Self-assembly of phthalocyanine and polyacrylic acid composite multilayers on cellulose nanofibers

Article abstract of DOI:10.1016/j.carbpol.2009.12.041

In this study, a novel nanocomposite multilayers was deposited on the electrospun nanofibrous mats by an electrostatic layer-by-layer (LBL) self-assembly technique. The positively charged water-insoluble 2,9,16,23-tetraaminophthalocyanine copper (CuTaPc) and the negatively charged water-soluble poly(acrylic acid) (PAA) were alternately deposited on the surface of negatively charged nanofibrous cellulose mats. The cationic CuTaPc was synthesized and characterized by UV-Vis and Fourier transform infrared (FT-IR) spectroscopy. The template nanofibrous cellulose mats were obtained from the alkaline hydrolysis of electrospun nanofibrous cellulose acetate mats. The resultant nanofibrous mats were characterized by scanning electron microscopy (SEM) and FT-IR spectroscopy. The SEM images showed that the composite LBL structured films were homogeneously deposited on the surface of the nanofibers. The diameters of nanofibers increased with the number of deposition bilayers. The average thickness of each CuTaPc/PAA bilayer is about 10 nm. Additionally, the FT-IR spectra results also indicated that the CuTaPc and PAA were coated on the nanofibrous cellulose mats.

Full text of DOI:10.1016/j.carbpol.2009.12.041

Carbohydrate Polymers 80 (2010) 839–844
Contents lists available at ScienceDirect
Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol
Self-assembly of phthalocyanine and polyacrylic acid composite multilayers
on cellulose nanofibers
Xue Mao a,b,d, Bin Ding a,b, , Moran Wang , Yanbing Yin
c
d
*
a
Key Laboratory of Textile Science and Technology, Ministry of Education, Donghua University, Shanghai 201620, China
Nanomaterials Research Center, Modern Textile Institute, Donghua University, Shanghai 200051, China
Earth and Environmental Sciences Division and Center of Nonlinear Study (CNLS), Los Alamos National Laboratory, Los Alamos, NM 87545, USA
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China
b
c
d
a r t i c l e i n f o
a b s t r a c t
Article history:
In this study, a novel nanocomposite multilayers was deposited on the electrospun nanofibrous mats by
an electrostatic layer-by-layer (LBL) self-assembly technique. The positively charged water-insoluble
Received 9 December 2009
Received in revised form 20 December 2009
Accepted 23 December 2009
Available online 7 January 2010
2
(
,9,16,23-tetraaminophthalocyanine copper (CuTaPc) and the negatively charged water-soluble poly-
acrylic acid) (PAA) were alternately deposited on the surface of negatively charged nanofibrous cellulose
mats. The cationic CuTaPc was synthesized and characterized by UV–Vis and Fourier transform infrared
FT-IR) spectroscopy. The template nanofibrous cellulose mats were obtained from the alkaline hydroly-
(
Keywords:
sis of electrospun nanofibrous cellulose acetate mats. The resultant nanofibrous mats were characterized
by scanning electron microscopy (SEM) and FT-IR spectroscopy. The SEM images showed that the
composite LBL structured films were homogeneously deposited on the surface of the nanofibers. The
diameters of nanofibers increased with the number of deposition bilayers. The average thickness of each
CuTaPc/PAA bilayer is about 10 nm. Additionally, the FT-IR spectra results also indicated that the CuTaPc
and PAA were coated on the nanofibrous cellulose mats.
Nanocomposites
Layered structure
Electrospinning
Ó 2010 Elsevier Ltd. All rights reserved.
