Distinguishing Surface versus Bulk Hydroxyl Groups of Cellulose Nanocrystals Using Vibrational Sum Frequency Generation Spectroscopy

Makarem, Mohamadamin; Lee, Christopher M.; Sawada, Daisuke; O’Neill, Hugh M.; Kim, Seong H.

doi:10.1021/acs.jpclett.7b02729

Title: Distinguishing Surface versus Bulk Hydroxyl Groups of Cellulose Nanocrystals Using Vibrational Sum Frequency Generation Spectroscopy

Journal Article · Tue Dec 12 00:00:00 EST 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b02729· OSTI ID:1470026

Makarem, Mohamadamin ^[1]; Lee, Christopher M. ^[1];

^[2];

^[1]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemical Engineering, and Materials Research Inst.
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biology and Soft Matter Division

In plant cell walls and cellulose-containing composites, nanocrystalline cellulose interacts with water molecules or matrix polymers through hydrogen bonding of the hydroxyl groups at the cellulose surface. These interactions play key roles in cellulose assembly in plant cell walls and mechanical properties of cellulose composites; however, they could not be studied properly due to the spectroscopic difficulty of selectively detecting the surface hydroxyl groups of nanocrystalline domains. This study employed the sum frequency scattering principle to distinguish the hydroxyl groups inside of the crystalline nanodomain of cellulose and those exposed at the surface of crystalline domains. The comparison of the spectra at various scattering angles revealed that the OH peak near ~3450 cm^–1 comes from the weakly hydrogen-bonded OH groups at the surface of crystalline cellulose. Also, a time delay measurement found that the sharp vibrational features observed near 3700 cm–1 can be attributed to isolated OH groups not accessible by ambient water molecules. These findings allow the distinction of surface versus bulk OH groups in sum frequency generation vibrational spectroscopy.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001090

OSTI ID:: 1470026

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 1; Related Information: CLSF partners with Pennsylvania State University (lead); North Carolina State University; University of Rhode Island; Virginia Tech University; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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Title: Distinguishing Surface versus Bulk Hydroxyl Groups of Cellulose Nanocrystals Using Vibrational Sum Frequency Generation Spectroscopy

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