

Enhancing the Mn-Removal Efficiency of Acid-Mine Bacterial Consortium: Performance Optimization and Mechanism Study.

In this study, an acclimated manganese-oxidizing bacteria (MnOB) consortium, QBS-1, was enriched in an acid mine area; then, it was used to eliminate Mn(Ⅱ) in different types of wastewater. QBS-1 presented excellent Mn removal performance between pH 4.0 and 8.0, and the best Mn-removal efficiency was up to 99.86% after response surface methodology optimization. Unlike other MnOB consortia, the core bacteria of QBS-1 were Stenotrophomonas and Achromobacter, which might play vital roles in Mn removal. Besides that, adsorption, co-precipitation and electrostatic binding by biological manganese oxides could further promote Mn elimination. Finally, the performance of the Mn biofilter demonstrated that QBS-1 was an excellent inoculant, which indicates good potential for removing Mn contamination steadily and efficiently.

miR-3133 inhibits gastrointestinal cancer progression through activation of Hippo and p53 signalling pathways via multi-targets.

BACKGROUND: Malignant cell growth and chemoresistance, the main obstacles in treating gastrointestinal cancer (GIC), rely on the Hippo and p53 signalling pathways. However, the upstream regulatory mechanisms of these pathways remain complex and poorly understood. METHODS: Immunohistochemistry (IHC), western blot and RT-qPCR were used to analyse the expression of RNF146, miR-3133 and key components of Hippo and p53 pathway. CCK-8, colony formation, drug sensitivity assays and murine xenograft models were used to investigate the effect of RNF146 and miR-3133 in GIC. Further exploration of the upstream regulatory mechanism was performed using bioinformatics analysis, dual-luciferase reporter gene, immunoprecipitation assays and bisulfite sequencing PCR (BSP). RESULTS: Clinical samples, in vitro and in vivo experiments demonstrated that RNF146 exerts oncogenic effects in GIC by regulating the Hippo pathway. Bioinformatics analysis identified a novel miRNA, miR-3133, as an upstream regulatory factor of RNF146. fluorescence in situ hybridization and RT-qPCR assays revealed that miR-3133 was less expressed in gastrointestinal tumour tissues and was associated with adverse pathological features. Functional assays and animal models showed that miR-3133 promoted the proliferation and chemotherapy sensitivity of GIC cells. miR-3133 affected YAP1 protein expression by targeting RNF146, AGK and CUL4A, thus activating the Hippo pathway. miR-3133 inhibited p53 protein degradation and extended p53's half-life by targeting USP15, SPIN1. BSP experiments confirmed that miR-3133 promoter methylation is an important reason for its low expression. CONCLUSION: miR-3133 inhibits GIC progression by activating the Hippo and p53 signalling pathways via multi-targets, including RNF146, thereby providing prognostic factors and valuable potential therapeutic targets for GIC.

Co engineered CoP catalyst for photochemical CO2 reduction with accelerated electron transfer endowed by the space-charge region.

Photocatalytic CO2 reduction has been regarded as an ideal method to simulate photosynthesis for achieving carbon neutralization. However, poor charge transfer efficiency limits its development. Herein, an efficient Co/CoP@C catalyst was prepared with compact contact of Co and CoP layer by using MOF as precursor. At the interface of Co/CoP, the difference in functionality between the two phases may result in uneven distribution of electrons, thus forming a self-driven space-chare region. In this region, spontaneous electron transfer is guaranteed, thus facilitating the effective separation of photogenerated carriers as well as boosting the utilization of solar energy. Furthermore, the electron density of active site Co in CoP is increased and more active sites are exposed, which promotes the adsorption and activation of CO2 molecules. Together with suitable redox potential, low energy barrier for *COOH formation and easy desorption of CO, the reduction rate of CO2 catalyzed by Co/CoP@C is 4 times higher than that of CoP@C.

Construction of a transition-metal sulfide heterojunction photocatalyst driven by a built-in electric field for efficient hydrogen evolution under visible light.

