In this study, a nanogel was developed from a natural polymer, chitosan, to be used in the Lippia origanoides essential oil encapsulation. The encapsulation process was used in order to improve the functional capacity of this essential oil as an antioxidant. To obtain the nanogel, the chitosan was modified with caffeic acid using EDC coupling agent. The obtained material was characterized by FTIR and TGA, revealing the formation of the chitosan-caffeic acid bond. The size, morphology and essential oil amount incorporated to the nanogel were investigated by DLS, SEM and gravimetric analysis, respectively. SEM and gravimetric analysis indicated that oil were efficiently trapped inside the CS-CA matrix, with encapsulation efficiency of 42 ± 2%. The EDL studies showed that the encapsulation of essential oil in the nanogel significantly affected your structure, with a average particle size of 417.26 ± 55.96. After essential oil incorporation into the CS-CA nanogel it was also observed a increase in its antioxidant capacity in terms of elimination of DPPH and ABTS radicals, and ferric reducing antioxidant power (FRAP). The successful development of this CS-CA nanogel loaded with L. origanoides essential oil will lead to a better applicability of this essential oil as an effective antioxidant.

Bionanocomposites derived from poly(L-Lactide) (PLLA) were reinforced with chemically modified cellulose nanocrystals (m-CNCs). The effects of these modified cellulose nanoparticles on the mechanical and hydrolytic degradation behavior of polylactide were studied. The m-CNCs were prepared by a method in which hydrolysis of cellulose chains is performed simultaneously with the esterification of hydroxyl groups to produce modified nanocrystals with ester groups. FTIR, elemental analysis, TEM, XRD and contact angle measurements were used to confirm and characterize the chemical modifications of the m-CNCs. These bionanocomposites gave considerably better mechanical properties than neat PLLA based on an approximately 100% increase in tensile strength. Due to the hydrophobic properties of the esterified nanocrystals incorporated into a polymer matrix, it was also demonstrated that a small amount of m-CNCs could lead to a remarkable decrease in the hydrolytic degradation rate of the biopolymer. In addition, the m-CNCs considerably delay the degradation of the nanocomposite by providing a physical barrier that prevents the permeation of water, which thus hinders the overall absorption of water into the matrix. The results obtained in this study show the nanocrystals can be used to reinforce polylactides and fine-tune their degradation rates in moist or physiological environments.

Poly(3-hydroxybutyrate), PHB, is a polymer with broad potential applications because of its biodegradability and biocompatibility. However, its high crystallinity is a limiting factor for many applications. To overcome this drawback, one strategy currently employed involves the reduction of the molecular weight of PHB with the concomitant formation of end-functionalized chains, such as those obtained via glycolysis. The glycolysis of PHB can be catalyzed by acid, base, or organometallic compounds. However, to our knowledge, there are no reports regarding PHB glycolysis catalyzed enzymatically. Among the major types of enzymes used in biocatalysis, the lipases stand out because they have the ability to catalyze reactions in both aqueous and organic media. Thus, in this study, we performed the enzymatic glycolysis of PHB using the lipase Amano PS (Pseudomonas cepacia) with ethane-1,2-diol (ethylene glycol) as the functionalizing agent. The results indicated that the glycolysis was successful and afforded hydroxyl-terminated oligomeric PHB polyols. Nuclear magnetic resonance spectra of the products showed characteristic signals for the terminal hydroxyl groups of the polyols, while thermogravimetric and differential scanning calorimetry analyses confirmed an increase in the thermal stability and a decrease in the crystallinity of the polyols compared with the starting PHB polymer, which were both attributed to the reduction in the molecular weight due to glycolysis.

This review reports the preparation and characterization of bionanocomposites based on biodegradable polymers reinforced with cellulose nanocrystals (CNC) described in the literature. The outstanding potential of cellulose nanocrystals as reinforcement fillers of biodegradable polymers is presented with an emphasis on the solution casting process, which is an appropriate method to investigate the physico-chemical effects of the incorporation of CNC into the polymeric matrices. Besides solution casting, other small scale methods such as electrospinning and layer-by-layer are also covered.

Poly(D,L-lactide), PDLLA, is a polymer with potential applications in medical, environmental, and pharmaceutical areas. Despite its versatility, the hydrophobicity limits its applications. To overcome this problem, one strategy is the preparation of blends with hydrophilic polymers such as poly(vinylpyrrolidone), PVP. In this study, we report the preparation and characterization of blends based on PDLLA and PVP and the biodegradation studies by the Sturm test. It was observed that the components of the blends PDLLA/PVP are thermodynamically immiscible, however the biodegradation is faster than that of pure PDLLA.

O copolímero poli(3-hidroxibutirato-co-ε-caprolactona) foi sintetizado por transesterificação, a partir dos homopolímeros PHB e PCL, usando acetilacetonato de zircônio(IV), como catalisador, nas concentrações de 20, 50 e 80% de PHB em massa. Os copolímeros foram caracterizados por GPC, métodos espectroscópicos (RMN-¹H, RMN-13C e IV-FT) e métodos térmicos (TG e DSC). A rota de síntese utilizada mostrou-se eficaz na síntese dos copolímeros P(HB-co-CL), os quais mostraram diminuição das cadeias poliméricas, apresentando Mw inferior a 24.000Daltons. Todos os copolímeros obtidos são termicamente mais estáveis que o PHB e com menor cristalinidade que os homopolímeros de partida. Esses materiais são bons candidatos para utilização como biomateriais em matrizes para liberação controlada de fármacos ou mesmo como compatibilizante em blendas PHB/PCL.

In the present work, the copolymer poly(3-hydroxybutyrate-co-ε-caprolactone), P(HB-co-CL), was prepared by transesterification reaction from PHB and PCL. Zirconium (IV) acetylacetonate was used as catalyst and the copolymers were obtained in a wide range of compositions of PHB/PCL (20/80, 50/50, 80/20). These copolymers were characterized by GPC, FT-IR, ¹H-NMR, 13C-NMR, TG, and DSC. The copolymers had weight average molecular weight less than 24.000 Daltons. All the systems were thermally more stable than PHB, showing lower crystallinity than the homopolymers. These materials are good candidates to be used as biomaterials, in drug release matrices, or even as PHB/PCL blends compatibilizers.

Films of collagen (CLG) and poly(N-isopropylacrylamide), PNIPAAm, were prepared by casting from water solutions. These bioartificial polymeric materials were studied to examine the influence of PNIPAAm content and glutaraldehyde vapor cross-linking on the thermal and biological stability of CLG. Mixtures, ranging from 20-80 wt% CLG composition, were cross-linked through exposure to glutaraldehyde vapors. Thermal and morphological properties of the films, cross-linked or not, were investigated by differential scanning calorimetry, thermogravimetry, and scanning electron microscopy, with the aim of evaluating miscibility, thermal stability, and interactions among the constituents. The experimental results indicated that the homopolymers are not thermodynamically compatible. However, there is good evidence that effective interactions, probably due to hydrogen bond formation, takes place between the constituents. These interactions are more evident on the samples that were not cross-linked. DSC studies revealed that PNIPAAm exerts a thermal stabilizing effect on uncross-linked CLG, while the cross-linking with glutaraldehyde affects only the biological polymer, preventing the interactions with PNIPAAm. SEM micrographs of the uncross-linked mixtures showed that the morphology, in all compositions studied, remains similar to the pure collagen. In the corresponding cross-linked samples, a more compact aggregation is observed although no appreciably changes can be seen.