Journal of Molecular Liquids 260 (2018) 323–341

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Journal of Molecular Liquids

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

Influence of rhodamine B on interaction behaviour of lanthanide nitrates

with 1st tier dendrimer in aqueous DMSO: A physicochemical, critical
aggregation concentration and antioxidant activity study
Nidhi Vashistha, Abhishek Chandra, Man Singh ⁎
School of Chemical Sciences, Central University of Gujarat, Gandhinagar 382030, India

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

Article history: Density, viscosity, sound velocity, and molar conductivity for hexahydrate nitrates of gadolinium, samarium and
Received 6 January 2018 neodymium from (0.0012–0.0072) mol∙kg−1 in (a) 40% (v/v) aq. DMSO (b) Trimesoyl 1,3,5-tridimethyl malonate
Received in revised form 24 February 2018 (TTDMM) from (0.00010–0.00030) mol∙kg−1 + 40% (v/v) aq. DMSO (c) Rhodamine B (RB) + 40% (v/v) aq.
Accepted 14 March 2018
DMSO (d) RB + TTDMM from (0.00010–0.00030) mol∙kg−1 + 40% (v/v) aq. DMSO at 298.15 K and atmospheric
Available online 17 March 2018
pressure are reported. By using these primary parameters; the apparent molar volume, limiting apparent molar
Keywords:
volume, apparent molar isentropic compressibility, viscosity B-coefficient, and limiting molar conductivity have
Trimesoyl 1,3,5-tridimethyl malonate been calculated. The trends of these physicochemical parameters are discussed in terms of solute-solvent and
Viscosity B-coefficient solute-solute interactions. The trends inferred weaker solute-solvent interactions in presence of RB with
Apparent molar volume TTDMM + aq. DMSO, causing structural changes. The aggregation tendency of TTDMM was studied using con-
Isentropic compressibility ductivity measurements, well supported by RB based UV–visible absorption spectroscopy through the L-form
to Z-form shifting dynamics. To the best of our knowledge, this is the first attempt reporting the impact of triva-
lent lanthanide ions on the critical aggregation concentration of a 1st tier dendrimer (TTDMM) in aq. DMSO. This
work is the first report, as far as we know, on the influence of Ln(NO3)3 towards the antioxidant activity of den-
drimer, wherein the IC50 value of TTDMM was found in range with ascorbic acid. Our study with such significant
outcomes may hold great promise for various biological applications.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Currently, lanthanides are attracting significant attention because of
their unique luminescent, optical and magnetic properties [1–4]. Owing
to their unique properties, they are being widely used in optical and an-
alytical applications such as drug delivery [5], luminescent probes [6],
bioimaging, biosensors [7], and contrasting agents in MRI scans [8,9].
For example, gadolinium (III) chelates are widely used as MRI contrast-
ing agent for imaging of cancerous tumour detection [10,11]. Gd (III) be-
cause of its strong paramagnetism reduces the T1 relaxation time and to
some extent the T2 and T2* relaxation times in NMR and MRI spectros-
copy, with therapeutic applications [12,13]. Samarium (III) exhibits in-
tense and long-lived photoluminescence for in vitro luminescent
biodetection [7]. Neodymium (III) emits radiation in the NIR spectral
range and thus, has major application in laser designing for biomedical
purposes [14]. Neodymium based luminescent probes are useful in time
resolved imaging of tissues and is widely used in cancer detection [15].
Recently, more emphasis is being given to develop MRI contrast agents
with higher relaxivity, which reduces the administered Ln3+ quantity in
⁎ Corresponding author.
E-mail address: mansingh50@hotmail.com (M. Singh).
MRI diagnostics. The Gd(III) complexes are used in clinical MRI to in-
crease the contrast by selectively relaxing the water molecules near
the complex. There is a desire to improve the sensitivity (relaxivity) of
these contrast agents in order to detect molecular targets. Paramagnetic
gadolinium based contrast agents are examples of T1 agents because it
increases the longitudinal relaxation 1/T1 rate more than transverse re-
laxation (1/T2) rate owing to the fast endogenous transverse relaxation
in tissue. The ability of a contrast agent to change a relaxation rate is
represented quantitatively as relaxivity [16,17]. All T1 commercial con-
trast agents suffer decreased efficiency at higher field strengths, and to
counteract this, an increased dosage is required to maintain the contrast
levels [18]. These large dosage of contrast agents have evolved problem
like nephrogenic system fibrosis in few MRI patients (due to Gd3+ che-
lates) [19,20]. The Ln3+ faces low solubility in inorganic media, which
leads to clustered Ln3+ species, with increased Ln3+ luminescence
quenching (self-quenching processes) [21,22]. In view of this, the con-
jugation of Ln3+ with macromolecular carriers such as dendrimers
with structural uniqueness have been used to increase the T1
relaxivities [23,24], with improved solubility and biocompatibility
[18,22]. In the MRI field, dendrimers allow Ln3+ to retain their lumines-
cence, enhance the signal to noise ratio of various imaging modalities,
slow down molecular rotation for higher relaxation time, and increase

https://doi.org/10.1016/j.molliq.2018.03.056
0167-7322/© 2018 Elsevier B.V. All rights reserved.
324 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

