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

Mohamadamin Makarem, Daisuke Sawada, Hugh M. O'Neill, Christopher M. Lee, Kabindra Kafle, Yong Bum Park, Ashutosh Mittal, Seong H. Kim

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

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. 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.

Original languageEnglish (US)
Pages (from-to)10249-10257
Number of pages9
JournalJournal of Physical Chemistry C
Volume121
Issue number18
DOIs
StatePublished - May 11 2017

Fingerprint

Alkalies
cellulose
Cellulose
alkalies
Cells
Crystalline materials
matrices
methylidyne
Crystals
Vibrational spectra
Hydroxyl Radical
Spectroscopy
cancellation
crystals
Molecules
dipoles
symmetry
spectroscopy

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

@article{de06785b46f64dd2bb65246908e783a1,
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",
abstract = "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. 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.",
author = "Mohamadamin Makarem and Daisuke Sawada and O'Neill, {Hugh M.} and Lee, {Christopher M.} and Kabindra Kafle and Park, {Yong Bum} and Ashutosh Mittal and Kim, {Seong H.}",
year = "2017",
month = "5",
day = "11",
doi = "10.1021/acs.jpcc.7b02770",
language = "English (US)",
volume = "121",
pages = "10249--10257",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "18",

}

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. / Makarem, Mohamadamin; Sawada, Daisuke; O'Neill, Hugh M.; Lee, Christopher M.; Kafle, Kabindra; Park, Yong Bum; Mittal, Ashutosh; Kim, Seong H.

In: Journal of Physical Chemistry C, Vol. 121, No. 18, 11.05.2017, p. 10249-10257.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Dependence of Sum Frequency Generation (SFG) Spectral Features on the Mesoscale Arrangement of SFG-Active Crystalline Domains Interspersed in SFG-Inactive Matrix

T2 - A Case Study with Cellulose in Uniaxially Aligned Control Samples and Alkali-Treated Secondary Cell Walls of Plants

AU - Makarem, Mohamadamin

AU - Sawada, Daisuke

AU - O'Neill, Hugh M.

AU - Lee, Christopher M.

AU - Kafle, Kabindra

AU - Park, Yong Bum

AU - Mittal, Ashutosh

AU - Kim, Seong H.

PY - 2017/5/11

Y1 - 2017/5/11

N2 - 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. 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.

AB - 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. 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.

UR - http://www.scopus.com/inward/record.url?scp=85020620292&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85020620292&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.7b02770

DO - 10.1021/acs.jpcc.7b02770

M3 - Article

AN - SCOPUS:85020620292

VL - 121

SP - 10249

EP - 10257

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 18

ER -