Dyes and Pigments 82 (2009) 401–408

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Dyes and Pigments

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Control of C.I. Basic Violet 10 aggregation in aqueous solution by the use of

poly(sodium 4-styrenesulfonate)
Ignacio Moreno-Villoslada a, b, *, Felipe González a, Luis Arias a, José Miguel Villatoro a, Ricardo Ugarte a,
Susan Hess a, Hiroyuki Nishide c
a
Instituto de Quı́mica, Facultad de Ciencias, Universidad Austral de Chile, Casilla 567, Valdivia, Chile
b
Departamento de Farmacia e Tecnoloxı́a Farmacéutica, Facultade de Farmacia, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
c
Department of Applied Chemistry, School of Science and Engineering, Waseda University, Tokyo 169-8555, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The aggregation behavior of C.I. Basic Violet 10 in the presence of poly(sodium 4-styrenesulfonate) was
Received 8 September 2008 modified, as a consequence of short-range interactions. In aqueous acidic media, the cationic dye forms
Received in revised form hydrophobic ion pairs with polymeric benzene sulfonate groups which tend to aggregate in H-contacts,
3 March 2009
this tendency being readily influenced by the relative concentration of the macromolecule with respect
Accepted 4 March 2009
Available online 12 March 2009
to that of the dye. In the case of dilute aqueous dye solutions (104 M), for which the probability of dye
self-aggregation is small, C.I. Basic Violet 10 self-contacts are forced in the presence of a moderate excess
of poly(sodium 4-styrenesulfonate). At dye concentrations >104 M, for which the probability of dye
Keywords:
C.I. Basic Violet 10 self-aggregation increases, dye-dye contacts are minimized in the presence of a large excess of the
Aromatic–aromatic interactions polymer. Hence, the luminescence of dye solutions can be tuned insorar as, that of dilute dye solutions is
Fluorescence enhancement quenched whilst that of concentrated dye solutions can be enhanced. This behavior was not observed for
other polyelectrolytes such as poly(sodium vinylsulfonate), or the more hydrophobic poly(sodium 2-(N-
acrylamido)-2-methyl-propanesulfonate).
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction certain cases, experiments indicate the influence of short-range

site-specific interactions. These short-range interactions may
The interaction of rhodamines with colloidal particles, as exceed in strength the long-range electrostatic interaction. In most
micelles [1], vesicles [2], clays [3–5], and latex [6], has been cases, both modes of binding occur simultaneously where one
investigated in the literature. The adsorption of these molecules to mode is the dominant.
several solid materials has also been investigated [7,8]. By means of C.I. Basic Violet 10 is an interesting molecule with spectral-
their interactions with these objects, the luminescent properties of luminescent properties ascribed to its state of aggregation. Changes
the dyes may change, and some effects observed by emission and in its luminescence are due to self-contacts in sandwich H-type or
absorption UV–vis spectroscopy have been interpreted in terms of head-to-tail J-type geometries, showing variable orders of aggre-
the self-aggregation of the dyes on the surface of these particles. gation (dimer, trimer, etc.). Recently, we have shown that C.I. Basic
Interactions between low molecular-mass species (LMMS) and Violet 10 interacts with WSP containing aromatic rings such as
water-soluble polymers (WSP) have been extensively studied poly(sodium 4-styrenesulfonate) (PSS) or poly(N-methacryloyl-5-
[9–16]. Polymers containing sulfonate groups behave as negatively aminosalicylic acid) [17–19]. Results by 1H NMR spectroscopy
charged strong polyelectrolytes, and undergo long-range electro- indicated the existence of specific short-range p–p interactions
static interactions with their counterions, which are generally between PSS and C.I. Basic Violet 10 [17–19], and a geometrical
described by the counterion condensation theory of Manning structure for the contact between C.I. Basic Violet 10 and PSS at pH
[9,10]. According to this, long-range electrostatic interactions 7 has been proposed [19].
produce non-site-specific territorial binding, and the counterions Aromatic–aromatic interactions, such as p–p interactions, are
are able to move around the polyelectrolyte surface. However, in one of the principal non-covalent forces governing molecular
recognition and biomolecular structure [20–27]. These interactions
* Corresponding author. Instituto de Quı́mica, Facultad de Ciencias, Universidad
have a short-range character, which implies that water molecules
Austral de Chile, Casilla 567, Valdivia, Chile. Fax: þ56 63 293520. of the hydration sphere of the aromatic groups are released when
E-mail address: [email protected] (I. Moreno-Villoslada). these groups contact each other in aqueous solutions. Thus, the

