Encapsulation of sunflower and flaxseed oils using Opuntia (Cactaceae) mucilage as a core-shell material through coacervation methods: A study on formulation, characterization, and in vitro digestion.

Sunflower oil (SFO) and Flaxseed oil (FSO) were microencapsulated using simple and complex coacervation techniques with Opuntia (Cactaceae) mucilage (Mu) and with a combination of Mu with chitosan (Chit). The encapsulation efficiency (EE) of SFO and FSO in emulsions using Mu/Chit shells was 96.7% and 97.4%, respectively. Morphological studies indicated successful entrapment of oils in core shells with particle sizes ranging from 1396 ± 42.4 to 399.8 ± 42.3 nm. The thermogravimetric analyses demonstrated enhanced core protection with thermal stability noted for microcapsules regardless of encapsulation method. The stability of the microcapsules, during in vitro digestion was studied. The obtained results revealed that the microcapsules are intact in oral conditions and have a slow release of oil over stomach digestion and rapid release in the small intestine. The results showed that Mu and Mu/Chit coacervates can be used as effective carrier systems to encapsulate sensitive ingredients and functional oils.

Electrospun Cactus Mucilage/Poly(vinyl alcohol) Nanofibers as a Novel Wall Material for Dill Seed Essential Oil (Anethum graveolens L.) Encapsulation: Release and Antibacterial Activities.

This study aimed to create long-lasting carriers by producing electrospun nanofibers loaded with dill seed (Anethum graveolens L.) essential oil (DSEO), using cactus mucilage (CM) and poly(vinyl alcohol) (PVA). Continuous and uniform electrospun nanofibers with a diameter of 158 ± 18 to 230 ± 26 nm were successfully made from the CM/PVA blend solution and the CM/PVA/DSEO emulsion. Atomic force microscopy topographic images revealed that the electrospun nanofibers had a tubular morphology. The thermogravimetric curves of DSEO, CM, pure PVA, and electrospun nanofibers demonstrate that the polymers used and the essential oil have effective chemical interactions. The water contact angle results suggest that the manufactured nanofibers are hydrophilic. CM/PVA consistently achieves a remarkable encapsulation efficiency of 100% DSEO. The electrospun nanofibers enabled the controlled release of free and encapsulated DSEO, resulting in sustained long-term release. The agar disk diffusion technique was used to study the antimicrobial activity of electrospun nanofibers and nanofibers containing DSEO against Gram-positive and Gram-negative bacteria. With a minimum inhibitory concentration of 2.5 mg/mL and a minimum bactericidal concentration of 5 mg/mL, electrospun nanofibers containing DSEO demonstrated bacteriostatic and bactericidal activities against foodborne pathogenic bacteria (Staphylococcus aureus and Pseudomonas aeruginosa). The DSEO-loaded electrospun nanofibers derived from carbohydrates show promise as an active interior coating for use in biomedical and food packaging applications.

Biodegradable composite films based on mucilage from Opuntia ficus-indica (Cactaceae): Microstructural, functional and thermal properties.

This study evaluated the feasibility of using cactus mucilage (CM) to elaborate biobased composite films blended with styrene-butadiene rubber latex (SBL). The CM was extracted and precipitated with ethanol (CMET) and isopropanol (CMIS). Mucilage-based films were formulated using three levels of mucilage (4, 6, and 8 wt%). The microstructure, thickness, moisture content, density, water contact angle, water vapor permeability, film solubility, thermal stability, and toughness of mucilage films blended with SBL (SBL/CMET and SBL/CMIS) were measured. The properties of mucilage-based films varied systematically, depending on the concentration of mucilage. The addition of SBL to CM film produces compatible, hydrophobic, flexible, and stiffer films with low moisture contents and good barrier properties. The mucilage film incorporated with 6 wt% CMET and CMIS reached the highest Young's modulus of 1512 ± 21 and 1988 ± 55 MPa, respectively. The DSC of produced films reveals that the Tg of SBL/CMIS is lower than that of SBL/CMIS. The synthesized films were structurally stable at high temperatures. The biodegradability of the composite films buried in the ground shows that the produced films are 100 % biodegradable after 40 days. Thus, CM blended with SBL can benefit specific applications, especially food packaging.

Mandacaru cactus as a source of nanofibrillated cellulose for nanopaper production.

