Photoinduced Metal-Free Atom Transfer Radical Polymerization for the Modification of Cellulose with Poly(N-isopropylacrylamide) to Create Thermo-Responsive Injectable Hydrogels.

Photoinduced metal-free ATRP has been successfully applied to fabricate thermo-responsive cellulose graft copolymer (PNIPAM-g-Cell) using 2-bromoisobuturyl bromide-modified cellulose as the macroinitiator. The polymerization of N-isopropylacrylamide (NIPAM) from cellulose was efficiently activated and deactivated with UV irradiation in the presence of an organic-based photo-redox catalyst. Both FTIR and 13C NMR analysis confirmed the structural similarity between the obtained PNIPAM-g-Cell and that synthesized via traditional ATRP methods. When the concentration of the PNIPAM-g-Cell is over 5% in water, it forms an injectable thermos-responsive hydrogel composed of micelles at 37 °C. Since organic photocatalysis is a metal-free ATRP, it overcomes the challenge of transition-metal catalysts remaining in polymer products, making this cellulose-based graft copolymer suitable for biomedical applications. In vitro release studies demonstrated that the hydrogel can continuously release DOX for up to 10 days, and its cytotoxicity indicates that it is highly biocompatible. Based on these findings, this cellulose-based injectable, thermo-responsive drug-loaded hydrogel is suitable for intelligent drug delivery systems.

Structural changes of hemicellulose during pulping process and its interaction with nanocellulose.

It is believed that hemicellulose plays a crucial role in binding cellulose and lignin in plant cells. It may provide significant implications through figuring out the interaction between hemicellulose and microfibers and gaining insights how the structure of hemicellulose affects its association with cellulose nanofibers. Herein, the hemicellulose and nanocellulose fractions from pulps obtained by controlling the H-factors of kraft pulping process were quantitatively evaluated for their adsorption behavior using QCM-D. The results showed that harsher cooking (corresponding to high H-factor) significantly affected the chemical composition of hemicellulose, leading to a decrease of its molecular weight and gradually turning it into a linear structure. Hemicellulose possesses a strong natural affinity for CNC-coated sensors. The hemicellulose from the pulp cooked by high H-factor process decreases its ability to adsorb onto nanocellulose, the adsorption rate also slows down, and the conformation of the adsorbed layer changes which makes the binding weak and reversible. In conclusion, the pulping process in high H-factor significantly changed the structure of hemicellulose, leading to a variation in the strength of its interaction with nanocellulose.

Fabrication of Low-Temperature Fast Gelation ß-Cyclodextrin-Based Hydrogel-Loaded Medicine for Wound Dressings.

ß-Cyclodextrin (ß-CD) is often used as a drug carrier for biomedical materials due to its unique cavity structure. Herein, ß-CD was modified by acryloyl chloride and further copolymerized with N-isopropylacrylamide (NIPAM) and acrylic acid (AA) to obtain PNIPAM-co-ß-CD-AC. The results showed that the critical phase transition temperature of PNIPAM/ß-CD-AC could be controlled at 19 °C, and the fast sol-gel phase transition was realized in 2-10 s. The hydrophobic drug carried in this hydrogel can constantly be released for more than 6 days at pH values (pH 5.5-8), and the duration may match the recovery of the wound. As a dressing hydrogel, its rapid gel formation and inversion as well as shear-thinning behavior prevent secondary wound damage. The ß-CD-based hydrogel also has good biocompatibility and antioxidant properties, which provide a good potential choice for wound dressings, especially for exposed wounds in winter.

Core-Shell Structured Magnetic Carboxymethyl Cellulose-Based Hydrogel Nanosorbents for Effective Adsorption of Methylene Blue from Aqueous Solution.

