Properties of APTES-Modified CNC Films.

Sulfated cellulose nanocrystals' (CNCs') facile aqueous dispersibility enables producing films, fibers, and other materials using only water as a solvent but prevents using sulfated CNCs in applications that require water immersion. We report that modifying CNCs with 3-aminopropyl-triethoxysilane (APTES) via a simple, single-pot reaction scheme dramatically improves the hydrolytic stability of CNC films. The effects of APTES modification on CNCs' properties were studied using attenuated total reflectance Fourier transform infrared spectroscopy, atomic force and optical microscopy, thermogravimetric analysis, dynamic light scattering, and ultimate analysis. Substituting a mere 12.6% of the CNCs' available hydroxyl groups with APTES dramatically increased the hydrolytic stability of shear cast films while only having minor impacts on their mechanical properties. In addition, quartz crystal microbalance with dissipation monitoring (QCMD) and multiparametric surface plasmon resonance (MP-SPR) studies showed that the CNC-APTES films also had a greater irreversible binding with carbofuran, a pesticide and emerging contaminant. These results highlight that APTES modification is a promising method for increasing the utility of sulfated CNCs in sensors, adsorbents, and other applications requiring water immersion.

Recent Advances in the Microencapsulation of Essential Oils, Lipids, and Compound Lipids through Spray Drying: A Review.

In recent decades, the microcapsules of lipids, compound lipids, and essential oils, have found numerous potential practical applications in food, textiles, agricultural products, as well as pharmaceuticals. This article discusses the encapsulation of fat-soluble vitamins, essential oils, polyunsaturated fatty acids, and structured lipids. Consequently, the compiled information establishes the criteria to better select encapsulating agents as well as combinations of encapsulating agents best suited to the types of active ingredient to be encapsulated. This review shows a trend towards applications in food and pharmacology as well as the increase in research related to microencapsulation by the spray drying of vitamins A and E, as well as fish oil, thanks to its contribution of omega 3 and omega 6. There is also an increase in articles in which spray drying is combined with other encapsulation techniques, or modifications to the conventional spray drying system.

Antibody Immobilization on Sulfated Cellulose Nanocrystals.

Exploiting cellulose nanocrystals' high aspect ratio and tailorable surface for immunological biosensors has been hindered by the relatively limited research on using commonly available sulfated cellulose nanocrystals (CNCs) for antibody immobilization and by the low hydrolytic stability of dried assemblies produced from sulfated CNCs. Herein, we report a reaction scheme that enables both hydrolytic stability and antibody immobilization through 3-aminopropyl-triethoxysilane and glutaric anhydride chemistry. Immobilization was demonstrated using three model antibodies used in the detection of the cancer biomarkers: alpha-fetoprotein, prostate-specific antigen, and carcinoembryonic antigen. Thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy provided evidence of CNC modification. Quartz crystal microbalance with dissipation monitoring was used to monitor binding during each step of the immobilization scheme as well as binding of the corresponding antigens. The general reaction scheme was tested using both aqueous CNC dispersions and CNC films. Film modification is slightly simpler as it avoids centrifugation and washing steps. However, modifying the dispersed CNCs provides access to their entire surface area and results in a greater capacity for antigen binding.

Comparison between nanocellulose-polyethylenimine composites synthesis methods towards multiple water pollutants removal: A review.

Nanocellulose/polyethylenimine composites have attracted growing attention due to their versatility as new materials for application in different fields. Water remediation is one of the traditional applications of these composites and their investigation as adsorbents for single water pollutants is well established. However, most water resources such as rivers, lakes, and even oceans contain complex mixtures of pollutants. Despite several recently published reviews on water purification technology, they only focused on these material as single pollutant removers and hardly mentioned their capacity to simultaneously recover multiple pollutants. Therefore, there is still a gap in the archived literature considering nanocellulose/polyethylenimine composites targeting water remediation with multiple water pollutants. In this review, methods for synthesizing such composites are classified and compared according to the mechanism of reactions, such as chemical crosslinking and physical adsorption, while outlining advantages and limitations. Then, the water pollutants mainly targeted by those composites are discussed in detail to expound the relationship between the synthesis method and the type and adsorption capacity. Finally, the last section presents challenges and opportunities of these nanocellulose/polyethylenimine composites as emerging sorbents for sustainable multiple water pollutants purification technologies. This review aims to lay out the basis for future developments of these composites for multiple water pollutants.

