Sensors and Actuators B 139 (2009) 532537

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

A polydiacetylene multilayer lm for naked eye detection of aromatic compounds

Thoedtoon Champaiboon a , Gamolwan Tumcharern b , Anupat Potisatityuenyong c ,
Sumrit Wacharasindhu c , Mongkol Sukwattanasinitt c,d,
a

Program of Petrochemical and Polymer Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
Thailand National Nanotechnology Center, National Science and Technology Development Agency, Patumthanee 12120, Thailand
c
Organic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
d
Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok 10330, Thailand
b

a r t i c l e

i n f o

Article history:
Received 16 December 2008
Received in revised form 16 March 2009
Accepted 19 March 2009
Available online 31 March 2009
Keywords:
Colloid
Colorimetric
Liposome
Self-assembly
Nanoparticle
Sensor

a b s t r a c t
A blue-colored polyelectrolyte multilayer (PEM) lm of poly(10,12-pentacosadiynoic acid), or poly(PCDA)
vesicles, was successfully prepared by layer-by-layer deposition with polycationic chitosan, and its
application as a colorimetric chemo-sensor for water soluble aromatic compounds was investigated in
comparison to the same poly(PCDA) vesicles as a liquid sol. The color of the PEM lm changes from blue
to red within 5 min when immersed into 10 mM -cyclodextrin (-CD) solution giving the colorimetric response (CR) of 65%. The -CD induced color transition of the PEM lm was completely inhibited
in the presence of 10 mM of either benzoic acid or 4-nitrophenol, which represents a 1:1 mole ratio
of aromatic compound:-CD, showing nearly zero percent CR and the lm remained blue. In contrast,
only partial inhibition was observed by eyes in the presence of 20 mM 4-methoxyphenol and indole as
the lm appeared purple with 15% CR. Phenol and nitrotoluene did not show inhibition detectable by
naked eyes but the low level of inhibition, 35% CR remained, was observed spectroscopically at 20 mM.
For nitrophenols, the degree of inhibition is varied by the isomeric structures in the following order:
4-nitrophenol > 3-nitrophenol > 2-nitrophenol. The competitive inclusion of the aromatic compound into
the -CD cavity is probably responsible for the observed inhibition of color transition. Compared with the
liquid sol of poly(PCDA) vesicles, the PEM lm, as a solid sol, offers less color interference from turbidity
and intrinsic color of the samples being analyzed that the results of inhibition can be readily justied by
naked eyes.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Colorimetric detection that is clearly observable by the naked
eye is highly desirable for on-site analyses of toxic substances. Polydiacetylene (PDA) is one of the most successful polymeric materials
currently being developed as colorimetric indicators for temperature [18], chemicals [914] and biological agents [1525]. The
external stimuli generally disturb the side chain packing that affects
the electronic absorption of the ene-yne conjugated backbone of
PDA, resulting in its color transition from either blue to red or red
to yellow [2629].
The color transition of PDA from blue to red in contact with
-cyclodextrin (-CD) solution was observed for the rst time
in a LangmuirSchaefer (LS) lm prepared from PDA containing
an aniline head group [30]. This color transition can be inhibited

Corresponding author at: Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand. Tel.: +66 2218 7620;
fax: +66 2218 7598.
E-mail address: smongkol@chula.ac.th (M. Sukwattanasinitt).
0925-4005/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2009.03.047

by 4-nitrophenol (4-NP) by competitive formation of an inclusion

complex with the -CD. Subsequent research has conrmed that
-CD has an effect on the formation and color change of PDA vesicles by insertion of the PDA head group into the cavity of -CD
[31,32]. The sensitivity of each type of PDA has not been specically
addressed in the literature reports. Nevertheless, the concentration
of -CD used for the induction of color transition of PDA containing a carboxylic head group was reported to be signicantly lower
than that of PDA containing an amide head group, implying the
higher sensitivity of the former toward -CD [3032]. To expand
the utility of the PDA-based chemo-sensors, fabrication of PDA in
various forms has been reported. A micro-multichannel lled with
PDA-embedded PEG hydrogel matrix has been prepared for the
simultaneous analyses of multiple samples [33]. However, the gelbased device required a long detection time, in the range of an hour,
and exhibited a low sensitivity which is probably due to the slow
diffusion rate in the very viscous gel medium. In contrast, the LS
lm revealed a higher sensitivity and a shorter detection time, but
the fabrication of LS lm into naked eye detectable devices is technically demanding. Alternatively, polyelectrolyte multilayer (PEM)
membrane interchanging electrostatic layer-by-layer assembly of

