Curing kinetics of the epoxy system diglycidyl ether of bisphenol A/isophoronediamine by Fourier transform infrared spectroscopy

The curing reaction of an epoxy system consisting of a diglycidyl ether of bisphenol A (BADGE, n = 0) and isophoronediamine (IPD), was studied by Fourier transform infrared spectroscopy (FTIR). The degree of conversions and the reaction rates at different isothermal curing temperatures were calculated from the infrared spectra using a method derived from Beer's law. This method is based on the ratio of the height of the characteristic absorbance peak to reference absorbance peak. A kinetic model proposed by Sourour and Kamal has been used to fit experimental data. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and Investigation of Thermally Annealed Zein–Propolis Electrospun Nanofibers for Biomedical Applications

Zein, a corn-derived protein, has a variety of applications ranging from drug delivery to tissue engineering and wound healing. This work aims to develop a biocompatible scaffold for dermal applications based on thermally annealed electrospun propolis-loaded zein nanofibers. Pristine fibers' biocompatibility is determined in vitro. Next, propolis from Melipona quadrifasciata is added to the fibers at different concentrations (5% to 25%), and the scaffolds are studied. The physicochemical properties of zein/propolis precursor dispersions are evaluated and the results are correlated to the fibers' properties. Due to zein's and propolis' very favorable interactions, which are responsible for the increase in the dispersions surface tension, nanometric size ribbon-like fibers ranging from 420 to 575 nm are obtained. The fiber's hydrophobicity is not dependent on propolis concentration and increases with the annealing procedure. Propolis inhibitory concentration (IC₅₀) is determined as 61.78 µg mL⁻¹. When loaded into fibers, propolis is gradually delivered to cells as Balb/3T3 fibroblasts and are able to adhere, grow, and interact with pristine and propolis-loaded fibers, and cytotoxicity is not observed. Therefore, the zein–propolis nanofibers are considered biocompatible and safe. The results are promising and provide prospects for the development of wound-healing nanofiber patches—one of propolis' main applications.     

Tail fitting for truncated and non-truncated Pareto-type distributions

In extreme value analysis, natural upper bounds can appear that truncate the probability tail. At other instances ultimately at the largest data, deviations from a Pareto tail behaviour become apparent. This matter is especially important when extrapolation outside the sample is required. Given that in practice one does not always know whether the distribution is truncated or not, we consider estimators for extreme quantiles both under truncated and non-truncated Pareto-type distributions. We make use of the estimator of the tail index for the truncated Pareto distribution first proposed in Aban et al. (J. Amer. Statist. Assoc. 101(473), 270–277, 2006). We also propose a truncated Pareto QQ-plot and a formal test for truncation in order to help deciding between a truncated and a non-truncated case. In this way we enlarge the possibilities of extreme value modelling using Pareto tails, offering an alternative scenario by adding a truncation point T that is large with respect to the available data. In the mathematical modelling we hence let T→∞ at different speeds compared to the limiting fraction (k/n→0) of data used in the extreme value estimation. This work is motivated using practical examples from different fields, simulation results, and some asymptotic results.     

Analysis of curing of diglycidyl ether of bisphenol A (BADGE n = 0) with 2‐adamantylethanamine

The epoxy resin diglycidyl ether of Bisphenol A (BADGE n = 0) has been cured with a new synthesized hardener (2‐adamantylethanamine) and the crosslinking reaction was characterized by DSC. Values of 413.3 J/g and 95°C have been obtained for the enthalpy of the reaction and the glass transition temperature, respectively. The experimental results obey Kamal's model over all conversion range of temperatures (70°C‐100°C). The activation energies of the mechanisms involved in the curing reaction have been determined for both the autocatalytic and the n‐order mechanism, the values being 63.3 and 29.8 kJ/mol, respectively. The value for T_g is 23°C higher than the one for (BADGE n = 0)/amantadine, while the activation energy for the n‐order mechanism is around 13 kJ/mol lower. This is consistent with a higher steric effect of the adamantyl group in the second hardener since it will hinder the opening the oxirane ring by the nitrogen atom of the amino group. As the polymerization reaction progress, this effect will disappear as the distance adamantyl‐oxirane increase when new oxirane groups react with the hydroxyl groups (autocatalyzed reaction). Consequently, by selecting the appropriate cross‐linking agent, it is possible to simultaneously increase T_g while reducing theactivation energy, two effects which may be desirable for some industrial applications of the material.     

On the nucleation of hadronic domains in the quark-hadron transition

We present numerical results on bubble profiles, nucleation rates and time evolution for a weakly first-order quark-hadron phase transition in different expansion scenarios. We confirm the standard picture of a cosmological first-order phase transition, in which the phase transition is entirely dominated by nucleation. We also show that, even for expansion rates much lower than those expected in heavy-ion collisions nucleation is very unlikely, indicating that the main phase conversion mechanism is spinodal decomposition.     

Can a strong magnetic background modify the nature of the chiral transition in QCD?

The presence of a strong magnetic background can modify the nature and the dynamics of the chiral phase transition at finite temperature: for high enough magnetic fields, comparable to the ones expected to be created in noncentral high-energy heavy ion collisions at RHIC and the LHC, the original crossover is turned into a first-order transition. We illustrate this effect within the linear sigma model with quarks to one loop in the scheme for N_f=2.     

