Synthesis and conductive performance about a kind of high-proton conductor, Dawson structure heteropoly acid H6P2W16Mo2O40 ⋅ 29H2O

A heteropoly acid (HPA) with Dawson structure, H6P2W[Formula: see text]Mo2O[Formula: see text]⋅29H2O, is synthesized with characterization and the investigation toward its proton conductive behavior. Actually, at 18[Formula: see text]C with 80% relative humidity (RH), H6P2W[Formula: see text]Mo2O[Formula: see text] ⋅ 29H2O displays the conductivity as 2.30 × 10[Formula: see text] S ⋅ cm[Formula: see text], indicating an excellent protonic conductor. The proton conduction activation energy is 32.19 kJ ⋅ mol[Formula: see text], implying proton migration following vehicle mechanism. During the measured range, higher temperature can boost the conductivity.

Identification of a Wells–Dawson polyoxometalate-based AP-2γ inhibitor with pro-apoptotic activity

AP-2 gamma (AP-2γ) is a transcription factor that plays pivotal roles in breast cancer biology. To search for small molecule inhibitors of AP-2γ, we performed a high-throughput fluorescence anisotropy screen and identified a polyoxometalate compound with Wells–Dawson structure K6[P2Mo18O62] (Dawson-POM) that blocks the DNA-binding activity of AP-2γ. We showed that this blocking activity is due to the direct binding of Dawson-POM to AP-2γ. We also provided evidence to show that Dawson-POM decreases AP-2γ-dependent transcription similar to silencing the gene. Finally, we demonstrated that Dawson-POM contains anti-proliferative and pro-apoptotic effects in breast cancer cells. In summary, we identified the first small molecule inhibitor of AP-2γ and showed Dawson-POM-mediated inhibition of AP-2γ as a potential avenue for cancer therapy.

Effect of protonation, composition and isomerism on the redox properties and electron (de)localization of classical polyoxometalates

This publication reviews some relevant features related with the redox activity of two inorganic compounds: [XM12O40]q- (Keggin structure) and [X2M18O62]q- (Wells-Dawson structure). These are two well-known specimens of the vast Polyoxometalate (POM) family, which has been the subject of extensive experimental and theoretical research owing to their unmatched properties. In particular, their redox activity focus a great deal of attention from scientists due to their prospective related applications. POMs are habitually seen as ‘electron sponges’ since many of them accept several electrons without losing their chemical identity. This makes them excellent models to study mechanisms of electrochemical nature. Their redox properties depend on: (i) the type and number of transition metal atoms in the structure, (ii) the basicity of the first reduced species and, occasionally, of the fully oxidized species; (iii) the size of the molecule, (iv) the overall negative charge of the POM, and (v) the size of the central heteroatom. In the last years, important collaboration between the experimental and theoretical areas has been usual on the development of POM science. In the present chapter three of these synergies are highlighted: the influence of the internal heteroatom upon the redox potentials of Keggin anions; the dependence of the redox waves of Fe-substituted Wells-Dawson compounds with pH; and the role of electron delocalization and pairing in mixed-metal Mo/W Wells-Dawson compounds in their ability to accept electrons. In these three cases, a complete understanding of the problem would not have been possible without the mutual benefit of experimental and computational data.

PREPARATION AND ELECTROCHEMICAL PERFORMANCE OF HYBRID MATERIALS CONTAINING HETEROPOLY ACID WITH DAWSON STRUCTURE AND POLYMERS

Highly proton-conducting hybrid materials ( P2W17V /PEG and P2W17V/PEG/SiO2 ) were prepared by heptadecatungstovanadodiphosphoric heteropoly acid with Dawson structure ( P2W17V , 90 wt.%), polyethylene glycol (PEG, 10 wt.% and 5 wt.%) and silica gel ( SiO2 , 0 wt.% and 5 wt.%). The products were characterized by the infrared (IR) spectrum, X-ray powder diffraction (XRD) analysis and electrochemical impedance spectrum (EIS). The result reveals that their conductivity values are 1.02 × 10-2 and 2.58 × 10-2S ⋅ cm-1 at room temperature (26°C) and 75% relative humidity (RH), respectively. Their conductivities increase with higher temperature and these activation energies of proton conduction are 9.51 and 14.95 kJ⋅mol-1, which are lower than that of pure heteropoly acid (32.23 kJ⋅mol-1). These mechanisms of proton conduction for these two materials are Grotthuss mechanism.

Clean Oxidation of Cyclohexanone to Adipic Acid Catalyzed by Ammonium Phosphomolybdate with Dawson Structure under Microwave Irradiation

Ammonium Phosphomolybdate with Dawson structure was prepared by hydrothermal synthesis and characted by means of FT-IR, UV-Vis,XRD and SEM. The synthesis of adipic acid with cyclohexanone and 30 percent hydrogen peroxide under microwave irradiation was carried out as a probe reaction to study the catalytic activity. Effects of catalyst amount,30wt.% H2O2 amount,microwave power, reaction time were investigated and optimized with orthogonal experiments and simple fact experiments. The results show that under the optimal condition, i.e. the mole ratio of C6H10O: H2O2:H2C2O4•2H2O:(NH4)6P2Mo18O62•nH2O =100:500:2.0:0.087, the reaction temperature was 100°C, microwave power was 400W, irradiation time was 3.5 h，the isolated yield of adipic acid could reach 72.5%．The catalyst could be reused for 5 times and the isolated of adipic acid was still above 43.2%.