In situ X-ray absorption near edge structure studies and charge transfer kinetics of Na6[V10O28] electrodes.

Polyoxometalates (POMs) have been reported as promising electrode materials for energy storage applications due to their ability to undergo fast redox reactions with multiple transferred electrons per polyanion. Here we employ a polyoxovanadate salt, Na6[V10O28], as an electrode material in a lithium-ion containing electrolyte and investigate the electron transfer properties of Na6[V10O28] on long and short timescales. Looking at equilibrated systems, in situ V K-edge X-ray absorption near edge structure (XANES) studies show that all 10 V5+ ions in Na6[V10O28] can be reversibly reduced to V4+ in a potential range of 4-1.75 V vs. Li/Li+. Focusing on the dynamic response of the electrode to potential pulses, the kinetics of Na6[V10O28] electrodes and the dependence of the fundamental electron transfer rate k0 on temperature are investigated. From these measurements we calculate the reorganization energy and compare it with theoretical predictions. The experimentally determined reorganization energy of λ = 184 meV is in line with the theoretical estimate and confirms the hypothesis of small values of λ for POMs due to electrostatic shielding of the redox center from the solvent.

CrIII-Substituted Heteropoly-16-Tungstates [CrIII2(B-ß-XIVW8O31)2]14- (X = Si, Ge): Magnetic, Biological, and Electrochemical Studies.

The dichromium(III)-containing heteropoly-16-tungstates [CrIII2(B-ß-SiIVW8O31)2]14- (1) and [CrIII2(B-ß-GeIVW8O31)2]14- (2) were prepared via a one-pot reaction of the composing elements in aqueous, basic medium. Polyanions 1 and 2 represent the first examples of CrIII-containing heteropolytungstates comprising the octatungstate unit {XW8O31} (X = Si, Ge). Magnetic studies demonstrated that, in the solid state, the two polyanions exhibit a weak antiferromagnetic interaction between the two CrIII centers with J = -3.5 ± 0.5 cm-1, with no long-range ordering down to 1.8 K. The ground-state spin of polyanions 1 and 2 was thus deduced to be 0, but the detection of a complex set of EPR signals implies that there are thermally accessible excited states containing unpaired spins resulting from the two S = 3/2 CrIII ions. A comprehensive electrochemistry study on 1 and 2 in solution was performed, and biological tests showed that both polyanions display significant antidiabetic and anticancer activities.

Hen egg-white lysozyme crystallisation: protein stacking and structure stability enhanced by a Tellurium(VI)-centred polyoxotungstate.

As synchrotron radiation becomes more intense, detectors become faster and structure-solving software becomes more elaborate, obtaining single crystals suitable for data collection is now the bottleneck in macromolecular crystallography. Hence, there is a need for novel and advanced crystallisation agents with the ability to crystallise proteins that are otherwise challenging. Here, an Anderson-Evans-type polyoxometalate (POM), specifically Na6 [TeW6 O24 ]⋅22 H2 O (TEW), is employed as a crystallisation additive. Its effects on protein crystallisation are demonstrated with hen egg-white lysozyme (HEWL), which co-crystallises with TEW in the vicinity (or within) the liquid-liquid phase separation (LLPS) region. The X-ray structure (PDB ID: 4PHI) determination revealed that TEW molecules are part of the crystal lattice, thus demonstrating specific binding to HEWL with electrostatic interactions and hydrogen bonds. The negatively charged TEW polyoxotungstate binds to sites with a positive electrostatic potential located between two (or more) symmetry-related protein chains. Thus, TEW facilitates the formation of protein-protein interfaces of otherwise repulsive surfaces, and thereby the realisation of a stable crystal lattice. In addition to retaining the isomorphicity of the protein structure, the anomalous scattering of the POMs was used for macromolecular phasing. The results suggest that hexatungstotellurate(VI) has great potential as a crystallisation additive to promote both protein crystallisation and structure elucidation.

Synthesis and Structure of Hexatungstochromate(III), [H3Cr(III)W6O24]6-.

The hexatungstochromate(III) [H(3)Cr(III)W(6)O(24)](6-) (1) was synthesized in aqueous, basic medium by simple reaction of chromium(III) nitrate nonahydrate and sodium tungstate dihydrate in a 1:6 ratio. Polyanion 1 represents the first Anderson-Evans type heteropolytungstate with a trivalent hetero element. The sodium salt of 1 with the formula Na(6)[H(3)Cr(III)W(6)O(24)]·22H(2)O (1a) was fully characterized in the solid state by single crystal XRD, FT-IR spectroscopy, and thermogravimetric analysis.

Latent and active abPPO4 mushroom tyrosinase cocrystallized with hexatungstotellurate(VI) in a single crystal.

