ARTICLE IN PRESS

Journal of Luminescence 121 (2006) 431–440

www.elsevier.com/locate/jlumin

Micellar effects on the molecular aggregation and fluorescence

properties of benzazole-derived push–pull butadienes
Tarek A. Fayed, Safaa El-Din H. Etaiw, Naglaa Z. Saleh
Chemistry Department, Faculty of Science, Tanta University, 31527-Tanta, Egypt
Received 8 August 2005; accepted 18 November 2005
Available online 4 January 2006

Abstract

The absorption and fluorescence spectral behaviour of 1-(2-benzoxazolyl)-4-(p-dimethylaminophenyl)buta-1,3-diene

and its benzothiazolyl analogue (abbreviated as BODB and BTDB, respectively) have been investigated in
dioxane–water mixtures and micellar environments using steady-state techniques. In water, water-rich mixtures or
premicellar solutions, BODB and BTDB tend to form molecular aggregates labelled as H-aggregates. These aggregates
dissociate on adding surfactants forming micellized monomers. In all micellar media the fluorescence quantum yield is
greatly enhanced along with a large hypsochromic shift. Also, in TX-100, CTAB and SDS both dienes show dual
emission from the locally excited (LE) and intramolecular charge transfer (ICT) states. For BTDB in TX-100 and
DODB in all solutions, the LE fluorescence predominates, while for BTDB in CTAB and SDS, the ICT fluorescence is
the predominant. The fluorescence shifts suggest that the fluorescing molecules penetrate the core of the micellar unit in
TX-100, whereas in CTAB and SDS they occupy the interfacial region. The binding constants and the micelle properties
(such as polarity and CMC) have been determined using both dienes as probes.
r 2005 Elsevier B.V. All rights reserved.

Keywords: Diarylbutadienes; Benzazole; Dual fluorescence; Micelles; Probes; H-aggregates

1. Introduction conformationally relaxed intramolecular charge

A variety of organic molecules containing
donor–acceptor moieties exhibit fluorescence pro-
perties that depend on the physical and chemical
nature of the medium. This is due to population of
Corresponding authors. Tel.: +20403120708;
fax: +20403350804.
E-mail addresses: tfayed2003@yahoo.co.uk (T.A. Fayed),
safaaehe@gega.net (S.H. Etaiw).
transfer (ICT) or twisted ICT (TICT) excited
states as emissive states [1–3]. The high sensitivity
of these states to solvation, polarity and molecular
mobility changes render such molecules to be effi-
cient reporters (provide a wealth of information)
of their microenvironments. Push–pull stilbenes,
i.e. stilbenes substituted with an electron donor
and an acceptor group in conjugated positions,
have attracted great interest in view of their fluore-
scence sensing properties [2,4–7]. Donor–acceptor