Understanding the current state-of-the-art of long-lasting insecticide nets and potential for sustainable alternatives.

Long-lasting insecticide-treated nets (LLINs) are widely distributed to communities where malaria is a major cause of mortality, especially to those under the age of 5 years-old. To protect people from this illness, LLINs provide physical and chemical barriers by containing insecticides within the matrix of the polymer fibers or on the surface. Synthetic polymers including polyethylene and polyester are common material choices for these nets, and pyrethroids, along with other additives, are the insecticides of choice for this application. Many studies have shown the effectiveness of these nets on the impact of malaria is highly significant, but there is a demand for more durable nets that last longer than only a few years as the available products are rated for 2-3 years of use. Improvements in this area would increase cost effectiveness, because better durability would reduce the frequency of manufacturing and worldwide shipping. Additionally, due to the plastic fibers, the waste can build quickly, damaging the environment. To deal with the sustainability and durability issues, biodegradable and renewable materials should be chosen as an alternative.

Delignified wood aerogels as scaffolds coated with an oriented chitosan-cyclodextrin co-polymer for removal of microcystin-LR.

Nano-porous aerogels are an advantageous approach to produce low-density materials with high surface area, particularly when using biobased materials. Frequently, most biobased aerogels are synthesized through a bottom-up approach, which requires high energy inputs to break and rebuild the raw materials, and for elimination of water. To curb this, this work focused on generating aerogels by a top-down approach through the delignification of a wood substrate while eliminating water by solvent exchange. To diversify the surface chemistry for use in water treatment, the delignified wood-nanowood-was coated with a chitosan-cyclodextrin co-polymer and tested in the capture of microcystin-LR. The generated nanowood structure had 75% porosity after coating, with up to 339% water swelling and an adsorption capacity of 0.12 mg g-1 of the microcystin. This top-down technique enables the generation of low-cost aerogels by reducing steps, using a biobased self-assembled coating with hydrophobic active sites, and avoiding costly energetic input.

5-Fluorouracil drug delivery system based on bacterial nanocellulose for colorectal cancer treatment: Mathematical and in vitro evaluation.

Colorectal cancer (CRC) is the third most common worldwide. Its treatment includes adjuvant chemotherapy with 5-fluorouracil (5FU) administered intravenously. 5FU is an antineoplastic drug of the fluoropyrimidines group, widely used in the treatment of solid tumors, mainly CRC. Nevertheless, it causes several adverse effects and poor effectiveness due to its short half-life. This work aimed to employ bacterial nanocellulose (BNC) as an encapsulation material for the oral administration of 5FU. First, the adsorption phenomena were analyzed by isotherms, thermodynamic parameters, and kinetic models. Then, encapsulation was carried out using spray-drying, and encapsulated 5FU desorption profiles were assessed in simulated fluids. The biological behavior was evaluated on colon cancer SW480 and SW620 cell lines. As result, it was found that at 25 °C a monolayer of 5FU was formed and the process showed to be the most spontaneous one. In the characterization of the nanocapsules, important changes were detected by the presence of 5FU. The delivery in the colon corresponded to a controlled release behavior. The in vitro assay indicated an improvement in the toxicity effect of the drug and its mechanism of action. Accordingly, BNC is a promising biomaterial for the development of a colon drug delivery platform of 5FU.

Environmentally dependent adsorption of 2,4-dichlorophenol on cellulose-chitosan self-assembled composites.

With the increasing need for bio-based materials developed by environmentally friendly procedures, this work shows a green method to develop shape-controlled structures from cellulose dissolving pulp coated by chitosan. This material was then tested to adsorb a common and widespread pollutant, 2,4-dichlorophenol under different pH conditions (5.5 and 9). Herein it was noticed that the adsorption only occurred in acidic pH (5.5) where electrostatic interaction drove the adsorption, demonstrating the potential to tune the response under desired conditions only. The adsorption was successful in the hydrogel structure with an adsorption capacity of 905 ± 71 mg/g from a solution with 16.6 ppm; furthermore, adsorption was also possible with dried hydrogel structures, presenting a maximum of adsorption of 646 ± 50 mg/g in a similar 16.6 ppm solution. Finally, adsorbent regeneration was successfully tested for both, dry (rewetted) and never-dried states, showing improved adsorption after regeneration in the case of the never dried hydrogel structures.

