Semi‐analytical integration of the 8‐node plane element stiffness matrix using symbolic computation

The semi‐analytical integration of an 8‐node plane strain finite element stiffness matrix is presented in this work. The element is assumed to be super‐parametric, having straight sides. Before carrying out the integration, the integral expressions are classified into several groups, thus avoiding duplication of calculations. Symbolic manipulation and integration is used to obtain the basic formulae to evaluate the stiffness matrix. Then, the resulting expressions are postprocessed, optimized, and simplified in order to reduce the computation time. Maple symbolic‐manipulation software was used to generate the closed expressions and to develop the corresponding Fortran code. Comparisons between semi‐analytical integration and numerical integration were made. It was demonstrated that semi‐analytical integration required less CPU time than conventional numerical integration (using Gaussian‐Legendre quadrature) to obtain the stiffness matrix. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2006     

Dynamic contact angle and spreading rate measurements for the characterization of the effect of dentin surface treatments

A new methodology capable of providing reliable and reproducible contact angle (theta) data has been employed to study the effect of clinical treatments grinding, acid etching, and deproteinization on medial dentin tissue. It is based on the application of the ADSA-CD algorithm to the determination of low-rate dynamic contact angles, obtained from slowly growing drops, and on contact angle measurement, as well as spreading behavior analysis, during the relaxation of the system (water on treated dentin) after initial drop growth. The theta data obtained were substantially more reproducible than those obtained with classical methods. A net effect of the treatment on theta was found, increasing dentin wettability: theta (polished) >theta (etched) >theta (deproteinized). The spreading rates correlate with the angles and are adequate for the dentin surface characterization. ANOVA and SNK tests show that for advancing contact angles the means corresponding to all treatments are significantly different. In the relaxing phase, mean angle and spreading rates on polished dentin differ significantly from those on etched and deproteinized dentin, but the latter do not differ significantly from each other.     

Kinetic study on the homogeneous esterification of acetic acid with isoamyl alcohol

The liquid‐phase esterification of acetic acid and isoamyl alcohol has been studied to develop a kinetic model using a sequential experimental design based on the divergence criterion. Data come from batch reactor experiments, performed in the temperature range of 316–363 K. Discrimination among 36 possible kinetic models, written in terms of activity, mole fractions, and molar densities, is possible through the deviance information criterion, as estimated by a Markov chain Monte Carlo technique. The obtained results indicate a negligible heat of reaction and a clear autocatalytic effect of acetic acid on the esterification rate. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 10–18, 2013     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Gas phase thermolysis of allylphosphines,kinetic study

Diallylphenyl, allylbenzylphenyl and allylmethylphenyl phosphines were pyrolized in a stirred-flow reactor at 380–429°C/7-20 torr, using toluene as carrier gas. The reaction products were propene, 1-phospha-1,3-butadiene, 1-phospha-1,2-diphenylethylene and 1-phosphaethylene. The phospha-alkenes formed evolve into cyclo addition products. The propene elimination reaction showed first-order kinetics with rate coefficients following the Arrhenius equations: Diallylphenylphosphine: k(s⁻¹) = 10^{10.57 ± 0.31} exp(-143 ± 4 kJ/mol.RT) Allylbenzylphenylphosphine: k(s⁻¹) = 10^{9.71 ± 0.47} exp(-135 ± 6 kJ/mol.RT) Allylbenzylphenylphosphine: k(s⁻¹) = 10^{9.61 ± 0.61} exp(-144 ± 9 kJ/mol.RT) A six-center cyclic transition state unimolecular reaction mechanism, consistent with the above Arrhenius parameters, is proposed for the propene elimination reaction.     

A mixed integer programming model for multistage mean–variance post-tax optimization

In this paper, we introduce a mixed integer stochastic programming approach to mean–variance post-tax portfolio management. This approach takes into account of risk in a multistage setting and allows general withdrawals from original capital. The uncertainty on asset returns is specified as a scenario tree. The risk across scenarios is addressed using the probabilistic approach of classical stochastic programming. The tax rules are used with stochastic linear and mixed integer quadratic programming models to compute an overall tax and return-risk efficient multistage portfolio. The incorporation of the risk term in the model provides robustness and leads to diversification over wrappers and assets within each wrapper. General withdrawals and risk aversion have an impact on the distribution of assets among wrappers. Computational results are presented using a study with different scenario trees in order to show the performance of these models.     

Effectiveness of Photodynamic Therapy in Elimination of HPV‐16 and HPV‐18 Associated with CIN I in Mexican Women

This study aimed to determine the effectiveness of photodynamic therapy (PDT), using δ‐aminolevulinic acid (5‐ALA), in the elimination of premalignant cervical lesions in Mexican patients with human papillomavirus (HPV) infection and/or cervical intraepithelial neoplasia (CIN). Thirty women diagnosed with CIN I and/or positive for HPV participated in the study. Topical 6% 5‐ALA in gel form was applied to the uterine cervix; after 4 h, the lesion area was irradiated with a light dose of 200 J cm^?2 at 635 nm. This procedure was performed three times at 48‐h intervals. Clinical follow‐up was performed at 3, 6, and 12 months after the initial PDT administration, by colposcopy, cervical cytology, histopathological analysis, polymerase chain reaction, and hybrid capture. Of HPV‐infected patients without evidence of CIN I, 80% cleared the infection, while HPV associated with CIN I was eliminated in 83% of patients (P < 0.05). At 12 months, CIN I had regressed in 57% of patients, although this response was not statistically significant. PDT using 6% 5‐ALA is concluded to be effective in eliminating HPV infection associated or not with CIN I.