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Amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives: self-assembly and rheological behaviour in aqueous solution

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Abstract

The self-assembly of amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives (CCMCs) from individual molecules to self-aggregates, in addition to their rheological behaviour in aqueous solution were investigated. The conformations of the individual CCMC individual molecules and self-aggregates, and the microstructures of CCMC self-aggregates were characterized using the static and dynamic light scattering analyses, and the steady fluorescence technology. The results showed that the individual CCMC chains became compact, and aqueous NaCl solution changed from an approximate θ solvent to a bad one when the number of hydrophobic cholesteryl groups increased. The CCMC self-aggregates exhibited as compact spheres. The microstructural characterization indicated that one CCMC self-aggregate consisted of multiple individual CCMC molecules and hydrophobic microdomains, and multiple cholesteryl groups self-associated into one hydrophobic microdomain. The atomic force microscopy images of CCMC self-aggregates in phase mode showed that the multiple interior hydrophobic phase separation regions were surrounded by hydrophilic polysaccharide chains, providing an evidence for multiple hydrophobic microdomains in one self-aggregate. The rheological analysis proved that the CCMC self-aggregates were a microgel, in which the associations of cholesteryl groups provided multiple cross-linking points in the polymer network. The microgel solutions displayed a unique thixotropy and a shear thinning behaviour.

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Abbreviations

A 2 :

The second virial coefficient

AFM:

Atomic force microscopy

CAC:

Critical aggregation concentration

CMC:

Carboxymethylcellulose

CCMC:

Cholesteryl-bearing carboxymethylcellulose derivatives

DCC:

N,N′-dicyclohexylcarbodiimide

DLS:

Dynamic light scattering

DMAP:

4-(N,N′-dimethylamino)pyridine

DMSO:

Dimethyl sulfoxide

DS chol :

Degree of substitution by cholesteryl groups

G′ :

The storage modulus

G′′ :

The loss modulus

HEC:

Hydroxyethyl cellulose

HPC:

Hydroxypropyl cellulose

MC:

Methylcellulose

M w :

The weight averaged molecular weight

N CCMC :

The aggregation number of CCMC molecules per one self-aggregate

N chol :

The aggregation number of cholesteryl groups per one microdomain

N domain :

The number of the hydrophobic microdomains per one CCMC self-aggregate

R g :

The radius of gyration

SLS:

Static light scattering

pTSA:

p-Toluenesulfonic acid

ω :

The frequency

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (No.20574089 and No.30470476), the Foundation of the Key Laboratory of Cellulose and Lignocellulosics Chemistry from the Chinese Academy of Sciences, and Co-operation Project of Science and Technology between Governments of China and Japan from the Ministry of Science and Technology of the People’s Republic of China.

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Authors and Affiliations

  1. Institute of Polymer Science, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, P.R. China

    Liqun Yang, Jianliang Kuang, Zhiquan Li, Bifang Zhang, Xiang Cai & Li-Ming Zhang

  2. Key Laboratory of Cellulose and Lignocellulosics Chemistry, Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou, 510650, China

    Liqun Yang

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  1. Liqun Yang
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  2. Jianliang Kuang
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Correspondence to Liqun Yang.

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Yang, L., Kuang, J., Li, Z. et al. Amphiphilic cholesteryl-bearing carboxymethylcellulose derivatives: self-assembly and rheological behaviour in aqueous solution. Cellulose 15, 659–669 (2008). https://doi.org/10.1007/s10570-008-9218-4

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