Bacterial cellulose nanocrystals obtained through enzymatic and acidic routes: A comparative study of their main properties and in vitro biological responses.

Cellulose nanocrystals (CNCs) are crystalline domains isolated from cellulosic fibers. They have been utilized in a wide range of applications, such as reinforcing fillers, antibacterial agents and manufacturing of biosensors. Whitin this context, the aim of this work was to obtain and analyze CNCs extracted from bacterial nanocellulose (BNC) using two distinct methods combined with milling pre-treatment: an acidic hydrolysis using 64 % sulfuric acid and an enzymatic hydrolysis using a commercial cellulase enzyme mixture. The CNCs obtained from the enzymatic route (e-CNCs) were observed to be spherical nanoparticles with diameter of 56 ± 11 nm. In contrast, the CNCs from the acid hydrolysis (a-CNCs) appeared as needle-shaped nanoparticles with a high aspect ratio with lengths/widths of 158 ± 64 nm/11 ± 2 nm. The surface zeta potential (ZP) of the a-CNCs was -30,8 mV, whereas the e-CNCs has a potential of +2.70 ± 3.32 mV, indicating that a-CNCs consisted of negatively charged particles with higher stability in solution. Although the acidic route resulted in nanocrystals with a slightly higher crystallinity index compared to the enzymatic route, e-CNCs was found to be more thermally stable than BNC and a-CNCs. Here, we also confirmed the safety of a-CNCs and e-CNCs using L929 cell line. Lastly, this article describes two different CNCs synthesis approaches that leads to the formation of nanoparticles with different dimensions, morphology and unique physicochemical properties. To the best of our knowledge, this is the first study to yield spherical nanoparticles as a result of BNC enzymatic treatment.

Hydrophobic enzymatic cellulose nanocrystals via a novel, one-pot green method.

Cellulose nanocrystals (CNCs) are a rapidly growing bionanomaterial with remarkable properties that have been harnessed in various applications, including mechanical reinforcement, biomedical materials, and coatings. However, for non-water-based applications, hydrophobization of CNCs while preserving their integrity is crucial. In this study, we propose a new eco-friendly, one-pot surface esterification method for hydrophobizing enzymatic CNCs in aqueous suspension without solvent exchange. By establishing an appropriate set of reaction conditions, it was possible to create a miscibility gradient that enabled a low-cost, and renewable fatty acid to be utilized as an acyl donor and solvent, allowing direct hydrophobic modification of the as-produced aqueous suspension of enzymatic CNC. FT-IR and AFM-IR analyses confirmed the formation of ester groups, while 13C NMR confirmed the emergence of carboxyl groups. XPS revealed a high degree of surface substitution (0.39) in the modified CNC, while a substantial increase in contact angle (from 40 to approximately 90°) quantitatively confirmed the high efficiency of the enzymatic CNC's hydrophobic modification. Additionally, important properties such as morphology remained practically unchanged, except for a slight increase in thermal stability and crystallinity of the CNCs. Therefore, hydrophobic enzymatic CNCs were successfully produced via a simple, scalable, and environmentally friendly approach without compromising their properties. These hydrophobic CNCs have the potential to enhance nanocomposite compatibility, improve packaging performance for electronics and foods, optimize adhesion in coatings, and offer advancements in cosmetics and drug delivery. However, comprehensive studies are needed to confirm their applicability across these sectors.

Thermoplastic Starch Biocomposite Films Reinforced with Nanocellulose from Agave tequilana Weber var. Azul Bagasse.

