Tpy-Mn(II)-Tpy (Tpy = 2,2':6',2″-terpyridine)-Based Pentagonal Prism for Green Photodriven Oxidation.

In coordination-driven metal-organic cages, the transition metal ions are generally utilized as linkages. Employment of its unique properties with the aim of achieving specific applications still presents great challenges. Herein, we report a decametric metal-organic cage named pentagonal prism (Mn20LC10) based on Tpy-Mn(II)-Tpy connectivity (Tpy = 2,2':6',2″-terpyridine) in which Mn(II) serves as a linker and endows the resulting metal-organic cage with good photosensitivity. In the photooxidation of benzaldehyde, pentagonal prism Mn20LC10 showed a significantly increased level of 1O2 production, the fastest conversion time, good recyclability, and substrate versatility due to its greatly improved intersystem crossing ability. Notably, the abundant active sites of metal pentagonal prism Mn20LC10 enable its photooxidation under solvent-free and daylight conditions. This work provides approaches for the development of inexpensive, green, and low-cost photosensitizer systems.

Anion-Regulated Hierarchical Self-Assembly and Chiral Induction of Metallo-Tetrahedra.

The precise control over hierarchical self-assembly of superstructures relying on the elaboration of multiple noncovalent interactions between basic building blocks is both elusive and highly desirable. We herein report a terpyridine-based metallo-cage T with a tetrahedral motif and utilized it as an efficient building block for the controlled hierarchical self-assembly of superstructures in response to different halide ions. Initially, the hierarchical superstructure of metallo-cage T adopted a hexagonal close-packed structure. By adding Cl- /Br- or I- , drastically different hierarchical superstructures with highly-tight hexagonal packing or graphite-like packing arrangements, respectively, have been achieved. These unusual halide-ion-triggered hierarchical structural changes resulted in quite distinct intermolecular channels, which provided new insights into the mechanism of three-dimensional supramolecular aggregation and crystal growth based on macromolecular construction. In addition, the chiral induction of the metallo-cage T can be realized with the addition of chiral anions, which stereoselectively generated either PPPP- or MMMM-type enantiomers.

MOF-derived nitrogen-doped carbon-based trimetallic bifunctional catalysts for rechargeable zinc-air batteries.

Zinc-air battery (ZAB) is a promising new metal-air energy system, but the large overpotentials of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) around the air electrode lead to their poor energy efficiency. Herein, a novel bifunctional oxygen electrocatalyst is reported with the preparation of a zeolite imidazolate framework (ZIF-67) derived trimetallic composites decorated nitrogen-doped carbon, which consist of NiFe alloy and Co nanoparticles. The ZIF-derived porous N-doped carbon shell can speed up the mass transfer efficiency. Whereas the electronic effect between the formed NiFe alloy and Co nanoparticles, as well as the N-doped carbon framework can enrich the active centers and enhance the electrical conductivity. As a result, the NiFe-Co@NC-450 catalyst shows superior performance manifested as a small potential gap (ΔE = 0.857 V) between the overpotential at 10 mA cm-2(Ej=10) for OER (460 mV) and half-wave potential (E1/2) for ORR (0.833 V). The liquid ZABs exhibit a high specific capacity reaching 798 mAh/gZnand a stable cycling performance at 10 mA cm-2for more than 200 h. Meanwhile, the NiFe-Co@NC-450 based flexible ZABs also presents robust flexibility and stability. This study has certain implications for the development of economical, powerful and stable bifunctional catalysts for ZABs.

Ag/MnO2 Nanorod as Electrode Material for High-Performance Electrochemical Supercapacitors.

A one-dimensional hierarchical Ag nanoparticle (AgNP)/MnO2 nanorod (MND) nanocomposite was synthesized by combining a simple solvothermal method and a facile reduction approach in situ. Owing to its high electrical conductivity, the resulting AgNP/MND nanocomposite displayed a high specific capacitance of 314 F g-1 at a current density of 2 A g-1, which was much higher than that of pure MNDs (178 F g-1). Resistances of the electrolyte (Rs) and charge transportation (Rct) of the nanocomposite were much lower than that of pure MNDs. Moreover, the nanocomposite exhibited outstanding long-term cycling ability (9% loss of initial capacity after 1000 cycles). These results indicated that the nanocomposite could serve as a promising and useful electrode material for future energy-storage applications.

Metal-ion-determined geometrical configurations of metallo-cages with different emission properties.

The formation of metallo-cages is affected by a variety of factors such as the ligands, metals, and anions, among which the impact of metals with different binding capacities is particularly important, but has rarely been studied in three-dimensional metallo-cages. Herein, we report the design of truxene-centered terpyridine ligands and the self-assembly of a series of tetrameric metallo-cages. The utilization of metal ions with strong (Zn2+, Fe2+) or weak (Cd2+) binding strength afforded 3D metallo-cages with low symmetry or highly symmetric metallo-tetrahedra, respectively, possessing totally different geometrical configurations. In addition, their photophysical properties and host-guest chemical properties were investigated.

A truncated triangular prism constructed by using imidazole-terpyridine building blocks.

The construction of low-symmetry topological supramolecular structures using bistable building blocks remains challenging. We report an unusual truncated triangular prismatic cage with D3h symmetry using a ligand with both cis- and trans-configurations upon coordination with metal. This work provides new ideas and methods for the future synthesis of low-symmetry topological supramolecules.

[Lipoprotein lipase gene mutations and the risk of cardiovascular diseases in children with obesity].

OBJECTIVE: To inquire into the relationship between lipoprotein lipase (LPL) gene D9N, N291S and S447X polymorphisms and the development of cardiovascular diseases in children with obesity. METHODS: The polymerase chain reaction (PCR) and restriction fragment length polymorphism (RLFP) techniques were used to detect three common mutations of LPL gene exon D9N, N291S and S447X in 157 obese children and 175 normal controls. Plasma lipid and lipoprotein levels between children with different genotypes were compared. RESULTS: The D9N and N291S gene mutations were not detected in either the obese or the control groups. There were no significant differences in the frequency of S447X gene mutation between the two groups. There were no significant differences in the levels of plasma lipid and lipoprotein between children with S447 and X447 genotypes. CONCLUSIONS: D9N and N291S gene mutations may not be risk factors associated with cardiovascular diseases in children with obesity. S447X gene mutation might not play an important role in the development of cardiovascular diseases in childhood.