T. Champaiboon et al. / Sensors and Actuators B 139 (2009) 532537

cationic and ionic electrolyte become a powerful way to prepare

multilayer thin lm [34,35].We have recently reported a convenient
method for the preparation of polyelectrolyte multilayer (PEM)
lms containing intact PDA vesicles using layer-by-layer deposition
[36]. The color intensity of the lm can be effectively controlled by
the number of the vesicle layers deposited. In this article, the application of the PEM lm containing poly(10,12-pentacosadiynoic
acid), poly(PCDA), vesicles for detection of aromatic compounds in
water is reported. As a solid sol, the PEM lm exhibits a few benets
over the liquid sol of the vesicles.
2. Experimental
2.1. Materials
The diacetylenic monomer, 10,12-Pentacosadiynoic acid (97%
(w/w) purity; PCDA), was purchased from Fluka, USA. Chitosan
was purchased from Seafresh Chitosan (Lab) Company, Thailand.
The viscosity-averaged molecular weight (Mv ) was 8.0 105 , and
the degree of deacetylation determined by colloidal titration was
84%. Diethyl ether was purchased from Lab-Scan, Thailand. Generally, deionized water was used for reagent preparation and rinsing,
except for the vesicle preparation where milli-Q water with a resistance of 18.1 M was used. All other solvents and chemicals were
analytical or reagent grade purchased from Fluka and used as
received without further purication, unless specied otherwise.
2.2. Preparation of poly(PCDA) vesicles
PCDA was dissolved in diethyl ether and the solvent was evaporated by purging with N2 . After the addition of milli-Q water, the
PCDA suspension (0.5 mM) was sonicated by using a 230 W bath
sonicator (Ultrasonicator, Elma, Germany) for 20 min at 7585 C.
The resulting colloid was kept at 4 C overnight before the temperature was then brought up to room temperature and polymerized
by UV irradiation at 254 nm for 5 min to yield a blue sol of
poly(PCDA). The blue-colored poly(PCDA) vesicle sol was ltered
through 1/125 mm lter paper to remove any undesired lipid aggregates.

533

reported in percentage (%CR). The %CR is 100 (PB0 PB)/PB0 ,

where PB is the percent blue calculated from Ablue /(Ablue + Ared ).
The Ablue and Ared were the absorbance of the blue and red phases
of poly(PCDA) measured at max around 635 and 540 nm, respectively. The initial percent blue (PB0 ) was determined on the samples
before exposure to the stimulus.
2.6. Study of color transition induced by -cyclodextrin
A chitosan/poly(PCDA) multilayer lm was introduced into a
quartz cuvette lled with the deionized water (pH 6.0, temp = 25 C)
and allowed to stand for 5 min before an electronic absorption spectrum was taken. The spectra were collected from 800 to 400 nm
with the absorbance at 800 nm set to zero. The procedure was
repeated after replacing the water with -cyclodextrin (-CD) solutions, the concentrations of which were varied from 0 to 20 mM.
At each concentration, a lm/solution contact time of 5 min was
allowed prior to spectrum acquisition. The color transition of the
vesicle liquid sol was studied in comparison to the lm by mixing a
fresh sol of poly(PCDA) vesicles (A635 = 0.150.20) with -CD solution at each concentration tested and the absorption spectrum was
acquired.
2.7. Study of inhibition of color transition by aromatic compounds
An aqueous solution of -CD (10 mM) was mixed with each
tested aromatic compound, i.e. phenol, 2-, 3- and 4-nitrophenol,
4-nitrotoluene, 4-methoxyphenol, benzoic acid and indole, at various concentrations (020 mM) and sonicated for 2 min. Starting
from the solution containing the highest concentration of the aromatic compound, the PEM lm was dipped into the solution for
10 min. The lm was then withdrawn from the solution and dipped
into a quartz cuvette lled with deionized water and the absorption spectrum was collected from 800 to 400 nm. The same lm was

2.3. Preparation of chitosan solution (the polycationic solution)

The chitosan powder (0.5 g) was dissolved in 1.0 mL of glacial
acetic acid and diluted to 100 mL with deionized water. The solution
was stirred at room temperature for 12 h to allow the complete
dissolution and diluted again with water to make a total volume
of 500 mL (0.1%, w/v). The solution was centrifuged to discard any
insoluble polymer and the clear solution was collected.
2.4. Preparation of chitosan/poly(PCDA) multilayer lm
A chitosan/poly(PCDA) multilayer lm was prepared in accordance with the published method [36]. The pH of the poly(PCDA)
and chitosan solutions were adjusted within the range of 3.03.3
by using HCl (0.1 mM). A clean glass slide, used as a substrate, was
dipped in the chitosan solution for 5 min and then rinsed by deionized water three times. The glass slide was then dipped into the
poly(PCDA) sol for 5 min, rinsed again three times and then dipped
into the chitosan solution to form another layer. The dipping and
rinsing cycle was repeated until the lm with desired color intensity
was obtained.
2.5. Colorimetric measurements
The colorimetric response (CR) was used to quantitatively evaluate the blue-to-red transition which is generally determined and