1
. Introduction
In recent years, a growing attention has been devoted to the
ness, while the use of dissolved species makes the technique
extremely versatile. Large varieties of charged materials, including
almost all kinds of polyions, dyes, organic/inorganic particles,
proteins, and viruses have been incorporated into multilayer
assembly films using the electrostatic LBL self-assembly technique
(Ding, Kim, Miyazaki, & Shiratori, 2004; Ding, Li, Fujita, & Shiratori,
2006; Karim et al., 2009). Among various deposition materials, the
phthalocyanines (Pcs) are good candidates because of their out-
standing high thermal (Ding, Gong, Kim, & Shiratori, 2005) and
photochemical stability (Kinzhybalo & Janczak, 2009).
Pcs exhibit an important class of organic semiconducting mate-
rials, which have attracted the world-wide interests because they
possess a centrosymmetric, planar structure with various polymor-
phic forms (Ziolo, Gunther, & Troup, 1981). Although Pcs are hardly
soluble in organic solvents, the solubility and process ability of Pcs
may be enhanced by introducing some functional groups into the
macrocycle. The electrical and optical properties of Pcs are highly
sensitive to the environment, especially in the case when they
form with functional groups. These groups lead Pcs to a mass of
applications such as semiconductors (Ogunsipe et al., 2008),
sensors (Schmechel, 2003), fuel cells (Zhang & Hu, 2009), catalysts
research of ultra-thin films with organic and inorganic composi-
tions for nanometer-scale electronic devices such as data-storage
devices (Majumdar, Bandyopadhyay, & Pal, 2003), memory devices
(
Jiang, Baba, & Advincula, 2007; Lee et al., 2007), sensors (Costa,
Filip, Figueirinhas, & Godinho, 2007; Ding, Kim, Kimura, & Shirato-
ri, 2004; Ding, Fujimoto, & Shiratori, 2005), etc. The technique of
electrostatic layer-by-layer (LBL) self-assembly developed by De-
cher and Hong (1991), provides an elegant way of controlling the
composition of the resulting assemblies and the thickness of a
monolayer at the nanometer scale. These assembly films have
the unique characteristic of less expensive, solution-based, and
finely controlled and used for a variety of device fabrication appli-
cations, which are distinct from conventional thin films process
such as vacuum deposition (Ji, Wong, Tse, Kwok, & Lau, 2002)
and Langmuir–Blodgett techniques (Seki & Nakanishi, 1989).
During the process of electrostatic LBL self-assembly, the num-
ber of adsorption steps allows one to strictly control the film thick-
(
Vivo, Ojala, Chukharev, Efimov, & Lemmetyinen, 2009), optical
*
Corresponding author. Address: Key Laboratory of Textile Science and Tech-
data-storage devices (Song, She, Ji, & Zhang, 2005), etc. Recently,
Rollet et al. (2008) reported a novel LBL structured film of the
water-soluble tetrasulfonated phthalocyanine nickel and
nology, Ministry of Education, Donghua University, Shanghai 201620, China. Tel.:
86 21 62378202; fax: +86 21 62378392.
+
E-mail address: binding@dhu.edu.cn (B. Ding).
0
144-8617/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2009.12.041

8
40
X. Mao et al. / Carbohydrate Polymers 80 (2010) 839–844
poly(allylamine hydrochloride) on indium doped tin oxide (ITO)
glass as electrochromic and sensing devices. In a pair of similar sys-
tem, Cooper, Campbell, and Crane (1995) fabricated the composite
LBL films with water-soluble tetrasulfonated phthalocyanine iron
and poly(allylamine hydrochloride) as a potential sensing material.
These achievements indicated that the Pcs are applicable in
fabricating multi-layered films and expanding the applications of
LBL structured ultra-thin films. Although the LBL deposition of
Pcs and polyelectrolytes were successful on various templates such
as the ITO substrate (Ingrosso, Petrella, & Cosma et al., 2006;
Ingrosso, Petrella, & Curri et al., 2006; Song et al., 2005), silanized
glass (Cooper et al., 1995), and particles (Tao, Li, Hartmanna, &
Mohwalda, 2004), the approach on porous three-dimensional
O
O
O
CO(NH2)2
HNO
3
NH
O
O
NH
2
O N
O
O
O
2
N
N
N
CuCl
2 2
CO(NH )
2
N
NO
2
N
Cu
N
N
2
O N
N
N
(
3D) fibrous mats has never been reported. Additionally, it is still
a great challenge to combine the water-insoluble Pcs with the
water-soluble polyelectrolyte into the multilayer films through
the LBL self-assembly technology.