Effects of Chemical Post-treatments on Structural and Physicochemical Properties of Silk Fibroin Films Obtained From Silk Fibrous Waste.

Silk fibroin (SF) is a protein polymer claimed to have outstanding potential for medical applications. However, because of the manufacturing process, materials from regenerated SF exhibit a higher percentage of amorphous structures. The amorphous structures cause the material to be water soluble and can significantly limit its applications in wet biological environments. In order to increase the amount of crystalline structures and decrease the water solubility of SF materials, post-treatment with alcohols is usually employed. SF can be obtained from silk fibrous wastes (SFW), usually discarded in silk textile processes. This represents an opportunity to produce materials with high added value from low-cost natural sources. In this study, SF was obtained from SFW, and films were made thereof followed by a post-treatment by immersion or in a saturated atmosphere of methanol (MeOH) or ethanol (EtOH), using different exposure times. The resulting films were analyzed according to crystallinity, the percentage of crystalline and amorphous structures, and thermal stability. Also, water absorption and weight loss in aqueous media were determined. The results showed a significant increase in crystalline structures in all treated samples, varying according to the type and time of exposure to post-treatment conducted. The highest increase was shown in the case of the post-treatment by immersion in MeOH for 1 h, with a 23% increase over the untreated sample. This increase in crystallinity was reflected in an increase in the degradation temperature and a degradation rate of 5.3% on day 7. The possibility of tuning the degree of crystallinity, as well as thermal stability and aqueous integrity of thin films of SFW, can be applied to adjust these materials to the requirements of specific biomedical applications.

Cellulose-Cyclodextrin Co-Polymer for the Removal of Cyanotoxins on Water Sources.

With increasing global water temperatures and nutrient runoff in recent decades, the blooming season of algae lasts longer, resulting in toxin concentrations that exceed safe limits for human consumption and for recreational use. From the different toxins, microcystin-LR has been reported as the main cyanotoxin related to liver cancer, and consequently its abundance in water is constantly monitored. In this work, we report a methodology for decorating cellulose nanofibrils with ß-cyclodextrin or with poly(ß-cyclodextrin) which were tested for the recovery of microcystin from synthetic water. The adsorption was followed by Quartz Crystal Microbalance with Dissipation monitoring (QCM-D), allowing for real-time monitoring of the adsorption behavior. A maximum recovery of 196 mg/g was obtained with the modified by cyclodextrin. Characterization of the modified substrate was confirmed with Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), Thermogravimetric Analysis (TGA), and Atomic Force Microscopy (AFM).

Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper.

Complexes of xylan and synthetic polyelectrolytes. Characterization and adsorption onto high quality unbleached fibres.

In this work, polyelectrolyte complexes (PECs) were formed by adding polyacrylic acid (PAA) or 4-O-methylglucuronoxylan (Xyl) on poly(allylamine hydrochloride) (PAH) solutions, at different ionic strength and neutral pH. Turbidity curves, charge densities of the cationic complexes determined by polyelectrolyte titration method, and z-potential values showed clear differences between both complexes. Stirring favourably reverses the effects of sedimentation of Xyl/PAH complexes, as demonstrated by colloidal stability tests. Adsorption studies on silica surfaces, performed by Quartz Crystal Microbalance with Dissipation (QCM-D) showed that PAA/PAH adsorbed complexes layers were rigid, while the corresponding Xyl/PAH layers were viscoelastic. Despite the different conformations, both complexes were adsorbed as spherical particles, as observed by Atomic Force Microscopy (AFM). Adsorption isotherms performed on fibre suspensions showed that the ionic strength of the liquid medium determines the amount of PEC retained. Finally, it was found that the papermaking properties were significantly increased due to the addition of these PECs.

Effect of moisture on electrospun nanofiber composites of poly(vinyl alcohol) and cellulose nanocrystals.

