Journal of Molecular Liquids 345 (2022) 117812

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

SDS triggered transformation of highly hydrophobic PluronicsÒ

nanoaggregate into polymer-rich and surfactant-rich mixed micelles
Divya Patel a, Debes Ray b, Sanjay Tiwari c, Ketan Kuperkar a,⇑, Vinod K. Aswal b, Pratap Bahadur d
a
Department of Chemistry, Sardar Vallabhbhai National Institute of Technology (SVNIT), Ichchhanath, Surat 395 007, Gujarat, India
b
Solid State Physics Division, Bhabha Atomic Research Centre (BARC), Trombay, Mumbai 400 085, Maharashtra, India
c
Department of Pharmaceutics, National Institute of Pharmaceutical Education and Research (NIPER), Raebareli 226 301, Lucknow, India
d
Department of Chemistry, Veer Narmad South Gujarat University (VNSGU), Udhana-Magdalla Road, Surat 395 007, Gujarat, India

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

Article history: This work reveals the role of sodium dodecylsulphate (SDS, anionic surfactant) in altering the phase beha-
Received 19 July 2021 viour and aggregation characteristics of five very hydrophobic polyethylene oxide-polypropylene oxide-
Revised 7 October 2021 polyethylene oxide (PEO-PPO-PEO) triblock copolymers containing 10% PEO but with different molecular
Accepted 9 October 2021
weight. These copolymers are molecularly dissolved in water at 15–20 °C and exist as unstable vesicular
Available online 13 October 2021
structure at temperature close to cloud point (CP) >20 °C. SDS enhanced the aqueous solubility and CP of
copolymers in water; progressive addition of SDS triggered the transformation of unstable vesicles into
Keywords:
spherical mixed micelles. A correlation between the molecular orbital energy levels of PluronicsÒ and
PluronicsÒ
Surfactant
SDS is well comprehended using computational simulation approach where the perception of SDS stabi-
Vesicles lized PluronicsÒ micelles is predicted and correlated with optimized parameters. The size/ shape of
Mixed micelle copolymer-surfactant mixed nanoscale aggregates was evaluated using dynamic light scattering (DLS)
Micellar shape transformation and small-angle neutron scattering (SANS). The scattering studies showed the presence of spherical
Scattering analysis mixed aggregates, whose size expanded with increase in hydrophobicity of PluronicsÒ. In high SDS con-
Dye solubilization centration regime, SANS analysis uncovered the diminishing size of vesicles into spherical mixed aggre-
gates. The nanoscale PluronicsÒ-SDS mixed micelles remained stable in water where this investigation
discloses the conceivable ability of orange-OT solubilization using UV–vis spectroscopy.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction multiple point of view and their self-assembly into core-shell

micelles, phase behaviour, gelation have been extensively studied
Polyethylene oxide-polypropylene oxide-polyethylene oxide using various physicochemical techniques [2,5,16-20]. However,
(PEO-PPO-PPO) triblock copolymers commercially available as the effect of polymer hydrophobicity on the nanoscale micellar
PluronicsÒ (BASF trade name) with varying molecular characteris- assemblies formed have received lesser attention [2, 5, 21 and
tics come up with a wide range of hydrophobic-hydrophilic bal- 22]. It is observed that very hydrophobic PluronicsÒ (those with
ance (HLB); show unique surface-activity/ self-assembly/ high molecular weight PPO and 20% PEO) do not form micelles
reversible thermo-rheological behaviour in aqueous solution [1- and remain molecularly dissolved up to 20 °C and later undergo
4]. An assorted scope of varied block copolymeric aggregate forma- phase separation (2/) as unstable dispersions dominated by vesi-
tion viz., spherical, ellipsoids, rod-like micelles, along with rich liq- cles around the cloud point (CP) where the solution turns turbid
uid crystalline phases such as cubic, hexagonal, or lamellar [1,2,5,7]. Therefore, investigations on vesicle development and
morphology has been reported [3,5–10]. As a result, these Pluron- aggregation pattern for such hydrophobic precursors of varied
icsÒ perceive widespread applications in paints and coatings, molecular features in water is staying scanty. These copolymers
beauty care products, tertiary oil recuperation and nanovehicles can markedly show increase in CP in the presence of ionic surfac-
for drug delivery systems [2,5,6,11-15]. tants and form small spherical mixed micelles [2,5,17-20]. Here,
The aqueous solution behavior of PluronicsÒ is allied to the the ionic surfactant present at low concentration (few mM) unex-
behavior of ‘‘conventional” low molecular weight surfactants from pectedly raises the CP with a possibility to transform vesicular
structures into core-shell mixed micelle morphology. Hence,
polymer-surfactant mixed systems have been of interest since past
⇑ Corresponding author.
few decades as these offer improved solubilization features
E-mail address: [email protected] (K. Kuperkar).

