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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 Coupling of Amines with Carbazates: An Approach to Carbamates.

A new approach for the preparation of carbamates via the copper-catalyzed cross-coupling reaction of amines with alkoxycarbonyl radicals generated from carbazates is described. This environmentally friendly protocol takes place under mild conditions and is compatible with a wide range of amines, including aromatic/aliphatic and primary/secondary substrates.

Carbon Nitride Supported High-Loading Fe Single-Atom Catalyst for Activation of Peroxymonosulfate to Generate 1 O2 with 100 % Selectivity.

Singlet oxygen (1 O2 ) is an excellent active species for the selective degradation of organic pollutions. However, it is difficult to achieve high efficiency and selectivity for the generation of 1 O2 . In this work, we develop a graphitic carbon nitride supported Fe single-atoms catalyst (Fe1 /CN) containing highly uniform Fe-N4 active sites with a high Fe loading of 11.2 wt %. The Fe1 /CN achieves generation of 100 % 1 O2 by activating peroxymonosulfate (PMS), which shows an ultrahigh p-chlorophenol degradation efficiency. Density functional theory calculations results demonstrate that in contrast to Co and Ni single-atom sites, the Fe-N4 sites in Fe1 /CN adsorb the terminal O of PMS, which can facilitate the oxidization of PMS to form SO5 .- , and thereafter efficiently generate 1 O2 with 100 % selectivity. In addition, the Fe1 /CN exhibits strong resistance to inorganic ions, natural organic matter, and pH value during the degradation of organic pollutants in the presence of PMS. This work develops a novel catalyst for the 100 % selective production of 1 O2 for highly selective and efficient degradation of pollutants.

Great Divergence Exists in Chinese Provincial Trade-Related CO2 Emission Accounts.

Accurate accounting of greenhouse gas (GHG) emissions considering interregional trade are important for developing regional-specific strategies for climate mitigation in countries like China where vast heterogeneity exists among regions. Trade-related provincial CO2 emission accounts have been reported and analyzed for China using three independently developed multiregional input-output (MRIO) models which have been widely used. Here we show that significant divergence exists in both consumption-based and income-based CO2 emission accounts for Chinese provinces in 2012 using different MRIO models. For example, the difference of CO2 emissions for Shandong Province calculated from two MRIO models can reach 208Mt, more than the terrestrial emissions of Argentina, United Arab Emirates, or The Netherlands. Reducing such divergence, however, requires only the agreement among various MRIO models on a small number of critical data elements. Our results demonstrate the need of careful interpretation of previous studies on trade-related provincial GHG emission accounts in China, and prioritize future efforts to harmonize GHG emission accounting within China.

Asymmetric Coupling of Carbon-Centered Radicals Adjacent to Nitrogen: Copper-Catalyzed Cyanation and Etherification of Enamides.

The first copper-catalyzed asymmetric cyanation and etherification reactions of enamides have been established, where a carbon-centered radical adjacent to a nitrogen atom (CRAN) is enantioselectively trapped by a chiral copper(II) species. Moreover, the asymmetric cyanation of vinyl esters was disclosed as well. These reactions feature very mild reaction conditions and high functional group tolerance, and give a series of chiral α-cyano amides, α-cyano esters and α-hemiaminals in good yields with excellent enantioselectivity. The chiral α-cyano amides can be easily converted into enantioenriched 1,2-diamines and amino acids.

Silver Single Atom in Carbon Nitride Catalyst for Highly Efficient Photocatalytic Hydrogen Evolution.

