Fabiano Vargas Pereira

Biobased Nanocomposites from Layer-by-Layer Assembly of Cellulose Nanowhiskers with Chitosan

A new biodegradable nanocomposite was obtained from layer-by-layer (LBL) technique using highly deacetylated chitosan and eucalyptus wood cellulose nanowhiskers (CNWs). Hydrogen bonds and electrostatic interactions between the negatively charged sulfate groups on the whisker surface and the ammonium groups of chitosan were the driving forces for the growth of the multilayered films. The film growth was followed by UV-vis spectroscopy through the maximum value of the absorption band at 194 nm and showed the deposition of 14.7 mg.m(-2) of chitosan polymer in each cycle. Scanning electron microscopy showed high density and homogeneous distribution of CNWs adsorbed on each chitosan layer. Cross-section characterization of the assembled films indicates an average of approximately 7 nm of thickness per bilayer. The results presented in this work indicate that the methodology used can be extended to different biopolymers for the design of new biobased nanocomposites in a wide range of applications such as biomedical and food packaging.

Bio-based nanocomposites obtained through covalent linkage between chitosan and cellulose nanocrystals

Bio-based nanocomposites were obtained through covalent linkage between cellulose nanocrystals (CNCs) and the natural polymer chitosan (CH). The CNCs were first functionalized with methyl adipoyl chloride (MAC) and the reactive end groups on the surface of the CNCs were reacted with the amino groups of the CH biopolymer in an aqueous medium. The functionalized CNCs and the resulting nanocomposites were characterized using FTIR, TEM, XRD, and elemental analyses. Characterization of the functionalized CNCs showed that up to 8% of the hydroxyl groups in the nanocrystals were substituted by the MAC residue. The covalent linkage between the CNCs and CH was confirmed by FTIR spectroscopy. The nanocomposites demonstrated a significant improvement in the mechanical performance and a considerable decrease in the hydrophilicity relative to the neat chitosan. The approach used in this work can be extended to other natural polymers.

Hybrid layer-by-layer assembly based on animal and vegetable structural materials: multilayered films of collagen and cellulose nanowhiskers

Layer-by-layer (LBL) assembly was used to combine crystalline rod-like nanoparticles obtained from a vegetable source, cellulose nanowhiskers (CNWs), with collagen, the main component of skin and connective tissue found exclusively in animals. The film growth of the multilayered collagen/CNW was monitored by UV-Vis spectroscopy and ellipsometry measurements, whereas the film morphology and surface roughness were characterized by SEM and AFM. UV-Vis spectra showed the deposition of the same amount of collagen, 5 mg m−2, in each dipping cycle. Ellipsometry data showed an increment in thickness with the number of layers, and the average thickness of each bilayer was found to be 8.6 nm. The multilayered bio-based nanocomposites were formed by single layers of densely packed CNWs adsorbed on top of each thin collagen layer where the hydrogen bonding between collagen amide groups and OH groups of the CNWs plays a mandatory role in the build-up of the thin films. The approach used in this work represents a potential strategy to mimic the characteristics of natural extracellular matrix (ECM) which can be used for applications in the biomedical field.

Cassava starch-based films plasticized with sucrose and inverted sugar and reinforced with cellulose nanocrystals.

UNLABELLED Bionanocomposites films of cassava starch plasticized with sucrose and inverted sugar and reinforced by cellulose nanocrystals (CNCs) were prepared by solution casting method incorporating 0.1 to 5 wt% of eucalyptus CNCs. The nanocrystals were characterized using transmission electron microscopy, whereas the bionanocomposites properties were studied using Fourier transform infrared spectroscopy, tensile measurements, water solubility, swelling behavior, and water activity (a(w)). The water resistance properties (solubility and swelling behavior) of the nanocomposites were enhanced with the addition of cellulose nanofillers. These results were explained in terms of the high crystallinity of the nanocrystals and the formation of a rigid network with the nanofillers, which provide physical barriers to the permeation of water within the hydrophilic cassava matrix. The addition of CNCs in the bionanocomposites decreases a(w) linearly, reaching values below 0.5 (for CNCs concentration higher than 4 wt%), a reference value for no microbial proliferation for food product design. The presence of small concentrations of CNCs (0.1-0.3 wt%) also effectively increased the maximum tensile strength (more than 90%) and elastic modulus (more than 400%), indicating the formation of a suitable percolation network in this concentration range. Because the cellulose nanofillers enhanced the mechanical and water stability properties of the nanocomposites, the obtained results in this work may be applied to the development of biodegradable packaging or coatings to enhance shelf life of food products. PRACTICAL APPLICATION The main drawbacks of using starch-based polymers as packaging or coating in the food industry are their low mechanical properties and inherent water sensitivity. This study demonstrates that cellulose nanocrystals can be used to: (i) obtain better mechanical properties (increasing the tensile strength and modulus more than 90% and 400%, respectively; (ii) enhance the water stability and (iii) water activity of starch-based films. These results indicate that the obtained environmentally friendly nanocomposites in this work can be used to the development of films or coatings to enhance the shelf life of food products.

Effect of cellulose nanocrystals and gelatin in corn starch plasticized films.

Cellulose at the nanoparticle scale has been studied as a reinforcement for biodegradable matrices to improve film properties. The goal has been to investigate the properties of starch/gelatin/cellulose nanocrystals (CNC) films. Eleven treatments were considered using RCCD (rotatable central composite design), in addition to four control treatments. For each assay, the following dependent variables were measured: water vapor permeability (WVP), thickness, opacity and mechanical properties. The microstructure and thermal properties of the films were also assessed. Increases in gelatin and CNC concentrations lead to increases in film thickness, strength and elongation at break. The films containing only gelatin in their matrix displayed better results than the starch films, and the addition of CNC had a positive effect on the assessed response variables. The films exhibited homogeneous and cohesive structures, indicating strong interactions between the filler and matrix. Films with low levels of gelatin and CNC presented the maximum degradation temperature.