https://doi.org/10.1016/j.molliq.2021.117812
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

unattainable by the single component. This is in contrast to the ing shear due to the water squeezing out of the vesicles [22]. Y. Li
properties of moderately hydrophobic polymeric aggregates which et al. examined the polymer-surfactant complexation between SDS
disintegrate in the presence of ionic surfactants and produce and poly(vinylpyrrolidone) (PVP) [23]. Likewise Atanase et al. pre-
surfactant-rich small micelles [7,20]. sented the improved hydrophobic interaction between Poly(vinyl
In this context, studies were made ascertaining the interaction alcohol-co-vinyl acetate) (PVA) and SDS [24,25].
between amphiphilic polymers with higher hydrophobicity and However, there is a dearth of studies or solution containing
low molecular weight ionic surfactants where the interactions hydrophobic PluronicsÒ with SDS. Hence, it will be very interesting
are observed to occur more prominently at surfactant concentra- to explore the plausible interactions when anionic surfactant is
tion below its critical micelle concentration (CMC) forming differ- added to the aqueous dispersion of varied PluronicsÒ. Thus, the
ent morphological aggregates. However, the micellar behavior present study inspects the solution behavior of 1 %w/v PluronicsÒ
strongly depends on the hydrophobicity of copolymers. Reported (L31, L61, L81, L101 and L121) in water and in presence of varying
work has illustrated the use of anionic surfactant in particular concentration of SDS employing phase behaviour characterization
sodium dodecylsulfate (SDS) to interact strongly with PluronicsÒ and scattering techniques. Theoretical approach accounts to
molecules/ micelles compared to cationic analogues. Herein, most understand the charge dispersion and engagement of SDS with
of these studies have used very hydrophilic copolymers (those the PluronicsÒ molecule which attempts to rationalise the interac-
which remain molecularly dissolved) and moderately hydrophilic tion between them. The scattering approaches viz., dynamic light
copolymers (those which form micelles at ambient temperature) in scattering (DLS) and small-angle neutron scattering (SANS) were
presence of SDS which approached in evaluating interaction employed to uncover the different morphologies and size/ shape
parameter considering non-ideal systems and showed synergism, of mix aggregates with progressive addition of SDS in the explored
or examined the effect of either surfactant or polymer on the framework. As the investigated system exhibit nanoscale core-
micelles of the other [3,4,8,10,20]. General conclusions thus high- shell mixed micelles with SDS addition, this study discloses the
lighted that even a trace amount of SDS in PluronicsÒ show a high conceivable solubilization ability of water insoluble azo dye
increase in CP and facilitates mixed micelle formation with inter- (Orange OT) utilizing UV–vis spectroscopy.
esting characteristics that could be favourably used in designing
surfactant-based finished products [3,5,8,9,13,20]. Several
hydrophobic PluronicsÒ have been used for the extraction of bioac- 2. Experimental section
tive compounds using CP based aqueous micellar systems
[2,5,6,20]. Prameela et al. from studies on hydrophobic PluronicsÒ 2.1. Materials
with SDS using spectral/ scattering studies observed that L31-
rich and SDS-poor and SDS-rich and L31-poor mixed aggregates In our study, all the PluronicsÒ were received from BASF Corpo-
are formed as a function of L31 and SDS concentrations, respec- ration (NJ, USA) as gift samples and were used without any purifi-
tively. Here, L121-SDS combination in aqueous medium inferred cation. The composition of the selected five different 1 %w/v
vesicles at low [SDS] (below 10 mM), and transform into L121- PluronicsÒ (L31, L61, L81, L101 and L121) are presented in
SDS mixed aggregates at higher [SDS] (10 mM) [2,5]. In addition, Scheme 1. For all these taken copolymers, the last digit ‘1’ indicate
W. Han et al. observed the proportion-dependent toxicity of binary 10% hydrophilicity due to the presence of PEO (terminal) blocks.
surfactant mixtures containing SDS and non-ionic fatty alcohol- However, due to the varying PPO block contribution i.e., increasing
polyoxyethlene ether (AEO) toward Photobacterium phosphoreum molecular weight of PPO (middle) block trails the overall
[21]. F. Nettesheim et al. reported the influence of added SDS on hydrophobicity of the PluronicsÒ in the order:
non-ionic surfactant tetraethyleneglycol-monododecyl ether L121 > L101 > L81 > L61 > L31. Sodium dodecylsulphate (SDS)
(C12E4) that showed a decrease in MLV layer spacing with increas- (Mol. wt. = 288 g/mol; CMC = 8 mM and Kraft temperature = 8 °

