Thermal studies on polymorphic structures of tibolone

Tibolone polymorphic forms I (monoclinic) and II (triclinic) have been prepared by recrystallization from acetone and toluene, respectively, and characterized by different techniques sensitive to changes in solid state, such as polarized light microscopy, X-ray powder diffractometry, thermal analysis (TG/DTG/DSC), and vibrational spectroscopy (FTIR and Raman microscopy). The nonisothermal decomposition kinetics of the obtained polymorphs were studied using thermogravimetry. The activation energies were calculated through the Ozawa`s method for the first step of decomposition, the triclinic form showed a lower E (a) (91 kJ mol(-1)) than the monoclinic one (95 kJ mol(-1)). Furthermore, Raman microscopy and DSC at low heating rates were used to identify and follow the thermal decomposition of the triclinic form, showing the existence of three thermal events before the first mass loss.

Compatibility and decomposition kinetics studies of prednicarbate alone and associated with glyceryl stearate

In this work, TG/DTG and DSC techniques were used to the determination of thermal behavior of prednicarbate alone and associated with glyceryl stearate excipient ( 1: 1 physical mixture). TG/DTG curves obtained for the binary mixture showed a reduction of approximately 37 degrees C to the thermal stability of drug (T(dm/dt-0) (Max)(DTG)). The disappearance of stretching band at 1280 cm(-1) (nu(as) C-O, carbonate group) and the presence of streching band with less intensity at 1750 cm(-1) (nu(s) C-O, ester group) in IR spectrum obtained to the binary mixture submitted at 220 degrees C, when compared with IR spectrum of drug submitted to the same temperature, confirmed the chemical interaction between these substances due to heating. Kinetics parameters of decomposition reaction of prednicarbate were obtained using isothermal (Arrhenius equation) and non-isothermal (Ozawa) methods. The reduction of approximately 45% of activation energy value (E(a)) to the first step of thermal decomposition reaction of drug in the 1:1 (mass/mass) physical mixture was observed by both kinetics methods.

Biobased films prepared from NaOH/thiourea aqueous solution of chitosan and linter cellulose

In the present study, films based on linter cellulose and chitosan were prepared using an aqueous solution of sodium hydroxide (NaOH)/thiourea as the solvent system. The dissolution process of cellulose and chitosan in NaOH/thiourea aqueous solution was followed by the partial chain depolymerization of both biopolymers, which facilitates their solubilization. Biobased films with different chitosan/cellulose ratios were then elaborated by a casting method and subsequent solvent evaporation. They were characterized by X-ray analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis, and tests related to tensile strength and biodegradation properties. The SEM images of the biofilms with 50/50 and 60/40 ratio of chitosan/cellulose showed surfaces more wrinkled than the others. The AFM images indicated that higher the content of chitosan in the biobased composite film, higher is the average roughness value. It was inferred through thermal analysis that the thermal stability was affected by the presence of chitosan in the films; the initial temperature of decomposition was shifted to lower levels in the presence of chitosan. Results from the tests for tensile strength indicated that the blending of cellulose and chitosan improved the mechanical properties of the films and that an increase in chitosan content led to production of films with higher tensile strength and percentage of elongation. The degradation study in a simulated soil showed that the higher the crystallinity, the lower is the biodegradation rate.

Thermal and spectrophotometric studies of new crosslinking method for collagen matrix with glutaraldehyde acetals

Despite the many existing crosslinking procedures, glutaraldehyde (GA) is still the method of choice used in the manufacture of bioprosthesis. The major problems with GA are: (a) uncontrolled reactivity due to the chemical complexity or GA solutions; (b) toxicity due to the release of GA from polymeric crosslinks; and (c) tissue impermeabilization due to polymeric and heterogeneous crosslinks formation, partially responsible for the undesirable calcification of the bioprosthesis. A new method of crosslinking glutaraldehyde acetals has been developed with GA in acid ethanolic solution, and after the distribution inside de matrix, GA is released to crosslinking. Concentrations of hydrochloride acid in ethanolic solutions between 0.1 and 0.001 mol/L with GA concentration between 0.1 and 1.0% were measured in an ultraviolet spectrophotometer to verify the presence of free aldehyde groups and polymeric compounds of GA. After these measurements, the solutions were used to crosslink bovine pericardium. The spectrophotometric results showed that GA was better protected in acetal forms for acid ethanolic solution with HCl at 0.003 mol/L and GA 1.0%(v/v). The shrinkage temperature results of bovine pericardium crosslinked with acetal solutions showed values near 85 C after the exposure to triethylamine vapors.

On statistical bounds of heuristic solutions to location problems

Solutions to combinatorial optimization problems, such as problems of locating facilities, frequently rely on heuristics to minimize the objective function. The optimum is sought iteratively and a criterion is needed to decide when the procedure (almost) attains it. Pre-setting the number of iterations dominates in OR applications, which implies that the quality of the solution cannot be ascertained. A small, almost dormant, branch of the literature suggests using statistical principles to estimate the minimum and its bounds as a tool to decide upon stopping and evaluating the quality of the solution. In this paper we examine the functioning of statistical bounds obtained from four different estimators by using simulated annealing on p-median test problems taken from Beasley’s OR-library. We find the Weibull estimator and the 2nd order Jackknife estimator preferable and the requirement of sample size to be about 10 being much less than the current recommendation. However, reliable statistical bounds are found to depend critically on a sample of heuristic solutions of high quality and we give a simple statistic useful for checking the quality. We end the paper with an illustration on using statistical bounds in a problem of locating some 70 distribution centers of the Swedish Post in one Swedish region.