Crystal-Plane-Engineered TiO2-Anchored Vanadium Single Atoms and Clusters for Boosting Ultradeep Aerobic Oxidative Desulfurization of Diesel.

The crystal plane effect has gained extensive attention in heterogeneous catalysis reactions; however, it is far from being systematically probed in titanium dioxide (TiO2)-supported vanadium catalysts. Herein, a series of vanadium (V) single atoms and clusters anchored on TiO2 with different crystal planes was fabricated by an improved "top-down" protocol. The dispersion state, electronic structure, and redox properties of the V single-atom and VOx cluster-supported catalysts were systematically analyzed by a series of characterization methods, including X-ray absorption near edge structure (XANES) and density functional theory (DFT) calculations, and their catalytic performances were examined for aerobic oxidative desulfurization (AODS) of 4,6-dimethyl-dibenzothiophen (4,6-DMDBT) with O2 as the oxidant. The results unveiled that the synergistic effect between the V single atom and the VOx cluster perceptibly promoted the catalytic performances of VOx/TiO2 samples. Therein, VOx/TiO2-(001) shows the lowest apparent activation energy (Ea) value of 46.3 kJ/mol and the optimal AODS performance with complete 4,6-DMDBT conversion to 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) within 60 min at 120 °C as compared with VOx/TiO2-(101) (81.9 kJ/mol and 180 min) and VOx/TiO2-(100) (68.0 kJ/mol and 240 min), which should be attributed to its higher V5+/V4+ ratio, the optimal redox behavior of the V species, the moderate adsorption energy between 4,6-DMDBT and VOx active centers, and the synthetic effect of V single atoms and VOx clusters. Moreover, VOx/TiO2-(001) exhibits robust durability in seven cycles of reuse, showcasing the potential for practical applications in the future.

Design, synthesis and biological evaluation of 2,4,6- trisubstituted triazine derivatives as new nonpeptide small-molecule SIRT5 inhibitors.

Human sirtuin 5 (SIRT5) participates in a variety of metabolic disorder-associated diseases, including cancer. Inhibition of SIRT5 has been confirmed to provide a new strategy for treatment of related diseases. Previously, we discovered a pyrimidine skeleton inhibitor XIV, which showed low micromolar inhibitory activity against SIRT5. Herein, we utilized the scaffold-hopping strategy to design and synthesize a series of 2,4,6- trisubstituted triazine derivatives. The SAR analysis led to the discovery of several new SIRT5 inhibitors with low micromolar inhibition levels. The most potent compounds 10 (IC50 = 5.38 µM), and 14 (IC50 = 4.07 µM) were further confirmed to be the substrate-competitive SIRT5 inhibitors through enzyme kinetic assays, which is consistent with the molecular docking analyses. Fluorescence-based thermal shift assays proved that these compounds may stabilize SIRT5 by binding withprotein.. In addition, compounds 10 and 14 were also revealed to have moderate selectivity to SIRT5 over SIRT1-3. This study will aid further efforts to develop highly potent and selective SIRT5 inhibitors for the treatment of cancer and other related diseases.

Structure-Activity Relationship Studies of 2,4,5-Trisubstituted Pyrimidine Derivatives Leading to the Identification of a Novel and Potent Sirtuin 5 Inhibitor against Sepsis-Associated Acute Kidney Injury.

Sepsis-associated acute kidney injury (AKI) is a serious clinical problem without effective drugs. Inhibition of sirtuin 5 (SIRT5) has been confirmed to protect against AKI, suggesting that SIRT5 inhibitors might be a promising therapeutic approach for AKI. Herein, structural optimization was performed on our previous compound 1 (IC50 = 3.0 µM), and a series of 2,4,5-trisubstituted pyrimidine derivatives have been synthesized. The structure-activity relationship (SAR) analysis led to the discovery of three nanomolar level SIRT5 inhibitors, of which the most potent compound 58 (IC50 = 310 nM) was demonstrated to be a substrate-competitive and selective inhibitor. Importantly, 58 significantly alleviated kidney dysfunction and pathological injury in both lipopolysaccharide (LPS)- and cecal ligation/perforation (CLP)-induced septic AKI mice. Further studies revealed that 58 regulated protein succinylation and the release of proinflammatory cytokines in the kidneys of septic AKI mice. Collectively, these results highlighted that targeting SIRT5 has a therapeutic potential against septic AKI.

