Making solar fuels by artificial photosynthesis

In order for solar energy to serve as a primary energy source, it must be paired with energy storage on a massive scale. At this scale, solar fuels and energy storage in chemical bonds is the only practical approach. Solar fuels are produced in massive amounts by photosynthesis with the reduction of CO(2) by water to give carbohydrates but efficiencies are low. In photosystem II (PSII), the oxygen-producing site for photosynthesis, light absorption and sensitization trigger a cascade of coupled electron-proton transfer events with time scales ranging from picoseconds to microseconds. Oxidative equivalents are built up at the oxygen evolving complex (OEC) for water oxidation by the Kok cycle. A systematic approach to artificial photo synthesis is available based on a ""modular approach"" in which the separate functions of a final device are studied separately, maximized for rates and stability, and used as modules in constructing integrated devices based on molecular assemblies, nanoscale arrays, self-assembled monolayers, etc. Considerable simplification is available by adopting a ""dyesensitized photoelectrosynthesis cell"" (DSPEC) approach inspired by dye-sensitized solar cells (DSSCs). Water oxidation catalysis is a key feature, and significant progress has been made in developing a single-site solution and surface catalysts based on polypyridyl complexes of Ru. In this series, ligand variations can be used to tune redox potentials and reactivity over a wide range. Water oxidation electrocatalysis has been extended to chromophore-catalyst assemblies for both water oxidation and DSPEC applications.

EPR of gamma-induced paramagnetic centers in tellurite glasses

Intrinsic paramagnetic responses were observed in the 60TeO(2)-25ZnO-15Na(2)O and 85TeO(2)-15Na(2)O mol% glasses, after gamma-irradiation at room temperature: (1) a shoulder at g(1) = g(parallel to) = 2.02 +/- 0.01 and an estimated g(perpendicular to)similar to 2.0 attributed to tellurium-oxygen hole center (TeOHC); (2) a narrow resonance at g(2)= 1.9960 +/- 0.0005 related to the modifiers and (3) a resolved resonance at g(3) = 1.9700 +/- 0.0005 ascribed to a tellurium electron center (TeEC) of an electron trapped at an oxygen vacancy (V(o)(+)) in a tellurium oxide structural center. It is suggested that the creation of (NBO(-),V(o)(+)) pair follows a mechanism where the modifier oxide molecule actuates as a catalyser. An additional model for the NBO radiolysis produced by the gamma-irradiation is proposed on the basis of the evolution of the g(1), g(2) and g(3) intensities with increasing dose (kGy). Crown Copyright (C) 2010 Published by Elsevier B.V. All rights reserved.

Synthesis and Crystal Structures of Octahedral Sn(IV) Complexes Prepared from SnCl(2)center dot 2H(2)O and 2-Hydroxyacetophenone (S-benzydithiocarbazate) Ligand (H(2)L)

Two coordination octahedral Sn(IV) complexes [Sn(L)(2)] and cis-[SnCl(2)(L)(dmso)], where H(2)L is 2-hydroxyacetophenone (S-benzydithiocarbazate), were prepared and characterized by elemental analysis, IR, NMR ((1)H, (13)C), (119)Sn Mossbauer spectroscopies and X-ray diffraction techniques to investigate their structural properties. Both crystallize in the Monoclinic system, with parameters: a = 8.1905(3), b = 30.8811(15), c = 12.8959(7) angstrom, beta = 94.465(3)degrees and Z = 4 for [Sn(L)(2)] and a = 8.5247(2), b = 21.5445(7), c = 12.3706(3) angstrom, beta = 96.932(2)degrees and Z = 4 for cis-[SnCl(2)(L)(dmso)]. In both complexes, the Sn(IV) central atom is coordinated in a distorted octahedral geometry with the thiolate ligand (L(2-)) coordinated via O, N and S atoms. The (119)Sn Mossbauer spectroscopy of the complexes were studied and the results revealed that both complexes posses isomer shift (delta) and quadrupole splitting (Delta), which are almost the same.