In this work, nanofibrillated cellulose (NFC) was extracted from cactus Cereus jamacaru DC. (mandacaru) for nanopaper production. The technique adopted includes alkaline treatment, bleaching, and grinding treatment. The NFC was characterized according to its properties and scored based on a quality index. Particle homogeneity, turbidity, and microstructure of the suspensions were evaluated. Correspondingly, the optical and physical-mechanical properties of the nanopapers were investigated. The chemical constituents of the material were analyzed. The sedimentation test and the zeta potential analyzed the stability of the NFC suspension. The morphological investigation was performed using environmental scanning electron microscopy (ESEM) and transmission electron microscopy (TEM). X-ray diffraction (XRD) analysis revealed that Mandacaru NFC has high crystallinity. Thermogravimetric analysis (TGA) and mechanical analysis were also used and revealed good thermal stability and good mechanical properties of the material. Therefore, the application of mandacaru is interesting in sectors such as packaging and electronic device development, as well as in composite materials. Given its score of 72 points on a quality index, this material was presented as an attractive, facile, and innovative source for obtaining NFC.

Flexible doctor blade-coated abiotic cathodes for implantable glucose/oxygen biofuel cells.

Implantable devices powered by batteries have been used for sixty years. In recent devices, lithium-based batteries are the most widely used power source. However, lithium batteries have many disadvantages in terms of safety, reliability, and longevity and require regular monitoring and substitution. Implantable glucose biofuel cells (BFCs) are increasingly seen as a potential future technology for replacing lithium-based batteries because they do not require surgical replacement after 8-10 years and have a theoretically unlimited lifetime thanks to the continued recovery of glucose and oxygen present in the human body. This paper shows the fabrication of flexible implantable abiotic cathodes, based on a nitrogen/iron-doped graphene catalyst, for glucose/oxygen biofuel cell application. An ink, based on nitrogen-iron doped graphene as the abiotic catalyst and chitosan as a binder, was prepared and coated on a flexible teflonated gas diffusion layer using doctor blade coating. The characterization of the biocathode shows an open potential circuit corresponding to the potential of the abiotic catalyst and a high oxygen reduction current density of up to 66 µA cm-2 under physiological conditions. Those cathodes remain stable for up to two years with a current density loss of only 25%. The flexible abiotic electrode cytotoxicity was evaluated by cell culture experiments showing living cells' high tolerance on the biocathode surface. This work demonstrates that this abiotic catalyst can be a promising alternative for the development of implantable glucose BFCs due to its stability and its cytocompatibility.

Cellulose Nanofibers from Schinus molle: Preparation and Characterization.

Schinus molle (SM) was investigated as a primary source of cellulose with the aim of discovering resources to generate cellulose nanofibers (CNF). The SM was put through a soda pulping process to purify the cellulose, and then, the fiber was treated with an enzymatic treatment. Then, a twin-screw extruder and/or masuko were utilized to help with fiber delamination during the nanofibrillation process. After the enzymatic treatment, the twin-screw extruder and masuko treatment give a yield of 49.6 and 50.2%, respectively. The optical and atomic force microscopy, morfi, and polymerization degrees of prepared cellulosic materials were established. The pulp fibers, collected following each treatment stage, demonstrated that fiber characteristics such as length and crystallinity varied according to the used treatment (mechanical or enzymatic treatment). Obviously, the enzymic treatment resulted in shorter fibers and an increased degree of polymerization. However, the CNF obtained after enzymatic and extrusion treatment was achieved, and it gave 19 nm as the arithmetic width and a Young's modulus of 8.63 GPa.

Influence of hemicellulose content and cellulose crystal change on cellulose nanofibers properties.

This study aimed to evaluate the properties of cellulose nanofibers (CNFs) with different hemicellulose contents and cellulose II polymorphs. A link was found between these polysaccharides and the properties of CNFs. A decrease in crystallinity (from 69 to 63%) and changes in the crystalline structure of cellulose subjected to an alkaline environment were observed, promoting the partial conversion of cellulose I to cellulose II (from 2 to 42%) and preventing CNFs production at NaOH concentrations higher than 5%. Most treatments showed pseudoplastic fluid behavior, except for the 10% NaOH treatment over 2 h, which showed Newtonian fluid behavior. The quality index of the reference CNFs (TEMPO-oxidized) was the highest (80 ± 3), followed by that of the 5% NaOH-treated (68 ± 3 and 22% energy savings compared to the untreated sample), and the untreated (63 ± 3) samples; and the 10% NaOH treatments had quality indices of 51 ± 3 and 32 ± 1, respectively.

Multilayers of Renewable Nanostructured Materials with High Oxygen and Water Vapor Barriers for Food Packaging.

