4-Organochalcogenoyl-1H-1,2,3-triazoles: synthesis and functionalization by a nickel-catalyzed Negishi cross-coupling reaction

A general method for the synthesis of triazoles containing selenium and tellurium was accomplished via a CuCAAC reaction between organic azides and a terminal triple bond, generated by in situ deprotection of the silyl group. The reaction tolerates alkyl and arylazides, with alkyl and aryl substituents directly bonded to the chalcogen atom. The products were readily functionalized by a nickel-catalyzed Negishi cross-coupling reaction, furnishing the aryl-heteroaryl products at the 4-position in good yields. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of selenium-linked neoglycoconjugates and pseudodisaccharides

The introduction of organoselenium moieties within the structure of carbohydrates has received attention recently. Herein, we report on the synthesis of selenium-containing neoglycoconjugates and pseudodisaccharides by the reaction of nucleophilic selenium species, generated from sugar diselenides, with chiral N-Boc aziridines and sugar tosylates. The reaction proceeds with moderate to good yields for various substrates. The introduction of organoselenium moieties within the framework of various sugars, with increased levels of complexity, thus allowing the synthesis of disaccharide and glycoconjugate mimetics. (C) 2012 Elsevier Ltd. All rights reserved.

Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

Metallic chalcogenolates mediated modular Michael-aldol cascade reaction: an easy route to multi-functionalized chalcogenides and Morita-Baylis-Hillman adducts

Chalcogenolate mediated Michael-aldol cascade reactions consists of a very efficient route to multi-functionalized gamma-hydroxichalcogenides. Although, when selenolates are employed, these gamma-hydroxichalcogenides can be readily converted into the corresponding Morita-Baylis-Hillman adducts by oxidative elimination of the selenium moiety. In this context, herein we present a complete study on the scope and limitations of this reaction. (C) 2012 Elsevier Ltd. All rights reserved.

Direct assembly of a metallodendrimer encompassing seven triruthenium clusters units

A general strategy for the assembly of dendrimeric metallo-cluster species based on tritopic trinuclear ruthenium acetate complexes is demonstrated. First, a central core consisting of a [Ru3O(CH3COO)(6)(TPEB)(3)]PF6 complex (G0), where TPEB is the tripodal 1,3,5-tri-4-pyridyl-1,2-ethenylbenzene ligand, was synthesized and then reacted with the end-capping complex [Ru3O(CH3COO)(6)(py)(2)(MeOH)]PF6, thus composing the first generation shell of a dendrimer encompassing twenty-one ruthenium ions (G1). The core and dendrimeric complexes were characterized by elemental analysis, UV-Vis, H-1 NMR, ESI-MS spectrometry and Differential pulse voltammetry. All results were consistent with the structure of that multinuclear cationic dendrimeric species. The isotopologic profile of daughter fragments and the strength of the metal-ligand bonds were carefully investigated providing the fragmentation pathway for the metallo-dendrimer upon ESI-MS dissociation conditions. (C) 2012 Elsevier B.V. All rights reserved.

Effect of Brazil Nut Supplementation on Plasma Levels of Selenium in Hemodialysis Patients: 12 Months of Follow-up

Background: Large amounts of reactive oxygen species are produced in hemodialysis (HD) patients, and, at higher concentrations, reactive oxygen species are thought to be involved in the pathogenesis of cardiovascular disease. It has been proposed that selenium (Se) may exert an antiatherogenic influence by reducing oxidative stress. The richest known food source of Se is the Brazil nut (Bertholletia excelsa, family Lecythidaceae), found in the Amazon region. Objective: The objective of this work was to determine if Se plasma levels in HD patients submitted to a program of supplementation during 3 months with 1 Brazil nut by day could be sustained after 12 months. Methods: A total of 21 HD patients (54.2 +/- 15.2 years old; average time on dialysis, 82.3 +/- 51.6 months; body mass index, 24.4 +/- 3.8 kg/m(2)) from the RenalCor Clinic in Rio de Janeiro, Brazil, were followed up 12 months after the supplementation study ended. The Se plasma levels were determined by atomic absorption spectrophotometry with hydride generation. Results: The Se Plasma levels (17.3 +/- 19.9 mg/L) were below the normal range (60 to 120 mu g/L) before nut supplementation, and after 3 months of supplementation, the levels increased to 106.8 +/- 50.3 mu g/L (P < .0001). Twelve months after supplementation, the plasma Se levels decreased to 31.9 +/- 14.8 mu g/L (P < .0001). Conclusions: The data showed that these patients were Se deficient and that the consumption of Brazil nut was effective to increase the Se parameters of nutritional status. Se levels 12 months after the supplementation period were not as low as presupplementation levels but yet significantly lower, and we needed to motivate patients to adopt different dietary intake patterns. (C) 2012 by the National Kidney Foundation, Inc. All rights reserved.

