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ARTICLE

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Solvent polarity studies of highly uorescent laser dye

ADS740WS and its uorescence quenching with silver
nanoparticles
V.B. Tangod, Prasad Raikar, B.M. Mastiholi, and U.S. Raikar

Abstract: Determination of ground state and excited state dipole moments of a highly uorescent laser dye molecule ADS740WS
and comparison of excited state dipole moment by Lippert, Bakhashiev, KawskiChammaViallet, McRae, Suppan, and solvent
polarity methods. KamletAbboudTaft and Katritzky multilinear analysis for characterizing the solvent contribution into
spectral features of the dye has also been studied. Correlation analysis of spectroscopic data with multiple polarity parameters
was carried out by multiple linear regression analysis. Optical absorption and uorescence of ADS740WS in alcohol and other
solvents with attachment of silver nanoparticles (AgNPs) shows quenching of absorption and uorescence intensities. This is due
to size, shape, and coupling between the AgNPs and the dye, and energy transfer between the dye and the AgNPs. Fluorescence
quenching of ADS740WS leads to many applications notably for advancement in biomolecular labeling and uorescence
patterning and chemotherapy in cancer treatment.
PACS No.: 33.50.j.
Rsum : Nous dterminons le fondamental, le moment dipolaire dtats excits de la molcule de colorant laser trs uorescent
ADS740WS et comparons avec les rsultats de moment dipolaire dtats excits obtenus de la mthode de polarit par Lippert,
Bakhashiev, KawskiChammaVallet, McRae, Suppan et Solvent. Nous tudions aussi la mthode multilinaire de Kamlet
AbboudTaft et Katritzky pour caractriser la contribution du solvant aux proprits spectrales du colorant. Utilisant lanalyse
de rgression linaire multiple, nous compltons une tude de corrlation des donnes spectroscopiques. Labsorption optique
et la uorescence de ADS740WS dans lalcool et dautres solvants avec attachement AgNP montrent une extinction des intensits
dabsorption et de uorescence. Ceci est d a` la grosseur, a` la forme, au couplage entre lAgNP et le colorant et au transfert
dnergie entre le colorant et lAgNP. Lextinction de la uorescence de ADS740WS mne a` plusieurs applications, spcialement
des progrs en tiquetage biomolculaire, en ajustement du patron de uorescence et en traitement de chimiothrapie du
cancer. [Traduit par la Rdaction]

1. Introduction
This article is a continuation of our work related to systematic
studies of highly uorescent laser dyes [15]. Herein, we have estimated the ground state and excited state dipole moments of
ADS740WS laser dye by various methods.
Determination of ground state and excited state dipole moments of a dye molecule is important as the dipole moment provides information regarding changes in electronic distribution
upon excitation, the nature of excited states and photochemical
transformations. To nd the dipole moment in an excited state
many methods are available, for example, solvatochromic [6], Lippert [7], Bakhashiev [8], KawskiChammaViallet [9, 10], McRae
[11], Suppan [12], and solvent polarity.
Dye molecule ADS740WS is a highly uorescent probe. It is
commonly used [13, 14] in the laser industry, chemotherapy in
cancer treatment, and increasingly used in energy transfer processes. It is widely used to label proteins in biochemistry and to
understand uorescence quenching processes. The large number
of usages for ADS740WS inspires detailed scientic investigation
studies.
Metal nanoparticles [15] have attracted signicant attention because of their interesting optical and electronic properties. These
particles have a number of applications in physics, chemistry,

material science, medicine, catalysis, and biochemistry. The resonance plasmon effect while studying photophysical properties of
organic chromophores like dyes is still an intricate phenomenon. Quenching of the uorescence efciency when laser dye
ADS740WS is in contact with silver nanoparticles (AgNPs) depends on electronic coupling between the electronic transition
dipole moment and surface plasmon.
The solvent dependency of Stokes shift can originate from the
dielectric constant and specic (hydrogen bonding) solutesolvent
interactions. Further solvent effects can be analyzed by solvatochromic parameters and solvent polarity [1618]. For a large number of solutesolvent interactions, these individual parameters
cannot effectively be explaind. Stokes shift can be used to explain
the multiparameter solvent polarity scales for solutesolvent interactions. The effect of solvent polarity on the spectral features of
the solute can be interpreted by means of the linear salvation
energy relationship concept, which can be formulated as Kamlet
AbboudTaft or Katritzky parameters [1921].
Here we report quenching of optical absorption and uorescence of ADS740WS laser dye with AgNPs. The effect of AgNPs on
compound ADS740WS has important applications, such as in chemotherapy for cancer treatment. However, so far no systematic
study related to the effect of optical absorption and uorescence

Received 14 May 2013. Accepted 1 September 2013.