their relaxivity [25,26]. Thus, in recent years, dendrimers have attracted
wide attention in the field of functional materials with desired applica-
tions in biomedical research and therapeutics [27]. Dendrimers are
well-defined synthetic polymeric architectures with low polydispersity
and controlled surface functionalities. Dendrimers exhibit three main
architectural components, an interior core to which dendron are at-
tached, branching layers or repeating units (generations) surrounding
the internal core, and a multivalent shell [28,29]. Dendrimers have
gained a broad range of applications in supramolecular chemistry, par-
ticularly in host-guest reactions and self-assembly processes. Self-
assembly is the spontaneous, precise association or aggregation of
chemical species by specific, complementary intermolecular forces
[30]. The ability of dendrimers to self-assemble into smaller dimensions,
discrete size, and tailorable structures has led to their exploration for a
range of applications, e.g., scaffolds for drug delivery [31], carriers for
gene transfection [32,33], biosensors, and so on [34].
Rhodamine B (RB) is one of the conventional laser dyes that have
been used in dye lasers because of its high absorption coefficient and
fluorescent yield [35]. Unfortunately, RB aggregates in alcoholic and
aqueous solutions at high concentration, leading to fluorescence
quenching and ineffective lasing [36]. With RB, even at a low concentra-
tion of 10−4 M, its emission efficiency declines owing to fluorescence
quenching due to aggregation. Hence, RB must be kept at a very low
concentration to achieve highly efficient spontaneous emission in solu-
tion. Thus, enhancing the optical efficiency of RB is desirable to improve
its performance. Recently, dendrimers being hyperstructured three-
dimensional materials with regular molecular weight distribution, are
gaining popularity in laser application [35,36]. Dyes doped with
dendrimers form host–guest systems, and may be used to increase the
concentration of the laser dye in solutions with reduced aggregation.
The enhancement of emission efficiency obtained by changing the mi-
croenvironment of RB may provide a new physicochemical understand-
ing of such systems, to be used in a variety of applications such as
fluorescent probes in biotechnology and dye lasing. Therefore, our in-
vestigation on the influence of RB as a model laser dye on interaction be-
haviour of Ln(NO3)3 with TTDMM as a model dendrimer in dilute
solution is valuable for the development of better formulations for en-
hanced optical properties. Furthermore, RB may be used as a simple
probing system for determining the critical aggregation concentration
(CAC) of TTDMM, and the information may be used for further applica-
tions of TTDMM.
Additionally, the luminescent properties of dendrimer-lanthanide
complexes could further be sensitized or enhanced with organic lumi-
nescent ligands which easily absorb light due the higher absorption co-
efficient than the intrinsically low molar absorption coefficients of Ln3+,
subsequently excite Ln3+ via energy transfer from a donor state with
adequate energy [ 37,38,21]. Such sensitisation of Ln3+ is based on the
FRET phenomenon which was further extended as lanthanide based
resonance energy transfer (LRET) have been extensively studied [39].
Thus, we have chosen Rhodamine B (RB), a fluorescent dye having
long absorption and emission wavelengths, large absorption coeffi-
cients, and high quantum yields making it suitable for FRET based lan-
thanide sensitisation and have been widely used for studying
biological systems [40–43]. Moreover, since the lanthanide lumines-
cence may be dramatically enhanced by chelating the Ln3+ ions with
In light of this, in the present study, we have tried to chemically tune the
fluorescence of Ln3+ with the fluorescence of another source like RB and
TTDMM in aq. DMSO. Concerning the complexation of lanthanide with
dendrimers and dyes, a lot is reported and most of them are focused
on the photochemical studies and very less is known about their inter-
actions in solutions, and this is a critical point for biomedical applica-
tions. Thus, in the present work, we discuss in detail, the interactions
prevailing in such systems by studying their physicochemical proper-
ties. These properties were studied in terms of physicochemical interac-
tions prevailing in the aq. formulations for genesis of stoichiometrically
stable compositions with efficient interactions needed for useful formu-
lations. Physicochemical interaction study of these formulations could
provide a deeper insight of solubility, interacting activity, binding and
dispersing features. Along with this antioxidant activity of TTDMM is
also studied. The high impact of free radicals on human health has
prompted the search of new antioxidants to protect the cell damage
[46]. Cellular environment is very sensitive to free radicals, which are re-
lated to oxidative stress and associated to the pathogenesis of various
disorders, including atherosclerosis, cancer, diabetes, Alzheimer's dis-
ease, rheumatoid arthritis, and inflammatory bowel disease etc. [47]
Dendrimers due to their architecture appear as very promising vehicles
that can be used as antioxidants [48].
In view of the above mentioned facts, the present work is focused on
ion-hydrophilic and ion-hydrophobic interactions of Ln(NO3)3, Pr(NO3)
−1
3, Sm(NO3)3, and Gd(NO3)3 with TTDMM (0.0001–0.0003 mol∙kg ) in
−1
presence and absence of Rhodamine B (0.0001 mol∙kg ), in 40% (v/v)
aq. DMSO solution evaluated from physicochemical properties (PCPs):
density, apparent molar volume, sound velocity, apparent molar isen-
tropic compressibility, viscosity, molar conductivity. Further the critical
aggregation concentration of TTDMM is predicted using the conductiv-
ity data. These PCPs were used to investigate the solute-solute and
solute-solvent interactions persisting between dye-dendrimer and Ln3
+
for their application as stable medium for biochemical and biophysical
processes. The antioxidant activity of TTDMM in absence and presence
of Ln(NO3)3 is also studied. Our study could further be extended to
other dyes, lanthanides, transition metals and dendrimers of higher
generation for genesis of stable formulations in industrial and biochem-
ical applications.
2. Experimental section
2.1. Materials
Specifications of chemicals are given in Table 1. All the chemicals
were of analytical reagent grade and were used as received. Before solu-
tions preparation, the chemicals were dried at 303.15 K for 3 h and kept
over anhydrous calcium chloride in a vacuum desiccator for at least 72 h
before use.
Table 1
Specifications of chemicals used.

an appropriate organic ligand, the present study on the interaction be- Name of chemicals Puritya Mw Source CAS No.
haviour of Ln3+ ions with dendrimer in absence and presence of RB, (g∙mol−1)
may help in the development of dye based luminescent dendrimers en- 1,3,5-Benzenetricarbonyl trichloride 99.9% 265.48 Sigma 4422-95-1
capsulated with luminescent Ln3+ ions as a controlled assembly of su- Dimethyl malonate 99.9% 132.12 Sigma 108-59-8
pramolecular architectures. Such assembly may lead to species Sodium 99.9% 22.99 Sigma 7440-23-5
Methanol A.R. 32.04 Rankem 67-56-1
capable of exhibiting remarkable properties like metal ions sensing
Neodymium(III) nitrate hexahydrate 99.9% 438.35 CDH 16454-60-7
and conversion of UV light into visible or infra-red emission for bio- samarium(III) nitrate hexahydrate 99.9% 444.47 CDH 13759-83-6
imaging and photodynamic therapy applications. gadolinium(III) nitrate hexahydrate 99.9% 541.36 CDH 19598-90-4
Our previous work was based on the synthesis and characterization Rhodamine B 99.9% 479.017 Sigma 81-88-9
of TTDMM, a first generation (G1) dendrimer [44]. TTDMM with larger DMSO A.R 78.13 SRL 67-68-5

surface area may have various applications in the biomedical field [45]. a
Purity as provided by suppliers; A.R. = Analytical grade.
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341 325