In this work, cellulose nanocrystals (CNCs), bleached cellulose nanofibers (bCNFs), and unbleached cellulose nanofibers (ubCNFs) isolated by acid hydrolysis from Agave tequilana Weber var. Azul bagasse, an agro-waste from the tequila industry, were used as reinforcements in a thermoplastic starch matrix to obtain environmentally friendly materials that can substitute contaminant polymers. A robust characterization of starting materials and biocomposites was carried out. Biocomposite mechanical, thermal, and antibacterial properties were evaluated, as well as color, crystallinity, morphology, rugosity, lateral texture, electrical conductivity, chemical identity, solubility, and water vapor permeability. Pulp fibers and nanocelluloses were analyzed via SEM, TEM, and AFM. The water vapor permeability (WVP) decreased by up to 20.69% with the presence of CNCs. The solubility decreases with the presence of CNFs and CNCs. The addition of CNCs and CNFs increased the tensile strength and Young's modulus and decreased the elongation at break. Biocomposites prepared with ubCNF showed the best tensile mechanical properties due to a better adhesion with the matrix. Images of bCNF-based biocomposites demonstrated that bCNFs are good reinforcing agents as the fibers were dispersed within the starch film and embedded within the matrix. Roughness increased with CNF content and decreased with CNC content. Films with CNCs did not show bacterial growth for Staphylococcus aureus and Escherichia coli. This study offers a new theoretical basis since it demonstrates that different proportions of bleached or unbleached nanofibers and nanocrystals can improve the properties of starch films.

Reinforcement of Acrylamide Hydrogels with Cellulose Nanocrystals Using Gamma Radiation for Antibiotic Drug Delivery.

In this paper, we report the synthesis of acrylamide hydrogels (net-AAm) reinforced with cellulose nanocrystals (CNCs) using gamma radiation, a powerful tool to obtain crosslinked polymers without the use of chemical initiators and crosslinking agents. Some slight changes in the chemical structure and crystallinity of CNCs took place during gamma irradiation without affecting the nanofiller function. In fact, cellulose nanocrystals had a notable influence over the swelling and mechanical properties on the reinforced hydrogels (net-AAm/CNC), obtaining more rigid material since the Young compression modulus increased from 11 kPa for unreinforced net-AAm to 30 kPa for net-AAm/CNC (4% w/w). Moreover, the studies of retention and release of ciprofloxacin (Cx), a quinolone antibiotic drug, showed that reinforced hydrogels were able to load large amounts of ciprofloxacin (1.2-2.8 mg g-1) but they distributed 100% of the drug very quickly (<100 min). Despite this, they exhibited better mechanical properties than the control sample, allowing their handling, and could be used as wound dressings of first response because they can absorb the exudate and at the same time deliver an antibiotic drug directly over the injury.

The emergence of hybrid cellulose nanomaterials as promising biomaterials.

Cellulose nanomaterials (CNs) are promising green materials due to their unique properties as well as their environmental benefits. Among these materials, cellulose nanofibrils (CNFs) and nanocrystals (CNCs) are the most extensively researched types of CNs. While they share some fundamental properties like low density, biodegradability, biocompatibility, and low toxicity, they also possess unique differentiating characteristics such as morphology, rheology, aspect ratio, crystallinity, mechanical and optical properties. Therefore, numerous comparative studies have been conducted, and recently, various studies have reported the synergetic advantages resulting from combining CNF and CNC. In this review, we initiate by addressing the terminology used to describe combinations of these and other types of CNs, proposing "hybrid cellulose nanomaterials" (HCNs) as the standardized classifictation for these materials. Subsequently, we briefly cover aspects of properties-driven applications and the performance of CNs, from both an individual and comparative perspective. Next, we comprehensively examine the potential of HCN-based materials, highlighting their performance for various applications. In conclusion, HCNs have demonstraded remarkable success in diverse areas, such as food packaging, electronic devices, 3D printing, biomedical and other fields, resulting in materials with superior performance when compared to neat CNF or CNC. Therefore, HCNs exhibit great potential for the development of environmentally friendly materials with enhanced properties.

Nanocellulose-based porous materials: Regulation and pathway to commercialization in regenerative medicine.