Scheme 1. Structural formula and constitutional details of the PluronicsÒ used.

2
D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

C) and Orange OT (Mol. wt. = 262 g/mol; and solubility in using Gaussian 09 calculating window and Gauss View 5.0.9 soft-
water = 5 g/L) used were purchased from Merck, India. ware package with (DFT)/B3LYP method and 3-21G basis sets.
In all measurements, the PluronicsÒ concentration was fixed to The selection of this basis sets was given an account due to its sig-
1 %w/v and SDS concentration was varied from 0 to 50 mM. The nificant degree of accuracy. Various optimized parameters like the
sample solutions were prepared in deuterium oxide (D2O) for neu- energies of the MO i.e., highest occupied one is EHOMO and lowest
tron scattering study while double-distilled water was used for unoccupied one is ELUMO, energy gap (DE = ELUMO EHOMO), total
rest of the experiments. energy (T.E.), and dipole moment (l) were evaluated. In addition,
the counter plot of 3D-Molecular Electrostatic Potential (MEP) sur-
2.2. Methods face is also presented using this simulation method to show the
charge dispersion by colour mapping [32-35].
2.2.1. Phase behaviour
The phase separation (2/) phenomenon expressed as cloud 2.2.3. Scattering conduct
point (CP) was scrutinized to perceive the impact of SDS in trigger- The hydrodynamic diameter (Dh) of micelles/ vesicles as
ing the aggregation behaviour of the selected 1 %w/v PluronicsÒ obtained from dynamic light scattering (DLS) for different mixed
(L31, L61, L81, L101 and L121) in presence of 0–50 mM [SDS] by system was obtained from Zetasizer (Malvern Instruments, UK).
progressively warming the solution in thin glass vial dipped in a The He-Ne, 4 mW laser (wavelength ko = 635 nm) was used as
stirred heating bath. Here, the CP has been deliberated with an the incident beam with the scattering angle of 90°. The average
abrupt turbidity appearance in the solution with progressive particle size was recorded considering three consecutive measure-
increase in the temperature. The CP measurements were repeated ments for each sample [31,34-36].
minimum three times within the variation ±0.1 °C [1,2,26-31]. Small-angle neutron scattering (SANS) experiments were per-
formed to determine the aggregate size/ shape in the examined
2.2.2. Computational framework systems from SANS diffractometer at Dhruva reactor, BARC, Mum-
To get definite interaction parameters of PluronicsÒ with SDS, bai, India. The measured SANS data were corrected by SASFIT soft-
respective molecular orbital (MO) energy levels were assessed ware where coherent differential scattering cross-section (dR/dX)

Table 1
Clouding behavior in 1 %w/v solution of PluronicsÒ (CP1%w/v) with varying concentration of SDS.