0143-7208/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2009.03.004
402 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408

main forces driving these interactions are solvophobic, while site- 2.3. Procedures
specific interactions such as short-range electrostatic interactions,
hydrogen bond formation, p–p interactions, or cation–p interac- Conventional procedures have been followed. Particular exper-
tions also contribute to the free energy and define the geometry of imental conditions are provided in the figure captions.
the complexes [20,21]. They are important in the stabilization of Details for diafiltration procedures can be found elsewhere [35–
DNA and its association with intercalators. They also play an 37]. The polyelectrolyte concentration has been chosen so that
important role in protein stabilization and protein functionality, as enough sensitivity is obtained by diafiltration at every pH. Briefly,
in enzymes [28–32], trans-membrane channels [33,34], etc. The solutions in twice-distilled water (10 mL) were prepared contain-
dual relevance of these interactions motivates the development of ing one or more of the following components: a WSP (polymeric
synthetic systems whose structures and functionalities may be molecular-mass fraction over 10,000 Dalton, 2.0  104 M and
tuned by aromatic–aromatic interactions. 103 M in monomeric units at pH 2 and 7, respectively) and C.I.
In this context, we will show in this paper that the luminescence Basic Violet 10 (1.0  104 M at pH 2 or 7). The solutions were
of C.I. Basic Violet 10 solutions can be modulated in the presence of placed into the diafiltration cell. The pH of the aqueous solution
PSS. Diafiltration and emission and absorption UV–vis spectro- contained in the reservoir was adjusted to the same value as in the
scopic results on the interaction of these two species will be shown cell solution. The filtration runs were carried out over a regenerated
and compared with those obtained with other polyelectrolytes cellulose membrane with a molecular-mass cut-off of 5000 Dalton
containing sulfonate groups such as poly(sodium vinylsulfonate) under a total pressure of 3 bar, keeping constant the solution
(PVS), or the more hydrophobic poly(sodium 2-(N-acrylamido)-2- volume in the cell by creating a continuous flux of liquid through
methyl-propanesulfonate) (PAMPS). the cell solution from the reservoir (around 0.008 mL s1). Vigorous
stirring is held in order to minimize concentration polarization and
fouling. Filtration fractions (ranging between 6.0 and 8.0 mL) were
2. Experimental
collected and C.I. Basic Violet 10 concentrations analyzed by UV–vis
spectroscopy. Calibration curves (absorbance ¼ 107,842 [C.I. Basic
2.1. Reagents
Violet 10] at pH 2, and absorbance ¼ 108,174 [C.I. Basic Violet 10] at
pH 7) were obtained at 558 nm for pH 2, and 554 nm for pH 7, in
Commercially available PSS (Aldrich, synthesized from the para-
a range of C.I. Basic Violet 10 concentrations between 1.0  106 and
substituted monomer), PVS (Aldrich), PAMPS (Aldrich), and C.I.
1.0  105 M, with square linear regression factors of 1.00. Blank
Basic Violet 10 (Sigma) were used to prepare solutions in deionized
experiments were performed with the same procedure in the
distilled water. The structures of C.I. Basic Violet 10 and the
absence of the WSP. At least one replicate is done for every
different polyelectrolytes are shown in Fig. 1, as well as the
experiment.
proposed geometry for the contact between PSS and C.I. Basic
The change in the pH caused by the interaction between C.I.
Violet 10 at pH 7 [19]. The pH was adjusted with minimum amounts
Basic Violet 10 and PSS has been explored by mixing 20 mL of
of NaOH and HCl.
104 M C.I. Basic Violet 10 solutions at different pHs with 100 mL
of concentrated PSS in order to achieve a PSS final concentration of
2.2. Equipment 2  103 M. In order to have absorbances in a range of 0.1–1.0, the
optical path length was adjusted between 101 and 103 cm for
The unit used for diafiltration studies consisted of a filtration cell solutions containing C.I. Basic Violet 10 at concentrations ranging
(Amicon 8010, 10 mL capacity) with a magnetic stirrer, a regen- between 104 and 102 M. When done, decomposition of spectra in
erated cellulose membrane with a molecular-mass cut-off of Gaussians was performed with the Origin50 software. Fluorescence
5000 Dalton (Ultracel PBCC, 25 mm diameter), a reservoir, measurements were done under the following parameters:
a selector, and a pressure source. Distilled water was deionized in a voltage in the range 330–450 V was applied to control the light
a Simplicity Millipore deionizer. The pH was controlled on Hanna intensity of the high pressure Xenon arc lamp for C.I. Basic Violet 10
pH211 and Horiba F-15 pH meters. UV–vis experiments were per- concentrations ranging between 106 and 102 M; the excitation
formed at 293 K in Jasco V-570 and in Helios g spectrophotometer. wavelength was 530 nm; the bandwidth was 5.0 nm. For series of
Fluorescence measurements were done in a Kontron SFM25 fluo- experiments where highly concentrated C.I. Basic Violet 10 solu-
rescence spectrophotometer. tions are observed, luminescence measurements have been

