Enantiomeric Selective Adsorption of Amino Acid by Polysaccharide Composite Materials

A composite containing cellulose (GEL) and chitosan (CS) synthesized by a simple and recyclable method by using butylmethylimmidazolium chloride, an ionic liquid, was found to exhibit remarkable enantiomeric selectivity toward the adsorption of amino acids. The highest adsorption capacity and enantiomeric selectivity are exhibited by 100% CS. A racemic amino acid can be enantiomerically resolved by 100% CS in about 96-120 h. Interestingly, adsorption by 50:50 CEL/CS is more similar to that by 100% CS than to 100% GEL. Specifically, whereas 100% GEL has the lowest adsorption capacity and enantiomeric selectivity, 50:50 CEL/CS has sufficient enantiomeric selectivity to enable it to be used for chiral resolution. This is significant because in spite of its high enantiomeric selectivity 100% CS cannot practically be used because it has relatively poor mechanical properties and undergoes extensive swelling. Adding 50% GEL to CS substantially improves the mechanical properties and reduces its swelling while it retains sufficient enantiomeric selectivity to enable it to be used for routine chiral separations. The kinetic results indicate that the enantiomerically selective adsorption is due not to the initial surface adsorption but rather to the subsequent stage in which the adsorbate molecules diffuse into the pores within the particles of the composites and consequently are adsorbed by the interior of each particle. The strong intermolecular and intramolecular hydrogen bond network in GEL enables it to adopt a very dense structure that makes it difficult for adsorbate molecules to diffuse into its interior, thereby leading to low enantiomeric selectivity. Compared to hydroxy groups, amino groups cannot form strong hydrogen bonds. The hydrogen bond network in CS is not as extensive as in CEL, and its inner structure is relatively less dense than that of GEL. Adsorbate molecules can, therefore, diffuse from the outer surface to its inner structure relatively more easily than in GEL, thereby leading to higher enantiomeric selectivity for 100% CS.