NO
2
H N
2
In this study, we select the nanofibrous cellulose mats as the
template to deposit the LBL films because of their negatively
charged surfaces, 3D structures, high specific surface area, low fi-
ber density, and good water insolubility. The positively charged
water-insoluble 2,9,16,23-tetraaminophthalocyanine copper (Cu-
TaPc) and negatively charged water-soluble poly(acrylic acid)
N
N
N
NH
2
Na
2
S · 9H
2
O
N
N
Cu
N
2
H N
N
N
(
PAA) were assembled as LBL structured multilayers on the nega-
tively charged cellulose nanofibers. The effect of the number of
coating bilayers will be studied on the formation of LBL multilayer
films on cellulose nanofibers.
NH
2
Fig. 2. Synthesis of CuTaPc.
2
. Experimental details
2.1. Materials
2.2. Fabrication of template nanofibers
Cellulose acetate (CA) (M
n v
30,000, Aldrich Co., USA) and PAA (M
50,000, Wako Pure Chemical Industries, Ltd., Japan) were used as
Nanofibrous CA mats were fabricated by electrospinning a
0 wt.% CA solution; they were prepared from acetone and DMAc
2
1
received. The chemical structures of CA, cellulose and PAA are
shown in Fig. 1. Phthalic anhydride, urea, sodium sulfide, acetone,
N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc),
and copper(G) chloride were purchased from Aladdin Chemical
Co., China and used without further purification. All aqueous solu-
with the acetone/DMAc weight ratio of 2:1. The schematic of elec-
trospinning process is shown in Fig. 3. The CA solution was trans-
ferred into a 10 mL plastic syringe. Then the syringe was fixed on a
syringe pump (LSP10-1B, Baoding Longer Precision Pump Co., Ltd.,
China). The feeding rate of solution by the syringe pump was
tions were prepared using pure water with a resistance of 18.2
X.
0
.3 mL/h. The positive electrode of a high voltage power supply
The preparation of CuTaPc, using phthalic anhydride as the
starting material, comprising 4 steps, e.g. imidization by urea, nitri-
(
DW-P303-1ACD8, Tianjin Dongwen High Voltage Co., China) was
clamped to the metal needle tips, which were connected to the
plastic syringe. The applied voltage was 16 kV, and the distance
from the tip of syringe to collector was 20 cm. The nanofibrous
CA mats were obtained on a piece of aluminum foil covered tubular
layer which rotated with a linear velocity of 100 m/min. The pre-
pared fibrous mats were dried at 353 K for 24 h under vacuum to
remove the trace solvent. Hydrolysis of the nanofibrous CA mats
was performed in alkaline aqueous solutions at ambient tempera-
ture following previously report procedures (Ingrosso, Petrella, &
Curri et al., 2006). Complete hydrolysis to generate nanofibrous
2
fication, solid-phase melt with urea and CuCl , and reduction by
Na S. The obtained blue powders were collected by a vacuum fil-
2
tration and purified by Soxhlet extraction in ethanol and acetone
for 24 h, in a 35% total yield. The reaction pathway is illustrated
in Fig. 2.
(
a)
(b)
OCOCH3
OH
OH
O
O
H.V. Power Source
Roller Collector
O
O
OCOCH3
OH
OCOCH
3
n
n
Syringe Pump
(
c)
H
H
H
C
C
COOH
n
Fig. 1. Chemical structures of CA (a), cellulose (b), and PAA (c).
Fig. 3. Schematic of the electrospinning process.