0022-2313/$ - see front matter r 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2005.11.006
 ARTICLE IN PRESS
432 T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440
styryl derivatives have been fruitfully employed in
cellular calcium sensing [8] and in the visualization
of membrane nerve potential [9]. Also, they are
utilized in structural investigations of systems
including micelles [10,11], vesicles [12] and poly-
mers [13,14].
Diphenylbutadienes are interesting models of
the retinyl polyenes that are involved in biological
sensory and energy transduction [15]. Recent
studies with donor–acceptor-substituted diphenyl-
butadienes [14,16–18] have shown that these
compounds are also capable of exhibiting fluores-
cence from conformationally relaxed ICT excited
states. Therefore, these compounds have been used
to characterize the microenvironment of micelles
[16,19,20] as well as probes for saccharides [21] and
metal ions [22]. However, nature and dynamics of
excited state of diphenylpolyenes are not clearly
known and the sensing applications are very
limited.
In this respect, very recently we have synthesized
and investigated the photophysical properties of
two new diphenylbutadiene derivatives [23], viz, 1-
(2-benzoxazolyl)-4-(p-dimethylaminophenyl)buta-
1,3-diene and its benzothiazolyl analogue, abbrevi-
ated as BODB and BTDB, respectively, Scheme 1.
The absorption and fluorescence characteristics of
these derivatives exhibit large solvent polarity and
viscosity as well as acidity-dependent changes.
Hence, they could be utilized as sensors for the
microenvironment of organized assemblies.
Surfactant molecules aggregate in water with
their polar head-groups pointing toward water to
form micelles. These aggregates are interesting
models of biological systems. Thus, in the present
work, the absorption and fluorescence properties
X concentrations (the ethanol content is less than
N within the range 0.1–12.5 mM depending on the
NMe2
X = O, (BODB)
X = S, (BTDB)
Scheme 1.
of BODB and BTDB have been investigated in 1,4-
dioxane–water binary mixtures and in micro-hetero-
geneous media of sodium dodecyl sulphate (SDS),
cetyltrimethyl ammonium bromide (CTAB) and
Triton X-100 (TX-100) as examples of anionic,
cationic and neutral surfactants, respectively. This is
to examine the effect of micelles on the diene H-
aggregates formed in aqueous media. The study aims
also to explore the usefulness of these dienes as
fluorescence probes for characterization of the
micelle properties.
2. Experimental
The investigated diarylbutadienes (BODB and
BTDB) were prepared and characterized as
reported in a previous study [23]. SDS and CTAB
were from BDH while TX-100 from Aldrich were
used without purification. Double distilled water
was used for preparation of micelle solutions
whereas highly spectroscopic-grade ethanol and
dioxane (Merck) were used for preparation of
binary mixtures.
The absorption spectra were measured on a
Shimadzu UV-3101PC scanning spectrophot-
ometer. The steady-state fluorescence measure-
ments were preformed using a Perkin-Elmer LS
50B spectrofluorimeter fitted with a temperature
controlled unit (Fischer Scientific Isotherm Refri-
gerated Circular Model 9000). The fluorescence
quantum yield (ff) was measured relative to
quinine sulphate (ff ¼ 0:54 in 0.1 M H2SO4) [24].
For all measurements, 2.0
105 M diene solu-
tions were used and handled under dim light to
avoid the trans/cis photoreaction. Since the dienes
are sparingly soluble in water, their stock solutions
were made in ethanol and added to the appro-
priate amounts of surfactant to make different
2%). The surfactant concentration was varied
nature of the used surfactant. For recording
fluorescence spectra of BODB and BTDB in
mixed solvents or micellar solutions, the samples
were excited at the maximum of the long-
wavelength absorption band to ensure excitation
of monomers.
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T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440 433

3. Results and discussion arrangement of molecules [25]. The theory predicts

that the strong coupling of the several similar
3.1. Molecular aggregation of the investigated monomers in the J- and H-aggregates results in a
dienes in aqueous solutions red and blue shift of their absorption bands,
respectively, relative to the monomer [25]. In
The structure and spectroscopy of molecular addition, the spectrum gets narrower due to the
aggregates in which the molecular arrangement is absence of vibrational coupling to the molecular
highly ordered (namely; J- and H-aggregates) are mode [25].
of much interest because of their special properties The absorption and fluorescence spectra of
and possible technological applications [25–27]. BODB in water, ethanol and dioxane are shown
Briefly, J-aggregates are one-dimensional side- in Fig. 1, while the spectral peak positions of both
by-side while the H-aggregates are face-to-face dienes in the mentioned solvents as well as in
dioxane–water mixtures are collected in Table 1.
Fluorescence intensity (a. u.) There are significant variations in the shape and
spectral peak position on going from organic
1.2 solvents to water. The broad absorption band of
DODB that appears at 417 or 411 nm in ethanol
Absorbance

0.8 and dioxane, respectively, is replaced by a narrow

band at 354 nm in water, with a broad tail
extending to over 500 nm. The spectral behaviour
0.4 of BTDB is similar except for red shifts in the
absorption maximum. Thus, based on the shape of
0.0 the absorption band, the large hypsochromic shift
300 400 500 600 700 and narrowing of the band in water, is due to
Wavelength (nm) formation of H-aggregates [25,26] while the broad
Fig. 1. Absorption and fluorescence emission spectra of BODB tail was attributed to absorption of monomers.
in: dioxane (- - -), ethanol (y.)and water (—). Excitation The very low solubility of the investigated dienes
wavelength is 415 nm. in water makes it difficult to study the effect of

Table 1
Polarity parameters of dioxane–water mixtures as well as the absorption and emission maxima (nm) of the dienes measured in these
mixtures