V.B. Tangod, B.M. Mastiholi, and U.S. Raikar. Department of Physics, Karnatak University, Dharwad-580 003, Karnataka, India.
P. Raikar. BMS College of Engineering, Bangalore-560 019, India.
Corresponding author: U.S. Raikar (e-mail: usraykar_kud@yahoo.co.in).
Can. J. Phys. 92: 116123 (2014) dx.doi.org/10.1139/cjp-2013-0250

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of ADS740WS in different solvents in the presence of AgNPs has

been carried out. We reveal new and unique optical properties
with respect to optical absorption and uorescence quenching of
ADS740WS laser dye with AgNPs.
The main aim of the present work is to estimate the ground and
excited state dipole moments using various methods, and comparison studies of the excited state dipole moment. In addition,
we have characterized the nature and extent of solutesolvent
interactions using correlation multiparameter solvent polarity
scales. We have also studied the absorption and uorescence
quenching of a laser dye when it is in contact with AgNPs.

Fig. 1. Molecular formula of ADS740WS C35H43N2O6S2Na

2-[7-(1,3-Dihydro-3,3-dimethyl-1-(4-sulfobutyl)-2H-indol-2-ylidene)-1,3,5heptatrienyl]-3,3-dimethyl-1-(4-sulfobutyl)-3H-indolium.

2. Experiment
2.1. Chemicals used
The laser dye ADS740WS was obtained from American Dye
Source, Inc. Canada. The molecular formula and chemical structure of ADS740WS is given in Fig. 1. The solvents used in our
presentstudyaremethanol,ethanol,2-propanol,1-butanol,dimethyl sulfoxide (DMSO), and acetonitrile. These solvents are of spectroscopic grade and were purchased from Sigma Aldrich, USA. The
required solutions are prepared of the order of 105 mol/L concentration.
Silver nitrate, sodium boroxide, and trisodium citrate were purchased from Himedia Laboratories Pvt. Ltd., India.

Fig. 2. Plasmon resonance absorption spectrum of AgNPs.

2.2. Synthesis of AgNPs

AgNPs were synthesized by the chemical reduction method [15].
1.0 mmol/L of AgNO3 was dissolved in 20 ml of highly deionised
water. To the solution of AgNO3 is further added 0.1 mmol/L trisodium citrate. With continuous stirring and further mixing, 0.6 mL
of 0.1 mmol/L NaBH4 was added, drop by drop, until a yellow
solution formed. The preparation process was free from directly
incident light. The formation of AgNPs was conrmed by absorption spectroscopy (Fig. 2) of the yellow solution.
2.3. Spectroscopic measurements
Optical absorption and uorescence measurements of ADS740WS
laser dye with and without AgNPs were recorded on an Ocean
Optics HR 4000 high resolution spectrometer.

a m5F4() const

(5)

3. Theory and calculations

3.1. Determination of dipole moment
The excited and ground state dipole moments and their ratios
of a probe molecule can be estimated by the following equations:
Lipperts equation [7]

a f m1F(, n) const

(1)

Bakhshievs equation [8]

a f m2F1(, n) const

a f
2

m3F2(, n) const

(2)
F2(, n)

(3)

McRaes equation [11]

a m4F3() const
Suppans equation [12]

F(, n)

F1(, n)

KawskiChammaViallet equation [9]

where F, n, Lipperts polarity parameter; F1, n, Bakhshievs

polarity parameter; F2, n, KawskiChammaViallet polarity parameter; F3, McRaes polarity parameter; and F4, Suppans polarity parameter. These are estimated using the following equations:

2 1

n2 1

n2 2 2

2n2 1

2(n 2) 2
2

(6)

2n2 1

2n2 1 1

2( 21)
2( 1)
F ()

2 2
F3()

(4)

n2 1
n2 2

n2 1
2

n 2

(7)

3(n4 1)
2(n2 2)2

(8)

(9)

(10)

where a and f are absorption and uorescence maxima (wave

numbers (cm1)), respectively; and and n are dielectric constant
and refractive index, respectively, of the solvent (Fig. 3).
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Fig. 3. (Colour online) Absorption and emission spectra of

ADS740WS in methanol (red) with and (black) without AgNPs
(A, absorbance; F, uorescence; 105 mol/L concentration solution
and uorescence spectra is taken with excitation wavelength of
741.1 nm in methanol solvent).