2.2. Apparatus and procedure Before the conductivity measurements, the conductivity cell was cali-
brated using aq. (0.01–1) mol·kg−1 KCl solutions. The solution temper-
Synthesis of TTDMM is done as reported in our previous communi- ature was controlled with a Lauda Alpha KA 8 thermostat with ±0.05 K
cations [44,45]. Initially sodium dimethyl malonate ester (SDMME) control. The cell was calibrated using the method proposed by Lind et al.
was prepared by taking sodium metal and dimethyl malonate ester [50]. The conductance data were reported at 50 Hz.
(DMME) as starting materials at 1:1 ratio in a round bottom (RB) flask Antioxidant activities were evaluated via DPPH free radical assay,
and stirred at room temperature (RT) for 3 h. After that trimesoyl chlo- with a little modification in the reported method [51]. Briefly, 8.4
ride (TMC) and SDMME at 1:3 w/w ratios in methanol were taken in a × 10−5 M DPPH solution in methanol was prepared as a stock solution.
RB followed by continuous stirring for 3 h at RT. The obtained product To prepare samples, 2 mL of this stock solution was added into 1 mL of
settled at the bottom was filtered through a Whatmann filter paper each sample (prepared in WD) to be tested for antioxidant activity,
and washed with ice-cold water several times to remove the NaCl which is followed by incubation in dark at RT for 120 min. Absorbance
formed during the reaction. The presence of NaCl in the filtrate was was measured at 520 nm with Spectro 2060 plus model UV/Vis
tested with aq. AgNO3. Formation of TTDMM was further characterised spectrophotometer.
by 1H NMR (Fig. S1, Supporting Information).
For solution preparation, initially a stock solution of 40% (v/v) aq. 3. Processing of results
DMSO (WD) with 0.22% accuracy was prepared and used to prepare
0.00010 mol∙kg−1 RB (WDR). Solutions of TTDMM in WD (WDT) and 3.1. Apparent molar volume (Vϕ)
WDR (WDRT) respectively, were prepared in the range (0.00010 to
0.00030) mol∙kg−1. Molal solutions of Ln(NO3)3: Nd(NO3)3, Sm(NO3)3, Densities have been used to calculate the apparent molar volume, Vϕ
and Gd(NO3)3 ranging from (0.0012 to 0.0072) mol·kg−1 with WD, (m3∙mol−1), using Eq. (1):
WDT, WDR, and WDRT were prepared. All the solutions were prepared
at 298.15 K and of atmospheric pressure (p = 0.1 MPa), using a Mettler 1000ðρ0 −ρÞ M
Vϕ ¼ þ ð1Þ
Toledo New Classic MS balance with b±0.1 × 10−6 kg repeatability. mρ0 ρ ρ
Milli-Q water of 7 × 10−7 S∙cm−1 was used in all the preparations. The
solutions were kept in airtight volumetric flask to avoid evaporation, Where, m (mol∙kg−1) is the molality of Ln(NO3)3, ρ0 and ρare the den-
contamination and photochemical reactions. sity of the solvents (Table 2) and solutions (Tables 3–8), respectively,
Low TTDMM concentrations were conceptually chosen in order to and M (kg∙mol−1) is the molecular weight of Ln(NO3)3. The limiting ap-
avoid its self-aggregation on Ln(NO3)3 addition as the salts in general parent molar volume of Ln(NO3)3, V0ϕ, were obtained by fitting the Vϕ
have higher affinity towards water in aq. medium. Further with similar values to Eq. (2):
considerations the lanthanide salts from 0.0012 to 0.0072 mol·kg−1
were also used as precautionary measure so as to maintain a complete V ϕ ¼ V 0ϕ þ Sv m1=2 þ Bv m ð2Þ
homogeneity in their solution. TTDMM with delocalized malonate
ester groups (MEG) and large surface area are highly efficient to initiate Where, V0ϕ (m3∙mol−1) depicts the nature of solute−solvent interaction
intermolecular interactions. Thus, to avoid secondary chemical pro- (SLSOI), while Sv (kg1/2∙m3∙mol-3/2) and Bv (kg∙m3∙mol−2) are empirical
cesses the molecular compositions of TTDMM and Ln(NO3)3 were parameters which provide quantitative estimates of solute–solute inter-
tuned to maintain equal distribution with higher homogeneity. Hence, actions (SLSLI) (Table S2).
the concentrations were of low order to initiate maximum chemical ac-
tivities in terms of solute-solvent interactions. However the research 3.2. Isentropic compressibility (kS)
works with similar systems with adequately higher concentrations are
being pursued with certain precautions so that the TTDMM is not Densities and sound velocities were used to calculate the isentropic
phased out because of higher affinities of lanthanide salt with water in compressibility by Newton–Laplace equation:
aq. medium.
kS ¼ 1=ρu2 ð3Þ
Densities (ρ) and sound velocities (u) were measured by Anton Paar
DSA 5000 M densimeter, with ±0.001 K temperature controlled by a
Where, ks is the isentropic compressibility, ρ is the density and u is the
built-in Peltier device, with 5 × 10−3 kg∙m−3 and 0.10 m∙s−1 precision,
sound velocity. Apparent molar isentropic compressibility ks, ϕ were cal-
respectively. The instrument was calibrated with Milli-Q water at
culated using Eq. (4):
298.15 K, while methanol, DMSO and hexane were used to check the
performance of the instrument and the values were in agreement ( )  
0
kS ρ0 −kS ρ kS m
with the literature within the experimental uncertainties (Table S1). κ S;ϕ ¼ þ ð4Þ
mρρ0 ρ
The reported densities and sound velocities were an average of three re-
peated measurements. Viscosity (η) was measured with Borosil
Mansingh Survismeter [49] (cal.no. 06070582/1.01/C-0395, NPL,
Table 2
India) through viscous flow time (VFT) method. The temperature of Density (ρ0/103kg∙m−3) of solvents.
the Survismeter unit was controlled by Lauda Alpha KA 8 thermostat
with ±0.05 K. After the attainment of thermal equilibrium, the viscous Solvent ρ0