Dioxane % (v/v) e (D) ET(30) BODB BTDB

(kcal mol1)
la lf la lf

0 78.48 63.6 354 (417) 580 (531) 363 (422) 600 (560)
10 70.33 — 357 578 368 588
20 61.86 — 360 573 368 586
30 53.28 — 415 567 419 585
40 44.54 55.8 416 563 423 582
50 35.85 — 418 553 427 579
60 27.21 52.1 419 547 427 573
70 19.07 — 418 537 426 569
80 11.86 49.2 416 531 424 562
90 6.07 46.3 414 519 421 550
95 3.89 43.8 411 514 420 537
100 2.21 36.6 408 503 416 516

Values in parenthesis are the maxima in ethanol.


434 T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440
concentration on the absorption spectra. To get
information about the effect of solvents on the
aggregation of the used dienes, their absorption
spectra have been studied in aqueous binary
mixtures containing dioxane or ethanol. The
absorption spectra of BODB in various dioxane–-
water mixtures are depicted in Fig. 2a as a
representative example. Similar behaviour was
observed in the case of BTDB. As the water
content increases, the long-wavelength absorption
band suffers a pronounced red shift (ca. 10 nm)
relative to that in dioxane due to increase in the
polarity of the medium. This shift is accompanied
by a decrease in the absorbance and build-up of
the H-aggregates narrow band at the shorter
wavelength side with appearance of a well-defined
isosbestic point. The appearance of an isosbestic
point indicates the monomer-H-aggregate equi-
librium. Using a protic solvent such as ethanol as a
cosolvent instead of dioxane results in similar
spectral changes, see Fig. 2b. So, attribution of the
blue-shifted absorption band to hydrogen-bonded
complex formation (due to interaction between
–NMe2 group and water molecules) was ruled out.
Also, it indicates that the self-association of the
present dienes takes place only in pure or water-
rich solvent mixtures.
The fluorescence emission of both dienes was
also studied in the mentioned solvents and
dioxane–water mixtures. As shown in Fig. 1, the
fluorescence spectrum of BODB is red shifted on
going from dioxane to water. However, the
1.2 95.0
100.0
Absorbance
0.8
0.4
0.0
300 350 400
(a) Wavelength (nm)
Fig. 2. UV–visible absorption spectra of BODB in: (a) dioxane–water and (b) ethanol–water mixtures. The composition of the
mixtures is mentioned in the figure.
ARTICLE IN PRESS
fluorescence spectra of both dienes, recorded in
water, are independent of the excitation wave-
length and the intensity decreases strongly upon
excitation at lexc o370 nm (not shown here). Thus,
it was concluded that the formed aggregates are
non-fluorescent and the emission in water is due to
monomers. Consequently, the strong red shift is
due to stabilization of the charge transfer excited
state of BODB and BTDB in the polar media [23].
The fluorescence spectra of both dienes (lexc ¼
410 nm) are strongly influenced by changing the
water content in dioxane. The fluorescence max-
ima are highly red shifted (ca. 73 and 64 nm for
BODB and BTDB, respectively) when the solvent
is changed from dioxane to 80% water in the
dioxane mixture, Table 1. In addition, the spectra
exhibit dual emission where two overlapping
bands appear in dioxane–water binary mixtures
containing 20–80% water. Fig. 3 shows such
spectral changes for BTDB in dioxane–water
mixtures. One possible explanation for the ob-
served dual emission is the participation of a polar
ICT excited state and/or formation of a hydrogen-
bonded complex in addition to the local excited
state (LE). However, contribution of emission
from a hydrogen-bonded complex was ruled out
since both dienes exhibit dual emission also in
aprotic solvents, e.g. DMF [23]. The fluorescence
maximum has been correlated with the dielectric
constant and the empirical polarity parameter
ET(30) of the used dioxane–water mixtures [28,29].
The ET(30) correlation plots are linear (r40:97)
Dioxane
1.2 % of H2O (v/v)
%(v/v)
70.0 0.0
50.0 50
Absorbance
40.0 0.8 70
30.0 75
20.0 80
10.0 90
0.4
0.0 100
0.0
450 500 300 400 500 600
(b) Wavelength (nm)
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T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440 435

400
Dioxane (v%)
Fluorescence intensity (a. u.)

100 BTDB
90
80
70
50
200
30
20
0

0
450 500 550 600 650 700
Wavelength (nm)

Fig. 3. Fluorescence spectra of BTDB in dioxane–water Fig. 5. Effect of CTAB concentration on the absorption
mixtures. The composition of the mixtures is shown in the spectrum of BODB. Inset is the surfactant concentrations.
figure.

