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Benzo[ghi]perylene and coronene: ratiometric

fluorescent probes for the sensing of
Cite this: New J. Chem., 2018,
42, 6949 microenvironment changes and micelle
formation in aqueous medium†
Ejaz Hussain,ab Zhenzhen Hu,ab Huipeng Zhou,ab Chunhua He,ab
Sohail Anjum Shahzadac and Cong Yu *ab

Received 13th February 2018,
Accepted 17th March 2018
DOI: 10.1039/c8nj00739j
rsc.li/njc
Benzo[ghi]perylene and coronene were used as ratiometric fluorescent probes to monitor microenvironment
changes and monomer-micelle transition for the first time. The perturbations in vibronic bands in the
emission spectra of probes displayed microenvironment sensing behavior in various solvents and surfactants.
The monomer–micelle transitions of anionic, cationic and neutral surfactants were monitored by changes in
the ratios of vibronic band intensities. Clear CMC values were obtained, which is an advantage over the
conventional probes such as pyrene with clear CMC values sometimes difficult to obtain due to less steep
changes of S-shaped plots. They revealed a redshift in emission which offers a good substitute
in situations where the fluorescence of pyrene and the background fluorescence of the assay mixture
interfere with each other. BzP exhibited reverse behavior in the perturbations of vibronic band intensities
in anionic SDS and SLS relative to cationic and non-ionic surfactants, which was not observed when
pyrene was used. In addition, the vibronic band ratios of BzP are thermally more stable than those of
pyrene, which is advantageous since strict assay temperature control may not be necessary. These
probes are thus helpful for various applications in the areas of sensing and interface science.

Introduction The growth of micelles and formation of microemulsions

Fluorescence probes are commonly used to explore micro-
heterogeneous systems like micelle self-assembly, cellular
physiology, and biology-oriented applications.1–4 The fluorescence
intensities of some probes are sensitive to micro-environmental
factors such as dielectric constant, dipole moment, microviscosity,
solute–solvent interactions, etc. These factors induce perturbations
in the vibronic bands. This could be used to establish novel
sensing techniques for applications like biophysical studies of
aggregates, surfactants, bio-surfactants and cell membranes.5–7
For the study of micellization and aggregation behaviors, various
methods have been reported based on surface tension,8 conductivity,
and spectroscopy.9–12 The fluorescence probe method is a simple
approach to investigate the mechanism of self-assembly and
microenvironment changes, as it does not require sophisticated
instrumentation compared to other techniques.11–14
a
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022,
P. R. China. E-mail: congyu@ciac.ac.cn; Fax: +86-431-85262710
b
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China
c
Department of Chemistry, COMSATS Institute of Information Technology,
Abbottabad 22060, Pakistan
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8nj00739j
were monitored via direct observation of micelle transition
under a fluorescence microscope by employing a surfactant
fluorescent probe synthesized with a tetraphenylethene core.13
Fluorescent surfactants like a hexavanadate cluster at the head
group were designed for micelles based applications.15 Time-
resolved anisotropies of micelles were measured by fluorescent
probes, and fluorescence depolarization dynamics of the probes
in the micelles were studied.16 Auramine-O and 8-anilino-1-
naphthalenesulfonic acid were employed as fluorescent probes
to determine water/surfactant molar ratios for the transition of
reverse micelles to microemulsions.17 Hence, fluorescence probes
have extensive applications in interfacial systems.16–18
Micelles have found a wide range of applications in biological
science. Models for lipid digestibility and bio-accessibility of
carotenoid were developed based on carotenoid micellization.19
Fullerene-based water compatible imprinted micelles were used
for the electrochemical determination of anticancer drug
chlorambucil.20 Micelles also play a key role as drug carriers.21
Glutathione-responsive Gemini polymeric micelles with an average
diameter of 26.9 nm were used as an indomethacin (IMC) carrier
with potential for high load and controlled drug delivery.22 The
adhesive properties of thiolated chitosan micelles on mucosal
membranes made them excellent drug carriers.23

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Surfactants display concentration-dependent organization
and dynamics in structural transition. Critical micelle concen-
tration (CMC) is the narrow range of surfactant concentration
above which micelles are formed, and surface tension becomes
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independent of surfactant concentration.24–26 Bio-surfactants
and surfactants with low CMC values are excellent emulsifiers
that reduce the air/water surface tension to very low level.27
Based on the CMC values the composition of micelles can be
adjusted to modulate protein denaturation and the association
mechanism.28,29 The interactions of various surfactants with
nano-particles depend on CMC values.30 Hence, it is important
to study the CMC to optimize various micellization processes.
