Combining and concentrating nanocelluloses for cryogels with remarkable strength and wet resilience.

Cellulose cryogels are promising eco-friendly materials that exhibit low density, high porosity, and renewability. However, the applications of these materials are limited by their lower mechanical and water resistance compared to petrochemical-based lightweight materials. In this work, nanocelluloses were functionalized with cationic and anionic groups, and these nanomaterials were combined to obtain strong and water-resilient cryogels. To prepare the cryogels, anionic and cationic micro- and nanofibrils (CNFs) were produced at three different sizes and combined in various weight ratios, forming electrostatic complexes. The complex phase was concentrated by centrifugation and freeze-dried. Porous and open cellular structures were assembled in all compositions tested (porosity >90 %). Compressive testing revealed that the most resistant cryogels (1.7 MPa) were obtained with equivalent amounts of negatively and positively charged CNFs with lengths between 100 and 1200 nm. The strength at this condition was achieved as CNF electrostatic complexes assembled in thick cells, as observed by synchrotron X-ray tomography. In addition to mechanical strength, electrostatic complexation provided remarkable structural stability in water for the CNF cryogels, without compromising their biodegradability. This route by electrostatic complexation is a practical strategy to combine and concentrate nanocelluloses to tailor biodegradable lightweight materials with high strength and wet stability.

Development of a novel cryostructured composite coating of xanthan-bovine collagen-oregano essential oil spraying applied for the preservation of commercial biscuits marketed in Mexico.

Cryostructured gels, better known as cryogels, are a very important emerging class of biomaterials that have diverse applications in food preservation. This work shows a novel alternative to prepare a cryostructured composite coating made from a blend of xanthan, bovine collagen, and oregano essential oil. The composite coating was suitably applied onto the surface of preservative-free biscuits which were stored for 15 days at 25 ± 2°C and 52% ± 1% relative humidity. The evaluation focused mainly on the changes in the physicochemical, textural, and microbiological characteristics of the biscuits. It was found that the coated samples significantly (p < 0.05) decreased moisture absorption, water activity, and fungal growth. However, the composite coating minimally impacted the quality of biscuits in terms of color, texture profile, and surface microstructure. Overall, the cryostructured composite coating constitutes an advance in technological strategies aimed at the preservation of baked products. This will allow, in the future, the development of novel coatings on bakery products to generate new trends in the conservation of their properties and extension of shelf life. This could be achieved through the implementation of new technologies in the food industry, with the aim of making them more environmentally friendly and contributing to the generation of less plastic waste. PRACTICAL APPLICATION: The study and application of cryogels, as innovative systems in the food industry, allow to expand and diversify the materials that can function as coatings to maintain some quality characteristics, in this case in bakery products, so it is important to analyze their effects and consider them to improve conservation processes.

Environmentally friendly starch/alginate aerogels for copper adsorption from aqueous media. A microstructural and kinetic study.

This work investigated the synthesis and characterization of alginate/starch porous materials and their application as copper ions adsorbents from aqueous media. Initially, pregel aqueous solutions with different biopolymer concentrations (1, 3, and 5% w/w) and alginate contents (25, 50, and 75% w/w) were prepared. Hydrogel formation was performed by internal and external gelation methods. Finally, the drying step was done via CO2sc leading to aerogels and via freeze-drying leading to cryogels. Process parameters influence on the final properties of materials was evaluated by BET isotherms, SEM, EDS, and TGA. Regardless the gelation method applied, interesting materials with meso- and macro-pore structure were prepared from pregel mixtures with 3% w/w biopolymer concentration and an alginate content of only 25% w/w. Low alginate content reduces the final cost of the materials. Concerning copper removal, the adsorption data were well fitted to the pseudo-second order kinetic model for aerogels and cryogels, showing aerogels the highest adsorption capacity (40 mg/g) and removal efficiency (∼ 92%). Materials demonstrated excellent reusability throughout five consecutive adsorption/desorption cycles. Hence, environmentally friendly materials with a high practical value as low-cost bioadsorbents were synthesized, having great performance in the removal of copper ions from aqueous solution.