Fig. 4. Stokes shift versus F(, n), that is, Lipperts polarity
parameter of ADS740WS in different solvents: (line) linear t;
(1) methanol; (2) ethanol; (3) 2-propanol; (4) 1-butanol; (5) DMSO; and
(6) acetonitrile.

Using (1)(5) with Figs. 48 having slopes m1, m2, m3, m4, and m5,
respectively, as
m1

m2

m3

m4

2(e g)2

Fig. 5. Stokes shift versus F1(, n), that is, Bakshievs polarity
parameter of ADS740WS in different solvents: (line) linear t;
(1) methanol; (2) ethanol; (3) 2-propanol; (4) 1-butanol; (5) DMSO; and
(6) acetonitrile.

(11)

hca3
2(e g)2

(12)

hca3
2e2 g2

(13)

hca3

g(e g)

(14)

hca3

and
m5

g(e g)

(15)

hca3

where g and e are the ground and excited state dipole moments,
respectively, of the solute molecule; h and c are Planks constant
and velocity of light in vacuum, respectively; and a is the Onsager
cavity radius, which is determined using the atomic increment
method [22], assuming that the ground and excited state dipole
moments are almost parallel to one another. The following expressions are obtained on the basis of (12) and (13):

m3 m2 hca3
2

m3 m2 hca3
2

2m2

m2 m3
m3 m2

(18)

(16)

These theoretical calculations are also compared using the correlation method proposed by Reichardt [23] and improved by Ravi
et al. [24]. The following the relation for spectral shift with ETN:

(17)

a f 11 307.6

1/2

2m2

and

1/2

aB
a

ETN const

(19)

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Tangod et al.

119

Fig. 6. 1/2a f versus F2(, n), that is, KawskiChammaViallet

polarity parameter of ADS740WS in different solvents: (line) linear
t; (1) methanol; (2) ethanol; (3) 2-propanol; (4) 1-butanol; (5) DMSO;
and (6) acetonitrile.

Fig. 8. a versus F4(), that is, Suppans polarity parameter of

ADS740WS in different solvents: (line) linear t; (1) methanol;
(2) ethanol; (3) 2-propanol; (4) 1-butanol; (5) DMSO; and (6) acetonitrile.

Fig. 7. a versus F3(), that is, McRaes polarity parameter of

ADS740WS in different solvents: (line) linear t; (1) methanol;
(2) ethanol; (3) 2-propanol; (4) 1-butanol; (5) DMSO; and (6) acetonitrile.

Fig. 9. a versus ENT , that is, solvent polarity parameter of

ADS740WS in different solvents: (line) linear t; (1) methanol;
(2) ethanol; (3) 2-propanol; (4) 1-butanol; (5) DMSO; and (6) acetonitrile.

where B and aB are change in dipole moment on excitation and

Onsager cavity radius of a betadine dye, respectively; and and a
are corresponding quantities of ADS740WS laser dye of our present interest. The change in dipole moment can be evaluated from
the slope of the Stokes shift versus ETN plot (Fig. 9) and is given by
the equation [19]

81m
(6.2/a3)11 307.6

(20)

Generally the dipole moments g and e are not parallel to each

other, but have an [25, 26] angle

cos

1
2ge

g2 e2

m2
m3

e2 g2

(21)

3.2. Correlation with multiparameter solvent polarity scale

To explain the multiparameter solvent polarity scales for
solutesolvent interactions, the spectroscopic Stokes shift can be
used. The effect of solvent polarity on the spectral features of the
solute can be interpreted [6, 16] by means of the linear salvation
energy relationship concept that can be formulated as Kamlet
AbboudTaft, (22), and Katritzky, (23), equations [27, 28]
(a f) (a f)0 a b s

(22)

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Table 1. Spectroscopic polarity parameters and polarity functions.

