Analyst

View Article Online / Journal Homepage / Table of Contents for this issue

Dynamic Article Links <

Cite this: Analyst, 2011, 136, 3343

PAPER

Published on 13 July 2011. Downloaded by University of New Hampshire on 04/06/2014 20:16:46.

www.rsc.org/analyst

Aggregation-induced emission of tetraphenylethene derivative as

a fluorescence method for probing the assembling/disassembling of
amphiphilic molecules
Congshan Zhu, Shaopeng Pang, Jianping Xu, Lan Jia, Fangming Xu, Ju Mei, Anjun Qin, Jingzhi Sun, Jian Ji*
and Benzhong Tang*
Received 3rd March 2011, Accepted 27th May 2011
DOI: 10.1039/c1an15176b
The aggregation-induced emission (AIE) of a 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE) was explored as
a novel fluorescence method for probing the assembling/disassembling of amphiphilic molecules. The
fluorescence intensity was able to monitor the formation of micelles and determine the critical micelle
concentration (CMC) of surfactants. The temperature-dependent micellization of the pharmaceutically
important PEOPPOPEO copolymer, Pluronic F127, was further studied by using the TPE
fluorescence spectrum intensity. Our results showed good agreement with those reported in the
literature by using other methods. The special advantage of the AIE probe method was further explored
to determine the assembling/disassembling process of the colored amphiphilic molecule, 1-[4-(3phenylazophenoxy)butyl]triethylamine bromide (AzoC4), whose CMC value has not previously been
described. Since the TPE fluorescence signal mainly comes from the aqueous phase, not from the inside
of hydrophobic core, it provides a possible platform to study the CMC of those colored surfactants.
Based on the novel fluorescence properties of TPE in the aggregated and dispersed states, one can
conclude that the TPE method is a promising method for the determination of the CMC and critical
micellization temperature (CMT), particularly having a special advantage to determine the assembling/
disassembling process of colored amphiphilic molecules.

1. Introduction
Surfactant molecules and micelle solutions are playing a more
and more important role in biochemistry and pharmaceutical
applications such as the solubilization of hydrophobic drugs,
delivery of genes, and in biological detection systems.1 In view of
these advantageous applications of surfactants, a good understanding of the micellization of surfactants and the determination of the critical micelle concentration (CMC) of surfactants is
of fundamental importance.24 Various techniques have been
routinely used to determine the CMC in aqueous solution. These
include surface tension, conductivity, light scattering techniques,
UV/vis and fluorescence spectroscopy, which are all based on an
abrupt change in the related physical properties upon micelle
formation.58 As is known, the methods mentioned above still
MOE Key Laboratory of Macromolecular Synthesis and
Functionalization, Department of Polymer Science and Engineering,
Zhejiang University, Hangzhou 310027, China. E-mail: jijian@zju.edu.
cn; tangbenz@zju.edu.cn; tangbenz@ust.hk
Electronic supplementary information (ESI) available: The structure of
1-[4-(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4), CMC
determination of [CTAB], [SDS], [Chol-PEO] by TPE and pyrene
methods, CMT determination of F127 by TPE method, Comparisons
between CMT values obtained by TPE method and literature values.
See DOI: 10.1039/c1an15176b

This journal is The Royal Society of Chemistry 2011

have some limitations. For example, surface tension-based

methods need complex sequences of operations, and must
consider the radius of capillary tube, density of solution, and
contact angle. Also, conductivity-based methods are not suitable
for non-ionic surfactants whose conductivity is low and transition cannot be observed. In particular, luminescence probing
techniques have attracted great of interest because of their
simplicity and high sensitivity.912 A frequently used fluorescence
method is the excitation spectra of a pyrene probe. However, the
fluorescence intensity of pyrene can hardly reflect the CMC
directly. A complex fitting curve of the ratio of the excitation of
I338/I333 was necessary to detect the CMC.13,14 Furthermore, the
fluorescence property of pyrene belongs to aggregation-caused
quenching (ACQ) of light emission in the aggregates.15 Its fluorescence emission mainly comes from the inner core of the micelle
when it is applied to be the sensor for determination of the CMC.
So it could not detect the CMC of some colored surfactants,
which may absorb the fluorescence emission.
Recently, a new phenomenon of aggregation-induced emission (AIE) has been observed in some fluorescent dyes.1621 The
main principle of the AIE effect can be attributed to restricted
intramolecular rotation (RIR) of its phenyl peripheries against
the central double bond in the aggregate state,15,22,23 which
inspired us to explore an alternative method to investigate the
Analyst, 2011, 136, 33433348 | 3343

Published on 13 July 2011. Downloaded by University of New Hampshire on 04/06/2014 20:16:46.

