Photoresponsive Ion Gating Function of an Azobenzene Polyelectrolyte

Multilayer Spin-Self-Assembled on a Nanoporous Support

Surjith K. Kumar and Jong-Dal Hong*
Department of Chemistry, UniVersity of Incheon, 177 Dohwa-dong, Nam-gu, Incheon 402-749, Korea
ReceiVed October 29, 2007. In Final Form: January 4, 2008
The fabrication of a polyelelctrolyte multilayer (PEM) on a porous membrane was successfully improved by using
spin-coating electrostatic self-assembly. Surprisingly, the quality of the PEMfilmobtained on the nanoporous alumina
substrate (i.e., its thickness and surface morphology) was comparable to that of a film deposited on silicon. An optical
molecular switch that acts as an ion-gating channel was realized using a PEM membrane deposited layer-by-layer
on an alumina support. One of the layer components of this device was a poly(acrylamide) copolymer containing an
azobenzene chromophore, which is known to reveal strong voluminous expansion and contraction during light-induced
reversible cis/trans isomerizations. The permeability of the bulk SO
4
2-
ions was found to be sensitive to the changed
channel sizes; for instance, the ion-permeation rate of SO
4
2-
increased about 1.6 times after UV irradiation of the
PEM, whereas that of the Cl
-
ion increased only 1.2 times. In the study, it was successfully demonstrated that the
ion flow through the PEM membrane could be reversibly switched on and off over several azobenzene isomerization
cycles.
Introduction
Among the known addressable nanoscale devices, photoin-
duced molecular switches have opened a particularly challenging
and appealing research area for applications in the development
of gating channels for externally modulating ion flow and drug
release.
1
Azobenzene could be regarded as an excellent candidate
for an optical molecular switch to control mass transport through
a membrane due to well-known light-triggered reversible trans/
cis isomerization.
2
The formation of cis isomers accompanies
remarkable changes of the size (0.90-0.55 nm), dipole moment
(0.5-3.1 D), and geometry (planar-spherical). Only several
examples have been found in the literature for photochemically
switchable membranes modifiedwithazobenzene. The switchable
properties have been used to control size-selective mass transport
(electron, gas, inorganic and organic ions) through a membrane.
However, it has beenshownthat the size change of the azobenzene
in the trans/cis isomerization affects the pore sizes of the
membrane in a controversial way to either enlarge or shrink
depending on the local environment of the chromophores and
morphology of the membranes. For instance, the enlarged mean
free volume of cis isomers appeared to increase the pore sizes
of a membrane that is composed of vesicles,
3
a cross-linked
copolymer of (chloromethyl)styrene and divinylbenzene,
4
or a
rigidinorganic scaffoldwithmonosizedpores, whichare modified
with azobenzene.
5
In contrast, the spherical cis form is known
to act rather as a more effective diffusion obstacle than the
elongated trans isomer, when azobenzene materials are densely
packedinside microporous ceramic or zeolite membrane cavities.
6
Studies have shown that polyelectrolyte multilayer (PEM)
membranes possess a unique suitability for salt
7,8
and gas
9
separations and pervaporation from water/organic solvent
mixtures
10
and as reverse osmosis membranes.
11
Recently, much
effort has been devoted to developing PEMs for gating
membranes, which respond to various stimuli such as pH,
12
salt,
13
and temperature.
14
To our best knowledge, the development of
a PEM functionalized with a light-gated ion switch has not been
reported before, although it is very important question how the
size and dipole moment changes of the azobenzene during trans/
cis photoisomerization affect the pore size of the PEM which is
composed of three-dimensionally cross-linked matrixes due to
the salt formation among the layer components, positively and
negatively charged polyelectrolytes.
Thus, this paper aims to functionalize a PEM membrane with
light-activated channels that allow rapid, remote, noninvasive,
andreversible control. The idea is touse photochromic azobenzene
derivatives as layer components of the PEM; these species have
been extensively studied as model photoswitching compounds.
