Water Absorption and Physicochemical Characterization of Novel Zeolite-PMAA-co-PAAm Nanocomposites.

The growth in global population has caused an increase in the demand for food production, leading to an increase in the use of agrochemicals. Their overuse causes serious damage to the environment. In this way, nanocomposite hydrogels are promising materials for use as carrier vehicles for the controlled release of agrochemicals, which helps reduce the damage caused by their indiscriminate use. In this work, a novel hydrogel nanostructure based on carboxymethylcellulose (CMC) and zeolite with a poly(methacrylic acid)-co-polyacrylamide (PMAA-co-PAAm) support network was synthesized. The CMC polysaccharide increased the zeolite stability in the solution. Increasing the concentration of acrylamide (AAm) monomer improved the mechanical stability of the nanocomposites. FTIR, XRD and TG results confirmed the presence of zeolite in the PMAA-co-PAAm matrices. In addition, the zeolite decreased the water absorption of the nanocomposites from 33 ± 2 g/g to approximately 22 ± 1 g/g, but increased the thermal stability of the nanocomposites. However, the reduction in water absorption in saline solutions was more significant in hydrogels without zeolite. Fertilizer desorption studies confirmed the controlled release behavior and this trend may be improved by zeolite structure. Thus, the presence of zeolite increased the amount of monobasic potassium phosphate (KH2PO4) release from 250 to 275 mg of fertilizer per gram of hydrogel. Controlling the water absorption and kinetic properties by adjusting the nanocomposite constituents may increase the applicability of the composites in agriculture, specifically as carrier vehicles in the controlled release of agrochemicals.

Hybrid Biodegradable Hydrogels Obtained from Nanoclay and Carboxymethylcellulose Polysaccharide: Hydrophilic, Kinetic, Spectroscopic and Morphological Properties.

In this paper, series of novel nanocomposite hydrogels based on polyacrylamide (PAAm), carboxymethylcellulose (CMC) and nanoclay were synthesized. Hydrophilic, kinetic, spectroscopic and morphological properties were investigated as function of their constituents. Spectroscopic properties confirmed the obtaining of the nanocomposites. It was also observed that the nanocomposites have walls of pores with a more rugged morphology compared with the morphology of the hydrogel without clay, contributing to repel the water molecules. Besides, the results showed that the velocity and quantity of water uptake may be controlled by adjusting of matrix rigidity, i.e., nanoclay content into polymeric matrix. This behavior is required to future application in agriculture fields, specifically as carrier vehicle in controlled release of agrochemicals. Thus, these nanocomposites have technological application.

Hybrid nanocomposites containing carboxymethylcellulose and silver nanoparticles.

Silver nanoparticles have high temperature stability and low volatility, and at the nanoscale are known to be an effective antifungal and antimicrobial agent. The present investigation involves the synthesis of silver nanoparticle/carboxymethylcellulose nanocomposites. The nanoparticles synthesised in this study had sizes in the range of 100 and 40 nm. The nanocomposites formed by a combination of metallic nanoparticles and carboxymethylcellulose were characterised by contact angle measurements, solubility tests, thermal and mechanical analyses, and morphological images. Improvements in the hydrophobic properties were observed with inclusion of the nanoparticles in the nanocomposites, with the best results occurring after the addition of 40 nm nanoparticles in a carboxymethylcellulose matrix. The silver nanoparticles tend to occupy the empty spaces in the pores of the carboxymethylcellulose matrix, inducing the collapse of these pores and thereby improving the tensile and barrier properties of the film.

Combining Chitosan Nanoparticles and Garlic Essential Oil as Additive Fillers to Produce Pectin-Based Nanocomposite Edible Films.

Edible films were produced by combining a pectin (PEC) matrix with chitosan nanopar-ticle (CSNP), polysorbate 80 (T80), and garlic essential oil (GEO) as an antimicrobial agent. CSNPs were analyzed for their size and stability, and the films, throughout their contact angle, scanning electron microscopy (SEM), mechanical and thermal properties, water vapor transmission rate, and antimicrobial activity. Four filming-forming suspensions were investigated: PGEO (control); PGEO@T80; PGEO@CSNP; PGEO@T80@CSNP. The compositions are included in the methodology. The average particle size was 317 nm, with the zeta potential reaching +21.4 mV, which indicated colloidal stability. The contact angle of the films exhibited values of 65°, 43°, 78°, and 64°, respec-tively. These values showed films with variations in hydrophilicity. In antimicrobial tests, the films containing GEO showed inhibition only by contact for S. aureus. For E. coli, the inhibition occurred in films containing CSNP and by direct contact in the culture. The results indicate a promising al-ternative for designing stable antimicrobial nanoparticles for application in novel food packaging. Although, it still shows some deficiencies in the mechanical properties, as demonstrated in the elongation data.