Tyrosinases, bifunctional metalloenzymes, catalyze the oxidation of monophenols and o-diphenols to o-quinones, the precursor compounds of the brown-coloured pigment melanin. In eukaryotic organisms, tyrosinases are expressed as latent zymogens that have to be proteolytically cleaved in order to form highly active enzymes. This activation mechanism, known as the tyrosinase maturation process, has scientific and industrial significance with respect to biochemical and technical applications of the enzyme. Here, not only the first crystal structure of the mushroom tyrosinase abPPO4 is presented in its active form (Ser2-Ser383) and in its 21 kDa heavier latent form (Ser2-Thr545), but furthermore the simultaneous presence of both forms within one single-crystal structure is shown. This allows for a simple approach to investigate the transition between these two forms. Isoform abPPO4 was isolated and extensively purified from the natural source (Agaricus bisporus), which contains a total of six polyphenol oxidases (PPOs). The enzyme formed crystals (diffracting to a resolution of 2.76 Å) owing to the employment of the 6-tungstotellurate(VI) salt (Na6[TeW6O24]·22H2O) as a cocrystallization agent. Two of these disc-shaped Anderson-type polyoxoanions [TeW6O24](6-) separate two asymmetric units comprising one crystallographic heterodimer of abPPO4, thus resulting in very interesting crystal packing.

A polyoxovanadate as an advanced electrode material for supercapacitors.

Polyoxovanadate Na(6)V(10)O(28) is investigated for the first time as electrode material for supercapacitors (SCs). The electrochemical properties of Na(6)V(10)O(28) electrodes are studied in Li(+) -containing organic electrolyte (1 M LiClO(4) in propylene carbonate) by galvanostatic charge/discharge and cyclic voltammetry in a three-electrode configuration. Na(6)V(10)O(28) electrodes exhibit high specific capacitances of up to 354 F g(-1). An asymmetric SC with activated carbon as positive electrode and Na(6)V(10)O(28) as negative electrode is fabricated and exhibits a high energy density of 73 Wh kg(-1) with a power density of 312 W kg(-1), which successfully demonstrates that Na(6)V(10)O(28) is a promising electrode material for high-energy SC applications.

Synthesis, detailed characterization, and theoretical understanding of mononuclear chromium(III)-containing polyoxotungstates [Cr(III)(HX(V)W7O28)2]¹³â» (X = P, As) with exceptionally large magnetic anisotropy.

Two monochromium(III)-containing heteropolytungstates, [Cr(III)(HP(V)W7O28)2](13-) (1a) and [Cr(III)(HAs(V)W7O28)2](13-) (2a), were prepared via simple, one-pot reactions in aqueous, basic medium, by reaction of the composing elements, and then isolated as hydrated sodium salts, Na13[Cr(III)(HP(V)W7O28)2]·47H2O (1) and Na13[Cr(III)(HAs(V)W7O28)2]·52H2O (2). Polyanions 1a and 2a comprise an octahedrally coordinated Cr(III) ion, sandwiched by two {PW7} or {AsW7} units. Both compounds 1 and 2 were fully characterized in the solid state by single-crystal XRD, IR spectroscopy, thermogravimetric and elemental analyses, magnetic susceptibility, and EPR measurements. Magnetic studies on 1 and 2 demonstrated that both compounds exhibit appreciable deviation from typical paramagnetic behavior, and have a ground state S = 3/2, as expected for a Cr(III) ion, but with an exceptionally large zero-field uniaxial anisotropy parameter (D). EPR measurements on powder and single-crystal samples of 1 and 2 using 9.5, 34.5, and 239.2 GHz frequencies and over 4-295 K temperature fully support the magnetization results and show that D = +2.4 cm(-1), the largest and sign-assigned D-value so far reported for an octahedral Cr(III)-containing, molecular compound. Ligand field analysis of results from CASSCF and NEVPT2-correlated electronic structure calculations on Cr(OH)6(3-) model complexes allowed to unravel the crucial role of the second coordination sphere of Cr(III) for the unusually large magnetic anisotropy reflected by the experimental value of D. The newly developed theoretical modeling, combined with the synthetic procedure for producing such unusual magnetic molecules in a well-defined and essentially magnetically isolated environment, appears to be a versatile new research area.

Synthesis and characterization of multinuclear manganese-containing tungstosilicates.