15
Here, the fabrication of a PEM on a porous support is also
attempted, for the first time, by using spin-coating electrostatic
self-assembly (SCESA),
16
a technique which has been shown
not only to facilitate the rapid fabrication of the layers but also
* To whom correspondence should be addressed. Phone: 82-32-770-
8234. Fax: 82-32-770-8238. E-mail: hong5506@incheon.ac.kr.
(1) Kocer, A.; Walko, M.; Meijberg, W.; Feringa, B. L. Science 2005, 309,
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Inc.: Boca Raton, FL, 1990; Vol. 4, Chapter 4, p 120.
(3) Lei, Y.; Hurst, J. K. Langmuir 1999, 15, 3424.
(4) Sata, T.; Shimokawa, Y.; Matsusaki, K. J. Membr. Sci. 2000, 171, 31.
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G. P.; Boyle, T. J.; Brinker, C. J. Nano Lett. 2004; 4, 551.
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J. Chem. Eng. Technol. 1998, 21, 5. Weh, K.; Noack, M.; Hoffmann, K.; Schroder,
K. -P.; Caro, J. Microporous Mesoporous Mater. 2002, 54, 15.
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2003, 15, 245.
(8) (a) Balachandra, A. M.; Dai, J.; Bruening, M. L. Macromolecules 2002,
35, 3171. (b) Hong, S. U.; Malaisamy, R.; Bruening, M. L. Langmuir 2007, 23,
1716.
(9) (a) Levasalmi, J.-M.; McCarthy, T. J. Macromolecules 1997, 30, 1752. (b)
Sullivan, D. M.; Bruening, M. L. Chem. Mater. 2003, 15, 281.
(10) (a) Krasemann, L.; Tieke, B. J. Membr. Sci. 1998, 150, 23. (b) Sun, L.;
Baker, G. L.; Bruening, M. L. Macromolecules 2005, 38, 2307.
(11) Jin, W.; Toutianoush, A.; Tieke, B. Langmuir 2003, 19, 2550.
(12) (a) Hiller, J.; Rubner, M. F. Macromolecules 2003, 36, 4078. (b) Park,
M.-K.; Deng, S.; Advincula, R. C. J. Am. Chem. Soc. 2004, 126, 13723.
(13) (a) Antipov, A. A.; Sukhorukov, G. B.; Mohwald, H. Langmuir 2003, 19,
2444. (b) Ito, Y.; Inaba, M.; Chung, D. J.; Imanishi, Y. Macromolecules 1992,
25, 7313.
(14) (a) Jaber, J. A.; Schlenoff, J. B. Macromolecules 2005, 38, 1300. (b)
Kharlampieva, E.; Kozlovskaya, V.; Tyutina, J.; Sukhishvili, S. A. Macromolecules
2005, 38, 10523.
(15) Dugave, C.; Demange, L. Chem. ReV. 2003, 103, 2475.
(16) (a) Cho, J.; Char, K.; Hong, J.-D.; Lee, K.-B. AdV. Mater. 2001, 13, 1076.
(b) Lee, S. S.; Hong, J.-D.; Kim, C. H.; Kim, K.; Koo, J. P.; Lee, K.-B.
Macromolecules 2001, 34, 5358.
4190 Langmuir 2008, 24, 4190-4193
10.1021/la7033615 CCC: $40.75 2008 American Chemical Society
Published on Web 02/27/2008
to allowprecise control of the filmthickness on a solid substrate.
The multilayered membranes were obtained on a porous alumina
support by the layer-by-layer (LBL) deposition of a negatively
charged poly(styrenesulfonate) (PSS) and positively charged
polyacrylamide copolymer containing a photochromic chro-
mophore, 2-nitro-4-methoxyazobenzene (PNA; Scheme 1).
The synthesis and detailed characterization of PNA were
described previously.
17
The basic operation of the ion gate
membrane is schematicallyillustratedinFigure 1a: UVirradiation
on the PEM induces trans-to-cis isomerization of the nitroa-
zobenzene species incorporated into the layer component PNA,
which is supposed to enlarge pores inside the membrane as a
result of the bent molecular structure, thus making ion transport
easier. Subsequent exposure to visible light restores the original
dense state of the membrane matrix, which in turn restrains the
ion flow. The 15 PSS/PNAbilayer filmappears transparent with
a uniformly yellow color (Figure 1b).
