Self-Assembled Aminated and TEMPO Cellulose Nanofibers (Am/TEMPO-CNF) Aerogel for Adsorptive Removal of Oxytetracycline and Chloramphenicol Antibiotics from Water.

Antibiotics are used for the well-being of human beings and other animals. Detectable levels of antibiotics can be found in pharmaceutical, municipal, and animal effluents. Therefore, the treatment of antibiotic contaminated water is of great concern. In this study, we fabricated a sustainable aminated/TEMPO cellulose nanofiber (Am/TEMPO-CNF) aerogel to remove oxytetracycline (OTC) and chloramphenicol (CAP) from synthetic wastewater. The prepared aerogel was characterized using different analytical techniques such as elemental analysis, FTIR, TGA, SEM-EDS, and N2 adsorption-desorption isotherms. The characterization techniques confirmed the presence and interaction of quaternary amine -[NR3]+ and -COOH groups on Am/TEMPO-CNF with OTC and CAP, which validates the successful modification of Am/TEMPO-CNF. The adsorption process of the pollutants was examined as a function of solution pH, concentrations, reaction time, and temperatures. The maximum adsorption capacity was 153.13 and 150.15 mg/g for OTC and CAP, respectively. The pseudo-second order (PSO-2) was well fitted to both OTC and CAP, confirming the removal is via chemisorption. Hydrogen bonding and electrostatic attraction have been postulated as key factors in facilitating OTC and CAP adsorption according to spectroscopic studies. Energetically, the adsorption was spontaneous and endothermic for both pollutants. In conclusion, the efficient removal rate and excellent reusability of Am/TEMPO-CNF indicate the strong potential of the adsorbent for antibiotics' removal.

Amino-Functionalized Cellulose Nanofiber/Lignosulfonate New Aerogel Adsorbent for the Removal of Dyes and Heavy Metals from Wastewater.

Due to the increasingly widespread water pollutants and the high cost of treatment methods, there is a demand for new, inexpensive, renewable, and biodegradable adsorbent materials for the purification of wastewater contaminants. In this study, a new biocomposite aerogel (Amf-CNF/LS) was prepared using a chemically cross-linking method between the amino-functionalized cellulose nanofibers (Amf-CNF) and lignosulfonates (LS). The physical and chemical properties of the prepared aerogel were investigated using several techniques including elemental analysis, scanning electron microscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and N2 adsorption-desorption analysis. The Amf-CNF/LS aerogel was then applied for the removal of methylene blue (MB), rhodamine B dye (RhB), and the heavy metal cadmium ion (Cd2+) from synthetic wastewater solutions. The adsorption parameters controlling the adsorption process including the pH, contact time, adsorbent dosage, and adsorbate concen-tration were optimized. High adsorption kinetics and isotherms were observed, with the adsorption isotherms of the Amf-CNF/LS aerogel fitting the Langmuir model with maximum adsorption capacities of 170.94, 147.28, and 129.87 mg/g for MB, RhB, and Cd2+, respectively. These results show that Amf-CNF/LS aerogel is a promising green and inexpensive adsorbent for MB, RhB, and Cd2+ removal from wastewater.

Recent Developments in Cellulose Nanomaterial Composites.

Cellulose nanomaterials (CNMs) are a class of materials that have recently garnered attention in fields as varied as structural materials, biomaterials, rheology modifiers, construction, paper enhancement, and others. As the principal structural reinforcement of biomass giving wood its mechanical properties, CNM is strong and stiff, but also nontoxic, biodegradable, and sustainable with a very large (Gton yr-1 ) source. Unfortunately, due to the relatively young nature of the field and inherent incompatibility of CNM with most man-made materials in use today, research has tended to be more basic-science oriented rather than commercially applicable, so there are few CNM-enabled products on the market today. Herein, efforts are presented for preparing and forming cellulose nanomaterial nanocomposites. The focus is on recent efforts attempting to mitigate common impediments to practical commercialization but is also placed in context with traditional efforts. The work is presented in terms of the progress made, and still to be made, on solving the most pressing challenges-getting properties that are competitive with currently used materials, removing organic solvent, solving the inherent incompatibility between CNM and polymers of interest, and incorporation into commonly used industrial processing techniques.

Acrylic Functionalization of Cellulose Nanocrystals with 2-Isocyanatoethyl Methacrylate and Formation of Composites with Poly(methyl methacrylate).