flow time were recorded with an electronic timer of ±0.01 s accuracy. WD 1.053472
The Survismeter was washed with Milli-Q water, followed by acetone 1.0 × 10−4 mol∙kg−1 WDT 1.053944
1.5 × 10−4 mol∙kg−1 WDT 1.056061
and was properly dried before viscous flow time measurements. Meth-
2.0 × 10−4 mol∙kg−1 WDT 1.057208
anol (AR grade, Rankem) and DMSO (AR grade, Rankem) were used to 2.5 × 10−4 mol∙kg−1 WDT 1.057816
check the performance of the Survismeter and the values are in compli- 3.0 × 10−4 mol∙kg−1 WDT 1.058551
ance with that of the literature values, given in Table S1 (Supporting In-
WDR 1.054623
formation). The reported viscosities are an average of three repeated 1.0 × 10−4 mol∙kg−1 WDRT 1.053289
measurements with 2 × 10−5 kg∙m−1∙s−1 combined uncertainties. 1.5 × 10−4 mol∙kg−1 WDRT 1.054241
The conductivity (κ) values were measured with a digital conductiv- 2.0 × 10−4 mol∙kg−1 WDRT 1.056563
ity meter (Lab India Conductivity meter PIC=O+) using a dip-type im- 2.5 × 10−4 mol∙kg−1 WDRT 1.056967
3.0 × 10−4 mol∙kg−1 WDRT 1.057208
mersion conductivity cell, with a cell constant Kcell = 0.089 cm−1.
326 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

Table 3
Effect of Gd(NO3)3 on Density (ρ/103kg∙m−3), Sound Velocity (u/m∙s−1), Viscosity (η/10−3 kg∙m−1∙s−1), Isentropic Compressibility (κ/1011 m∙s2∙kg−1), Apparent Molar Volume (Vϕ/
10−6 m3·mol−1) and Apparent Molar Isoentropic compressibility (κs, ϕ/1014 m5·N−1∙mol−1) of WD and WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.

m/mol∙kg−1 ρ u η κ Vϕ κs, ϕ

WD
0 1.053472 1681.19 2.2335 33.585 25.35 ± 0.01 0.851 ± 1.70
0.0012 1.055319 1681.44 2.2690 33.516 −1059.18 ± 25.22 −89.882 ± 9.10
0.0024 1.056405 1682.03 2.3041 33.458 −773.17 ± 10.54 −75.976 ± 4.53
0.0036 1.057073 1682.51 2.3399 33.418 −573.50 ± 6.10 −63.175 ± 3.01
0.0048 1.057653 1682.98 2.3798 33.381 −457.20 ± 4.19 −55.582 ± 2.25
0.0060 1.058215 1683.31 2.4160 33.350 −384.71 ± 3.17 −49.960 ± 1.80
0.0072 1.058853 1683.97 2.4583 33.304 −345.80 ± 2.55 −48.551 ± 1.49

1.0 × 10−4 mol∙kg−1 WDT

0 1.053944 1679.11 2.2491 33.653 25.36 ± 0.00 0.854 ± 1.71
0.0012 1.054614 1678.78 2.2675 33.645 −176.83 ± 13.47 −12.399 ± 9.00
0.0024 1.055699 1681.13 2.2981 33.516 −332.06 ± 7.60 −65.147 ± 4.53
0.0036 1.056849 1683.13 2.3382 33.400 −399.65 ± 5.34 −79.930 ± 3.02
0.0048 1.057668 1683.98 2.3798 33.341 −371.43 ± 3.91 −74.091 ± 2.26
0.0060 1.057996 1684.11 2.4204 33.325 −281.19 ± 2.92 −61.185 ± 1.80
0.0072 1.058047 1684.18 2.4634 33.321 −186.59 ± 2.26 −49.972 ± 1.50

1.5 × 10−4 mol∙kg−1 WDT

0 1.056061 1683.96 2.3045 33.392 25.31 ± 0.00 0.845 ± 1.70
0.0012 1.055672 1681.23 2.2952 33.513 615.94 ± 11.61 116.027 ± 9.07
0.0024 1.056497 1682.24 2.3300 33.447 162.09 ± 5.45 26.928 ± 4.45
0.0036 1.057245 1683.66 2.3694 33.367 30.12 ± 3.88 −5.705 ± 2.96
0.0048 1.057834 1684.19 2.4108 33.327 −6.14 ± 2.97 −13.042 ± 2.22
0.0060 1.058342 1684.58 2.4512 33.296 −15.79 ± 2.39 −15.754 ± 1.77
0.0072 1.058454 1684.61 2.4928 33.291 26.98 ± 1.94 −12.411 ± 1.48

2.0 × 10−4 mol∙kg−1 WDT

0 1.057208 1685.01 2.3592 33.315 25.29 ± 0.00 0.842 ± 1.68
0.0012 1.055932 1681.31 2.3217 33.502 1277.60 ± 18.96 190.38 ± 9.37
0.0024 1.056616 1682.33 2.3474 33.440 545.69 ± 5.58 67.494 ± 4.46
0.0036 1.057299 1683.73 2.3816 33.362 302.05 ± 3.52 22.637 ± 2.95
0.0048 1.057931 1684.61 2.4200 33.308 189.80 ± 2.70 4.951 ± 2.21
0.0060 1.058479 1684.77 2.4614 33.284 135.00 ± 2.20 −0.318 ± 1.77
0.0072 1.058737 1684.83 2.5036 33.274 134.50 ± 1.83 −0.911 ± 1.47

2.5 × 10−4 mol∙kg−1 WDT

0 1.057816 1685.73 2.4152 33.267 25.27 ± 0.04 0.841 ± 1.68
0.0012 1.056021 1681.44 2.3340 33.494 1664.12 ± 24.52 234.412 ± 9.61
0.0024 1.056681 1682.36 2.3535 33.436 747.94 ± 6.33 91.689 ± 4.48
0.0036 1.057531 1683.84 2.3853 33.351 395.36 ± 3.53 35.167 ± 2.95
0.0048 1.058058 1684.67 2.4225 33.301 279.39 ± 2.64 16.051 ± 2.21
0.0060 1.058388 1684.91 2.4675 33.281 239.18 ± 2.13 10.228 ± 1.77
0.0072 1.058745 1685.16 2.5112 33.260 209.02 ± 1.78 6.072 ± 1.47

