Stabilization of Cuδ+ Sites Within MnO2 for Superior Urea Electro-Synthesis.

Electrocatalytic C-N coupling between NO3 - and CO2 has emerged as a sustainable route for urea production. However, identifying catalytic active sites and designing efficient electrocatalysts remain significant challenges. Herein, the synthesis of Cu-doped MnO2 nanotube (denoted as Cu-MnO2) with stable Cuδ+-oxygen vacancies (Ovs)-Mn3+ dual sites is reported. Compared with pure MnO2, Cuδ+ doping can effectively enhance urea production performance in the co-reduction of CO2 and NO3 -. Thus, Cu-MnO2 catalyst exhibits a maximum Faradaic efficiency (FE) of 54.7% and the highest yield rate of 116.7 mmol h-1 gcat. -1 in a flow cell. Remarkably, the urea yield rate remains over 78 mmol h-1 gcat. -1 across a wide potential range. Further experimental and theoretical results elucidate the unique role of Cu-MnO2 solid-solution for stabilizing Cuδ+ sites in Cuδ+-Ovs-Mn3+, endowing the catalyst with superior structural and electrochemical stabilities. This thermodynamically promotes urea formation and kinetically lowers the energy barrier of C-N coupling.

A novel route of intercellular copper transport and detoxification in oyster hemocytes.

Bivalve hemocytes are oyster immune cells composed of several cellular subtypes with different functions. Hemocytes accumulate high concentrations of copper (Cu) and exert critical roles in metal sequestration and detoxification in oysters, however the specific biochemical mechanisms that govern this have yet to be fully uncovered. Herein, we demonstrate that Cu(I) is predominately sequestered in lysosomes via the Cu transporter ATP7A in hemocytes to reduce the toxic effects of intracellular Cu(I). We also found that Cu(I) is translocated along tunneling nanotubes (TNTs) relocating from high Cu(I) cells to low Cu(I) cells, effectively reducing the burden caused by overloaded Cu(I), and that ATP7A facilitates the efflux of intracellular Cu(I) in both TNTs and hemocyte subtypes. We identify that elevated glutathione (GSH) contents and heat-shock protein (Hsp) levels, as well as the activation of the cell cycle were critical in maintaining the cellular homeostasis and function of hemocytes exposed to Cu. Cu exposure also increased the expression of membrane proteins (MYOF, RalA, RalBP1, and cadherins) and lipid transporter activity which can induce TNT formation, and activated the lysosomal signaling pathway, promoting intercellular lysosomal trafficking dependent on increased hydrolase activity and ATP-dependent activity. This study explores the intracellular and intercellular transport and detoxification of Cu in oyster hemocytes, which may help in understanding the potential toxicity and fate of metals in marine animals.

Copper redox state in cells and aquatic organisms: Implication for toxicity.

Copper (Cu) redox state has been an important issue in biology and toxicology research, but many research gaps remain to be explored due to the limitations in the detecting techniques. Herein, the regulation of Cu homeostasis, including absorption, translocation, utilization, storage, and elimination behavior is discussed. Cuproptosis, a newly identified type of cell death caused by excessive Cu accumulation, which results in the aggregation of DLAT protein or the loss of Fe-S cluster and finally proteotoxic stress, is reviewed. Several longstanding mysteries of diseases such as Wilson disease and toxic effects, may be attributed to cuproptosis. Furthermore, we review the advanced detection methods and application of Cu(I) and Cu(II), especially the in-situ imaging techniques such as XANES, and chemosensors. Most of the existing studies using these detection techniques focus on the bioaccumulation and toxicity of Cu(I) and Cu(II) in cells and aquatic organisms. Finally, it will be important to identify the roles of Cu(I) and Cu(II) in the growth, development, and diseases of organisms, as well as the relationship between bioaccumulation and toxicity of Cu(I) and Cu(II) in cellular and aquatic toxicology.

Bottom-up Growth of Convex Sphere with Adjustable Cu(0)/Cu(I) Interfaces for Effective C2 Production from CO2 Electroreduction.