View Article Online

assembling/disassembling of amphiphilic molecules via the AIE

effect. Tetraphenylethene derivatives are typical AIE dyes,24
which are non-emissive when they are dissolved in good
solvents, but which become highly emissive when distributed in
poor solvents. Herein, 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE)
was explored as the fluorescence probe for determining the
CMCs and critical micellization temperatures (CMTs) of
various surfactants. Our hypothesis can be summarized briefly
in Scheme 1. At low concentration of surfactants, a lot of TPE
molecules aggregate in the water phase, and produce a strong
fluorescence emission. However, when the concentration of
surfactant is increased, TPE molecules might be incorporated
into and dispersed well in the hydrophobic core. The fluorescence intensity of TPE might decrease due to the loss of the
restricted intramolecular rotation of its phenyl peripheries.
Considering the completely different fluorescence properties of
TPE and pyrene between the aggregated and dispersed states,
TPE may provide a good alternative method for detecting the
CMC of surfactants and monitor the assembly/disassembly of
amphiphilic molecules.

2. Materials and methods

2.1 Materials
The AIE-active compound used as the fluorescence probe was
1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE), whose chemical structures is shown in Fig. S1. It was synthesized according to the
literature. Water used in all experiments was purified via deionization and filtration with Millipore purification apparatus to the
resistivity higher than 18 MU.cm. Pyrene (Alfa Aesar, 99%) was
used as received. Cholesterol-end-capped PEO (Chol-PEO20)
was kindly supplied by Nihon Emulsion Co., Ltd. F127 (BASF).
Cetyltrimethylammonium bromide (CTAB, 99%) was purchased
from Chinese Medical Company (Shanghai). A positivelycharged azobenzene-containing surfactant, 1-[4-(3-phenylazophenoxy)butyl]triethylamine
bromide
(AzoC4),
was
synthesized according to the literature.25,26 The chemical structure of AzoC4 was shown in Fig. S1(b). All other reagents were
of analytical reagent grade and used as received.

Scheme 1 Schematic illustration of the detection of the CMC based on

the mechanism of aggregation-induced emission (AIE) and the structure
of chemical compound 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE).

3344 | Analyst, 2011, 136, 33433348

2.2 Determination of the critical micelle concentration of the

surfactants in aqueous solution
A TPE stock solution in acetone was prepared and a given
volume of TPE solution was added dropwise to aqueous
surfactant solutions of various concentrations and finally all
samples got the same concentration of probe equal to 0.5 mM.
These samples underwent ultrasonic treatment for 20 min and
then were allowed to stand for 1 h. Finally, the mixtures were
transferred to the fluorescence study. A Shimadzu LS-55
Luminescence Spectrometer (PerkinElmer) was used to measure
TPE solution fluorescence. The wavelengths of excitation and
emission were 310 nm and 470 nm, respectively. The temperature was controlled with a water bath circulator (SLM Instruments). The described fluorescence probe technique required
very low (0.5 mM) concentrations of probe, thus minimizing the
perturbation of micelle formation by TPE insertion. In the
present study, TPE was used as a probe to determine the CMC
of CTAB, Chol-PEO, AzoC4 and the CMT of various
concentrations of F127. Also, a pyrene fluorescence probe was
used as a comparative method. The experimental details of the
pyrene fluorescence method for probing the CMC of surfactant
are according to the literature.27,28 Each measurement was done
in triplicate, the mean value of the three was used as the final
result.

