Fluorescent Carbon Dots Capped with PEG<Subscript>200</Subscript> and Mercaptosuccinic Acid

The synthesis and functionalization of carbon nanoparticles with PEG₂₀₀ and mercaptosuccinic acid, rendering fluorescent carbon dots, is described. Fluorescent carbon dots (maximum excitation and emission at 320 and 430 nm, respectively) with average dimension 267 nm were obtained. The lifetime decay of the functionalized carbon dots is complex and a three component decay time model originated a good fit with the following lifetimes: τ ₁ = 2.71 ns; τ ₂ = 7.36 ns; τ ₃ = 0.38 ns. The fluorescence intensity of the carbon dots is affected by the solvent, pH (apparent pK _a of 7.4 ± 0.2) and iodide (Stern-Volmer constant of 78 ± 2 M⁻¹).     

Optimization of Verapamil Drug Analysis by Excitation-Emission Fluorescence in Combination with Second-order Multivariate Calibration

Excitation emission fluorescence matrices (EEMs) of Verapamil drug were obtained by direct and by derivatization fluorescence spectroscopy. The fluorescence excitation and emission wavelengths were displaced to longer wavelengths and the fluorescence intensity was enhanced upon derivation with respect to the native fluorescence of the drug. The complete EEM of the native fluorescence of the drug and of the derivatization product were rapidly acquired by using a charged-coupled device detector (CCD), which is advantageous in terms of speed in the analysis, with respect to the use of a conventional photomultiplier detector. The EEMs were analyzed by several second-order multivariate calibration methods exploiting the second order advantage. The three-dimensional decomposition methods used, based in different assumptions about the trilinearity of the three way data structure under analysis, were parallel factor analysis (PARAFAC), bilinear least squares (BLLS), parallel factor analysis 2 (PARAFAC2) and multivariate curve resolution—alternating least squares (MCR-ALS). The determination was performed by using the standard addition approach. The figures of merit of the PARAFAC and BLLS methods were calculated, obtaining a lower limit of detection with the derivatization procedure, when compared with the direct measurement of the fluorescence of the drug. In Verapamil drug the best estimations were found with the BLLS and the MCR-ALS models. In the quantification of Verapamil in a pharmaceutical formulation the best estimation, when compared with the result obtained by the US Pharmacopeia high performance liquid chromatography approach, was obtained by direct fluorescence spectroscopy with MCR-ALS and by derivatization fluorescence spectroscopy with the PARAFAC2 model.     

Effect of aluminum on the morphological and textural properties of CuO-ZnO/H-Ferrierite

Hybrid catalysts containing CuO-ZnO or CuO-ZnO-Al₂O₃ as the metallic component and the zeolite H-ferrierite as support were prepared by both the coprecipitation-impregnation and coprecipitation-sedimentation methods. They were characterized by XRD, BET, and TEM. Aluminum was added to the metallic component, and the effects on the hybrid catalyst properties were studied. The metallic component blocked the zeolite micropore volume, and spaces were created between agglomerate particles of the first component, increasing mesopore volume. Aluminum introduction at a Cu/Zn/Al ratio of 55/30/15 favored the formation of hydrotalcite as a precursor to CuO/ZnO/Al₂O₃. In this case, small, highly dispersed particles of these oxides were obtained. In the coprecipitation-impregnation method, greater contact between the H-ferrierite zeolite and the metallic component was observed.     

Conservative force fields in non-Gaussian statistics

In this Letter, we determine the κ-distribution function for a gas in the presence of an external field of force described by a potential U(r). In the case of a dilute gas, we show that the κ-power law distribution including the potential energy factor term can rigorously be deduced in the framework of kinetic theory with basis on the Vlasov equation. Such a result is significant as a preliminary to the discussion on the role of long range interactions in the Kaniadakis thermostatistics and the underlying kinetic theory.     

3H‐1,2‐Dithiole‐3‐thione derivatives as novel solvatochromic dyes

The UV–Vis spectrum of 5‐(1‐butylthio)‐3H‐1,2‐dithiole‐3‐thione (1a) and that of the chromium pentacarbonyl complex of 5‐methyl‐3H‐1,2‐dithiole‐3‐thione (3) present significant changes with the solvent polarity. The two absorption bands shown by the compounds in the region above 300 nm were identified by theoretical calculations. For Compound 1a these are n→π^* and →π^* transitions and for Compound 3 the longest wavelength absorption corresponds to a charge transfer band and shows a remarkably negative solvatochromism. Not only has the wavelength of maximum absorption changed with the solvent but also the ratio of the absorbances at the two wavelengths. The effect of solvents was correlated with solvatochromic parameters such as π^* and α. The spectrum of 5‐(1‐butylthio)‐3H‐1,2‐dithiole‐3‐one ( 2 ) was also measured in different solvents but in this case the changes observed are less significant than for the other two compounds. The spectra of 1a and 3 were also determined in the presence of anionic (SDS), cationic (CTAB), and neutral surfactants (Brig‐35) and it is shown that these compounds can be used as probes for the polarity of the binding sites of organized assemblies. Copyright © 2008 John Wiley & Sons, Ltd.     

