Edvani C. Muniz

Silver sulfadiazine loaded chitosan/chondroitin sulfate films for a potential wound dressing application

Silver sulfadiazine (AgSD) loaded chitosan/chondroitin sulfate (CHI/CS) films were formed to be applied as a potential wound dressing material. The liquid uptake capacity of both, CHI/CS and CHI/CS/AgSD, films exhibited a pH-dependent behavior. Tensile tests showed that the amount of CS used to form the films and the further incorporation of AgSD affect the mechanical properties of the films. In vitro AgSD-release assays showed that the CHI/CS mass ratio influences the AgSD release rate. All the investigated CHI/CS/AgSD films sustain the AgSD release up to 96h at physiological pH. Antibacterial activity and cell viability assays showed that all the CHI/CS/AgSD films have activity against Pseudomonas aeruginosa and Staphylococcus aureus but they were not toxic to Vero cells. The results presented in this work indicate that the CHI/CS/AgSD exhibits potential to be applied as a wound dressing material.

Chitosan-sheath and chitin-core nanowhiskers

Chitosan-sheath and α-chitin-core nanowhiskers (CsNWs) have been successfully generated by surface deacetylation of chitin nanowhiskers (CtNWs) in the never-dried state. Acid hydrolysis (3N HCl, 30 mL/g, 104°C) of pure chitin derived from crab shell yielded 65% 4-10nm thick, 16 nm wide and 214 nm long chitin whiskers (CtNWs) that were 86% crystalline and 81% acetylated. Surface deacetylation of CtNWs was robust in their never-dried state in 50% NaOH at a moderate 50°C for 6h, yielding 92% CsNWs. All deacetylated CsNWs retain the same α-chitin crystalline core at reduced 50% crystallinity and similar dimensions (4-12 nm thick, 15 nm wide, 247 long) as CtNWs, but reduced 60% acetylation reflecting the deacetylated surface layers. Progressive surface deacetylation was evident by the increased IP as well as increased positive charges under acidic pH and reduced negative charges at alkaline pH with increasing reaction time.

Starch-based microspheres for sustained-release of curcumin: Preparation and cytotoxic effect on tumor cells

Curcumin (CUR) has been proved to be highly cytotoxic against different tumor cell lines. However, its poor solubility in aqueous medium and fast degradation in physiological pH are the common drawbacks preventing its efficient practical use. Herein, we report the development of original microspheres based on the biopolymer starch crosslinked with N,N-methylenebisacrylamide (MBA) to be applied as an efficient delivering system for CUR. The starch-based microspheres showed high loading efficiency even in loading solution with different CUR concentrations. In vitro release assays data showed that the CUR release is governed by anomalous transport (n=0.73) and it is pH-dependent. Cytotoxicity assays showed that starch microspheres could improve the cytotoxicity of CUR toward Caco-2 and HCT-116 tumor cell lines up to 40 times than that found for pure CUR. This behavior was attributed to the slowly and sustained release of CUR from the microspheres.

Synthesis and characterization of pectin derivative with antitumor property against Caco-2 colon cancer cells

New pectin derivative (Pec-MA) was obtained in specific reaction conditions. The presence of maleoyl groups in Pec-MA structure was confirmed by (1)H NMR and FTIR spectroscopy. The substitution degree of Pec-MA (DS=24%) was determined by (1)H NMR. The properties of Pec-MA were investigated through WAXS, TGA/DTG, SEM and zeta potential techniques. The Pec-MA presented amorphous characteristics and higher-thermal stability compared to raw pectin (Pec). In addition, considerable morphological differences between Pec-MA and Pec were observed by SEM. The cytotoxic effect on the Caco-2 cells showed that the Pec-MA significantly inhibited the growth of colon cancer cells whereas the Pec-MA does not show any cytotoxic effect on the VERO healthy cells. This result opens new perspectives for the manufacture of biomaterials based on Pec with anti-tumor properties.

Synthesis of a microhydrogel composite from cellulose nanowhiskers and starch for drug delivery.

This work describes the preparation of a microhydrogel composite from cellulose nanowhiskers (CNW) and starch in an ultrasound assisted-emulsion. CNW, which showed rod-like morphology, was obtained by acid hydrolysis of cane-based cellulose. The introduction of vinyl bonds to both CNW and starch enabled us to create the microhydrogel composite in which CNW played a role as a covalent cross-linker. Furthermore, CNW may act as an emulsifying agent for emulsion, improving both sphericity and homogeneity of the microparticles. The drug release was regulated in response to changes in the CNW amounts. The modeling of the release kinetics indicated that the drug release is driven by an anomalous mechanism and that the addition of CNW to starch microparticles led to differences in that mechanism. The release rate became ca. 2.9 times slower when CNW is added. When combined with starch, CNW played a role as a retardant factor for drug release.

1H NMR and 1H–13C HSQC surface characterization of chitosan–chitin sheath-core nanowhiskers

Surface deacetylation of chitin nanowhiskers (CtNWs) to chitosan-sheath/chitin-core nanowhiskers (CsNWs) was successfully monitored by liquid-state high-resolution NMR of colloidal suspensions of these never-dried nanowhiskers. CtNWs were derived from acid hydrolysis (3N HCl, 30mL/g, 90min, 104°C) of chitin at 65% yield and 86% CrI. Deacetylation (50% NaOH, 48h, 50°C) of CtNWs generated CsNWs with unchanged nanowhisker morphology and overall length and width dimensions, but a reduced CrI of 54%. Successful step-wise exchanging the aqueous media with acetone, then D2O prevented agglomeration of nanowhiskers and enabled NMR detection of individual nanowhiskers. The crystalline structure of CtNWs and CsNWs provided different chemical environments for the glucosamine hydrogen atom H2, splitting the NMR signals into 2 peaks (δ 3.0 and δ 3.35ppm) which differed from that reported for soluble chitosan (δ 3.2ppm). Besides, (1)H-(13)C HSQC was only possible for CsNWs indicating the NMR phenomenon observed to represent that of the surfaces where the outer layers were highly mobile and less crystalline. The degree of acetylation at the surfaces was determined from (1)H NMR data to be 56% and 9% for CtNWs and CsNWs, respectively.

