Hermínio P. Diogo

The slow relaxation dynamics in active pharmaceutical ingredients studied by DSC and TSDC: Voriconazole, miconazole and itraconazole.

The slow molecular mobility of three active pharmaceutical drugs (voriconazole, miconazole and itraconazole) has been studied by differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC). This study yielded the main kinetic features of the secondary relaxations and of the main (glass transition) relaxation, in particular their distribution of relaxation times. The dynamic fragility of the three glass formers was determined from DSC data (using two different procedures) and from TSDC data. According to our results voriconazole behaves as a relatively strong liquid, while miconazole is moderately fragile and itraconazole is a very fragile liquid. There are no studies in this area published in the literature relating to voriconazole. Also not available in the literature is a slow mobility study by dielectric relaxation spectroscopy in the amorphous miconazole. Apart from that, the results obtained are in reasonable agreement with published works using different experimental techniques.

Thermal Stability of Simvastatin under Different Atmospheres

Simvastatin (SV) is a widely used drug for the treatment of hypercholesterolemia in humans. Nevertheless, serious efforts are still being made to develop new SV formulations with, for example, improved tabletability or bioavailability properties. These efforts frequently involve heating the compound well above ambient temperature or even fusion. In this work, the thermal stability of solid SV under different atmospheres was investigated by using isothermal tests in glass ampules, differential scanning calorimetry, and Calvet-drop microcalorimetry experiments. These tests were combined with analytical data from diffuse reflectance infrared Fourier-transform spectroscopy and liquid chromatography coupled with tandem mass spectrometry or Fourier transform ion cyclotron resonance mass spectrometry (LC-FT-ICR-MS). No decomposition was observed when the sample was kept at a temperature ≤373 K under N2 or reduced pressure (13.3 Pa) atmospheres. Thermal degradation was, however, observed for temperatures ≥353 K in the presence of pure or atmospheric oxygen. The nature of the two main oxidative degradation products was determined through MS/MS experiments and accurate mass measurements of the precursor ions using FT-ICR-MS. The obtained results indicated that the decomposition process involves the oxidation of the hexahydronaphthalene fragment of SV.

Assessment and comparison of the properties of biodiesel synthesized from three different types of wet microalgal biomass

In recent years, microalgae-based carbon-neutral biofuels (i.e., biodiesel) have gained considerable interest due to high growth rate and higher lipid productivity of microalgae during the whole year, delivering continuous biomass production as compared to vegetable-based feedstocks. Therefore, biodiesel was synthesized from three different microalgal species, namely Tetraselmis sp. (Chlorophyta) and Nannochloropsis oculata and Phaeodactylum tricornutum (Heterokontophyta), and the fuel properties of the biodiesel were analytically determined, unlike most studies which rely on estimates based on the lipid profile of the microalgae. These include density, kinematic viscosity, total and free glycerol, and high heating value (HHV), while cetane number (CN) and cold filter plugging point (CFPP) were estimated based on the fatty acid methyl ester profile of the biodiesel samples instead of the lipid profile of the microalgae. Most biodiesel properties abide by the ASTM D6751 and the EN 14214 specifications, although none of the biodiesel samples met the minimum CN or the maximum content of polyunsaturated fatty acids with ≥4 double bonds as required by the EN 14214 reference value. On the other hand, bomb calorimetric experiments revealed that the heat of combustion of all samples was on the upper limit expected for biodiesel fuels, actually being close to that of petrodiesel. Post-production processing may overcome the aforementioned limitations, enabling the production of biodiesel with high HHV obtained from lipids present in these microalgae.

The Slow Molecular Mobility in Amorphous Ketoprofen and Ibuprofen

The slow molecular dynamics in two active pharmaceutical drugs, ketoprofen and ibuprofen, have been studied by differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC). This study allowed finding the main kinetic features of the fast secondary (γ) relaxation, of the Johari-Goldstein relaxation, and of the main (glass transition) relaxation, in particular their distribution of relaxation times. The fragility index of the two glass formers was determined based on data from DSC and from TSDC. The obtained results were compared with those obtained by other experimental techniques, namely, dielectric relaxation spectroscopy.

The determination of the glass transition temperature by thermally stimulated depolarization currents. Comparison with the performance of other techniques

ABSTRACT Several experimental techniques are currently used for the determination of the glass transition temperature, Tg. Thermally stimulated depolarization currents (TSDC) is a thermal analysis technique whose experimental results display a very clean glass transition signature and that, nevertheless, is seldom used as a technique for Tg determination. In the present work we explain how to get the glass transition temperature from TSDC data, and we compare the values obtained for a vast number of glass forming systems (with Tgs in a wide range between −145 and +180 °C and fragilities between m = 15 and m = 100), with the values obtained by differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). We conclude that the Tg determination by TSDC is direct, accurate and reproducible and that the obtained values correlate very well with those obtained by DSC and DRS. This general survey thus suggests TSDC as a valuable alternative technique for determining Tg.

Determinação de parâmetros cinéticos em fluxo com câmara de gradiente e deteção espectrofotométrica: aplicação à reação entre o violeta de cristal e o ião hidróxido

A didactic experiment is proposed aimed to extend the Flow Injection Analysis (FIA) based methodology to the area of physical chemistry/chemical reactors for undergraduate labs. Our prime objective was to describe the use of a gradient chamber for determination of the rate constant for the reaction between crystal violet and the hydroxide ion. The study was complemented by determining the effect of temperature on the rate constant. The kinetic parameters, activation energy and reaction rate constant are determined based on an assumption of rate orders. The main didactic advantages of the proposed experimental set-up are the use of less reagents, contributing to a more environmental friendly experiment. The experiment illustrates also the reduction of associated errors and time by using automated analysis owing to decreased operator manipulation.