Photocatalytic H2 evolution is of prime importance in the energy crisis and in lessening environmental pollution. Adopting a single semiconductor as a photocatalyst remains a formidable challenge. However, the construction of an S-scheme heterojunction is a promising method for efficient water splitting. In this work, CdS nanoparticles were loaded onto NiS nanosheets to form CdS/NiS nanocomposites using hollow Ni(OH)2 as a precursor. The differences in the Fermi energy levels between the two components of CdS and NiS resulted in the formation of a built-in electric field in the nanocomposite. Density functional theory (DFT) calculations reveal that the S-scheme charge transfer driven by the built-in electric field can accelerate the effective separation of photogenerated carriers, which is conducive to efficient photocatalytic hydrogen evolution. The hydrogen evolution rate of the optimized photocatalyst is 39.68 mmol·g-1 h-1, which is 6.69 times that of CdS under visible light. This work provides a novel strategy to construct effective photocatalysts to relieve the environmental and energy crisis.

Development and performance evaluations of an HER-2 kit.

Objective To develop a kit for detecting human epidermal growth factor receptor 2 (HER-2) in the human body. Methods The HER-2 kit was evaluated based on an automated magnetic particle chemiluminescence platform. The kit was developed using the double antibody sandwich-complexation method. Results The kit showed a linear range of 0.01-800 ng/mL, with a linear R2 of >0.999. The limit of the blank was 0.0039 ng/mL, and the precision at 1.00 ng/mL was 9.4%. The recovery rate at 10.00 ng/mL was 97.81-101.81%. The negative serum reference range was 0-8.23 ng/mL. Conclusions The kit had a wide linear range, high accuracy, good precision, and high sensitivity, indicating that it has good application prospects.

Targeted Decomplexation of Metal Complexes for Efficient Metal Recovery by Ozone/Percarbonate.

Traditional methods cannot efficiently recover Cu from Cu(II)-EDTA wastewater and encounter the formation of secondary contaminants. In this study, an ozone/percarbonate (O3/SPC) process was proposed to efficiently decomplex Cu(II)-EDTA and simultaneously recover Cu. The results demonstrate that the O3/SPC process achieves 100% recovery of Cu with the corresponding kobs value of 0.103 min-1 compared with the typical •OH-based O3/H2O2 process (81.2%, 0.042 min-1). The carbonate radical anion (CO3•-) is generated from the O3/SPC process and carries out the targeted attack of amino groups of Cu(II)-EDTA for decarboxylation and deamination processes, resulting in successive cleavage of Cu-O and Cu-N bonds. In comparison, the •OH-based O3/H2O2 process is predominantly responsible for the breakage of Cu-O bonds via decarboxylation and formic acid removal. Moreover, the released Cu(II) can be transformed into stable copper precipitates by employing an endogenous precipitant (CO32-), accompanied by toxic-free byproducts in the O3/SPC process. More importantly, the O3/SPC process exhibits excellent metal recovery in the treatment of real copper electroplating wastewater and other metal-EDTA complexes. This study provides a promising technology and opens a new avenue for the efficient decomplexation of metal-organic complexes with simultaneous recovery of valuable metal resources.

WWP2 drives the progression of gastric cancer by facilitating the ubiquitination and degradation of LATS1 protein.

BACKGROUND: Large tumor suppressor kinase 1 (LATS1), one of the predominant components of the Hippo pathway, has been characterized as a key player controlling the proliferation and invasion of cancer cells, including gastric cancer (GC) cells. However, the mechanism by which the functional stability of LATS1 is modulated has yet to be elucidated. METHODS: Online prediction tools, immunohistochemistry and western blotting assays were used to explore the expression of WW domain-containing E3 ubiquitin ligase 2 (WWP2) in GC cells and tissues. Gain- and loss-of-function assays, as well as rescue experiments were performed to determine the role of the WWP2-LATS1 axis in cell proliferation and invasion. Additionally, the mechanisms involving WWP2 and LATS1 were assessed by coimmunoprecipitation (Co-IP), immunofluorescence, cycloheximide and in vivo ubiquitination assays. RESULTS: Our results demonstrate a specific interaction between LATS1 and WWP2. WWP2 was markedly upregulated and correlated with disease progression and a poor prognosis in GC patients. Moreover, ectopic WWP2 expression facilitated the proliferation, migration and invasion of GC cells. Mechanistically, WWP2 interacts with LATS1, resulting in its ubiquitination and subsequent degradation, leading to increased transcriptional activity of YAP1. Importantly, LATS1 depletion abolished the suppressive effects of WWP2 knockdown on GC cells. Furthermore, WWP2 silencing attenuated tumor growth by regulating the Hippo-YAP1 pathway in vivo. CONCLUSIONS: Our results define the WWP2-LATS1 axis as a critical regulatory mechanism of the Hippo-YAP1 pathway that promotes GC development and progression. Video Abstract.

