Ionic Conductive Cellulose Mats by Solution Blow Spinning as Substrate and a Dielectric Interstrate Layer for Flexible Electronics.

Renewable cellulose substrates with submicron- and nanoscale structures have revived interest in paper electronics. However, the processes behind their production are still complex and time- and energy-consuming. Besides, the weak electrolytic properties of cellulose with submicron- and nanoscale structures have hindered its application in transistors and integrated circuits with low-voltage operation. Here, we report a simple, low-cost approach to produce flexible ionic conductive cellulose mats using solution blow spinning, which are used both as dielectric interstrate and substrate in low-voltage devices. The electrochemical properties of the cellulose mats are tuned through infiltration with alkali hydroxides (LiOH, NaOH, or KOH), enabling their application as dielectric and substrate in flexible, low-voltage, oxide-based field-effect transistors and pencil-drawn resistor-loaded inverters. The transistors exhibit good transistor performances under operation voltage below 2.5 V, and their electrical performance is strictly related to the type of alkali ionic specie incorporated. Devices fabricated on K+-infiltrated cellulose mats present the best characteristics, indicating pure capacitive charging of the semiconductor. The pencil-drawn load resistor inverter presents good dynamic performance. These findings may pave the way for a new generation of low-power, wearable electronics, enabling concepts such as the "Internet of Things".

Rheological and thermo-mechanical evaluation of bio-based chitosan/pectin blends with tunable ionic cross-linking.

Bio-based chitosan/pectin blend films were prepared by solution casting and fully characterized in terms of their viscoelastic, thermo-mechanical and water affinity properties. Dynamic light scattering and rheological analyses served as a probe that polyelectrolyte complexes were formed through COO-/NH3+ ionic cross-linking, changing the chitosan/pectin solutions from Newtonian to pseudoplastic gel-like systems. The highest degree of ionic cross-linking has been found at a specific mass ratio (chitosan/pectin 25/75) and solid-state data were obtained in detail using dynamic mechanical thermal analysis. Ionic cross-linking was determining on the physical properties of chitosan/pectin blends, which was demonstrated by the thermo-mechanical spectra, high water contact angle and tensile strength of films. The specific thermo-mechanical properties of the chitosan/pectin films can be specifically modulated according to the chitosan/pectin mass ratio to ensure successfully applications in medicine, drug delivery, agricultural and food coatings.

Bionanocomposites produced from cassava starch and oil palm mesocarp cellulose nanowhiskers.

Cassava starch films reinforced with cellulose nanowhiskers from oil palm mesocarp fibers were produced by casting. Nanowhiskers were obtained by sulphuric acid hydrolysis followed by microfluidization and incorporated in starch films at various loadings (1-10wt%). Morphological and mechanical characterizations showed that the reinforcing effect of oil palm cellulose nanowhiskers was significant at loadings of up to 6wt%, which was determined to be the nanowhiskers percolation threshold. Above this content, formation of agglomerates became more significant, causing a decrease in mechanical properties of starch bionanocomposites. Below percolation threshold, such as 2wt%, elongation at break increased by 70%, showing an effective reinforcing effect. Dynamic mechanical analyses revealed filler/matrix interactions through hydrogen bonding in bionanocomposites.

A new approach to obtain cellulose nanocrystals and ethanol from eucalyptus cellulose pulp via the biochemical pathway.

The feasibility of integration of cellulosic ethanol production with the manufacture of cellulose nanofibers (CNF) and cellulose nanocrystals (CNC) was evaluated using eucalyptus cellulose pulp as feedstock and employing the biochemical route alone. For the enzymatic hydrolysis step, experimental central composite design (CCD) methodology was used as a tool to evaluate the effects of solids loading (SL) and enzymatic loading (EL) on glucose release and cellulose conversion. Glucose concentrations from 45 to 125 g/L were obtained after 24 h, with cellulose conversions from 35 to 96%. Validation of the statistical model was performed at SL of 20% and EL of 10 mg protein/g, which was defined by the desirability function as the optimum condition. The sugars released were used for the production of ethanol by Saccharomyces cerevisiae, resulting in 62.1 g/L ethanol after 8 h (yield of 95.5%). For all the CCD experimental conditions, the residual solids presented CNF characteristics. Moreover, the use of a new strategy with temperature reduction from 50 to 35°C after 24 h of enzymatic hydrolysis enabled CNC to be obtained after 144 h. The CNC showed a crystallinity index of 83%, length of 260 nm, diameter of 15 nm, and aspect ratio (L/D) of 15. These characteristics are suitable for many applications, such as reinforcement in polymeric materials and other lower volume higher value bio-based products. The findings indicate the viability of obtaining ethanol and CNC using the biochemical route exclusively, potentially contributing to the future implementation of forest biorefineries. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1085-1095, 2017.