Benzo[ghi]perylene (BzP) and coronene (Cron) are condensed
polycyclic aromatic hydrocarbons [PAHs] that possess excellent
photostability, a higher quantum yield, and a longer lifetime
(Table 1). They were used to establish a solvent polarity scale.36,37
The systematic perturbations in fluorescence intensities of PAHs
make them ideal probes for sensing, imaging, diagnostics,
therapeutic and interfacial applications.31 Herein, they were used
as fluorescent probes to monitor microenvironment changes and
monomer-micelle transition for the first time. The changes in
vibronic band ratios displayed clear CMC values. The emission
spectra are red-shifted as compared to conventional dye pyrene.
The reverse behavior was observed in perturbations of relative
band intensities of BzP monomer fluorescence in anionic
surfactants (SDS and SLS) as compared to cationic and neutral
surfactants, which was not observed when pyrene was used. In
addition, the vibronic ratios of BzP are thermally stable. These
interesting findings suggest that these probes are ideal candidates
for next-generation applications.
Results and discussion
Microenvironment sensing of fluorescent probes in different
solvents
Benzo[ghi]perylene and coronene exhibited systematic micro-
environment-dependent changes in vibronic band intensities
in different solvents of varying polarity and dielectric constants.
The fluorescence spectra of BzP recorded at an excitation
wavelength of 365 nm displayed five distinct primary vibration
bands extended along 400 to 450 nm (I–V) showing a redshift of
more than 35 nm relative to pyrene emission (Fig. 1 and Fig. S1,
S3, ESI†). The systematic attenuations in relative intensities of
vibronic bands were observed moving from polar to non-polar
Table 1 The photophysical properties of benzo[ghi]perylene and
coronene6,38,39
ta Principal vibronic bands
Probe (ns) Fa (nm) Symmetry
Benzo[ghi]perylene 400 0.7 397, 406, 419, 430, 445 C2v
at lext 365
Coronene 224 0.6 427, 433, 445, 454, 475, 484 D6h
at lext 305
a
Experimental parameters were reported in cyclohexane at 273 K.
t = fluorescence lifetime, F = quantum yield.
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Fig. 1 Fluorescence emission of benzo[ghi]perylene in solvents of different
polarity and dielectric constants (normalized with reference to peak III,
lext = 365 nm, slit width = 3 nm).
solvents. Peak intensities were normalized with reference to
peak III that is the least sensitive to the microenvironment
demonstrating the allowed transitions.39 The most significant
changes were observed in the relative intensities of peaks II and
IV that are sensitive towards hydrophilic and hydrophobic
environments. The suppression of relative intensity of peaks
II and IV from more polar solvent acetonitrile to less polar
n-hexane revealed that the intensity of these peaks is sensitive
to solvent polarity. The numerical values of relative changes in
vibronic band intensities of BzP fluorescence are tabulated in
Table S1 (see the ESI†).
The systematic changes in band intensities in different
solvents can be seen in Fig. 1, 3 and Fig. S1 (ESI†). The changes
in various ratios of the relative vibronic band intensities in
different micro-environmental systems ensured benzo[ghi]perylene
as the sensitive probe for monitoring monomer-micelle transitions.
Furthermore, the vibronic band ratios of the probe are thermally
stable.37
Fluorescence spectra of coronene recorded at an excitation
wavelength of 305 nm have six distinct primary vibronic bands
at 427, 433, 445, 454, 475, and 484 nm (Fig. 2). The emission
spectra displayed a bathochromic shift (about 50 nm) compared
to pyrene (Fig. S3, ESI†). Coronene fluorescence spectra also
exhibited systematic variations in vibronic band intensities in
various solvents. Different kinds of responses were observed by
comparing attenuations in relative intensities of vibronic bands
as illustrated in Fig. 2, 3 and Fig. S2, Table S2 (ESI†). The peak
intensities were normalized with reference to peak III. This
demonstrated an allowed transition.39 The relative vibronic intensity
of peak I decreased moving from acetonitrile to n-hexane which
indicates environment polarity significantly influenced the intensity
of the peak. Slight changes were observed in the relative peak
intensity of peak II. Peak IV displayed the same trend in changes
as peak II. The relative intensities of peak V remained unaltered,
and peak VI showed negligible changes in relative intensities as
displayed in Fig. 2, 3, and Fig. S2 (ESI†). Furthermore, the

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Fig. 2 Fluorescence emission of coronene in solvents of different polarity
and dielectric constants (normalized with reference to peak III, lext =
305 nm, slit width = 3 nm).