Experimental Section
Materials. Poly(allylamine hyhrochloride) (PAH; M
w
)70 000),
poly(styrenesulfonate, sodium salt) (PSS; M
w
) 70 000), and
-carrageenan (CAG) were purchased from Aldrich and KCl and
K
2
SO
4
(ACS grade) from Samchun Chemicals. All reagents were
used as received. The alumina membranes (pore size 0.02 m) were
purchased from Whatman Corp. The synthesis and the detailed
structural ananlysis of poly{N-[3-(4-(4-methoxyphenylazo)-2-ni-
trophenoxy)propyl]-N-[3-(dimethylamino)propylmethacrylamide}
(PNA) was described elsewhere in a previous paper.
17
Deionized
water (Milli-Q, >18.2 Mcm
-1
) was employed for preparation of
polyelectrolyte solutions and spin-assembled multilayer films and
also for ion permeation studies.
Spin-Coating Electrostatic Self-Assembly (SCESA) on a
Porous Alumina Support. The porous alumina supports were
cleaned as described in an earlier paper.
18
The cleaned alumina
substrates were dipped for a short period (10 min) into water (pH
5) before film deposition, and then they were fixed on a flat solid
plate layered with mica by means of a clear tape. For LBLdeposition
of polyelectrolytes, ca. 0.5 mL of PSS solution (5 mM in H
2
O) was
poured onto the cleaned alumina support, and then the support was
spun at a speed of 5000 rpmfor 20 s. Subsequently, 1 mL of Milli-Q
deionized water was put on the substrate and then the substrate spun
againat 5000rpmfor 20s toremove the weaklyboundpolyelectrolyte.
The washing steps were repeated three times. After that, the substrate
was further rinsed in 1 mL of water three times, 1 min each time,
toguarantee the removal of the nonspecificallyboundpolyelectrolytes
on the surface. The subsequent film deposition using 1 mM PNA
(1:20 DMSO/H
2
O) solution adopted a procedure identical to the
former one. Note that regular multilayer growth of PSS/PNAbilayers
on the alumina support was estimated fromtheir UV/vis absorbance
spectra of the multilayers onfusedsilica andfromtheir ellipsometrical
thickness on a silicon wafer.
Methods. The thickness of the multilayer films on silicon wafers
was measured by using a real-time spectroscopic ellipsometer
(NanoView, SMG-1000) equipped with a Xe arc lamp (350-820
nm), a rotating polarizer, a liquid cell with optical access at an
incidence angle of 60, an analyzer, and a multichannel detection
system which can collect 128 data points from 1.577 to 4.843 eV
in 20 ms. A self-made computer program calculates the change in
polarization of linearly polarized incident light upon reflection from
a sample in terms of and as a function of the photon energy,
where and correspond to the changes in the phase and the
amplitude of the incident polarized radiation, respectively. and
determined for both the bare clean substrate and the film were
converted to thickness. As usual, the refractive index of the
polyelectrolyte film was assumed to be 1.54.
19
Electron microscope images of the membrane were obtained using
a Hitachi S-4700II field-emission scanning electron microscope.
For the cross-sectional images of the membrane, the samples were
mechanically cut using a sharp razor, sputter-coated with a few
angstroms of platinum, rinsed in methanol, and dried with nitrogen.
For field-emissionscanningelectronmicroscopy(FE-SEM) imaging,
a 5.5 kV accelerating voltage and 10 A beam current were used to
obtain fine surface details.
The AFM measurements were performed on a Si wafer in air at
room temperature by using a Nanoscope IV multimode microscope
(Digital Instruments). Usinga 125 mlongSi cantilever (Micromash,
NSC18/AIBS) with a force constant of 3.5 N/m, topographic images
were recorded in tapping mode (1 m 1 m size) at a scan rate
of 1.35 Hz. Data were manipulated using Nanoscope III software.