3. Results and discussion

3.1 Determination of the critical micelle concentration
The fluorescence spectra of the solutions recorded at different
CTAB concentrations ([CTAB]) were shown in Fig. 1(a). The
excitation wavelength of the TPE probe was selected at 310 nm,
and the concentration was adjusted to 0.5 mM. In order to
determine the CMC, the fluorescence intensity of the most
intensive peak at lmax 470 nm was plotted against the CTAB
concentrations. As shown in Fig. 1(b), all plots were adequately
described by a sigmoidal function of the Boltzmann type. The
CMC was determined at the inflection points of the fitted
sigmoid traces. From Fig. 1(b), we could easily obtain the CMC
of CTAB through a tangent method. There was a sharp decrease
in the fluorescence intensity when the [CTAB] approaches about
0.25 mg mL1. The inflexion on the plot of the maximum on the
fluorescence curves vs. [CTAB] indicated that the CMC of CTAB
was 0.42 mg mL1 (1.15 mM), which was a little higher than
results from the pyrene method. But it was still inside the scope of
the data reported in the literatures by different methods such as
conductometry and polargraphy, etc.6,7,13,2932 It was a common
phenomenon that different methods gave rise to different CMC
values for the same surfactant.33
These behaviors can be explained as follows: TPE is a lipophilic AIE compound, which is poorly soluble in water but highly
soluble in organic solvents. Since water is a poor solvent for TPE,
the TPE molecules thus aggregate in the water solution. There
should be strong fluorescence when TPE was added to the water,
even with a small amount of TPE probe. If a large amount of
TPE molecules were introduced to water, they could form
precipitates and the solution wasnt stable. A suitable concentration of TPE fluorescence probe was chosen to be 0.5 mM and
no particles existed in the water solution studied by Dynamic
This journal is The Royal Society of Chemistry 2011

View Article Online

Table 1 Comparison between the Determined CMCs and the Literature

Values of selected surfactants

Published on 13 July 2011. Downloaded by University of New Hampshire on 04/06/2014 20:16:46.

CMC values/mM
Surfactant

TPE method

Pyrene method

Literature

Refs

CTAB
SDS
Chol-PEO

1.15
8.9
7.1  103

0.58
5.6
5.5  103

0.21.26
310

2932
30,31,34,35

3.2 Determination of the critical micelle concentration of the

colored surfactant in aqueous solution

Fig. 1 (a) Fluorescence spectra of aqueous solution of TPE with

different [CTAB] (mg mL1); (b) plot of fluorescence peak intensity vs.
[CTAB].

Light Scattering. These results suggested that the TPE at a low

concentration aggregated in water solution, but it was still
homogenous with no precipitate. Obviously, it would appear
with stronger luminescence in the aqueous phase than in the
hydrophobic phase.
Upon introducing TPE into the CTAB aqueous solution,
a strong fluorescence was expected to be observed for the systems
when the surfactant concentration was lower than the CMC.
Once the concentration was higher than the CMC, the surfactant
molecules must self-assemble into micelles. Driven by hydrophobic interactions, the lipophilic TPE molecules would enter
and disperse in the hydrophobic cores of the micelles. As a result,
decline of fluorescence would be recorded with the increase of the
concentration of surfactant. From the transition of the curve, we
could easily determine the CMC of the surfactants.
Table 1 shows a comparison between the CMC values determined in this study and the reported literature values for various
surfactants. The CMCs of cationic CTAB, anionic SDS, and
non-ionic Chol-PEO from TPE fluorescence measurements were
found to be 1.15 mM, 8.9 mM, and 7.1  103 mM, respectively.
These values were generally in agreement with literature
results.6,7,13,29,30,34 For a given surfactant at a given temperature
the change in some physical properties occurs at approximately
the same concentration. The TPE probe is an effective and
convenient method to study the micelle formation and disassociation. Compared with the classic ACQ method, the AIE
method could directly track the formation of micelles. Additional treatment of the data was not necessary.
This journal is The Royal Society of Chemistry 2011