[SDS], mM CP1%w/v (°C)

L31 L61 L81 L101 L121
0 30 [29.5] 24 [23] 20 [19] 15 [14] 14 [13]
5 42 [42] 32 28 23 19
10 53 [52] 45 38 32 26
20 75 [74] 69 65 60 55
25 >100 [>100] >100 85 79 75
50 >100 [>100] >100 >100 >100 >100

Note: CP values in [ ] are in well-agreement with the reported literature [2,24,25].

Fig. 1. Electron transfer between HOMO and LUMO lobes illustrating the energies of the analogous molecular orbitals (EHOMO and ELUMO) and the energy gap (DE) with its 3D-
MEP surface charge distribution in the PluronicsÒ-SDS system.

3
D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

per unit volume was evaluated as a function of wave vector trans- study the behavior of PluronicsÒ in combination with ionic species,
fer Q (=4psinh/2)/k, where k is the wavelength of the incident neu- in which we are ultimately interested. In this section, only one
trons and h is the scattering angle). The mean wavelength of the molecule of PEO-PPO-PEO and one molecule of SDS are taken due
monochromatized beam was 5.26 Å with Dk/k 15%. The angular to computation run and time limitations.
distribution of neutrons scattered by a sample is recorded using a The T.E. predicts the plausible interaction probability in the
1 m long one-dimensional He3 position sensitive detector. Instru- examined system [38,41]. Here, PluronicsÒ has higher T.E. value
mental smearing was taken care of throughout the data analysis.  574.04 a.u. and SDS has moderate T.E. value  1326.44 a.u.
The calculated scattering profiles for the suitable models were However, the addition of SDS in PluronicÒ stabilizes the micelle
smeared by the resolution function and then compared with the
measured data (Necessary equations are presented in Supporting
information). The parameters in the analysis were optimized by
means of nonlinear least-squares fitting program using SAS fit soft-
ware package [2,5,6,31,37-39].

2.2.4. Dye solubilization

The dye loaded micellar system were prepared by adding excess
amount of orange OT dye into the micellar solutions and were agi-
tated at 30 °C with constant stirring for 2–3 days. In order to
remove the undissolved dye, these solutions were further filtered
using 0.45 lm filter and diluted with ethanol about 10 times to
minimize the higher intensity which was measured in the UV
range 200–800 nm [40-42]. The absorption spectra were ana-
lyzed using Model-Cary 50 Varian to confirm the solubilization
efficiency of orange-OT dye (kmax = 470 nm).

3. Results and discussion

3.1. Solution demeanor

The clouding conduct is a compelling method for understanding

the phase behavior of PluronicsÒ in aqueous solution and is often
deciphered by the dehydration of the PEO moiety (decreased
hydrogen bonding between ethereal oxygen of PEO and water)
and polar-nonpolar compliance change of PEO with temperature
[2,26,27,31,34,35]. Studies have reported that the clouding phe-
nomenon of PluronicsÒ and other thermoresponsive polymers
can be influenced in the presence of some additives; where both
deferral and improvement were found [35,43-45].
CP value of PEO based non-ionic surfactants and few other ther-
moresponsive polymers in the presence of ionic surfactants has
been reported earlier where the interaction of uncharged polymers
has been found more prominent for anionic surfactants than their
cationic counterparts having identical alkyl chain [2,7]. Table 1
portrays the influence of SDS concentration on the clouding beha-
viour of 1 %w/v PluronicsÒ solution. The turbid feature of the
examined PluronicsÒ system at ambient temperature contains
vesicular structures which slowly get transformed to charged
PluronicsÒ-SDS mixed micelles that results to clear solution show-
ing two phase at higher temperature which could be evidently
visualized through the solution appearance (Vial images presented
in Supporting information Fig. S1). Thus, SDS interacts strongly
both with PPO and PEO moieties and induces hydrophilic character
to copolymer with higher CP values. A marked increase observed in
CP in the presence of little amount of SDS even 5–10 mM (CMC of
SDS is 8 mM) that result to a clear transparent solution at ambi-
ent temperature. A steep rise in such conduct is ascribed to the
strong hydrophobic associations between SDS and the PPO (hy-
drophobic) core region of the polymeric micelles.