Ion Permeation Studies. The dialysis apparatus consists of two
glass cells (volume 100 mL), which are interconnected by a 2.5 cm
longneckinwhichthe membrane separates the source- andreceiving-
phase sides. The exposed area of the membrane was 2.0 cm
2
. The
receiving phase contains Milli-Qwater and is connected to the source
phase with the appropriate 0.1 Msalt solution of KCl or K
2
SO
4
. The
receiving-phase solution was stirred to minimize concentration
polarization at the membrane surface.
Prior to the measurement of ion permeation, the multilayer
membrane comprising 10 PNA/PSSbilayers on nanoporous alumina
was irradiated with UV light ( ) 360 nm, p ) 2 mW/cm
2
) for 1
min, which induces trans-to-cis isomerization of the azobenzene
chromophore inthe PNAlayers, andthenit was immediatelyinstalled
in the dialysis apparatus. The ion conductivity in the receiving-
phase cell was monitored at room temperature in a 10 min interval
for 60 min by means of a conductivity meter (Orion model 115).
After the measurement, the membrane was immersed in Milli-Q
water for 15 min to remove unwanted salt attached to the membrane.
The permeation rate (P
R
) and selectivity (R) of the ions were then
calculated according to the equation
11
P
R
) (/t)
m
-1
V(Ac)
-1
and R)P
R1
/P
R2
, where /t is the conductivity change with time
(i.e., the slope of a plot of the salt concentration in the receiving cell
vs time),
m
is the molar conductivity of the corresponding salt
solution, V is the solution volume in the receiving cell, A is the
(17) Kumar, S. K.; Hong, J.-D.; Lim, C.-K.; Park, S.-Y. Macromolecules 2006,
39, 3217.
(18) 18. Nagale, M.; Kim, B. Y.; Bruening, M. L. J. Am. Chem. Soc. 2000,
122, 11670. (19) Schlenoff, J. G.; Dubas, S. T. Macromolecules 2001, 34, 592.
Scheme 1. Structures of the Polyelectrolytes Used in the
Present Study
Figure 1. (a) Schematic illustration of the photoresponsive behavior
of the PEM as an ion switch. (b) Photo of a PEM comprising 15
PSS/PNA bilayers spin-assembled on a porous alumina support.
Ion Gating Function of an Azobenzene PEM Langmuir, Vol. 24, No. 8, 2008 4191
exposed membrane area, c is the salt concentration in the source-
phase solution, and the subscripts 1 and 2 represent two different
ions.
Results and Discussion
The LBL deposition of polyelectrolyte layers on a porous
alumina support by using SCESAis considered to be a challenge
with no guarantee of obtaining a high-quality film. To determine
the optimal conditions for the LBL deposition of PNA and PSS
on the support, the thickness of a film deposited on silicon was
examined by means of optical ellipsometry. The deposition
proceeds uniformly and regularly, as shown in Figure 2a, and
the thickness of the film composed of 15 PNA/PSS bilayers was
determined to be about 43 ( 2.7 nm. The formation of a PEM
membrane on the surface of the nanoporous supportswithout
penetration into the poresscould be clearly identified from the
cross-section FE-SEM image of the PEM (Figure 2b). The film
thickness was estimated to be ca. 58 (6.9 nm, which is in good
agreement with the ellipsometry result, taking into consideration
the poorly defined interface between the film and the support.
The topographical morphology of the spin-assembled PEM
composed of 15 PNA/PSS bilayers on the alumina membrane
was investigatedwithFE-SEM. First, the topsurface of the porous
alumina membrane is completely covered with the pinhole-free
smoothfilm, whereas the original bottomstate contains unblocked
free pores (with a size of 0.02 m), as revealed by the FE-SEM
image of the PEM comprising the 15 PSS/PNA bilayers (Figure
3). These results demonstrate that SCESA is well suited to the
preparation of PEMs on both dense and porous substrate surfaces.