Natural biopolymers have become key players in the preparation of biodegradable food packaging. However, biopolymers are typically highly hydrophilic, which imposes limitations in terms of barrier properties that are associated with water interactions. Here, we enhance the barrier properties of biobased packaging using multilayer designs, in which each layer displays a complementary barrier function. Oxygen, water vapor, and UV barriers were achieved using a stepwise assembly of cellulose nanofibers, biobased wax, and lignin particles supported by chitin nanofibers. We first engineered several designs containing CNFs and carnauba wax. Among them, we obtained low water vapor permeabilities in an assembly containing three layers, i.e., CNF/wax/CNF, in which wax was present as a continuous layer. We then incorporated a layer of lignin nanoparticles nucleated on chitin nanofibrils (LPChNF) to introduce a complete barrier against UV light, while maintaining film translucency. Our multilayer design which comprised CNF/wax/LPChNF enabled high oxygen (OTR of 3 ± 1 cm3/m2·day) and water vapor (WVTR of 6 ± 1 g/m2·day) barriers at 50% relative humidity. It was also effective against oil penetration. Oxygen permeability was controlled by the presence of tight networks of cellulose and chitin nanofibers, while water vapor diffusion through the assembly was regulated by the continuous wax layer. Lastly, we showcased our fully renewable packaging material for preservation of the texture of a commercial cracker (dry food). Our material showed functionality similar to that of the original packaging, which was composed of synthetic polymers.

Eco-friendly laccase and cellulase enzymes pretreatment for optimized production of high content lignin-cellulose nanofibrils.

Lignin-cellulose nanofibrils (LCNF) are of attracting an increasing interest due to the benefits of maintaining the lignin in the nanomaterial composition. The production of LCNF requires considerable energy consumption, which has been suppressed employing pretreatment of biomass, in which it highlights those that employ enzymes that have the advantage of being more environmentally friendly. Some negative aspects of the presence of lignin in the fiber to obtain cellulose nanofibrils is that it can hinder the delamination of the cell wall and act as a physical barrier to the action of cellulase enzymes. This study aimed to evaluate the impact of a combined enzymatic pretreatment of laccase and endoglucanase for high content lignin LCNF production. The morphological and chemical properties, visual aspect and stability, crystallinity, mechanical properties, rheology, barrier properties and quality index were used to characterize the LCNF. The laccase loading used was efficient in modifying the lignin to facilitate the action of the endoglucanase on cellulose without causing the removal of this macromolecule. This pretreatment improved the quality of LCNF (61 ± 3 to 71 ± 2 points) with an energy saving of 42% and, therefore, this pretreatment could be suitable for industrial production for a variety of applications.

Thermally reversible nanocellulose hydrogels synthesized via the furan/maleimide Diels-Alder click reaction in water.

The study deals with the synthesis of thermally reversible hydrogels from modified cellulose nanofibers via the Diels-Alder "click" reaction in an aqueous medium. "Never-dried" cellulose fibres derived from hardwood were submitted to shearing and surface TEMPO-oxidation before being modified with furfurylamine. The ensuing pendant furan moieties were reacted with a water-soluble bismaleimide via Diels-Alder coupling at 65 °C to produce a hydrogel, whose deconstruction was induced by the corresponding retro-Diels-Alder reaction carried out at 95 °C. Differential scanning calorimetry and rheological measurement were used to characterize the hydrogels. These aqueous cellulosic materials should provide original applications in such areas as strong paper-based artefacts and biocompatible gels.

Effect of variable aminoalkyl chains on chemical grafting of cellulose nanofiber and their antimicrobial activity.

Recent focus on the preparation of antimicrobial surfaces using cellulose nanofibers (CNF) has gained considerable attention. In this work, functionalization of CNF films in 100% aqueous solution with three different aminosilanes, including 3-aminopropyl trimethoxysilane (APMS), 2-aminoethyl 3-aminopropyl trimethoxysilane (DAMS)and 3-2-(2-aminoethylamino) ethylamino propyl-trimethoxysilane (TAMS) is reported for the fabrication of contact active antimicrobial materials. Grafted CNF films were comprehensively characterized by FTIR, TGA, contact angle, elemental analysis, solid-state 29Si NMR, FEG-SEM and SEM-EDX. It was found that all the silanes were grafted on the surface of nanofibers without any change in the morphology or fibril structure through different grafting efficiency, depending on the aminoalkyl chain length. The effect of variable aminoalkyl length and initial grafting concentration was analyzed against gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli) by qualitative and quantitative standards. The most promising results were obtained with 3-2-(2-aminoethylamino) ethylamino propyl-trimethoxysilane at very low concentration which completely restrict bacterial growth after 24h with Gram-positive bacteria. This study, for the first time, established the relationship between the aminoalkyl chain length and its corresponding antibacterial activity.

