Effect of the anionic azo dye Sunset Yellow in lyotropic mixtures with
uniaxial and biaxial nematic phases
Erol Akpinar
a,
⁎, Gokhan Topcu
a
, Dennys Reis
b
, Antônio Martins Figueiredo Neto
b
a
Bolu Abant Izzet Baysal University, Faculty of Arts and Sciences, Department of Chemistry, 14030 Golkoy, Bolu, Turkey
b
Universidade de Sao Paulo, Instituto de Fisica, Rua do Matao, no. 1371, 05508-090 Sao Paulo, SP, Brazil
abstract article info
Article history:
Received 3 June 2020
Received in revised form 23 July 2020
Accepted 6 August 2020
Available online 10 August 2020
Keywords:
Lyotropic liquid crystal
Nematic phase
Biaxial nematic phase
Anionic azo dye Sunset Yellow
Hofmeister series
Polarizing optical microscopy
Laser conoscopy
Small-angle X-ray scattering
The effects of the anionic azo dye Sunset Yellow on the stabilization of lyotropic uniaxial and biaxial nematic
phases and on the uniaxial to biaxial phase transitions were studied. The dye was added in different concentra-
tions to the host ternary mixture of cationic surfactant dodecyltrimethylammonium bromide, 1-dodecanol, and
water. Furthermore, an investigation examined the role of the dye in the lyotropic host mixture in comparison to
some inorganic salts containing anions of the Hofmeister series. The following inorganic salts were added to the
same host mixture: NaBr, NaNO
3
, NaClO
3
, NaI, NaSCN, and NaClO
4
. All the samples were investigated by polariz-
ing optical microscopy, laser conoscopy, and small-angle X-ray scattering. The results indicated that (a) the an-
ionic dye Sunset Yellow has a chaotropic character between that of the I
-
and SCN
-
ions, being similar to the
last one, (b) it gives a larger biaxial nematic phase temperature range in the partial phase diagram in comparison
with the SCN
-
ion and other inorganic salts, and (c) it shifts the temperatures of both uniaxial to the biaxial ne-
matic phase transitions. The small-angle X-ray scattering results also indicated that, at least in the investigated
concentration range, the dye is mainly located on the micelles' surfaces, just like a conventional ion, and that
on increasing concentration the dye molecules induces higher aggregation number of the micelles.
© 2020 Elsevier B.V. All rights reserved.
1. Introduction
Surfactant-based lyotropic nematic phases (LNPs) and their phase
diagrams as a function of concentration and/or temperature have been
investigated in a wide range of studies [1–7]. In general, the mixtures
presenting the LNPs are obtained by the dissolution of surfactant mole-
cules in water. In most cases, electrolytes and/or cosurfactants are
added to those solutions [8–12]. Considering the symmetry of the
LNPs, they are classified as uniaxial (discotic, N
D
, and calamitic, N
C
)
with D
∞h
symmetry and biaxial (N
B
) with D
2h
symmetry [13–16]. The
main characteristic of those uniaxial phases is that the local symmetry
axis of their structural units, so-called micelles, exhibits an average
alignment along a preferred direction (optical axis or director, n
!
).
While only one optical axis exists in the N
D
and N
C
phases, the N
B
phase has two optical axes and three orthogonal two-fold symmetry
axes ( l
!
, m
!
and n
!
, where n
!
¼ l
!
 m
!
)[15,17,18]. Furthermore, studies
in the literature proposed that the three LNPs consist of micelles having
the same orthorhombic symmetry [19]. Another important point for the
LNPs is that the N
B
phase is mainly located between the other two uni-
axial phases in the phase diagrams of lyotropic mixtures presenting the
three nematic phases [20–22]. As theoretically predicted by a Landau-
type mean-field theory and experimentally verified, the uniaxial to bi-
axial transition is of second-order [20–24].
Another class of lyotropic liquid crystals is the lyotropic chromonic
liquid crystals (LCLC) [25–28]. They are obtained from aqueous solu-
tions of substances such as drugs (e.g. disodium chromoglycate
[29,30]) and dyes (e.g. Sunset Yellow [31,32]). Those kinds of com-
pounds, in general, have plank-like molecular structures [32]. While
polyaromatic parts form the main body of these structures, ionic groups
connected to these parts form the outer part of the structure. When
these molecules are dispersed in water, they stack in columns due to
the π-π interactions between the polyaromatic parts, and, if the concen-
tration of the substance is high enough, they form the LCLC phases [31].
Depending on the aggregation of the molecules, two different LCLC
structures were reported in the literature: nematic with orientational
ordering, and hexagonal with both translational and orientational or-
dering [28].
Not only in surfactant-based LNPs but also in lyotropic chromonic
nematic phases (LCNPs), some aspects about the stabilization mecha-
nism of those phases have been investigated. For instance, Kumar
et al. studied the effect of dye concentration, temperature, and ionic ad-
ditives from the inter- and intra-aggregate spacings change point of
view via X-ray diffraction and polarizing microscopy [31]. However,
the surfactant-based LNPs were more investigated if compared with
Journal of Molecular Liquids 318 (2020) 114010
⁎ Corresponding author.
E-mail address: akpinar_e@ibu.edu.tr (E. Akpinar).
https://doi.org/10.1016/j.molliq.2020.114010
0167-7322/© 2020 Elsevier B.V. All rights reserved.
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