3.2. Computational framework

A number of computational studies have addressed the behav-

Fig. 2. The size distribution profile expressed in number versus hydrodynamic
ior of EO and PO units at different levels using several theoretical diameter (Dh) for 1 %w/v PluronicsÒ (a) without SDS; and with SDS: (b) 10 mM, (c)
approaches to investigate mesoscale structures of polymers [32- 25 mM, and (d) 50 mM at 30 °C. The Dh profile of (e) 1 %w/v L81 and (f) 1 %w/v L121
35]. Hence, Quantum chemical study is an ideal framework to as a function of SDS concentration at 30 °C.

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D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

Fig. 3. Scattering profile for 1 %w/v PluronicsÒ at (a) 20 °C and (a) 30 °C. (The solid lines represent the best fit with the model employed).

which is a clear indicative by its lower value for the combined sys- Table 2
tem T.E. ( 1900.62 a.u.) that hints the favorable interactions Fitted SANS parameters for 1 %w/v PluronicsÒ in D2O at different temperatures.
between PluronicsÒ-SDS. Studies have revealed the impact of 1 %w/v PluronicsÒ T, °C Micellar parameter, nm Micellar shape
polarity influencing the m leading to interaction; however, m relies
L31 15 Rg = 1.44 Gaussian chain
upon the nature of molecules considered. Several investigations 20 Rg = 1.05 Gaussian chain
have additionally shown that high m favours the accumulation of 25 Rg = 0.89 Gaussian chain
adsorbed molecules onto the surface, which leads to morphology 30 Rg = 0.71 Gaussian chain
changes. The l identify the hydrophobic characteristics in the L61 15 Rg = 1.48 Gaussian chain
PluronicsÒ and SDS system and play a significant role to under- 20 Rg = 1.44 Gaussian chain
stand the accumulation mechanism. Interestingly in our system, 25 Rg = 1.43 Gaussian chain
30 Rv = 7.06, tv = 1.22 ULV
the lower m is observed for PluronicsÒ (0.76 D) and SDS (8.79
L81 15 Rg = 1.58 Gaussian chain
D) in comparison to the mixed system i.e., (9.06 D) which infer
20 Rg = 1.45 Gaussian chain
to the SDS stabilized PluronicsÒ micelles. Moreover, higher value 25 Rv = 9.62, tv = 1.57 ULV
of EHOMO routinely aligned with the capacity of electron donation 30 Rr = 14.57 MLV
to the appropriate unoccupied acceptor molecular orbital of ELUMO L101 15 Rg = 1.29 Gaussian chain
[34,35]. Here the orbital might actually tie with the filled HOMO of 20 Rcr = 1.78, L > 50 Rod-like micelles
the SDS though could give the electron to the unfilled LUMO orbital 25 Rr = 19.87 MLV
of the PluronicsÒ which credits the conceivable synergistic interac- 30 Rr = 19.87 MLV

