Preparation and physical properties of chitin fatty acids esters.
Trifluoroacetic anhydride is an effective promoter for the preparation of chitin single- and mixed-acid esters. Complete dissolution is achieved within 30 min when powdered chitin is heated at 70 degrees C in a mixed solution of carboxylic acid(s) and trifluoroacetic anhydride. Chitin esters prepared are chitin acetate, chitin butyrate, chitin hexanoate and chitin octanoate, chitin co-acetate/butyrate, chitin co-acetate/hexanoate, chitin co-acetate/octanoate, chitin co-acetate/palmitate, each from a solution of the respective reactants. The products have degrees of O-acyl substitution in a range of DS 1-2 depending on the nature of acyl group, as analyzed by gas-liquid and high-pressure liquid chromatography. Acetic acid as a mutual component for the mixed-acid esters increases the total degree of substitution, and the acetyl substitution is close to the relative distribution in the reaction mixture for chitin co-acetate/butyrate. It is favored over hexanoate, octanoate, and palmitate. The parent molecules, as calculated by the composition of the chitin esters and their molecular weights by light-scattering spectroscopy, are 30 kDa for the smallest and 150-151 kDa for the largest. Films of these chitin derivatives when cast from solution are strong and flexible with limited extensibility. By dynamic mechanical analysis of the ester film, it was found that both the glass transition temperature (T(g)) and the tensile modulus (E' at 25 degrees C) are highest for chitin acetate (218 degrees C and 5.8 GPa), and lowest for chitin octanoate (182 degrees C and 1.5 GPa). For the other esters, these values lie between the above-cited values, where the T(g) and the E' decrease with an increase in the chain length of the acyl constituent.
Yang
Byung Y
BY
Department of Biochemistry, College of Medicine, The University of Iowa, Iowa City, IA 52242, USA. byung-yang@uiowa.edu
Ding
Qiong
Q
Montgomery
Rex
R
D019342:Acetic Acid / Q000737:chemistry; D000818:Animals; D003386:Brachyura / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D002686:Chitin / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry*; D005227:Fatty Acids / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008970:Molecular Weight; D014269:Trifluoroacetic Acid / Q000737:chemistry
D002264:Carboxylic Acids; D004952:Esters; D005227:Fatty Acids; D002686:Chitin; D014269:Trifluoroacetic Acid; D019342:Acetic Acid