Synthesis and characterization of cellulose carbonate using greenchemistry: Surface modification of Avicel.

The development of new derivatives based on renewable natural resources using green chemistry is a concept gaining recognition in several industries. This work focused on the preparation and characterization of cellulose carbonate using dimethyl carbonate as the green reagent in ethanoic KOH solution. The effect of several reaction parameters were evaluated, i.e., temperature (25°C, 50°C, 90°C, 120°C, 150°C, and 180°C), time (6, 24, 48, and 72h), KOH concentration (15% and 30%), and the use of a catalyst (DBU). The degree of substitution (DS) of the resulting materials was evaluated by 13C CP/MAS NMR. The spectra of the prepared cellulose carbonate exhibited the main peaks associated with cellulose macromolecules (C1-C6) and those corresponding to carbonate functions at approximately 162ppm. Moreover, XPS was performed and confirmed the reaction modifications. Nevertheless, it is worth noting that 13C NMR and XPS spectra showed a significant difference in DS value, due to the difference between both techniques. However, our results from NMR and XPS experiments confirm that the major modifications during all the reactions occurred mainly at the surface. This green process opens the way for the easy production of a new class of cellulose derivatives.

Current Progress in Rheology of Cellulose Nanofibril Suspensions.

Cellulose nanofibrils (CNFs) are produced and commonly used in the form of aqueous suspensions or gels. A number of studies have focused lately on rheological properties of CNF suspensions, which gives insight into properties of such materials and can reflect their behavior during handling. This Review summarizes the recent progress in rheological studies on CNF aqueous suspensions using rotational rheometry. Here, we discuss linear viscoelastic properties, i.e., frequency-dependent storage and loss moduli; shear flow behavior, i.e., apparent viscosity and shear stress as a function of shear rate; local flow characteristics, etc. In this Review, we point out that the rheological behavior of at least two types of CNF suspensions should be distinguished: (i) ones produced using mechanical fibrillation with or without enzymatic pretreatment (no surface chemical modification), which possess highly flocculated structure, and (ii) ones produced involving chemical modification pretreatments, e.g., carboxylation, carboxymethylation, quaternization, or sulfonation, which possess better colloidal stability and do not evidently flocculate.

Surface cationized cellulose nanofibrils for the production of contact active antimicrobial surfaces.

In the last decade, a new fiber pretreatment has been proposed to make easy cellulose fibrillation into microfibrils. In this context, different surface cationized MFC was prepared by optimizing the experimental parameters for cellulose fibers pretreatment before fibrillation. All MFCs were characterized by conductometric titration to establish degree of substitution, field emission gun scanning electron microscopy (FEG-SEM), atomic force microscopy (AFM) and optical microscopy assessed the effect of pretreatment on the morphology of the ensuing MFCs. Antibacterial activities of neat and cationized MFC samples were investigated against Gram positive bacteria (Bacillus subtilis, Staphylococcus aureus) and Gram negative bacteria (Escherichia coli). The CATMFC sample at DS greater than 0.18 displayed promising results with antibacterial properties without any leaching of quaternary ammonium into the environment. This work proved the potential of cationic MFCs with specific DS for contact active antimicrobial surface applications in active food packaging, medical packaging or in health and cosmetic field.

Effect of the oxidation treatment on the production of cellulose nanofiber suspensions from Posidonia oceanica: The rheological aspect.

Different grades of cellulose nanofibrils (CNF) were prepared from Posidonia oceanica balls and leaves (POB and POL). Pretreatment using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation was performed to facilitate the fibrillation during ultrafine friction grinding process. The ensuing CNF batches were compared in terms of morphology and degree of fibrillation. The rheological properties of the produced CNF suspensions were also analyzed for varying doses of sodium hypochlorite used during the TEMPO- mediated oxidation procedure. The stronger fibrous network structures were formed when increasing the oxidant concentration, which was confirmed by the increase of the storage moduli value. P. oceanica balls were found to undergo stronger fibrillation and, consequently, to form stronger networks, compared to P. oceanica leaves, when using equivalent concentration of the oxidizing agent.

Mechanical and thermal properties of Posidonia oceanica cellulose nanocrystal reinforced polymer.