Biocompatibility assessment of fibrous nanomaterials in mammalian embryos.

Currently there is a growing interest in the use of nanotechnology in reproductive medicine and reproductive biology. However, their toxic effects on mammalian embryos remain poorly understood. In this work, we evaluate the biocompatibility of two fibrous nanomaterials (NMs): cotton cellulose nanofibers (CNF) and carboxylated multiwalled carbon nanotubes (MWCNT-COOH), by performing an investigation of the embryonic development, gene expression (biomarkers focused on cell stress, apoptosis and totipotency) and in situ apoptosis in bovine embryos. Exposure to NMs did not interfere in preimplantation development or in the incidence of apoptosis in the bovine embryo, but they did affect the gene expression. The results presented are important for an understanding of the toxicity of cotton CNF and MWCNT-COOH on mammalian embryos. To our knowledge, we report the first evaluation of biocompatibility between these NMs on preimplantation embryos, which may open a new window for reproductive biomedical applications.

Direct and indirect toxic effects of cotton-derived cellulose nanofibres on filamentous green algae.

Recently, cellulose nanofibers (CNFs) have attracted considerable attention as natural, abundant polymers with excellent mechanical properties and biodegradability. CNFs provide a new materials platform for the sustainable production of high-performance nano-enable products for various applications. Given the increasing rates of CNF production, the potential for their release to the environment and the subsequent impact on ecosystem is becoming an increasing concern that needs to be addressed. Here, we used the Klebsormidium flaccidum as a bioindicator organism of terrestrial and freshwater habitats pollution using a battery of biomarkers. Our results show that cotton CNFs inhibit the proliferation of algae and induce morphological changes in them. The two main toxicity mechanisms induced by cotton CNFs are: (i) a direct contact of CNFs with the cell wall and cellular membrane and (ii) an indirect effect through the generation of reactive oxygen species (ROS).

Polyethylene Films Containing Silver Nanoparticles for Applications in Food Packaging: Characterization of Physico-Chemical and Anti-Microbial Properties.

This paper reports the antibacterial effect and physico-chemical characterization of films containing silver nanoparticles for use as food packaging. Two masterbatches (named PEN and PEC) con- taining silver nanoparticles embedded in distinct carriers (silica and titanium dioxide) were mixed with low-density polyethylene (LDPE) in different compositions and extruded to produce plain films. These films were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA) and Fourier Transform Infrared Spectroscopy (FTIR). The morphology of the films showed the formation of agglomerates of nanoparticles in both PEN and PEC composites. X-ray analyses confirmed the presence of SiO2 in PEN samples and TiO2 in PEC samples. Thermal analyses indicated an increase in thermal stability of the PEC compositions. The antimicrobial efficacy was determined by applying the test strain for Escherichia coli and Staphylococcus aureus, according to the Japanese Industrial Standard Method (JIS Z 2801:2000). The films analyzed showed antimicrobial properties against the tested microorganisms, presenting better activity against the S. aureus than E. Coli. These findings suggest that LDPE films with silver nanoparticles are promising to provide a significant contribution to the quality and safety of packaged food.

Evaluation of antimicrobial activity of silver nanoparticles for carboxymethylcellulose film applications in food packaging.

