Probing crystal structure and mesoscale assembly of cellulose microfibrils in plant cell walls, tunicate tests, and bacterial films using vibrational sum frequency generation (SFG) spectroscopy.
This study reports that the noncentrosymmetry and phase synchronization requirements of the sum frequency generation (SFG) process can be used to distinguish the three-dimensional organization of crystalline cellulose distributed in amorphous matrices. Crystalline cellulose is produced as microfibrils with a few nanometer diameters by plants, tunicates, and bacteria. Crystalline cellulose microfibrils are embedded in wall matrix polymers and assembled into hierarchical structures that are precisely designed for specific biological and mechanical functions. The cellulose microfibril assemblies inside cell walls are extremely difficult to probe. The comparison of vibrational SFG spectra of uniaxially-aligned and disordered films of cellulose Iβ nanocrystals revealed that the spectral features cannot be fully explained with the crystallographic unit structure of cellulose. The overall SFG intensity, the alkyl peak shape, and the alkyl/hydroxyl intensity ratio are sensitive to the lateral packing and net directionality of the cellulose microfibrils within the SFG coherence length scale. It was also found that the OH SFG stretch peaks could be deconvoluted to find the polymorphic crystal structures of cellulose (Iα and Iβ). These findings were used to investigate the cellulose crystal structure and mesoscale cellulose microfibril packing in intact plant cell walls, tunicate tests, and bacterial films.
Department of Chemical Engineering and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA. shkim@engr.psu.edu.
Christopher M
CM
Lee
Kabindra
K
Kafle
Yong Bum
YB
Park
Seong H
SH
Kim
D000818:Animals; D002473:Cell Wall / Q000737:chemistry*; D002482:Cellulose / Q000737:chemistry*; D019597:Flax / Q000737:chemistry* / Q000166:cytology; D041822:Gluconacetobacter xylinus / Q000737:chemistry*; D020894:Microfibrils / Q000737:chemistry*; D015394:Molecular Structure; D013057:Spectrum Analysis; D014561:Urochordata / Q000382:microbiology
D002482:Cellulose