3.0 × 10−4 mol∙kg−1 WDT

0 1.058551 1686.39 2.4612 33.218 25.26 ± 0.03 0.839 ± 1.68
0.0012 1.056058 1681.52 2.3521 33.489 2183.46 ± 32.48 286.906 ± 9.97
0.0024 1.056697 1682.62 2.3641 33.425 1015.47 ± 7.79 115.643 ± 4.51
0.0036 1.057547 1684.11 2.3962 33.340 573.72 ± 3.77 51.044 ± 2.95
0.0048 1.058193 1684.75 2.4410 33.294 390.98 ± 2.65 27.967 ± 2.21
0.0060 1.058496 1684.97 2.4853 33.276 332.48 ± 2.11 20.155 ± 1.76
0.0072 1.058646 1685.28 2.5304 33.259 312.48 ± 1.76 15.744 ± 1.47

m is the molality (mol∙kg−1) of Gd(NO3)3 in WD and WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM). Standard uncertainties u are u(m) = 0.00001 mol∙kg−1, u(ρ) = 5 × 10−3 kg∙m−3, u
(u) = 0.1 m∙s−1 and the expanded uncertainties Uc (0.95 level of confidence) in viscosity and Isentropic Compressibility are Uc(η) ≤ 0.53 × 10−7 kg∙m−1 s−1, Uc(κ) ≤ 0.01 × 1011 m∙s2∙kg−1.

ο
Where, ρ0, ρ, kS, and kS are density of solvent, density of solution, is- 3.3. Viscosity (η)
entropic compressibility, and apparent molar isentropic compress-
ibility, respectively. The limiting apparent molar isentropic The relative viscosity (ηr) values were calculated and analysed using
compressibility, k
0
were obtained by fitting the ks, ϕ values in the Jones–Dole Eq. (6):
Sϕ ,
Eq. (5):

ηr ¼ η=η0 ¼ 1 þ Am1=2 þ Bm ð6Þ

þ Sk m =2 þ Bk m
0 1
ks;ϕ ¼ k s;ϕ ð5Þ
Where, η and η0 are the viscosities of the solution and solvent, respec-
tively, and m is the molality. Here, A (m3/2∙mol-1/2) is the Falkenhagen
constant, specific of SLSLI and B is the viscosity B−coefficient
(m3∙mol−1) and is a measure of structural modifications induced by
0
Where, SK and k s;ϕ depicts solute–solute and solute–solvent interac-
tions, respectively. SLSOI.
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341 327

Table 4
Effect of Sm(NO)3 on Density (ρ/103kg∙m−3), Sound Velocity (u/m∙s−1), Viscosity (η/10−3 kg∙m−1∙s−1), Isentropic Compressibility (κ/1011 m∙s2∙kg−1), Apparent Molar Volume (Vϕ/
10−6 m3·mol−1) and Apparent Molar Isoentropic compressibility (κs, ϕ/1014 m5·N−1∙mol−1) of WD and WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.

m/mol∙kg−1 ρ u η κ Vϕ κs, ϕ

WD
0.0012 1.054937 1681.27 2.2629 33.535 −779.65 ± 21.02 −65.564 ± 9.17
0.0024 1.055732 1681.95 2.2951 33.483 −528.06 ± 8.80 −58.093 ± 4.69
0.0036 1.056551 1682.46 2.3286 33.436 −450.04 ± 5.54 −54.180 ± 3.24
0.0048 1.057332 1682.9 2.3659 33.394 −403.82 ± 4.01 −51.173 ± 2.53
0.0060 1.057956 1683.22 2.3993 33.362 −352.59 ± 3.08 −47.037 ± 2.13
0.0072 1.058405 1683.79 2.4374 33.325 −296.66 ± 2.46 −44.123 ± 1.87

1.0 × 10−4 mol∙kg−1 WDT

0.0012 1.054189 1678.45 2.2628 33.537 135.33 ± 11.04 19.298 ± 9.06
0.0024 1.055386 1680.87 2.2940 33.411 −221.44 ± 6.95 −53.413 ± 4.69
0.0036 1.056659 1683.02 2.3276 33.348 −358.85 ± 5.15 −75.837 ± 3.27
0.0048 1.057545 1683.91 2.3673 33.334 −355.00 ± 3.85 −72.231 ± 2.56
0.0060 1.057748 1684.09 2.4074 33.329 −250.69 ± 2.84 −58.810 ± 2.14
0.0072 1.057885 1684.11 2.4434 33.672 −172.95 ± 2.22 −48.482 ± 1.88

1.5 × 10−4 mol∙kg−1 WDT

0.0012 1.055359 1680.92 2.2876 33.536 843.62 ± 13.68 141.277 ± 9.13
0.0024 1.056109 1682.04 2.3174 33.467 300.58 ± 5.29 39.554 ± 4.56
0.0036 1.056919 1683.31 2.3513 33.391 104.74 ± 3.71 3.146 ± 3.15
0.0048 1.057593 1684.08 2.3854 33.339 32.30 ± 2.89 −9.403 ± 2.48
0.0060 1.057778 1684.34 2.4237 33.323 61.83 ± 2.28 −8.868 ± 2.08
0.0072 1.058003 1684.47 2.4607 33.311 76.54 ± 1.88 −8.165 ± 1.83

2.0 × 10−4 mol∙kg−1 WDT

0.0012 1.055856 1681.2 2.3182 33.509 1327.91 ± 19.75 197.431 ± 9.32
0.0024 1.056463 1682.14 2.3376 33.452 596.33 ± 5.76 74.081 ± 4.54
0.0036 1.057168 1683.57 2.3682 33.373 328.13 ± 3.52 26.263 ± 3.13
0.0048 1.057617 1684.58 2.4056 33.319 241.85 ± 2.66 8.870 ± 2.46
0.0060 1.057783 1684.71 2.4426 33.308 232.31 ± 2.13 6.753 ± 2.07
0.0072 1.058064 1684.79 2.4818 33.296 211.64 ± 1.78 4.648 ± 1.82