Fig. 1. Electronic absorption spectra of poly(PCDA) vesicles recorded at 25 C and

5 min after the addition of various concentrations of -CD solution into liquid sol
(a), and the 10-layered PEM lm (b).

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T. Champaiboon et al. / Sensors and Actuators B 139 (2009) 532537

Fig. 2. TEM images of poly(PCDA) vesicles before (a), and after (b), exposure to 10 mM -CD solution.

dipped into the solutions containing the next highest concentration

of the test aromatic compound and the spectrum was acquired in
the same manner. The experiment was continued, assaying sequentially more dilute samples, until all solutions were examined. The
inhibition of the color transition of the vesicle liquid sol was studied in comparison to the lm by mixing a fresh sol of poly(PCDA)
vesicles (A635 = 0.150.20) with each mixture of aromatic compound and -CD solution tested and the absorption spectrum was
acquired.
2.8. Transmission electron microscope (TEM) imaging of
poly(PCDA) nanovesicles

(not shown). A blue to red color change of the multilayer lm

was observed when the lm was immersed in a 10 mM -CD
solution for 5 min. This color transition has been attributed to
the inclusion complex between -CD and the poly(PCDA) side
chain. Fig. 1 illustrates the visible absorption spectra of the
PEM lm and the liquid sol in the presence of 020 mM CD. Increasing the concentration of -CD leads to an increase
in the absorption band at a max of 540 nm at the expense
of the band with a max of 635 nm, demonstrating that -CD
induces a blue to red color transition of both the poly(PCDA)
PEM lm and its liquid sol. For liquid sol, turbidity of the sol

Poly(PCDA) vesicle sol (0.5 mM) was separated into two samples.
One of them was mixed with -CD (10 mM) and kept overnight for
complete color transition. A droplet of each sample was dropped
on a formvar coated copper grid (200 mesh), stained with 2% (w/v)
uranyl acetate for 5 min, and then dried in a desiccator. All samples were imaged through Transmission Electron Microscope (JEOL
TEM-2100, Japan), using an accelerating voltage of 200 kV.
3. Results and discussion
3.1. Color transition of poly(PCDA) vesicles induced by -CD
The as-fabricated poly(PCDA)/chitosan polyelectrolyte multilayer PEM lm possessed a blue color which develops into a
deeper blue color as the number of layers deposited was increased

Fig. 3. The colorimetric response of poly(PCDA) liquid sol and poly(PCDA)/chitosan

PEM lm recorded 5 min after addition of 10 mM -CD solution at 25 C.

T. Champaiboon et al. / Sensors and Actuators B 139 (2009) 532537

due to aggregation of the vesicles was clearly observed along

with the change of color. Above 4 mM of -CD solution, the
electronic absorption spectra of the liquid sol displayed unacceptably high baselines, especially in the shorter wavelength region,
masking real changes and signifying a serious interference from
the light scattered by the aggregated particles (Fig. 1a). For the
PEM lms, the shifts of the spectral baselines were insignicant
(Fig. 1b).
The aggregation of the vesicles is evidenced by the TEM images
of the dry samples of poly(PCDA) vesicles before and after addition
of -CD (Fig. 2). Poly(PCDA) vesicles as prepared had a uniform
smooth spherical shape (Fig. 2a). The addition of 10 mM -CD
into the vesicle sol results in breakage, fusion and aggregation of
these particles. The deformation of the vesicles is probably caused
by a disruption of the hydrogen bonding between the carboxylic
head-groups on the vesicle surface upon the insertion of -CD to
form the inclusion complex with the carboxylic head group of the
side chain. The average size of poly(PCDA) vesicles, determined by
dynamic light scattering (DLS), was also increased from 70 5 to
170 30 nm consistent with the proposed aggregation. Poly(PCDA)
vesicles immobilized as a solid sol in the PEM lm are, however,
not allowed to move into proximity of each other preventing the
deformed vesicles from aggregating.
Colorimetric response (CR) has been one of the most effective
and convenient parameters to semi-quantify the bluered color
transition. The %CR of the PEM lm showed a relatively wider linear response to -CD concentrations (310 mM) compared with
the much narrower linear response range (45 mM) of the liquid sol (Fig. 3), revealing another benet of the PEM lm over
the liquid sol. The wider linear colorimetric response of the PEM
lm is in good agreement with the stable baseline observed in the
electronic absorption spectra (Fig. 1). It is also important to note
that the %CR of the PEM lm can reach over 80%, whilst the liquid sol can only attain a maximum of less than 60%, which is likely
to be due to the serious precipitation at this point in the liquid
sol.