Tuning the Mechanical and Thermal Properties of Hydroxypropyl Methylcellulose Cryogels with the Aid of Surfactants.

The mechanical and thermal properties of cryogels depend on their microstructure. In this study, the microstructure of hydroxypropyl methylcellulose (HPMC) cryogels was modified by the addition of ionic (bis (2-ethylhexyl) sodium sulfosuccinate, AOT) and non-ionic (Kolliphor® EL) surfactants to the precursor hydrogels (30 g/L). The surfactant concentrations varied from 0.2 mmol/L to 3.0 mmol/L. All of the hydrogels presented viscous behavior (G″ > G'). Hydrogels containing AOT (c > 2.0 mmol/L) led to cryogels with the lowest compressive modulus (13 ± 1 kPa), the highest specific surface area (2.31 m2/g), the lowest thermal conductivity (0.030 W/(m·°C)), and less hygroscopic walls. The addition of Kolliphor® EL to the hydrogels yielded the stiffest cryogels (320 ± 32 kPa) with the lowest specific surface area (1.11 m2/g) and the highest thermal conductivity (0.055 W/(m·°C)). Density functional theory (DFT) calculations indicated an interaction energy of -31.8 kcal/mol due to the interaction between the AOT sulfonate group and the HPMC hydroxyl group and the hydrogen bond between the AOT carbonyl group and the HPMC hydroxyl group. The interaction energy between the HPMC hydroxyl group and the Kolliphor® EL hydroxyl group was calculated as -7.91 kcal/mol. A model was proposed to describe the effects of AOT or Kolliphor® EL on the microstructures and the mechanical/thermal properties of HPMC cryogels.

Nanocellulose for peripheral nerve regeneration in rabbits using citric acid as crosslinker with chitosan and freeze/thawed PVA.

This work investigates peripheral nerve regeneration using membranes consisting of pure chitosan (CHI), which was further blended with nanofibrillated cellulose, with citric acid as crosslinker, with posterior addition of polyvinyl alcohol, with subsequent freeze thawing. Nanocellulose improves the mechanical and thermal resistance, as well as flexibility of the film, which is ideal for the surgical procedure. The hydrogel presented a slow rate of swelling, which is adequate for cell and drug delivery. A series ofin vitrotests revealed to be non-toxic for neuronal Schwann cell from the peripheral nervous system of Rattus norvegicus, while there was a slight increase in toxicity if crosslink is performed-freeze-thaw. Thein vivoresults, using rabbits with a 5 mm gap nerve defect, revealed that even though pure CHI was able to regenerate the nerve, it did not present functional recovery with only the deep pain attribute being regenerated. When autologous implant was used jointly with the biomaterial membrane, as a covering agent, it revealed a functional recovery within 15 d when cellulose and the hydrogel were introduced, which was attributed to the film charge interaction that may help influence the neuronal axons growth into correct locations. Thus, indicating that this system presents ideal regeneration as nerve conduits.

Effect of Cryostructuring Treatment on Some Properties of Xanthan and Karaya Cryogels for Food Applications.

Cryogels are novel materials because the manufacturing process known as cryostructuring allows biopolymers to change their properties as a result of repeated controlled freeze-thaw cycles. Hydrogels of xanthan and karaya gums were evaluated after undergoing up to four controlled freeze-thaw cycles in indirect contact with liquid nitrogen (up to -150 °C) to form cryogels. Changes in structural, molecular, rheological, and thermal properties were evaluated and compared to those of their respective hydrogels. Samples were also analyzed by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy with Attenuated Total Reflection (FTIR-ATR), Rotational Rheology (RR), Modulated Differential Scanning Calorimetry (MDSC) and zeta potential (ζ). In general, significant differences (p < 0.05) between the numbers of freeze-thaw cycles were found. Karaya cryogels were not stable to repeated cycles of cryostructuring such as the three-cycle xanthan cryogel, which has the best structural order (95.55%), molecular interactions, and thermal stability, which allows the generation of a novel material with improved thermal and structural properties that can be used as an alternative in food preservation.

