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Effectively converting greenhouse gas CO2 into value-added chemicals, without the need for cocatalysts or solvents, is a vital objective in order to attain carbon neutrality and promote sustainable development. However, achieving this goal continues to pose significant challenges. In this study, the in-situ formed octadentate N5O3 tripodal ligand (H3L) reacts with ZnBr2 and ZnI2 to produce two ionic-type zinc catalysts, [Zn2(L)]2[ZnBr4]·4CH3OH (IZ-1) and [Zn2(L)]I·CH3OH (IZ-2), respectively. In the [Zn2(L)] subunit, the two Zn ions exhibit non-symmetry and are coordinated with the N5O3 ligand in a five- and six-coordinate mode, respectively. Due to the coexistence of Lewis acidic Zn sites and nucleophilic Br- ions, IZ-1 shows remarkable catalytic performance in the cycloaddition of CO2 with epoxides. Under cocatalyst- and solvent-free conditions, it achieves an excellent yield of cyclic carbonates, reaching up to 99 %. The ionic-type zinc catalyst can be readily recovered and reused at least for five times without a noticeable loss in catalytic activity. Mechanistic investigation demonstrates that the improved activity of IZ-1 is attributed to the synergistic effect of Lewis acidic Zn centers and nucleophilic Br-. Moreover, the broad substrate scope of IZ-1 further highlights its versatility and applicability in the cycloaddition reaction.

Incorporating two organic ligands with different functionalities into a titanium-oxo cluster entity simultaneously can endow the material with their respective properties and provide synergistic performance enhancement, which is of great significance for enriching the structure and properties of titanium-oxo clusters (TOCs). However, the synthesis of such TOCs is highly challenging. In this work, we successfully synthesized a TBC4A-functionalized TOC, [Ti2(TBC4A)2(MeO)2] (Ti2; MeOH = methanol, TBC4A = tert-butylcalix[4]arene). By adjusting the solvent system, we successfully introduced 1,10-phenanthroline (Phen) and prepared TBC4A and Phen co-protected [Ti2(TBC4A)2(Phen)2] (Ti2-Phen). Moreover, when Phen was replaced with bulky 4,7-diphenyl-1,10-phenanthroline (Bphen), [Ti2(TBC4A)2(Bphen)2] (Ti2-Bphen), which is isostructural with Ti2-Phen, was obtained, demonstrating the generality of the synthetic method. Remarkably, Ti2-Phen demonstrates good stability and stronger light absorption, as well as superior photoelectric performance compared to Ti2. Density functional theory (DFT) calculations reveal that there exists ligand-to-core charge transfer (LCCT) in Ti2, while an unusual ligand-to-ligand charge transfer (LLCT) is present in Ti2-Phen, accompanied by partial LCCT. Therefore, the superior light absorption and photoelectric properties of Ti2-Phen are attributed to the existence of the unusual LLCT phenomenon. This study not only deeply explores the influence of Phen on the performance of the material but also provides a reference for the preparation of materials with excellent photoelectric performance.

A series of benzofuran and benzo[b]thiophen derivatives was synthesized via a transition-metal-free one-pot process at room temperature. This one-pot protocol enables the synthesis of compounds with high reaction efficiency, mild conditions, simple methods, and a wide-ranging substrate scope. Regioselective five-membered heterocycles were constructed in good-to-excellent yields.

The oxidation of benzyl alcohols is an important reaction in organic synthesis. Traditional methods for benzyl alcohol oxidation have not been widely utilized due to the use of significant amounts of precious metals and environmentally unfriendly reagents. In recent years, electrocatalytic oxidation has gained significant attention, particularly electrochemical anodic oxidation, which offers a sustainable alternative for oxidation without the need for external oxidants or reducing agents. Here, a copper monosubstituted phosphotungstate-based polyacrylate resins (Cu-LPOMs@PPAR) catalyst has been fabricated with immobilization and recyclability using 3D printing technology that can be successfully applied in the electrocatalytic oxidation of benzyl alcohol to benzaldehyde, achieving atom economy and reducing pollution. In this protocol, we obtain benzaldehyde in good yields with excellent functional group toleration under metal-free and oxidant-free conditions. This strategy could provide a new avenue for heterogeneous catalysts in application for enhancing the efficiency and selectivity of electrocatalytic oxidation processes.

Polyoxometalates (POMs) exhibit unique structural characteristics and excellent physical and chemical properties, which have attracted significant attention from scholars in the fields of anticancer research and chemotherapy. Herein, we successfully synthesized and structurally characterized two novel polyoxovanadates (POVs), denoted as POVs-1 and POVs-2, where [M(1-vIM)4]2[VV4O12]·H2O (M: NiII and MnII, 1-vinylimidazole abbreviated as 1-vIM) serve as ligands. The two POVs are isomeric and consist of fundamental structural units, each comprising one [V4O12]4− cluster, two [M(1-vIM)4]2+ cations, and one water molecule. Subsequently, we evaluated the cell viability of human hepatocellular carcinoma (HepG-2) cells treated with the synthesized POVs using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazoliumbromide) assay. And the changes in cell nucleus morphology, mitochondrial membrane potential (Δψm), and reactive oxygen species levels in HepG-2 exposed to POVs were monitored using specific fluorescent staining techniques. Both hybrid POVs showed potent inhibitory activities, induing apoptosis in HepG-2 cells along with significant mitochondria dysfunction and a burst of reactive oxygen species. Notably, the inhibitory effects of POVs-2 were more pronounced than those of POVs-1, which is primarily attributed to the different transition metal ions present. These findings underscore the intricate relationship between the metal components, structural characteristics, and the observed antitumor activities in HepG-2 cells.

Isolation piles are widely used to control the influence of shield tunnelling on adjacent buildings as an effective protective measure. However, the restraint effect of isolation pile on surface settlement trough is rarely explored from the internal mechanism. Firstly, the restraint mechanism of isolation piles is investigated from the pile-soil-tunnel interaction mechanism. Secondly, based on the Melan solution and the Loganathan formula, the analytical solution of surface settlement trough under the influence of adjacent isolation piles is derived. Thirdly, in order to satisfy the engineering analysis scale and reflect the friction characteristics between isolation pile and soil particles simultaneously, the FDM-DEM coupling technique is introduced to establish a numerical model including discrete medium and continuum medium. Finally, the applicability and reliability of the analytical solution and the FDM-DEM coupling numerical solution are verified by comparing field measured data. The results indicate that the surface settlement trough under the influence of isolation piles will have an asymmetric distribution. Surface settlement tends to develop more to the opposite side of the tunnel when isolation piles are pre-installed on one side. The findings of the study have substantial theoretical significance and engineering reference value.