620 Table 2
Spectral maxima (nm) and fluorescence quantum yields of the
Fluorescence maximum (nm)

600 dienes in SDS, CTAB and TX-100 (12.5, 2.5 and 1.25 mM,
respectively)
580
Medium BODB BTDB
560 la lf ff la lf ff

540 SDS 418 532, 565 0.0085 422 533, 583 0.0093
CTAB 424 532, 562 0.0101 435 534, 582 0.0115
520 TX-100 421 532, 543 0.019 431 531, 567 0.013
Water 354 580 o103 363 600 o103
500
0 10 20 30 40 50 60 70 80
Dielectric constant or ET(30) solutions having different concentrations of the
three surfactants. Representative spectra are pre-
Fig. 4. Plots of the fluorescence maximum of BODB (closed
sented in Fig. 5, and the spectral data are
symbols) and BTDB (open symbols) versus dielectric constant
(squares) and ET(30), (circles) of the dioxane–water mixtures. summarized in Table 2. On adding CTAB, as an
example, the absorbance of the H-aggregates
whereas those of the dielectric constant are non- narrow band (at 354 and 363 nm for BODB
linear, Fig. 4. Both correlations show that the and BTDB, respectively) diminishes and a broad
fluorescence maximum is red shifted by increasing absorption band appears at longer wavelengths
the polarity of the medium. Therefore, the large (around 424 and 435 nm, respectively) with distinct
red-shifted fluorescence band is attributed to a isosbestic point. Similar changes were also ob-
polar ICT excited state, which is stabilized in served in SDS and TX-100. These results indicate
water-rich mixtures. that the addition of surfactants promotes disag-
gregation of BODB and BTDB, and the resulting
diene monomers are solubilized by the surfactant
3.2. Disaggregation and fluorescence spectra of the molecules to give stable structures (micellized
investigated dienes in micellar solutions monomers). At relatively higher surfactant con-
centrations (beyond critical micelle concentration,
The absorption spectra of BODB and BTDB CMC) almost all diene molecules are present as
(ca. 2
105 M) have been recorded in aqueous micellized monomers as evident from the absence

436
400
Fluorescence intnsity (a. u.)
BODB
TX-100
200
SDS
0 0
450 500
Wavelength (nm)
400
Fluorescence intensity (a. u.)
BTDB
200
TX-100
0 length and the biexponential decay of fluorescence
450 500
Wavelength (nm)
Fig. 6. Fluorescence spectra of BODB (upper panel) and
BTDB (lower panel) recorded in micellar solutions with
concentrations of 12.5, 2.5 and 1.25 mM for SDS, CTAB and
TX-100, respectively.
of the narrow absorption band characteristic for
the H-aggregates.
The fluorescence spectra of BODB and BTDB in
the three surfactants (above CMC) are shown in
Fig. 6. The emission profile shows two overlapping
bands whose intensities and maxima change on
going from water to anionic, cationic and neutral
micelles. The fluorescence maxima and quantum
yields are given in Table 2. In addition, the
excitation spectra monitored at both the emission
maxima in CTAB and SDS for BTDB as
examples, Fig. 7, are independent on the emission
wavelength. This indicates that only one species is
responsible for the observed dual emission. The
fluorescence decay profiles of BTDB in ethanol
and DMF follow biexponential fits suggest emis-
sion from two states. The lifetime values in ethanol
are 0.028 and 0.102 ns while those in DMF are
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T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440
CTAB 200
Intensity (a. u.)
100
H2O
300 350 400 450 500 550 600
550 600 650 700
Wavelength (nm)
Fig. 7. Fluorescence excitaion spectra of BTDB measured in
CTAB (- - -) and SDS (—) solutions as in Fig. 6, monitored at
lem ¼ 530 and 580 nm, lower and higher intensities, respec-
tively.
CTAB
0.088 and 0.169 ns [30]. Unfortunately, the fluor-
escence decay could not be measured in dioxane–
water mixtures or micellar solutions due to
SDS
technical reasons. Based on the insensitivity of
H2O
the excitation spectra to the monitoring wave-
550 600 650 700
in ethanol and DMF, it was suggested that the
dual emission is due to participation of an ICT
excited state in addition to LE one [23]. In
addition, the maximum of the short-wavelength
emission is independent of the polarity of the used
micelle (Table 2) while that of the long wavelength
one is strongly red shifted on going from TX-100
to CTAB or SDS, which justifies our conclusion.
In SDS and CTAB aqueous solutions, the ICT
fluorescence of BTDB (around 580 nm) predomi-
nates with the fluorescence from the LE state as a
shoulder around 530 nm. In case of TX-100, the
LE fluorescence with maximum at 530 nm is
predominant while the ICT fluorescence appears
as a shoulder around 565 nm. In contrast, the LE
fluorescence of BODB predominates in all micellar
media, and the ICT fluorescence appears as a
shoulder at longer wavelengths.
Fig. 8 illustrates the fluorescence spectra of
BTDB in aqueous TX-100 micellar solutions as a
function of the surfactant concentration. Gener-
ally, gradual addition of CTAB or TX-100 is
associated with a hypsochromic shift of the
emission maximum along with a great enhance-
ment of fluorescence intensity. Both observations

