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cellulase

cellulase

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N O TE
R e la tio n s h ip B e tw e e n C e llu la s e T r e a tm e n t a n d D ir e c t D y e D y e in g
fo rC o tto n
IN T R O D U C T IO N
I n o r d e r t o u tiliz e
cellulase in the finishing of cellulose
m a te ria ls s u c h
a s c o tto n
fabric, th e
effect of
c e llu la s e

treatm ent on th e dyeability of th e m aterials m ust be stud- ied. H ow ever, system atic studies cannot be found in this fie ld . M o s t r e c e n tly , t h e c e llu lo s e w h ic h

w a s p re v io u s ly
d y e d w ith re a c tiv e d y e s , w a s h y d ro ly z e d b y c e llu la s e fo r
a n a ly tic a l p u rp o s e .'
Cellulase includes different types of enzym e such as
e x o -
a n d
e n d o -P -g lu c o x id a s e s .'
T hey
s h o w
d iffe re n t
m echanism s of hydrolysis' an d their roles w ere discussed
in connection w ith th e m icrostructure of cellulose.'

C e llu la se is a p o ly m e r. T h e re fo re , th e re is o n e p o ssi- b ility t h a t h y d ro ly s is b y c e llu la s e c o u ld o c c u r o n ly in t h e disordered region of cellulose, due to steric hindrance. In a d d itio n , i t is in te re s tin g t o e v a lu a te t h e e x te n t o f h y d ro - ly s is o f c e llu lo s e , w h ic h w a s p re v io u s ly d y e d w ith d ir e c t d y e s , b y c e llu la s e .

F ro m

th e s e p o in ts of v ie w , c o tto n fa b ric s tre a te d w ith c e llu la se w e re d y e d w ith C o n g o R e d a n d a lso c o tto n fa b ric s d y e d w ith s e v e ra l d ir e c t d y e s w e re h y d ro ly z e d w ith c e l- lu la s e .

E X P E R IM E N T A L
M a te r ia ls
C otton fabric used w as0 .0 2 1 cm
thick and w eighed
1 0 8
g /m '.
C o u n ts o f w a rp a n d w eft fo r th e fa b ric w ere1 9 a n d
1 8 te x , re s p e c tiv e ly . T h r e a d s p e r c m
for th e fabric w ere
3 2in e n d s a n d 2 7 in picks, respectively. T he fabric w as
p u rifie d w ith a q u e o u s s o lu tio n of 0 .2 % nonionic surfactant
a t40\u00b0C before cellulase treatm ent.
C ongo R ed (C .I. D irect R ed2 8 )used w as of specific
reagent grade. C hrysophenine (C .I.D irect Y ellow1 1 )a n d
J o u r n a lo f A p p lie d P o ly m e r S c ie n c e , V o l. 4 5 , 1869-1872 (1992)
0
1 9 9 2J o h n W iley&
Sons,I n c .
C C C 0 0 Z l-8 9 9 5 /9 2 /1 0 1 8 6 9 -0 4 $ 0 4 .0 0
C hrysam ine (C .I. D irect Y ellow
1 )w ere purified by the
R o b in s o n -M ills
m e th ~ d .~
C o m m e rc ia l c e llu la s e ( M e ic e la s e ) w a s k in d ly g iv e n b y
M eiji S eik a C o. L td . T h is is from
T r ic h o d e r m a v ir id ea n d
w as used
w ith o u t f u r th e r p u rific a tio n .
C a rb o x y m e th y l-
c e llu la s e a c tiv ity w a s2 3 3 ,0 0 0u n its /g
a sd e te rm in e d b y
th e
N elson-Som ogyi
rn e th ~ d .~
O ne
u n it
o f
c a rb o x y -
m e th y lc e llu la s e
w as
d e fin e d
a s th e
am ount of
enzym e
w h ic h lib e ra te1 0 y g of g lu c o s e e q u iv a le n ts p e r1 0 m in u te s .
C e llu la s e T r e a tm e n t
A bout 0 .2 g of the sam ples w as treated w ith an aqueous
solution of 0 .2 % cellulase under the condition of pH
4 .5 ,

40"C, and a liquor to sam ple ratio of1 :lO Ofo r a g iv e n tim e. A fter the treatm ent, the cellulase w as inactivated in t h e b o ilin g w a te r. T h e s a m p le s w e re t h e n n e u tra liz e d w ith

0 .0 3 %
a m m o n iu m
a q u e o u s
s o lu tio n , th o ro u g h ly
w a s h e d w ith d e io n iz e d a n d d is tille d w a te r , a n d d rie d .
W e ig h tL o s s M e a s u re m e n ts
W e ig h t
lo s s
(W L ) was
c a lc u la te d
fro m
th e
fo llo w in g
e q u a tio n :
w
-W '
W
W L (% )=
~
x
100
(1 )
w hereW

an dW ' are w eights of the sam ples before and after cellulase treatm en t, respectively. T h e sam ples w ere d rie da t85\u00b0C for2 4 h before m easurem ent.

