The {AsW12O40} clusters are grafted into Ag-MOF to yield two 3D polyoxometallate-based metal organic frameworks (POMOFs), (imi)2[{Ag3(tpb)2}2(H2O){AsW12O40}2]·6H2O (1) and [(Ag7bpy7Cl2){AsWV2WVI10O40}]·H2O (2) (imi = imidazole; tpb = 1, 2, 4, 5-tetrakis...

The spontaneous formation of discrete spherical nanosized molecules is prevalent in nature, but the authentic structural mimicry of such highly symmetric polyhedra from edge sharing of regular polygons has remained elusive. Here we present a novel ball-shaped {(HNEt3)[Ag37S4(SC6H4(t)Bu)24(CF3COO)6(H2O)12]} cluster () that is assembled via a one-pot process from polymeric {(HNEt3)2[Ag10(SC6H4(t)Bu)12]}n and CF3COOAg. Single crystal X-ray analysis confirmed that is a Td symmetric spherical molecule with a [Ag36(SC6H4(t)Bu)24] anion shell enwrapping a AgS4 tetrahedron. The shell topology of belongs to one of 13 Archimedean solids, a truncated tetrahedron with four edge-shared hexagons and trigons, which are supported by a AgS4 Platonic solid in the core. Interestingly, the cluster emits green luminescence centered at 515 nm at room temperature. Our investigations have provided a promising synthetic protocol for a high-nuclearity silver cluster based on underlying geometrical principles.

A new one-dimensional chain-like compound of tungstobismuthate, [(W(OH)2)2 (Mn(H2O)3)2(Na3(H2O)14)(BiW9O33)2](Himi)2·16H2O (1) (imi = iminazole), has been synthesized in aqueous solution. The structure of 1 was identified by elemental analysis, IR, thermogravimetry (TG), X-ray photoelectron spectroscopy (XPS), (183)W-NMR, and single crystal X-ray diffraction. To investigate the inhibitory effect of 1 on human gastric adenocarcinoma SGC-7901 cells, cell proliferation and apoptosis initiation were examined by MTT assay (MTT = 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazoliumbromide), flow cytometry, nuclear staining, transmission electron microscopy, single cell gel electrophoresis, DNA fragmentation, and Western blotting. The results showed that 1 inhibited cell proliferation and induced apoptosis in SGC-7901 cells in dose-dependent manner. In addition, 1 also decreased the expression of bcl-2 protein and nuclear factor-κB p65 protein in SGC-7901 cells. And expression of bcl-2 protein exhibits a decreasing trend with increase of concentration of 1. Thus, 1 possessed a potential antitumor activity in SGC-7901 cells. This suggests that polyoxotungstates will provide a promising and novel antitumor agent in prevention and treatment of gastric adenocarcinoma.

A new cobalt-based polyoxometalate, (Himi)2[Bi(2)W2(0)O(66)(OH)(4)Co2(H2O)(6)Na(4) (H2O)14] · 17H2O (imi = iminazole) (BWCN) has been synthesized and structurally characterized. The inhibitory activities against selected human cancer lines were also determined in this study. The cell viability and chemoresistance of BWCN on human colon carcinoma HT-29 cells were assessed by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazoliumbromide), cell morphology changes, a comet assay and western blot analysis. The typical morphologic changes of apoptosis and DNA damage indicated that BWCN could have a distinct proliferation inhibitory effect on cancer cells. BWCN as a chemotherapeutic agent also induced apoptosis on HT-29 cells and showed a significant expression of cleaved-caspase-3. These results suggested that the active site of BWCN is the polymeric anion based on the basic tectonic block {BiW(9)}, and the possible mechanism is related to the interference of DNA synthesis in cancer cells.