Cellulose nanocrystals (CNCs) derived from renewable plant-based materials exhibit strong potential for improving properties of polymers by their dispersal in the polymer matrix as a composite phase. However, the hydrophilicity and low thermal stability of CNCs lead to compromised particle dispersibility in common polymers and limit the processing conditions of polymer-CNC composites, respectively. One route that has been explored is the modification of CNCs to alter surface chemistry. Acrylic materials are used in a broad class of polymers and copolymers with wide commercial applications. Yet, the available methods for adding groups that react with acrylics to enhance dispersion are quite limited. In this work, a versatile chemical modification route is described that introduces acryloyl functional groups on CNCs that can in turn be polymerized in subsequent steps to create acrylic-CNC composites. The hydroxyl group on CNC surfaces was reacted with the isocyanate moiety on 2-isocyanatoethyl methacrylate (IEM), a bifunctional molecule possessing both the isocyanate group and acryloyl group. The resulting modified CNCs (mCNCs) showed enhanced hydrophobicity and dispersibility in organic solvent relative to unmodified CNCs. Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis verified the surface modification and allowed an estimation of the degree of modification as high as 0.4 (26.7% surface hydroxyl substitution CNC). The modified CNCs were copolymerized with methyl methacrylate, and the composites had improved dispersion relative to composites with unmodified CNCs and enhanced (104%) tensile strength at 2 wt % CNC when compared to the neat poly(methyl methacrylate) (PMMA), indicating a benefit of the reactive acryloyl groups added to the CNC surface. Overall, the modification strategy was successful in functionalizing CNCs, opening possibilities for their use in organic media and matrices.

Biohybrid Hydrogel and Aerogel from Self-Assembled Nanocellulose and Nanochitin as a High-Efficiency Adsorbent for Water Purification.

A simple and novel method, self-assembly of nanocellulose and nanochitin, was developed to produce high-efficiency and versatile biohybrid hydrogel (BHH) and aerogel (BHA) for water purification. The self-assembly process was driven by the electrostatic force between one-dimensional (1D) negatively charged TEMPO-oxidized cellulose nanofiber (TOCNF) and positively charged partly deacetylated chitin nanofiber (PDChNF). The self-assembly process was performed at room temperature and without adding any cross-linking agents throughout the process. This results in the three-dimensional (3D) BHH that physically cross-linked via both electrostatic interactions and hydrogen bonding between TOCNF and PDChNF. The obtained BHA from lyophilized BHH exhibited a highly porous interconnected structure with a specific surface area of 54 m2·g-1, which assures the availability of its internal active site for the adsorption of toxic metalloid ions and organic pollutants. Consequently, the BHA displayed super-high adsorption capacities of 217 mg·g-1 for As(III) under the neutral pH conditions and 531 mg·g-1 for methylene blue (MB) under an alkaline aqueous condition with rapid adsorption kinetics, in sharp contrast to conventional biobased adsorbents. Moreover, the BHA is reusable, which still exhibited a high MB adsorption capacity of 505 mg·g-1 even after five successive adsorption-desorption cycles. This versatile BHA produced via a facile preparation strategy is proven to be a promising renewable adsorbent for water purification, offering simple and green alternatives to the conventional adsorbent from synthetic polymers.

Site-Selective Modification of Cellulose Nanocrystals with Isophorone Diisocyanate and Formation of Polyurethane-CNC Composites.

The unequal reactivity of the two isocyanate groups in an isophorone diisocyante (IPDI) monomer was exploited to yield modified cellulose nanocrystals (CNCs) with both urethane and isocyanate functionality. The chemical functionality of the modified CNCs was verified with ATR-FTIR analysis and elemental analysis. The selectivity for the secondary isocyanate group using dibutyl tin dilaurate (DBTDL) as the reaction catalyst was confirmed with (13)C NMR. The modified CNCs showed improvements in the onset of thermal degradation by 35 °C compared to the unmodified CNCs. Polyurethane composites based on IPDI and a trifunctional polyether alcohol were synthesized using unmodified (um-CNC) and modified CNCs (m-CNC). The degree of nanoparticle dispersion was qualitatively assessed with polarized optical microscopy. It was found that the modification step facilitated superior nanoparticle dispersion compared to the um-CNCs, which resulted in increases in the tensile strength and work of fracture of over 200% compared to the neat matrix without degradation of elongation at break.