Cationic surface functionalization of cellulose nanocrystals

The surface of cellulose nanocrystals, prepared by sulfuric acid hydrolysis of cotton, was rendered cationic through a reaction with epoxypropyltrimethylammonium chloride. The resultant nanocrystal suspensions were characterized by ζ-potential, conductometric titration and polarized light microscopy. Atomic force microscopy (AFM) showed no change in the size or shape of the nanocrystals, but the functionalization process reversed the surface charge and led to a reduction of the total surface charge density. These modifications led to stable aqueous suspensions of nanocrystalline cellulose with unexpected gelling and rheological properties. Shear birefringence was observed, but no liquid crystalline chiral nematic phase separation was detected.

[1]  Redouane Borsali,et al.  Rodlike Cellulose Microcrystals: Structure, Properties, and Applications , 2004 .

[2]  V. Rudraraju,et al.  Rheological characterization of Microcrystalline Cellulose/Sodiumcarboxymethyl cellulose hydrogels using a controlled stress rheometer: part I. , 2005, International journal of pharmaceutics.

[3]  J. W. Goodwin,et al.  Rheology for Chemists: An Introduction , 2008 .

[4]  F. Morehead,et al.  Some hydrodynamic properties of neutral suspensions of cellulose crystallites as related to size and shape , 1961 .

[5]  Alain Dufresne,et al.  Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. , 2005, Biomacromolecules.

[6]  D. Gray,et al.  Effects of Ionic Strength on the Isotropic−Chiral Nematic Phase Transition of Suspensions of Cellulose Crystallites , 1996 .

[7]  A. Dufresne,et al.  Preparation of Cellulose Whiskers Reinforced Nanocomposites from an Organic Medium Suspension , 2004 .

[8]  M. Roman,et al.  Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. , 2005, Biomacromolecules.

[9]  O. Ikkala,et al.  Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. , 2007, Biomacromolecules.

[10]  M. Sefton,et al.  Poloxamine hydrogels with a quaternary ammonium modification to improve cell attachment. , 2005, Journal of biomedical materials research. Part A.

[11]  B. Chabert,et al.  Immobilization of residual dyes onto ion-exchanger cellulosic materials , 2000 .

[12]  D. Gray,et al.  Induced phase separation in low-ionic-strength cellulose nanocrystal suspensions containing high-molecular-weight blue dextrans. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[13]  D. Gray,et al.  Effect of Counterions on Ordered Phase Formation in Suspensions of Charged Rodlike Cellulose Crystallites , 1997 .

[14]  V. Fávere,et al.  Preparation and characterization of quaternary chitosan salt: adsorption equilibrium of chromium(VI) ion , 2004 .

[15]  V. Rudraraju,et al.  Rheology of Microcrystalline Cellulose and Sodiumcarboxymethyl Cellulose hydrogels using a controlled stress rheometer: part II. , 2005, International journal of pharmaceutics.

[16]  D. Gray,et al.  Induced phase separation in cellulose nanocrystal suspensions containing ionic dye species , 2006 .

[17]  Janne Laine,et al.  Cellulose nanocrystal submonolayers by spin coating. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[18]  M. Vignon,et al.  Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO-mediated oxidation , 2005 .

[19]  Daisuke Tatsumi,et al.  Effect of Fiber Concentration and Axial Ratio on the Rheological Properties of Cellulose Fiber Suspensions , 2002 .

[20]  D. Gray,et al.  Influence of dextran on the phase behavior of suspensions of cellulose nanocrystals , 2002 .

[21]  H. Barnes,et al.  An introduction to rheology , 1989 .

[22]  Thomas Heinze,et al.  Cationic Xylan Derivatives with High Degree of Functionalization , 2005 .

[23]  B. Rånby Fibrous macromolecular systems. Cellulose and muscle. The colloidal properties of cellulose micelles , 1951 .

[24]  W. Winter,et al.  Nanocomposites of Cellulose Acetate Butyrate Reinforced with Cellulose Nanocrystals , 2002 .

[25]  M. Vignon,et al.  TEMPO-mediated surface oxidation of cellulose whiskers , 2006 .

[26]  Takeshi Okano,et al.  Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose , 1998 .

[27]  A. Žemaitaitis,et al.  Peculiarities of Starch Cationization with Glycidyltrimethylammonium Chloride , 2006 .

[28]  Takayoshi Matsumoto,et al.  Rheological properties and molecular structure of tunicate cellulose in LiCl/1,3-dimethyl-2-imidazolidinone. , 2004, Biomacromolecules.

[29]  William J. Orts,et al.  Enhanced Ordering of Liquid Crystalline Suspensions of Cellulose Microfibrils: A Small Angle Neutron Scattering Study , 1998 .

[30]  G. Maret,et al.  Chiral nematic suspensions of cellulose crystallites; phase separation and magnetic field orientation , 1994 .

[31]  J. Araki,et al.  Steric Stabilization of a Cellulose Microcrystal Suspension by Poly(ethylene glycol) Grafting , 2001 .

[32]  Enyong Ding,et al.  Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups , 2007 .

[33]  Hua Dong,et al.  New nanocomposite materials reinforced with flax cellulose nanocrystals in waterborne polyurethane. , 2007, Biomacromolecules.

[34]  Shigenori Kuga,et al.  Surface acylation of cellulose whiskers by drying aqueous emulsion. , 2006, Biomacromolecules.