tion between HOMO-LUMO orbitals of PluronicsÒ-SDS which is L121 15 Rg = 2.64 Gaussian chain
additionally acknowledged effectively by the lower value of ELUMO. 20 Rv > 50, tv = 6.08 ULV
25 Rr = 22.59 MLV
Additionally, the electron transfer process between PluronicsÒ and
30 Rr = 18.10 MLV
SDS molecule is portrayed by showing the energy gap values (DE).
In our situation, SDS has lower DE value i.e., 0.1748 eV, Pluron- Note: Rg = radius of gyration (Å), Rv = radius of ULV (Å), Rr = lamellar repeat distance
of MLV (Å), Rcr = cross-sectional radius of rod-like micelles (Å), L = Length of rod-like
icsÒ has higher DE value i.e., 0.3075 eV. SDS and PluronicsÒ has
micelles and tv = vesicle thickness (Å).
moderate DE value i.e., 0.2182 eV which too depict SDS stabilized
PluronicsÒ micelles (Fig. 1).
For better understanding of the interaction and charge disper- hydrophobic interactions in our examined systems which could
sion between the PluronicsÒ-SDS, the 3D-molecular electrostatic be due to the solubilization of SDS in respective PluronicsÒ
potential (MEP) is mapped with the most negative potential site micelles. It was clearly seen that the Dh of pure 1 %w/v PluronicsÒ
assigned in red as nucleophilic centres of SDS, while the most pos- i.e., 1 %w/v L31, 1 %w/v L61, 1 %w/v L81, 1 %w/v L101 and 1 %w/v
itive potential site assigned in blue as electrophilic site in Pluron- L121 showed their Dh 9.2 nm, 310.1 nm, 288.7 nm, 258.2 nm
icsÒ which led to plausible interactions (Fig. 1). and 236.8 nm in water (without SDS) at 30 °C, respectively
(Fig. 2a) which now decreases slightly with addition of 10 mM
SDS i.e., to Dh, 8.5 nm, 306.6 nm, 279.5 nm, 230.0 nm and
3.3. Scattering analysis 191.20 nm respectively (Fig. 2b). Such, higher Dh of 1 %w/v
copolymers due to the presence of 10 mM SDS initiate more
Unearthly investigations have obviously detailed the indispens- hydrophilicity, thereby depicting a difficult level of breakdown of
able part of the positive connections between the blended the hydrogen bonding between water and the PEO group thereby
PluronicsÒ-SDS systems that illustrates the influence of varying depicting the presence of polymer-rich mixed micelles and hence
[SDS] on the hydrodynamic diameter (Dh) of PluronicsÒ micelles suggesting the plausible micellar transition. Furthermore, increas-
(expressed in number) at 30 °C (Fig. 2). However, the Dh profile (ex- ing concentration of SDS to 25 mM and 50 mM to 1 %w/v Pluron-
pressed in intensity) is presented in Fig. S2 of Supporting informa- icsÒ show some drastic fall in Dh i.e., in 25 mM SDS it appears as
tion. Here, the scattering study inferred the involvement of 103.5 nm, 101.5 nm, 82.3 nm, 72.1 nm and 66.7 nm,
5
D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

Fig. 4. SANS curves depicting the structure factor conformations for 1 %w/v PluronicsÒ with varying concentration of SDS at different temperatures. (The solid lines represent
the best fit with the model employed).

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D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

Table 3
Fitted SANS parameters for 1 %w/v PluronicsÒ in varying concentration of SDS.

1 %w/v PluronicsÒ SDS conc. Micellar parameter, nm Rhs, nm ɸ Micellar shape

@ 30 °C
L31 25 mM a = 5.12, b = 1.41 2.10 0.066 Ellipsoidal
L61 a = 5.39, b = 1.29 2.09 0.053 Ellipsoidal
L81 a = 4.62, b = 1.49 1.94 0.060 Ellipsoidal
L101 a = 2.75, b = 1.48 1.94 0.029 Ellipsoidal
L121 a = 2.93, b = 1.45 2.35 0.032 Ellipsoidal
@ 20 °C
L31 50 mM Rg = 0.80 – – Gaussian chain
L61 Rg = 1.12 – – Gaussian chain
L81 Rg = 1.45 – – Gaussian chain
L101 Rg = 1.80 – – Gaussian chain
L121 Rv > 50, tv = 9.38 – – ULV
@ 30 °C
L31 50 mM Rg = 0.78 – – Gaussian chain
L61 Rv > 50, tv = 3.85 – – ULV
L81 Rr = 13.20 – – MLV
L101 Rr = 16.70 – – MLV
L121 Rv > 50, tv = 5.34 – – ULV

Note: a = semi-major axis (Å), b = semi-minor axis (Å), Rhs = Hard sphere radius (Å) and ɸ = Volume fraction.

Table 4
Fitted SANS Parameters for 1 %w/v L81 and 1 %w/v L121 in presence of varying [SDS] at different temperatures.

