Solid electrolytes for electrochromic devices based on reversible metal electrodeposition

Air conditioning and lighting costs can be reduced substantially by changing the optical properties of "intelligent windows." The electrochromic devices studied to date have used copper as an additive. Copper, used here as an electrochromic material, was dissolved in an aqueous animal protein-derived gel electrolyte. This combination constitutes the electrochromic system for reversible electrodeposition. Cyclic voltammetry, chronoamperometric and chromogenic analyses indicated that were obtained good conditions of transparency (initial transmittance of 70%), optical reversibility, small potential window (2.1 V), variation of transmittance in visible light (63.6%) and near infrared (20%) spectral regions. Permanence in the darkened state was achieved by maintaining a lower pulse potential (-0.16 V) than the deposition potential (-1.0 V). Increasing the number of deposition and dissolution cycles favored the transmittance and photoelectrochemical reversibility of the device. The conductivity of the electrolyte (10(-3) S/cm) at several concentrations of CuCl2 was determined by electrochemical impedance spectroscopy. A thermogravimetric analysis confirmed the good thermal stability of the electrolyte, since the mass loss detected up to 100 degrees C corresponded to water evaporation and decomposition of the gel started only at 200 degrees C. Micrographic and small angle X-ray scattering analyses indicated the formation of a persistent deposit of copper particles on the ITO. (C) 2012 Elsevier B.V. All rights reserved.

A LED Based Photometer for Solid Phase Photometry: Zinc Determination in Pharmaceutical Preparation Employing a Multicommuted Flow Analysis Approach

In this work, a LED (light emitting diode) based photometer for solid phase photometry is described. The photometer was designed to permit direct coupling of a light source (LED) and a photodiode to a flow cell with an optical pathlength of 4 mm. The flow cell was filled with adsorbing solid phase material (C-18), which was used to immobilize the chromogenic reagent 1-(2-thiazolylazo)-2-naphthol (TAN). Aiming to allow accuracy assessment, samples were also analyzed employing ICP OES (inductively coupled plasma optical emission spectrometry) methodology. Applying the paired t-test at the 95% confidence level, no significant difference was observed. Other useful features were also achieved: linear response ranging from 0.05 to 0.85 mg L-1 Zn, limit of detection of 9 mu g L-1 Zn (3 sigma criterion), standard deviation of 1.4% (n = 10), sampling throughput of 36 determinations per h, and a waste generation and reagent consumption of 1.7 mL and of 0.03 mu g per determination, respectively.

In vitro evaluation of combined hyperthermia and photodynamic effects using magnetoliposomes loaded with cucurbit[7]uril zinc phthalocyanine complex on melanoma

The aims of this study were two fold; to develop magnetoliposomes (MLs) loaded with zinc phthalocyanine (ZnPc) complexed with cucurbituril (CB) (CB:ZnPc-MLs) and to evaluate their in vitro photodynamic (PD) and/or hyperthermia (HT) effects while using melanoma cells (B16-F10) as model. The liposomal formulations were characterized by both average diameter and zeta potential. The vesicle average size ranged from 150 to 200 nm and the polydispersity index (PdI) from 0.093 to 0.230. The zeta potential was significantly positive with values between 48 and 57 mV. The cell viability (CV) after PD and HT treatments was assessed by colorimetric MTI method. Melanoma cells were initially treated with the liposome formulation without light and magnetic field application, revealing cell viability not different from the control cells (p > 0.05). Photodynamic and hyperthermia assays were also applied separately, demonstrating that PD is more effective than HT in reducing the CV of the neoplastic cells. Combined application of both PD and HT treatments was even more effective in reducing the CV of B16-F10 cells. At the highest light dose (2 J/cm(2)) and under magnetic field activation the CV was about half than PD applied alone. Therefore, the use of the photosensitizer-loaded magnetoliposome for combined photodynamic therapy (PDT) and magnetohyperthermia (MHT) application can be considered as a potential tool to treat malignant melanoma. (C) 2012 Elsevier B.V. All rights reserved.