D y e in g M e th o d
A bout 0 .2 g of the fabrics w ere dyed to equilibrium

u n d e r t h e c o n d itio n s ofaliquor to sam ple ratio of1:1 0 0 and 0 .0 5 N of N aC 1. D y ein g te m p e ra tu re s w ere in th e ra n g e of 7 0 -9 0 \u00b0C . D y e in g p e rio d s w e re2 4 ,7 2 ,a n d 1 2 0h at 7 0 ,8 0 , a n d 9 0 \u00b0 C , re s p e c tiv e ly .

1869
1870
JO U R N A L
O F
A P P L IE D
PO LY M ER
S C IE N C E , V O L .4 5
(1 9 9 2 )
-1 .2
-m
Y
.. -
5
- l . L
m8
--2m -1 .6 .
0
- I
C a lc u la tio n M e th o do f A ffin ityo f D y e in g -A p e
-A p o
of the dye w as represented by the follow ing equa-
ti~ n :~

w here[ D ]4= dye uptake of the fiber (g ion/kg), w hich w a s o b ta in e d h e re u s in g c o lo rim e tric a n a ly s is of re s id u a l s o lu tio n ,[ N a ]4= N a + c o n c e n tra tio n in th e fib e r ( g io n / k g ),[D ]u

=
dye concentration in residual solution
( g
io n /L ),[N a]u
=N a + c o n c e n tra tio n in re sid u a l s o lu tio n
( g
io n /L ),
z
=
num ber of
N a
i n
a
d y e
m o le c u le ,
V
=
e ffe c tiv e v o lu m e t e r m
o f m o le c u le s o f d y e in g fo r t h e
fib e r,R
=
g a s c o n s t a n t 1 .9 9X
c a l/d e g , a n dT= a b -
s o lu te te m p e ra tu re .
[N a ]4 w a s c a lc u la te d b y=
V [N aIi
(3 )
w h e re[ N a I i is t h e N a + c o n c e n tra tio n in t h e e ffe c tiv e v o l-
um e of th e fiber.
RESULTS A N D
D IS C U S S IO N
T h e C h a n g e in D y e U p ta k e b y P re c e d in g T re a tm e n t
w ith C e llu la s e
W L of th e fabrics increased linearly w ith an increase in
tre a tin g tim e w ith cellu lase, a t least, u p to2 4 h. W L ob-
-1 .7 0
7J
-E " 1 .6 0 .
.-m
V
Y
-
1.50.
r
.
0
c
z
1.40.
>C
K-
I-'
+
130.
1 .2 0 '
'
2 .7 5
2 .8 0
2 .8 5
2 .9 0
2 .9 5
I / T
lo 3
(
~
-
1
)
F ig u r e2
(-A p e /T+RI n V * + l )p l o t s a g a i n s t1/ T f o r
u n tre a te d fa b ric a n d c e llu la s e -tre a te d fa b ric w ith
1 7 .7 %
w e ig h t lo ss. A b b re v ia tio n s a r e in c lu d e d in th is a rtic le .

ta in e d b y th e tre a tm e n t fo r4a n d2 4 h w a s 4 .2 a n d 1 7 .7 % , re s p e c tiv e ly . U n tr e a te d fa b ric a n d c e llu la s e tr e a te d fa b ric s w ith W L a b o v e w e re d y e d t o e q u ilib riu m

w ith C o n g o R e d
a t 9 0 \u00b0 C a n d a t t h e in itia l d y e c o n c e n tra tio n o f4X
g ion/L . W e attem pted first to calculate apparent values
o f-A po for th ese fabrics; from
eq.(2 ) using a constant
v a lu e0 .2 2L /k g
o fV .6 .7-A p o
c a lc u la te d w e re8 .1 5 , 8 .0 6 ,
a n d8 .2 5 k c a l/m o l fo r0 %
( u n t r e a t e d ) ,4 .2 % , a n d 1 7 .7 %
o f W L , re s p e c tiv e ly .

