ABSTRACT
Chitosan is a naturally occurring polysaccharide derived from chitin with a wide range of uses. Phthalocyanines are macroheterocyclic compounds that have a number of useful properties such as coloring and catalytic and antioxidant activity. Phthalocyanines are able to immobilize on chitosan, forming complexes with new useful properties. In this work, we evaluated the ability of phthalocyanines to increase the thermal stability of chitosan. Chitosan (CS) forms complexes with copper(II)-(CuPc) and cobalt(II)-(CoPc) tetrasulphophthalocyanines. The processes of destruction of chitosan (CS) and its complexes with sulphophthalocyanines CuPc and CoPc in oxidizing and inert atmospheres have been studied. It was established that, regardless of the atmosphere composition, the first chemical reactions taking place in the studied systems are elimination reactions. The latter ones in the case of chitosan and complex CS-CuPc lead to the formation of spatially crosslinked polymer structures, and it causes the release of CuPc from the polymer complex. It was found that in the case of CS-CoPc elimination reactions did not lead to the formation of crosslinked polymer structures but caused the destruction of the pyranose rings with a partial release of CoPc. Metallophthalocyanines showed antioxidant properties in the composition of complexes with chitosan, increasing the temperature of the beginning of glycosidic bond cleavage reaction by 30-35 °C in comparison with the similar characteristics for chitosan.
ABSTRACT
The complexation processes of chitosan with cobalt(II)tetrasulfophthalocyanine (CoPc) and copper(II)tetrasulfophthalocyanine (CuPc) were studied calorimetrically in solution. It was established that CoPc forms two types of complexes with chitosan, while CuPc forms a single type of complex with chitosan, in which copper(II)tetrasulfophthalocyanine is in dimerized form. The complexes are thermodynamically stable, which was allowed to study them in a solid form by different methods. Joint application of DSC and TG/DTG methods allowed us to identify the temperature intervals for evaporation of physically and chemically bounded water and thermal decomposition of chitosan and its complexes. The glass transition temperature of chitosan (110.8⯰C) is greater than the glass transition temperature of the complexes with CuPc (74.7⯰C) and CoPc (71.2⯰C). Using SEM images and X-ray data of heated, unheated chitosan and its complexes, it was shown that the complexes are predominantly amorphous. Heating of chitosan and its leads to increasing of amorphous phase. Modification of chitosan by phthalocyanines leads to decreasing of thermal stability of complexes insignificantly.
Subject(s)
Chitosan/chemistry , Indoles/chemistry , Sulfonic Acids/chemistry , Temperature , Drug Stability , IsoindolesABSTRACT
Thermal stability of polyvinyl alcohol/cellulose nanocrystals (PVA/CNCs) composites prepared with solution casting technique was studied. The PVA/CNCs composites were characterized by Fourier transform infrared spectrometry, X-ray diffraction, differential scanning calorimeter (DSC) and thermogravimetric (TG) analysis. Due to the presence of CNCs nanoparticles, thermal degradation of the composites occurs at much higher temperatures compared to that of the neat PVA. Thermal stability of the PVA/CNCs composites is maximally enhanced with CNCs content of 8-12 wt%. Some thermal degradation products of the PVA/CNCs composites were identified by mass spectrometric analysis. TG measurements with synchronous recording of mass spectra revealed that the thermal degradation of both CNCs and PVA in the composites with CNCs content of 8-12 wt% occurs simultaneously at a much higher temperature than that of CNCs or the neat PVA. However, with increasing CNCs content more than 12 wt% the thermal stability of the composites decreases. In this case, the degradation of CNCs comes first followed by the degradation of PVA.
