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Liquid Crystals of Cellulosics: Fascinating Ordered Structures for the Design of Functional Material Systems

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Cellulose Chemistry and Properties: Fibers, Nanocelluloses and Advanced Materials

Part of the book series: Advances in Polymer Science ((POLYMER,volume 271))

Abstract

This article surveys progress in both fundamental and applied research related to cellulosic liquid crystals, mainly of chiral nematic order. These liquid crystals are divided into two different classes, namely cellulosic macromolecules and cellulose nanocrystals (CNCs), depending on the mesogenic constituent. We start with a review of the fundamental and chiroptical characteristics of molecular liquid crystals of representative cellulose derivatives and then discuss recent efforts on the design and construction of functional material systems (such as stimuli-sensitive optical media and novel hybrids with minerals). These systems make use of the liquid crystalline molecular assembly of cellulosics. The survey of the other class of cellulosic liquid crystals deals with colloidal suspensions of CNCs obtained by acid hydrolysis of native cellulose fibers. Following the review of fundamental aspects related to the isotropic–anisotropic phase separation behavior of CNC suspensions, attention is directed to current applications of free-standing colored films, polymer composites reinforced with CNCs as mesofiller, and inorganic hybridizations using CNC chiral nematics as template. Some comments and the outlook for future explorations are also offered.

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Abbreviations

(E-CE)C:

Ethyl cyanoethyl cellulose

3-CF3-CTC:

Cellulose 3-(trifluoromethyl)phenycarbamate

3-Cl-CPC:

Cellulose 3-chlorophenylcarbamate

4-Cl-CPC:

Cellulose 4-chlorophenylcarbamate

5FPEC:

Pentafluoropropionyl ethyl cellulose

AA:

Acetic acid

AEC:

Acetyl ethyl cellulose

AGU:

Anhydroglucose unit

APC:

Acetoxypropyl cellulose

ATBC:

Amylose tris(n-butylcarbamate)

ATEC:

Amylose tris(ethylcarbamate)

ATHC:

Amylose tris(n-hexylcarbamate)

ATPC:

Aamylose triphenylcarbamate

ATRP:

Atom transfer radical polymerization

BC:

Bacterial cellulose

BEC:

Butyryl ethyl cellulose

CD:

Circular dichroism

ChtNC:

Chitin nanocrystal

CNC:

Cellulose nanocrystal (or nanocrystallite)

CPC:

Cellulose phenylcarbamate

CTC:

Cellulose triphenylcarbamate (or tricarbanilate)

CtsPC:

Chitosan phenylcarbamate

DCA:

Dichloroacetic acid

DEME:

Diethylene glycol monoethyl ether

DEMM:

Diethylene glycol monomethyl ether

DMA:

Dynamic mechanical analysis

DMAc:

N,N-Dimethylacetamide

DMF:

N,N-Dimethyformamide

DMSO:

Dimethyl sulfoxide

DPs :

Degree of polymerization (or polyaddition) in the side chain

DS:

Degree of substitution

DSacyl :

Degree of acyl substitution

EC:

Ethyl cellulose

FTIR:

Fourier transform infrared spectroscopy

HAp:

Hydroxyapatite

HPC:

Hydroxypropyl cellulose

IL:

Ionic liquid

IPN:

Interpenetrating network

LCST:

Lower critical solution temperature

MS:

Molar substitution

ORD:

Optical rotatory dispersion

P :

Chiral nematic (or cholesteric) pitch

PAA:

Poly(acrylic acid)

PEC:

Propionyl ethyl cellulose

PEDOT:

Poly(3,4-ethylenedioxythiophene)

PEG:

Poly(ethylene glycol)

PEO:

Poly(ethylene oxide)

PHEMA:

Poly(2-hydroxyethyl methacrylate)

POM:

Polarized optical microscope

PVP:

Poly(N-vinyl pyrrolidone)

SEM:

Scanning electron microscope

T c :

Cloud point

TEM:

Transmission electron microscope

TEMPO:

2,2,6,6-Tetramethylpiperidine-1-oxyl

TEOS:

Tetraethyl orthosilicate (or Tetraethoxysilane)

T g :

Glass transition temperature

THF:

Terahydrofuran

T i :

Isotropization temperature

TMOS:

Tetramethl orthosilicate (or Tetramethoxysilane)

TRIMM:

Triethylene glycol monomethyl ether

WAXD:

Wide angle X-ray diffraction

λ M :

Wavelength of maximum light reflectance

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Acknowledgements

One of the authors (YN) is grateful to Professor O. J. Rojas of Aalto University for his encouragement and helpful suggestions as well as for his kind invitation to contribute to this special volume. The authors also wish to convey many thanks to Professor Y. Teramoto of Gifu University, and to the graduate students K. Horikiri, T. Ogiwara, and T. Hirata in our laboratory for their assistance in the preparation of this chapter.

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Authors and Affiliations

  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kyoto, 606-8502, Japan

    Yoshiyuki Nishio, Junichi Sato & Kazuki Sugimura

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  1. Yoshiyuki Nishio
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  2. Junichi Sato
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  3. Kazuki Sugimura
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Correspondence to Yoshiyuki Nishio .

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Editors and Affiliations

  1. Departments of Forest Biomaterials and Chemical and Biomolecular Engineering; Bio-based Colloids and Materials (BiCMat) Department of Forest Products Technology School of Chemical Technology, North Carolina State University; Aalto University, Espoo, FInland, Raleigh, North Carolina, USA

    Orlando J. Rojas

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Nishio, Y., Sato, J., Sugimura, K. (2015). Liquid Crystals of Cellulosics: Fascinating Ordered Structures for the Design of Functional Material Systems. In: Rojas, O. (eds) Cellulose Chemistry and Properties: Fibers, Nanocelluloses and Advanced Materials. Advances in Polymer Science, vol 271. Springer, Cham. https://doi.org/10.1007/12_2015_308

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