n
SO3- N
H COO-
COO- HCl n
PVS
H + O

n H
N+ O N H

SO3 - O NH SO3- N
H
PSS
C.I. Basic Violet 10
SO3- C.I. Basic Violet 10 - PSS contact

PAMPS

Fig. 1. Molecular structures of C.I. Basic Violet 10 and PSS, and proposed structure for their mutual contact at pH 7.
 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408 403

performed in the front-face mode by the use of a quartz vessel of constant volume in the diafiltration cell, the concentration in the
triangular base, and the emitted light has been analyzed at the filtrate of the LMMS under study (cfiltrate LMMS ), the concentration of free
fluorescence maxima: 581 nm for C.I. Basic Violet 10 104 M, pH 2; LMMS in the cell solution (cfree LMMS), the concentration of LMMS
589 nm for C.I. Basic Violet 10 104 M, PSS 102 M, pH 2; 576 nm for reversibly bound to the WSP (crev-bound
LMMS ), the apparent dissociation
C.I. Basic Violet 10 104 M, pH 7; 583 nm for C.I. Basic Violet 10 constant (Kdiss-WSP free
LMMS ), defined as the ratio cLMMS/cLMMS
rev-bound
, the dia-
m
104 M, PSS 102 M, pH 7; 580 nm for C.I. Basic Violet 10 103 M, pH filtration parameters k , j, u, and v, and the polymer concentration
2; 594 nm for C.I. Basic Violet 10 103 M, PSS 101 M, pH 2; 573 nm in mole per liter of monomeric units (cP). km and j parameters (the
for C.I. Basic Violet 10 103 M, pH 7; 587 nm for C.I. Basic Violet 10 absolute value of the slope of the curve ln cfiltrate LMMS versus F in the
103 M, PSS 101 M, pH 7. absence and in the presence of the WSP, respectively) are related
with the strength of the interaction, while v and u are related with
3. Results and discussion the amounts of LMMS reversibly or irreversibly bound to the
polymer, respectively. By irreversibly bound we consider molecules
3.1. C.I. Basic Violet 10 self-aggregation bound in processes that may be reversible with an apparent
dissociation constant that tend to zero at the conditions of the
Due to the presence of a positively charged xanthene group and experiment.
a negatively charged carboxylic unit (see Fig. 1), C.I. Basic Violet 10 Diafiltration experiments have been done to evaluate the
is zwitterionic at pH 7, and positively charged at pH 2. The pKa of interaction between C.I. Basic Violet 10 and PSS, PVS, and PAMPS at
this dye has been described to be 3.2 at a concentration 105 M pH 2 and 7 and the results are shown in Fig. 3a and b, respectively,
[17,38]. Both zwitterionic and cationic species show different UV– and Table 1. At pH 2, C.I. Basic Violet 10 is positively charged, so
vis absorption spectra as can be seen in Fig. 2 for several C.I. Basic long-range electrostatic interactions should take place between the
Violet 10 concentrations. It is generally accepted that at a C.I. Basic WSP and the dye. However, the strong ionic strength associated
Violet 10 concentration up to 104 M the molecule is found in its with such a low pH may screen the long-range electrostatic inter-
monomeric state, showing its maximum of absorbance at 556 nm actions. This is believed to be the main force concerning the
at pH 2 and 554 nm at pH 7 (Fig. 2, labels a and b). Increasing the C.I. interaction between PVS and C.I. Basic Violet 10, so that a negligible
Basic Violet 10 concentration from 104 M produces an increase of binding is found for this polymer, as shown by the filtration rates
the bands at 524–522 nm (pH 2–7) relative to those at 556–554 nm similar to blank experiments (Fig. 3a) and the corresponding high
(Fig. 2, labels c–d). This is accepted to be a consequence of the apparent dissociation constant (see Table 1). On the contrary, the
formation of dimers and higher-order aggregates of C.I. Basic Violet interaction with PAMPS or PSS is not negligible. This may be due to
10 in solution. The formation of these aggregates is normally the high hydrophobicity of these polymers. The lack of linearity in
accompanied by a decrease in the fluorescence of the dye due to H- the case of PAMPS does not allow analytical interpretation of the
contacts between the molecules [8]. results. In the case of PSS, the low value of the parameter j is related
to practically quantitative binding. On the other hand, at pH 7, at
3.2. Different binding in the presence of different polyelectrolytes which C.I. Basic Violet 10 is zwitterionic and thus long-range
electrostatic interactions are avoided, PVS and PAMPS do not bind
Diafiltration is a suitable technique to evaluate overall interac- C.I. Basic Violet 10, while PSS shows a significant binding ability,
diss-PSS
tions between polyelectrolytes and LMMS such as metal ions or and the corresponding KC.I. Basic Violet 10 was found to be 0.50  0.05.
charged molecules, since it is a separation technique that The existence of interaction between C.I. Basic Violet 10 and PSS
discriminates the species by their size [35–37]. It allows calculating at pH 7 has been reported before. With the aid of 1H NMR spec-
the apparent dissociation constants of the interaction between troscopy it has been determined that aromatic–aromatic interac-
polyelectrolytes and specific counterions. The main magnitudes tions take place between the macromolecule and the dye (see
managed in diafiltration analyses are the filtration factor (F), Fig. 1) [18,19]. This kind of interaction has a short-range character,
defined as the ratio between the volume in the filtrate and the a fact that may determine the behavior of the system by means of