The topographical AFM image of the spin-assembled PEM
composed of 15 PNA/PSS bilayers on a silicon wafer is shown
inFigure 4a for the comparisonwiththat ona nanoporous alumina
support (Figure 4b). The surface morphology of the PEM on
silicon is almost identical to the typical images of azobenzene
polyelectrolyte multilayers on a smooth surface of the substrate,
which exhibits a granular structure with uniformsize, as reported
previously in the literature.
20
In contrast, the PEMon the alumina
membrane tends to produce larger feature sizes with increased
roughness, which directly reflects a highly porous and rough
initial surface. Note that the root-mean-squared (rms) surface
roughness of the PEM on the silicon and the alumina substrates
was determined to be 6.38 and 21.47 nm, respectively.
Chloride and sulfate ion transport through PEM comprising
10 PSS/PNAbilayers on a porous alumina support was measured
by monitoring the increase of conductivity in the receiving phase
for 90 min. After the measurement of ion permeation through
the PEM with trans-azobenzene, the PSS/PNA multilayer
(20) (a) Hong, J.-D.; Jung, B.-D.; Kim, C. H.; Kim, K. Macromolecules 2000,
33, 7905-7911. (b) Advincula, R.; Park, M.-K.; Baba, A.; Kaneko, F. Langmuir
2003, 19, 654-66.
Figure 2. (a) Ellipsometric thicknesses of PNA/PSS multilayers
versus the number of layers. (b) FE-SEM cross-sectional image of
a PEM comprising 15 PNA/PSS bilayers spin-self-assembled on an
alumina support.
Figure 3. FE-SEMimages of the porous alumina support modified
with a PEM comprising 15 PSS/PNA bilayers: top side (a) and
bottom side (b).
Figure 4. Topographical AFM image of the PEM composed of 15
PNA/PSS bilayers on silicon (a) and an alumina support (b). Note
that the AFM image recorded in the tapping mode is given in a top
viewpresentation with the lighter areas denoting higher regions and
the darker areas representing lower regions.
4192 Langmuir, Vol. 24, No. 8, 2008 Kumar and Hong
membrane was irradiated with UVlight for 1 min, which induces
trans-to-cis isomerization of the azobenzene chromophore. A
wavelength-dependent photostationary state between both trans/
cis isomers of PNAis established after about 50 s of irradiation.
17
PNA is a highly photosensitive nitroazobenzene chromophore
with relatively fast photoresponsiveness. The receiving-phase
conductivity of both KCl and K
2
SO
4
was plotted as a function
of the measurement time, as shown in Figure 5. The flux was
found to increase in the cis-state PEM for both chloride and
sulfate ions, revealing that the trans/cis isomerization of the
chromophores attributed to enlargement of the pore sizes in the
membrane. The linearity of the conductivity values with time,
which occurs with the cis- and trans-state membrane, demon-
strates steady-state anion transport where the receiving-phase
concentration is negligible compared to that in the source phase.
The permeation rate (P
R
) was measured for the Cl
-
and SO
4
2-
ions by using a membrane composed of 35 PNA/PSS bilayers
(values of 4.76 10
-7
and 0.07 10
-7
cms
-1
were obtained,
respectively). The selectivity (R) of a membrane with a thickness
of about 100 nm was calculated to be 68.9 for the Cl
-
/SO
4
2-
system, which is a relatively high value.
A light-gated ion switch was realized with a PEM composed
of 10 PSS/PNA bilayers deposited on a porous alumina support
(see Figure 6). The PEMmembrane was irradiated with UVlight
for 1 min prior to the measurements. The value of P
R
increased
about 1.2 times [from (6.40 ( 0.07) 10
-7
to (7.74 ( 0.07)
10
-7
cms
-1
] and 1.6 times [from (2.66 (0.21) 10
-7
to (4.06
( 0.09) 10
-7
cms
-1
] for Cl
-
and SO
4
2-
, respectively. Note
that about 10% of the cis isomers in the PEM undergo thermal
back-relaxation to the trans state during the measurement in the
dark, which is, however, a rather small and negligible amount
considering the scope of this experiment. In the case of Cl
-
, the
permeation rate decreased againsalmost reaching its initial
valuesas a result of the cis-to-trans isomerization of the azo
chromophores upon subsequent exposure to visible light ( )
450 nm, p ) 100 mW cm
-2
).