We review the recent progress that have led to the development of porous materials based on cellulose nanostructures found in plants and other resources. In light of the properties that emerge from the chemistry, shape and structural control, we discuss some of the most promising uses of a plant-based material, nanocellulose, in regenerative medicine. Following a brief discussion about the fundamental aspects of self-assembly of nanocellulose precursors, we review the key strategies needed for material synthesis and to adjust the architecture of the materials (using three-dimensional printing, freeze-casted porous materials, and electrospinning) according to their uses in tissue engineering, artificial organs, controlled drug delivery and wound healing systems, among others. For this purpose, we map the structure-property-function relationships of nanocellulose-based porous materials and examine the course of actions that are required to translate innovation from the laboratory to industry. Such efforts require attention to regulatory aspects and market pull. Finally, the key challenges and opportunities in this nascent field are critically reviewed.

Assessing the Effect of Cellulose Nanocrystal Content on the Biodegradation Kinetics of Multiscale Polylactic Acid Composites under Controlled Thermophilic Composting Conditions.

This work studied the effect of cellulose nanocrystal (NCC) content on the biodegradation kinetics of PLA-based multiscale cellulosic biocomposites (PLAMCBs). To facilitate biodegradation, the materials were subjected to thermo-oxidation before composting. Biodegradation was carried out for 180 days under controlled thermophilic composting conditions according to the ASTM D 5338 standard. A first-order model based on Monod's kinetics under limiting substrate conditions was used to study the effect of cellulose nanocrystal (NCC) content on the biodegradation kinetics of multiscale composite materials. It was found that thermo-oxidation at 70 °C for 160 h increased the biodegradability of PLA. Also, it was found that the incorporation of cellulosic fibrous reinforcements increased the biodegradability of PLA by promoting hydrolysis during the first stage of composting. Likewise, it was found that partial substitution of micro cellulose (MFC) by cellulose nanocrystals (NCCs) increased the biodegradability of the biocomposite. This increase was more evident as the NCC content increased, which was attributed to the fact that the incorporation of cellulose nanocrystals facilitated the entry of water into the material and therefore promoted the hydrolytic degradation of the most recalcitrant fraction of PLA from the bulk and not only by surface erosion.

High-yield production of rod-like and spherical nanocellulose by controlled enzymatic hydrolysis of mechanically pretreated cellulose.

In this study, a simple and scalable mechanical pretreatment was evaluated as means of enhancing the accessibility of cellulose fibers, with the objective of improving the efficiency of enzymatic reactions for the production of cellulose nanoparticles (CNs). In addition, the effects of enzyme type (endoglucanase - EG, endoxylanase - EX, and a cellulase preparation - CB), composition ratio (0-200UEG:0-200UEX or EG, EX, and CB alone), and loading (0 U-200 U) were investigated in relation to CN yield, morphology, and properties. The combination of mechanical pretreatment and specific enzymatic hydrolysis conditions substantially improved CN production yield, reaching up to 83 %. The production of rod-like or spherical nanoparticles and their chemical composition were highly influenced by the enzyme type, composition ratio, and loading. However, these enzymatic conditions had minimal impact on the crystallinity index (approximately 80 %) and thermal stability (Tmax within 330-355 °C). Overall, these findings demonstrate that mechanical pretreatment followed by enzymatic hydrolysis under specific conditions is a suitable method to produce nanocellulose with high yield and adjustable properties such as purity, rod-like or spherical forms, high thermal stability, and high crystallinity. Therefore, this production approach shows promise in producing tailored CNs with the potential for superior performance in various advanced applications, including, but not limited to, wound dressings, drug delivery, thermoplastic composites, 3D (bio)printing, and smart packaging.

Preparation and characterization of starch-based composite films reinforced by quinoa (Chenopodium quinoa Willd.) straw cellulose nanocrystals.

