From Sample Processing to Quantification: A Full Electrochemical Approach for Neutral Analyte Derivatization, Capillary Electrophoresis Separation, and Contactless Conductivity Detection

A thin-layer electrochemical flow cell coupled to capillary electrophoresis with contactless conductivity detection (EC-CE-(CD)-D-4) was applied for the first time to the derivatization and quantification of neutral species using aliphatic alcohols as model compounds. The simultaneous electrooxidation of four alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) to the corresponding carboxylates was carried out on a platinum working electrode in acid medium. The derivatization step required 1 min at 1.6 V vs. Ag/AgCl under stopped flow conditions, which was preceded by a 10 s activation at 0 V. The solution close to the electrode surface was then hydrodynamically injected into the capillary, and a 2.5 min electrophoretic separation was carried out. The fully automated flow system operated at a frequency of 12 analyses per hour. Simultaneous determination of the four alcohols presented detection limits of about 5 x 10(-5) mol As a practical application with a complex matrix, ethanol concentrations were determined in diluted pale lager beer and in nonalcoholic beer. No statistically significant difference was observed between the EC-CE-(CD)-D-4 and gas chromatography with flame ionization detection (GC-FID) results for these samples. The derivatization efficiency remained constant over several hours of continuous operation with lager beer samples (n = 40).

Exponential depletion of neutral dangling bonds density (D-0) by rare-earth doping in amorphous Si films

In this work we study the effect reduction in the density of dangling bond species D-0 states in rare-earth (RE) doped a-Si films as a function concentration for different RE-specimens. The films a-Si-1_(x) REx, RE=Y3+, Gd3+, Er3+, Lu3+) were prepared by co-sputtering and investigated by electron spin resonance (ESR) and Raman scattering experiments. According to our data the RE-doping reduces the ESR signal intensity of the D-0 states with an exponential dependence on the rare-concentration. Furthermore, the reduction produced by the magnetic rare-earths Gd3+ and Er3+ is remarkably greater than that caused by Y3+ and Lu3+, which led us to suggest an exchange-like coupling between the spin of the magnetic REs3+ and the spin of silicon neutral dangling bonds. (C) 2011 Elsevier B.V. All rights reserved.

Framing the difficulties resulting from implementing a Participatory Management Model in a public hospital

Objective: This study aims to address difficulties reported by the nursing team during the process of changing the management model in a public hospital in Brazil. Methods: This qualitative study used thematic content analysis as proposed by Bardin, and data were analyzed using the theoretical framework of Bolman and Deal. Results: The vertical implementation of Participatory Management contradicted its underlying philosophy and thereby negatively influenced employee acceptance of the change. The decentralized structure of the Participatory Management Model was implemented but shared decision-making was only partially utilized. Despite facilitation of the communication process within the unit, more significant difficulties arose from lack of communication inter-unit. Values and principals need to be shared by teams, however, that will happens only if managers restructure accountabilities changing job descriptions of all team members. Conclusion: Innovative management models that depart from the premise of decentralized decision-making and increased communication encourage accountability, increased motivation and satisfaction, and contribute to improving the quality of care. The contribution of the study is that it describes the complexity of implementing an innovative management model, examines dissent and intentionally acknowledges the difficulties faced by employees in the organization.

Periodic solutions of abstract neutral functional differential equations

We characterize the existence of periodic solutions of some abstract neutral functional differential equations with finite and infinite delay when the underlying space is a UMD space. (C) 2011 Elsevier Inc. All rights reserved.

Existence of Solutions for Abstract Non-Autonomous Neutral Differential Equations

In this paper we discuss the existence of mild and classical solutions for a class of abstract non-autonomous neutral functional differential equations. An application to partial neutral differential equations is considered.

Neutral pion and eta meson production in proton-proton collisions at root s=0.9 TeV and root s=7 TeV

The first measurements of the invariant differential cross sections of inclusive pi(0) and eta meson production at mid-rapidity in proton-proton collisions root s = 0.9 TeV and root s = 7 TeV are reported. The pi(0) measurement covers the ranges 0.4 < p(T) < 7 GeV/c and 0.3 < p(T) < 25 GeV/c for these two energies, respectively. The production of eta mesons was measured at root s = 7 TeV in the range 0.4 < p(T) < 15 GeV/c. Next-to-Leading Order perturbative QCD calculations, which are consistent with the pi(0) spectrum at root s = 0.9 TeV, overestimate those of pi(0) and eta mesons at root s = 7 TeV, but agree with the measured eta/pi(0) ratio at root s = 7 TeV. (C) 2012 CERN. Published by Elsevier B.V. All rights reserved.