Photodynamic inactivation of biofilms formed by Candida spp., Trichosporon mucoides, and Kodamaea ohmeri by cationic nanoemulsion of zinc 2,9,16,23-tetrakis(phenylthio)-29H, 31H-phthalocyanine (ZnPc)

The biofilms formed by opportunistic yeasts serve as a persistent reservoir of infection and impair the treatment of fungal diseases. The aim of this study was to evaluate photodynamic inactivation (PDI) of biofilms formed by Candida spp. and the emerging pathogens Trichosporon mucoides and Kodamaea ohmeri by a cationic nanoemulsion of zinc 2,9,16,23-tetrakis(phenylthio)-29H,31H-phthalocyanine (ZnPc). Biofilms formed by yeasts after 48 h in the bottom of 96-well microtiter plates were treated with the photosensitizer (ZnPc) and a GaAlAs laser (26.3 J cm(-2)). The biofilm cells were scraped off the well wall, homogenized, and seeded onto Sabouraud dextrose agar plates that were then incubated at 37A degrees C for 48 h. Efficient PDI of biofilms was verified by counting colony-forming units (CFU/ml), and the data were submitted to analysis of variance and the Tukey test (p < 0.05). All biofilms studied were susceptible to PDI with statistically significant differences. The strains of Candida genus were more resistant to PDI than emerging pathogens T. mucoides and K. ohmeri. A mean reduction of 0.45 log was achieved for Candida spp. biofilms, and a reduction of 0.85 and 0.84, were achieved for biofilms formed by T. mucoides and K. ohmeri, respectively. Therefore, PDI by treatment with nanostructured formulations cationic zinc 2,9,16,23- tetrakis (phenylthio)- 29H, 31H- phthalocyanine (ZnPc) and a laser reduced the number of cells in the biofilms formed by strains of C. albicans and non-Candida albicans as well the emerging pathogens T. mucoides and K. ohmeri.

Preparation and Structural Characterization of Vulcanized Natural Rubber Nanocomposites Containing Nickel-Zinc Ferrite Nanopowders

Single-phase polycrystalline mixed nickel-zinc ferrites belonging to Ni0.5Zn0.5Fe2O4 were prepared on a nanometric scale (mean crystallite size equal to 14.7 nm) by chemical synthesis named the modified poliol method. Ferrite nanopowder was then incorporated into a natural rubber matrix producing nanocomposites. The samples were investigated by means of infrared spectroscopy, X-ray diffraction, scanning electron microscopy and magnetic measurements. The obtained results suggest that the base concentration of nickel-zinc ferrite nanoparticles inside the polymer matrix volume greatly influences the magnetic properties of nanoconnposites. A small quantity of nanoparticles, less than 10 phr, in the nanocomposite is sufficient to produce a small alteration in the semi-crystallinity of nanocomposites observed by X-ray diffraction analysis and it produces a flexible magnetic composite material with a saturation magnetization, a coercivity field and an initial magnetic permeability equal to 3.08 emu/g, 99.22 Oe and 9.42 X 10(-5) respectively.

Evidence of zinc deficiency in competitive swimmers

Objective: The aim of this study was to assess the nutritional zinc (Zn) status of elite swimmers during different training periods. Methods: A longitudinal paired study was performed at the University of Sao Paulo in eight male swimmers 18 to 25 y old who had been swimming competitively at the state and national levels for at least 5 y. The swimmers were evaluated over a total period of 14 wk: before the basic and specific preparatory period (BSPP-baseline), at the end of the basic and specific preparatory period (post-BSPP), and at the end of the polishing period (PP). Levels of Zn were determined in the plasma, erythrocyte, urine, and saliva by atomic absorption spectrophotometry. Anthropometric measurements and a 3-d food record were also evaluated. Results: The median plasma Zn concentration was below the reference value in all training periods (BSPP-baseline 59 mu g/dL, post-BSPP 55.9 mu g/dL, after PP 58.8 mu g/dL, P > 0.05), as were threshold values for erythrocytes (BSPP-baseline 36.5 mu g of Zn/g of hemoglobin, post-BSPP 42 mu g of Zn/g of hemoglobin, after PP 40.7 mu g of Zn/g of hemoglobin, P > 0.05), urinary Zn (BSPP-baseline 280 mu g/24 h, post-BSPP 337 mu g/24 h, after PP 284 mu g/24 h, P > 0.05), and salivary Zn (BSPP-baseline 66.1 mu g/L, post-BSPP 54.1 mu g/L, after PP 79.7 mu g/L, > 0.05). Salivary Zn did not correlate with plasma and erythrocyte Zn levels. Conclusion: The results suggest that the elite swimmers studied presented a possible Zn deficiency and that salivary Zn was not adequate to evaluate the Zn nutritional status. (C) 2012 Elsevier Inc. All rights reserved.