This article reports effective removal of methylene blue (MB) dyes from aqueous solutions using a novel magnetic polymer nanocomposite. The core-shell structured nanosorbents was fabricated via coating Fe3O4 nanoparticles with a layer of hydrogel material, that synthesized by carboxymethyl cellulose cross-linked with poly(acrylic acid-co-acrylamide). Some physico-chemical properties of the nanosorbents were characterized by various testing methods. The nanosorbent could be easily separated from aqueous solutions by an external magnetic field and the mass fraction of outer hydrogel shell was 20.3 wt%. The adsorption performance was investigated as the effects of solution pH, adsorbent content, initial dye concentration, and contact time. The maximum adsorption capacity was obtained at neutral pH of 7 with a sorbent dose of 1.5 g L-1. The experimental data of MB adsorption were fit to Langmuir isotherm model and Pseudo-second-order kinetic model with maximum adsorption of 34.3 mg g-1. XPS technique was applied to study the mechanism of adsorption, electrostatic attraction and physically adsorption may control the adsorption behavior of the composite nanosorbents. In addition, a good reusability of 83.5% MB recovering with adsorption capacity decreasing by 16.5% over five cycles of sorption/desorption was observed.

Cellulose-based thermo-enhanced fluorescence micelles.

Recently, cellulose-based stimuli-responsive nanomaterials have received significant attention because of its natural source and biocompatibility. In this study, cellulose-graft-poly(nisopropylacrylamide)-co-2-methyl-acrylic acid 2-carbazol-9-yl-ethyl ester (cellulose-g-(PNIPAAm&PCz)) block polymers were successfully synthesized by homogeneous atom transfer radical polymerization (ATRP) in LiCl/N,N-dimethylacetamide (DMAc) dissolution system. The block polymers showed different properties due to the different PCz content. The block polymer with low PCz content (cellulose-g-(PNIPAAm&PCz)1) was dispersed in water at 25 °C and self-assembled into micelles at 37 °C. On the other hand, the block polymer with high PCz content (cellulose-g-(PNIPAAm&PCz)2) was dissolved in DMF, THF, DMSO firstly, and dialyzed at 25 °C, 37 °C and 60 °C respectively to obtain the micelles. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) indicated that the distribution range of micelles formed by cellulose-g-(PNIPAAm&PCz)1 was narrower than cellulose-g-(PNIPAAm&PCz)2. And the sizes of the micelles formed by cellulose-g-(PNIPAAm&PCz)2 had little difference under different solvents, but became bigger with the temperature increased. The micelles displayed thermo-enhanced fluorescence due to the thermal-driven chain dehydration of the grafted PNIPAAm brushes, which is contrary to the decrease of the fluorescence of the monomer when the temperature increased. The results provided a potential for the application of cellulose-based stimuli-responsive micelles in the field of drug delivery and fluorescent probes.

Enhanced degradation of Acid Red 73 by using cellulose-based hydrogel coated Fe3O4 nanocomposite as a Fenton-like catalyst.

Carboxymethyl cellulose-based hydrogel coated Fe3O4 magnetic nanoparticles were prepared using a coprecipitation combining graft copolymerization method, and characterized by various techniques to study their structure-property relationships. The nanocomposite was used as a heterogeneous Fenton-like catalyst for Acid Red 73 degradation. The effects of several key parameters, solution pH, H2O2 concentration, catalyst dosage, and temperature of the reaction medium on the pseudo-first-order kinetics of dye degradation was evaluated. The results showed that the nanocomposite catalyst were highly effective in activating H2O2 to produce reactive radicals for dye degradation, achieving complete decomposition under optimal conditions of 300 min at 25 °C and pH 3.5 with 100 mM H2O2 and 200 mg·L-1 catalyst. The complexing hydrogel-Fe2+/Fe3+ were the key factors that speed up the redox cycling between Fe2+ and Fe3+ species, thus accelerate the fast degradation rate of target pollutants. Scavenging experiments and electron paramagnetic resonance analyses revealed that Acid Red 73 was decomposed mainly by the attack of •OH radicals. Besides, reusability of the prepared nanocatalyst was also tested.