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Enzymatic modifi cation of polyacrylonitrile and cellulose acetate fi bres 113


            fabrics treated with nitrilase without additives). Further assays without
            additives were performed to study the progression of the modifi cation of
            PAN catalysed by nitrilase over a maximum period of 36 h, at 40 °C and pH
            7.8. The conversion of nitrile groups into carboxylic groups was followed
            by the release of ammonia and by improvement in the basic staining with

            methylene blue (Fig. 5.6). There was no significant ammonia release before
            8 h of treatment; after this point a linear release of ammonia was verifi ed
            which implies the absence of activity decay during the 36 h of treatment.
            The values of K/S, represented as a percentage of the initial value, demon-
            strated a varying behaviour with time, the maximum K/S value was observed
            for a treatment over eight hours and it corresponded to a relative K/S of
            135%. The increase in carboxylic groups, evaluated by K/S was not steady
            during the 36 h of treatment. Instead, a succession of K/S values higher and
            lower than the controls, creating an oscillating pattern, was observed. The
            hypothesis proposed is that somehow the groups left the surface of the

            fabric. This was confirmed when PAA was determined in the treatment
            solutions (Fig. 5.6). A hypothetical model of surface erosion of acrylics was

                                      Total nitrogen
                                      Relative K/S
                30                    Polyacrylic acid         160      100
                                                               150
                                                                        90
                                                               140
                25                                             130      80
                                                               120      70
              Total nitrogen (mg l –1 )  15                    100  Relative K/S (l max = 660 nm) (%)  60 Polyacrylic acid (mg l –1 )
                                                               110
                20
                                                               90
                                                               80
                                                                        50
                                                               70
                                                                        40
                                                               60
                10
                                                               50
                                                               40       30
                 5                                             30       20
                                                               20
                                                                        10
                                                               10
                 0                                             0        0
                   0    5    10    15   20    25   30   35    40
                                     Time (h)
                   5.6  Total nitrogen and polyacrylic acid concentrations in solution, and
                   relative K/S values for acrylic fabric samples as a function of reaction
                   time. The acrylic samples were treated with 412 U of nitrilase per
                   gram of fabric, at pH 7.8 and 40 °C. Samples and controls were
                   competitively coloured at 70 °C with Basic Blue 9, C.I. 52015, and
                   relative K/S values were calculated as K/S enzyme/K/S control (%) (adapted
                   from Matamá et al., 2007).




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