Present bounds on new neutral vector resonances from electroweak gauge boson pair production at the LHC

Several extensions of the standard model predict the existence of new neutral spin-1 resonances associated with the electroweak symmetry breaking sector. Using the data from ATLAS (with integrated luminosity of L = 1.02 fb(-1)) and CMS (with integrated luminosity of L = 1.55 fb(-1)) on the production of W+W- pairs through the process pp --> l(+)l(-)' is not an element of(T), we place model independent bounds on these new vector resonances masses, couplings, and widths. Our analyses show that the present data exclude new neutral vector resonances with masses up to 1-2.3 TeV depending on their couplings and widths. We also demonstrate how to extend our analysis framework to different models with a specific example.

Neutral Gold Complexes with Tridentate SNS Thiosemicarbazide Ligands

Na[AuCl4].2H(2)O reacts with tridentate thiosemicarbazide ligands, H(2)L1, derived from N-[N',N'-dialkylamino(thiocarbonyl)]benzimidoyl chloride and thiosemicarbazides under formation of air-stable, green [AuCl(L1)] complexes. The organic ligands coordinate in a planar SNS coordination mode. Small amounts of gold(I) complexes of the composition [AuCl(L3)] are formed as side-products, where L3 is an S-bonded 5-diethylamino-3-phenyl-1-thiocarbamoyl-1,2,4-triazole. The formation of the triazole L3 can be explained by the oxidation of H(2)L1 to an intermediate thiatriazine L2 by Au3+, followed by a desulfurization reaction with ring contraction. The chloro ligands in the [AuCl(L1)] complexes can readily be replaced by other monoanionic ligands such as SCN- or CN- giving [Au(SCN)(L1)] or [Au(CN)(L1)] complexes. The complexes described in this paper represent the first examples of fully characterized neutral Gold(III) thiosemicarbazone complexes. All the [AuCl(L1)] compounds present a remarkable cell growth inhibition against human MCF-7 breast cancer cells. However, systematic variation of the alkyl groups in the N(4)-position of the thiosemicarbazone building blocks as well as the replacement of the chloride by thiocyanate ligands do not considerably influence the biological activity. On the other hand, the reduction of Au-III to Au-I leads to a considerable decrease of the cytotoxicity.

EXISTENCE OF SOLUTIONS FOR A FRACTIONAL NEUTRAL INTEGRO-DIFFERENTIAL EQUATION WITH UNBOUNDED DELAY

In this article, we study the existence of mild solutions for fractional neutral integro-differential equations with infinite delay.

Impact of thermal bridging on the performance of buildings using Light Steel Framing in Brazil

The Light Steel Framing building technology was introduced in Brazil in the late 1990s for the construction of residential houses. Because the design system was imported from the United States and is optimised to work well in that temperate climate, some modi fi cations must be made to adapt it for the Brazilian climate. The objective of this paper was to assess the impact of thermal bridging across enclosure elements on the thermal performance of buildings designed with Light Steel Framing in Brazil. The numerical simulation program EnergyPlus and a speci fi c method that considered the effects of metallic structures in the hourly simulations were used for the analysis. Two air-conditioned commercial buildings were used as case studies. The peak thermal load increased approximately 10% when an interior metal frame was included in the numerical simulations compared to non-metallic structures. Even when a metal frame panel was used only for vertical elements in the facade of a building with a conventional concrete structure, the simulations showed a 5% increase in annual energy use.

Studies on the interaction of surfactants and neutral cyclodextrins by capillary electrophoresis. Application to chiral analysis

In the present study, mixed systems composed of SDS in the presence of neutral cyclodextrins were considered. Firstly, the effect of the CDs on the CMC of the surfactant was evaluated by CE experiments. Furthermore, a new CE approach based on electric current measurement was developed for the estimation of the stoichiometry as well as of the binding constants of SDS-CDs complexes. The results of these investigations were compared to those obtained with a different technique, electronic paramagnetic resonance (EPR). The obtained results suggested that methylated CDs, in particular (2,6-di-O-methyl)-beta-cyclodextrin (DM-beta-CD), strongly affect the micellization of SDS in comparison to the other studied CDs. This effect also paralleled the chiral CD-MEKC performance, as indicated by the enantioresolution of (+/-)-Catechin, which was firstly selected as a model compound representative of important chiral phytomarkers. Then a CD-MEKC system, composed of sodium dodecyl sulfate as surfactant (90 mM) and hydroxypropyl-beta-cyclodextrin (25 mM) as chiral selector, under acidic conditions (25 mM borate – phosphate buffer, pH 2.5) was applied to study the thermal epimerisation of epi-structured catechins, (-)-Epicatechin and (-)-Epigallocatechin, to non epi-structured (-)-Catechin and (-)-Gallocatechin. The latter compounds, being non-native molecules, were for the first time regarded as useful phytomarkers of tea sample degradation. The proposed method was applied to the analysis of more than twenty tea samples of different geographical origins (China, Japan, Ceylon), having undergone different storage conditions and manufacturing processes.

Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.