Levels of Selenomonas species in generalized aggressive periodontitis

Goncalves LFH, Fermiano D, Feres M, Figueiredo LC, Teles FRP, Mayer MPA, Faveri M. Levels of Selenomonas species in generalized aggressive periodontitis. J Periodont Res 2012; 47: 711718. (c) 2012 John Wiley & Sons A/S Background and Objective: To compare the levels of Selenomonas sputigena and uncultivated/unrecognized Selenomonas species in subgingival biofilms from periodontally healthy subjects and from subjects with generalized aggressive periodontitis. Material and Methods: Fifteen periodontally healthy subjects and 15 subjects with generalized aggressive periodontitis were recruited and their clinical periodontal parameters were evaluated. Nine subgingival plaque samples were collected from each subject and all were individually analyzed for the levels of 10 bacterial taxa, including cultured and uncultivated/unrecognized microorganisms, using the RNA-oligonucleotide quantification technique. Between-group differences in the levels of the test taxa were determined using the MannWhitney U-test. Results: Subjects with generalized aggressive periodontitis showed significantly higher mean counts of Porphyromonas gingivalis, S. sputigena and the Mitsuokella sp. Human Oral Taxon (HOT) 131 (previously described as Selenomonas sp. oral clone CS002), while higher mean counts of Actinomyces gerencseriae and Streptococcus sanguinis were found in periodontally healthy subjects (p < 0.01). Selenomonas sp. HOT 146 was only detected in the generalized aggressive periodontitis group. In the generalized aggressive periodontitis group, the levels of P.gingivalis and S.sputigena were higher in deep sites (probing depth = 5 mm) than in shallow sites (probing depth = 3 mm) (p < 0.01). Furthermore, in subjects with generalized aggressive periodontitis, sites with probing depth of = 3 mm harbored higher levels of these two species than sites with the same probing depth in periodontally healthy subjects. There were positive correlations between probing depth and the levels of P.gingivalis (r = 0.77; p < 0.01), S.sputigena (r = 0.60; p < 0.01) and Selenomonas dianae (previously described as Selenomonas sp. oral clone EW076) (r = 0.42, p < 0.05). Conclusion: S. sputigena and Mitsuokella sp. HOT 131 may be associated with the pathogenesis of generalized aggressive periodontitis, and their role in the onset and progression of this infection should be investigated further.

Electrodeposition of PVA-protected PtCo electrocatalysts for the oxygen reduction reaction in H2SO4

In this paper we report the electrosynthesis of PVA-protected PtCo films (PVA = poly(vinylalcohol)) and their activities towards the oxygen reduction reaction (ORR). PtCo electrodeposits were potentiostatically obtained in the presence and absence of PVA at distinct potentials. The film morphology and composition were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX), which revealed that the use of PVA in the electrodeposition of PtCo films was decisive to achieve better film composition control. Cyclic voltammetry for PVA-protected PtCo films showed that the electrochemical surface area is dependent on the electrodeposition potentials and suggested different adsorption strengths of oxygen-containing species. Films produced in the presence of PVA presented the following activity order towards ORR as a function of the electrodeposition potential (vs. Ag/AgCl): -0.9 V> -0.8 V> -1.0 V> -0.7 V. In contrast, PtCo films electrodeposited in the absence of PVA displayed very similar activities regardless of the electrodeposition potential. The simplicity of the electrodeposition method combined with its effectiveness enabled the production of "model electrodes" for investigating the fundamental aspects of the reactions taking place in the fuel cell cathodes. (C) 2011 Elsevier B.V. All rights reserved.