Temperature dependence of the quenching of N<Subscript>2</Subscript> (C <Superscript>3</Superscript>Π<Subscript>u</Subscript>) by N<Subscript>2</Subscript> (X) and O<Subscript>2</Subscript> (X)

The temperature dependences of the quenching rate constants of the states N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}}${\rm C} \ {^{3}{ \rm \Pi }_{u}} v^′=0,1) by N₂ (X) and of the state N₂ (${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0${\rm C} \ {^{3}{ \rm \Pi }_{u}} \ v^{\prime}=0) by O₂ (X) are studied. Time-resolved light emission from the gas was analyzed in the temperature range from 300 K to 210 K keeping the gas at constant density. In case of quenching by N₂ (X), the quenching rate constant for the vibrational level v^′= 0 increases by (13 ±3)% with gas cooling whereas the quenching rate constant for v^′= 1 decreases by (5.0 ±2.5)% in this temperature range. For quenching by O₂ (X), the quenching rate constant decreases by (3 ±2)% with gas cooling. The temperature variation of the N₂ (C ³Π_u v^′=0) emission intensity for pure nitrogen and dry air are calculated using the obtained quenching rate constants and is compared with the experimental data available in the literature.     

Analysis of an optical logic gate using a symmetric coupler operating with pulse position modulation (PPM)

In this paper we propose the operation of an all-optical logical gate based in a symmetric nonlinear directional coupler (NLDC) operating with a pulse position modulation (PPM). The performance of a symmetric NLDC realizing two-input AND/OR logical functions, which can be applied in transmission and processing of signals in all-optical form in TDM systems, is examined. This integrated symmetric NLDC logical gate operates with two ultrashort soliton light pulses (2 ps), which are modulated in agreement with the technique of pulse position modulation (PPM). Initially, we evaluate the effect resulting of an increment in the PPM coding parameter offset (ε), for the temporal position of the output pulse, considering the anomalous group-velocity dispersion (GVD), nonlinear self phase modulation (SPM) and without loss propagation regime of input pulses, in the cores 1 and 2 of the NLDC. In this situation, we analyze the four possible situations for the two-input logical gate, modulating the 1 and 2 input pulses through temporal displacement and allowing a variation in the coding parameter offset. We can conclude that is possible to get AND/OR logical operations for the cores 1 or 2, without to insert PPM error, since a phase control (Δ?) exists applied in agreement with the logical level of the input pulse in the core 1. Finally we define the truth table, considering the adequate phase difference and coding parameter offset for the stable operation of the AND/OR logical gate based in the symmetric NLDC.     

Enhancing the Limit of Detection for Comprehensive Two‐Dimensional Gas Chromatography (GC×GC) using Bilinear Chemometric Analysis

The chemometric method referred to as the generalized rank annihilation method (GRAM) is used to improve the precision, accuracy, and resolution of comprehensive two‐dimensional gas chromatography (GC×GC) data. Because GC×GC signals follow a bilinear structure, GC×GC signals can be readily extracted from noise by chemometric techniques such as GRAM. This resulting improvement in signal‐to‐noise ratio (S/N) and detectability is referred to as bilinear signal enhancement. Here, GRAM uses bilinear signal enhancement on both resolved and unresolved GC×GC peaks that initially have a low S/N in the original GC×GC data. In this work, the chemometric method of GRAM is compared to two traditional peak integration methods for quantifying GC×GC analyte signals. One integration method uses a threshold to determine the signal of a peak of interest. With this integration method only those data points above the limit of detection and within a selected area are integrated to produce the total analyte signal for calibration and quantification. The other integration method evaluated did not employ a threshold, and simply summed all the data points in a selected region to obtain a total analyte signal. Substantial improvements in quantification precision, accuracy, and limit of detection are obtained by using GRAM, as compared to when either peak integration method is applied. In addition, the GRAM results are found to be more accurate than results obtained by peak integration, because GRAM more effectively corrects for the slight baseline offset remaining after the background subtraction of data. In the case of a 2.7‐ppm propylbenzene synthetic sample the quantification result with GRAM is 2.6 times more precise and 4.2 times more accurate than the integration method without a threshold, and 18 times more accurate than the integration method with a threshold. The limit of detection for propylbenzene was 0.6 ppm (parts per million by mass) using GRAM, without implementing any sample preconcentration prior to injection. GRAM is also demonstrated as a means to resolve overlapped signals, while enhancing the S/N. Four alkyl benzene signals of low S/N which were not resolved by GC×GC are mathematically resolved and quantified.     

Determination of some anticancer 6-thiopurine compounds by high-performance liquid chromatography with micelles as the mobile phase

Aqueous solutions of the anionic surfactant sodium dodecyl sulfate are evaluated as mobile phases for the reversed-phase liquid chromatographic separation of the anti-cancer drugs 6-mercaptopurine and 6-thioguanine, and three of their metabolites (6-mercaptopurine riboside, 6-thioguanine riboside and 6-thioxanthine). The pertinent chromatographic parameters are determined and the effect of organic modifiers or temperature on retention and efficiency is evaluated. The resulting chromatographic procedure allows the determination of two or three of the analytes investigated in serum without any sample preatreatment.