As we all know, there are many probes for the fluorescence

detection of CMC, such as pyrene, DPH, DAF etc.30,3537 At the
same time, there are few probes that can detect surfactants with
colors. It was analyzed that the probes mainly reflected the
changes of signals which came from the inner changes of the
micelle. It was obvious that the colored substance owned some
special spectral absorption. Fluorescence emission from the inner
micelle might be disturbed by the colored surfactants, resulting in
failure in determining the CMC values. But TPE was based on
AIE theory and its luminescence lay in the water phase rather
than inside of the micelles. These analyses enabled us to suppose
that TPE could be a good means to investigate the CMC of those
colored compounds.
A positively-charged azobenzene-containing surfactant, 1-[4(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4),
was synthesized according to the literature.25,26 The chemical
structure of AzoC4 is shown in Fig. S1(b). The aqueous solution
of AzoC4 was yellowish-brown. We have taken some tentative
studies to study the solution by the TPE method and the pyrene
method. At the two fixed concentrations, 0.01 mg mL1, and
0.1 mg mL1, Fig. 2(a) shows the fluorescence emission spectra
of pyrene. In Fig. 2(a), at a low concentration of AzoC4
(0.01 mg mL1), pyrene exhibited a low fluorescence emission
intensity. At high concentration (0.1 mg mL1), its fluorescence
disappeared completely, which was contrary to those noncolored normal surfactant results.
This phenomenon could be ascribed to the UV-Vis absorption
of AzoC4 to fluorescence emission which was produced by pyrene. The AzoC4 had a broad absorption wavelength from
200 nm to 500 nm (see Fig. S2 in the supporting information).
The spectrum emission wavelength of the pyrene probe was in
the range of the absorption wavelength of the AzoC4 surfactant
molecules. When AzoC4 formed a micelle, the micelle would be
enclosed by the molecules with a quenching feature. When
micelles formed, pyrene molecules were solubilized in the interior
micellar phase and their emissions were popularly distributed in
micelles. It was obvious that the fluorescence of pyrene could not
be detected when pyrene was quenched. Pyrene was known to
exhibit ACQ of light emission in the condensed phase. When it
was applied to determine the CMC values, its fluorescence
emission was used, which mainly came from the inner core of the
micelle. If the fluorescence emission was quenched, it was hard to
determine the CMC. So it could not detect the CMC of AzoC4,
which absorbed the fluorescence emission.
At the same time, the TPE probe was used to study the CMC of
AzoC4. Fig. 2(b) shows the results of the fluorescence
Analyst, 2011, 136, 33433348 | 3345

Published on 13 July 2011. Downloaded by University of New Hampshire on 04/06/2014 20:16:46.

View Article Online

Fig. 2 (a) Fluorescence spectra of pyrene at different concentrations of

[AzoC4] (excitation 339 nm, voltage 800 V, slit: 10 nm, 10 nm); (b)
fluorescence spectra of TPE at different concentrations of [AzoC4]
(excitation 310 nm, voltage 800 V, slit: 10 nm, 10 nm).

measurement by the TPE method at the two fixed concentrations.

At low concentration (0.01 mg mL1), it exhibited strong fluorescence. At high concentration (0.1 mg mL1), a weak fluorescence was observed. The results are consistent with theoretical
prediction. The TPE molecule exhibits AIE, whose fluorescence
mainly comes from the aqueous phase. At low concentration of
AzoC4, there were many molecules aggregated in the aqueous
phase. At high concentration, there were many molecules
distributed in hydrophobic part of micelle. As a result, its fluorescence would appear stronger at low concentration than high
concentration of AzoC4. Further, we tentatively detected the
CMC of AzoC4 by the TPE method. Fig. 3(a) shows the fluorescence spectra of the solutions recorded at different AzoC4
concentrations. It was noted that the fluorescence intensity
became weaker with the concentration of AzoC4 increase higher
below the CMC. The plot of the maximum on fluorescence curves
vs. [AzoC4] is given in Fig. 3(b) and an inflexion at around 0.02 mg
mL1 could be derived. Compared with the classic ACQ method,
the AIE method described in this manuscript, which depends on
the decreasing of TPE fluorescence in aqueous phase, will be more
general and versatile than the classic ACQ probe method.
3.3 Determination of the critical micelle temperature of the
F127 surfactant in aqueous solution
The strong dependence of the CMC on temperature has led to an
extensive use of the concept of the CMT.3840 PEOPPOPEO
3346 | Analyst, 2011, 136, 33433348