T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440
BTDB
220
Fluorescence intensity (a.u.)
110
0 0
500
wavelength (n.m)
Fig. 8. Fluorescence spectra of BTDB measured in TX-100
micellar solutions, lexc ¼ 431 nm. The surfactant concentra-
tions are shown in the figure.
reflect that the microenvironment around the
dienes in micellar solutions is quite different from
that in pure aqueous phase. The blue shift in the
fluorescence spectra as well as the great enhance-
ment of the fluorescence intensity within the
micellar solutions indicates that the polarity sensed
by BODB and BTDB is less than the polarity of
bulk water. It was reported that the fluorescence
yield of the present dienes decreases with increas-
ing the solvent polarity [23]. In addition, the
enhancement of fluorescence quantum yield in
micelles, Table 2, can be attributed to restrictions
imposed on the radiationless free rotational
motions (mainly twisting around the CQC
bonds) and/or disaggregation of the non-fluores-
cent H-aggregates.
Away from CTAB and TX-100, the fluorescence
spectra of both dienes show anomalous behaviour
on changing the concentration of SDS, Fig. 9. In
solutions containing lower SDS concentrations
(o4.0 mM), the fluorescence spectra suffer a
strong blue shift (ca. 58 nm) along with a great
enhancement in intensity of the LE emission. On
adding more SDS, the fluorescence intensity
decreases with developing of the ICT emission
and a red shift in the emission maximum (ca. 18
and 50 nm for BODB and BTDB, respectively).
The great enhancement in the fluorescence inten-
sity (more than 10 fold) as well as the blue shift, at
lower SDS concentrations, is attributed to associa-
tion of dienes with free SDS molecules and/or
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437
500
[TX-100]x10-5 ,M [SDS]x10-3, M
Fluorescence intensity (a.u.)
125 4.0
85 3.0
60 5.0
50 2.0
40 250 7.5
12.5
30
20 1.0
10 0.5
0 0.0
600 700 500 600 700
Wavelength (nm)
Fig. 9. Fluorescence spectra of BODB measured in SDS
micellar solutions, lexc ¼ 418 nm. The concentrations of SDS
are shown in the figure.
small premicellar aggregates, in such a way that
their exposure to water is minimized [10] hence
sense a less polar environment. On the other hand,
the fluorescence quenching and the observed red
shift near and above CMC are due to changes
in the shape and size of the micelle. This is
also consistent with the fact that the micellar
environment of SDS is richer in water content
than that in CTAB and TX-100 [31] and the
dye molecules occupy the interfacial region, vide
infra. So, the red shift of the fluorescence is due
to increased polarity of the SDS micelle–water
interface.
3.3. Probing of the micelle properties
The micropolarity [expressed as the dielectric
constant (e) and ET(30)] as well as CMC of the
used micelles has been determined by using BODB
and BTDB. The obtained values are listed in
Table 3. The dielectric constant and ET(30) of the
micelle–water interface in SDS, CTAB and TX-
100 micelles were estimated by using Fig. 4 and the
measured ICT fluorescence maximum (Table 2).
Table 3 gives also the polarity parameters of these
micelles as determined by some other probes for
comparison [32,33]. The values indicate that the
dienes occupy interfacial region, which may be due
to presence of the dimethylamino group. Also, the
data show that the polarity of the interface is
dependent on the nature of the surfactant where it
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438 T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440