Fig. 3 Bar charts showing relative attenuations in vibronic band intensities
of BzP (left) and Cron (right) fluorescence emissions in polar and non-polar
solvents (fluorescence intensities were normalized relative to peak III).
dynamic range of characteristic changes in the ratios of relative
vibronic band intensities was observed in the probes.
Several factors were reported to be involved in perturbation
of vibronic bands such as solvent polarity, solute–solvent
interaction, micro-viscosity, and dielectric constants, etc.37–39
The variable state of dipole moments of probe molecules in
different microenvironments is also an important reason.8 As a
Fig. 4 The behavior of vibronic peak intensity of benzo[ghi]perylene above and below CMC of surfactants (SDS, CTAB, and Triton X-100) showing
systematic changes in relative peak intensities (BzP = 2 mM, lext = 365 nm, slit width = 3 nm, fluorescence intensities were normalized relative to peak III).
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result of excitation, probe molecules were promoted from the
ground state of the low dipole moment to the related vibrational
level of the excited state. Micro-environmental parameters
influence the electronic distribution in its ground and excited
states. In the excited state lifetime of the probe, the more stable
dipole moment of the probe is reoriented by the influence of the
solvent molecules. The fluorescence emission of the molecular
probe varies with the formation of the solute–solvent pair.8
The redshifts in the fluorescence emissions displayed by both
probes relative to pyrene (Fig. S3, ESI†) are advantageous for some
analytical applications where the background fluorescence of the
assay matrix interferes with pyrene.
Microenvironment sensing of beno[ghi]peryelen at phase
transition in micelle formation process
The attenuations in fluorescence emissions of probes were used
for microenvironment sensing of aqueous surfactant solutions
and quantification of CMC. Benzo[ghi]perylene showed an
interesting trend of changes in relative intensities of peaks in
varying concentrations of surfactants which enabled monitoring
the micelle formation. The relative intensities of peaks II and IV
were significantly higher below the CMC of SDS. However, with
the increase of surfactant concentration, the intensities of these
peaks decreased slightly. Interestingly, an opposite trend in the
behavior of concentration-dependent perturbations of peak
intensities was observed in CTAB and Triton X-100 relative to
SDS as illustrated in Fig. 4.
The plots obtained by peak ratios of BzP monomer fluorescence
(I/II, III/VI or II/III) against the surfactant concentration showed
clear changes in the trend of lines at CMC (Fig. 5 and Fig. S4, ESI†).
For example, below the CMC, the ratio of III/IV gradually increased
with the increase in SDS concentration. However, above the
CMC, the ratio of III/IV showed little changes (Fig. 5). And the
intersecting point gave the clear CMC value. The opposite trend
in the changes of the ratio of III/IV was observed in cationic and
neutral surfactants. The spectral behavior sensed the monomer-
micelle transitions in aqueous solutions of anionic (SDS), cationic
(CTAB), and neutral surfactants (Triton X-100). The plots displayed
by II/III and I/II indicated similar changes in behavior near the CMC
as illustrated in Fig. S4 (ESI†). The standard deviations were
estimated from three experimental measurements. The changes
in fluorescence intensities were found to be small. The intersection
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Fig. 5 Monitoring of micelle formation in aqueous solutions of SDS, CTAB and Triton X-100 by changes in III/IV of BzP as a function of surfactant
concentration. Error bars were estimated from three measurements.

Table 2 The critical micelle concentration (CMC) values determined by Multiples ratios of vibronic band intensities of coronene
vibronic band ratios of fluorescent probes displayed detectable changes in behavior at CMC of surfactants.
CMC (mM  SD) The plots of I/II, and II/III gave the clear values of CMC from the
Vibronic inflection point of two lines with a different slope (Fig. 6 and
Probe ratio SDS CTAB TX-100
Fig. S6, ESI†). The ratio of I/II gradually increased with increase
BzP I/II 7.9  0.003 0.91  0.003 0.31  0.005 in the concentration of surfactants below CMC and remained
II/III 8.1  0.04 0.92  0.04 0.31  0.03
III/IV 7.8  0.04 0.91  0.02 0.29  0.02 constant above CMC. The ratio of II/III decreased with the
increase in the concentration of surfactants. However, it
Coronene I/II 7.9  0.02 0.84  0.02 0.29  0.03 remained constant with negligible changes above CMC. Hence,
II/III 7.7  0.02 0.88  0.01 0.29  0.03
I/IV — 0.88  0.01 0.31  0.03 these ratios gave clear values of CMC. I/IV and I/VI can be used
I/VI — 0.89  0.04 0.31  0.02 for the CMC determination of surfactants of low CMC values.