The development of green and biodegradable nanomaterials is significant for the sustainable utilization of renewable lignocellulosic biomass. This work aimed to obtain the cellulose nanocrystals from quinoa straws (QCNCs) by acid hydrolysis. The optimal extraction conditions were investigated by response surface methodology, and the physicochemical properties of QCNCs were evaluated. The maximum yield of QCNCs (36.58 ± 1.42 %) was obtained under the optimal extraction conditions of 60 % (w/w) sulfuric acid concentration, 50 °C reaction temperature, and 130 min reaction time. The characterization results of QCNCs showed that it is a rod-like material with an average length of 190.29 ± 125.25 nm, an average width of 20.34 ± 4.69 nm, excellent crystallinity (83.47 %), good water dispersibility (Zeta potential = -31.34 mV) and thermal stability (over 200 °C). The addition of 4-6 wt% QCNCs could significantly improve the elongation at break and water resistance of high-amylose corn starch films. This study will pave the route for improving the economic value of quinoa straw, and provide relevant proof of QCNCs for the preliminary application in starch-based composite films with the best performance.

Toxicological effects resulting from co-exposure to nanomaterials and to a ß-blocker pharmaceutical drug in the non-target macrophyte species Lemna minor.

The wide use of carbon-based materials for various purposes leads to their discharge in the aquatic systems, and simultaneous occurrence with other environmental contaminants, such as pharmaceutical drugs. This co-occurrence can adversely affect exposed aquatic organisms. Up to now, few studies have considered the simultaneous toxicity of nanomaterials, and organic contaminants, including pharmaceutical drugs, towards aquatic plants. Thus, this study aimed to assess the toxic effects of the co-exposure of propranolol (PRO), and nanomaterials based on cellulose nanocrystal, and graphene oxide in the aquatic macrophyte Lemna minor. The observed effects included reduction of growth rate in 13% in co-exposure 1 (nanomaterials + PRO 5 µg L-1), and 52-64% in co-exposure 2 (nanomaterials + PRO 51.3 mg L-1), fresh weight reduction of 94-97% in co-exposure 2 compared to control group, and increased pigment production caused by co-exposure treatments. The analysis of PCA showed that co-exposure 1 (nanomaterials + PRO 5 µg L-1) positively affected growth, and fresh weight, and co-exposure 2 positively affected pigments content. The results suggested that the presence of nanomaterials enhanced the overall toxicity of PRO, exerting deleterious effects in the freshwater plant L. minor, suggesting that this higher toxicity resulting from co-exposure was a consequence of the interaction between nanomaterials and PRO.

Hydrophobization of aerogels based on chitosan, nanocellulose and tannic acid: Improvements on the aerogel features and the adsorption of contaminants in water.

Hydrophobic chitosan aerogels are promising adsorbents for immiscible contaminants such as oils and organic solvents. However, few studies have reported the application of hydrophobic aerogels as adsorbent for organic contaminants dissolved in water. Herein, novel highly hydrophobic chitosan (CS) beads containing cellulose nanocrystals (CNC) and hydrophobized tannic acid (HTA) composite were prepared with different CS and CNC-HTA content to achieve an optimized adsorbent to remove emerging contaminants from water in batch and fixed-bed assays. The CS@CNC-HTA beads properties were assessed by FTIR, XRD, SEM, XPS, Micro-CT, WCA, and zeta potential. Supramolecular interactions and physical interlacements between CS and CNC-HTA enabled the formation of CS@CNC-HTA beads with high porosity (98.6%), great volume of open pore space (10.16 mm3) and hydrophobicity (121.8°). The 1:1 CS@CNC-HTA beads showed the best performance for removing the pharmaceutical sildenafil citrate, the basic blue 26 dye, and the surfactant cetylpyridinium chloride, reaching adsorption capacities of 86 (73%), 375 (84%), and 390 (90%) mg.g-1, respectively. The 1:1 CS@CNC-HTA beads efficiently removed sildenafil citrate, basic blue 26 and cetylpyridinium chloride in fixed-bed experiments with exhaustion times of 890, 300, and 470 min, respectively. Theoretical calculations and adsorption assays indicate that the main attractive interactions are pyridinium-π, π-π, electrostatic and hydrophobic.

Ascidian-Inspired Supramolecular Cellulose Nanocomposite Hydrogels with Antibacterial Activity.