Fig. 3 (a) Fluorescence spectra of aqueous solution of TPE with

different [AzoC4] (mg mL1); (b) plot of fluorescence peak intensity vs.
[AzoC4].

block copolymers are an important class of surfactants and are

found to be widespread in pharmaceutics (drug solubilization
and controlled release), bioprocessing (protecting microorganisms against mechanical damage), and separations (solubilization of organics in aqueous solutions).41,42 Temperaturedependent micellization is the most characteristic property of
aqueous PEOPPOPEO block copolymer solutions. Perhaps
the parameter of greatest fundamental value is the CMT at which
micelles appear in a PEOPPOPEO solution at a given
concentration.
In this study, TPE probe was chosen to study the CMT of
F127, which is a typical PEOPPOPEO block copolymer. The
representative fluorescence spectra of the F127 solutions at
a concentration of 0.5 mg mL1 were recorded at different
temperatures, as shown in Fig. 4(a). Fig. 4(b) shows the dependence of the intensities at 470 nm (spectral maximum due to
TPE) upon the temperature when the F127 concentration was
fixed at 0.5 mg mL1. At low temperature, Pluronic F127 did not
associate in aqueous solution, TPE was not solubilized in
a hydrophobic environment; as a result, the fluorescence intensity was strong. At high temperatures, the Pluronic F127 formed
micelles, and TPE was solubilized in the hydrophobic micelle
interior, giving a low intensity. The CMT values for F127 of
various concentrations were obtained from the inflection of the
plot of emission intensity at 470nm vs. temperature. The experiment results reported here are well consistent with the reference
report.39,43,44
This journal is The Royal Society of Chemistry 2011

Published on 13 July 2011. Downloaded by University of New Hampshire on 04/06/2014 20:16:46.

View Article Online

The CMT values of F127 with concentrations in the range of

0.110 mg mL1 are shown in the supporting information. The
CMT values obtained from the TPE method agree very well with
the literature.39,43 The use of TPE to determine the CMT have
proved to be a reliable and convenient method.
Since the fluorescence emission of the TPE probe in water
solution belonged to AIE, its luminescence should have some
connection with the temperature. The thermal motion of the TPE
molecules should be influenced by temperature. If the TPE
molecules move intensely, it must change the molecular aggregation state. As Fig. 4(c) proves, the fluorescence intensity of the
pure TPE probe water solution has a linear relationship with
temperature.
Fig. 5 Fluorescence emission intensity of the TPE and F127
(0.5 mg mL1) system solution.

Compared with the determination of CMT values, the straight

slope of the pure TPE water solution was slightly lower, as was
shown in Fig. 4(c). In the presence of F127 polymer, the fluorescence of the TPE probe turns not only weaker but also
abruptly. Apparently, it would improve the sensitivity of the
TPE, reflecting the temperature in the presence of F127.
Although the TPE probe itself was influenced by temperature, it
could still be an effective method to determine the CMC and
CMT values.
Furthermore, we studied the reverse property of the F127/TPE
complex system. Fig. 5 shows the fluorescence reversibility of the
0.5 mg mL1 F127 complex system between 15 and 35  C. A good
fluorescence recovery was observed as we changed the temperature of the system. It occurred to us that the F127/TPE system
also could be used to sense the change of temperature.

4. Conclusions
This work has established a new fluorescence method to determine
the CMC of various surfactants via the AIE effect. Based on
a comparison of the CMC values obtained by the TPE probe
method with those obtained by the conventional pyrene-based
method and other methods in the literature, the TPE method is
useful for determining the CMC of various surfactants, including
cationic, anionic, and amphiphilic neutral molecules. Furthermore, the fluorescence intensity could directly track the formation
of micelles and determined the CMC of surfactant. Additional
treatment of the data was not necessary. While the conventional
fluorescence based method might have problems to study the
CMC of colored surfactants due to its ACQ disturbed by colored
surfactants, the AIE based method can study it since the TPE
fluorescence signal mainly comes from the aqueous phase.
Through the further investigation of the F127/TPE system, a good
reversibility of fluorescence intensity was observed. The AIE
based method provides an alternative method to investigate the
assembling/disassembling of amphiphilic molecules.