2.5 × 10−4 mol∙kg−1 WDT

0.0012 1.055893 1681.28 2.3295 33.504 1753.30 ± 25.96 245.639 ± 9.57
0.0024 1.056497 1682.31 2.3458 33.444 810.15 ± 6.66 96.852 ± 4.54
0.0036 1.057245 1683.77 2.3738 33.363 459.99 ± 3.60 40.425 ± 3.12
0.0048 1.057768 1684.62 2.4108 33.312 326.95 ± 2.64 19.826 ± 2.44
0.0060 1.057786 1684.88 2.4456 33.302 322.47 ± 2.11 16.177 ± 2.06
0.0072 1.058147 1684.97 2.4870 33.287 276.82 ± 1.76 11.788 ± 1.81

3.0 × 10−4 mol∙kg−1 WDT

0.0012 1.055908 1681.39 2.3443 33.499 2289.08 ± 34.24 298.289 ± 9.90
0.0024 1.056481 1682.57 2.3565 33.434 1089.63 ± 8.29 121.604 ± 4.55
0.0036 1.057299 1684.05 2.3848 33.350 628.89 ± 3.91 55.565 ± 3.10
0.0048 1.057834 1684.69 2.4219 33.308 451.39 ± 2.69 32.675 ± 2.43
0.0060 1.058093 1684.91 2.4607 33.291 386.06 ± 2.12 24.312 ± 2.05
0.0072 1.058254 1685.11 2.5038 33.278 354.69 ± 1.76 19.652 ± 1.81

3.4. Molar conductivity (Λm) 3.5. Antioxidant activity

For calculation of molar conductivities (Λm), density values were The antioxidant activity of TTDMM in presence and absence of Ln
used to convert molality into molarity. The Λm values are evaluated as (NO3)3 was evaluated using DPPH free radical scavenging assay. The
following: percentage free radical scavenging activity of the samples was calcu-
lated using Eq. (9):
κ−κ 0  
Λm ¼ ð7Þ Aο −As
c % Scavenging activity ¼  100 ð9Þ
As

where, κ (S·cm−1) and κ0 (S·cm−1) are the specific conductance of so-
lution and solvent respectively, while c (mol·cm−3) is the molar con-
centration of Ln(NO3)3.
The limiting molar conductivity (Λ0m) is obtained by fitting the Λm
values in Eq. (8):
Λm ¼ Λ0m þ Am þ Bm 2
ð8Þ
where, Λ0m (S·cm2·mol−1) is limiting molar conductivity of Ln(NO3)3,
depicting nature of solute-solvent interaction, while A (S·cm2·mol−2)
and B (S·cm5·mol−3) are the empirical parameters to interpret
solute-solute (interionic) interactions (Table 11).
where, A0 and As depicts the absorbance of blank methanolic DPPH so-
lution and DPPH test solutions, respectively at 520 nm.
4. Results
4.1. Density (ρ) and apparent molar volume (Vϕ)
Densities (ρ) of Ln(NO3)3: Nd(NO3)3, Sm(NO3)3, and Gd(NO3)3 with
WD, WDT, WDR, and WDRT as a function of their molalities at T =
298.15 K are summarized in Tables 3–8. A perusal of Table 2 reveals
that for the mixed solvents (WD, WDR, WDT, and WDRT); in absence
of TTDMM, the ρ of WDR is 0.11% higher than of WD. In presence of
0.00010 mol∙kg−1 TTDMM, the ρ of WD increases by 0.04%, which on
328 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

Table 5
Effect of Nd(NO3)3 on Density (ρ/103kg∙m−3), Sound Velocity (u/m∙s−1), Viscosity (η/10−3 kg∙m−1∙s−1), Isentropic Compressibility (κ/1011 m∙s2∙kg−1), Apparent Molar Volume (Vϕ/
10−6 m3·mol−1) and Apparent Molar Isoentropic compressibility (κs, ϕ/1014 m5·N−1∙mol−1) of WD and WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.

m/mol∙kg−1 ρ u η κ Vϕ κs, ϕ

WD
0.0012 1.054484 1681.23 2.2609 33.551 −445.97 ± 16.43 −41.722 ± 9.30
0.0024 1.055395 1681.72 2.2923 33.503 −407.73 ± 7.99 −46.219 ± 5.01
0.0036 1.056275 1682.39 2.3248 33.448 −387.05 ± 5.25 −49.041 ± 3.69
0.0048 1.057019 1682.83 2.3633 33.407 −351.17 ± 3.83 −46.914 ± 3.08
0.0060 1.057771 1683.17 2.3942 33.370 −330.76 ± 3.01 −45.075 ± 2.75
0.0072 1.058202 1683.61 2.4258 33.339 −277.21 ± 2.41 −41.696 ± 2.55

1.0 × 10−4 mol∙kg−1 WDT

0.0012 1.053308 1678.37 2.2590 33.703 790.97 ± 13.23 66.208 ± 9.19
0.0024 1.054089 1680.55 2.2889 33.591 258.93 ± 5.33 −15.920 ± 4.97
0.0036 1.055156 1682.81 2.3227 33.467 10.26 ± 3.91 −48.760 ± 3.70
0.0048 1.055898 1683.86 2.3609 33.402 −53.02 ± 3.05 −51.489 ± 3.10
0.0060 1.056345 1683.99 2.3944 33.382 −46.79 ± 2.43 −44.387 ± 2.76
0.0072 1.056759 1684.02 2.4254 33.368 −38.52 ± 2.02 −38.853 ± 2.56

1.5 × 10−4 mol∙kg−1 WDT

0.0012 1.054492 1680.82 2.2853 33.567 1487.31 ± 22.11 187.820 ± 9.34
0.0024 1.054874 1682.02 2.3127 33.507 757.05 ± 6.45 70.634 ± 4.83
0.0036 1.055882 1683.19 2.3438 33.429 357.37 ± 3.53 21.475 ± 3.57
0.0048 1.056537 1683.88 2.3800 33.381 223.71 ± 2.67 5.125 ± 3.00
0.0060 1.056856 1684.13 2.4136 33.361 193.78 ± 2.15 1.437 ± 2.69
0.0072 1.056968 1684.21 2.4486 33.354 199.60 ± 1.79 1.586 ± 2.51