The design of ultratough hydrogels has recently emerged as a topic of great interest in the scientific community due to their ability to mimic the features of biological tissues. An outstanding strategy for preparing these materials relies on reversible and dynamic cross-links within the hydrogel matrix. In this work, inspired by the composition of ascidians' tunic, stretchable supramolecular hydrogels combining poly(vinyl alcohol), green tea-derived gallic acid, and rigid tannic acid-coated cellulose nanocrystals (TA@CNC) were designed. The addition of TA@CNC nanofillers in concentrations up to 1.2 wt % significantly impacted the mechanical and viscoelastic properties of the hydrogels due to the promotion of hydrogen bonding with the polymer matrix and polyphenols π-π stacking interactions. These supramolecular associations endow the hydrogels with excellent stretchability and strength (>340%, 540 kPa), low thermoreversible gel-sol transition (60 °C), and remolding ability, while the natural polyphenols provided potential antibacterial properties. These versatile materials can be anticipated to open up new prospects for the rational design of polyphenol-based cellulosic hydrogels for different biomedical applications.

Effect of the Addition of Corn Husk Cellulose Nanocrystals in the Development of a Novel Edible Film.

The cellulose from agroindustrial waste can be treated and converted into nanocrystals or nanofibers. It could be used to produce biodegradable and edible films, contributing to the circular economy and being environmentally friendly. This research aimed to develop an edible film elaborated with activated cellulose nanocrystals, native potato starch, and glycerin. The activated cellulose nanocrystals were obtained by basic/acid digestion and esterification with citric acid from corn husks. The starch was extracted from the native potato cultivated at 3500 m of altitude. Four film formulations were elaborated with potato starch (2.6 to 4.4%), cellulose nanocrystals (0.0 to 0.12%), and glycerin (3.0 to 4.2%), by thermoforming at 60 °C. It was observed that the cellulose nanocrystals reported an average size of 676.0 nm. The films mainly present hydroxyl, carbonyl, and carboxyl groups that stabilize the polymeric matrix. It was observed that the addition of cellulose nanocrystals in the films significantly increased (p-value < 0.05) water activity (0.409 to 0.447), whiteness index (96.92 to 97.27), and organic carbon content. In opposition to gelatinization temperature (156.7 to 150.1 °C), transparency (6.69 to 6.17), resistance to traction (22.29 to 14.33 N/mm), and solubility in acidic, basic, ethanol, and water media decreased. However, no significant differences were observed in the thermal decomposition of the films evaluated through TGA analysis. The addition of cellulose nanocrystals in the films gives it good mechanical and thermal resistance qualities, with low solubility, making it a potential food-coating material.

Ex vivo UV-vis and FTIR photoacoustic spectroscopy of natural nanoemulsions from cellulose nanocrystals and saponins topically applied into the skin: Diffusion rates and physicochemical evaluation.

Nanoemulsions are increasingly gaining importance in the development of topically applied medicine and cosmetic products because their small droplets favor the penetration rates of active compounds into the body. In this scenario, the measurements of their diffusion rates as well as eventual physicochemical changes in the target tissues are of utmost importance. It is also recognized that the use of natural surfactants can avoid allergic reactions as frequently observed for synthetic products. The natural saponins extracted from Sapindus Saponaria have the property of forming foam and are exploited as biocompatible and biodegradable, while cellulose nanocrystals are known to increase the stability of a formulation avoiding the coalescence of drops at the interface. Therefore, nanoemulsions combining natural saponins and cellulose nanocrystals are promising systems that may facilitate greater diffusion rates of molecules into the skin, being candidates to substitute synthetic formulations. This study applied the Photoacoustic Spectroscopy technique to measure the diffusion rates and the physicochemical properties of nanoemulsified formulations containing saponins and cellulose nanocrystals topically applied to the skin. The ex vivo study combined the first-time photoacoustic measurements performed in both ultraviolet-visible and mid-infrared spectral regions. The toxicity of these formulations in L929 cells was also evaluated. The results showed that the formulations were able to propagate throughout the skin to a depth of approximately 756 µm, reaching the dermal side. The non-observation of absorbing band shifting or new bands in the FTIR spectra suggests that there were no structural changes in the skin as well as in the formulations after the nanoemulsions administration. The cytotoxicity results showed that the increase of cellulose nanocrystals concentration decreased cellular toxicity. In conclusion, the results demonstrated the advantage of combining photoacoustic methods in the ultraviolet-visible and mid-infrared spectral regions to analyze drug diffusion and interaction with the skin tissues. Both methods complement each other, allowing the confirmation of the nanoemulsion diffusion through the skin and also suggesting there were no detectable physicochemical changes in the tissues. Formulations stabilized with saponins and cellulose nanocrystals showed great potential for the development of topically administered cosmetics and drugs.

