Subscriber access provided by HACETTEPE UNIVERSITESI KUTUPHANESI
Article
Filaments with Affinity Binding and Wet Strength can be achieved by Spinning Bifunctional Cellulose Nanofibrils Maija Vuoriluoto, Hannes Orelma, Meri Johanna Lundahl, Maryam Borghei, and Orlando J. Rojas Biomacromolecules, Just Accepted Manuscript • Publication Date (Web): 24 Apr 2017 Downloaded from http://pubs.acs.org on April 26, 2017
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Biomacromolecules is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
!" # $ ,
"
"
%
#
" &'((()*" $
$ -
"
+
"
,)*./" %
0
"
0
%
"
+
'
0
0
0
+
1
2!
3
' "
!+ '
"
4
1
"
'
& '
1 %5
ACS Paragon Plus Environment
6
+
"
2'
1
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 2 of 39
7 (/ !+ :
2
6
78(9
"
;
(+/9
!+ '= !
!
'
'
%5
' 6 +
)
' +: :>
1
%5 $# C = !
"
.
2! '
"
" "
' "
+:
ACS Paragon Plus Environment
?
Page 5 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
'
!"
"
4 1
+
?'
1
:$ 2> F?,*B*.!" F(B?/(!"
'
F ? ?(,!"
'
'B'GB'
4
"
!
=
= F B(*),!"
'= F=?8.(!"
F=)B).!"
=
&: F?*./(!
!
#$
'
.(9!
(9
4
+
1
'
(+?
#
+
1
$# C =
=
>!+
1 1
+ : +"
"
(2 " %
1
!
,(((
' :>
"
+
!
'
1 ,((
2'
)
'
:$ 2>" ?+*/
'
$# 4
'
(+ B 1
(+
1
1
>" = (!
+ :
1
>
:$ 2>' 4
"/
' ' ! 4
'
=
/ *!'
6"
'
H
FB.8 B*!" F ./
,","*"*'
(( J
"
" :$ 2>' 4
1
1
ACS Paragon Plus Environment
/
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
+:
4
'
Page 6 of 39
:>
+B*
, '
)+/
2'
(
!
'
E
, +:
' 6
!
2' +:
2'
4
,B N :
/(9 +
O
6 '
6 " :>
ACS Paragon Plus Environment
*
Page 7 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
6 , 6
'
+
:> !+
:
"
$
S
" !+
E +" R S3T
! '
"
!
' "
8( N
(
ACS Paragon Plus Environment
)
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
+ 2 !
2'
I
4 "%
/ # '
2-
2'
',
D
!
" %K!" +
'
,((" >
2 E +" R S3T
' %
" *
1
0/! 2
2' 2-
B/*
"
" '
'#
%5
E /(8E %5
+:
Page 8 of 39
-
"
!
'= !
1 2'
+
2-" 1 +
4
+?? : 6
-&! +?/" ?* :
2-
6
" 0=
?@ABCD
>
@
?
" " ??/
$
ROQSTUD=
)! 1
1 +/ : ,+ " I'
" 5T
S
"
5 "
I':
"
!
ACS Paragon Plus Environment
.
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
2' B
!
+ B
(+((
/ ") ". "
6
'
"
1 +/, "
$# C = (+?
I
0 $2
3
$
0
& $2 $
+
# '
!&)*+
#
I
(
2- 4
+
2
" (+
$#
= /!
/ +:
E' " (
'= " (+
0 3
'
' 2'
=
I
'# 4 '
(( U &
4
B "
6
!+
,B N
$
O
!+ :
/"
5
#
'B
,(( 6
&
"
'
" = /!
+
" = /!+ $
( (+,
I'
"
= 8+/!
=
(
" = /!+ :
= (+ '=
'= +
$# C = + = )+?!
" = )+?! '
'=
2'
= ,+/!
'= + = )+?
(
= ,+/! "
'=
+
'
((( 6
!
B
! "
Page 10 of 39
" ( E'
" (+
= !
'= "
( 2'
6
ACS Paragon Plus Environment
(
Page 11 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
+:
'= =
!
'=
+ =
'= '=
=
2>$A
,'
2#
$
!" #?*'
!
'$A
B."
!
B,
6 "
E' " (
!
!
2' (+/
E' !
(+
6
+ !
E'
(+
2
!+ : = )+?!
=
6
/
+ #
& $$
# ' #
'=
"
$
+ =
=
' E' !
(+(
'= '=
"
= )+?
1
= ,+/!+
E' =
"
E' =
" (+
+
'= +
2'
"
" '=
+-
= #?*'
6
'$A
'
' + '
(+/
E' "
= )+?!
