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Title: Dependence of Sum Frequency Generation (SFG) Spectral Features on the Mesoscale Arrangement of SFG-Active Crystalline Domains Interspersed in SFG-Inactive Matrix: A Case Study with Cellulose in Uniaxially Aligned Control Samples and Alkali-Treated Secondary Cell Walls of Plants

Vibrational sum frequency generation (SFG) spectroscopy can selectively detect not only molecules at two-dimensional (2D) interfaces but also noncentrosymmetric domains interspersed in amorphous three-dimensional (3D) matrixes. However, the SFG analysis of 3D systems is more complicated than 2D systems because more variables are involved. One such variable is the distance between SFG-active domains in SFG-inactive matrixes. In this study, we fabricated control samples in which SFG-active cellulose crystals were uniaxially aligned in an amorphous matrix. Assuming uniform separation distances between cellulose crystals, the relative intensities of alkyl (CH) and hydroxyl (OH) SFG peaks of cellulose could be related to the intercrystallite distance. The experimentally measured CH/OH intensity ratio as a function of the intercrystallite distance could be explained reasonably well with a model constructed using the theoretically calculated hyperpolarizabilities of cellulose and the symmetry cancellation principle of dipoles antiparallel to each other. In conclusion, this comparison revealed physical insights into the intercrystallite distance dependence of the CH/OH SFG intensity ratio of cellulose, which can be used to interpret the SFG spectral features of plant cell walls in terms of mesoscale packing of cellulose microfibrils.
Authors:
 [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [1] ;  [3] ;  [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Report Number(s):
NREL/JA-5100-68692
Journal ID: ISSN 1932-7447
Grant/Contract Number:
AC36-08GO28308
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; sum frequency generation; spectroscopy; matrixes
OSTI Identifier:
1364049