Development of novel guava puree films containing chitosan nanoparticles.

One of the overall goals of industries is to use packages that do not cause environmental problems at disposal time, but that have the same properties as the conventional ones. The goal of this study is to synthesize edible films based on hydroxypropyl methylcellulose (HPMC) with guava puree and chitosan (CS) nanoparticles. This was divided into two stages, the first is the synthesis of chitosan nanoparticles and the second is the production of the films. For the nanoparticles, average size and zeta potential measurements were performed. The characterizations of mechanical and thermal properties, solubility and water vapor permeability tests were conducted in the films. It was observed that when the nanoparticles were added to HPMC and guava puree films, they improved their mechanical and thermal properties, as well as decreased the films solubility and permeability. The potential application of the films prepared would be in edible films with flavor and odor to extend the shelf life of products.

Performance of Gelatin Films Reinforced with Cloisite Na+ and Black Pepper Essential Oil Loaded Nanoemulsion.

The concern about consuming eco-friendly products has motivated research in the development of new materials. Therefore, films based on natural polymers have been used to replace traditional polymers. This study consists of a production of films based on gelatin reinforced with black pepper essential oil-loaded nanoemulsions and Cloisite Na+. The films were characterized by water vapor permeability, mechanical and thermal properties, surface contact angle, X-ray diffraction and scanning electron microscopy. It was observed that the films containing the nanoemulsion have higher permeability values and an increase in their mechanical resistance. The addition of nanoclay contributed to an increase in the surface hydrophobicity of the film and an increase in the tensile strength, at break, by about 150%. The addition of essential oil nanoemulsions led to an increase in thermal stability. The presence of clay dispersion contributed to the formation of a surface that was slightly rougher and grainier. The addition of the black pepper essential oil nanoemulsion resulted in an increase in porosity of the gelatin matrix. Through X-ray diffraction analysis, it was possible to conclude that both the polymeric gelatin matrix and the essential oils nanoemulsion are intercalated with the clay dispersion.

Upcycling Microbial Cellulose Scraps into Nanowhiskers with Engineered Performance as Fillers in All-Cellulose Composites.

Cellulose is everywhere and renovates in nature continuously and rapidly, while petroleum does not. Unlike the latter, cellulose biodegrades and may represent a carbon sink. Inspired by the multiscale architecture of cellulose, we report on all-cellulose composites comprising cellulose ether as a matrix and highly pure bacterial cellulose nanocrystals (BCNCs) as fillers. Optimum performance as a packaging material was achieved by engineering BCNC surface chemistry as well as the filler-in-matrix dispersion, targeting the replacement of unsustainable, fossil-derived plastics intended for single-use applications. Cost could pose a hurdle, eliminated through the valorization of underutilized scraps from industrial operations, which is also in line with the circular bioeconomy in terms of the integral use of biomass. As far as performance, the optically transparent hydroxypropyl methylcellulose (HPMC) films presented improved tensile strength (from 61 ± 6 to 86 ± 9 MPa) and Young's modulus (from 1.5 ± 0.2 to 2.7 ± 0.4 GPa) while reduced elongation at break (from 15 ± 2 to 12 ± 2%) and water vapor permeability (from 0.40 ± 0.02 to 0.31 ± 0.01 g mm h-1 m-2 kPa-1) when filled with only 5 wt % of (120 ± 31) nm long, (13 ± 3) nm wide, 88% crystalline BCNC. This dual, win-win effect of BCNCs on the mechanical and barrier properties of HPMC films was enabled by a suitable dispersion state, achieved via high-energy mixing, and quenched by casting. This study adds to the current literature on all-cellulose composites and helps pave the route for the technical and economical feasibilities of replacing non-renewable, non-biodegradable plastics in short-term applications by materials that are both renewable and biodegradable, that are also produced through green protocols and isolated from surplus biomass, and that still perform similarly or even better.

Combining Cupuassu (Theobroma grandiflorum) Puree, Pectin, and Chitosan Nanoparticles into Novel Edible Films for Food Packaging Applications.

Every year, the residues generated by the disposal of packaging materials produced from fossil fuels have been growing, denoting a major environmental problem that can be mitigated by the development of biodegradable materials from natural polymers, particularly edible films. This work aimed at the development of pectin films added by cupuassu puree and chitosan nanoparticles and to evaluate the improvement of the physical-mechanical performance of the composite films. The nanostructures displayed an average size of 110 nm and a zeta potential of approximately +40 mV. The films were produced by casting, and they exhibited manageability, homogeneity, and continuity. Based upon the mechanical analysis of maximum stress and elongation, it was concluded that the nanoparticles functioned as fillers, increasing the toughness of the pectin films. Water vapor permeability assays demonstrated that the nanostructured films containing cupuassu exhibited improved barrier properties. The glass transition temperature of the films was not strongly affected by the addition of nanoparticles. Conversely, the initial degradation temperature decreased with the addition of nanoparticles and cupuassu puree. The outcomes of this research pave a new route for the development of nonconventional food packaging materials.