3.2. Inhibition of -CD induced color transition observed by

naked eyes
The inhibition of the -CD induced color transition of
poly(PCDA) vesicles by 4-nitrophenol in liquid sol has been
reported before [30] and was attributed to the inclusion of 4nitrophenol with -CD that precludes -CD from interacting with
the poly(PCDA) vesicles. We contemplated that this inhibition event
could be useful for detection of certain aromatic compounds which
can form inclusion complexes with -CD in water.
To verify if the color transition of our poly(PCDA)/chitosan
PEM lm can be inhibited by 4-nitrophenol, -CD (10 mM) was
mixed with 4-nitrophenol at various concentrations in the range

535

Fig. 4. The colorimetric response of poly(PCDA)/chitosan PEM lm after exposure

to the mixture of 10 mM -CD and various concentrations of 4-nitrophenol at 25 C
for 5 min.

of 020 mM before being immersed with the PEM lm. The %CR
decreased almost linearly with increasing 4-nitrophenol concentrations in the 010 mM range (Fig. 4) to a %CR of almost zero at
10 mM 4-nitrophenol. This suggests a 1:1 stoichiometic amount of
4-nitrophenol is required to completely suppress the color transition.
Several other aromatic compounds (Fig. 5), which have been
reported to form inclusion complexes with -CD [35], were tested
for the inhibition of the -CD induced color transition of poly(PCDA)
vesicles in both the liquid sol and the PEM lm. The addition of
the solution mixture, containing the test aromatic compound at
20 mM and 10 mM -CD, to the liquid sol showed that only benzoic
acid (4) and, perhaps, 4-nitrophenol (2) fully inhibited the bluered
color transition (Fig. 6a), whilst phenol (1), 4-methoxyphenol (3),
4-nitrotoluene (5) and indole (6) could not inhibit the color transition. For 4-nitrophenol (2) the degree of inhibition is masked,
and so unclear, since although the green color corresponds to the
result of the combination of the blue color of the vesicles with
the yellow color of the test sample, the actual shade of blue to
red attained is masked by the yellow. Evidently, the color observation of the liquid sol can be signicantly masked by the color
of the test samples. However, for the PEM lms, the lms can
be withdrawn after being immersed in the tested solution allowing the color observation to be taken outside the sample solution.
Moreover, since the color transition induced by -CD is irreversible, the color of the lms can best be observed after rinsing
the lm with deionized water. The color transition of the PEM
lms (Fig. 6b) was completely inhibited by 4-nitrophenol (2), as
inferred but not established by the liquid sol, and benzoic acid (4),
whilst phenol and 4-nitrotoluene showed no inhibition (1 and 5).
Even a partial inhibition by 4-methoxyphenol and indole, which
was not detected in the liquid sol, can be justied by the pur-

Fig. 5. The chemical structures of the principal aromatic compounds tested for the inhibition of -CD induced color transition.

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T. Champaiboon et al. / Sensors and Actuators B 139 (2009) 532537

Fig. 6. Color photographs of poly(PCDA) vesicles in (a) liquid sol, and (b) 10-layered PEM lm, after 5 min exposure to the mixture of the test aromatic compound (20 mM)
and -CD (10 mM), at 25 C. DI water is used as a positive inhibition control (Positive Control). The aromatic compounds are phenol (1), 4-nitrophenol (2), 4-methoxyphenol
(3), benzoic acid (4), 4-nitrotoluene (5) and indole (6). A solution of 10 mM -CD is used as a negative inhibition control (Negative Control).

