Danilo Martins dos Santos

Optimization of carboxymethyl chitosan synthesis using response surface methodology and desirability function.

In this paper, chitosan was reacted with monochloroacetic acid under alkaline conditions to prepare carboxymethyl chitosan. A 2(3) full-factorial central composite design was applied to evaluate the effect of molar ratio sodium hydroxide (NaOH)/Chitosan (Ch), time and molar ratio monochloroacetic acid (MCA)/Chitosan (Ch) on the reaction yield and on the characteristics of carboxymethyl chitosan such as average degree of substitution (DS¯) and solubility. An optimization strategy based on response surface methodology was used together with the desirability function approach to optimize this process. The occurrence of carboxymethylation was evidenced by FTIR and (1)H NMR spectroscopy. The optimum conditions for carboxymethylation process were found to be 12.4, 10.6h and 5 for molar ratio sodium hydroxide (NaOH)/Chitosan (Ch), time and molar ratio monochloroacetic acid (MCA)/Chitosan (Ch), respectively. Under these optimal conditions, it was possible to obtain carboxymethyl chitosan with DS¯ of 1.86 and solubility of 99.6%. X-ray diffraction and thermogravimetry analysis showed that crystallinity and thermal stability of derivatives was lower than chitosan and decreased with increase of DS¯.

Response surface methodology applied to the study of the microwave-assisted synthesis of quaternized chitosan

A quaternized derivative of chitosan, namely N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (QCh), was synthesized by reacting glycidyltrimethylammonium chloride (GTMAC) and chitosan (Ch) in acid medium under microwave irradiation. Full-factorial 2(3) central composite design and response surface methodology (RSM) were applied to evaluate the effects of molar ratio GTMAC/Ch, reaction time and temperature on the reaction yield, average degree of quaternization (DQ) and intrinsic viscosity ([η]) of QCh. The molar ratio GTMAC/Ch was the most important factor affecting the response variables and RSM results showed that highly substituted QCh (DQ = 71.1%) was produced at high yield (164%) when the reaction was carried out for 30min. at 85°C by using molar ratio GTMAC/Ch 6/1. Results showed that microwave-assisted synthesis is much faster (≤30min.) as compared to conventional reaction procedures (>4h) carried out in similar conditions except for the use of microwave irradiation.

Microwave-assisted carboxymethylation of cellulose extracted from brewer's spent grain.

Cellulose was extracted from brewers spent grain (BSG) by alkaline and bleaching treatments. The extracted cellulose was used in the preparation of carboxymethyl cellulose (CMC) by reaction with monochloroacetic acid in alkaline medium with the use of a microwave reactor. A full-factorial 2(3) central composite design was applied in order to evaluate how parameters of carboxymethylation process such as reaction time, amount of monochloroacetic acid and reaction temperature affect the average degree of substitution (DS) of the cellulose derivative. An optimization strategy based on response surface methodology has been used for this process. The optimized conditions to yield CMC with the highest DS of 1.46 follow: 5g of monochloroacetic acid per gram of cellulose, reaction time of 7.5min and temperature of 70°C. This work demonstrated the feasibility of a fast and efficient microwave-assisted method to synthesize carboxymethyl cellulose from cellulose isolated of brewers spent grain.

PDLLA honeycomb-like scaffolds with a high loading of superhydrophilic graphene/multi-walled carbon nanotubes promote osteoblast in vitro functions and guided in vivo bone regeneration

Herein, we developed honeycomb-like scaffolds by combining poly (d, l-lactic acid) (PDLLA) with a high amount of graphene/multi-walled carbon nanotube oxides (MWCNTO-GO, 50% w/w). From pristine multi-walled carbon nanotubes (MWCNT) powders, we produced MWCNTO-GO via oxygen plasma etching (OPE), which promoted their exfoliation and oxidation. Initially, we evaluated PDLLA and PDLLA/MWCNTO-GO scaffolds for tensile strength tests, cell adhesion and cell viability (with osteoblast-like MG-63 cells), alkaline phosphatase (ALP, a marker of osteoblast differentiation) activity and mineralized nodule formation. In vivo tests were carried out using PDLLA and PDLLA/MWCNTO-GO scaffolds as fillers for critical defects in the tibia of rats. MWCNTO-GO loading was responsible for decreasing the tensile strength and elongation-at-break of PDLLA scaffolds, although the high mechanical performance observed (~600MPa) assures their application in bone tissue regeneration. In vitro results showed that the scaffolds were not cytotoxic and allowed for osteoblast-like cell interactions and the formation of mineralized matrix nodules. Furthermore, MG-63 cells grown on PDLLA/MWCNTO-GO significantly enhanced osteoblast ALP activity compared to controls (cells alone), while the PDLLA group showed similar ALP activity when compared to controls and PDLLA/MWCNTO-GO. Most impressively, in vivo tests suggested that compared to PDLLA scaffolds, PDLLA/MWCNTO-GO had a superior influence on bone cell activity, promoting greater new bone formation. In summary, the results of this study highlighted that this novel scaffold (MWCNTO-GO, 50% w/w) is a promising alternative for bone tissue regeneration and, thus, should be further studied.