Acknowledgements
Fig. 4 (a) Fluorescence spectra of aqueous solution of F127
(0.5 mg mL1) at various temperatures. (b) Plot of fluorescence peak
intensity vs. T/ C. (c) Fluorescence emissions for aqueous solutions as
a function of temperature at various concentrations of F127.

This journal is The Royal Society of Chemistry 2011

Financial support from the NSFC-50830106, National Science

Fund for Distinguished Young Scholars (51025312) and Open
Project of State Key Laboratory of Supramolecular Structure
and Materials (SKLSSM201103) is gratefully acknowledged.
Analyst, 2011, 136, 33433348 | 3347

View Article Online

Published on 13 July 2011. Downloaded by University of New Hampshire on 04/06/2014 20:16:46.

References
1 H. Alkanonyuksel, S. Ramakrishnan, H. B. Chai and J. M. Pezzuto,
Pharm. Res., 1994, 11, 206212.
2 K. L. Mittal and P. Mukerjee, Plenum Press: New York, 1977, Vol. 1.
3 R. D. Vold and M. Vold, J. Colloid and Interface Chemistry, Addison
Wesley, Reading, MA, 1983, ch. 18.
4 R. Hunter, J. Foundations of Colloid Science, Oxford University Press,
New York, 1991, ch. 10.
5 R. M. M. Brito and W. L. C. Vaz, Anal. Biochem., 1986, 152, 250255.
6 P. Mukerjee and K. J. Mysels, National Bureau of Standards, 1970.
7 K. Nesmerak and I. Nemcova, Anal. Lett., 2006, 39, 10231040.
8 E. Devendittis, G. Palumbo, G. Parlato and V. Bocchini, Anal.
Biochem., 1981, 115, 278286.
9 W. Lu, J. P. Gao, Z. Y. Wang, Y. Qi, G. G. Sacripante, J. D. Duff and
P. R. Sundararajan, Macromolecules, 1999, 32, 88808885.
10 B. Liu, Biosens. Bioelectron., 2008, 24, 756760.
11 C. P. Chang, C. Y. Chao, J. H. Huang, A. K. Li, C. S. Hsu, M. S. Lin,
B. R. Hsieh and A. C. Su, Synth. Met., 2004, 144, 297301.
12 K. Li and B. Liu, Anal. Chem., 2009, 81, 40994105.
13 K. Kalyanasundaram and J. K. Thomas, J. Am. Chem. Soc., 1977, 99,
20392044.
14 N. J. Turro and P. L. Kuo, Langmuir, 1986, 2, 438442.
15 Y. N. Hong, J. W. Y. Lam and B. Z. Tang, Chem. Commun., 2009,
43324353.
16 M. Wang, D. Q. Zhang, G. X. Zhang, Y. L. Tang, S. Wang and
D. B. Zhu, Anal. Chem., 2008, 80, 64436448.
17 J. W. Chen, B. Xu, X. Y. Ouyang, B. Z. Tang and Y. Cao, J. Phys.
Chem. A, 2004, 108, 75227526.
18 J. D. Luo, Z. L. Xie, J. W. Y. Lam, L. Cheng, H. Y. Chen, C. F. Qiu,
H. S. Kwok, X. W. Zhan, Y. Q. Liu, D. B. Zhu and B. Z. Tang, Chem.
Commun., 2001, 17401741.
19 J. W. Chen, C. C. W. Law, J. W. Y. Lam, Y. P. Dong, S. M. F. Lo,
I. D. Williams, D. B. Zhu and B. Z. Tang, Chem. Mater., 2003, 15,
15351546.
20 H. Tong, Y. N. Hong, Y. Q. Dong, M. Haussler, J. W. Y. Lam, Z. Li,
Z. F. Guo, Z. H. Guo and B. Z. Tang, Chem. Commun., 2006, 3705
3707.
21 M. Wang, X. G. Gu, G. X. Zhang, D. Q. Zhang and D. B. Zhu, Anal.
Chem., 2009, 81, 44444449.
22 Q. Zeng, Z. Li, Y. Q. Dong, C. A. Di, A. J. Qin, Y. N. Hong, L. Ji,
Z. C. Zhu, C. K. W. Jim, G. Yu, Q. Q. Li, Z. A. Li, Y. Q. Liu,
J. G. Qin and B. Z. Tang, Chem. Commun., 2007, 7072.