Preparation of chitosan nanoparticles using methacrylic acid.

In this work the preparation of chitosan nanoparticle was investigated using methacrylic acid in different conditions and studied by particle size analyzer, zeta-potential, Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM). The particle size was dependent on the chitosan concentration used during the preparation method. Nanoparticles with sizes as small as 60 nm were achieved, that can be extremely important for several applications. The nanoparticles solution was also pH-sensitive, due to swelling and aggregation of the nanoparticles. The nanoparticles obtained presented a very homogeneous morphology showing a quite uniform particles size distribution and a rather spherical shape.

Macro- and Micronutrient Simultaneous Slow Release from Highly Swellable Nanocomposite Hydrogels.

Clay-loaded hydrogels have been arousing great interest from researchers and academics due to their unique properties and broad applicability range. Here we developed hydrogel-based nanocomposites intended for slow/controlled release of macro- and micronutrients into independent or concurrent systems. The produced nanocomposites underwent a hydrolysis treatment that improved their physicochemical properties. We obtained materials capable of absorbing water contents 5000 times greater than their weights, an outcome that makes them promising, particularly if compared with commercially available materials. Though swelling degree was affected by the presence of calcium montmorillonite (MMt), MMt has increased nutrient (urea and boron) loading capacity and, as a consequence of its interaction with the studied nutrients, has led to a slower release behavior. By evaluating the simultaneous release behavior, we observed that both the ionic (sodium octaborate) and the nonionic (urea) sources competed for the same active sites within the nanocomposites as suggested by the decreased loading and release values of both nutrients when administrated simultaneously. Because of its great swelling degree, higher than 2000 times in water, the nanocomposites formulated with high MMt contents (approximately 50.0% wt) as well as featuring high loading capacity and individual (approximately 74.2 g of urea g(-1) of nanocomposite and 7.29 g of boron g(-1) of nanocomposite) and simultaneous release denote interesting materials for agricultural applications (e.g., carriers for nutrient release).

Nanocomposite PAAm/methyl cellulose/montmorillonite hydrogel: evidence of synergistic effects for the slow release of fertilizers.

In this work, we synthesized a novel series of hydrogels composed of polyacrylamide (PAAm), methylcellulose (MC), and calcic montmorillonite (MMt) appropriate for the controlled release of fertilizers, where the components presented a synergistic effect, giving very high fertilizer loading in their structure. The synthesized hydrogel was characterized in relation to morphological, hydrophilic, spectroscopic, structural, thermal, and kinetic properties. After those characterizations, the application potential was verified through sorption and desorption studies of a nitrogenated fertilizer, urea (CO(NH2)2). The swelling degree results showed that the clay loading considerably reduces the water absorption capability; however, the hydrolysis process favored the urea adsorption in the hydrogel nanocomposites, increasing the load content according to the increase of the clay mass. The FTIR spectra indicated that there was incorporation of the clay with the polymeric matrix of the hydrogel and that incorporation increased the water absorption speed (indicated by the kinetic constant k). By an X-ray diffraction technique, good nanodispersion (intercalation) and exfoliation of the clay platelets in the hydrogel matrix were observed. Furthermore, the presence of the montmorillonite in the hydrogel caused the system to liberate the nutrient in a more controlled manner than that with the neat hydrogel in different pH ranges. In conclusion, excellent results were obtained for the controlled desorption of urea, highlighting the hydrolyzed hydrogels containing 50% calcic montmorillonite. This system presented the best desorption results, releasing larger amounts of nutrient and almost 200 times slower than pure urea, i.e., without hydrogel. The total values of nutrients present in the system show that this material is potentially viable for application in agriculture as a nutrient carrier vehicle.

Preparation and characterization of novel micro- and nanocomposite hydrogels containing cellulosic fibrils.

The main objective of this article was to report a simple, fast, and low cost strategy for the synthesis of micro- and nanocomposites by adding cellulose nanofibers, obtained by acid hydrolysis, and added to hydrogels as reinforcing agents. Specifically, when cellulose nanofibers were added to hydrogels, morphologic analyses showed significant decreases in pore size and formation of three-dimensional well-oriented porous microstructure. It was also observed that cellulose nanoparticles improved the mechanical and structural network properties without negatively impacting their thermal and hydrophilic properties. The value of maximum compressive stress was 2.1 kPa for the PAAm-MC, and it increased to 4.4 kPa when the cellulose nanofiber was incorporated into the hydrogel. By investigation of XRD patterns, it was found that the incorporation of cellulose nanofiber affected the crystallinity of PAAm-MC hydrogels, thus contributing to improvements in mechanical, structural, and hydrophilic properties of the PAAm-MC hydrogels.