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Enzymatic functionalization of cellulosic fi bres for textiles   267


            following liberation from the plant tissue source. This may involve selec-
            tive removal of components, such as associated lignin, hemicelluloses and
            extractives, by pulping and bleaching chemicals to improve the optical

            properties of the final paper or textile product. Realization of the full

            potential of cellulosic fibres, however, requires the addition of chemistry
            to the fibre surface in many applications. Some common examples

            include the application of strength-building compounds, retention aids,

            hydrophobic molecules, and inorganic fillers during papermaking, as
            well as the binding of dyes, optical brighteners, and sizing agents to textile

            fibres and fabrics. Clearly, the need for surface functionalization extends

            to high performance products based on cellulose fibres, such as  ‘smart’
            textiles, electronic paper, cellulosic biocomposite materials, and biomedical
            devices.
              Indeed, a wide range of classical chemical methods have been developed
            to modify cellulosic fibre surfaces, either through physical adsorption or

            direct covalent attachment of molecules. Although powerful, the covalent
            derivatization of cellulose has certain limitations. Cellulose polysaccharide
            chains exist as insoluble, paracrystalline aggregates, which are characterized
            by low reactivity of the tightly hydrogen-bonded hydroxyl groups. Further,
            extensive reaction of these same hydroxyl groups leads to disruption of
            cellulose crystallinity, chain degradation, and, ultimately, a loss of fi bre
            strength (Sassi and Chanzy, 1995; Sassi et al., 2000; Klemm et al., 2005). In
            some cases, reactions may require non-aqueous media, thus necessitating a
            solvent exchange or drying step, which may result in altered cellulose mor-
            phology or be technically impractical on a large scale. These concerns are
            particularly relevant for cellulosic hydrogels, such as bacterial cellulose or
            microfibrillated cellulose/nanocellulose suspensions, which are emerging as

            promising new biomaterial templates (Bodin et al., 2006, 2007a, 2007b;
            Henriksson et al., 2008; Iwamoto et al., 2005; Nakagaito and Yano, 2005;
            Yano et al., 2005).
              With the potential of cellulosic fibre functionalization in focus, a number

            of years ago our laboratory began work on a biomimetic approach to cir-
            cumvent the inherent challenges of direct chemical approaches. In this
            approach, the strong interaction of cellulose with the cell-wall-matrix poly-
            saccharide xyloglucan (XG) was harnessed, together with the unique cata-
            lytic properties of an endogenous plant transglycosylating enzyme,
            xyloglucan  endo-transglycosylase (XET).  The subsequent sections will
            provide an overview of some of the basic biochemistry of XG and XET in
            the context of the plant cell wall, and highlight how this system has been
            appropriated, in conjunction with organic chemistry, to install a range of

            functional groups on cellulose fibres. The practical application of this system
            has a strong foundation in the historical use of native XG as a sizing agent
            in textile and paper industries.




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