Singlet oxygen reacts with 2 `,7 `-dichlorodihydrofluorescein and contributes to the formation of 2 `,7 `-dichlorofluorescein

There are controversial reports in the literature concerning the reactivity of singlet oxygen ((1)O(2)) with the redox probe 2`,7`-dichlorodihydrofluorescein (DCFH). By carefully preparing solutions in which (1)O(2) is quantitatively generated in the presence of DCFH, we were able to show that the formation rate of the fluorescent molecule derived from DCFH oxidation, which is 2`,7`-dichlorofluorescein (DCF), increases in D(2)O and decreases in sodium azide, proving the direct role of (1)O(2) in this process. We have also prepared solutions in which either (1)O(2) or dication (MB(center dot 2+)) and semi-reduced (MB(center dot)) radicals of the sensitizer and subsequently super-oxide radical (O(2)(center dot-)) are generated. The absence of any effect of SOD and catalase ruled out the DCFH oxidation by O(2)(center dot-), indicating that both (1)O(2) and MB(center dot 2+) react with DCFH. Although the formation of DCF was 1 order of magnitude larger in the presence of MB(center dot 2+) than in the presence of (1)O(2), considering the rate of spontaneous decays of these species in aqueous solution, we were able to conclude that the reactivity of (1)O(2) with DCFH is actually larger than that of MB(center dot 2+). We conclude that DCFH can continue to be used as a probe to monitor general redox misbalance induced in biologic systems by oxidizing radicals and (1)O(2).

Singlet oxygen generation in the reaction centers of Rhodobacter sphaeroides

Singlet oxygen ((1)O(2)) generation in the reaction centers (RCs) of Rhodobacter sphaeroides wild type was characterized by luminescent emission in the near infrared region (time resolved transients and emission spectra) and quantified to have quantum yield of 0.03 +/- 0.005. (1)O(2) emission was measured as a function of temperature, ascorbate, urea and potassium ferricyanide concentrations and as a function of incubation time in H(2)O: D(2)O mixtures. (1)O(2) was shown to be affected by the RC dynamics and to originate from the reaction of molecular oxygen with two sources of triplets: photoactive dimer formed by singlet-triplet mixing and bacteriopheophytin formed by direct photoexcitation and intersystem crossing.

Electrocatalysis of oxygen reduction on carbon-supported Pt-Co nanoparticles with low Pt content

The oxygen reduction reaction (ORR) was investigated on carbon-supported Pt-Co nanoparticle electrocatalysts with low Pt content in alkaline electrolyte. High resolution transmission electron microscopy, In situ X-ray absorption spectroscopy, and X-ray diffraction analysis evidenced large structural differences of the Pt-Co particles depending oil the route of the catalyst synthesis. It was demonstrated that although the Pt-Co materials contain low amounts of Pt, they show very good activities when the particles are formed by a Pt-rich shell and a Pt-Co core, which was obtained after submitting the electrocatalyst to a potential cycling in acid electrolyte. The high activity of this material was due to a major contribution from its higher surface area, as a result of the leaching of the Co atoms from the particle Surface. Furthermore, its high activity was ascribed to a minor contribution from the electronic interaction of the Pt atoms, at the particle surface, and the Co atoms located in the beneath layer, lowering the Pt cl-band center. As these electrocatalysts presented high activity for the ORR with low Pt content, the cost of the fuel cell cathodes could be lowered considerably. (c) 2009 Elsevier B.V. All rights reserved.

Calibration of the dietary data obtained from the Brazilian center of the Natural History of HPV Infection in Men study: the HIM Study

The objective of this study was to estimate the regressions calibration for the dietary data that were measured using the quantitative food frequency questionnaire (QFFQ) in the Natural History of HPV Infection in Men: the HIM Study in Brazil. A sample of 98 individuals from the HIM study answered one QFFQ and three 24-hour recalls (24HR) at interviews. The calibration was performed using linear regression analysis in which the 24HR was the dependent variable and the QFFQ was the independent variable. Age, body mass index, physical activity, income and schooling were used as adjustment variables in the models. The geometric means between the 24HR and the calibration-corrected QFFQ were statistically equal. The dispersion graphs between the instruments demonstrate increased correlation after making the correction, although there is greater dispersion of the points with worse explanatory power of the models. Identification of the regressions calibration for the dietary data of the HIM study will make it possible to estimate the effect of the diet on HPV infection, corrected for the measurement error of the QFFQ.

Reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam fac-[Ru(NO)Cl(2)(kappa(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl center dot H(2)O