Solvent

ET(30)

F(, n)

F1(, n)

F2(, n)

F3(, n)

F4(, n)

ENT

Methanol
Ethanol
2-propanol
1-butanol
DMSO
Acetonitrile

33.7
24.3
20.2
17.4
47.2
38.8

1.329
1.361
1.377
1.399
1.479
1.344

55.4
51.9
48.4
49.7
45.1
45.6

0.98
0.86
0.76
0.84
0.00
0.19

0.66
0.75
0.84
0.84
0.76
0.4

0.60
0.54
0.48
0.47
1.00
0.66

0.309
0.289
0.277
0.263
0.263
0.306

0.857
0.812
0.781
0.749
0.841
0.866

0.653
0.652
0.647
0.646
0.744
0.667

1.832
1.772
1.730
1.691
1.878
1.853

0.956
0.940
0.928
0.916
0.969
0.962

0.762
0.654
0.546
0.543
0.444
0.460

2 11 b2nn 11 sE (30)
2

(a f) (a f)0 a

(23)

where is the scale of the solvent hydrogen bond donor (HBD)

acidities [20], is the scale of solvent hydrogen bond acceptor (HBA)
basicities, * is measure of the solvent dipolaritypolarizability [27],
is the dielectric constant, n is the refractive index, ET(30) is the
empirical polarity parameter of the solvent, and a f0 is the
regression value of the solute property in the reference solvent.
The Katritzky equation estimates [6, 20, 21] the independent contribution of the dipolarizability, polarizability, and other specic
interactions, such as hydrogen bonding and interactions. The
regression coefcients, a, b, and s in these equations, measure the
relative susceptibilities of the solute property (i.e., absorption,
uorescence, and other spectroscopic parameters) to the indicated solvent parameters.
3.3. Theoretical explanation of effect of AgNPs on
ADS740WS laser dye
Optical properties of isolated colloidal particles have been intensively investigated through Mies scattering theory with respect to their dependence on particle size, environment, and
effect on a chosen dye in the presence of alcoholic solvents. Mie
theory [2833] is a mathematical and physical description of the
scattering of electromagnetic radiation by spherical particles immersed in a continuous medium. The Mie scattering explanation
begins with the macroscopic Maxwells equations.
The effect of the particular size of the nanoparticles on the peak
resonant wavelength results from two different mechanisms depending on the particle size range. In the limit of 2R (where
R is the radius of the particles and is the wave length of the light
in the medium), only the electric dipole term contributes signicantly [33, 34] to the extinction cross section (ext).
2()
3/2
ext 9 m
V
c
1() 2m2 2()2

(24)

where V = (4/3)R3 is volume of the spherical particle, is the

angular frequency of the exciting light, c is the velocity of light, m
and () (() = 1() + i2()) are the dielectric frictions of the
surrounding medium and the material itself, respectively. The
resonance condition is fullled when 1() = 2m provided 2 is
small or weakly dependent on .

4. Results and discussion

4.1. Estimation of ground state and excited state dipole
moments
To estimate ground state and excited state dipole moments of
the solute molecule, the solvent polarity functions (F(, n), F1(, n),
F2(, n), F3(, n) and F4(, n)) are calculated and presented in Table 1.
For estimating the dipole moments we have used linear correlations (Table 2) with spectral shifts a f versus F(, n), a f
versus F1(, n), 1/2a f versus F2(, n), a versus F3(), and a

Table 2. Absorption and uorescence data of ADS740WS dye in various solvents.

Solvent

Absorption
max (nm)

Fluorescence
max (nm)