Encapsulation of Trichoderma harzianum with nanocellulose/carboxymethyl cellulose nanocomposite.

This study proposes the use of green matrices of cellulose nanocrystals (CNC) and a nanocomposite of CNC with carboxymethyl cellulose (CMC) for efficiently encapsulating the plant biocontrol agent Trichoderma harzianum. Beads containing spores of the microorganism were produced by dripping dispersions of the polymers into a CaCl2 coagulation bath, resulting in the crosslinking of CNC chains by Ca2+ ions. SEM micrographs evidenced the T. harzianum spores in the encapsulation matrices. X-ray microtomography confirmed the random distribution of the microorganism within the polymeric matrix and the presence of internal pores in the CNC:CMC:spores beads. Encapsulation in the CNC:CMC nanocomposite favored growth of the fungus after 10 days of storage at room temperature, which could be attributed to the presence of internal pores and to the extra carbon source provided by the CMC. The results indicated that CNC:CMC nanocomposites are promising materials for protecting and delivering microbial inoculants for agricultural applications.

Evaluation of the Antimicrobial, Thermal, Mechanical, and Barrier Properties of Corn Starch-Chitosan Biodegradable Films Reinforced with Cellulose Nanocrystals.

Packaging materials play an essential role in the preservation and marketing of food and other products. To improve their conservation capacity, antimicrobial agents that inhibit bacterial growth are used. Biopolymers such as starch and chitosan are a sustainable alternative for the generation of films for packaging that can also serve as a support for preservatives and antimicrobial agents. These substances can replace packaging of synthetic origin and maintain good functional properties to ensure the quality of food products. Films based on a mixture of corn starch and chitosan were developed by the casting method and the effect of incorporating cellulose nanocrystals (CNC) at different concentrations (0 to 10% w/w) was studied. The effect of the incorporation of CNC on the rheological, mechanical, thermal and barrier properties, as well as the antimicrobial activity of nanocomposite films, was evaluated. A significant modification of the functional and antimicrobial properties of the starch-chitosan films was observed with an increase in the concentration of nanomaterials. The films with CNC in a range of 0.5 to 5% presented the best performance. In line with the physicochemical characteristics which are desired in antimicrobial materials, this study can serve as a guide for the development this type of packaging for food use.

Rheological and Thermal Study about the Gelatinization of Different Starches (Potato, Wheat and Waxy) in Blend with Cellulose Nanocrystals.

The goal of this work was to analyze the effect of CNCs on the gelatinization of different starches (potato, wheat and waxy maize) through the characterization of the rheological and thermal properties of starch-CNC blends. CNCs were blended with different starches, adding CNCs at concentrations of 0, 2, 6 and 10% w/w. Starch-CNC blends were processed by rapid visco-analysis (RVA) and cooled to 70 °C. Pasting parameters such as pasting temperature, peak, hold and breakdown viscosity were assessed. After RVA testing, starch-CNC blends were immediately analyzed by rotational and dynamic rheology at 70 °C. Gelatinization temperature and enthalpy were assessed by differential scanning calorimetry. Our results suggest that CNCs modify the starch gelatinization but that this behavior depends on the starch origin. In potato starch, CNCs promoted a less organized structure after gelatinization which would allow a higher interaction amylose-CNC. However, this behavior was not observed in wheat and waxy maize starch. Insights focusing on the role of CNC on gelatinization yielded relevant information for better understanding the structural changes that take place on starch during storage, which are closely related with starch retrogradation. This insight can be used as an input for the tailored design of novel materials oriented towards different technological applications.