e e
1 1

0,9 0,9
d
0,8 0,8 d
normalized absorbance

0,7 0,7

0,6 0,6

0,5 c
0,5 c
0,4 0,4
b
a, b
0,3 a 0,3

0,2 0,2

0,1 0,1

0 0
450 500 550 600 450 500 550 600
wavelength (nm) wavelength (nm)

Fig. 2. Normalized UV–vis spectra at pH 2 (left) and 7 (right) of (a) C.I. Basic Violet 10 106 M; (b) C.I. Basic Violet 10 105 M; (c) C.I. Basic Violet 10 104 M; (d) C.I. Basic Violet 10
103 M; (e) C.I. Basic Violet 10 102 M.
404 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408

F F
-8 -8
0 2 4 6 8 0 2 4 6 8

-9 -9
a b

ln <cC.I. Basic Violet 10filtrate>

-10 -10

-11 -11

-12 -12

-13 -13

-14 -14

-15 -15

Fig. 3. Diafiltration profiles at pH 2 (left) and 7 (right) of C.I. Basic Violet 10 104 M in the absence of any polyelectrolyte (x); and in the presence of 2  104 M (pH 2) and 103 M
(pH 7) of PVS ( ), PAMPS ( ), and PSS ( ) (see Table 1 for linear adjustments).