It is clear th at th e m icrostructure of cellulose changes b y c e llu la s e -c a ta ly z e d h y d ro ly tic c le a v a g e . If t h e c le a v a g e c a u s e s

a
c h a n g e
i n
-A p e ,-A p o
w o u ld
m o n o to n o u s ly

c h a n g e in th e s a m e d ire c tio n w ith in c re a s in g W L . H o w - e v e r,-A poo b ta in e d a b o v e is n o t c o n s is te n t w ith t h i s a s - sum ption. It can be assum ed th at th e change in V accom - p a n ie d b y

c e llu la s e t r e a t m e n t w o u ld p la y
a n im p o rta n t
role in the change in apparent value of -A p o
c a lc u la te d
a b o v e .

I f-A po is a p p ro x im a te ly c o n s ta n t re g a rd le ss of c e l- lu la se tre a tm e n t a n dasuitable valuei s takena s Vo,the re la tiv e v a lu eo fV e /V o c a n b e o b ta in e d u s in g e q . (2 ) b y n u m e ric a l c a lc u la tio n , w h e re

Vo a n d
V, are
V 's
fo r u n -
tr e a te d a n d c e llu la s e -tre a te d fa b ric s , re sp e c tiv e ly .
D y e in g is o th e rm s a t 9 0 \u00b0 C w e re o b ta in e d fo r u n tre a te d
fa b ric a n d c e llu la s e -tre a te d fa b ric h a v in g
1 7 .7 %
of W L .
L in e a r re la tio n s h ip b e tw e e n

lo g [D ] 4 a n d lo g [D ]u c a n b e o b s e rv e d fo r e a c h fa b ric , a s s h o w n in F ig u re1 .Iso th erm s o b e y F re u n d lic h ty p e '

regardless of the treatm ent. T w o slopes observed here w ere nearly 0 .3 .It w as suggested th a t the dye adsorption m echanism

m ig h t be sim ilar for u n -
tre a te d a n d c e llu la s e -tre a te d fa b ric s.

T he change in enthalpy of dyeing w ould give one of th e m ost im portant criteria' to estim ate th e change in th e nature of the interaction betw een dye m olecule and bind- ing site of cellulose,caused by cellulase treatm en t.( -A po/

T+R I n V 2 + l )c a n b e p l o t t e d a g a i n s t1/T f r o m e q . (2 ).
N O T E
1871

T h e p lo ts fo r u n tre a te d fa b ric a n d c e llu la s e -tre a te d fa b ric w ith1 7 .7 % W L are show n in Figure 2 . T h e lin e a r lin e c a n be observed for each fabric, an d th e tw o slopes observed, w hich are enthalpy of dyeing, are nearly equal.

T h e a b o v e e x p e rim e n ta l re s u lts re g a rd in g d y e in g iso -
th e rm
a n d e n th a lp y o f d y e in g a r e c o in c id e n t w ith t h e a s -
s u m p tio n th a t
-A p o
may be nearly equal for cellulase-
tre a te d a n d u n tre a te d fa b ric s.
T h e fa b ric s h a v in g v a rio u s
v a lu e s o f W L

were dyed w ith C o n g o R e d a t9 0 \u00b0 C a n da t a n in itia l d y e c o n c e n tra tio n o f4

X
g io n /L , a n d th e n
V e /V ow a s o b ta in e d fo r

e a c h s a m p le . C a lc u la tio n o f V e /V ow as done using 0 .2 2 L / kg ofV o,on the assum ption that-A po m ay be constant regardless of the extent of hydrolysis. V e /V op lo ts a g a in s t W L a re sh o w n in F ig u re3 .I t is n o te w o rth y t h a t V ,/V o is sm aller th an1a t sm aller W L . V e /V oshow s m inim um

i n
the curve and then gradually increases w ith W L . V e /V o
is greater than
1a ta c o n s id e ra b ly
la r g e r v a lu e o f W L .
F ro m

these results, it can be assum ed th at cellulase-cat- a ly z e d h y d ro ly s is w o u ld o c c u r m a in ly in t h e a m o r p h o u s re g io n