a f

1/2
a f

Methanol
Ethanol
2-propanol
1-butanol
DMSO
Acetonitrile

741.1
742.1
739.2
743.8
749.5
740.2

806.3
796.6
841.3
779.5
805.3
780.2

1092.16
921.04
1642.22
614.69
924.45
693.75

12948.10
13014.66
12707.76
13136.41
12879.65
13163.44

versus F4(). Figures represent the linear graphs with slopes m1, m2,
m3, m4, and m5 (Table 3), respectively. Using the linear curve tting
approach (Origin 6.1 software), the data are tted to a straight line.
The ground state and excited state dipole moments are calculated
using (11)(18), also the angles between excited state and ground
state dipole moments are calculated using (21) and are summarized in Table 4.
The calculated dipole moment of ADS740WS indicates that the
excited state dipole moment is greater than the ground state dipole moment. It demonstrates that the ADS740WS dye is more
polar in the excited state than in the ground state. The ground
state dipole moment (g) of the ADS740WS laser dye is estimated
using (16). However, no other experimental data on g could be
obtained from the literature for comparison. The values of e
were obtained from (11)(18) and the ratio e/g obtained from (18).
The values of g, e, and the ratio e/g are presented in Table 4.
The difference in the values of e may be because of the various
assumptions and simplications made in the use of different
methods. The value e obtained using the Lippert method is large,
because it does not consider the polarizability. The e value obtained using the Suppan method is large compared to all other
methods. The e values obtained by the McRae and ETN methods
almost agree with one another. The change in the dipole moment
between the excited state and ground state is due to intermolecular charge transfer. Further, a large change in dipole moment on
excitation suggests that the excited state is twisted intramolecular charge transfer. Presence of a large twisted intramolecular
charge transfer and increase in polarity on excitation render the
molecule more polar (than the ground state) giving rise to a large
change in the dipole. In the literature one may nd that a large
number of investigators has used the Solvatochromic shift
method to estimate the excited state dipole moment.
4.2. Analysis of multiparameter solvent polarity scales
We have employed KamletAbboudTaft and Katritzky multilinear analysis for characterizing the solvent contribution into
spectral features of the dye. Correlation analysis of spectroscopic
data with multiple polarity parameters was carried out by multiple linear regression analysis. It was found that Stokes shift data
for ADS740WS dye show satisfactory correlations with different
polarity parameters. The results of the multiple regressions are
tabulated in Table 5.
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Table 3. Slope, intercept, and correlation coefcient data of ADS740WS

by different methods.
Method

Slope

Intercept

Correlation
coefcient

No. of
data

Lipperts
Bakhshievs
Kawski Chamma
Viallets
McRaes
Suppans
ENT

10 005.23
307.01
758.7

694.89
730.35
12 468.44

0.06
0.11
0.17

6
6
6

370.25
1 961.06
670.32

12 801.84
11 612.01
600.53

0.35
0.04
0.22

6
6
6

Table 4. Ground state and excited state dipole moment (D) of

ADS740WS dye.
Onsager cavity
radius, a ()
g*
5.27

e/g**

1.55 3.67 5.38 8.49 38.27 11.98 2.35

1.590

*Ground state dipole moment calculated from (16).

Excited state dipole moment calculated from (17) Solvotochromic method.
Excited state dipole moment calculated from Lipperts equation, (11).
Excited state dipole moment calculated from McRaes equation, (14).
Excited state dipole moment calculated from Suppans equation, (15).
Excited state dipole moment calculated from microscopic solvent polarity
function, ENT .
**Ratio of excited to ground state dipole moments calculated from (18).
Angle between excited state to ground state dipole moment with solvotochromic data.

The sign of the s coefcient for KamletAbboudTaft polarity as

well as the sign of the overall contribution of dipolarity and polarizability for Katritzky polarity [6, 20] scale show that the contribution of dipolaritypolarizability decreases stabilization of
the excited state of the dye in various solvents. However, the
coefcients a and b are positive. This suggests that the stabilization of the excited state of the dye is through the HBD and hydrogen bond acceptor ability of the solvents. Furthermore, in the
case of Katritzky the coefcient a is negative and b is positive for
ADS740WS dye and therefore stabilization of excited state of the
solvent media arises from the HBD ability of the solvents. Additionally, HBD ability of the solvents prohibits stabilization of the
excited state of the chosen dye.
The percentage contributions of solvatochromic parameters
(Table 6) for ADS740WS with different solvents show the major
solvent contribution is because of HBD acidities (P) and dipolarity
polarizability. Percentage contribution of shows highest effect
on reorientation process of solvent molecule around the chromophore, it can be attributed to the presence of hydrogen bond
acceptor groups in both the ground and excited states originate
signicant contributions of the solvent molecule reorientations.
Further the presence of hydrogen donor groups in the ADS740WS
terminal chain increases percentage contributions of in the
same dye.
4.3. Fluorescence quenching of ADS740WS with AgNPs
In the present case the absorption spectrum of AgNPs has a
maximum wavelength 470480 nm having a peak at 475 nm,
which is related to the plasmon resonance formed because of the
nano-sized (412 nm) AgNPs. This absorption band results from
interactions of free electrons conned to small metallic spherical
objects with incident electromagnetic radiation. The observed
plasmon resonance band (Fig. 2) shows that the AgNPs are spherical in shape.
Figure 10 shows the absorption spectrum of ADS740WS in alcohols (dotted) with and (lined) without AgNPs. The absorption spec-