1 %w/v PluronicsÒ SDS conc. Micellar parameter, nm Rhs, nm ɸ Micellar shape

@ 30 °C
L81 0 mM Rr = 14.57 – – MLV
5 mM Rg = 1.83 – – Gaussian chain
25 mM a = 4.62, b = 1.49 1.94 0.060 Ellipsoidal
50 mM Rr = 13.20 – – MLV
@ 20 °C
L121 0 mM Rv > 50 tv = 6.08 – ULV
5 mM Rv > 50 tv = 2.62 – ULV
10 mM Rc = 1.68 – – Spherical
25 mM a = 3.0, b = 1.30 2.56 0.032 Ellipsoidal
50 mM Rv > 50 tv = 9.38 – ULV
@ 30 °C
L121 0 mM Rr = 18.10 – – MLV
5 mM Rv > 50 tv = 2.69 – ULV
10 mM Rv > 50 tv = 2.69 – ULV
25 mM a = 2.92, b = 1.40 2.35 0.024 Ellipsoidal
50 mM Rv > 50, Rc = 1.05 tv = 5.75 – Spherical + ULV

respectively at 30 °C (Fig. 2c) while in 50 mM SDS it appeared In aqueous solution environment, all copolymers remain as
around 2.2 nm, 2.8 nm, 2.9 nm, 3.1 nm and 3.4 nm respec- molecularly dissolved below their CP. Size decreases with increas-
tively at room temperature (Fig. 2d) which depict the presence of ing in temperature and increases with increase in molecular
surfactant-rich mixed micelles. weight. In our case, vesicular structure either unilamellar (ULV)
Interestingly, to comprehend the impact of SDS on the tested or multilamellar (MLV) was observed around CP which followed
PluronicsÒ, we discovered the Dh of 1 %w/v L81 and 1 %w/v L121 the order: L121 > L101 > L81 > L61. Such behavior is ascribed giving
copolymers with expanding concentration of SDS (0–50 mM) at an account to the degree of hydrophobicity of the copolymers.
30 °C. It is clearly seen that very low concentration of SDS (2– While L31 only showed the presence of Gaussian chain due to its
10 mM) show significant micellar growth because that little less hydrophobicity compared to other copolymers (Table 2). For
amount of SDS get solubilize or mixed with copolymer thereby L31 the SANS profiles exhibit features pertaining to associating liq-
forming polymer-rich micelles. But on increasing concentration uids. The data are fitted to a Gaussian distribution of the L31 unim-
of SDS (25–50 mM), the Dh decreases drastically assuming the ers [2,30,46].
copolymer to get solubilize in SDS micellar core thereby forming In addition, presence of 25 mM SDS in 1 %w/v copolymers
surfactant-rich micelles (Fig. 2e, Table S2). A similar trend is fol- encountered different behavior in comparison to the system with-
lowed for 1 %w/v L121 with increasing concentration of SDS out SDS at 30 °C (Fig. 4). There was an overall increase in the scat-
(Fig. 2f). These findings are further endorsed by neutron scattering tering profile which contributed the structure factor indicating the
results. association of hydrophobic PluronicsÒ in the presence of SDS. The
We utilized SANS with contrast coordination to acquire direct observed outcomes introduced in Table 3 addressed the evidence
proof of polymer-rich and SDS-rich mixed micelles by gathering of ellipsoidal mixed micelles/ aggregates which clearly indicate
the structure details in the aqueous solution at 20 °C and 30 °C polymer-rich mixed micelles (Fig. 4a).
(Fig. 3) while the scattering profile of 1 %w/v PluronicsÒ as a func- While on addition of 50 mM SDS to all copolymers aside from
tion of temperature is presented in Fig. S3 of Supporting L121 stay as Gaussian chain at 20 °C. While L121 show ULV due
information. to its low CP. Overall, the CP increase in the presence of SDS but

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D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