Interfacially Super-Assembled Benzimidazole Derivative-Based Mesoporous Silica Nanoprobe for Sensitive Copper (II) Detection and Biosensing in Living Cells.

Mesoporous silica nanoparticles (MSNs) functionalized with benzimidazole-derived fluorescent molecules (DHBM) are fabricated via a feasible interfacial superassembly strategy for the highly sensitive and selective detection of Cu2+ . DHBM-MSN exhibits an obvious quenching effect on Cu2+ in aqueous solutions, and the detection limit can be as low as 7.69×10-8  M. The DHBM-MSN solid-state sensor has good recyclability, and the silica framework can simultaneously improve the photostability of DHBM. Two mesoporous silica nanoparticles with different morphologies were specially designed to verify that nanocarriers with different morphologies do not affect the specific detectionability. The detection mechanism of the fluorescent probe was systematically elucidated by combining experimental results and density function theory calculations. Moreover, the detection system was successfully applied to detect Cu2+ in bovine serum, juice, and live cells. These results indicate that the DHBM-MSN fluorescent sensor holds great potential in practical and biomedical applications.

Wood-Derived Bimetallic and Heteroatomic Hierarchically Porous Carbon Aerogel for Rechargeable Flow Zn-Air Batteries.

It is necessary to correctly research and synthesize efficient and inexpensive catalysts to achieve reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which is also a prerequisite for zinc-air batteries (ZABs). However, it is still a huge challenge to manufacture electrocatalysts with durable and high electrocatalytic performance from biomass. Here, a convenient method of delignification was used to transform natural balsa wood into a layered porous carbon material, FeCo alloy supported on a N, S-doped wood-based carbon aerogel (FeCo@NS-CA) as the cathode in rechargeable flow ZAB. The obtained FeCo@NS-CA with the porous lamellar architecture exhibits superior bifunctional electrocatalysis, including excellent electrochemical activities and superior stabilities. For ORR, relative to the reversible hydrogen electrode, the onset potential of FeCo@NS-CA is 0.97 V, and the half-wave potential is 0.85 V, which is consistent with the potential of commercial Pt/C. For OER, FeCo@NS-CA obtained an overpotential of 450 mV, which is very similar to the overpotential of the benchmark RuO2. The superior performance could be owing to the alloy carrier interaction between the FeCo alloy and the wood-based carbon aerogel co-doped with N and S. Moreover, the bifunctional air cathode in a flow ZAB assembled with the FeCo@NS-CA catalyst at a current density of 10 mA cm-2; the power density is 140 mW cm-2, and the specific capacitance is 760 mA h gZn-1, with a remarkable long-term stability of 400 h better than ZAB of benchmark Pt/C + RuO2. This research lays the foundation for transforming abundant biomass resources into high environmental protection materials for energy-related applications.

Facet-dependent photocatalytic decomposition of N2O on the anatase TiO2: a DFT study.

The photocatalytic N2O dissociation on anatase TiO2 is an attractive reaction and the mechanism of the photocalytic process, the role of excited electrons, and the favorable facet for higher activity need a more detailed study at the molecular level. Using DFT + U calculations, we investigate the dissociation process of N2O into N2 with and without photoexcited electrons on anatase TiO2 (001) and (101) facets to unravel such puzzles. The optical absorption properties of TiO2 (001) and (101) facets are compared in combination with electronic analysis. The localization of excited electrons on the two surfaces with the existence of oxygen vacancies is explored. When there is no photo-excitation, on a perfect TiO2 surface, N2O decomposition is difficult due to the inhibitive high reaction energy. In contrast, the reaction energy decreases dramatically in the presence of photoexcited or excess electrons on the TiO2 surface. The reaction energy is related to the electronic state of dissociated O. The more negative charges make O more stable, and accordingly lead to higher exothermic reaction energy. Based on this point, the influence of surface morphology and excited states can be understood. This is the first theoretical study of the photocatalytic process of N2O elimination, which will guide further experimental study and improve its activity.