trum of ADS740WS in alcohol shows a broad band in the visible

region 720750 nm.
Figure 11 shows the uorescence spectrum of ADS740WS in
alcohols (dotted) with and (lined) without AgNPs. The uorescence spectrum of ADS740WS in alcohol also shows a broad band
in the 840845 nm region.
The surface plasmon (Fig. 2) of AgNPs (412 nm) shows a maximum wavelength peak at 475 nm. When ADS740WS is added to
AgNPs, the plasmon band shifts towards [3436] higher wavelength (red shift) peaking at (methanol) 740 nm, (ethanol) 735 nm,
(propanol) 738 nm, and absorbance value quenches. Dampening
and broadening of the surface plasmon band is evident as these
molecules are complexed with the AgNPs. The damping of the
silver plasmon band indicates that attachment with ADS740WS
alters the electron density of the AgNPs, thereby directly affecting
the absorption of the surface bound ADS740WS as well as surface
plasmon absorption band (Fig. 6).
When AgNPs are in contact with the ADS740WS, the vibrational
features of ADS740WS are well resolved and the intensity is
quenched because AgNPs are adsorbed on the hydroxyl group and
hydrogen bonds form with the ADS740WS laser dye (Fig. 7).
In the present case quenching of absorption and uorescence is
observed for the ADS740WS molecule in alcohols attached to AgNPs. Quenching due to the energy transfer rate from the dye to
the AgNPs is governed by [37] three factors:
1. Coulombic overlap integral;
2. position (surface plasmon frequency); and
3. width (inverse surface plasmon life time) of the absorption
spectrum of AgNPs relative to the dye.
The inuence of coulombic interactions on the energy transfer
has been studied with two factors.
1. Interaction between dye and AgNPs depends upon respective
charge densities.
2. The interaction within the dipole approximation, the charge
densities of a dye.
Dipole moments of a dye and AgNPs are responsible for the
energy transfer between dye and AgNPs, which leads to quenching in optical absorption UVvisible spectra (Fig. 5), exhibits a
band between 720750 nm because of * transitions.
The attachment of AgNPs with (Fig. 12) a dye, induces a strong
enhancementquenching [37] of uorescence, which is observed
depending on the nature of the chosen dye. In our case quenching
is observed.
Broadening of a surface plasmon explains the changes of molecular uorescence near AgNPs, in close proximity to a metal.
The uorescence rate of the molecules is a function of the distance between the probe molecule and the AgNP metal surface.
When a molecule is in direct contact [3335] with the metal, the
uorescence of a molecule is completely quenched. So, in our case
AgNPs and a dye attachment is little longer.
The solvent effect on the position of the surface plasmon band
of alcoholic functionalized AgNPs is investigated by measuring
the UV-visible absorbance spectra in the range 450800 nm. Alcohols were chosen as solvent for specic interactions with the OH
group and ADS740WS dye chain, which could lead to marked
effects on the optical properties of AgNPs. Shift of the SPR band to
longer wavelengths is attributed to the induced clustering of the
nanoparticles in the aggregates.
When the dimensions of the nanoparticles become smaller
than the wavelength of the exciting light, energy can be conned
in small spatial regions through the local excitation of surface
plasmon resonance. The optical properties of metal nanoparticles
are strongly inuenced by their size, shape, and surrounding environment, in addition, resonant energy transfers between closely
spaced metal nanoparticles with the surrounding molecule.
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Table 5. Regression ts to solvatochromic polarity scales for Stokes shift of ADS740WS laser dye.
Multiparameter scale

a
f0 (103 cm1)

a (103 cm1)

b (103 cm1)

S (103 cm1)

R*

SD

Katritzky
KamletAbboudTaft

0.621 (0.067)
0.473 (0.019)

5.958 (0.23)
0.635 (0.12)

5.927 (1.73)
7.618 (1.65)

0.858 (0.08)
1.112 (0.22)

0.05
0.16

564
531

3
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Note: Six solvents were used in each case.

*R, square.
SD, standard error.
F, statistic.

Table 6. Percentage contribution of solvatochromic parameters of ADS740WS laser dye.