Organic and inorganic sources of zinc, copper and selenium in diets for dairy cows: intake, blood metabolic profile, milk yield and composition

The present study was carried out with the objective of evaluating the effects of feeding dairy cows with organic or inorganic sources of zinc (Zn), copper (Cu) and selenium (Se) on blood concentrations of these minerals, blood metabolic profiles, nutrient intake and milk yield and composition. Nineteen Holstein cows were selected and randomly assigned to two groups for receiving organic (n = 9) or inorganic (n = 10) sources of Zn, Cu and Se from 60 days before the expected date of calving to 80 days of lactation. Samples of feed, orts and milk were collected for analysis. Body condition score (BCS) was determined and blood samples were collected for analysis of Zn, Cu and Se concentrations, as well as for metabolic profile. Supplying organic or inorganic sources of Zn, Cu, and Se did not affect dry matter and nutrient intake, blood metabolic profile, milk yield and composition, plasma concentration of these minerals, and BCS or change the BCS in cows from 60 days before the expected date of calving to 80 days of lactation. An effect of time was observed on all feed intake variables, plasma concentrations of Zn and Se, milk yield, milk protein content, BCS and change in BCS.

Supplementation of diets for Santa Ines sheep with organic and inorganic zinc sources

This research was conducted with objective to evaluate the effect of different zinc (Zn) sources and doses in the diet for Santa Ines sheep. Forty lambs at weaning, with 18.4 kg of body weight were supplemented with three different sources of zinc (zinc oxide (ZnO), zinc amino acid and zinc proteinate) and three doses of zinc (200, 400 and 600 mg/kg DM) added to the basal diet. At every 28 days, animals were weighted and blood samples were collected for analyses of zinc (Zn), alkaline phosphatase and immunoglobulin G (IgG) and M (IgM). At the end of experiment, liver samples were collected for determination of the hepatic zinc levels. Zinc was analyzed with atomic absorption spectrophotometer, while phosphatase alkaline and immunoglobulins G and M were analyzed using Laborlab and Bioclin kits, respectively. There was no effect of diets on phosphatase alkaline levels and hepatic zinc, but there was difference in the plasmatic zinc levels and IgG and IgM levels. Based on the accumulation of hepatic zinc, the estimate of the zinc bioavailability, through the regression equation, showed that supplementation with organic and inorganic sources of zinc did not differ in the diet of Santa Ines sheep.

Transparent UV-absorbers thin films of zinc oxide: Ceria system synthesized via sol-gel process

Transparent nanostructure ZnO:CeO2 and ZnO thin films to use as solar protector were prepared by non-alkoxide sol-gel process and deposited on boronsilicate glass substrate by dip-coating technique and then heated at 300-500 degrees C. The films were characterized structurally, morphologically and optically by X-ray diffraction (XRD), atomic force microscopy (AFM), field emission gun-scanning electron microscopy (FEG-SEM), scanning electron microscopy (SEM) and UV-Vis transmittance spectroscopy. The coatings presented high transparency in the visible region and excellent absorption in the UV. The band gap of the deposited films was estimated between 3.10 and 3.18 eV. Absorption of the films in the UV was increased by presence of cerium. The results suggest that the materials are promising candidates to use as coating solar protective. (C) 2012 Elsevier B.V. All rights reserved.

Mechanistic implications of zinc(II) ions on the degradation of phenol by the fenton reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3+ + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.