At this stage, an important question is worth considering about
whether the higher swelling of the films due to the more
hydrophilic nature of the cis isomers could also contribute to the
increased permeability of the ions through the PEM membrane
uponUVirradiation. The difference betweenthe swelling degrees
of the films with trans and cis isomers (10.9 (1.0% versus 11.6
(0.9%) was found to be negligibly small because of the highly
polar character of the polyelectrolytes (see the Supporting
Information). Apparently, the size change of the azobenzene in
the trans/cis isomerization seems to dominatingly affect the pore
sizes of the membrane.
Three important issues should be discussed here: First, sulfate
ions were much more difficult to permeate through the PEM
membrane compared with chloride ions. This might be due to
the bulkiness of the sulfate ions and higher rejection of the
multipolar PEM.
21
Second, the UV irradiation of the PEM
membranes has a stronger influence on the permeation rate of
SO
4
2-
ions than on that of the Cl
-
ions; this can be attributed
to the enlarged pores for the larger sized anions. Third, the
permeation rate of the Cl
-
and SO
4
2-
ions in the trans state
increased gradually during the cis/trans isomerization cycles.
This findingindicates anincomplete recoveryof the PEMmatrixes
caused by the slow relaxation process of the polyelectrolyte
networks during the irradiation with the visible light.
Conclusion
The fabrication of PEM membranes on a porous alumina
support was improved by using the spin-coating electrostatic
method instead of the conventional solution-dip-coating tech-
nique. Surprisingly, the filmqualityof the SCESAfilms deposited
on porous alumina (i.e., their thickness and surface morphology)
was comparable to that of the films obtained on a silicon substrate.
An optical molecular switch that acts as a gating channel for
reversibly opening and closing ion flow through the PEM
membrane was successfully realized by using a layer component
composed of an azobenzene chromophore, which is known to
reveal strong voluminous expansion and contraction during the
cis/trans isomerizations. The ion permeation rate of SO
4
2-
was
found to increase about 1.6 times in the UV-irradiated PEM, an
effect that is significantly stronger than that observed for Cl
-
.
Also, the permeability of the bulky SO
4
2-
ions was more sensitive
tothe channel sizes. The newlydevelopedlight-activatedchannels
can be applied to fabricate sophisticated modern tools that require
a rapid, remote, and noninvasive control, including filtration
systems, membrane-based separation units, and sensors.
Acknowledgment. This work was supported by a Korea
Research Foundation Grant funded by the Korean Government
(MOEHRD) (KRF-2006-311-C00437). We are very grateful to
Prof. Il-Sin Ahn at Hanyang University for allowing us to use
his ellipsometer and thank Prof. Merlin Bruening (Michigan
State University) for his generous help in designing the ion
permeation cell.
SupportingInformationAvailable: Details of the experimental
procedure to determine the change in swelling degree of a polyelectrolyte
multilayer membrane upon UV irradiation. This material is available
free of charge via the Internet at http://pubs.acs.org.
LA7033615
(21) (a) Krasemann, L.; Tieke, B. Langmuir 2000, 16, 287. (b) Harris, J. J.;
Stair, J. L.; Bruening, M. L. Chem. Mater. 2000, 12, 1941.
Figure 5. Receiving-phase conductivity as a function of time, when
the source phase (0.1 M salt) is separated from the receiving phase
by a PEM composed of 10 PSS/ PNA bilayers: KCl at the cis state
(0) and at the trans state (9), K
2
SO
4
at the cis state (O) and at the
trans state (b) of azobenzene.
Figure 6. Cyclic photoswitching of the chloride and sulfate ion
permeations through a PEM comprising 10 PSS/PNA bilayers by
alternate irradiation with UV and visible lights.
Ion Gating Function of an Azobenzene PEM Langmuir, Vol. 24, No. 8, 2008 4193