The five manganese-containing, Keggin-based tungstosilicates [Mn(II)3(OH)3(H2O)3(A-α-SiW9O34)](7-) (1), [Mn(III)3(OH)3(H2O)3(A-α-SiW9O34)](4-) (2), [Mn(III)3(OH)3(H2O)3(A-ß-SiW9O34)](4-) (3), [Mn(III)3Mn(IV)O3(CH3COO)3(A-α-SiW9O34)](6-) (4), and [Mn(III)3Mn(IV)O3(CH3COO)3(A-ß-SiW9O34)](6-) (5) were synthesized in aqueous medium by interaction of [A-α-SiW9O34](10-) or [A-ß-SiW9O34H](9-) with either MnCl2 (1) or [Mn(III)8Mn(IV)4O12(CH3COO)16(H2O)4] (2-5) under carefully adjusted reaction conditions. The obtained salts of these polyanions were analyzed in the solid state by single-crystal X-ray diffraction, IR spectroscopy, and thermogravimetric analysis. The salts of polyanions 1, 2, and 4 were further characterized in the solid state by magnetic studies, as well as in solution by electrochemistry.

Photocatalytic water oxidation by a mixed-valent Mn(III)3Mn(IV)O3 manganese oxo core that mimics the natural oxygen-evolving center.

The functional core of oxygenic photosynthesis is in charge of catalytic water oxidation by a multi-redox Mn(III)/Mn(IV) manifold that evolves through five electronic states (S(i), where i=0-4). The synthetic model system of this catalytic cycle and of its S0→S4 intermediates is the expected turning point for artificial photosynthesis. The tetramanganese-substituted tungstosilicate [Mn(III)3Mn(IV)O3(CH3COO)3(A-α-SiW9O34)](6-)(Mn4POM) offers an unprecedented mimicry of the natural system in its reduced S0 state; it features a hybrid organic-inorganic coordination sphere and is anchored on a polyoxotungstate. Evidence for its photosynthetic properties when combined with [Ru(bpy)3](2+) and S2O8(2-) is obtained by nanosecond laser flash photolysis; its S0→S1 transition within milliseconds and multiple-hole-accumulating properties were studied. Photocatalytic oxygen evolution is achieved in a buffered medium (pH 5) with a quantum efficiency of 1.7%.

The mixed-valent 10-manganese(III/IV)-containing 36-tungsto-4-arsenate(V), [MnIII6MnIV4O4(OH)12(H2O)12(A-ß-AsW9O34)4]22.

Interaction of the mixed-valent 12-manganese coordination complex [MnIII8MnIV4O12(CH3COO)16(H2O)4] with the lacunary 9-tungstoarsenate(V) [A-α-AsW9O34]9- resulted in the 10-manganese(III/IV)-containing 36-tungsto-4-arsenate(V), [MnIII6MnIV4O4(OH)12(H2O)12(A-ß-AsW9O34)4]22- (1). Polyanion 1 was isolated as a hydrated mixed potassium-sodium salt, K14Na8[MnIII6MnIV4O4(OH)12(H2O)12(A-ß-AsW9O34)4]·104H2O, which crystallizes in the orthorhombic space group Pbcn and was characterized by FT-IR spectroscopy and single-crystal X-ray diffraction, as well as elemental and thermogravimetric analyses. The title polyanion contains a unique [MnIII6MnIV4O4(OH)12(H2O)12]14+ core stabilized within the 36-tungsto-4-arsenate(V) framework.

A novel SWCNT-polyoxometalate nanohybrid material as an electrode for electrochemical supercapacitors.

A novel nanohybrid material that combines single-walled carbon nanotubes (SWCNTs) with a polyoxometalate (TBA)5[PVMoO40] (TBA-PV2Mo10, TBA: [(CH3(CH2)3)4N](+), tetra-n-butyl ammonium) is investigated for the first time as an electrode material for supercapacitors (SCs) in this study. The SWCNT-TBA-PV2Mo10 material has been prepared by a simple solution method which electrostatically attaches anionic [PV2Mo10O40](5-) anions with organic TBA cations on the SWCNTs. The electrochemical performance of SWCNT-TBA-PV2Mo10 electrodes is studied in an acidic aqueous electrolyte (1 M H2SO4) by galvanostatic charge/discharge and cyclic voltammetry. In this SWCNT-TBA-PV2Mo10 nanohybrid material, TBA-PV2Mo10 provides redox activity while benefiting from the high electrical conductivity and high double-layer capacitance of the SWCNTs that improve both energy and power density. An assembled SWCNT-TBA-PV2Mo10 symmetric SC exhibits a 39% higher specific capacitance as compared to a symmetric SC employing only SWCNTs as electrode materials. Furthermore, the SWCNT-TBA-PV2Mo10 SC exhibits excellent cycling stability, retaining 95% of its specific capacitance after 6500 cycles.

Crystallization and preliminary X-ray crystallographic analysis of latent isoform PPO4 mushroom (Agaricus bisporus) tyrosinase.