Multiparameter scale

Pr + Pn

Katritzky
Multiparameter scale

66
P*

KamletAbboudTaft

37

37

26

Fig. 12. Attatchment of AgNPs with ADS740WS.

PET(30)
34

Fig. 10. Absorption spectra of ADS740 in: (1) methanol; (2) ethanol;
(3) propanol, (dashed line) with and (solid line) without AgNPs.

The observed uorescence quenching is attributed to the resonance energy transfer from ADS740WS to AgNPs. This nonradiative decay can be theoretically studied by using the Forster energy
transfer theory [38]. When some amounts of silver colloidal nanoparticles are added into the solutions of ADS740WS, molecules
would tend to cluster around silver particles because of physical
adsorption. Increasing the ADS740WS concentration leads to
more and more molecules tending to adsorb silver particles, so
the silver particle will be coated by a dielectric shell. The thickness
and dielectric constant of the shell are controlled by the concentration of ADS740WS and silver colloidal content. To nd the
effect of the dielectric shell on the uorescence quenching from
the silver particles we may calculate the quantum efciency (Q) of
the shell-coated silver nanosphere by the following equation:
Q
Fig. 11. Fluorescence Spectra of ADS740 in: (1) methanol; (2) ethanol; (3) propanol, (dashed line) with and (solid line) without AgNPs.

R
R NR

(25)

where R, radiative decay rate; and NR, nonradiative decay rate.

When a particle has been excited and is oscillating in the incident electromagnetic eld, the excited system may have a uctuating electric dipole moment [39], which causes radiation. This
light radiation from the dipole moment provides the channel for
radiative decay. On the other hand, the Joule heating and plasmon
absorption caused by these elds open nonradiative decay channels. The competition between radiative decay and nonradiative
decay energy transfer affects the uorescence emission of the
molecules located near the particle. If the nonradiative dominates, uorescence quenching occurs. The different distance behavior of the radiative and nonradiative rates explains why the
apparent quantum yield always vanishes at short distances from a
metallic AgNP.
Functional group SO3 has high afnity for Ag and Ag+ and ensures the binding of laser dye chains onto the nanocluster surface
while the laser dye chains prevent nanoclusters from coalescing
with neighboring clusters and thus inhibit at an early stage further growth of nanoclusters through electrostatic repulsion or
steric hindrance [40].
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Tangod et al.

These silver nanoclusters are highly reactive in solution and

very sensitive to UV light. Silver nanoclusters can be easily catalyzed to convert to larger metallic silver particles under UV light
irradiation. When a nuclophillic reagent (e.g., NH3, SH and CN,
SO3) is added to the silver nanocluster solution, a sharp strong
absorption band corresponding to larger metallic silver particles
appears and all the characteristic absorption bands of silver nanoclusters disappear. The great reactivity of silver nanoclusters towards nucleophillic reagents is ascribed to the fact that practically
all the atoms in a nanocluster are surface atoms and highly
reactive.

5. Conclusion
We have estimated ground state and excited state dipole
moments of a highly uorescent laser dye molecule, ADS740WS,
and comparison of excited state dipole moments by Lippert,
Bakhashiev, KawskiChammaViallet, McRae, Suppan, and solvent polarity methods. We found that dye possesses a higher dipole moment in the excited state than in the ground state. This
demonstrates that laser dye is more polar in the excited state than
in the ground. The change in the dipole moment between the
excited state and ground state is due to intermolecular charge
transfer, a large change in dipole moment on excitation suggests
that the excited state is twisted intramolecular charge transfer.
Multiparameter polarity parameter result shows that the solvent effect on absorption and emission spectra of investigated
ADS740WS dye strongly depends on the nature of the solvents and
the substituent groups. For investigating dye, solutesolvent interactions are generally controlled by dipolaritypolarizability
and basicity of the solvents.
Optical absorption and uorescence of ADS740WS in alcohol
solvents with and without attachment of AgNPs shows quenching
in absorption and uorescence intensities. This is because of size,
shape, coupling between the AgNPs and the dye, and energy transfer between AgNPs and the dye. Quenching of uorescence using
AgNPs with ADS740WS leads to many applications, especially for
advancement in biomolecular labeling, uorescence patterning,
and chemotherapy in cancer treatment.

123

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Acknowledgement

34.

We acknowledge the support by CAS-I, University Grants Commission at Karnatak University, Dharwad, India.

35.

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