One challenge confronting the Cu2O catalysts in the electrocatalysis of carbon dioxide reduction reaction (CO2RR) is the reduction of active Cu(I) species, resulting in low selectivity and quick deactivation. In this study, we for the first time introduce a bottom-up growth of convex sphere with adjustable Cu(0)/Cu(I) interfaces (Cux@Cu2O convex spheres). Interestingly, the interfaces are dynamically modulated by varying hydrothermal time, thus regulating the conversion of C1 and C2 products. In particular, the 4 h hydrothermal treatment applied to Cu0.25@Cu2O convex sphere with the favorable Cu(0)/Cu(I) interface results in the highest selectivity for C2 products (90.5 %). In situ Fourier-transform infrared spectroscopy measurements and density functional theory calculations reveal that the Cu(0)/Cu(I) interface lowers the energy barrier for the production of ethylene and ethanol while increasing the coverage of localized *CO adsorbate for increased dimerization. This work establishes a novel approach for transforming the state of valence-sensitive electrocatalysts into high-value energy-related engineering products.

Development of Novel Immobilized Copper-Ligand Complex for Click Chemistry of Biomolecules.

Copper-catalyzed azide-alkyne cycloaddition click (CuAAC) reaction is widely used to synthesize drug candidates and other biomolecule classes. Homogeneous catalysts, which consist of copper coordinated to a ligand framework, have been optimized for high yield and specificity of the CuAAC reaction, but CuAAC reaction with these catalysts requires the addition of a reducing agent and basic conditions, which can complicate some of the desired syntheses. Additionally, removing copper from the synthesized CuAAC-containing biomolecule is necessary for biological applications but inconvenient and requires additional purification steps. We describe here the design and synthesis of a PNN-type pincer ligand complex with copper (I) that stabilizes the copper (I) and, therefore, can act as a CuAAC catalyst without a reducing agent and base under physiologically relevant conditions. This complex was immobilized on two types of resin, and one of the immobilized catalyst forms worked well under aqueous physiological conditions. Minimal copper leaching was observed from the immobilized catalyst, which allowed its use in multiple reaction cycles without the addition of any reducing agent or base and without recharging with copper ion. The mechanism of the catalytic cycle was rationalized by density functional theory (DFT). This catalyst's utility was demonstrated by synthesizing coumarin derivatives of small molecules such as ferrocene and sugar.

Dual Role of a Novel Heteroleptic Cu(I) Complex in Visible-Light-Driven CO2 Reduction.

A novel mononuclear Cu(I) complex was synthesized via coordination with a benzoquinoxalin-2'-one-1,2,3-triazole chelating diimine and the bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), to target a new and efficient photosensitizer for photocatalytic CO2 reduction. The Cu(I) complex absorbs in the blue-green region of the visible spectrum, with a broad band having a maximum at 475 nm (ϵ =4500 M-1 cm-1), which is assigned to the metal-to-ligand charge transfer (MLCT) transition from the Cu(I) to the benzoquinoxalin-2'-one moiety of the diimine. Surprisingly, photo-driven experiments for the CO2 reduction showed that this complex can undergo a photoinduced electron transfer with a sacrificial electron donor and accumulate electrons on the diimine backbone. Photo-driven experiments in a CO2 atmosphere revealed that this complex can not only act as a photosensitizer, when combined with an Fe(III)-porphyrin, but can also selectively produce CO from CO2. Thus, owing to its charge-accumulation properties, the non-innocent benzoquinoxalin-2-one based ligand enabled the development of the first copper(I)-based photocatalyst for CO2 reduction.

Asymmetric Cu(I)─W Dual-Atomic Sites Enable C─C Coupling for Selective Photocatalytic CO2 Reduction to C2H4.

Solar-driven CO2 reduction into value-added C2+ chemical fuels, such as C2H4, is promising in meeting the carbon-neutral future, yet the performance is usually hindered by the high energy barrier of the C─C coupling process. Here, an efficient and stabilized Cu(I) single atoms-modified W18O49 nanowires (Cu1/W18O49) photocatalyst with asymmetric Cu─W dual sites is reported for selective photocatalytic CO2 reduction to C2H4. The interconversion between W(V) and W(VI) in W18O49 ensures the stability of Cu(I) during the photocatalytic process. Under light irradiation, the optimal Cu1/W18O49 (3.6-Cu1/W18O49) catalyst exhibits concurrent high activity and selectivity toward C2H4 production, reaching a corresponding yield rate of 4.9 µmol g-1 h-1 and selectivity as high as 72.8%, respectively. Combined in situ spectroscopies and computational calculations reveal that Cu(I) single atoms stabilize the *CO intermediate, and the asymmetric Cu─W dual sites effectively reduce the energy barrier for the C─C coupling of two neighboring CO intermediates, enabling the highly selective C2H4 generation from CO2 photoreduction. This work demonstrates leveraging stabilized atomically-dispersed Cu(I) in asymmetric dual-sites for selective CO2-to-C2H4 conversion and can provide new insight into photocatalytic CO2 reduction to other targeted C2+ products through rational construction of active sites for C─C coupling.