Synergistically interactive P-Co-N bonding states in cobalt phosphide-decorated covalent organic frameworks for enhanced photocatalytic hydrogen evolution.

Non-noble materials with high efficiency and stability are essential for renewable energy applications. Herein, cobalt phosphide nanoparticles-decorated covalent organic frameworks (CTF-CoP) are synthesized via an in situ self-assembly method combined with the calcination process. In such a configuration, an intimate interaction between CoP and CTF matrix is gained through the Co-N chemical bonds, which not only significantly enhance the recyclability of CoP nanoparticles but also significantly improve the charge separation efficiency. Besides, the synergistically interactive Pδ--Coδ+-Nδ- states induced by the polarization effect of N-anchoring sites benefit for the adsorption and dissociation of water molecules in CTF-CoP. Consequently, CTF-CoP exhibits a higher photocatalytic hydrogen evolution rate (261.7 µmol g-1 h-1) and better durability as compared with the physically fixed CTF/CoP composite (64.8 µmol g-1 h-1) and even the noble metal-based CTF-Pt (191.3 µmol g-1 h-1). This work provides an avenue to construct highly stable non-noble photocatalyst for energy conversion and also emphasizes the potential of CTFs in constructing efficient heterojunctions.

Copper-Catalyzed Radical Hydrazono-Phosphorylation of Alkenes.

An efficient copper-catalyzed radical hydrazono-phosphorylation of alkenes with hydrazine derivatives and diarylphosphine oxides is described. The reaction provides a general and convenient method toward the synthesis of diverse ß-hydrazonophosphine oxides in satisfactory yields. Based on conducted mechanistic experiments, a mechanism involving Ag-catalyzed oxidative generation of phosphinoyl radicals and subsequent addition to alkenes followed by Cu-assisted hydrazonation is proposed. Moreover, the practicability of the reaction is successfully demonstrated by its successful application on a gram scale.

Overcoming Electrostatic Interaction via Strong Complexation for Highly Selective Reduction of CN- into N2.

Limited by the electrostatic interaction, the oxidation reaction of cations at the anode and the reduction reaction of anions at the cathode in the electrocatalytic system nearly cannot be achieved. This study proposes a novel strategy to overcome electrostatic interaction via strong complexation, realizing the electrocatalytic reduction of cyanide (CN- ) at the cathode and then converting the generated reduction products into nitrogen (N2 ) at the anode. Theoretical calculations and experimental results confirm that the polarization of the transition metal oxide cathodes under the electric field causes the strong chemisorption between CN- and cathode, inducing the preferential enrichment of CN- to the cathode. CN- is hydrogenated by atomic hydrogen at the cathode to methylamine/ammonia, which are further oxidized into N2 by free chlorine derived from the anode. This paper provides a new idea for realizing the unconventional and unrealizable reactions in the electrocatalytic system.

Copper-Catalyzed Stereoselective Radical Phosphono-hydrazonation of Alkynes.

A copper-catalyzed stereoselective phosphono-hydrazonation of terminal alkynes with alkyl carbazates and diarylphosphine oxides is described. This methodology provides facile access to a variety of ß-hydrazonophosphine oxides in satisfactory yields. The reaction proceeds under mild conditions and exhibits good functional group tolerance. A mechanism featuring persulfate-mediated oxidative generation of phosphinoyl radicals and copper-assisted hydrazonation is proposed.

Subthreshold Schottky-contacted carbon nanotube network film field-effect transistors for ultralow-power electronic applications.

