Biomimetic biosensor based on lipidic layers containing tyrosinase and lutetium bisphthalocyanine for the detection of antioxidants

This paper describes the preparation of a biomimetic Langmuir-Blodgett film of tyrosinase incorporated in a lipidic layer and the use of lutetium bisphthalocyanine as an electron mediator for the voltammetric detection of phenol derivatives, which include one monophenol (vanillic acid), two diphenols (catechol and caffeic acid) and two triphenols (gallic acid and pyrogallol). The first redox process of the voltammetric responses is associated with the reduction of the enzymatically formed o-quinone and is favoured by the lutetium bisphthalocyanine because significant signal amplification is observed, while the second is associated with the electrochemical oxidation of the antioxidant and occurs at lower potentials in the presence of an electron mediator. The biosensor shows low detection limit (1.98 x 10(-6)-27.49 x 10(-6) M), good reproducibility, and high affinity to antioxidants (Km in the range of 62.31-144.87 mu M). The excellent functionality of the enzyme obtained using a biomimetic immobilisation method, the selectivity afforded by enzyme catalysis, the signal enhancement caused by the lutetium bisphthalocyanine mediator and the increased selectivity of the curves due to the occurrence of two redox processes make these sensors exceptionally suitable for the detection of phenolic compounds. (C) 2010 Elsevier B.V. All rights reserved.

Protein Adsorption onto Polyelectrolyte Layers: Effects of Protein Hydrophobicity and Charge Anisotropy

Ellipsometry was used to investigate the influence of ionic strength (I) and pH on the adsorption of bovine serum albumin (BSA) or beta-lactoglobulin (BLG) onto preabsorbed layers of two polycations: poly(diallyldimethylammonium chloride) (PDADMAC) or poly(4-vinylpyridine bromide) quaternized with linear aliphatic chains of two (QPVP-C2) or five (QPVP-C5) carbons. Comparisons among results for the three polycations reveal hydrophobic interactions, while comparisons between BSA and BLG-proteins of very similar isoelectric points (pI)-indicate the importance of protein charge anisotropy. At pH close to pI, the ionic strength dependence of the adsorbed amount of protein (Gamma) displayed maxima in the range 10 < I < 25 mM corresponding to Debye lengths close to the protein radii. Visualization of protein charge by Delphi suggested that these ionic strength conditions corresponded to suppression of long-range repulsion between polycations and protein positive domains, without diminution of short-range attraction between polycation segments and locally negative protein domains, in a manner similar to the behavior of PE-protein complexes in solution.(1-4) This description was consistent with the disappearance of the maxima at pH either above or below pI. In the former case, Gamma values decrease exponentially with I(1/2), due to screening of attractions, while in the latter case adsorption of both proteins decreased at low I due to strong repulsion. Close to or below pI both proteins adsorbed more strongly onto QPVP-C5 than onto QPVP-C2 or PDADMAC due to hydrophobic interactions with the longer alkyl group. Above pI, the adsorption was more pronounced with PDADMAC because these chains may assume more loosely bound layers due to lower linear charge density.

Layer-by-layer TiO(2) films as efficient blocking layers in dye-sensitized solar cells

Charge recombination at the conductor substrate/electrolyte interface has been prevented by using efficient blocking layers of TiO(2) compact films in dye-sensitized solar cell photoanodes. Compact blocking layers have been deposited before the mesoporous TiO(2) film by the layer-by-layer technique using titania nanoparticles as cations and sodium sulfonated polystyrene, PSS, as a polyanion. The TiO(2)/PSS blocking layer in a DSC prevents the physical contact of FTO and the electrolyte and leads to a 28% increase in the cell`s overall conversion efficiency, from 5.7% to 7.3%. (C) 2009 Elsevier B.V. All rights reserved.

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Oscar Wilde’s “The Happy Prince” : The Hidden Messages and the Debate on the Target Audience

Oscar Wilde’s fairytales have been read to children for more than a century. Nevertheless, since the time of their publication in 1888 and 1891, the target audience of The Happy Prince and Other Tales and A House of Pomegranates have been the concern of critics. Delving into the context behind the rich and colourful imagery, one can find implications of homosexuality, the Paterian aesthetic and religious connotations. According to Carol Tattersall, The Happy Prince and Other Tales successfully mislead the public that it is innocent of any intention to undermine established standards of living or writing. Tattersall’s argument is based on comparing the first collection to Wilde’s second, A House of Pomegranates, which was perceived as “offensive and immoral” (136). On the other hand, William Butler Yeats states in his introduction to The Complete Works of Oscar Wilde that overall the reviewers of The Happy Prince and Other Tales were hostile because of Wilde’s aesthetic views (ixxvi). But Yeats overlooks the fact that Wilde was very pleased and proud, dashing notes to friends and reviewers and signing copies to many people (Tattersall 129). In general, the reception of Wilde’s first collection was more positive than that of the second because it was milder and more subtle in its controversial themes.