the following hypothesis: when C.I. Basic Violet 10 interacts with is important to verify if PSS binds both cationic and zwitterionic
PSS, site-specific binding occurs due to short-range interactions; forms of C.I. Basic Violet 10, as depicted in Scheme 1.
when the cationic C.I. Basic Violet 10 is present (for example, at The shift of the maximum of absorbance with the pH is useful to
pH 2) ion pairs between C.I. Basic Violet 10 and the benzene follow the acid–base equilibrium of the dye. It can be seen in Fig. 5,
sulfonate groups of the polymer are formed; these ion pairs are where the maxima of absorbance of 104 M C.I. Basic Violet 10
hydrophobic, so they may tend to aggregate. solutions in the absence and in the presence of 103 M PSS are
Long-range interactions do not normally produce changes in the plotted versus the pH, that its apparent pKa is shifted from 3.2 to
UV–vis spectra of the interacting molecules. Thus, in the presence around 6 in the presence of the polymer. This reveals a higher
of 100 times PVS and 100 times PAMPS, the absorption spectra of affinity of the polymer to bind the cationic form of C.I. Basic Violet
105 M C.I. Basic Violet 10 solutions do not change from that of 10, provided that electrostatic interactions contribute to the overall
pristine C.I. Basic Violet 10 solutions at pH 2 or 7 (see Fig. 4). On the interaction. The relatively high acidity of the carboxylic acid of C.I.
contrary, as short-range interactions take place with PSS, the C.I. Basic Violet 10 is justified by the stabilization effect produced by
Basic Violet 10 absorption spectrum shows the same profile as that the positively charged xanthene group. As a consequence of the
of C.I. Basic Violet 10 monomer, but is shifted to lower energies, short-range interaction between C.I. Basic Violet 10 and PSS, the
revealing the molecular interaction at both pHs. The shift of the basicity of the carboxylate group increases. This can be caused by
absorbance band of xanthene dyes to lower energies is sometimes both the electrostatic stabilization of the electron deficient s plane
ascribed to formation of J-aggregates. However, the extent of the of the benzene carboxylic group of C.I. Basic Violet 10 by means of
aggregation should be a function of the polymer to dye relative the interaction with the p electrons of the polymeric benzene ring,
concentration, and should tend to decrease under a large excess of and the stabilization of the xanthene group of C.I. Basic Violet 10 by
the polymer. Due to the large excess of PSS used, we interpret this interaction with the sulfonate group of the polymer that should be
shift as caused by the interaction of the C.I. Basic Violet 10 transition placed next to it (see Fig. 1). A more hydrophobic environment may
moment with those of the polymer (as a consequence of the short- also contribute to the stabilization of the carboxylic form.
range interaction as depicted in Fig. 1) and surrounding water. On the other hand, the zwitterionic form of C.I. Basic Violet 10
also interacts with PSS. We can demonstrate this fact by the
3.3. Ion pair aggregation following analysis: if upon mixing at pH 7 sufficiently concentrated
C.I. Basic Violet 10 (in its zwitterionic form) and PSS solutions, all
3.3.1. Ion pair formation C.I. Basic Violet 10 molecules that bind to PSS protonate, there
Ion pairs are formed upon interaction of the cationic form of C.I. should be a significant increase in the pH, provided that diafiltra-
Basic Violet 10 and the benzene sulfonate groups of PSS, as tion experiments show that PSS binds a significant amount of C.I.
a consequence of the short-range aromatic–aromatic interaction. It Basic Violet 10 at this pH (see Fig. 3 and Ref. [19]). Thus, upon

Table 1
Results for diafiltration of 104 M C.I. Basic Violet 10 solutions at pH 2 and 7 and different WSP.a

Experiment cP (M) pH v u j km diss-WSP

KC.I. Basic Violet 10
b
Linear adjustments for the experimental data R2
C.I. Basic Violet 10-01 – 2 1.00 0.00 – 0.85 – y ¼ 0.85x  8.9 1.00
C.I. Basic Violet 10-02 – 7 0.91 0.09 – 0.84 – y ¼ 0.84x  9.5 1.00
PVS–C.I. Basic Violet 10-01 2  10-4 2 0.90 0.10 0.87 – /N y ¼ 0.87x  9.1 1.00
PAMPS–C.I. Basic Violet 10-01 2  10-4 2 – – – – – – –
PSS–C.I. Basic Violet 10-01 2  10-4 2 – – /0 – /0 – –
PVS–C.I. Basic Violet 10-02 1  10-3 7 0.82 0.18 0.88 – /N y ¼ 0.88x  9.3 1.00
PAMPS–C.I. Basic Violet 10-02 1  10-3 7 0.88 0.12 0.91 – /N y ¼ 0.91x  9.3 1.00
PSS–C.I. Basic Violet 10-02 1  10-3 7 0.89 0.11 0.31 – 0.50  0.05 y ¼ 0.31x  10.4 0.99
a
For linear adjustments: y ¼ ln <cfiltrate 2
C.I. Basic Violet 10>; x ¼ F; R ¼ linear regression factor.
b diss-WSP
KC.I. diss-WSP m m
Basic Violet 10 is calculated following j=ð1  jÞ  KC:I: Basic Violet 10  k j=ðk  jÞ.
 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408 405

