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Enzymatic functionalization of cellulosic fi bres for textiles   277



            onto cellulosic fibres in water results in gentle, surface-specifi c  chemical
            functionalization (Fig. 11.3, Step b). The incorporation of XGO-R into XG
            by the enzyme is essential since, as discussed above, short XG oligosaccha-

            rides do not have a signifi cant  affinity for cellulose. Thus, the extended
            polysaccharide chain of the XG-R product functions as a molecular anchor,
            the length of which can be adjusted by the molar ratio of XG to XGO-R.
            The functional group density on the cellulosic surface can therefore be
            controlled either by adjusting the length of the XG-R anchoring tail, or
            varying the loading amount of XG-R with respect to the cellulose. Depend-
            ing upon the nature of the  R group, further elaboration of the surface
            chemistry is possible (Fig. 11.3, step c).
              Our initial proof-of-concept work (Brumer et al., 2004) focused on the

            well-known fl uorophore  fluorescein, which was conjugated to aminated
            XGOs (XGO-NH 2 ) by reaction with fl uorescein isothiocyanate (FITC) to
            yield XGO–FITC. XET-catalyzed incorporation of XGO–FITC into XG,
            following the scheme shown in Fig. 11.3, produced XG–FITC. Both the
            enzyme-catalyzed production and binding of XG–FITC to the model cotton

            cellulose substrate Whatman No. 1 filter paper were extensively character-
            ized. To demonstrate the substrate versatility of the method, XG–FITC was

            adsorbed onto regenerated cellulose films and a XG–sulforhodamine con-
            jugate (XG–SR) was bound to regenerated cellulose fi bres (Brumer et al.,
            2004).


            Functionalized xyloglucan (XG-R) for the activation of cellulosic surfaces

            Although the production of yellow paper and pink fibres is somewhat

            trivial, the established methodology has a certain industrial relevance. The

            attachment of dyes and fluorophoric optical brightening agents (OBA) is
            widespread in both the paper and textile industries, whereas retention of

            these small organic molecules on cellulosic fibres is sometimes poor. Indeed,
            our laboratory collaborated with a large industrial wood pulp producer to
            test the potential of the XET/XG system to increase the efficiency of OBA

            retention. To this end, we generated a sulfated aminostilbene derivative of
            XG (XG–OBA) using XET, and demonstrated that it was quantitatively
            bound to pulp fibres, producing a dosage-dependent UV brightening effect

            (Fig. 11.5). Notably, the XG–OBA was retained on the pulp even after harsh
            mechanical refi ning  (Zhou et al., 2006b and Brumer  et al., unpublished
            results).
              Although inclusion of the final functionality on XG before cellulose

            binding may be preferred in some applications, in many cases it is desirable
            to produce activated (or activatible) cellulose surfaces that are capable of
            further reactions. As mentioned above, the amino group provides such a

            chemical handle for further elaboration, and cellulosic fibres activated with



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