Winning the Accreditation Game: The Library as Key Player and Hidden Gold Mine

Libraries are a central hub of information resources supporting college and university curricula. Several library strategies, cross-campus collaborations, and philosophical considerations of electronic and print offerings led to successful accreditations in business and engineering programs.

The Taylor rule under inquiry: Hidden states

This work empirically evaluates the Taylor rule for the US and Brazil using Markov-Switching Regimes. I find that the inflation parameter of the US Taylor rule is less than one in many periods, contrasting heavily with Clarida, Gal´ı and Gertler (2000), and the same happens with Brazilian data. When the inflation parameter is greater than one, it encompasses periods that these authors considered they should be less than one. Brazil is used for comparative purposes because it experienced a high level inflation until 1994 and then a major stabilization plan reduced the growth in prices to civilized levels. Thus, it is a natural laboratory to test theories designed to work in any environment. The findings point to a theoretical gap that deserves further investigation and show that monetary policy in Brazil has been ineffective, which is coherent with the general attitude of population in relation to this measure.

Taylor rule with hidden states

This work evaluates empirically the Taylor rule for the US and Brazil using Kalman Filter and Markov-Switching Regimes. We show that the parameters of the rule change significantly with variations in both output and output gap proxies, considering hidden variables and states. Such conclusions call naturally for robust optimal monetary rules. We also show that Brazil and US have very contrasting parameters, first because Brazil presents time-varying intercept, second because of the rigidity in the parameters of the Brazilian Taylor rule, regardless the output gap proxy, data frequency or sample data. Finally, we show that the long-run inflation parameter of the US Taylor rule is less than one in many periods, contrasting strongly with Orphanides (forthcoming) and Clarida, Gal´i and Gertler (2000), and the same happens with Brazilian monthly data.

Combating shoulder-surfing: a hidden button gesture based scheme

This project describes an authentication technique that is shoulder-surfing resistant. Shoulder surfing is an attack in which an attacker can get access to private information by observing the user’s interaction with a terminal, or by using recording tools to record the user interaction and study the obtained data, with the objective of obtaining unauthorized access to a target user’s personal information. The technique described here relies on gestural analysis coupled with a secondary channel of authentication that uses button pressing. The thesis presents and evaluates multiple alternative algorithms for gesture analysis, and furthermore assesses the effectiveness of the technique.

Limestone and oyster shell for brown layers in their second egg production cycle

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of different fat sources on the performance, egg quality, and lipid profile of egg yolks of commercial layers in the second laying cycle

This study was designed to evaluate the effects of different fat sources on the performance, egg quality, and lipid profile of the egg yolks of layers in their second production cycle. The fat sources were cottonseed oil, soybean oil, lard, sunflower oil, or canola oil. Experimental diets were fed to postmolt ISA Brown layers at 70 wk of age and the experimental period was 74 to 86 wk of age. The different fat sources did not influence performance or eggshell quality, but lipid profile of the egg yolk changed as a function of dietary fat sources. In general, the best changes, such as lower level of saturated fatty acids, higher levels of alpha-linolenic acid and DHA, and lower linoleic acid levels, were promoted by the addition of canola oil, but it did not promote enrichment of the eggs with polyunsaturated fatty acids.

Performance of layers submitted to different forced-molting methods and different temperatures

This study was carried out to evaluate the performance and egg quality of laying hens, in their second laying cycle submitted to different forced-molting methods and three environmental temperatures. Six hundred layers were distributed in a completely randomized experimental design with 15 treatments with five replicates of eight birds each, according to 5x3 factorial arrangement (molting methods vs. temperatures). The following forced-molting methods were applied: 90%, 70%, 50% dietary alfalfa inclusion, addition of 2,800 ppm zinc, and feed fasting. Temperatures were: 20 ºC, 27 ºC and 35 ºC. At the end of each period of the second laying cycle, bird performance and egg quality were evaluated. Data were submitted to analysis of variance and means were compared by orthogonal and polynomial contrasts. The highest alfalfa inclusion level (90% alfalfa and 10% basal diet) proved to be efficient as compared to the other methods, independently of temperature.

Modelling the effect of the physical and chemical characteristics of the materials used as casing layers on the production parameters of Agaricus bisporus

The aim of this research was to show the mathematical data obtained through the correlations found between the physical and chemical characteristics of casing layers and the final mushrooms' properties. For this purpose, 8 casing layers were used: soil, soil + peat moss, soil + black peat, soil + composted pine bark, soil + coconut fibre pith, soil + wood fibre, soil + composted vine shoots and, finally, the casing of La Rioja subjected to the ruffling practice. The conclusion that interplays in the fructification process with only the physical and chemical characteristics of casing are complicated was drawn. The mathematical data obtained in earliness could be explained in non-ruffled cultivation. The variability observed for the mushroom weight and the mushroom diameter variables could be explained in both ruffled and non-ruffled cultivations. Finally, the properties of the final quality of mushrooms were established by regression analysis.