Ultralow-power electronics is critical to wearable, portable, and implantable applications where the systems could only have access to very limited electrical power supply or even be self-powered. Here, we report on a type of Schottky barrier (SB) contacted single-walled carbon nanotube (SWCNT) network film field-effect-transistors (FETs) that are operated in the subthreshold region to achieve ultralow-power applications. The thin high-k gate dielectric and the overlap between the gate and the source electrodes offer highly efficient gate electrostatic control over the SWCNT channel and the SB at the source contact, resulting in steep subthreshold switching characteristics with a small subthreshold swing (∼67 mV dec-1), a large current on/off ratio (∼106), and a low off-state current (∼0.5 pA). Ap-channel metal-oxide-semiconductor inverter built with the subthreshold SB-SWCNT-FETs exhibits a well-defined logic functionality and small-signal amplification capability under a low supply voltage (∼0.5 V) and an ultralow power (∼0.05 pWµm-1). The low-voltage and deep subthreshold operations reported here could lay an essential foundation for high-performance and ultralow-power SWCNTs-based electronics.

Copper-Catalyzed Cross-Coupling of Alkyl and Phosphorus Radicals for C(sp3)-P Bond Formation.

A CuI-catalyzed cross-coupling of alkyl- and phosphorus-centered radicals for C(sp3)-P bond formation is introduced. Diacyl peroxides, generated in situ from aliphatic acids and H2O2, serve as a source for alkyl radicals and also an initiator for the generation of phosphorus radicals from H-P(O) compounds.

Therapeutic Value of Traditional Chinese Massage plus Moxibustion for Degenerative Knee Osteoarthritis.

Objective: To evaluate the therapeutic value of traditional Chinese massage plus moxibustion for degenerative knee osteoarthritis (DKOA). Methods: From January 2019 to October 2021, 152 patients with DKOA were enrolled. All patients were randomly divided into the treatment group and the control group. The control group was treated with oral glucosamine hydrochloride capsules. The treatment group was treated with traditional Chinese massage and moxibustion on the basis of the control group. The duration of treatment in the two groups was 8 weeks. The effectiveness, visual analog scale (VAS) score, the hospital for special surgery (HSS) score, World Health Organization Quality of Life Scale (WHOQOL-BREF) score, serum high-sensitivity C-reactive protein (CRP), and interleukin-6 (IL-6) levels were compared between the two groups before and after treatment. Results: There were no significant differences in age, sex, and the duration of disease between the two groups (P > 0.05). The overall response rate in the treatment group was significantly higher than that of the control group after treatment (92.1% vs 78.9%; P=0.038); the VAS score of both two groups were significantly decreased, and the VAS score in the treatment group was significantly lower than that of the control group (3.5 ± 1.4 vs 4.8 ± 1.1; P < 0.001); the HSS score and WHOQOL-BREF score significantly improved in both groups, and the HSS score and WHOQOL-BREF score improved more in the treatment group than those of the control group (P < 0.05). The high-sensitivity CRP level significantly decreased in both groups, and the high-sensitivity CRP level in treatment group is lower than that of the control group (2.79 ± 1.65 vs 4.37 ± 1.54; P < 0.001); the IL-6 level was significantly decreased in the treatment group than in the control group (7.22 ± 3.41 vs 4.59 ± 2.98; P < 0.001). Conclusion: Traditional Chinese massage plus moxibustion is worthy of clinical application, which has a significant clinical effect on DKOA, reducing pain and improving knee joint function and quality of life.

Degradation of pesticide wastewater with simultaneous resource recovery via ozonation coupled with anaerobic biochemical technology.

The effective treatment of pesticide wastewater with high organic content, complex composition and high-toxicity has attracted enormous attention of researchers. This work proposes a new idea for removing the pesticide wastewater with simultaneous resource recovery, which is different from the traditional view of mineralization of pesticide wastewater via composite technology. This novel strategy involved a sequential three-step treatment: (a) acidic Ozonation process, to remove the venomous aromatic heterocyclic compounds; (b) hydrolysis and ozonation in alkaline conditions, enhancing the biodegradability of pesticide wastewater, mainly due to the dehalogenation, elimination of C=C bonds and production of low molecular-weight carboxylate anions; (c) the final step is anaerobic biological reactions. Based on the characterizations, this two-stage acidic-alkaline ozonation can efficiently degraded the virulence of pesticide wastewater and enhance its biodegradability from 0.08 to 0.32. The final anaerobic biochemical treatment can stably remove the residuals and convert the low molecular-weight organics into CH4, achieving the resource recovery. This work explored the pH-dependent of ozonized degradation of pesticide wastewater and gives a new perspective of wastewater treatment.