The values of CMC of surfactants obtained by coronene are in
Literature6,32–35 7.8–8.1 0.87–0.92 0.28–0.31
good agreement with the literature as illustrated in Table 2.6,24
The plots of conventional dye pyrene are sigmoid shaped
points of lines of mean values gave clear CMC values. The values of with less steep changes near CMC. They may give uncertain
the CMC obtained were in good agreement with the literature values CMC values.42 The ratios of vibronic band intensities of pyrene are
as depicted in Table 2 and Table S3 (ESI†). also thermally less stable.37 Hence, the new probes with thermally
The reverse behavior in the perturbation of vibronic bands stable vibronic band ratios and clear CMC values obtained from
in monomer fluorescence of anionic SDS seems to be a complex inflection points could be more helpful to monitor micelle for-
phenomenon of interactions between the less symmetric BzP mation. There are more peak ratios available with the new
with the microenvironment. It is reported that the molecular probes to locate the CMC value as compared to other dyes.6,34
symmetry and the interactions of molecular probes with the The shape of plots obtained from vibronic ratios of BzP and
microenvironment play a critical role to determine the extent to Cron resembled with the plots reported by monitoring various
which mixed allowed and forbidden transitions should occur.36 properties of environments such as surface tension, conductiv-
The intensity ratios were affected by the specific interactions of ity, detergency and interfacial tension.8,9 The response of II/III
molecular probes with the solvent cage.39 Furthermore, the of coronene as a function of surfactant concentration resem-
dielectric constant, polarity, micro-viscosity of anionic SDS bles the shape of the plot obtained from interfacial tension.10,42
apparently differ greatly from the cationic and neutral media.40 The response of various peak ratios of BzP resembles the
plots obtained by monitoring osmotic pressure and conductivity
of the microenvironment.41 These results indicate the various
Microenvironment sensing of coronene at phase transition in
factors of the microenvironment that influence monomer
micelle formation process
fluorescence of the probes. These findings will help to under-
Coronene also exhibits concentration-dependent changes in stand the process of micellization and identify the factors
relative intensities of monomer fluorescence. It shows turn-on affecting the microenvironment.
monomer fluorescence in dilute aqueous solutions of surfactants.
The intensities of monomer fluorescence enhanced with the increase
in surfactant concentration. And the formation of micelles at a Experimental
higher concentration of surfactants leads to a higher intensity of
monomer fluorescence. Besides the gradual increase in monomer Materials and chemicals
fluorescence, microenvironment-dependent relative perturbations Sodium dodecyl sulfate (SDS), sodium lauryl sulfonate (SLS),
in peak intensities were observed as can be seen in Fig. S5 (ESI†). hexadecyl-trimethylammonium bromide (CTAB), didecyldimethyl-
The peak intensities of I and II showed significant attenuations in ammonium bromide (DDAB), Triton X-100, coronene, benzo[ghi]-
peak heights with the change in surfactant concentration. perylene and pyrene were purchased from commercial suppliers.

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Fig. 6 Critical micelle concentration of SDS, CTAB and Triton X-100 determined by various ratios of coronene vibronic bands as a function of surfactant
concentration. Error bars were estimated from three measurements.
Coronene and benzo[ghi]perylene were re-crystallized once from
ethanol before use. Purity was assessed by 1H NMR spectra
obtained at 500 MHz using a BRUKER NMR spectrometer in
CDCl3. Chemical shifts were recorded relative to TMS as an
internal standard. Ethanol, DMSO, acetonitrile, chloroform,
n-hexane, hexanol, methanol and all other solvents used were
of analytical grade. Corrected fluorescence spectra were collected
using a Fuoromax-4 spectro-fluorometer.
Methods
The stock solutions of surfactants were prepared in water
purified by a Milli-Q water purification system. Serial dilutions of
each surfactant were prepared in a desired range of concentrations.