Chemical reactivity, photolability, and computational studies of the ruthenium nitrosyl complex with a substituted cyclam, fac-[Ru(NO)Cl(2)(kappa(3)N(4),N(8),N(11)(1-carboxypropyl)cyclam)]Cl center dot H(2)O ((1-carboxypropyl) cyclam = 3-(1,4,8,11-tetraazacyclotetradecan-1-yl) propionic acid)), (I) are described. Chloride ligands do not undergo aquation reactions (at 25 degrees C, pH 3). The rate of nitric oxide (NO) dissociation (k(obs-NO)) upon reduction of I is 2.8 s(-1) at 25 +/- 1 degrees C (in 0.5 mol L(-1) HCl), which is close to the highest value found for related complexes. The uncoordinated carboxyl of I has a pK(a) of similar to 3.3, which is close to that of the carboxyl of the non coordinated (1-carboxypropyl) cyclam (pK(a) = 3.4). Two additional pK(a) values were found for I at similar to 8.0 and similar to 11.5. Upon electrochemical reduction or under irradiation with light (lambda(irr) = 350 or 520 nm; pH 7.4), I releases NO in aqueous solution. The cyclam ring N bound to the carboxypropyl group is not coordinated, resulting in a fac configuration that affects the properties and chemical reactivities of I, especially as NO donor, compared with analogous trans complexes. Among the computational models tested, the B3LYP/ECP28MDF, cc-pVDZ resulted in smaller errors for the geometry of I. The computational data helped clarify the experimental acid-base equilibria and indicated the most favourable site for the second deprotonation, which follows that of the carboxyl group. Furthermore, it showed that by changing the pH it is possible to modulate the electron density of I with deprotonation. The calculated NO bond length and the Ru/NO charge ratio indicated that the predominant canonical structure is [Ru(III)NO], but the Ru-NO bond angles and bond index (b.i.) values were less clear; the angles suggested that [Ru(II)NO(+)] could contribute to the electronic structure of I and b.i. values indicated a contribution from [Ru(IV)NO(-)]. Considering that some experimental data are consistent with a [Ru(II)NO(+)] description, while others are in agreement with [Ru(III)NO], the best description for I would be a linear combination of the three canonical forms, with a higher weight for [Ru(II)NO(+)] and [Ru(III)NO].

Signatures of oxygen on Cu(3)Au(100): From isolated impurity to oxide regimes

We analyze the scanning tunneling microscopy (STM) signatures for the O/Cu(3)Au(100) surface from the low-coverage (isolated impurity) to high-coverage (oxide) regimes. First-principles calculations show that oxygen signatures switch from dark to bright spots as the oxygen coverage increases. This behavior is nicely traced back to a change in the oxygen orbital character of the Fermi-level electronic states. Our results allow for the chemical identification by STM of oxygen and copper atoms in the fully ordered O/Cu(3)Au(100)-c(2x2) surface.

Genetic Background of Patients from a University Medical Center in Manhattan: Implications for Personalized Medicine

Background: The rapid progress currently being made in genomic science has created interest in potential clinical applications; however, formal translational research has been limited thus far. Studies of population genetics have demonstrated substantial variation in allele frequencies and haplotype structure at loci of medical relevance and the genetic background of patient cohorts may often be complex. Methods and Findings: To describe the heterogeneity in an unselected clinical sample we used the Affymetrix 6.0 gene array chip to genotype self-identified European Americans (N = 326), African Americans (N = 324) and Hispanics (N = 327) from the medical practice of Mount Sinai Medical Center in Manhattan, NY. Additional data from US minority groups and Brazil were used for external comparison. Substantial variation in ancestral origin was observed for both African Americans and Hispanics; data from the latter group overlapped with both Mexican Americans and Brazilians in the external data sets. A pooled analysis of the African Americans and Hispanics from NY demonstrated a broad continuum of ancestral origin making classification by race/ethnicity uninformative. Selected loci harboring variants associated with medical traits and drug response confirmed substantial within-and between-group heterogeneity. Conclusion: As a consequence of these complementary levels of heterogeneity group labels offered no guidance at the individual level. These findings demonstrate the complexity involved in clinical translation of the results from genome-wide association studies and suggest that in the genomic era conventional racial/ethnic labels are of little value.

VLT-FLAMES analysis of 8 giants in the bulge metal-poor globular cluster NGC 6522: oldest cluster in the Galaxy? Analysis of 8 giants in NGC 6522

Context. NGC 6522 has been the first metal-poor globular cluster identified in the bulge by Baade. Despite its importance, very few high-resolution abundance analyses of stars in this cluster are available. The bulge metal-poor clusters may be important tracers of the early chemical enrichment of the Galaxy. Aims. The main purpose of this study is to determine metallicity and elemental ratios in individual stars of NGC 6522. Methods. High-resolution spectra of 8 giants of the bulge's globular cluster NGC 6522 were obtained at the 8m VLT UT2-Kueyen telescope with the FLAMES+GIRAFFE spectrograph. Multiband V, I, J, K(s) photometry was used to derive effective temperatures as reference values. Spectroscopic parameters were derived from Fe I and Fe II lines, and adopted for the derivation of abundance ratios. Results. The present analysis provides a metallicity [Fe/H] = -1.0 +/- 0.2. The alpha-elements oxygen, magnesium and silicon show [O/Fe] = +0.4 +/- 0.3, [Mg/Fe] = [Si/Fe] = +0.25 +/- 0.15, whereas calcium and titanium show shallower ratios of [Ca/Fe] = [Ti/Fe] = +0.15 +/- 0.15. The neutron-capture r-process element europium appears to be overabundant by [Eu/Fe] = +0.4 +/- 0.4. The neutron-capture s-elements lanthanum and barium are enhanced by [La/Fe] = +0.35 +/- 0.2 and [Ba/Fe] = +0.5 +/- 0.5. The large internal errors, indicating the large star-to-star variation in the barium and europium abundances, are also discussed. Conclusions. The moderate metallicity combined to a blue horizontal branch (BHB), are characteristics similar to those of HP 1 and NGC 6558, pointing to a population of very old globular clusters in the Galactic bulge. Also, the abundance ratios in NGC 6522 resemble those in HP 1 and NGC 6558. The ultimate conclusion is that the bulge is old, and went through an early prompt chemical enrichment.

