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 β-cyclodextrin or with poly(β-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).
Biocatalytic pulp fibers were prepared using surface functionalization of bleached kraft pulp with amino groups (F) and further immobilization of a cross-linked glucose oxidase (G*) from Aspergillus niger. The cross-linked enzymes (G*) were characterized using X-ray spectroscopy, Fourier transform infrared spectroscopy, dynamic scanning calorimetry, and dynamic light scattering. According to standard assays, the G* content on the resulting fibers (FG*) was of 11 mg/g of fiber, and enzyme activity was of 215 U/g. The results from confocal- and stimulated emission depletion microscopy techniques demonstrated that glucose oxidase do not penetrate the interlayers of fibers. The benefit of pulp fiber functionalization was evident in the present case, as the introduction of amino groups allowed the immobilization of larger amount of enzymes and rendered more efficient systems. Using the approach described on this paper, several advanced materials from wood pulp fibers and new bioprocesses might be developed by selecting the correct enzyme for the target applications.
Gelatin and chitosan polysaccharides were chemically modified to get methacrylate functionality to obtain biocompatible hydrogels for use as tissue engineering scaffolds. The methacrylation reaction was verified by 1H‐NMR. The degree of methacrylation was varied from 7% to 40% by changing the molar ratio of polysaccharide to methacrylic anhydride and the type of polysaccharide utilized. After the modification, polysaccharide‐based hydrogels were prepared by free‐radical polymerization in the presence of UV light and Irgacure 184 as a photoinitiator. The physical, chemical, and mechanical performances of the hydrogels were further characterized. Also, the biodegradability and the viability of the polysaccharide hydrogels were investigated using fibroblast cells. These cells were seeded directly onto the hydrogel surface, populated the entirety of the hydrogel, and remained viable for up to 1 week. Altogether, the modified polysaccharides exhibit the properties which make them crucial for applications in the field of regenerative medicine.
Interactions at the molecular and surface chemistry are some of the key factors that determine the adsorption capacity of pollutants and emerging contaminants in porous materials. As filtration-based purification of water sources expands, the generation of green materials, such as biopolymers, is the priority. However, to increase the removal capacity, modification of natural polymers appears necessary. Nanomaterials, especially bio-based materials like cellulose nanofibrils, inherently have large surface areas as a consequence of their high aspect ratios. Their capacity to modulate the interactions with contaminants present in water can be modulated by incorporating selective active points, such as hydrophobic cavities, that can further improve their overall adsorption capability. A bio-based material that can fulfil this requirement is β-cyclodextrin, a cyclic oligosaccharide with seven glucose units, which provides an easy grafting strategy onto cellulose due to structural affinity. Another advantage of using cellulose nanofibril is their film formability, aerogels, and hydrogels without the need of harsh chemicals or processes. In this work, an oligosaccharide with a hydrophobic centre -β-cyclodextrin -was immobilized onto bleached softwood cellulose nanofibrils, and then used to generate high surface area aerogels with a density of 175 kg/m 3 and porosities above 88%. Charge density titration, Fourier transform infrared with attenuated total reflectance (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and atomic force microscopy (AFM) characterization techniques were used to assess the successful modification of the fibrils. Inductive coupled plasma mass spectroscopy (ICP-MS) was used to determine the lack of trace chlorine in the material from the grafting process while scanning electron microscopy (SEM) and dynamic vapor sorption (DVS) were used to determine porosity and surface area of the aerogels. The adsorption capacity was tested with two molecules of different natures: a cyanotoxin (microcystin-LR) and a dye (methylene blue), using high-performance liquid chromatography with a UV detector (HPLC-UV) and UV-vis spectroscopy, respectively. The adsorption in equilibrium for CNF-CD aerogels was calculated to be 0.078 mg/g of microcystin-LR and 3.46 mg/g of methylene blue, enlightening its possible use to improve water quality.
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