Designing highly active Keggin-anion anchored on pz-based frameworks is desirable but still a huge challenge. Herein, three new POM-based inorganic–organic hybrid compounds [{Ag5(pz)7}­(BW12O40)] (1), [{Ag5(pz)7}­(SiW12O40)]­(OH)·H2O (2), (Hpyr)­[{Ag­(pz)}2(PMo12O40)] (3) (pz = pyrazine, pyr = pyrrole) have been fabricated via a hydrothermal synthesis method. All compounds were characterized by elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), thermogravimetric (TG), scanning electron micrographs (SEM), and transmission electron microscope (TEM). Single-crystal X-ray diffraction displays that the configurations of compounds 1 and 2 are parallel. In compound 1, the [BW12O40]5– is as 8-connected node incorporated into the orifice of the Ag-pz framework forming the glamorous POM-based metal organic frameworks (POMOFs). And the 3D POMOFs possess a kind of novel topology {42·54}2{44·512·68·73·9}­{44·53·63}­{44·55·6·74·9}­{73}. There is a metal–organic nanotube structure constructed by four Ag-pz chains in compound 3. Then, the opened POMOFs consist of [PMo12O40]3– clusters encircled in metal–organic nanotubes with the topology {34·46·54·6}2­{34·48·58·64·74}. When used as electrode materials, as-prepared compounds 1, 2, and 3 have high specific capacitance of 1058, 986, and 1611 F g–1 at a current density of 2.16A g–1 and favorable cycling stability; after 1000 cycles, the retention rates of the capacitance are 90.3%, 94.5%, and 84.8% at 15.12 A g–1 in supercapacitors, respectively. Moreover, the ability of compounds 1–3 to degrade dyes is excellent under UV irradiation. The degradation rates of RhB are 94.89% for 1, 93.06% for 2, and 96.88% for 3 after 150 min, and the degradation rates of MB are 96.48% for 1, 94.28% for 2, and 98.58% for 3 after 90 min. These results illustrate that compounds 1–3 have potential applications in energy functional materials and organic pollutant degradation.

The crystal structure of pseudoazurin from Methylobacterium extorquens AM1 (PAZAM1) has been solved by the molecular replacement method using copper-copper distances as translation parameters, which were obtained from difference Patterson maps calculated with the synchrotron radiation data containing the multiwavelength anomalous-dispersion effect. The structure refinement was carried out by the use of molecular dynamics optimization and the restrained least-squares method. The final crystallographic R factor was 19.9% for the 14 365 reflections greater than 3sigma between 1.5 and 8.0 A resolution. This report describes the characteristic features of the structure of PAZAM 1 as well as the effectiveness of synchrotron radiation for structure analysis of metalloproteins. The environment of the metal active site and the structural differences among blue-copper proteins are discussed.

Four Preyssler P5W30 based inorganic-organic hybrids, formulated as {[Cu12(pbtz)2(Hpbtz)2(OH)4(H2O)16][Na(H2O)P5W30O110]}·16H2O (1; H2pbtz = 5'-(pyridin-2-yl)-1H,2'H-3,3'-bi(1,2,4-triazole)), {[Cu10(ttbz)2(Httbz)4(OH)6(H2O)8][K(H2O)H2P5W30O110]}·30H2O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni6(bpz)6(H2O)16][Na(H2O)H2P5W30O110]}·36H2O (3; bpz = 3,3',5,5'-tetramethyl-4,4-bipyrazole), {[Co4(bpz)6(H2O)9][K(H2O)H6P5W30O110]}·46H2O (4), have been isolated and structurally identified via microanalysis, thermogravimetry (TG), infrared (IR) spectroscopy, and X-ray single-crystal diffraction. Compound 1 exhibits a 3D binodal (3,6)-connected ant framework composed of dodeca-supported P5W30 polyoxometalate (POM) clusters and discrete [Cu6(pbtz)(Hpbtz)(OH)2(H2O)8] subunits. Compound 2 is a pillared-layer 3D network constructed from [Cu5(ttbz)(Httbz)2(OH)3(H2O)4] sheets pillared by individual P5W30 clusters. Compound 3 contains octa-supporting P5W30 POM clusters and novel [Ni6(bpz)6] crown-like metallamacrocycles, which construct a (4,4)-connected pts network. Compound 4 displays a complicated 3D (5,5)-connected {4(5)·6(4)·8}{4(5)·6(5)} network built by pentasupporting P5W30 POM clusters and discrete [Co4(bpz)6(H2O)9] subunits. In 1-4, the unified features are the Preyssler-type [P5W30O110] POM as the fundamental building block, which supports the transition-metal compounds with different modes to give the resultant diverse networks. The magnetism studies indicated antiferromagnetically coupled systems for the hexa- and pentanuclear Cu(II) units in 1 and 2, respectively. The electrochemical properties demonstrate that all compounds have electrocatalytic abilities toward the reduction of hydrogen peroxide. Furthermore, the catalytic activities of 1 in the cyanosilylation of aldehydes reaction have been investigated.

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