Pharmaceutical acrylic beads obtained by suspension polymerization containing cellulose nanowhiskers as excipient for drug delivery

Direct compression is one of the most popular techniques to prepare tablets but only a few commercial excipients are well adapted for this process into controlled release formulations. In the last years, the introduction of new materials for drug delivery matrix tablets has become more important. This paper evaluated the physicochemical and flow properties of new polymeric excipient of ethyl acrylate, methyl methacrylate and butyl metacrylate, synthesized by suspension polymerization using cellulose nanowhiskers as co-stabilizer, to be used as direct compression for modified release tablets. Infrared spectroscopy (FTIR) confirmed the success of the copolymerization reaction. Scanning electron microscopy (SEM) showed that excipient was obtained how spherical beads. Thermal properties of the beads were characterized by thermogravimetric (TG) analysis. Particle size analysis of the beads with cellulose nanowhiskers (CNWB) indicated that the presence of the nanowhiskers led to a reduction of particle size and to a narrower size distribution. In vitro test showed that the nanowhiskers and beads produced are nontoxic. Parameters such as Hausner ratio, Carrs index and cotangent of angle α were employed to characterize the flow properties of CNWB beads. Furthermore, the beads are used to produce tablets by direct compression contained propranolol hydrochloride as model drug. Dissolution tests performed suggested that beads could be used as excipient in matrix tablets with a potential use in drug controlled release.

Layer-by-layer assembled films of multi-walled carbon nanotubes with chitosan and cellulose nanocrystals

Chitosan solutions and cellulose nanocrystal suspensions were used to produce highly stable aqueous dispersions of multi-walled carbon nanotubes (MWCNTs). The different MWCNT dispersions, presenting positive and negative charges, were used to prepare multilayered hybrid thin films through electrostatic layer-by-layer (LBL) self-assembly. The MWCNTs are well dispersed and homogeneously distributed on each layer of chitosan and cellulose nanocrystals of the films. The nanotubes are densely packed in each multilayer, forming a random network. The surface of the LBL film exhibited a uniform and relatively smooth surface with a mean roughness value of ∼5.8±0.4nm. Electrochemical characterization revealed a decrease in two orders of magnitude in the film resistance as the number of bilayers increased from 5 to 20, which is a consequence of an increase in the amount of conductive material (MWCNT). The thin films with up to 20 bilayers exhibited transmittance higher than 90% in the visible range. The results presented in this work demonstrate the viability of the LBL technique for the deposition of active materials using the biopolymer pair chitosan/cellulose nanocrystals. The obtained films can be employed for the design of transparent and biocompatible carbon nanostructured based electrodes.

Obtenção de nanocelulose da fibra de coco verde e incorporação em filmes biodegradáveis de amido plastificados com glicerol

Composites strengthened with nanocellulose have been developed with the aim of improving mechanical, barrier, and thermal properties of materials. This improvement is primarily due to the nanometric size and the high crystallinity of the incorporated cellulose. Cassava starch films plasticized with glycerol and incorporated with nanocellulose from coconut fibers were developed in this study. The effect of this incorporation was studied with respect to the water activity, solubility, mechanical properties, thermal analysis, and biodegradability. The study demonstrated that the film properties can be significantly altered through the incorporation of small concentrations of nanocellulose.

Desenvolvimento e avaliação da eficácia de filmes biodegradáveis de amido de mandioca com nanocelulose como reforço e com extrato de erva-mate como aditivo antioxidante

The objective was to develop biodegradable packaging using a polymer matrix as the cassava starch plasticized with glycerol and reinforced with the incorporation of nanocelulose of coconut fiber, as well as to evaluate the effect of the addition of an additive nature (yerba mate) in nanobiocompositos formulations with antioxidant action. The nanocrystal cellulose (L/D=39) were obtained by acid hydrolysis with 65% H2SO4. The films were prepared by casting containing 4.5 and 6.0% starch, 0.5 and 1.5% glycerol, 0.3% nanocelulose and 20% extract of yerba mate. The palm oil storage packed with films containing the additive was monitored for 40 days under conditions of accelerated oxidation (63%UR/30°C). It was found that as the losses increase polyphenol films, there is a smaller increase of the peroxide value of the packaged product, thus demonstrating that instead of the product, the compounds of the packages who are suffering oxidation. The incorporation of yerba mate extract did not alter the mechanical and barrier properties of these films.

Dental glass ionomer cement reinforced by cellulose microfibers and cellulose nanocrystals.

The aim of this work was to evaluate if the addition of cellulose microfibers (CmF) or cellulose nanocrystals (CNC) would improve the mechanical properties of a commercial dental glass ionomer cement (GIC). Different amounts of CmF and CNC were previously prepared and then added to reinforce the GIC matrix while it was being manipulated. Test specimens with various concentrations of CmF or CNC in their total masses were fabricated and submitted to mechanical tests (to evaluate their compressive and diametral tensile strength,modulus, surface microhardness and wear resistance) and characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The incorporation of CmF in the GIC matrix did not greatly improve the mechanical properties of GIC. However, the addition of a small amount of CNC in the GIC led to significant improvements in all of the mechanical properties evaluated: compressive strength (increased up to 110% compared with the control group), elastic modulus increased by 161%, diametral tensile strength increased by 53%, and the mass loss decreased from 10.95 to 3.87%. Because the composites presented a considerable increase in mechanical properties, the modification of the conventional GIC with CNC can represent a new and promising dental restorative material.