In the present study, cellulose nanocrystals (CNC) were isolated from Posidonia oceanica balls and leaves. CNC was prepared from this marine biomass by sulfuric acid hydrolysis (H2SO4) treatment. The raw fibers were firstly isolated by a delignification-bleaching process then the acid hydrolysis treatment was performed at 55°C during 40min under mechanical stirring. The ensuing CNCs were characterized by their morphological and thermal properties using transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA), respectively. Nanocomposite materials using the CNC extracted from marine biomass were obtained by casting and evaporating a mixture of this suspension with poly(styrene-co-butyl acrylate). The effect of CNC loading on mechanical and thermal properties was studied. Dynamic mechanical analysis (DMA) results showed a strong reinforcing effect of CNC that depends on their origin (balls or leaves). The difference was attributed not only to differences in the aspect ratio of CNC but also to the stiffness of the percolating network of nanoparticles.

Antibacterial activity and biodegradability assessment of chemically grafted nanofibrillated cellulose.

Nanofibrillated cellulose (NFC) and their derivatives were prepared using three chemical surface modification strategies. All grafting was characterized by FTIR and contact angle measurements in order to evaluate the efficiency of grafting. Antibacterial activities of neat and grafted samples were investigated against two kinds of bacteria (i.e. Gram+ (Staphylococcus aureus) and Gram- (Klebsiella pneumoniae)). All the grafted samples displayed promising results with at least bacteriostatic effect or bactericidal properties. They also strongly enhanced the photo-catalytic antimicrobial effect of TiO2. This study proves that it is better to use grafted NFC either alone or for functionalization with TiO2 if anti-bacterial properties are desired. The cellulose backbone is known to be easily biodegradable in different biodegradation conditions and environments. The chemical surface modifications applied on NFC in the present work did not negatively influence this valuable property of cellulose but help for monitoring this property, which could be very useful for paper, packaging and composites.

Rheological properties of micro-/nanofibrillated cellulose suspensions: wall-slip and shear banding phenomena.

The rheological properties of enzymatically hydrolyzed and TEMPO-oxidized microfibrillated/nanofibrillated cellulose (MFC/NFC) aqueous suspensions were investigated in oscillation and steady-flow modes and were compared with the morphology of the studied materials. The flow instabilities, which introduce an error in the rheological measurements, were discovered during flow measurements. A wall-slip (interfacial slippage on the edge of geometry tools and suspension) was detected at low shear rates for two types of NFC suspensions while applying cone-plate geometry. A roughening of the tool surfaces was performed to overcome the aforementioned problem. Applying to TEMPO-oxidized NFC, a stronger suspension response was detected at low shear rates with higher values of measured shear stress. However, a shear banding (localization of shear within a sample volume) became more pronounced. The use of serrated tools for enzymatically hydrolyzed NFC produced lower shear stress at the moderate shear rates, which was influenced by water release from the suspension.

Nanofibrillated Cellulose Surface Modification: A Review.

Interest in nanofibrillated cellulose (NFC) has increased notably over recent decades. This bio-based nanomaterial has been used essentially in bionanocomposites or in paper thanks to its high mechanical reinforcement ability or barrier property respectively. Its nano-scale dimensions and its capacity to form a strong entangled nanoporous network have encouraged the emergence of new high-value applications. It is worth noting that chemical surface modification of this material can be a key factor to achieve a better compatibility with matrices. In order to increase the compatibility in different matrices or to add new functions, surface chemical modification of NFC appears to be the prior choice to conserve its intrinsic nanofibre properties. In this review, the authors have proposed for the first time an overview of all chemical grafting strategies used to date on nanofibrillated cellulose with focus on surface modification such as physical adsorption, molecular grafting or polymer grafting.

Water redispersible dried nanofibrillated cellulose by adding sodium chloride.

The present study reports for the first time a method to obtain water redispersible dried NFC using freeze-drying. No chemical surface modification was required to get this kind of product. Salt addition (sodium chloride: NaCl) strategy has been selected to block and then to regenerate hydrogen bonds during the drying and the redispersion steps, respectively. Several samples were produced at different pH (i.e., 4, 6, 8, and 10). All the redispersed NFC were characterized by different techniques (e.g., FE-SEM, XRD, EPMA-EDX) to check the effect of salt on NFC aggregation. The interactions between NFC and NaCl at different pH conditions have been discussed and the rheology of the redispersed NFC suspension has been performed. All the results prove a perfect water redispersion at pH 8 and exactly similar suspension is obtained after water dispersion of dried NFC following our procedure. These results are very promising for increasing application of NFC.