A green reaction-based turn-off fluorescence sensor for determination of copper ions: DFT calculations, quenching mechanism, green chemistry metrics, and application in environmental samples.

When Cu(II) reacts with ascorbic acid (AA) to form Cu(I), Cu(I) can combine with eosin Y (EY) to form ionic associations, resulting in significant fluorescence quenching of the EY. Based on the turn-off of fluorescence in the chemosensor EY, a green reaction is proposed herein for the detection of Cu(II). The novel detection method for Cu(II) demonstrates simplicity, high sensitivity, and excellent selectivity, rendering it suitable for analyzing environmental samples. A static fluorescence quenching mechanism is validated through the Stern-Volmer relationship, and the thermodynamic parameters of the reaction are explored using a van 't Hoff plot. The reaction mechanism is investigated via fluorescence spectra, absorption spectra, and density-functional theory (DFT) calculations. The probe's green nature is confirmed by applying four green analytical chemistry metrics.

[Effects of Biochar on Growth and Pollutant Accumulation of Lettuce in Soil Co-contaminated with Tetracycline and Copper].

Through lettuce potting experiments, the effects of different types of biochar (apple branch, corn straw, and modified sorghum straw biochar with phosphoric acid modification) on lettuce growth under tetracycline (TC) and copper (Cu) co-pollution were investigated. The results showed that compared with those under CK, the addition of biochar treatment significantly increased the plant height, root length, shoot fresh weight, and root fresh weight of lettuce (P < 0.05). The addition of different biochars significantly increased the nitrate nitrogen, chlorophyll, and soluble protein content in lettuce physiological indicators to varying degrees, while also significantly decreasing the levels of malondialdehyde, proline content, and catalase activity. The effects of biochar on lettuce physiological indicators were consistent during both the seedling and mature stages. Compared with those in CK, the addition of biochar resulted in varying degrees of reduction in the TC and Cu contents of both the aboveground and underground parts of lettuce. The aboveground TC and Cu levels decreased by 2.49%-92.32% and 12.79%-36.47%, respectively. The underground TC and Cu levels decreased by 12.53%-55.64% and 22.41%-42.29%, respectively. Correlation analysis showed that nitrate nitrogen, chlorophyll, and soluble protein content of lettuce were negatively correlated with TC content, whereas malondialdehyde, proline content, and catalase activity were positively correlated with TC content. The resistance genes of lettuce were positively correlated with TC content (P < 0.05). In general, modified biochar was found to be more effective in improving lettuce growth quality and reducing pollutant accumulation compared to unmodified biochar, with modified sorghum straw biochar showing the best remediation effect.

Study of CHF3/CH2F2 Adsorption Separation in TIFSIX-2-Cu-i.

Hydrofluorocarbons (HFCs) have important applications in different industries; however, they are environmentally unfriendly due to their high global warming potential (GWP). Hence, reclamation of used hydrofluorocarbons via energy-efficient adsorption-based separation will greatly contribute to reducing their impact on the environment. In particular, the separation of azeotropic refrigerants remains challenging, such as typical mixtures of CH2F2 (HFC-23) and CHF3 (HFC-32), due to a lack of adsorptive mechanisms. Metal-organic frameworks (MOFs) can provide a promising solution for the separation of CHF3-CH2F2 mixtures. In this study, the adsorption mechanism of CHF3-CH2F2 mixtures in TIFSIX-2-Cu-i was revealed at the microscopic level by combining static pure-component adsorption experiments, molecular simulations, and density-functional theory (DFT) calculations. The adsorption separation selectivity of CH2F2/CHF3 in TIFSIX-2-Cu-i is 3.17 at 3 bar under 308 K. The existence of similar TiF62- binding sites for CH2F2 or CHF3 was revealed in TIFSIX-2-Cu-i. Interactions between the fluorine atom of the framework and the hydrogen atom of the guest molecule were found to be responsible for determining the high adsorption separation selectivity of CH2F2/CHF3. This exploration is important for the design of highly selective adsorbents for the separation of azeotropic refrigerants.