Structure and Ionic Conductivity in the Mixed-Network Former Chalcogenide Glass System [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3)

Glasses in the system [Na2S](2/3)[(B2S3)(x)(P2S5)(1-x)](1/3) (0.0 <= x <= 1.0) were prepared by the melt quenching technique, and their properties were characterized by thermal analysis and impedance spectroscopy. Their atomic-level structures were comprehensively characterized by Raman spectroscopy and B-11, P-31, and Na-23 high resolution solid state magic-angle spinning (MAS) NMR techniques. P-31 MAS NMR peak assignments were made by the presence or absence of homonuclear indirect P-31-P-31 spin-spin interactions as detected using homonuclear J-resolved and refocused INADEQUATE techniques. The extent of B-S-P connectivity in the glassy network was quantified by P-31{B-11} and B-11{P-31} rotational echo double resonance spectroscopy. The results clearly illustrate that the network modifier alkali sulfide, Na2S, is not proportionally shared between the two network former components, B and P. Rather, the thiophosphate (P) component tends to attract a larger concentration of network modifier species than predicted by the bulk composition, and this results in the conversion of P2S74-, pyrothiophosphate, Na/P = 2:1, units into PS43-, orthothiophosphate, Na/P = 3:1, groups. Charge balance is maintained by increasing the net degree of polymerization of the thioborate (B) units through the formation of covalent bridging sulfur (BS) units, B S B. Detailed inspection of the B-11 MAS NMR spectra reveals that multiple thioborate units are formed, ranging from neutral BS3/2 groups all the way to the fully depolymerized orthothioborate (BS33-) species. On the basis of these results, a comprehensive and quantitative structural model is developed for these glasses, on the basis of which the compositional trends in the glass transition temperatures (T-g) and ionic conductivities can be rationalized. Up to x = 0.4, the dominant process can be described in a simplified way by the net reaction equation P-1 + B-1 reversible arrow P-0 + B-4, where the superscripts denote the number of BS atoms for the respective network former species. Above x = 0.4, all of the thiophosphate units are of the P-0 type and both pyro-(B-1) and orthothioborate (B-0) species make increasing contributions to the network structure with increasing x. In sharp contrast to the situation in sodium borophosphate glasses, four-coordinated thioborate species are generally less abundant and heteroatomic B-S-P linkages appear to not exist. On the basis of this structural information, compositional trends in the ionic conductivities are discussed in relation to the nature of the charge-compensating anionic species and the spatial distribution of the charge carriers.

Reforming of a model biogas on Ni and Rh-Ni catalysts: Effect of adding La

Ni catalysts supported on gamma-Al2O3 modified by Rh and La were prepared and evaluated on the reforming of a model biogas. The catalysts were characterized by EDS, XRD, TPR, XANES and surface area estimation (BET). The results showed that in the original Ni catalyst, the Ni interacted strongly with the alumina support, exhibiting high reduction temperatures in TPR tests. In the catalytic tests, the addition of Rh on Ni catalysts improved CH4 conversion but also increased carbon deposition, possible by causing the segregation of Ni species under the reaction conditions. The presence of La on Ni catalysts reduced the carbon deposition by favoring the gasification of carbon species. Addition of synthetic air to the process improved the CH4 conversion and also decreased the carbon formation. The catalysts Ni, Rh-NiLa, and Rh showed good results in the conversion of model sulfur-free biogas, which suggests that they are promising catalysts to be tested in conversion of real biogas. (C) 2012 Elsevier B.V. All rights reserved.

Exact correlation functions in particle-reaction models with immobile particles

Exact results on particle densities as well as correlators in two models of immobile particles, containing either a single species or else two distinct species, are derived. The models evolve following a descent dynamics through pair annihilation where each particle interacts once at most throughout its entire history. The resulting large number of stationary states leads to a non-vanishing configurational entropy. Our results are established for arbitrary initial conditions and are derived via a generating function method. The single-species model is the dual of the 1D zero-temperature kinetic Ising model with Kimball-Deker-Haake dynamics. In this way, both in finite and semi-infinite chains and also the Bethe lattice can be analysed. The relationship with the random sequential adsorption of dimers and weakly tapped granular materials is discussed.