2.0 × 10−4 mol∙kg−1 WDT

0.0012 1.054764 1681.12 2.3158 33.547 2139.55 ± 31.99 254.571 ± 9.63
0.0024 1.055092 1682.04 2.3346 33.499 1103.43 ± 8.43 109.798 ± 4.81
0.0036 1.055949 1683.39 2.3631 33.419 626.03 ± 3.92 48.233 ± 3.53
0.0048 1.056661 1684.37 2.3940 33.357 414.56 ± 2.67 22.220 ± 2.98
0.0060 1.056988 1684.63 2.4337 33.337 345.27 ± 2.11 14.973 ± 2.67
0.0072 1.05749 1684.70 2.4710 33.318 277.27 ± 1.76 9.681 ± 2.49

2.5 × 10−4 mol∙kg−1 WDT

0.0012 1.054875 1681.14 2.3266 33.542 2509.44 ± 37.82 300.940 ± 9.90
0.0024 1.055132 1682.28 2.3388 33.489 1314.97 ± 9.85 131.307 ± 4.80
0.0036 1.055972 1683.64 2.3660 33.408 771.31 ± 4.34 62.763 ± 3.52
0.0048 1.056778 1684.44 2.3985 33.351 505.96 ± 2.76 33.359 ± 2.96
0.0060 1.057238 1684.72 2.4355 33.325 398.52 ± 2.13 22.436 ± 2.66
0.0072 1.057504 1684.82 2.4711 33.313 351.04 ± 1.76 17.704 ± 2.48

3.0 × 10−4 mol∙kg−1 WDT

0.0012 1.054945 1681.26 2.3405 33.535 3003.99 ± 45.71 350.501 ± 10.24
0.0024 1.055184 1682.45 2.3475 33.480 1568.99 ± 11.68 155.759 ± 4.81
0.0036 1.055976 1683.95 2.3699 33.395 952.65 ± 5.00 78.411 ± 3.50
0.0048 1.056873 1684.48 2.4045 33.346 624.96 ± 2.94 46.078 ± 2.95
0.0060 1.057445 1684.77 2.4433 33.317 477.00 ± 2.18 31.436 ± 2.65
0.0072 1.057786 1685.06 2.4815 33.294 407.11 ± 1.78 23.594 ± 2.47

further inclusion of upto 0.00030 mol∙kg−1, increases by 0.48%. In pres-
ence of 0.00010 and 0.00015 mol∙kg−1 TTDMM, the ρ of WDR decreases
by 0.13 and 0.04%, respectively, which on further inclusion of upto
0.00030 mol∙kg−1, increases by 0.25%. Furthermore, at all TTDMM con-
centration, the ρ of WDT N WDRT.
With increasing Ln(NO3)3 concentration, the ρ values with WD
N WDR, while with WDT b WDRT, at all TTDMM concentrations. With
increasing Gd(NO3)3 and Sm(NO3)3 concentration, the ρ values with
WD b WDT (except at 0.00010 mol∙kg−1 TTDMM), while with Nd
(NO3)3 is WD N WDT (for all TTDMM concentrations). With increasing
Ln(NO3)3 concentration, the ρ values with WDR b WDRT (for all
TTDMM concentrations). In all the solvent mixtures, the ρ values with
Ln(NO3)3 followed the trend: Gd(NO3)3 N Sm(NO3)3 N Nd(NO3)3.
Tables 3–8 reports the apparent molar volume (Vϕ) and Figs. S2–S4
illustrate the trend of Vϕ values of increasing concentration of Gd(NO3)3,
Sm(NO3)3, and Nd(NO3)3, respectively, with WD, WDT, WDR, and
WDRT. A perusal of Tables 3–8 infers that with WDT, in presence of Ln
(NO3)3, the Vϕ value increases with increasing TTDMM concentration.
At 0.00010 mol∙kg−1 TTDMM, the Vϕ values for Ln(NO3)3 with WDR de-
creases, which then increases at [TTDMM] N 0.00010 mol∙kg−1. The Vϕ
values for Ln(NO3)3 in WDRT (N0.00015 mol∙kg−1 TTDMM) are higher
than the Vϕ values in WDR. On increasing the Ln(NO3)3 concentration
in WDRT (b0.00020 mol∙kg−1 TTDMM), the Vϕ values increases, which
otherwise decreases in WDR and WDRT (N0.00015 mol∙kg−1
TTDMM). Figs. S2–S4 elucidate that in WDR and WDRT (except
b0.00020 mol∙kg−1 TTDMM), the Vϕ value decreases with increasing
Ln(NO3)3 concentration.
m is the molality (mol∙kg−1) of Sm(NO3)3 in WD and WDT
(1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM). Standard uncer-
tainties u are u(m) = 0.00001 mol∙kg−1, u(ρ) = 5 × 10−3 kg∙m−3,
u(u) = 0.1 m∙s−1 and the expanded uncertainties Uc (0.95 level of
confidence) in viscosity and Isentropic Compressibility are Uc(η) ≤
0.53 × 10−7 kg∙m−1 s−1, Uc(κ) ≤ 0.01 × 1011 m∙s2∙kg−1.
m is the molality (mol∙kg−1) of Nd(NO3)3 in WD and WDT (1.0 × 10−4
to 3.0 × 10−4 mol∙kg−1 TTDMM). Standard uncertainties u are u(m) =
0.00001 mol∙kg−1, u(ρ) = 5 ×10−3 kg∙m−3, u(u) = 0.1 m∙s−1 and the
expanded uncertainties Uc (0.95 level of confidence) in viscosity and
Isentropic Compressibility are Uc(η) ≤ 0.53 × 10−7 kg∙m−1 s−1, Uc(κ) ≤
0.01 × 1011 m∙s2∙kg−1.
m is the molality (mol∙kg−1) of Gd(NO3)3 in WD and WDT (1.0 × 10−4
to 3.0 × 10−4 mol∙kg−1 TTDMM). Standard uncertainties u are u(m)=
0.00001 mol∙kg−1, u(ρ) = 5 × 10−3 kg∙m−3, u(u) = 0.1 m∙s−1 and
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341 329