Development of supermacroporous monolithic adsorbents for purifying lectins by affinity with sugars.

Affinity techniques are frequently used to purify biocompounds, because of specific interactions observed in many cases. One example are the lectins, proteins connected in a reversible manner and specific to carbohydrates or sugar-containing molecules. Four different methods were investigated (epoxy, Schiff base, glutaraldehyde and ethylenediamine) to immobilize the carbohydrate N-acetyl-d-glucosamine (d-GlcNAc) on the surface of supermacroporous cryogels made for lectin purification. The glutaraldehyde method presented the highest immobilization capacity of d-GlcNAc (147.77mg/g), while the ethylenediamine method presented the lowest capacity (32.47mg/g). FTIR spectra analysis confirmed the presence of the immobilized carbohydrate. The cryogels containing d-GlcNAc immobilized by the different methods were characterized in terms of swelling capacity, degree of expansion, porosity and constituent fractions. Results showed that the activation methods did not affect the macroporous structure. Images obtained from scanning electron microscopy evidenced the presence of interconnected macropores in the structure of the cryogels produced. The cryogels presented even lower flow resistance in the permeability analysis. Finally, the cryogel modified by the glutaraldehyde method was used in the Concanavalin A lectin adsorption process, presenting an adsorptive capacity of 44.49mg/g and high stability after five cycles of use.

Thermosensitive macroporous cryogels functionalized with bioactive chitosan/bemiparin nanoparticles.

Thermosensitive macroporous scaffolds of poly(N-isopropylacrylamide) (polyNIPA) loaded with chitosan/bemiparin nanoparticles are prepared by the free radical polymerization in cryogenic conditions. Chitosan/bemiparin nanoparticles of 102 ± 6.5 nm diameter are prepared by complex coacervation and loaded into polyNIPA cryogels. SEM image reveal the highly porous structure of cryogels and the integration of nanoparticles into the macroporous system. Volume phase transition temperature (VPT) and total freezing water content of cryogels are established by differential scanning calorimetry, and their porosity is determined by image-NMR. Swelling of cryogels (above and below the VPT) is highly dependent on nanoparticles concentration. In vitro release profile of bemiparin from cryogel is highly modulated by the presence of chitosan. Bemiparin released from nanoparticles preserves its biological activity, as shown by the BaF32 cell proliferation assay. Cryogels are not cytotoxic for the human fibroblast cells and present excellent properties for application on tissue engineering and controlled release of heparin.

Immobilized keratinase and enrofloxacin loaded on pectin PVA cryogel patches for antimicrobial treatment.

A keratinase isolated from Paecilomyces lilacinus (LPS #876) was tested against proteins present in the skin but the high enzyme activity was detected on collagen. Keratinase was physically immobilized onto PVA-pectin cryogels and enzyme release was 20.8±2.1%, 63.8±0.2%, 41.5±3.5% and 26.0±3.5% in cryogels containing pectins with esterification degrees (DE) 33.0%, 55.0%, 62.7% and 71.7% respectively at 37°C after 3h incubation. In presence of 0.75 M NaCl, the percentage of enzyme release changed to: 57.5±1.5, 65.8±3.8, 57.3±0.2 and 34.0±4.0 for the four pectins respectively. In-vitro studies of enrofloxacin release from PVA-pectin cryogels at pH close to the human skin (pH=5.5) showed 15.0% free antibiotic following first order kinetic at 37°C after 5h incubation. However, in the presence of keratinase only 6.9% of enrofloxacin was released under the same experimental conditions.