a t sm aller W L. It can be also assum ed that the
c ry s ta llin e re g io n
m a y b e h y d ro ly z e d
g ra d u a lly
fro m
i t s
surface and w ould
b e p a rtia lly
tran sfo rm ed
in to a m o r-
p h o u s re g io n , b y c e llu la s e tr e a tm e n t.
W e ig h tL o s so f th e D y e d F a b ric s b y H y d r o ly s is
T he fabrics, w hich
w e re p re v io u s ly
d y e d t o e q u ilib riu m

w ith C o n g o R e d , C h ry s a m in e a n d C h ry s o p h e n in e , w e re treated w ith cellulase for2 4 h and then the W L w as ex- a m in e d . T h e d y e in g w a s d o n ea t80\u00b0C in th e range of th e in itia l d y e c o n c e n tra tio n s of0 .7 4 8X

1 0 -4 -2 .9 9
X
g
io n /L
fo r C h ry s a m in e ,1
X
1 0 -4 -4
X
g io n /L
fo r
C h ry s o p h e n in e , a n d1X
1 0 -4 -8X
g io n /L fo r C ongo
Red. T he plots of W L

against dye uptake are show n in F ig u re4 . W L te n d s t o d e c re a s e w ith in c re a s in g d y e u p ta k e for all of th ree dyes used. It is clear th a t W L of th e fabrics dyed are sm aller in the order of Congo R ed, C hrysam ine,

1 .1 1
I
1 0
2 0
W e ig h t
lo s s
(% )
F ig u r e3
V JV 0p lo ts a g a in s t w e ig h t lo ss o f c o tto n fa b -

ric s c a u s e d b y c e llu la s e tr e a tm e n t.V oa n d V ,a r e e ffe c tiv e volum e term s of dyeing for untreated an d cellulase-treated fa b ric s , re s p e c tiv e ly .

2 0 1
. _
al
3
C hr y s o p h e ni n e
C ongo
R ed
F ig u r e4
R e la tio n s h ip b e tw e e n
w e ig h t lo s s c a u s e d b y
c e llu la se tr e a tm e n t a n d e q u ilib riu m
d y e u p ta k e o f fib e r
[D ]6. T h e fa b ric s w e re d y e d w ith t h e d y e s in d ic a te d a n d
t h e n h y d ro ly z e d b y c e llu la s e .
and C hrysopheninea ta g iv e n d y e u p ta k e .
-
A p0o b ta in e d
a t8 0 \u00b0 C
u sin g0 .2 2 L /k g

ofV o w as8 .3 3 , 5 .5 2 , a n d4 .8 5 kcal/m ol for C ongo R ed, C hrysam ine, and C hrysophenine, respectively. Therefore, it w as concluded

t h a t c e llu lo s e
m o le c u le s b o u n d b y t h e d y e s , t h e a ffin ity of w h ic h is la rg e r,
c o u ld b e a tta c k e d b y c e llu la s e w ith m o re d iffic u lty .
T h e chem ical structure of cellulose does not change by
dyeing w ith direct dyes. It w as considered

th at physical in te ra c tio n s s u c h a s h y d ro g e n b o n d in g , w h ic h w a s fo rm e d b e tw e e n t h e d ire c t d y e a n d t h e b in d in g s ite , m a y b lo c k t h e h y d ro ly s is o f c e llu lo s e b y c e llu la s e , t o t h e e x te n t a s - sociated w ith th e affinity of the dyes.

C O N C L U S IO N

E q u ilib riu m d y e u p ta k e of C o n g o R e d b y c o tto n fa b ric s , w hich w as previously treated w ith cellulase, w as m easured, an d th en th e relative volum e term of dyeing w as obtained in c o n n e c tio n w ith w e ig h t lo ss. A s a re s u lt, i t w a s a s s u m e d t h a t c e llu la s e -c a ta ly z e d h y d ro ly s is w o u ld o c c u r m a in ly in th e am o rp h o u s region a t sm aller W L . B esides, th e fabrics p re v io u s ly

d y e d t o e q u ilib riu m
w ith

several direct dyes w ere treated w ith cellulase. W L by hydrolysis tended to decrease w ith increasing dye uptake in every case of dye. A lso , W L d e c re a s e d w ith in c re a s in g a ffin ity o f t h e d y e fo r c e llu lo s e , a t a g iv e n d y e u p ta k e .

W e w ould like to thank D r.Y .K a to of H iro sak i U n iv ersity
for helpful suggestions and kind assistance.

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