Desenvolvimento e caracterização de micropartículas de amido reticuladas com agente fosfatado e avaliação da adsorção do azul de metileno

Starch has properties that make it one of the most studied biopolymers today. It is biodegradable, biocompatible, stable and non-toxic. This work has synthesis of starch and tapioca microparticles, through chemical modification by crosslinking with sodium tripolyphosphate agent in concentrations 7.5 and 15% (m / m). The amylose content was measured for starch and commercial cassava starch at 21.8% and 28.6%, respectively. According to the solubility index, processing in basic medium does not change the solubility of the material, but the addition of crosslinking agent increases this index, which changed from 12.8% for the control unprocessed, to 22.4% for the A5R15 sample. Soluble starch-based materials had a significant increase in the crosslinking density by increasing the concentration of crosslinker, from 1.4 in A5R7,5 sample, to 1.9 in A5R15. The cassava starch-based materials exhibited an opposite behavior: to increase the concentration of crosslinker crosslinking density decreased significantly in F5R7.5 from 2.9, to 1.9 in F5R15 sample. The point of zero charge (PZC) shows that below pH 4 the surface is positively charged. The surface area data is between 3,04 and 1,15 m2.g-1. The pore volume between 2.94 and 1.33 cm3.g-1 and pore size around 1.5 nm. The SEM indicates uneven distribution of microparticles, which are smooth, with no ridges. The maximum adsorption capacity of the materials were tested at pH 7.7 and for A5R15 and CA sample, at pH 2, 5, 6 and 9. It is noted that the processing in basic medium reduces the adsorption capacity of CA and CF in respect fo A and F. The adsorption in A5R15 sample has great dependency on the pH, reaching a value of 587 μg.g-1 in pH 7.7. The samples A5R15 and F5R7,5 adsorbed similar amounts, according to the statistical analysis, and significantly higher than their respective controls and showed lower desorption, indicating that the modification process was effective to control the release of methylene blue. The infrared spectra not show the characteristic bands of the phosphate bonds to the material formed, however, developments in hydroxyl characteristic band suggest modification in the way this group was linked after the reaction. After adsorption, the infrared spectra show different format in the band of hydroxyl. PCA analysis shows that the greatest changes observed in the IR spectra are observed in the region of 3500 cm-1. Thermal analysis showed three thermal events related to dehydration and material degradation. It is observed that the processing increases the temperature to the first mass loss, fixed at 12%, but not observed increased stability due to the presence of crosslinker or process.

Acetilação do exopolissacarídeo (1→6)-β-D-glucana (lasiodiplodana): derivatização química e caracterização

Lasiodiplodan is an exocellular β-glucan with biological functionalities such as antioxidant, antiproliferative, hypocholesterolemic, protective activity against DNA damage induced by doxorubicin and hypoglycemic activity. Chemical derivatization of polysaccharide macromolecules has been considered as a potentiating mechanism for bioactivity. In this context, this work proposes the derivatization of lasiodiplodan by acetylation. Acetic anhydride was used as derivatizing agent and pyridine as catalyst and reaction medium. The derivatives obtained were evaluated by its water solubility, degree of substitution (DS), antioxidant potential, and characterized by infrared spectroscopy (FT-IR), thermal analysis, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Acetylated derivatives with different degrees of substitution (1.26; 1.03; 0.66 and 0.48) were obtained, and there was correlation between the concentration of derivatizing agent and DS. FT-IR spectroscopy analysis confirmed the insertion of acetyl groups into derivatized macromolecules (LAS-AC) through of specific bands concerning to carbonyl group (C = O) and increase in C-O vibration. SEM analysis indicated that native lasiodiplodan presents morphological structure in the form of thin films with translucent appearance and folds along its length. Derivatization led to morphological changes in the polymer, including aspects thickness, translucency and agglomeration. Thermal analysis indicated the native sample and derivative with DS 0.48 presented three weight loss stages. The first stage occurred until 125 ° C (loss of water) and there were two consecutive events of weight loss (200 ° C - 400 ° C) attributed to molecule degradation. Samples with DS 1.26; 1.03 and 0.66 demonstrated four weight loss stages. The first stage occurred until 130 ° C (loss of water), following by two consecutive events of weight loss (200 ° C - 392 ° C) attributed to degradation of the biopolymer. The fourth stage was between 381 ° C and 532 ° C (final decomposition) with exothermic peaks between 472 ° C and 491 ° C. X-ray diffraction patterns showed that native and acetylated lasiodiplodan have amorphous structure with semicrystalline regions. Derivatization did not contribute to increased solubility of the macromolecule, but potentiated its antioxidant capacity. Acetylation of lasiodiplodan allowed to obtaining a new macromolecule with higher antioxidant potential than the native molecule and with technological properties applicable in various industrial sectors.