Fig. 5. UV–vis absorption spectra of orange-OT in 1 %w/v PluronicsÒ with (a) 25 mM and (b) 50 mM SDS. While the absorption spectra of orange-OT in (c) 1 %w/v L81 and (d)
1 %w/v L121 with increasing concentration of SDS. (Insight images of vials represent the physical appearance of the solution depicting the intensity change). (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

do not form any micelle. Such behaviour could be attributed to the micelles. At [SDS]  5 mM, there was a different development in
small SDS aggregation wrapped around the polymer coil (Fig. 4b). the scattering data at low Q values demonstrating the presence
With increasing temperature from 20 °C to 30 °C, all copolymers of mixed population of large vesicles either ULV or MLV structure
aside L31 remain as Gaussian chain while others formed spherical at 20 °C and 30 °C. The concentration of vesicles decreases with
and vesicular (ULV and MLV) structure. Such intriguing outcome increase in [SDS] which is consistent with the work reported by
depict surfactant-rich micellar system due to high [SDS] (Fig. 4c). G. Prameela et al. [2,5,6]. The SANS parameters extracted by fitting
SANS curves for 1 %w/v L81 in varying [SDS] at 30 °C are pre- the experimental data is shown in Table 4. In presence of 10 mM
sented in Fig. 4d. The scattering from 1 %w/v L81 do not show a SDS at 20 °C, 1 %w/v L121 show the presence of spherical micelle,
correlation peak in the absence of SDS; however, a strong correla- in 25 mM SDS, the ellipsoidal micelle which is polymer-rich is
tion peak emerges upon addition of [SDS]. Such behavior brings formed, while in 50 mM SDS, ULV are formed which infer the
about a huge reduction in the scattering value, reflecting a change micellar entity to be surfactant-rich. A similar micellar transition
in the aggregate dimension ranging from MLV to Gaussian chain to trend was observed for 1 %w/v L121 at 30 °C.
Ellipsoidal (polymer-rich) micelle and again to MLV (surfactant-
rich) micelle which is documented in Table 4. 3.4. Dye solubilization
On expansion of SDS concentration from 5 mM to 50 mM in 1 %
w/v L121 at 20 °C and 30 °C, the SANS information showed critical Giving an account to the clouding and scattering findings, addi-
changes contrasted with that of unadulterated L121 (0 mM SDS) tion of SDS to PluronicsÒ can be used to modulate overall size/ sta-
indicating structural changes (Fig. 4e and 4f). Such temperature bility/ charge of the mixed aggregates that can enhance the
effect along with the expansion of SDS on to 1 %w/v L121 uncov- solubility of hydrophobic molecules like dyes, drugs, or other bioac-
ered correlation peak at intermediate Q-regions (for tivates like fragrance, pesticides, etc. Reported studies have revealed
[SDS]  10 mM), indicating formation of interacting charged the role of hydrophobic connections and the electrostatic impact
8
D. Patel, D. Ray, S. Tiwari et al. Journal of Molecular Liquids 345 (2022) 117812

considering the chemical structure and aggregation of the Pluron- Acknowledgment

icsÒ and organic dyes leading to the self-assembly that comprehend
the solubilization phenomenon of dye in aqueous PluronicsÒ solu- The authors acknowledge Sardar Vallabhbhai National Institute of
tion [32-35,47-49]. However, not much has been debated. So, con- Technology (SVNIT), Gujarat, India for providing the instrumenta-
sidering the commercial application of PluronicsÒ in dye tion facilities.
solubilization, the water-insoluble organic dye: orange-OT was sug-
gested to solubilize in 1 %w/v PluronicsÒ with varying SDS solution Financial fundings
where an essential expansion in the solubilization of orange-OT was
noticed giving a record on the measured absorbance (Fig. 5). This work did not receive any specific grant from any funding
It was seen that Orange-OT dye remains insoluble in the 1 %w/v agencies in the public, commercial, or not-for-profit sectors.
L81 and L121 solution because of the presence of unimers geome-
try. However, with SDS addition from 2 mM to 50 mM, the mea-
sured absorbance expands which is credited to p ? p* change Appendix A. Supplementary material
which is obviously seen from the increased colour intensity of
dye, i.e., from lightest orange to dark orange (insight vial images Supplementary data to this article can be found online at
in Fig. 5 c, d) such behaviour shows that dye solubilization increase https://doi.org/10.1016/j.molliq.2021.117812.
as the examined system undergo micellization and further pro-
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