X. Mao et al. / Carbohydrate Polymers 80 (2010) 839–844
841
cellulose mats were conducted in 0.05 M NaOH aqueous solution
at ambient temperature for 4 days.
2.0
1.6
7
22
2.3. Formation of nanocomposite films on template nanofibers
3
38
The cationic CuTaPc solution was prepared by dissolving Cu-
TaPc powder in DMF at a fixed concentration of 0.3 mg/mL with
vigorous stirring. The anionic PAA was dissolved in a 0.5 M NaCl
1
.2
aqueous solution. The concentration of the PAA was fixed as
À2
1
3
0
M (based on the repeat unit) and its pH was adjusted to be
0
0
.8
.4
.5 with either HCl or NaOH solution.
The LBL structured composite films were formed by first
immersing nanofibrous cellulose mats into the CuTaPc solution
for 20 min followed by 2 min of rinsing in three DMF baths. The
mats were dried at 353 K for 24 h under vacuum to remove the sol-
vent. Then the mats were immersed into the PAA solution for
650
4
30
0
.0
2
0 min followed by 2 min of rinsing in three pure water baths.
4
00
500
600
700
800
900
The electrostatic adsorption and rinsing steps were repeated until
the desired number of deposition bilayers was completed. Here,
the composite films deposited from a CuTaPc solution and a PAA
solution referred to as CuTaPc/PAA. Meanwhile, five bilayers of
composite LBL films fabricated from a CuTaPc solution and a PAA
Wavelength (nm)
Fig. 5. UV–Vis absorption spectrum of CuTaPc in DMF.
tionally, the broad absorption peak observed from 403 to 465 nm
was caused by the C4V symmetry of the CuTaPc. As a result, the
conjugated structure of macrocycle was formed in the CuTaPc
molecules.
solution denoted as (CuTaPc/PAA)
rication of composite nanofilms on nanofibers is shown in Fig. 4.
5
. The schematic diagram for fab-
2.4. Characterization
Fig. 6 showed the FT-IR spectrum of CuTaPc. The absorption
À1
peaks around 738–760, 1050–1180, 1320–1550, 1580–1620 cm
Electronic absorption spectrum of CuTaPc was measured on a
which were assigned to phthalocyanine skeletal vibrations (Kumar
Perkin–Elmer Lambda 35 UV–Vis spectrophotometer. The mor-
phology of the fibrous mats was examined by a scanning electron
microscope (SEM, JSM-5600LV, Jeol Ltd., Japan). The diameters of
fibers were measured with 4 SEM images using image analyzer
&
Achar, 2006). Moreover, two weak absorption bands are ob-
À1
served at 3368 and 3214 cm in the IR spectrum of CuTaPc due
to the asymmetric and symmetric stretching of the amino groups.
The FT-IR spectrum together with the above UV–Vis absorption
spectrum supported the assertion the CuTaPc was prepared
successfully.
(
Adobe Photoshop 7.0) for each sample and 40 fibers were counted
for each SEM image. Fourier transform infrared (FT-IR) spectra of
CuTaPc and the ultra-thin films were recorded using a Nicolet
8
700 FT-IR spectrometer.
3.2. The morphology of fibrous mats
3
. Results and discussion
In previous reports (Ding & Gong et al., 2005; Ding, Kimura,
Sato, Fujita, & Shiratori, 2004; Ding & Yamazaki et al., 2005; Ding
et al., 2006), the electrospun nanofibrous CA mats with high spe-
cific surface area are selected as the template to deposit the LBL
structured polyelectrolytes ultra-thin films. However, the CA mats
are readily soluble in the DMF solvent. Moreover, the surfaces of
nanofibrous cellulose mats have more negative charges from the
complete hydrolysis of the surface ester groups than that of the
electrospun CA mats. The surface charge property of the template
fibers is critical to the deposition of the first monolayer. Therefore,
in this study, the nanofibrous cellulose mats were selected as the
template to deposit LBL structured composite films.
