Water Oxidation Catalysis by Molecular Metal-Oxides

Abstract Water oxidation catalysis is recognized as the bottleneck for the development of efficient devices based on artificial photosynthesis, that is the light driven water splitting into hydrogen and oxygen. A recent breakthrough in this field, is the development of a molecular, fast and robust water oxidation catalyst namely a fully inorganic tetranuclear ruthenium complex with polyoxometalate ligands. The crystal structure of [Ru4(μ-O)4(μ-OH)2(H2O)4(SiW10O36)2]10-, 1, evidences the entrapment of an adamantane like, tetranuclear ruthenium(IV)-oxo core, by two decatungtosilicate units. Several spectroscopic techniques confirm the maintenance of the structure in aqueous solution. In the presence of Ce(IV) as sacrificial electron acceptor, 1 catalyzes water oxidation to oxygen, showing up to 500 turnovers and a turnover frequency of 0.125 s-1. The synergistic effect of the four ruthenium centres has a fundamental effect on such astounding performance, as confirmed by spectroscopic and computational characterization of five competent intermediates involved in the catalytic cycle, in strict analogy with the natural paradigm of the oxygen evolving centre in Photosystem II. Interestingly, 1 efficiently catalyzes water oxidation in the presence of photogenerated oxidants, as well; this fundamental feature is probably related to very fast hole scavenging of anionic 1 from cationic photogenerated oxidants, such as Ru(bpy)33+. Thus, 1 is an ideal candidate for the assembly of high efficient oxygenevolving anodes into nanostructured devices for artificial photosynthesis

The VVV-SkZ pipeline: an automatic PSF-fitting photometric pipeline for the VVV survey

We present the VVV-SkZ_pipeline, a DAOPHOT-based photometric pipeline, created to perform PSF-fitting photometry of "VISTA Variables in the V\'ia L\'actea" (VVV) ESO Public Survey data. The pipeline replaces the user avoiding repetitive interaction in all the operations, retaining all of the benefits of the power and accuracy of the DAOPHOT suite. The pipeline provides an astrometrized photometric catalog reliable up to more than 2 magnitudes brighter than the saturation limit, where other techniques fail. It also produces deeper and more accurate photometry. These achievements allow the VVV-SkZ_pipeline to produce data well anchored to the selected standard photometric system and analyze important phenomena (i.e. TRGB, RGB slope, HB morphology, RR Lyrae), that other methods are not able to manage.Comment: Accepted by RevMexAA for vol. 49, n.2, October 201

Supramolecular organic???inorganic domains integrating fullerene-based acceptors with polyoxometalate-bis-pyrene tweezers for organic photovoltaic applications

A strategy to improve organic photovoltaics, and to enhance the device efficiency, builds on the design of interfacial layered (IFL) materials implementing the performance of the photoactive acceptor/donor system. A novel IFL blend has been engineered by a supramolecular organic-inorganic heterojunction integrating polyoxometalate-bis-pyrene (pyrPOM) receptors that can selectively bind fullerene-based acceptors through π-π interactions and in particular the most used phenyl-C61-butyric acid methyl ester (PCBM) PCBM. The resulting pyrPOM@PCBM IFL, assembled by means of the Langmuir-Blodgett approach, has been fully characterized both in solution and on solid supports by means of the Langmuir-Schaefer method, featuring a high dielectric function, good polarizability and piezo-responsive behavior, which suggest ferroelectric properties. An organic solar cell is realized interposing the IFL between poly(3-hexylthiophene) (P3HT) as polymer donor and the PCBM acceptor layers, thus enhancing the open circuit voltage of the solar device by about 34% under an applied bias of ±5 V. © 2021 The Royal Society of Chemistry

Selective targeting of proteins by hybrid polyoxometalates: Interaction between a bis-biotinylated hybrid conjugate and avidin

The Keggin-type polyoxometalate [\u3b3-SiW10O36]8 12 was covalently modified to obtain a bis-biotinylated conjugate able to bind avidin. Spectroscopic studies such as UV-vis, fluorimetry, circular dichroism, coupled to surface plasmon resonance technique were used to highlight the unique interplay of supramolecular interactions between the homotetrameric protein and the bis-functionalized polyanion. In particular, the dual recognition mechanism of the avidin encompasses (i) a complementary electrostatic association between the anionic surface of the polyoxotungstate and each positively charged avidin subunit and (ii) specific host-guest interactions between each biotinylated arm and a corresponding pocket on the tetramer subunits. The assembly exhibits peroxidase-like reactivity and it was used in aqueous solution for L-methionine methyl ester oxidation by H2O2. The recognition phenomenon was then exploited for the preparation of layer-by-layer films, whose structural evolution was monitored in situ by ATR-FTIR spectroscopy. Finally, cell tracking studies were performed by exploiting the specific interactions with a labeled streptavidin

Tuning the activity of a hybrid polymer–oxocluster catalyst: A composition—selectivity correlation