1 b, f", g" b" 1 b, f", g" b"

0,9 0,9
0,8 0,8
0,7 0,7

absorbance
0,6 0,6
0,5 0,5
0,4 0,4
0,3 0,3
0,2 0,2
0,1 0,1
0 0
450 500 550 600 450 500 550 600
wavelength (nm) wavelength (nm)

Fig. 4. Normalized UV–vis spectra at pH 2 (left) and 7 (right) of C.I. Basic Violet 10 105 M in the absence of any polyelectrolyte (b); and in the presence of 103 M of PSS (b00 ); PVS
(f00 ); and PAMPS (g00 ).

mixing 104 M C.I. Basic Violet 10 solutions at different original pHs Ion pair aggregation is induced in the presence of an excess of 10
with negligible volumes of concentrated PSS (see Experimental times PSS at a C.I. Basic Violet 10 concentration 105 M and pH 2.
section) a significant change in the pH is found between pH 3 and 5, This can be seen in Fig. 6 as an increase in the intensity of the band
indicating protonation of the dye as can be seen in Fig. 5. However, at around 524 nm relative to that at around 556 nm: the corre-
as the concentration of the zwitterionic form in solution increases, sponding spectra (b, and b0 at pH 2) have been decomposed in two
the increase in the pH upon mixing with PSS decreases, and at pH 7 Gaussians, and the ratio band area centered at around 524 nm/band
no significant pH change is detected. The lack of change in the pH area centered at around 556 was found to be 1.21 and 1.59,
together with the diafiltration results indicates that the zwitter- respectively. This effect is not observed at pH 7, since the C.I. Basic
ionic form binds the macromolecule. Violet 10/PSS adducts are negatively charged and less probable to
Thus, ion pairs are formed between cationic C.I. Basic Violet 10 be formed at such diluted conditions (revealed by the small shift of
and benzene sulfonate groups of PSS at pHs under the apparent pKa the maximum of absorbance) due to the lack of the long-range
of C.I. Basic Violet 10 in the presence of the polymer. The flexibility electrostatic component in the overall interaction. On the contrary,
of the polymer can produce that ion pairs, due to their hydropho- no significant spectral variation is found in the presence of PVS or
bicity, aggregate with a definite geometry. This ion pair aggregation PAMPS at any pH.
could eventually induce H-type contacts between stacked C.I. Basic However, in the presence of a large excess of PSS (100 times),
Violet 10s. This would be noticed by an increase of the intensities of H-contacts are minimized (see Fig. 4), and the intensity of the
the bands at 524–522 nm (pH 2–7) relative to those at 556–554 nm, band at around 524–522 nm (pH 2–7) corresponds approximately
and by a consequent fluorescence quenching. So, these two to that of the C.I. Basic Violet 10 monomeric state. At these
observations can help us to verify the hypothesis stated before. conditions, the C.I. Basic Violet 10 molecules should be far away
from each other, distributed in the binding sites of the
3.3.2. Ion pair aggregation for diluted C.I. Basic Violet 10 solutions polyelectrolyte.
There must be a correlation between the tendency of the ion
pairs to aggregate and the relative amount of benzene sulfonate
groups with respect to C.I. Basic Violet 10. Moreover, the pH should 568 1,5
influence the extent of ion pair aggregation, since for its formation
C.I. Basic Violet 10 must be protonated. 566
1
564
+
H
562
0,5
λmax (nm)

C. I. Basic Violet 10 C. I. Basic Violet 10-H+

Δ pH

560

558 0

C. I. Basic Violet 10 556

-0,5
+
C. I. Basic Violet 10-H
554

552 -1
2 4 6 8 10
pH

Fig. 5. Position of the maximum of absorbance of a 104 M C.I. Basic Violet 10 solution
as a function of the pH: ( ) in the absence of PSS ( ), in the presence of 103 M PSS;
and increase in the pH upon mixing a 104 M C.I. Basic Violet 10 solution with 103 M
Scheme 1. PSS ( ).
406 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408

1 b, f', g' b' 1 b,f',g' b'

0,9 0,9
0,8 0,8
0,7 0,7

absorbance
0,6 0,6
0,5 0,5
0,4 0,4
0,3 0,3
0,2 0,2
0,1 0,1
0 0
450 500 550 600 450 500 550 600
wavelength (nm) wavelength (nm)

Fig. 6. Normalized UV–vis spectra at pH 2 (left) and 7 (right) of C.I. Basic Violet 10 105 M in the absence of any polyelectrolyte (b); and in the presence of 104 M of PSS (b0 ); PVS
(f0 ); and PAMPS (g0 ).