Tyrosinase exhibits catalytic activity for the ortho-hydroxylation of monophenols to diphenols as well as their subsequent oxidation to quinones. Owing to polymerization of these quinones, brown-coloured high-molecular-weight compounds called melanins are generated. The latent precursor form of polyphenol oxidase 4, one of the six tyrosinase isoforms from Agaricus bisporus, was purified to homogeneity and crystallized. The obtained crystals belonged to space group C121 (two molecules per asymmetric unit) and diffracted to 2.78 Å resolution. The protein only formed crystals under low-salt conditions using the 6-tungstotellurate(VI) salt Na6[TeW6O24] · 22H2O as a co-crystallization agent.

Antidiabetic potential of polyoxotungstates: in vitro and in vivo studies.

Diabetes mellitus is a chronic metabolic disorder continuously affecting people all over the world. A common way to treat diabetes mellitus is to limit the conversion of carbohydrates into glucose which is mediated by glucosidase enzymes. Diabetes mellitus is also famous for its life-threatening microvascular (retinopathy, neuropathy and nephropathy) and macrovascular (atherosclerosis) complications. Aldose reductases present in eye lens (ALR1) and kidney (ALR2) are responsible for microvascular complications. The production of advanced glycation end products (AGEs) is involved in the development of atherosclerosis. The present work was aimed at the synthesis and in vitro/in vivo evaluation of different polyoxotungstates against glucosidases (α- and ß), aldose reductases (ALR1 and ALR2) and AGEs to discover a new treatment which may limit the complications associated with diabetes mellitus. The polyanion [P6W18O79](20-) was found to be the most potent inhibitor of α-glucosidase (IC50 = 1.33 ± 0.41 µM), ALR1 (IC50 = 0.4 ± 0.009 µM) and ALR2 (IC50 = 0.38 ± 0.02 µM). Animal studies showed that the polyanion [H2W12O40](6-) was very effective in reducing the blood glucose level to 84.25 ± 5.07 mg dL(-1) when compared with standard antidiabetic drug glibenclamide (150.62 ± 9.35 mg dL(-1)) measured after maximum 8 h of dose administration. The data obtained from in vitro and in vivo experiments confirm that [P6W18O79](20-) and [H2W12O40](6-) could be used as a new treatment of diabetes mellitus.

Cytotoxicity and enzyme inhibition studies of polyoxometalates and their chitosan nanoassemblies.

Polyoxometalates (POMs) have become very significant in biomedical research for their structural diversity which renders them highly active against bacterial, viral and cancer diseases. In this study three different POMs were synthesized and nanoassemblies were made with chitosan (CTS), a natural biodegradable polymer with excellent drug carrier properties. The compounds were tested on two isoenzymes of alkaline phosphatases including tissue specific calf intestine alkaline phosphatase (CIAP) and tissue non-specific alkaline phosphatase (TNAP). Compound [TeW6O24]6- (TeW6) showed the highest activity (45.4 ± 11.3 nM) among tested compounds against TNAP. Similarly, chitosan-[TeW6O24]6- (CTS-TeW6) was proved to be a potent inhibitor of CIAP with Ki value of 22 ± 7 nM. A comparative study was made to evaluate their cytotoxic potential against HeLa cells. Among all tested compounds, Chitosan-[NaP5W30O110]14- (CTS-P5W30) has showed higher percent cytotoxicity (88 ± 10%) at 10 µM when compared with the standard anticancer drug vincristine (72 ± 7%). The study revealed that selected POMs proved excellent anticancer potential and were equally effective against alkaline phosphatase enzyme, an increased level of which may indicate cancer metastasis.

Multilayer films made from poly(allylamine) and phosphorous containing polyoxometalates: focus on the zeta potential.

The physicochemical characterization of coatings deposited in a step-by-step (SBS) manner relies most often on thickness and homogeneity measurements by means of atomic force microscopy. In the case of coatings produced from oppositely charged species, their surface potential, estimated through their zeta potential, was for a long time expected to change alternatively as a prerequisite for the film deposition. However, some counterexamples appeared in the literature where the growth of the coating was observed when the number of deposition steps was increased but without a regular change in the sign of the surface potential. These data showed that the interpretation of the zeta potential of SBS deposited films should be subjected to more attention. In this article, we show the occurrence of ionic strength dependent instability of the surface potential of films made from the alternated deposition of poly(allylamine hydrochloride) and polyoxoanions. This instability may be due to a structural change in the coating, but we cannot exclude some shear induced desorption during the zeta potential measurement. In addition, a change in ionic strength between the deposition of the coating and the measurement of its streaming potential can have a huge importance on the result.