Single atom catalysts (SACs) with the maximized metal atom efficiency have sparked great attention. However, it is challenging to obtain SACs with high metal loading, high catalytic activity, and good stability. Herein, we demonstrate a new strategy to develop a highly active and stable Ag single atom in carbon nitride (Ag-N2 C2 /CN) catalyst with a unique coordination. The Ag atomic dispersion and Ag-N2 C2 configuration have been identified by aberration-correction high-angle-annular-dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and extended X-ray absorption. Experiments and DFT calculations further verify that Ag-N2 C2 can reduce the H2 evolution barrier, expand the light absorption range, and improve the charge transfer of CN. As a result, the Ag-N2 C2 /CN catalyst exhibits much better H2 evolution activity than the N-coordinated Ag single atom in CN (Ag-N4 /CN), and is even superior to the Pt nanoparticle-loaded CN (PtNP /CN). This work provides a new idea for the design and synthesis of SACs with novel configurations and excellent catalytic activity and durability.

Insights into the Mechanisms and Chemoselectivities of Carbamates and Amides in Reactions Involving Rh(II)-Azavinylcarbene: A Computational Study.

Reactions involving Rh(II)-azavinylcarbenes (Rh(II)-AVCs) to synthesize nitrogen-containing compounds have attracted significant research interest. Despite the importance of these reactions, controlling the chemoselectivities in the reactions involving Rh(II)-AVC remains a challenge. To understand the mechanisms and factors controlling the chemoselectivities between N-H and C═O groups of carbamates and amides in reactions involving Rh(II)-AVC, computational studies were employed. The results reveal that not only the greater nucleophilicity of the N-H group than that of the carbonyl group, but also the presence of H-bonding interactions, could favor the addition of the N-H group of primary carbamates to Rh(II)-AVC. However, for secondary carbamates and amides, they could undergo either chemoselective N-H or C═O addition. Secondary carbamates with less steric hindrance, such as oxazolidinone, prefer the N-H addition mode. However, a switch in chemoselectivity (preference for the C═O addition) was revealed for the sterically hindered secondary carbamates/amides. In addition, a possible O-H addition pathway via the keto-enol tautomerization for isatin and isatoic anhydride was disregarded due to the energetically demanding barrier. Instead, a pathway involving the chemoselective C═O addition, formal [3 + 2] cycloaddition, followed by ring opening was proposed. The origins of the chemoselectivity and the factors responsible were addressed.

Copper-Catalyzed Oxidative sp3-Carbon Radical Cross-Coupling with Trialkylphosphites Leading to α-Phosphonyl 1,3-Dicarbonyl Compounds.

A copper-catalyzed radical Csp3-H/P(OR)3 cross-coupling reaction for the formation of Csp3-P bonds is described. A range of 1,3-dicarbonyl compounds and trialkylphosphites were coupled in this fashion to give the corresponding products in moderate to good yields. This protocol provides direct access to α-phosphonyl 1,3-dicarbonyl compounds.

Dechlorination-Hydroxylation of Atrazine to Hydroxyatrazine with Thiosulfate: A Detoxification Strategy in Seconds.

Hydroxylation of atrazine to nontoxic hydroxyatrazine is generally considered an efficient detoxification method to remediate atrazine-contaminated soil and water. However, previous studies suggested that hydroxylation was not the dominant pathway for atrazine degradation in the hydroxyl radical-generating systems such as Fenton reaction, ozonation and UV/H2O2. Herein we report that the addition of sodium thiosulfate can realize rapid hydroxylation of atrazine to hydroxyatrazine at pH ≤ 4 under room temperature. High resolution mass spectra and isotope experiments results revealed that the hydroxylation of atrazine was involved with nucleophilic substitution and subsequent hydrolysis reaction as follows. HS2O3-, as a species of thiosulfate only at pH ≤ 4, first attacked C atom connecting to chlorine of atrazine to dechlorinate atrazine and produce C8H14N5S2O3-. Subsequently, the S-S bond of C8H14N5S2O3- was cleaved easily to form SO3 and C8H14N5S-. Next, C8H14N5S- was hydrolyzed to generate hydroxyatrazine and H2S. Finally, the comproportionation of SO3 and H2S in situ produced S0 during hydroxylation of atrazine with thiosulfate. This study clarifies the importance of degradation pathway on the removal of pollutants, and also provides a nonoxidative strategy for atrazine detoxification in seconds.