Nitric Oxide-Releasing Supramolecular Cellulose Nanocrystal/Silsesquioxane Foams.

Cellulose nanocrystals (CNC)-based foams are promising tissue engineering materials that may facilitate implant-tissue integration and allow localized and controlled drug delivery. Herein, hybrid CNC-based foams, which are ultralightweight (30-100 mg cm-3 ), highly porous (>95%), ominiphilic and superabsorbent (1500-3000 wt% of water and/or toluene uptake) are obtained by the in situ condensation of poly(ethylene glycol) ditriethoxysilyl (TES-PEG-TES) into a 3D network, where silsesquioxane nanoparticles (SS-NP) are the crosslinking nodes, and CNC are entrapped forming ionic interactions, in a supramolecular structure. In a new approach, using 3-mercaptopropyltrimethoxysilane, sulfhydryl groups are inserted on the SS-NP periphery and S-nitrosated to enable the functionalization of SS-NP with S-nitrosothiol groups, which can nitric oxide (NO), in a process triggered by the hydration of the foams and modulated by their supramolecular structure. CNC-SS-PEG foams exhibit elevated thermal and structural stability, compressive strength compatible with various soft human tissues, and NO release rates (1-18 pmol mg-1 min-1 ) within the range of the beneficial NO actions. Thus, the CNC-SS-PEG foams herein described represent a new platform of supramolecular hybrid materials for localized delivery of NO, with potential uses in tissue engineering and other biomedical applications.

Shear-Coated Linear Birefringent and Chiral Cellulose Nanocrystal Films Prepared from Non-Sonicated Suspensions with Different Storage Time.

Nanocelluloses are very attractive materials for creating structured films with unique optical properties using different preparation techniques. Evaporation-induced self-assembly of cellulose nanocrystals (CNC) aqueous suspensions produces iridescent films with selective circular Bragg reflection. Blade coating of sonicated CNC suspensions leads to birefringent CNC films. In this work, fabrication of both birefringent and chiral films from non-sonicated CNC suspensions using a shear-coating method is studied. Polarization optical microscopy and steady-state viscosity profiles show that non-sonicated CNC suspensions (concentration of 6.5 wt%) evolve with storage time from a gel-like shear-thinning fluid to a mixture of isotropic and chiral nematic liquid crystalline phases. Shear-coated films prepared from non-sonicated fresh CNC suspensions are birefringent, whereas films prepared from suspensions stored several weeks show reflection of left-handed polarized light. Quantification of linear and circular birefringence as well circular dichroism in the films is achieved by using a Mueller matrix formalism.

Nanocelluloses Reinforced Bio-Waterborne Polyurethane.

The aim of this work was to evaluate the influence of two kinds of bio- nano-reinforcements, cellulose nanocrystals (CNCs) and bacterial cellulose (BC), on the properties of castor oil-based waterborne polyurethane (WBPU) films. CNCs were obtained by the acidolysis of microcrystalline cellulose, while BC was produced from Komagataeibacter medellinensis. A WBPU/BC composite was prepared by the impregnation of a wet BC membrane and further drying, while the WBPU/CNC composite was obtained by casting. The nanoreinforcement was adequately dispersed in the polymer using any of the preparation methods, obtaining optically transparent compounds. Thermal gravimetric analysis, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, dynamical mechanical analysis, differential scanning calorimetry, contact angle, and water absorption tests were carried out to analyze the chemical, physical, and thermal properties, as well as the morphology of nanocelluloses and composites. The incorporation of nanoreinforcements into the formulation increased the storage modulus above the glass transition temperature of the polymer. The thermal stability of the BC-reinforced composites was slightly higher than that of the CNC composites. In addition, BC allowed maintaining the structural integrity of the composites films, when they were immersed in water. The results were related to the relatively high thermal stability and the particular three-dimensional interconnected reticular morphology of BC.