The methanol solutions of benzo[ghi]perylene and coronene were
prepared in the range of 0.2–0.3 mM. 5 mL of probe solutions was
added to 500 mL of corresponding diluted solutions of the surfac-
tants. The final aqueous solutions of surfactants contained 2 to 3 mM
probe concentration. Diluted solutions were mixed and sonicated for
30 minutes. Corrected fluorescence emission spectra of each
solution were recorded on a Fuoromax-4 spectrofluorometer.
Coronene and benzo[ghi]perylene solutions were excited at
wavelengths of 305 and 365 nm respectively with a slit width
of 3 nm.
Conclusions
Benzo[ghi]perylene and coronene were used as fluorescence
probes to monitor microenvironment changes and monomer–
micelle transition for the first time, based on the systematic
attenuation of vibronic band intensities. Various ratios of
vibronic band intensities of the probes sensed the monomer–
micelle transition in anionic, cationic and neutral surfactants.
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The probes offer precise and clear CMC values of surfactants
from the inflection point of lines, which are consistent with the
literature values.6,32–35 The redshift in emission made them
good alternatives to pyrene for studies where the interference of
background fluorescence with pyrene could not be easily
avoided. BzP displayed the reverse behavior in perturbations
of vibronic bands in anionic surfactants SDS and SLS as
compared to aqueous solutions of cationic (CTAB, DDAB) and
neutral surfactants (Triton X-100). Thermal stability of vibronic
band ratios of BzP is an additional advantage over pyrene.37 It
is envisioned that BzP and Cron could find a wide range of
applications in areas of colloids, microemulsions, polymers,
biosurfactants, and membrane structures.31,41
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the CAS-TWAS President’s PhD
Fellowship Program (2015CTF031), the National Natural
Science Foundation of China (21561162004, 51761145102),
and the Jilin Provincial Science and Technology Development
Project (International Collaboration Program, 20160414040GH).
Notes and references
1 J. Li, Y. Li, C. Y. K. Chan, R. T. K. Kwok, H. Li, P. Zrazhevskiy,
X. Gao, J. Z. Sun, A. Qin and B. Z. Tang, Angew. Chem., Int.
Ed., 2014, 53, 13518–13522.
New J. Chem., 2018, 42, 6949--6954 | 6953

Paper
2 L. Linlin, F. Chongchong, X. Jie, W. Fengyang, Y. Haijun,
X. Zhiai and Z. Wen, Biosens. Bioelectron., 2017, 92, 101–108.
3 F. Lei, X. Lu, D. Shuli and H. Jingcheng, Soft Matter, 2016,
12, 7495–7504.
Published on 21 March 2018. Downloaded by China University of Geosciences - Wuhan Campus on 12/18/2022 3:53:09 PM.
4 M. Almgren, F. Grieser and J. K. Thomas, J. Am. Chem. Soc.,
1979, 101, 279–291.
5 L. Piñeiro, N. Mercedes and A. Wajih, Adv. Colloid Interface
Sci., 2015, 215, 1–12.
6 K. Kalyanasundaram and J. K. Thomas, J. Am. Chem. Soc.,
1977, 99, 2039–2044.
7 H. W. Liu, K. Li, X. X. Hu, L. Zhu, Q. Rong, Y. Liu,
X. B. Zhang, J. Hasserodt, F. L. Qu and W. Tan, Angew.
Chem., Int. Ed., 2017, 56(39), 11788–11792.
8 L. Shi, D. Lundberg, D. G. Musaev and F. M. Menger, Angew.
Chem., 2007, 119, 5993–5995.
9 C. Ignac, Adv. Colloid Interface Sci., 2002, 97, 91–149.
10 W. Al-Soufi, L. Piñeiro and M. Novo, J. Colloid Interface Sci.,
2012, 379, 102–110.
11 L. Day, J. K. Raynes, A. Lies, L. H. Liu and R. P. W. Williams,
Food Hydrocolloids, 2017, 69, 150–163.
12 G. V. Jensen, R. Lund, J. Gummel, T. Narayanan and
J. S. Pedersen, Angew. Chem., 2014, 126, 11708–11712.
13 W. Guan, W. Zhou, C. Lu and B. Z. Tang, Angew. Chem., Int.
Ed., 2015, 54, 15160–15164.
14 G. V. Jensen, R. Lund, J. Gummel, M. Monkenbusch,
T. Narayanan and J. S. Pedersen, J. Am. Chem. Soc., 2013,
135, 7214–7222.