A LED based photometer for solid phase photometry: zinc determination in pharmaceutical preparation employing a multicommuted flow analysis approach

Neste trabalho é proposto um fotômetro baseado em LED (diodo emissor de luz) para fotometria em fase sólida. O fotômetro foi desenvolvido para permitir o acoplamento da fonte de radiação (LED) e do fotodetector direto na cela de fluxo, tendo um caminho óptico de 4 mm. A cela de fluxo foi preenchida com material sólido (C18), o qual foi utilizado para imobilizar o reagente cromogênico 1-(2-tiazolilazo)-2-naftol (TAN). A exatidão foi avaliada empregando dados obtidos através da técnica ICP OES (espectrometria de emissão por plasma indutivamente acoplado). Aplicando-se o teste-t pareado não foi observada diferença significativa em nível de confiança de 95%. Outros parâmetros importantes encontrados foram faixa de resposta linear de 0,05 a 0,85 mg L-1 Zn, limite de detecção de 9 µg L-1 Zn (n = 3), desvio padrão de 1,4 % (n = 10), frequência de amostragem de 36 determinações por h, e uma geração de efluente e consumo de reagente de 1,7 mL e 0,03 µg por determinação, respectivamente.

Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation

This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn2+TMPyP) and meso-tetrakis sulfonatophenyl (Zn2+TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.

The study of a novel zinc finger gene cluster TZF and a genomic region flanking the histone H 4 replacement gene H 4 r of Drosophila melanogaster

Part I : A zinc finger gene Tzf1 was cloned in the earlier work of the lab by screening a ë-DASH2 cDNA expression library with an anti-Rat SC antibody. A ë-DASH2 genomic DNA library and cosmid lawrist 4 genomic DNA library were screened with the cDNA fragment of Tzf1 to determine the genomic organization of Tzf1. Another putative zinc finger gene Tzf2 was found about 700 bp upstream of Tzf1.RACE experiment was carried out for both genes to establish the whole length cDNA. The cDNA sequences of Tzf and Tzf2 were used to search the Flybase (Version Nov, 2000). They correspond to two genes found in the Flybase, CG4413 and CG4936. The CG4413 transcript seems to be a splicing variant of Tzf transcripts. Another two zinc finger genes Tzf3 and Tzf4 were discovered in silico. They are located 300 bp away from Tzf and Tzf2, and a non-tandem cluster was formed by the four genes. All four genes encode proteins with a very similar modular structure, since they all have five C2H2 type zinc fingers at their c-terminal ends. This is the most compact zinc finger protein gene cluster found in Drosophila melanogaster.Part II: 34,056 bp insert of the cosmid 19G11

Polymer controlled mineralization of zinc phosphate hydrates and applications in corrosion protection, catalysis and biomedicine