3
.1. The structure and composition analysis of resultant CuTaPc
For Pcs, their electronic absorption spectra are characterized by
an intense Q-band in the far-red end of the visible spectrum of
light between 600 and 700 nm, and a B-band at 300–400 nm in
the blue end of the visible spectrum (Chen et al., 2007). In the spec-
tra of Pcs solutions, the intense Q-band arises from a doubly degen-
erate
first excited single state. The second allowed
band) is due to a transition between either an a2u or a b2u orbital
to the e orbital (LUMO).
2
p–
p
* transition between the A1g (a1u ) ground state to the
p–p
* transition (B-
g
The UV–Vis absorption spectrum of the resultant CuTaPc in the
DMF solution is shown in Fig. 5. The intense absorption bands lo-
cated at 722 and 650 nm were attributed to the Q-band, which
should be assigned to the
p–p
* transitions (Kumar & Achar,
2
006). The weak band at 338 nm was assigned to the B-band. Addi-
7
45
1
500
1
060
Ι
3368
3214
-
-
(+)
+ - +
+ - +
- + - + -
- + - + -
1600
(-)
CuTaPc
PAA
ΙΙ
-
-
Ι
+ -
+
ΙΙ
- + - + -
- + - + -
+ - +
4
000
3500
2000
1500
1000
-
1
Wavenumber (cm )
Fig. 4. Schematic diagram illustrating the modification of nanofibrous cellulose
mats with CuTaPc and PAA via LBL self-assembly.
Fig. 6. FT-IR spectrum of CuTaPc.

8
42
X. Mao et al. / Carbohydrate Polymers 80 (2010) 839–844
SEM images of various fibrous mats are shown in Fig. 7. The
and ten-bilayers deposition. Furthermore, the average thickness
of each CuTaPc/PAA bilayer was estimated at about 9.8 nm.
pure fibrous CA mats were consisted with loosely packed cylindri-
cal fibers (Fig. 7a). The diameters of the CA fibers were distributed
in the range of 200–400 nm. The fibers have an average diameter of
3.3. The composition analysis of various nanofibrous mats
3
05 nm with a standard deviation of 37 nm. The morphology of fi-
brous cellulose mats is shown in Fig. 7b. The hydrolyzed cellulose
fibers showed a little additional change in their overall appearance.
The average diameter of cellulose fiber was of 314 nm with a stan-
dard deviation of 139 nm (Table 1). It was found that the average
diameter and the standard deviation of cellulose nanofibers were
increased after the alkaline hydrolysis. The process of alkaline
hydrolysis generally caused the nanofibers to enlarge in width,
pack more closely, particularly in the thickness direction.
The investigation of molecular organization in the fibrous mats
was carried out through FT-IR absorption spectroscopy. As shown
in Fig. 8a, the pure nanofibrous CA mats exhibited a number of
À1
FT-IR absorption features below 2000 cm (Ding & Kimura et al.,
2
1
004). The CA mats showed a strong characteristic peak at
À1
748 cm which was attributed to C@O and exhibited the typical
À1
C–O–C vibration peak at 1630 cm . Moreover, the peak at
À1
1
050 cm
was assigned to symmetrical C–O stretching of CA
After the deposition of composite CuTaPc/PAA films on cellulose
nanofibers, the morphology of cellulose nanofibers showed obser-
vable changes in Fig. 7c and d. The diameters of the composite
films coated fibers were larger than that of the cellulose nanofibers
due to the additional coating of CuTaPc/PAA films. The diameters of
the composite films coated fibers distributed in a broad range of
nanofibers. The FT-IR spectrum of cellulose mats is shown in
Fig. 8b. The intensity of the acetyl carbonyl at 1748 cm was very
weak after the hydrolysis. This was consistent with the expected
nucleophilic substitution of the acetyl groups with hydroxyl
groups. The acetyl carbonyl peak became indistinguishable for cel-
À1
lulose, confirming the conversion of most acetyl to hydroxyl. The
À1
2
00–1000 nm. The region of the diameter distribution of the com-
hydroxyl stretching modes band was detected around 3400 cm
.