15 P. Yin, P. Wu, Z. Xiao, D. Li, E. Bitterlich, J. Zhang, P. Cheng,
D. V. Vezenov, T. Liu and Y. Wei, Angew. Chem., Int. Ed.,
2011, 50, 2521–2525.
16 C. N. Maiti, M. M. G. Krishan, P. J. Britto and N. Periasamy,
J. Phys. Chem. B, 1997, 101(46), 11051–11060.
17 F. Monzer, M. A. Sami and S. Mukhles, J. Dispersion Sci.
Technol., 2010, 31(11), 1561–1567.
18 M. Shannigrahi and S. Bagchi, J. Phys. Chem. B, 2004,
108(46), 17703–17708.
19 S. T. Laura, S. H. E. Verkempinck, L. Sun, A. M. Van Loey,
T. Grauwet and M. E. Hendrickx, Food Chem., 2017, 229,
653–662.
20 P. B. Bhim, S. Ragini and K. Anil, Biosens. Bioelectron., 2017,
94, 115–123.
21 E. Soussan, S. Cassel, M. Blanzat and I. Rico-Lattes, Angew.
Chem., Int. Ed., 2009, 48, 274–288.
6954 | New J. Chem., 2018, 42, 6949--6954 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018
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NJC
22 K. C. Hyun, K. Eunjoo, J. W. Sang, L. G. Se, L. J. Sung and
L. W. Seung, Macromol. Res., 2015, 23(2), 196–204.
23 M. Arshad, L. Melanie, L. Flavia, H. W. Christian and
B. S. Andreas, Carbohydr. Polym., 2017, 167, 250–258.
24 H. H. J. Joris, S. Peter, O. Gunter, H. Geoff, E. V. Charles,
K. Mattias and H. L. M. Joop, Environ. Toxicol. Chem., 2016,
35(9), 2173–2181.
25 F. Elisabet, R. Clara, R. Marti and B. Elisabeth, Anal. Chim.
Acta, 2005, 548, 95–100.
26 H. Dan and C. C. Keng, J. Am. Chem. Soc., 2014, 136,
15114–15117.
27 O. E. Daniel, Biochim. Biophys. Acta, 2017, 1859, 639–649.
28 O. E. Daniel, Biochim. Biophys. Acta, 2011, 1814(5), 562–591.
29 A. K. Kell, O. L. Cristiano, L. L. Kim, P. M. Flemming,
C. H. Thomas, W. Peter, P. S. Jan and O. Daniel, J. Mol.
Biotechnol., 2009, 391(1), 207–226.
30 Y. Tauran, B. Arnaud, P. Patrick, C. Cumbo, K. Beomjoon,
P. Florent, C. W. Anthony and M. Imed, Chem. Commun.,
2012, 48, 9483–9485.
31 Y. Jun, Y. Mei and D. Yixiang, Chem. Rev., 2014, 114,
6130–6178.
32 C. Prem, P. Somasundaran and T. J. Nicholas, J. Colloid
Interface Sci., 1987, 117(1), 31–46.
33 K. P. Ananthapadmanabhan, E. D. Goddard, N. J. Turro and
P. L. Kuo, Langmuir, 1985, 1, 352–355.
34 R. C. Dorrance and T. F. Hunter, J. Chem. Soc., Faraday
Trans. 1, 1972, 68, 1312–1321.
35 W. G. Margaret and J. T. Nicholas, Photochem. Photobiol.,
1975, 22, 273–276.
36 A. T. Sheryl, E. A. Willaim, W. S. Kenenth and C. F. John,
Appl. Spectrosc., 1989, 43(1), 162–164.
37 R. Waris, E. A. Willaim and K. W. Street, Analyst, 1988, 113,
1465–1467.
38 N. Nijegorodov, R. Mabbs and W. S. Downey, Spectrochim.
Acta, Part A, 2001, 57, 2673–2685.
39 M. M. Steven and B. M. Linda, Anal. Chem., 1991, 63,
2082–2086.
40 H. Chikako, I. Miwa, T. Rie and E. Kazutoyo, Langmuir,
2002, 18, 1999–2003.
41 C. Arunima, H. Sourav and C. Amitabha, Biochem. Biophys.
Res. Commun., 2009, 390, 728–732.
42 J. Aguiar, P. Carpena, J. A. M. Bolı́var and C. C. Ruiz,
J. Colloid Interface Sci., 2003, 258, 116–122.