Nanostructured electrospun nonwovens of poly(ε-caprolactone)/quaternized chitosan for potential biomedical applications

Blend solutions of poly(ε-caprolactone) (PCL) and N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (QCh) were successfully electrospun. The weight ratio PCL/QCh ranged in the interval 95/5-70/30 while two QCh samples were used, namely QCh1 (DQ¯ = 47.3%; DPv¯ = 2218) and QCh2 (DQ¯ = 71.1%; DPv¯ = 1427). According to the characteristics of QCh derivative and to the QCh content on the resulting PCL/QCh nonwoven, the nanofibers displayed different average diameter (175 nm-415 nm), and the nonwovens exhibited variable porosity (57.0%-81.6%), swelling capacity (175%-425%) and water vapor transmission rate (1600 g m-2 24 h-2500 g m-2 24 h). The surface hydrophilicity of nonwovens increases with increasing QCh content, favoring fibroblast (HDFn) adhesion and spreading. Tensile tests revealed that the nonwovens present a good balance between elasticity and strength under both dry and hydrated state. Results indicate that the PCL/QCh electrospun nonwovens are new nanofibers-based biomaterials potentially useful as wound dressings.

Investigation of the Internal Chemical Composition of Chitosan-Based LbL Films by Depth-Profiling X-ray Photoelectron Spectroscopy (XPS) Analysis

Chitosan-based thin films were assembled using the layer-by-layer technique, and the axial composition was accessed using X-ray photoelectron spectroscopy with depth profiling. Chitosan (CHI) samples possessing different degrees of acetylation ([Formula: see text]) and molecular weight ([Formula: see text]) produced via the ultrasound-assisted deacetylation reaction were used in this study along with two different polyanions, namely, sodium polystyrenesulfonate (PSS) and carboxymethylcellulose (CMC). When chitosan, a positively charged polymer in aqueous acid medium, was combined with a strong polyanion (PSS), the total positive charge of chitosan, directly related to its [Formula: see text], was the key factor affecting the film formation. However, for CMC/CHI films, the pH of the medium and [Formula: see text] of chitosan strongly affected the film structure and composition. Consequently, the structure and the axial composition of chitosan-based films can be finely adjusted by choosing the polyanion and defining the chitosan to be used according to its DA and [Formula: see text] for the desired application, as demonstrated by the antibacterial tests.

PREPARATION PREGELATIZED FLOUR BY THERMOPLASTIC EXTRUSION-BASED BAGASSE BARLEY AND CORN GRITS

Considerando o potencial nutritivo e o baixo valor agregado do bagaco de cevada, alem da alta produtividade e baixo custo do grits de milho, aliado a aplicabilidade e vantagem da tecnologia de extrusao termoplastica de alimentos, o presente trabalho estudou os efeitos do teor de agua na mistura, a temperatura da terceira zona de extrusao de um extrusor Brabender de parafuso unico, e concentracao de bagaco de cevada com tamanho de 180 µm sobre as propriedades tecnologicas do grits de milho extrudido. Foi empregado um planejamento experimental central composto rotacional 23 usando metodologia de superficie de resposta para avaliar o efeito do teor de agua (18-22%), formulacao (% de bagaco de cevada, 15-30%) e temperatura da terceira zona de extrusao (120-160 °C) no indice de expansao radial (REI), densidade aparente (BD), indice de absorcao de agua (WAI), indice de solubilidade em agua (WSI) e propriedades de pasta. Os resultados indicaram que o REI diminui com a adicao de bagaco de cevada e aumenta com o incremento da temperatura. A temperatura tem efeito negativo sobre a densidade enquanto que WAI foi diretamente proporcional sobre esta variavel. O teor de agua e a formulacao afetaram positivamente o WSI. A formulacao foi a variavel de maior importância nas propriedades de pasta: a viscosidade inicial foi diretamente proporcional a adicao de bagaco de cevada e as viscosidades maxima e final foram inversamente proporcional ao aumento da cevada bagaco.