Supercritical carbon dioxide biocatalysis as a novel and green methodology for the enzymatic acylation of fibrous cellulose in one step.

Aliphatic esters of cellulose have recently raised the interest on the field of biopolymers. The objective of this work is to develop a methodology for the enzymatic acylation of cellulose with long chain fatty groups in one step. Therefore we designed a system at which fibrous cellulose was enzymatically acylated with vinyl laurate in supercritical carbon dioxide (scCO(2)) and as a result cellulose laurate was formed. The biocatalysts used for this reaction were immobilized lipase Candida antarctica, immobilized esterase from hog liver and the immobilized cutinase Fusarium solani. The ester content of the product varied on the specificity of the biocatalyst used, reaching a maximum of 4.1% after 9h of reaction. In our knowledge, it is the first time where fibrous cellulose is enzymatically acylated by a long chain aliphatic group in one step, without the necessity of any pretreatment.

Direct enzymatic acylation of cellulose pretreated in BMIMCl ionic liquid.

Cellulose esters are an important class of functional biopolymers with great interest in the chemical industry. In this work the enzymatic acylation of Avicel cellulose with vinyl propionate, vinyl laurate and vinyl stearate, has been performed successfully in a solvent free reaction system. At first cellulose was putted into the ionic liquid BMIMCl (1-n-butyl-3-methylimidazolium chloride) in order to facilitate the unwrap of the structure of the polysaccharide molecule and make it accessible to the enzyme. Thus, after this pretreatment the enzymatic esterification reaction was performed using various hydrolases. The enzymes capable of catalyzing the acylation of cellulose were found to be the immobilized esterase from hog liver and the immobilized cutinase from Fusarium solani, while the lipases used did not show any catalytic activity. Cellulose esters of propionate, laurate and stearate were synthesized with a degree of esterification of 1.9%, 1.3% and 1.0%, respectively. It is the first successful direct enzymatic acylation of cellulose with long chain fatty acids.