In this study, silver nanoparticles were prepared and incorporated into carboxymethylcellulose films to evaluate the antimicrobial activity for food packaging applications. The techniques carried out for material characterization were: infrared spectroscopy and thermal analysis for the silver nanoparticles and films, as well as particle size distribution for the nanoparticles and water vapor permeability for the films. The antimicrobial activity of silver nanoparticles prepared by casting method was investigated. The minimum inhibitory concentration (MIC) value of the silver nanoparticles to test Gram-positive (Enterococcus faecalis) and Gram-negative (Escherichia coli) microorganisms was carried out by the serial dilution technique, tested in triplicate to confirm the concentration used. The results were developed using the Mcfarland scale which indicates that the presence or absence of turbidity tube demonstrates the inhibition of bacteria in relation to the substance inoculated. It was found that the silver nanoparticles inhibited the growth of the tested microorganisms. The carboxymethylcellulose film embedded with silver nanoparticles showed the best antimicrobial effect against Gram-positive (E. faecalis) and Gram-negative (E. coli) bacteria (0.1 microg cm(-3)).

Ecotoxicological effects of carbon nanotubes and cellulose nanofibers in Chlorella vulgaris.

BACKGROUND: MWCNT and CNF are interesting NPs that possess great potential for applications in various fields such as water treatment, reinforcement materials and medical devices. However, the rapid dissemination of NPs can impact the environment and in the human health. Thus, the aim of this study was to evaluate the MWCNT and cotton CNF toxicological effects on freshwater green microalgae Chlorella vulgaris. RESULTS: Exposure to MWCNT and cotton CNF led to reductions on algal growth and cell viability. NP exposure induced reactive oxygen species (ROS) production and a decreased of intracellular ATP levels. Addition of NPs further induced ultrastructural cell damage. MWCNTs penetrate the cell membrane and individual MWCNTs are seen in the cytoplasm while no evidence of cotton CNFs was found inside the cells. Cellular uptake of MWCNT was observed in algae cells cultured in BB medium, but cells cultured in Seine river water did not internalize MWCNTs. CONCLUSIONS: Under the conditions tested, such results confirmed that exposure to MWCNTs and to cotton CNFs affects cell viability and algal growth.

Nutraceutically inspired pectin-Mg(OH)2 nanocomposites for bioactive packaging applications.

This paper reports on the development of bioactive edible films based on pectin as a dietary matrix and magnesium hydroxide (Mg(OH)2) nanoplates as a reinforcing filler. Nanocomposites of high-methoxyl (HM) and low-methoxyl (LM) pectins were prepared using the casting method at concentrations of Mg(OH)2 ranging from 0.5 to 5 wt %. Atomic force microscopy and FTIR spectroscopy were employed to characterize the nanocomposite structure. The tensile properties and thermal stability of the nanocomposites were also examined to ascertain the effect of Mg(OH)2 inclusion and degree of methoxylation. The results provided evidence that the Mg(OH)2 nanoplates were uniformly dispersed and interacted strongly with the film matrix. The mechanical and thermal properties were significantly improved in the nanocomposite films compared to the control. Mg(OH)2 nanoplates were more effective in improving properties of LM pectin. Preliminary migration studies using arugula leaves confirmed that pectin-Mg(OH)2 nanocomposites can release magnesium hydroxide by contact, demonstrating their potential for magnesium supplementation in bioactive packaging.

Brucite nanoplates reinforced starch bionanocomposites.

In this paper the mechanical reinforcement of nano-sized brucite, Mg(OH)(2) in a series of bionanocomposite films based on starch was investigated. Brucite nanoplates with an aspect ratio of 9.25 were synthesized by wet precipitation and incorporated into starch matrices at different concentrations (0-7.5 wt.%). Scanning electron microscopy revealed a high degree of nanoplate dispersion within the starch bionanocomposites and good interfacial adhesion between the filler and matrix. The brucite nanoplates formed agglomerates at high concentrations. The reinforcement factor values of the bionanocomposites were higher than the values predicted from the Halphin-Tsai model, which was attributed mainly to the high surface area of the nanoplates. Brucite (1 wt.%) nearly doubled the elastic modulus of starch films. Thermogravimetric analyses indicated some interaction between starch and the brucite that modified their decomposition profiles. Mechanical tests of glycerol plasticized bionanocomposites showed that the reinforcing efficiency of brucite remained high even at 10 wt.% and 20 wt.% of plasticizer.