The different probability to undergo H-contacts can be also 3.3.3. Ion pair aggregation for concentrated C.I. Basic Violet
followed observing the fluorescence quenching in C.I. Basic Violet 10 solutions
10 solutions. Corresponding to the shift in absorbance, the fluo- As shown in Section 3.1, for C.I. Basic Violet 10 concentrations
rescence band is also shifted to lower energies in the presence of higher than 104 M the appearance of self-aggregates by means of
excess PSS, while no shift is found for PVS or PAMPS (data not H-contacts is produced and revealed by the corresponding fluo-
shown). The change in the fluorescence intensity as a function of rescence quenching and an increase of the bands at 524–522 nm
the PSS/C.I. Basic Violet 10 ratio for different pHs can be seen in (pH 2–7) relative to those at 556–554 nm (see Fig. 2).
Fig. 7. The fluorescence quenching is optimal at PSS/C.I. Basic Violet However, PSS is able to disrupt the C.I. Basic Violet 10 self-
10 around 10 at acidic pHs. Smaller ratios will result in less binding aggregation tendency. It can be seen in Fig. 8 that in the presence of
and higher conformational restrictions, and higher ratios may 100 times PSS, the corresponding absorption bands of C.I. Basic
result in a decrease in the probability of H-contacts between the ion Violet 10 at concentrated C.I. Basic Violet 10 solutions are all
pairs, since they should be far away from each other and sur- equivalent and shifted to lower energies (566–560 nm, at pH 2 and
rounded by hydrophilic groups. On the contrary, no significant 7, respectively) showing the formation of C.I. Basic Violet 10–PSS
fluorescence intensity variation is found for PVS and PAMPS (data complexes. At this PSS/C.I. Basic Violet 10 ratio, C.I. Basic Violet 10
not shown) at any pH or for PSS at pH over 5. should be found in its monomeric form, so that the high excess of
polymer is preventing C.I. Basic Violet 10 to self-aggregate. Thus,
despite the high C.I. Basic Violet 10 concentration, the dyes are
1,4
distributed in the polymer domain so that their aggregation is
minimized.
This effect can be contrasted with the effects produced when the
1,2
interaction has a predominant long-range nature: in the presence
fluorescence (a.u)/ absorbance at 530 nm

of 100 times PVS or PAMPS, at a C.I. Basic Violet 10 concentration of

103 M and pH 2, the systems undergo phase separation, showing
1
a cooperative behavior in the binding of the dye. In the environ-
ment of the polyelectrolytes the local concentration of C.I. Basic
Violet 10 increases and the dyes self-aggregate. These aggregates
0,8
may behave as supramolecular polymers, and thus interpolymer
complexes precipitate. The precipitates were filtered and the UV–
vis spectra of the supernatants were measured showing C.I. Basic
0,6 Violet 10 highly aggregated for these two polymer systems (see
Fig. 9).
In the presence of 10 times PSS with respect to C.I. Basic Violet
0,4 10 (see Fig. 8), the shifting of the bands reveals interaction with PSS,
and the intensity of the bands at around 524–522 nm (pH 2–7)
relative to those at around 556–554 nm are higher than that of the
0,2 monomeric C.I. Basic Violet 10 indicating the existence of H-
contacts between the dyes. However, a lower absorption intensity
is found at around 524–522 nm by comparison with the corre-
0 sponding absorption of the aqueous C.I. Basic Violet 10 solutions at
concentrations 102 and 103 M, which may indicate a different
0
0

75

85
5

15

25
10
1:

1:

1:

1:

1:
1:

1
1:

1:

aggregation state: in the presence of PSS, low-order aggregates

[C. I. Basic Violet 10]:[PSS] such as dimers may be formed, while higher-order aggregates may
Fig. 7. Ratio fluorescence at 630 nm (a.u.)/absorbance at 530 nm of C.I. Basic Violet 10
be found for the free dye at such high concentrations.
2  106 M solutions in the presence of variable amounts of PSS at pH 2 ( ); 3 ( ); 5 It is also noted that the probability of H-contacts at pH 7 is not
( ); and 6 ( ). zero, a fact that can be explained by the self-aggregation of C.I. Basic
 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408 407

e e
1 1
d
0,9 0,9
d
0,8 0,8

0,7 0,7

absorbance
0,6 0,6
e’
0,5 0,5 e’
d’
0,4 0,4 d’
d” , e”
0,3 0,3
d” , e”
0,2 0,2

0,1 0,1

0 0
450 500 550 600 450 500 550 600
wavelength (nm) wavelength (nm)

Fig. 8. Normalized UV–vis spectra at pH 2 (left) and 7 (right) of C.I. Basic Violet 10 103 M (d, d0 , d00 ) and C.I. Basic Violet 10 102 M (e, e0 , e00 ), in the absence of PSS (d, e), in the
presence of 10 times PSS (d0 , e0 ), and in the presence of 100 times PSS (d00 , e00 ).

Violet 10 in any of their states at this high concentration: free, concentrated regimes, at which the probability to undergo self-
stacked zwitterionic C.I. Basic Violet 10 on PSS, or stacked cationic association for C.I. Basic Violet 10 is high, the luminescence of the
C.I. Basic Violet 10 on PSS. solutions is enhanced, since C.I. Basic Violet 10 self-aggregation is
minimized. On the contrary, at a diluted regime, at which the
3.4. Luminescence modulation probability to undergo self-association for C.I. Basic Violet 10 is low,
the luminescence of the solution can be quenched by the addition of
The systems behave similarly at any C.I. Basic Violet 10 concen- 10 times PSS, as can be seen in Fig. 7.
tration in the presence of PSS at pH 2: under a moderate excess of PSS Similar tendencies are found at pH 7: although short-range
(10 times), the C.I. Basic Violet 10 bound to PSS undergoes H- aromatic–aromatic interactions are held with the polymer, the
contacts, but under a large excess of the polymer (100 times), the absence of long-range electrostatic interactions with the zwitter-
probability of H-contacts decreases. This has immediate conse- ionic form of C.I. Basic Violet 10 produces less binding, so the
quences in the solution luminescence that are directly appreciable to increase in the fluorescence in the concentrated regime is less
the eye: solutions containing an excess of 10 times PSS in relation to noticeable (see Fig. 10). The absence of ion pair formation at this pH
C.I. Basic Violet 10 present very low luminescence, while solutions due to the zwitterionic nature of the dye prevents aggregation and
containing an excess of 100 times PSS are luminescent. The emitting fluorescence quenching is not observed for very diluted C.I. Basic
light of concentrated C.I. Basic Violet 10 solutions in the presence and Violet 10 solutions (see Fig. 7).
in the absence of 100 times PSS, irradiated at 530 nm, is analyzed by The luminescence enhancement of highly concentrated C.I.
the front-face mode in Fig. 10. It can be seen that at these Basic Violet 10 solutions cannot be obtained with PVS or PAMPS.
Thus, the possibility of luminescence modulation of C.I. Basic Violet
10 aqueous solutions by means of aromatic–aromatic interaction
1,0
with PSS may be useful for C.I. Basic Violet 10 applications.
0,9
200
0,8 k''
180 b
normalized absorbance

0,7 160
d d
140
emitted light (a.u.)

0,6

120 b
0,5 c
j''
100
0,4
80
a
0,3 60
d''
c
0,2 40

20 a
0,1
0
0,0 -4 -3
450 500 550 600 650 log [C. I. Basic Violet 10]
wavelength (nm)
Fig. 10. Intensity of light emitted at pH 2 (a, b) and 7 (c, d) as a function of C.I. Basic
Fig. 9. Normalized UV–vis spectra at pH 2 of 103 M C.I. Basic Violet 10 filtered Violet 10 concentration in the absence of PSS (a, c), and in the presence of 100 times
solutions in the presence of (d00 ) 101 M PSS; (j00 ) 101 M PVS; (k00 ) 101 M PAMPS. PSS (b, d).
408 I. Moreno-Villoslada et al. / Dyes and Pigments 82 (2009) 401–408

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