Stable assemblies of cationic bilayer fragments and CpG oligonucleotide with enhanced immunoadjuvant activity in vivo

The cationic lipid dioctadecyldimethylammonium bromide (DODAB) and the CpG oligonucleotide (CpG) have been separately used as potent immunoadjuvants driving Th1 responses. Here DODAB bilayer fragments (BF) and CpG (5 -TTGACGTTCG-3) assemblies have their physical properties and immunoadjuvant activity determined using ovalbumin (OVA) as a model antigen. At 0.1 mg/mL OVA, the dependence of DODAB BF/OVA size and zeta-potential on time and [DODAB] establishes 0.1 mMDODAB as suitable for obtaining stable and cationic DODAB BF/OVA assemblies. At 0.1 mMDODAB, 0.1 mg/mL OVA and 0.006 mMCpG, the zeta-potential is zero. At [CpG]>0.006 mM, good colloidal stability for the anionic assemblies is due to charge overcompensation. At 0.020 mM CpG, these DODAB BF/OVA/CpG assemblies are highly effective in vivo generating responses similar to those elicited by the stable and cationic DODAB BF/OVA. The anti-OVA DTH reaction and the secretion of IFN-gamma and IL-12 are 6, 42 and 9 times larger for the DODAB BF/OVA/CpG-immunized mice than the same responses by OVA-immunized mice, respectively. This work shows for the first time that charge of small assemblies is not important to determine the immune response. (C) 2011 Elsevier B. V. All rights reserved.

No evidence of selenosis from a selenium-rich diet in the Brazilian Amazon

Selenium (Se) is an essential element and a well-known anti-oxidant. In the Lower Tapajos River region of the Brazilian Amazon, biomarkers of Se range from normal to very high. The local traditional diet includes important Se sources such as Brazil nuts, chicken, game meat and certain fish species. Some studies have reported alterations in keratin structure, gastrointestinal problems and paresthesia in populations with high Se intake. The objective of the present study was to evaluate cutaneous and garlic odor of the breath signs and sentinel symptoms of Se toxicity (selenosis) in relation to Se status in communities along the Tapajos River. Participants (N = 448), aged 15-87 years, were recruited from 12 communities. Se concentrations were measured in blood (B-Se) and plasma (P-Se) by ICP-MS. A nurse performed an examination of the hair, nails, skin and breath for signs of Se toxicity. Interview-administered questionnaires were used to collect information on socio-demographics, medical history and possible symptoms of Se toxicity. In this population, the median levels of B-Se and P-Se were 228.4 mu g/L (range 103.3-1500.2 mu g/L) and 134.8 mu g/L (range 53.6-913.2 mu g/L) respectively. Although B-Se and P-Se surpassed concentrations considered toxic (B-Se: 1000 mu g/L (U.S. EPA, 2002)), no dermal or breath signs or symptoms of Se toxicity were associated with the biomarkers of Se status. In the present study population, where Se intake is mostly from traditional diet, there is no evidence of selenosis. These findings support the need to re-assess Se toxicity considering factors such as the chemical form of Se exposure, route of exposure (inhaled versus ingested), co-exposures to toxic elements such as mercury. Considering the current food transition towards a western diet in the Amazon, further studies should address the possible association between high Se status and cardiometabolic health in this study population. (C) 2011 Elsevier Ltd. All rights reserved.

Investigation of the pore blockage of a Brazilian dolomite during the sulfation reaction

The influence of the temperature and reaction time on the sulfation process of a dolomite is investigated in this paper. The sulfation effectiveness was evaluated and correlated with changes in the physical characteristics of a Brazilian dolomite during the reactive process. Calcination and sulfation experiments were performed under isothermal conditions for dolomite samples with average particle sizes of 545 mu m at temperatures of 750 degrees C, 850 degrees C and 950 degrees C at different times of sulfation. Thermogravimetric tests were applied to establish the reactivity variation of the dolomite in function of the time in the sulfation reaction and evaluate the methodology of the samples preparation. Porosimetry tests were performed to study the pore blockage of dolomite during the sulfation reaction. The highest values of BET surface area were 25.55 m(2)/g, 29.55 m(2)/g and 12.62 m(2)/g for calcined samples and after their sulfation processes, conversions of 51.5%, 61.9% and 42.8% were obtained at 750 degrees C, 850 degrees C and 950 degrees C, respectively. Considering the process as a whole, the best fit was provided by a first-order exponential decay equation. Moreover, the results have shown that it is possible to quantify the decreasing in the dolomite reactivity for sulfur dioxide sorption and understand the changes in the behavior of the sulfation process of limestones when applied to technologies, as fluidized bed combustor, in which sulfur dioxide is present. (C) 2011 Elsevier B. V. All rights reserved.

Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.