The effect of humidity on the morphological and thermomechanical properties of electrospun poly(vinyl alcohol) (PVA) fiber mats reinforced with cellulose nanocrystals (CNs) was investigated. Scanning electron microscopy (SEM) images revealed that the incorporation of CNs improved the morphological stability of the composite fibers even in high humidity environments. Thermal and mechanical properties of the electrospun fiber mats were studied by using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and large deformation tensile tests under controlled humidity and temperatures. The balance between the moisture-induced plasticization and the reinforcing effect of rigid CN particles was critical in determining the thermomechanical behaviors of the electrospun fiber mats. Results indicated that the stabilizing effect of the CNs in the PVA matrix might be compromised by water absorption, disrupting the hydrogen bonding within the structure. The amount of this disruption depended on the surrounding humidity and the CN loading. The reduction in tensile strength of neat PVA fiber mats as they were conditioned from low relative humidity (10% RH) to high relative humidity (70% RH) was found to be about 80%, from 1.5 to 0.4 MPa. When the structure was reinforced with CNs, the reduction in strength was limited to 40%, from 2 to 0.8 MPa over the same range in relative humidity. More importantly, the CN-loaded PVA fiber mats showed a reversible recovery in mechanical strength after cycling the relative humidity. Finally, humidity treatments of the composite PVA fiber mats induced significant enhancement of their strength as a result of the adhesion between the continuous matrix and the CNs.

Nanofiber composites of polyvinyl alcohol and cellulose nanocrystals: manufacture and characterization.

Cellulose nanocrystals (CN) were used to reinforce nanofibers in composite mats produced via electrospinning of poly(vinyl alcohol) (PVA) with two different concentrations of acetyl groups. Ultrathin cross-sections of the obtained nanocomposites consisted of fibers with maximum diameters of about 290 nm for all the CN loads investigated (from 0 to 15% CN loading). The electrospinning process did not affect the structure of the PVA polymer matrix, but its degree of crystallinity increased significantly together with a slight increase in the corresponding melting temperature. These effects were explained as being the result of alignment and enhanced crystallization of PVA chains within the individual nanofibers that were subjected to high shear stresses during electrospinning. The strong interaction of the PVA matrix with the dispersed CN phase, mainly via hydrogen bonding or bond network, was reduced with the presence of acetyl groups in PVA. Most importantly, the elastic modulus of the nanocomposite mats increased significantly as a consequence of the reinforcing effect of CNs via the percolation network held by hydrogen bonds. However, this organization-driven crystallization was limited as observed by the reduction in the degree of crystallinity of the CN-loaded composite fibers. Finally, efficient stress transfer and strong interactions were demonstrated to occur between the reinforcing CN and the fully hydrolyzed PVA electrospun fibers.

Reinforcing poly(epsilon-caprolactone) nanofibers with cellulose nanocrystals.

We studied the use of cellulose nanocrystals (CNXs) obtained after acid hydrolysis of ramie cellulose fibers to reinforce poly(epsilon-caprolactone) (PCL) nanofibers. Chemical grafting with low-molecular-weight PCL diol onto the CNXs was carried out in an attempt to improve the interfacial adhesion with the fiber matrix. Grafting was confirmed via infrared spectroscopy and thermogravimetric analyses. The polymer matrix consisted of electrospun nanofibers that were collected as nonwoven webs. The morphology as well as thermal and mechanical properties of filled and unfilled nanofibers were elucidated by scanning electron microscopy, differential scanning calorimetry, and dynamic mechanical analysis, respectively. The addition of CNXs into PCL produced minimal changes in the thermal behavior of the electrospun fibers. However, a significant improvement in the mechanical properties of the nanofibers after reinforcement with unmodified CNXs was confirmed. Fiber webs from PCL reinforced with 2.5% unmodified CNXs showed ca. 1.5-fold increase in Young's modulus and the ultimate strength compared to PCL webs. Compared to the case of grafted nanocrystals, the unmodified ones imparted better morphological homogeneity to the nanofibrillar structure. The grafted nanocrystals had a negative effect on the morphology of nonwoven webs in which individual nanofibers became annealed during the electrospinning process and, therefore, could not be compared to neat PCL nonwoven webs. A rationalization for the different effects of grafted and unmodified CNXs in reinforcing PCL nanofibers is provided.