ple color of the PEM lm (3 and 6). It is also important to note

that 4-nitrotoluene, which has very low solubility in water, failed
to inhibit the color transition. The technique developed here is
thus suitable for detection of only water-soluble aromatic compounds.
3.3. Inhibition of -CD induced color transition determined by CR
The measurement of the CR of the PEM lm can be used for
quantitative comparisons of the ability of the aromatic compounds
to inhibit the color transition (Fig. 7). For example, benzoic acid and
4-nitrophenol fully inhibited the color transition of the PEM lm at
10 mM (a molar ratio to -CD of 1:1) showing nearly zero percent
CR comparing to 65% CR of the control test using only 10 mM -CD
without the test aromatic compounds. At the same concentration of
4-methoxyphenol and indole, the -CD induced color transition of
the PEM lm was 35 and 40% CR indicating lower inhibition ability.
The partial inhibition observed by eyes as purple lms, when 20 mM

4-methoxyphenol and indole were tested as described earlier, corresponded to 15% CR. Phenol and 4-nitrotuluene, which did not
show any observable inhibition of color transition by naked eyes,
gave CR 45 and 35% at 10 and 20 mM doses, respectively. Compared to 4-nitrophenol, 3-nitrophenol showed a lower inhibition
requiring 20 mM (a mole ratio of 2:1 to -CD) to completely inhibit
the color transition. The other isomer, 2-nitrophenol, showed an
even weaker still inhibition effect, attaining nearly 50% CR even at
20 mM.
The ability to inhibit -CD color transition, as judged from the
%CR observed, implies the inclusion binding strength of the aromatic guests to -CD host in the following order: benzoic acid
4-nitrophenol > 3-nitrophenol > p-methoxyphenol indole >
phenol 4-nitrotoluene > 2-nitrophenol. This order agrees well
with most of the association constants determined by other methods as reported in the literature, except for indole which was
previously determined by calorimetry to have a very high association constant [37] which, perhaps, was over estimated. The
differences in inhibition abilities among three nitrophenol regioisomers also suggest that this analysis technique can take advantage of
the shape selectivity of -CD cavity for identication the isomers
of aromatic compounds. The greater inhibition abilities of nitrophenol and benzoic acid comparing to that of phenol also suggests
signicant contribution of the acidity of the aromatic compounds.

4. Conclusions

Fig. 7. The colorimetric response of poly(PCDA)/chitosan PEM lm after exposure

to a mixture of the test aromatic compound (5, 10 and 20 mM) and 10 mM -CD at
25 C for 5 min.

Immobilization of polydiacetylene vesicles into PEM lm can

improve the properties of the vesicles toward the development
of naked eye detection of water-soluble aromatic compounds.
The blue to red color transition of poly(PCDA)/chitosan PEM lm
induced by -CD can be completely inhibited by benzoic acid
and nitrophenols at 1:1 mole ratio of the -CD:aromatic compound. Unlike the liquid sol, the color transition of the PEM lm
and its inhibition can be easily observed by eyes with no interference from the color of the samples or the turbidity caused by
the vesicle aggregation. The poly(PCDA)/chitosan PEM lm and
technique developed here can be quite convenient for on-site
screening of natural water for critical contamination by aromatic
substances.

T. Champaiboon et al. / Sensors and Actuators B 139 (2009) 532537

Acknowledgment
The authors gratefully acknowledge the research grant from
National Nanotechnology Center and the scholarships from Thailand Graduate Institute of Science and Technology (TGIST).
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Biographies
Thoedtoon Champaiboon is a graduate student in the Department of Petrochemical
and Polymer Science, Chulalongkorn University. His research interests include layerby-layer deposition of polydiacetylene vesicle for sensing applications.
Gamolwan Tumcharern received her PhD degree in inorganic chemistry from
Chulalongkorn University. Now she is a researcher at the Thailand National Nanotechnology Center. Her research interests include fabrication of nano-material for
sensing applications.
Anupat Potisatityuenyong received his PhD degree in organic chemistry from
Chulalongkorn University. His recent research eld is molecular assembly of lipid
molecule for sensing applications.
Sumrit Wacharasindhu received his PhD degree in organic chemistry from University of Missouri Columbia in 2005. During 20052007 he was a postdoctoral
researcher in Medicinal Chemistry Department at Wyeth Pharmaceuticals in New
York. He is now a lecturer at Department of Chemistry, Chulalongkorn University.
His current elds of interest include new strategies and tactics for organic chemistry,
and applications of synthesis to conjugated polymers.
Mongkol Sukwattanasinitt received his PhD degree in organic chemistry from
Iowa State University in 1996. During 19961997 he was a postdoctoral associate
in the Center for Advanced Materials at University of Massachusetts Lowell, Massachusetts, USA. He is now an associate professor at the Department of Chemistry,
Chulalongkorn University, Bangkok, Thailand. His current elds of interest involve
design and constructing of sensing systems from organic materials using organic
synthesis and supramolecular assembly.