= "
'=
+ '
"%
B."
6
=
& +"
2
! (+,
8
(
8
' " 08+ 2 !
1 '=
2
6
1
P 2'
" =
ACS Paragon Plus Environment
E' !
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 12 of 39
+ : $
/C &
!
V
,
J
"
":
"
+ +
+
'
0+9-)2
(
E
$
# E'
,
&
E
$
'
&:
#
(+ ?N
=
%
=
E'
+(
?(((
= .!+ : 6+ :
B( 6#
>
&: '
>
+:
' &: W
B(
(
= )+?
+: 4
&: '
'
'=
+:
?N
2'
+ $ '
'
.
'=
!&)*+ #
2'
2(+
/
$#
(+?
+:
=
=/
*(
2 " = )+?!
(
'=
(
+
2' " = )+?!
(+( " (+ + &
2' "
= /!
= )+? (
+ 2'
+:
( E' =
4
( E'
(+/
I
,
E'
(
&: '
'=
(
=
+
ACS Paragon Plus Environment
,
Page 13 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
)
# '
/'
'
' " 0) / 2
2'
Page 14 of 39
" !+
4
4 +
ACS Paragon Plus Environment
?
Page 15 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
' 2'
!
%5
2'
1
'
6
$# C =
'= !
' '
+
3
'
"
= !"
&: ' '
'=
! 2'
! :>
!+ VB((
!+
:
:> "
+
/
" :>
"
:
*" /B
4 "
4! :>
2' .8+ @ *
(((
,, @ B+B 4!
!
/
' 4 +
("(((
'
"
4"
4!
!+
2' :>
:
"
2'
+
2
"
1
%5
+ :>
6 ' !+
+: :>
(B @ B8
2 "
!+ :
!
" !+ :
"
78 9
,)
"
(B
2 "
6
?
6 6
2
,B('
(+?? @ (+(?
2'
2"
&
'
+/? >
!'
$4
6
$ &" !" )+( @ ?+
+/* =
'
:
$4
6
2'
6 "
//
:$ 2> 4
1 " + +"
:
! !+ :
2
ACS Paragon Plus Environment
*
Page 17 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
"
'
< ('
:>
6
3
' "
! /
+E6
6
%5'
+: " 2'
,(
6
2'
6 &
%"
2-B,
"
!"
I
+
(
3
+:
8+/+ &
& A
"
=
"
& *+/W.+//)!" :$ 2>' 4
1
+ &
$# C =
'=
!"
" I
2'
6
2-
"
+=
'=
" "
"
" +/8
:
3 $
'=
" +B, 2'
6
B.
(+/. @ (+()
& A
E' !
(+
2'
2-
!
5 !+ =
'=
6
=
2'
? !+ :
4
= " = +:
=
'=
6
4 &
7"
!
'=
=
6 + -
'=
=
E' !
(+( " (+ 6
=
2- 8
9 "
6
!+ :
'=
=
6 =
9 "
!+ &
= 6 4
E' = "
(+( "
(+?B @ (+(, "
(+? @ (+(,
',
"
!
=
= '=
9 !+ : =
" 6
'= 4
"
4
"
ACS Paragon Plus Environment
,)
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 28 of 39
+: 4
4
'
+
2 0 ( #( ,' '0
/, ( ' : (* - '#( ,' ! ; 0
- ! + '(. :
)
2'
,# 1 &
! +
$E& =
'
"
"
=
2' E
E 2'
"
" !
'
2'
'=
6
+
!
!
! 2'
'= "
2' &: '
'
'=
&: '
!
$ 1
6!+
!
6
&
!0
'= '=
,
4
= + =
E' !
ACS Paragon Plus Environment
,8
Page 29 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
!!+ : E'
(+ :
=
O
2'
"
#
" ",(
?
+,/ =
"
$A
6
5
Q =R $-!+ $ 6 +-
+:
6
2 3
?((+ # + K
T %
+
+
`" &+0 2
6
" #+ )
%= =
;" ?/.'?.?+
ACS Paragon Plus Environment
B,
Page 33 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
,+
" :+0 K
" -+0
" D+0
" E+
+0 &
"
+
'
'
%= &
+
?" ?,*' ?B,+ "
+0
"
+0
"
+0 # E
"
+0
" I+ 1
%= & @" ,(+ .+ K (+ >
" #+0
" #+0 %
" =+0
" %+0
" &+0 D
" +!
" E+0 b
"
!