Synthesis and controlled curcumin supramolecular complex release from pH-sensitive modified gum-arabic-based hydrogels

Curcumin (CUR) is a polyphenolic compound including a beta-diketone moiety, which is associated with numerous pharmacological activities, but applications are limited due to its low water solubility. Thus, in this work some inclusion complexes of CUR with alpha-cyclodextrin (α-CD) and beta-cyclodextrin (β-CD) were prepared using different host : guest proportions to improve drug solubilization in biological fluids. The formation of these complexes was confirmed by 1H NMR and thermogravimetric analysis. The stoichiometries of the CUR/α-CD and CUR/β-CD complexes were 1 : 1 and 1 : 2 and the association constants were 344 mol−1 L and 7.2 × 107 mol−2 L2 for α-CD and β-CD, respectively. The major stability of the CUR/β-CD complex is justified by an inclusion of the aromatic ring inside the CD cavity, whilst in the case of α-CD-complexes the interactions occur via H-bridges, showing the latter complexes’ slow exchange on the NMR time-scale. Even so, the solubility of curcumin complexes is clearly controlled by the solubility of CDs, showing the highest solubility for CUR/α-CD complexes. Hydrogels of modified gum arabic containing CUR/α-CD (1 : 4) were obtained and used for controlled release of CUR in simulated intestinal fluid (SIF) and simulated gastric fluid (SGF). The kinetics of release was pH-responsive and the percentage of CUR released was ca. 97% in SIF and 6.7% in SGF. For the toxicity studies on undifferentiated Caco-2 cells, IC50s of 63.4 ± 14.4 μg mL−1 and 85.2 ± 14.9 μg mL−1 for CUR and CUR/α-CD (1 : 4), respectively, were obtained. The toxicity of these samples on differentiated Caco-2 cells was lower than on undifferentiated cells. Additionally, the CUR incorporated into hydrogels showed no toxic effects on differentiated and undifferentiated Caco-2 cells, indicating the pharmaceutical potential of three-dimensional matrices of GAm for controlled release of CUR complexed with cyclodextrin.

Miscibility influence in the thermal stability and kinetic parameters of poly (3-hydroxybutyrate)/poly (ethylene terephthalate) sulphonated blends

The thermal degradation of miscible and immiscible poly (3-hidroxy butyrate) PHB/ poly (ethylene terephthalate) sulphonated (PETs) blends was investigated using thermogravimetric analyses. Model-free kinetic analysis, Vyazovkin and Flynn-Wall-Ozawas methods, were used to determine the apparent activation energy in the whole interval of degradation of the pure polymers, immiscible blends, and miscible blends. The thermal stability of both polymers in their blends is higher when compared to the pure polymers. The synergistic effect in the thermal stability in the blends is higher for the miscible blend where the formation of the specific interaction between PHB and PETs occurs. The apparent activation energy of the individual polymers is higher in PETs/PHB blends, and this effect is potentiated by the miscibility of the blend.

Modificação Química de Poli(Tereftalato de Etileno)Pós-Consumo por Reação com Ácido Sulfúrico:Estrutura e Propriedades

PET pos-consumo foi modificado quimicamente atraves de reacao com acido sulfurico por diferentes tempos. O material modificado foi caracterizado por DSC e FTIR-PAS e XPS. Verificou-se que a intensidade relativa do isomero trans diminui enquanto do isomero gauche aumenta para tempos de reacao entre 0 e 60 minutos. Apos 60 minutos de reacao observou-se a presenca de endotermas multiplas que podem ser relacionadas com o desenvolvimento de estruturas intermediarias porque as intensidades relativas dos isomeros trans e gauche nao apresentam variacao significativa. O valor determinado de capacidade de troca ionica do PET pos-consumo modificado (PETS-pc) e comparavel com os valores de resinas acidas comerciais e nao e afetado no intervalo de tempo de reacao utilizado. Os valores da capacidade maxima de adsorcao, qm, e do parâmetro de afinidade entre o adsorvente e o adsorvato, K, (111,18 ppm e 531,91 mg de corante/100g de adsorvente, respectivamente) para a adsorcao do corante Remazol vermelho na amostra quimicamente modificada por 30 minutos foram calculados a partir da isoterma de adsorcao de Langmuir. Os resultados indicam que esse material possui caracteristicas adsorventes, podendo vir a ser utilizado para tratamento de efluente de industria de tingimento textil.

Recentes Avanços no Design de Hidrogéis de Chitina e Derivados de Chitina e seu Impacto sobre Meio Ambiente e Agricultura: Uma Revisão

Our purpose is to show and discuss the most relevant data on the synthesis approach and the characterization of hydrogels based on chitin and chitin-derivatives, such as chitosan, as well as their applications in several materials technologies. The current and future relevance of materials based on chitin, chitosan and derivatives have been verified by the impressive number of scientific and technological publications (both papers and patents) that appears day-by-day. This review is divided into four Sections. Section 1 reports some basic concepts of hydrogels. Section 2 deals with properties of chitin, and gelation chemistries. Applications in environment and agriculture are described in Section 3. Future trends and perspectives are considered in Section 4.