3348 | Analyst, 2011, 136, 33433348

23 M. Wang, G. X. Zhang, D. Q. Zhang, D. B. Zhu and B. Tang, J.

Mater. Chem., 2010, 20, 18581867.
24 L. Tang, J. K. Jin, A. J. Qin, W. Z. Yuan, Y. Mao, J. Mei, J. Z. Sun
and B. Z. Tang, Chem. Commun., 2009, 49744976.
25 S. F. Xiao, X. M. Lu, Q. H. Lu and B. Su, Macromolecules, 2008, 41,
38843892.
26 Q. Zhang and C. G. Bazuin, Macromolecules, 2009, 42, 47754786.
27 M. Wilhelm, C. L. Zhao, Y. C. Wang, R. L. Xu, M. A. Winnik,
J. L. Mura, G. Riess and M. D. Croucher, Macromolecules, 1991,
24, 10331040.
28 I. Astafieva, X. F. Zhong and A. Eisenberg, Macromolecules, 1993,
26, 73397352.
29 J. Aguiar, P. Carpena, J. A. Molina-Bolivar and C. C. Ruiz, J. Colloid
Interface Sci., 2003, 258, 116122.
30 A. Mohr, P. Talbiersky, H. G. Korth, R. Sustmann, R. Boese,
D. Blaser and H. Rehage, J. Phys. Chem. B, 2007, 111, 1298512992.
31 A. Honnorat and P. Martinet, Electrochim. Acta, 1983, 28, 17031711.
32 G. B. Ray, I. Chakraborty and S. P. Moulik, J. Colloid Interface Sci.,
2006, 294, 248254.
33 L. Tang, J. K. Jin, S. Zhang, Y. Mao, J. Z. Sun, W. Z. Yuan, H. Zhao,
H. P. Xu, A. J. Qin and B. Z. Tang, Sci. China, Ser. B: Chem., 2009,
52, 755759.
34 Y. Nakahara, T. Kida, Y. Nakatsuji and M. Akashi, Langmuir, 2005,
21, 66886695.
35 M. V. Thorsteinsson, J. Richter, A. L. Lee and P. DePhillips, Anal.
Biochem., 2005, 340, 220225.
36 X. C. Zhang, J. K. Jackson and H. M. Burt, J. Biochem. Biophys.
Methods, 1996, 31, 145150.
37 A. P. Romani, A. E. D. Machado, N. Hioka, D. Severino,
M. S. Baptista, L. Codognoto, M. R. Rodrigues and H. P. M. de
Oliveira, J. Fluoresc., 2009, 19, 327332.
38 M. Almgren, W. Brown and S. Hvidt, Colloid Polym. Sci., 1995, 273,
215.
39 P. Alexandridis, J. F. Holzwarth and T. A. Hatton, Macromolecules,
1994, 27, 24142425.
40 Z. K. Zhou and B. Chu, J. Colloid Interface Sci., 1988, 126, 171180.
41 D. W. Murhammer and C. F. Goochee, Biotechnol. Prog., 1990, 6,
391397.
42 M. Yokoyama, Crit. Rev. Ther. Drug, 1992, 9, 213248.
43 G. Wanka, H. Hoffmann and W. Ulbricht, Macromolecules, 1994, 27,
41454159.
44 M. Bohorquez, C. Koch, T. Trygstad and N. Pandit, J. Colloid
Interface Sci., 1999, 216, 3440.

This journal is The Royal Society of Chemistry 2011