First stars XII. Abundances in extremely metal-poor turnoff stars, and comparison with the giants

Context. The detailed chemical abundances of extremely metal-poor (EMP) stars are key guides to understanding the early chemical evolution of the Galaxy. Most existing data, however, treat giant stars that may have experienced internal mixing later. Aims. We aim to compare the results for giants with new, accurate abundances for all observable elements in 18 EMP turno. stars. Methods. VLT/UVES spectra at R similar to 45 000 and S/N similar to 130 per pixel (lambda lambda 330-1000 nm) are analysed with OSMARCS model atmospheres and the TURBOSPECTRUM code to derive abundances for C, Mg, Si, Ca, Sc, Ti, Cr, Mn, Co, Ni, Zn, Sr, and Ba. Results. For Ca, Ni, Sr, and Ba, we find excellent consistency with our earlier sample of EMP giants, at all metallicities. However, our abundances of C, Sc, Ti, Cr, Mn and Co are similar to 0.2 dex larger than in giants of similar metallicity. Mg and Si abundances are similar to 0.2 dex lower (the giant [Mg/Fe] values are slightly revised), while Zn is again similar to 0.4 dex higher than in giants of similar [Fe/H] (6 stars only). Conclusions. For C, the dwarf/giant discrepancy could possibly have an astrophysical cause, but for the other elements it must arise from shortcomings in the analysis. Approximate computations of granulation (3D) effects yield smaller corrections for giants than for dwarfs, but suggest that this is an unlikely explanation, except perhaps for C, Cr, and Mn. NLTE computations for Na and Al provide consistent abundances between dwarfs and giants, unlike the LTE results, and would be highly desirable for the other discrepant elements as well. Meanwhile, we recommend using the giant abundances as reference data for Galactic chemical evolution models.

Hyperbaric Oxygen Prevents Early Death Caused by Experimental Cerebral Malaria

Background: Cerebral malaria (CM) is a syndrome characterized by neurological signs, seizures and coma. Despite the fact that CM presents similarities with cerebral stroke, few studies have focused on new supportive therapies for the disease. Hyperbaric oxygen (HBO) therapy has been successfully used in patients with numerous brain disorders such as stroke, migraine and atherosclerosis. Methodology/Principal Findings: C57BL/6 mice infected with Plasmodium berghei ANKA (PbA) were exposed to daily doses of HBO (100% O(2), 3.0 ATA, 1-2 h per day) in conditions well-tolerated by humans and animals, before or after parasite establishment. Cumulative survival analyses demonstrated that HBO therapy protected 50% of PbA-infected mice and delayed CM-specific neurological signs when administrated after patent parasitemia. Pressurized oxygen therapy reduced peripheral parasitemia, expression of TNF-alpha, IFN-gamma and IL-10 mRNA levels and percentage of gamma delta and alpha beta CD4(+) and CD8(+) T lymphocytes sequestered in mice brains, thus resulting in a reduction of blood-brain barrier (BBB)dysfunction and hypothermia. Conclusions/Significance: The data presented here is the first indication that HBO treatment could be used as supportive therapy, perhaps in association with neuroprotective drugs, to prevent CM clinical outcomes, including death.

The role of oxygen vacancy in the photoluminescence property at room temperature of the CaTiO(3)

In this paper, electron paramagnetic resonance, photoluminescence (PL) emission, and quantum mechanical calculations were used to observe and understand the structural order-disorder of CaTiO(3), paying special attention to the role of oxygen vacancy. The PL phenomenon at room temperature of CaTiO(3) is directly influenced by the presence of oxygen vacancies that yield structural order-disorder. These oxygen vacancies bonded at Ti and/or Ca induce new electronic states inside the band gap. Ordered and disordered CaTiO(3) was obtained by the polymeric precursor method. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3190524]