?" /* ' *(B+
/' %==
+0 - 3 " >+0 E
" D+
"
%= % ;" ' ,+ +> >+ D+0 E ,+ E
" =+0
" E+ >+0 D
" E+0 =
" &+ +0
" &+0
" +0 - 3 "
" D+ /) 8 A %= 5 + D+ 9
1
)
%= 7 @?" 8'
.+
ACS Paragon Plus Environment
BB
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
B+
" +
?+
. $
D+0 &66
" >+0 R
'E "
/+ &
" +0 &
*+
" +0 :
>5 >>" /** '/*)B+
'
" E+0
" D+0
" +0
"
+0 >1
" 2+0 " +0 A
1 1 "
" D+0 A +
'E
"
%==>
?" 8(.'
6
" + -+
8 ?+ ,(+
" 2+0
'
*
, +
6 %=
" A+ #+0
,,+ E " R+0 K +
" 2+0
+0
"
" K+
+0 P " I+0 K
" +)
! ' + %= &
"
+0
+ " +0
" K+ +0 # 6
%= %
,B+ - 6
"
6 " D+
+0
"
5" B8/'B88+
+0
" -+
+0 d
" K+0 :
" A+
=" , B?' , B.+ + K+0 K
" +
+0
" =+0 $ e " D+ :+ ! /
" $+
+0
%= 5 C" .
6" :+ E+0 - 1
" +0 =
" R+0
*.+
ACS Paragon Plus Environment
B?
Page 35 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
,?+
" :+ R+0
R " A+0 D
"
+0 a
" + =+0 E
,/+ :
"
"
+0 $
" D+0
" +8 '
+0
6
"
6"
+0
" -+ =+0
* 'D /
+0
"
+0 2
"
@" ,,.' ,B?+
>>>
+0 K
" -+ D+0
"
+0 D
6 " #+
8 A %= & > " **.'*8)+
' ,*+
1" +0
,)+ E " +0
" #+0
" I+0
,8+ a
" R+0
,.+ &
"
" -+0 a
"
+
" +0 # " D+0 E " D+
" -+ A+0 - 3 " >+ D+
+0
" +0 A
' %= & ;" (/ /( +
' #
@" ?./'/(B+
$ ) " %= 6
'
'
%= &
" 2+ 5+0 - 3 " >+ D+0
+ D+ 8)/ 8""
# '
8(B('8(B)+ B,+ 5 9
# ' BB+ >
"
+0 >
" =+0 a "
+0 D
" E+0 - 3 " >+ D+ 8)/ 8""
=" /**8'/*)8+
%=
" =+0 :
" :+0 D
" E+0 =
" +0 E
" D+
'
'
%= %
" &+0 - 3 " >+ D+0 E
" D+
'
'
%= %
>" (/ ' (/8+ B?+ >
" =+0 D
" E+0
>" ,8(,',8 (+
ACS Paragon Plus Environment
B/
Biomacromolecules 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
B/+ ES f " +0 D
" +
B*+ ES f " +0 D
" +0 $ + >>6
'
)
/ ' )
)
S " g0 =
"
" + #+0
" A+0 :
1
"
+
B8+
" + #+0
" A+0 :
1
"
+
B.+
" + #+0 :
1
?,+ #
" D+ +0 " D+
?B+
"
+
+0
" +0
+0 E
>=" /,*' /,8+
5" 8 B'8,,+
B)+
?(+ R " +0 2
Page 36 of 39
+8
%==5 ;?" *)*/'*))(+
)
" D+ D+ 8 !
" E+ '+0 E
+
)
!
'
%==6 ; "
/B' *,+
%= & > 1 1
=" ,B8(',B.,+ ?;" B,B8'B,? +
6 " 2+0 K
" +
A /' 9
>>6 ??"
B.,?'B.B(+
ACS Paragon Plus Environment
B*
Page 37 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Biomacromolecules
?.+
" A+ E
/(+ -
"
'
+0 K
/ + =SS6" +0 -
"
/,+ 5
"
+ 5+0 -
/B+ E
"
+ D+0 " %=
/?+ R " D+0
" +0
%= 7+ (+ (, C
+* "
/*+ #
'D
/)+
"
+0 D
"
" R+0
" + +0 K
>>9 " +!
96 ?" ,?' ,8+
"
8
$
& +O
6 " + +0 ! '
9 R 6" ,(((0
" D+ +0 %==>
" E+0 2 6 " D+ )
$ %
!
6
+ & '
: E
! " R+"
',?+ "
+ /'
' %==%
C@" )(,' )(/+
" B,'/ + + >7%