Studying the Impact of the Temperature and Sorbed Water during Microwave-Induced In Situ Amorphization: A Case Study of Celecoxib and Polyvinylpyrrolidone

Microwave-induced in situ amorphization of a drug into a polymeric amorphous solid dispersion (ASD) has been suggested to follow a dissolution process of the drug into the polymeric network, at temperatures above the glass transition temperature (Tg) of the polymer. Thus, increasing the compact temperature, above the Tg of the polymer, is expected to increase the rate of drug dissolution in the mobile polymer, i.e., the rate of amorphization, in a direct proportional fashion. To test this hypothesis, the present study aimed at establishing a linear correlation between the compact temperature and the rate of drug amorphization using celecoxib (CCX) and the polymers polyvinylpyrrolidone (PVP) 12 and PVP17 as the model systems. Water sorbed into the drug–polymer compacts during 2 weeks of storage at 75% relative humidity was used as the dielectric heating source for the present drug amorphization process, and therefore directly affected the compact temperature during exposure to microwave radiation; the loss of water during heating was also studied. For this, compacts prepared with 30 wt% CCX, 69.5 wt% PVP12 or PVP17 and 0.5 wt% magnesium stearate (lubricant) were conditioned to have a final water content of approx. 20 wt%. The conditioned compacts were exposed to microwave radiation for 10 min at variable power outputs to achieve different compact temperatures. For compacts containing CCX in both PVP12 and PVP17, a linear correlation was established between the measured compact end temperature and the rate of drug amorphization during 10 min of exposure to microwave radiation. For compacts containing CCX in PVP12, a fully amorphous ASD was obtained after 10 min of exposure to microwave radiation with a measured compact end temperature of 71 °C. For compacts containing CCX in PVP17, it was not possible to obtain a fully amorphous ASD. The reason for this is most likely that a fast evaporation of the sorbed water increased the Tg of the conditioned drug–polymer compacts to temperatures above the highest reachable compact temperature during exposure to microwave radiation in the utilized experimental setup. Supporting this conclusion, evaporation of the sorbed water was observed to be faster for compacts containing PVP17 compared to compacts containing PVP12.

Synthesis of Amorphous Zirconium Dioxide from Zirconyl Nitrate in Presence of Oxalic Acid

The article presents the results of studies on preparation of amorphous zirconium dioxide from zirconium nitrate by its hydrolysis in the presence of oxalic acid. It is determined that the balance of reagents taken for synthesis (1 ml 0,025 M ZrO(NO3)2 is 1.35 ml 4 M HOOC-COOH), and the optimum temperature of the received gel drying, which is 230 ̊С, is established, too. Morphology of the obtained ZrO2 samples was explored. It has been found that the calcining temperature is independent of the size and shape forming irregular agglomerates, consisting of smaller spherical particles, whose diameter varies between 50 and 300 nm. The X-ray analysis of the sample is represented, which showed a low degree of crystallinity of the substance. IR spectroscopy data showed the presence of zirconium dioxide-characteristic peaks on the IR spectrum. The same spectrum reflects the presence of a large amount of sorbed water in the obtained sample, as well as peaks characteristic of the gas adsorbed by the sample from the environment.

Convection-Induced vs. Microwave Radiation-Induced in situ Drug Amorphization

The aim of the study was to investigate the suitability of a convection oven to induce in situ amorphization. The study was conducted using microwave radiation-induced in situ amorphization as reference, as it has recently been shown to enable the preparation of a fully (100%) amorphous solid dispersion of celecoxib (CCX) in polyvinylpyrrolidone (PVP) after 10 min of continuous microwaving. For comparison, the experimental setup of the microwave-induced method was mimicked for the convection-induced method. Compacts containing crystalline CCX and PVP were prepared and either pre-conditioned at 75% relative humidity or kept dry to investigate the effect of sorbed water on the amorphization kinetics. Subsequently, the compacts were heated for 5, 10, 15, 20, or 30 min in the convection oven at 100 °C. The degree of amorphization of CCX in the compacts was subsequently quantified using transmission Raman spectroscopy. Using the convection oven, the maximum degree of amorphization achieved was 96.1% ± 2.1% (n = 3) for the conditioned compacts after 30 min of heating and 14.3% ± 1.4% (n = 3) for the dry compacts after 20 min of heating, respectively. Based on the results from the convection and the microwave oven, it was found that the sorbed water acts as a plasticizer in the conditioned compacts (i.e., increasing molecular mobility), which is advantageous for in situ amorphization in both methods. Since the underlying mechanism of heating between the convection oven and microwave oven differs, it was found that convection-induced in situ amorphization is inferior to microwave radiation-induced in situ amorphization in terms of amorphization kinetics with the present experimental setup.

The Effect of Heat Treatment Regimes of Polyphenylene Sulfides on their Thermal Properties

Thermal and thermo-oxidative degradation, as well as crosslinking and "curing" processes of polyphenylene sulfide, depending on the heat treatment regimes, have been studied using gas chromatography. The effect of sorbed water in the polymer on the processes of thermal and thermo-oxidative decomposition of polyphenylene sulfide is shown and the optimal modes of drying the samples are established.