Table 3
Polarity (e, D, and ET(30), kcal/mol) and critical micelle concentrations (CMC, mM) of SDS, CTAB and TX-100 estimated using
BODB and BTDB as fluorescence probes

Probe parameter BODB BTDB

SDS CTAB TX-100 SDS CTAB TX-100

e 47.6 (40) 43.6 (36) 22.8. (28) 44.7 40.5 19.0

ET(30) 58.0 (57.9) 57.0 (56.3) 51.8 (55.6) 56.2 55.1 52.3
CMC 6.5, 3.95 (8.0) 0.89 (0.9) 0.28 (0.3) 5.7, 4.0 0.86 0.25

Values in parenthesis were determined by using 4-aminophthalimide as a probe [32].

increases from neutral to cationic and anionic 12

SDS
micelles. Furthermore, the values obtained by both
probes are in fair agreement.
The fluorescent dienes studied herein have been 8
also employed to determine the CMC for SDS, o
If /If
CTAB and TX-100. This was achieved by plotting
CTAB
the ratios of fluorescence intensities (in the absence
and presence of surfactants) against the concen- 4
tration of surfactants, Fig. 10. The CMC values of
CTAB and TX-100 were calculated from the break
at the abrupt increase of the fluorescence intensity, 0
and the calculated values are given in Table 3. The 0 2 4 6 8 10 12 14 16
obtained values are in good agreement with those [Surfactant], (mM)
reported in the literature [32].
Fig. 10. Variation of fluorescence intensity ratios for BODB as
On the other hand, the plots of fluorescence a function of SDS and CTAB concentrations, calculated at 522
intensity against the concentration of SDS give and 552 nm, respectively. The [CTAB] scale is multiplied by 10.
rise to two break points. The first point is at
4.0 mM and the second one is around 6.0 mM.
Multiple CMCs for SDS are already reported 3.4. Estimation of the probe-micelle binding
in a number of current scientific reports [34,35]. constant
The lower CMC is often assigned to a phase
with premicellar aggregates while the higher In order to know how strongly BODB and
one is referred to some changes in the shape and BTDB bind with the surfactants, the binding
size of the micelle. These results clearly suggest constant between each and the different micelles
that the present probes perform a better role as has been determined using the following equation
sensors for monitoring the aggregation of surfac- [35]:
tant molecules than do other probes. For example,
nile red gave only one CMC value of 8.0 mM for ðI m  I o Þ=ðI t  I o Þ ¼ 1 þ ðK½MÞ1 , (1)
SDS [36]. where Io, It and Im are the fluorescence intensities
The previous results indicate that the ICT of the probe in the absence of surfactant, at an
fluorescence of BODB and BTDB can serve as a intermediate concentration [M] and under com-
good probe for the properties of the different plete micellization, respectively. K is the binding
micelles. Furthermore, it can sense the type of constant. The micellar concentration [M] is deter-
charge on the polar head group, thus differen- mined by
tiating between anionic, cationic and neutral
surfactants. ½M ¼ ðS  CMCÞ=N, (2)
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T.A. Fayed et al. / Journal of Luminescence 121 (2006) 431–440 439

CTAB References
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[M]-1 x10-5
Fig. 11. Plot of (Im–Io)/(It–Io) against [M]1 for DODB in
CTAB and TX-100.
Table 4
Binding constants (K,
105 l mol1) and the free energy
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Surfactant BODB BTDB
K DG K DG
CTAB 2.770.15 31.18 5.270.33
TX-100 2.170.076 30.55 1.670.078
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enhances their association with the charged
surfactant molecules.
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