Synergistic Adsorption of Heavy Metal Ions and Organic Pollutants by Supramolecular Polysaccharide Composite Materials from Cellulose, Chitosan and Crown Ether

We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm+Cl−], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm+Cl−] used was recovered for reuse, the method is recyclable. The [CEL/CS + B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS + B15C5] composites exhibit truly supramolecular properties. By itself CS, CEL and B15C5 can effectively adsorb Cd2+, Zn2+ and 2,4,5-trichlorophenol. However, adsorption capability of the composite was substantially and synergistically enhanced by adding B15C5 to either CEL and/or CS. That is, the adsorption capacity (qe values) for Cd2+ and Zn2+ by [CS + B15C5], [CEL + B15C5] and [CEL + CS + B15C5] composites are much higher than combined qe values of individual CS, CEL and B15C5 composites. It seems that B15C5 synergistically interact with CS (or CEL) to form more stable complexes with Cd2+ (or Zn2+), and as a consequence, the [CS + B15C5] (or the [CEL + B15C5]) composite can adsorb relatively larger amount Cd2+ (or Zn2+). Moreover, the pollutants adsorbed on the composites can be quantitatively desorbed to enable the [CS + CEL + B15C5] composites to be reused with similar adsorption efficiency

Facile Synthesis, Characterization, and Antimicrobial Activity of Cellulose-Chitosan-Hydroxyapatite Composite Material: A Potential Material for Bone Tissue Engineering

Hydroxyapatite (HAp) is often used as a bone-implant material because it is biocompatible and osteoconductive. However, HAp possesses poor rheological properties and it is inactive against disease-causing microbes. To improve these properties, we developed a green method to synthesize multifunctional composites containing: (1) cellulose (CEL) to impart mechanical strength; (2) chitosan (CS) to induce antibacterial activity thereby maintaining a microbe-free wound site; and (3) HAp. In this method, CS and CEL were co-dissolved in an ionic liquid (IL) and then regenerated from water. HAp was subsequently formed in situ by alternately soaking [CEL+CS] composites in aqueous solutions of CaCl2 and Na2HPO4. At least 88% of IL used was recovered for reuse by distilling the aqueous washings of [CEL+CS]. The composites were characterized using FTIR, XRD, and SEM. These composites retained the desirable properties of their constituents. For example, the tensile strength of the composites was enhanced 1.9 times by increasing CEL loading from 20% to 80%. Incorporating CS in the composites resulted in composites which inhibited the growth of both Gram positive (MRSA, S. aureus and VRE) and Gram negative (E. coli and P. aeruginosa) bacteria. These findings highlight the potential use of [CEL+CS+HAp] composites as scaffolds in bone tissue engineering

Cellulose, Chitosan and Keratin Composite Materials: Facile and Recyclable Synthesis, Conformation and Properties

A method was developed in which cellulose (CEL) and/or chitosan (CS) were added to keratin (KER) to enable [CEL/CS+KER] composites formed to have better mechanical strength and wider utilization. Butylmethylimmidazolium chloride ([BMIm⁺Cl^–]), an ionic liquid, was used as the sole solvent, and because the majority of [BMIm⁺Cl^–] used (at least 88%) was recovered, the method is green and recyclable. FTIR, XRD, ¹³C CP-MAS NMR and SEM results confirm that KER, CS and CEL remain chemically intact and distributed homogeneously in the composites. We successfully demonstrate that the widely used method based on the deconvolution of the FTIR bands of amide bonds to determine secondary structure of proteins is relatively subjective as the conformation obtained is strongly dependent on the choice of parameters selected for curve fitting. A new method, based on the partial least squares regression analysis (PLSR) of the amide bands, was developed, and proven to be objective and can provide more accurate information. Results obtained with this method agree well with those by XRD, namely they indicate that although KER retains its second structure when incorporated into the [CEL+CS] composites, it has relatively lower α-helix, higher β-turn and random form compared to that of the KER in native wool. It seems that during dissolution by [BMIm⁺Cl^–], the inter- and intramolecular forces in KER were broken thereby destroying its secondary structure. During regeneration, these interactions were reestablished to reform partially the secondary structure. However, in the presence of either CEL or CS, the chains seem to prefer the extended form thereby hindering reformation of the α-helix. Consequently, the KER in these matrices may adopt structures with lower content of α-helix and higher β-sheet. As anticipated, results of tensile strength and TGA confirm that adding CEL or CS into KER substantially increase the mechanical strength and thermal stability of the [CS/CEL+KER] composites