Structural and electronic effects in metallocene catalysts studied by x‐ray techniques

A series of metallocenes, namely, [Cp₂ZrCl₂], [(MeCp)₂ZrCl₂], [(nBuCp)₂ZrCl₂], [(iBuCp)₂ZrCl₂], [(tBuCp)₂ZrCl₂], [Et(Ind)₂ZrCl₂], [Et(IndH₄)₂ZrCl₂], and [MeSi₂(Ind)₂ZrCl₂)] were analyzed by extended x‐ray absorption fine structure (EXAFS) and x‐ray photoelectron spectroscopy (XPS). Complementary techniques, UV–vis spectroscopy and cyclic and differential pulse voltammetry, were employed to characterize the organometallic complexes. The catalysts were evaluated in ethylene polymerization, having methylaluminoxane (MAO) as the cocatalyst, and the resulting polymers were characterized by gel permeation chromatography. The structural and electronic effects caused by the coordination sphere around the metal center and their effects on the catalytic activity and polymer characteristics are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

The influence of shear bands on final structure and magnetic properties of 3% Si non-oriented silicon steel

The presence of shear bands in the deformed material before final annealing is very important for Goss and Cube textures formation in silicon steel [S.C. Paolinelli, M.A. Cunha, J. Magn. Magn. Mater. 255 (2003) pp. 379. [1]; J.T. Park, J.A. Szpunar, Acta Mater., 51 (2003) 3037. [2]]. The increase of the hot-band grain size can increase the number of shear bands, which favor the nucleation of these orientations. In this work, the effect of the hot band grain size variation, promoted by varying the hot rolling finishing temperature, on final structure and magnetic properties was investigated for 3% Si alloy. It was found that the increase of the hot-band grain size increases the occurrence of shear bands and promotes an increase of η fiber fraction and a reduction of γ fiber fraction, improving the magnetic induction. On the other hand, the final grain size is reduced when the hot-band grain size is larger than 190 μm, deteriorating the core loss values in spite of the texture benefits. The reduction of final grain size was explained by the increase of the number of nuclei at the beginning of the recrystallization caused by the increase of shear bands in the deformed material.     

Effect of radiofrequency on the sheath-plasma resonance in a low-density plasma

Summary Bohm's theory on plasma probes has been modified, by taking into account the effect of the applied RF voltage on the ion saturation current, for explaining the experimentally detected behaviour of the plasma sheath resonance frequency in a low-temperature and low-density plasma

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Riassunto La teoria di Bohm sulle sonde nei plasmi è stata modificata, tenendo conto dell'effetto dovuto alla tensione RF applicata sulla corrente ionica di saturazione. Si spiega cosi l'andamento della frequenza di risonanza plasma-guaina ionica, rilevato sperimentalmente, in un plasma a bassa temperatura e bassa densità.

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Резюме Предлагается модификация теории Бома для плазменных зондов, которая учитывает влияние приложенного радиочастотного напряжения на ионный ток насыщения. Предложенная модификация позволяет объяснить экспериментально обнаруженное поведение резонансной частоты плазменной оболочки при низкой температуре и при низкой плотности плазмы.

     

Mathematical programming methods for the optimal design of turbine blade shapes

This paper describes some optimization techniques for the design of turbine blade profiles with a vibration constraint. The vibration characteristics were modelled by a Timoshenko beam with idealized boundary conditions permitting the system dynamics to be simulated by differential equations. Elliptical cross-sectional shapes were assumed, resulting in an optimization problem in a finite number of variables. The methods used were (1) a direct handling of the differential equations describing the system, in which penalty function transformations were used, and (2) a finite difference discretization with the system equations replaced by finite difference approximations. In the latter formulation the vibrational frequencies are the eigenvalues of the system while in the former case they are regarded as control parameters.This paper includes a numerical study of these methods and their implementation together with a discussion of results.