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Title: Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)

Abstract

Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1182941
Report Number(s):
PNNL-SA-105805
47913; 47760; 46208; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Cellulose, 22(3):1469-1484
Country of Publication:
United States
Language:
English
Subject:
Vibrational; spectral; signatures; crystalline; cellulose; high resolution; broadband; vibrational; spectroscopy; Environmental Molecular Sciences Laboratory

Citation Formats

Zhang, Libing, Lu, Zhou, Velarde Ruiz Esparza, Luis A., Fu, Li, Pu, Yunqiao, Ding, Shi-You, Ragauskas, Art J., Wang, Hongfei, and Yang, Bin. Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS). United States: N. p., 2015. Web. doi:10.1007/s10570-015-0588-0.
Zhang, Libing, Lu, Zhou, Velarde Ruiz Esparza, Luis A., Fu, Li, Pu, Yunqiao, Ding, Shi-You, Ragauskas, Art J., Wang, Hongfei, & Yang, Bin. Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS). United States. doi:10.1007/s10570-015-0588-0.
Zhang, Libing, Lu, Zhou, Velarde Ruiz Esparza, Luis A., Fu, Li, Pu, Yunqiao, Ding, Shi-You, Ragauskas, Art J., Wang, Hongfei, and Yang, Bin. Tue . "Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)". United States. doi:10.1007/s10570-015-0588-0.
@article{osti_1182941,
title = {Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)},
author = {Zhang, Libing and Lu, Zhou and Velarde Ruiz Esparza, Luis A. and Fu, Li and Pu, Yunqiao and Ding, Shi-You and Ragauskas, Art J. and Wang, Hongfei and Yang, Bin},
abstractNote = {Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.},
doi = {10.1007/s10570-015-0588-0},
journal = {Cellulose, 22(3):1469-1484},
number = ,
volume = ,
place = {United States},
year = {Tue Mar 03 00:00:00 EST 2015},
month = {Tue Mar 03 00:00:00 EST 2015}
}
  • Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.« less
  • The emergence of sub-wavenumber high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BBSFG-VS) [Velarde et al., J. Chem. Phys., 2011, 135, 241102] has offered new opportunities in obtaining and understanding the spectral lineshape and temporal effects on the surface vibrational spectroscopy. Particularly, the high accuracy in the HR-BBSFG-VS spectral lineshape measurement provides detailed information on the complex coherent vibrational dynamics through spectral measurement. Here we present a unified formalism of the theoretical and experimental approaches for obtaining the accurate lineshape of the SFG response, and then present a analysis on the higher and lower spectral resolution SFG spectra as well as theirmore » temporal effects of the cholesterol molecules at the air/water interface. With the high spectral resolution and accurate lineshape, it is shown that the parameters from the sub-wavenumber resolution SFG spectra can be used not only to understand but also to quantitatively reproduce the temporal effects in the lower resolution SFG measurement. These not only provide a unified picture in understanding both the frequency-domain and the time-domain SFG response of the complex molecular interface, but also provide novel experimental approaches that can directly measure them.« less
  • Even though in principle the frequency-domain and time-domain spectroscopic measurement should generate identical information for a given molecular system, inhomogeneous character of surface vibrations in the sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with the time-domain SFGVS by mapping the decay of the vibrational polarization using ultrafast lasers, due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough line shape. Here with recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) we show that the inhomogeneous line shape can be obtained in the frequency-domain, for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuirmore » monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay (FID) results can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 + * 0.01 cm-1 with a total line width of 10.9 + - 0.3 cm-1 at half maximum. The Lorentzian contribution accounts only for 4:7 + -0:4 cm-1 to this width and the Gaussian (inhomogeneous) broadening for as much as 8:1+*0:2 cm-1. Polarization analysis of the -CN spectra showed that the -CN group is tilted 57 + - 2 degrees from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accomodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.« less