ZUSAMMENFASSUNG Die Tauglichkeit von Hybridmaterialien auf der Basis von Zinkphosphathydrat-Zementen zum Einsatz als korrosionshemmende anorganische Pigmente oder zur prothetischen und konservierenden Knochen- und Zahntherapie wird weltweit empirisch seit den neunziger Jahren intensiv erforscht. In der vorliegenden Arbeit wurden zuerst Referenzproben, d.h. alpha-und beta-Hopeite (Abk. a-,b-ZPT) dank eines hydrothermalen Kristallisationsverfahrens in wässerigem Milieu bei 20°C und 90°C hergestellt. Die Kristallstruktur beider Polymorphe des Zinkphosphattetrahydrats Zn3(PO4)2  4 H2O wurde komplett bestimmt. Einkristall-strukturanalyse zeigt, daß der Hauptunterschied zwischen der alpha-und beta-Form des Zinkphosphattetrahydrats in zwei verschiedenen Anordnungen der Wasserstoffbrücken liegt. Die entsprechenden drei- und zweidimensionalen Anordnungen der Wasserstoffbrücken der a-und b-ZPT induzieren jeweils unterschiedliches thermisches Verhalten beim Aufwärmen. Während die alpha-Form ihr Kristallwasser in zwei definierten Stufen verliert, erzeugt die beta-Form instabile Dehydratationsprodukt. Dieses entspricht zwei unabhängigen, aber nebeneinander ablaufenden Dehydratationsmechanismen: (i) bei niedrigen Heizraten einen zweidimensionalen Johnson-Mehl-Avrami (JMA) Mechanismus auf der (011) Ebene, der einerseits bevorzugt an Kristallkanten stattfindet und anderseits von existierenden Kristalldefekten auf Oberflächen gesteuert wird; (ii) bei hohen Heizraten einem zweidimensionalen Diffusionsmechanismus (D2), der zuerst auf der (101) Ebene und dann auf der (110) Ebene erfolgt. Durch die Betrachtung der ZPT Dehydratation als irreversibele heterogene Festkörperstufenreaktion wurde dank eines „ähnlichen Endprodukt“-Protokolls das Dehydratationsphasendiagramm aufgestellt. Es beschreibt die möglichen Zusammenhänge zwischen den verschiedenen Hydratationszuständen und weist auf die Existenz eines Übergangszustandes um 170°C (d.h. Reaktion b-ZPT  a-ZPT) hin. Daneben wurde auch ein gezieltes chemisches Ätzverfahren mit verdünnten H3PO4- und NH3 Lösungen angewendet, um die ersten Stufe des Herauslösens von Zinkphosphat genau zu untersuchen. Allerdings zeigen alpha- und beta-Hopeite charakteristische hexagonale und kubische Ätzgruben, die sich unter kristallographischer Kontrolle verbreitern. Eine zuverlässige Beschreibung der Oberfächenchemie und Topologie konnte nur durch AFM und FFM Experimente erfolgen. Gleichzeitig konnte in dieser Weise die Oberflächendefektdichte und-verteilung und die Volumenauflösungsrate von a-ZPT und b-ZPT bestimmt werden. Auf einem zweiten Weg wurde eine innovative Strategie zur Herstellung von basischen Zinkphosphatpigmenten erster und zweiter Generation (d.h. NaZnPO4  1H2O und Na2ZnPO4(OH)  2H2O) mit dem Einsatz von einerseits oberflächenmodifizierten Polystyrolatices (z.B. produziert durch ein Miniemulsionspolymerisationsverfahren) und anderseits von Dendrimeren auf der Basis von Polyamidoamid (PAMAM) beschritten. Die erhaltene Zeolithstruktur (ZPO) hat in Abhängigkeit von steigendem Natrium und Wassergehalt unterschiedliche kontrollierte Morphologie: hexagonal, würfelförmig, herzförmig, sechsarmige Sterne, lanzettenförmige Dendrite, usw. Zur quantitativen Evaluierung des Polymereinbaus in der Kristallstruktur wurden carboxylierte fluoreszenzmarkierte Latices eingesetzt. Es zeigt sich, daß Polymeradditive nicht nur das Wachstum bis zu 8 µm.min-1 reduzierten. Trotzdem scheint es auch als starker Nukleationsbeschleuniger zu wirken. Dank der Koordinationschemie (d.h. Bildung eines sechszentrigen Komplexes L-COO-Zn-PO4*H2O mit Ligandenaustausch) konnten zwei einfache Mechanismen zur Wirkung von Latexpartikeln bei der ZPO Kristallisation aufgezeigt werden: (i) ein Intrakorona- und (ii) ein Extrakorona-Keimbildungsmechanismus. Weiterhin wurde die Effizienz eines Kurzzeit- und Langzeitkorrosionschutzes durch maßgeschneiderte ZPO/ZPT Pigmente und kontrollierte Freisetzung von Phosphationen in zwei Näherungen des Auslösungsgleichgewichts abgeschätzt: (i) durch eine Auswaschungs-methode (thermodynamischer Prozess) und (ii) durch eine pH-Impulsmethode (kinetischer Prozess. Besonders deutlich wird der Ausflösungs-Fällungsmechanismus (d.h. der Metamorphismus). Die wesentliche Rolle den Natriumionen bei der Korrosionshemmung wird durch ein passendes zusammensetzungsabhängiges Auflösungsmodell (ZAAM) beschrieben, das mit dem Befund des Salzsprühteste und der Feuchtigkeitskammertests konsistent ist. Schließlich zeigt diese Arbeit das herausragende Potential funktionalisierter Latices (Polymer) bei der kontrollierten Mineralisation zur Herstellung maßgeschneiderter Zinkphosphat Materialien. Solche Hybridmaterialien werden dringend in der Entwicklung umweltfreundlicher Korrosionsschutzpigmente sowie in der Dentalmedizin benötigt.