Hydrolysis of the amorphous cellulose in cotton-based paper.
Hydrolysis of cellulose in Whatman no. 42 cotton-based paper was studied using gel permeation chromatography (GPC), electrospray ionization-mass spectrometry (ESI-MS), and uniaxial tensile testing to understand the course and kinetics of the reaction. GPC results suggested that scission reactions passed through three stages. Additionally, the evolution of soluble oligomers in the ESI-MS data and the steady course of strength loss showed that the hydrolysis reaction occurred at a constant rate. These findings are explained with a more detailed description of the cellulose hydrolysis, which includes multiple chain scissions on amorphous segments. The breaks occur with increasing frequency near the ends of amorphous segments, where chains protrude from crystalline domains. Oligomers unattached to crystalline domains are eventually created. Late-stage reactions near the ends of amorphous segments produce a kinetic behavior that falsely suggests that hydrolysis had ceased. Monte Carlo simulations of cellulose degradation corroborated the experimental findings.
Stephens
Catherine H
CH
Art Conservation Research Center, Mellon College of Science, Carnegie Mellon University, 700 Technology Drive, Pittsburgh, Pennsylvania 15219, USA. chs2@andrew.cmu.edu
Whitmore
Paul M
PM
Morris
Hannah R
HR
Bier
Mark E
ME
D002482:Cellulose / Q000737:chemistry* / Q000378:metabolism*; D002850:Chromatography, Gel / Q000379:methods; D003198:Computer Simulation; D032561:Cotton Fiber; D003368:Gossypium / Q000737:chemistry*; D006868:Hydrolysis; D007700:Kinetics; D008970:Molecular Weight; D009010:Monte Carlo Method; D010209:Paper; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods
D002482:Cellulose