Zr-based oxoclusters M$_{x}$O$_{y}$(OR)$_{w}$(OOR’)$_{z}$ are promising catalysts for the activation of hydrogen peroxide. However, they need to be integrated into suitable matrices to increase their hydrolytic stability and allow for their recovery after use. Polymeric materials can be successfully employed for this aim, since they modify the properties of the resulting hybrid materials, in terms of polarity and chemical affinity for the substrates, improving the catalytic activity. Herein, we report the synthesis of different acrylic polymers based on various co-monomers (methyl methacrylate (MMA), 2,2,2-trifluoroethylmethacrylate (TFMA) and 3-methacryloxypropyltrimethoxylsilane (MAPTMS)) covalently cross-linked by a Zr$_{4}$-based oxocluster, whose composition was tuned to optimise the catalytic oxidation of methyl p-tolyl sulphide. To assess their properties and stability, the materials were characterised via Fourier Transform Infrared (FT-IR) and Raman spectroscopies, Thermogravimetric Analysis (TGA), Solid-State NMR (SS-NMR) and X-Ray Absorption Spectroscopies XAS, before and after catalytic turnover

Anchors for the Cosmic Distance Scale: the Cepheid QZ Normae in the Open Cluster NGC 6067

Cepheids are key to establishing the cosmic distance scale. Therefore it's important to assess the viability of QZ Nor, V340 Nor, and GU Nor as calibrators for Leavitt's law via their purported membership in the open cluster NGC 6067. The following suite of evidence confirms that QZ Nor and V340 Nor are members of NGC 6067, whereas GU Nor likely lies in the foreground: (i) existing radial velocities for QZ Nor and V340 Nor agree with that established for the cluster (-39.4+-1.2 km/s) to within 1 km/s, whereas GU Nor exhibits a markedly smaller value; (ii) a steep velocity-distance gradient characterizes the sight-line toward NGC 6067, thus implying that objects sharing common velocities are nearly equidistant; (iii) a radial profile constructed for NGC 6067 indicates that QZ Nor is within the cluster bounds, despite being 20' from the cluster center; (iv) new BVJH photometry for NGC 6067 confirms the cluster lies d=1.75+-0.10 kpc distant, a result that matches Wesenheit distances computed for QZ Nor/V340 Nor using the Benedict et al. (2007, HST parallaxes) calibration. QZ Nor is a cluster Cepheid that should be employed as a calibrator for the cosmic distance scale.Comment: To appear in ApS

Modelagem da progressão da DBO obtida na incubação de esgoto doméstico sob diferentes temperaturas

Confiável quantificação da demanda bioquímica de oxigênio exercida (DBO exercida) poderá ser obtida com incubação das amostras sob temperaturas diferentes, desde que o valor da demanda bioquímica de oxigênio última (DBOU) não seja alterado nessas condições. Alguns autores têm relatado aumento no valor da DBOU com a elevação da temperatura de incubação das amostras, o que pode ser decorrente da ocorrência da nitrificação, da aclimatação diferenciada ou do mau ajuste dos modelos de progressão da demanda bioquímica carbonácea de oxigênio (DBO exercida). Neste estudo, objetivou-se avaliar o efeito da temperatura sobre a progressão da DBO exercida e o valor da DBOu em amostras de esgoto doméstico bruto, avaliando-se qual modelo melhor se ajusta aos dados obtidos. Os resultados indicaram pequena influência da temperatura de incubação das amostras nos valores da DBOU do esgoto sanitário e que os modelos de primeira e segunda ordens descreveram adequadamente a progressão da DBO exercida.Reliable quantification of biochemical oxygen demand exerted (exerted BOD) can be obtained by incubating samples at different temperatures, since the amount of ultimate biochemical oxygen demand (UBOD) does not change in these conditions. Some authors have found increased UBOD values with rise in temperature of incubating samples, which could be due to the occurrence of nitrification, the acclimatization or the inadequacy of modeling of carbonaceous oxygen demand (exerted BOD) progression. This study aimed to evaluate the effect of temperature on the progression of exerted BOD and UBOD values in samples of raw domestic sewage, checking which model best fits the data. The results indicated low influence of incubating sewage samples temperature on UBOD values, being that both models, first and second order, described properly the exerted BOD progression

Infrared photometry and CaT spectroscopy of globular cluster M 28 (NGC 6626)

Recent studies show that the inner Galactic regions host genuine bulge globular clusters, but also halo intruders, complex remnants of primordial building blocks, and objects likely accreted during major merging events. In this study we focus on the properties of M 28, a very old and massive cluster currently located in the Galactic bulge. We analysed wide-field infrared photometry collected by the VVV survey, VVV proper motions, and intermediate-resolution spectra in the calcium triplet range for 113 targets in the cluster area. Our results in general confirm previous estimates of the cluster properties available in the literature. We find no evidence of differences in metallicity between cluster stars, setting an upper limit of Delta[Fe/H]<0.08 dex to any internal inhomogeneity. We confirm that M 28 is one of the oldest objects in the Galactic bulge (13-14 Gyr). From this result and the literature data, we find evidence of a weak age-metallicity relation among bulge globular clusters that suggests formation and chemical enrichment. In addition, wide-field density maps show that M 28 is tidally stressed and that it is losing mass into the general bulge field. Our study indicates that M 28 is a genuine bulge globular cluster, but its very old age and its mass loss suggest that this cluster could be the remnant of a larger structure, possibly a primeval bulge building block.Comment: Accepted for publication in Astronomy & Astrophysic