posite films coated fibers was enlarged and the major region
moved to a larger value. The average diameter of composite nanof-
ibers with five- and ten-bilayers deposition was 412 and 515 nm,
respectively. Moreover, the standard deviation of diameters of
composite nanofibers with five and ten-bilayers coatings was cal-
culated to be 154 and 202 nm, respectively. The average diameters
of fiber increased with the deposition bilayers. Meanwhile, the
standard deviation of fiber diameters increased after the LBL depo-
sition because of the imperfect film deposition caused by the 3D
structure of the fibrous mats. The presence of NaCl in the PAA solu-
tion enhanced the ion strength of anionic PAA (Sukhorukov et al.,
After the LBL deposition, the composite films coated nanofi-
brous mats still maintained the FT-IR features of cellulose mats.
It was observed in Fig. 8c and d, the absorption peaks around
À1
1
370 and 1050 cm were broader than those of cellulose mats
(Fig. 8b). This observation was most likely attributed to the carbox-
ylic acid groups of PAA and vibrational mode of skeletal groups of
CuTaPc in LBL films. Although it seemed no intense CuTaPc charac-
teristic bands (Fig. 6) appeared in the spectra of composite films
coated mats compared with the cellulose mats. However, it should
be noted that the relative intensity of the broad peak around
À1
8
90 cm were higher for the LBL films, which assigned to phtha-
1
998) and as well the quantities and thickness of the LBL deposi-
locyanine skeletal vibrations as reference. Additionally, the absorp-
À1
tion of CuTaPc and PAA onto the template fibers. The average thick-
ness of the composite films, deduced from the average diameters of
composite films coated nanofibers, was 49 and 100 nm with five-
tion peak observed round 3400 cm of composite films coated
mats were broader than that of cellulose mats due to the asymmet-
ric stretching of the amino groups from CuTaPc. The FT-IR spectra
5
Fig. 7. SEM micrographs of fibrous CA (a), cellulose (b), (CuTaPc/PAA) coated (c), and (CuTaPc/PAA)10 coated (d) mats.

X. Mao et al. / Carbohydrate Polymers 80 (2010) 839–844
843
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CA
Cellulose
305
314
412
37
139
154
–
–
49
–
–
9.8
(
CuTaPc/PAA)
coated mats
5
(
CuTaPc/PAA)10 515
coated mats
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100
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050
(
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000
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3000
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Wavenumber (cm )
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5
coated (c), and
(
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The LBL structured ultra-thin CuTaPc/PAA films coated nanofi-
brous cellulose mats were successfully fabricated by a combination
of the electrospinning and the electrostatic LBL self-assembly tech-
niques. A relatively regular deposition was found in the CuTaPc/
PAA coated fibers, and the composite films coated fibers main-
tained their shapes. The formation and the morphology of the
LBL films containing CuTaPc/PAA films coated on the surface of
the cellulose nanofibers were controllable by regulating the num-
ber of CuTaPc/PAA deposition bilayers. The average thickness of
each CuTaPc/PAA bilayer was around 10 nm with deposition Cu-
TaPc/PAA composite films on nanofibrous cellulose mats from 5
to 10 bilayers. Such LBL films coated nanofibrous mats exhibit
great potential applications as catalysts and sensors.
Rollet, F., Morlat-Therias, S., Gardette, J. L., Fontaine, J. M., Perdereau, J., & Polack, J.
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This work was partly supported by the National Natural Science
Foundation of China under Grant No. 50803009. Partial support
from the Programme of Introducing Talents of Discipline to Univer-
sities (Nos. 111-2-04 and B07024) was appreciated.
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