Table 6
Effect of Gd(NO3)3 on Density (ρ/103kg∙m−3), Sound Velocity (u/m∙s−1), Viscosity (η/10−3 kg∙m−1∙s−1), Isentropic Compressibility (κ/1011 m∙s2∙kg−1), Apparent Molar Volume (Vϕ/
10−6 m3·mol−1) and Apparent Molar Isoentropic compressibility (κs, ϕ/1014 m5·N−1∙mol−1) of WDR and WDRT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.

m/mol.kg−1 ρ u η κ Vϕ κs, ϕ

WDR
0 1.054623 1681.41 2.2741 33.539 25.35 ± 0.00 0.850 ± 1.70
0.0012 1.054251 1681.13 2.2872 33.562 604.42 ± 11.56 38.469 ± 8.96
0.0024 1.055536 1681.37 2.3233 33.512 −16.53 ± 6.01 −11.385 ± 4.47
0.0036 1.056532 1682.58 2.3605 33.432 −151.01 ± 4.41 −33.269 ± 2.98
0.0048 1.057453 1682.84 2.3984 33.393 −204.05 ± 3.43 −35.770 ± 2.24
0.0060 1.058096 1683.27 2.4345 33.355 −194.30 ± 2.74 −35.547 ± 1.79
0.0072 1.058731 1683.82 2.4741 33.314 −186.77 ± 2.27 −35.946 ± 1.49

1.0 × 10−4 mol∙kg−1 WDRT

0 1.053289 1678.21 2.3195 33.710 25.38 ± 0.00 0.856 ± 1.71
0.0012 1.055379 1679.36 2.3105 33.597 −1241.53 ± 27.99 −130.971 ± 9.29
0.0024 1.056672 1681.41 2.3402 33.474 −941.634 ± 11.77 −124.762 ± 4.62
0.0036 1.057531 1683.37 2.3759 33.369 −733.26 3 ± 6.84 −114.329 ± 3.06
0.0048 1.058179 1684.34 2.4116 33.311 −589.634 ± 4.63 −98.673 ± 2.28
0.0060 1.058456 1684.64 2.4473 33.290 −448.132 ± 3.33 −81.400 ± 1.80
0.0072 1.058684 1684.87 2.4857 33.274 −347.72 ± 2.57 −69.115 ± 1.50

1.5 × 10−4 mol∙kg−1 WDRT

0 1.054241 1683.11 2.3582 33.484 25.36 ± 0.00 0.849 ± 1.70
0.0012 1.055813 1681.82 2.3290 33.485 −851.789 ± 22.15 −27.372 ± 8.94
0.0024 1.056948 1682.55 2.3523 33.420 −687.465 ± 9.93 −48.081 ± 4.48
0.0036 1.057728 1683.68 2.3851 33.351 −544.096 ± 5.97 −53.184 ± 2.99
0.0048 1.058134 1684.89 2.4206 33.290 −402.636 ± 4.02 −51.670 ± 2.24
0.0060 1.058467 1685.16 2.4590 33.269 −306.883 ± 2.98 −44.164 ± 1.79
0.0072 1.058767 1685.28 2.4980 33.255 −238.956 ± 2.35 −38.108 ± 1.49

2.0 × 10−4 mol∙kg−1 WDRT

0 1.056563 1684.71 2.3875 33.347 25.30 ± 0.00 0.844 ± 1.69
0.0012 1.056181 1681.81 2.3448 33.474 610.28 ± 11.57 120.757 ± 9.07
0.0024 1.056815 1682.63 2.3659 33.421 230.78 ± 5.34 37.102 ± 4.44
0.0036 1.057716 1683.93 2.3953 33.341 37.95 ± 3.86 −0.177 ± 2.95
0.0048 1.058414 1684.87 2.4293 33.282 −20.51 ± 3.00 −13.429 ± 2.21
0.0060 1.058672 1685.11 2.4669 33.265 10.00 ± 2.36 −12.638 ± 1.77
0.0072 1.058953 1685.23 2.5094 33.251 27.48 ± 1.94 −11.679 ± 1.48

2.5 × 10−4 mol∙kg−1 WDRT

0 1.056967 1685.37 2.4296 33.308 25.30 ± 0.02 0.843 ± 1.69
0.0012 1.056449 1681.96 2.3605 33.460 711.51 ± 12.34 143.325 ± 9.14
0.0024 1.057042 1682.76 2.3756 33.409 296.78 ± 5.28 49.743 ± 4.44
0.0036 1.057865 1684.22 2.4064 33.325 101.40 ± 3.73 7.896 ± 2.95
0.0048 1.058458 1684.97 2.4399 33.277 46.66 ± 2.88 −4.582 ± 2.21
0.0060 1.058773 1685.18 2.4804 33.259 55.25 ± 2.29 −5.939 ± 1.77
0.0072 1.059033 1685.26 2.5237 33.247 67.79 ± 1.89 −5.714 ± 1.47

3.0 × 10−4 mol∙kg−1 WDRT

0 1.057208 1685.78 2.4618 33.284 25.29 ± 0.01 0.842 ± 1.68
0.0012 1.056464 1681.84 2.3711 33.464 880.03 ± 13.98 171.080 ± 9.26
0.0024 1.057084 1682.81 2.3828 33.406 370.96 ± 5.29 60.281 ± 4.45
0.0036 1.057692 1684.69 2.4083 33.312 204.31 ± 3.58 14.119 ± 2.95
0.0048 1.058499 1685.09 2.4447 33.271 83.95 ± 2.82 0.160 ± 2.21
0.0060 1.058892 1685.29 2.4877 33.251 73.46 ± 2.27 −2.855 ± 1.77
0.0072 1.059231 1685.37 2.5345 33.237 73.17 ± 1.89 −3.796 ± 1.47

the expanded uncertainties Uc (0.95 level of confidence) in viscosity
and Isentropic Compressibility are Uc(η) ≤ 0.53 × 10−7 kg∙m−1 s−1,
Uc(κ) ≤ 0.01 × 1011 m∙s2∙kg−1.
m is the molality (mol∙kg −1 ) of Sm(NO 3 ) 3 in WD and WDT
(1.0 × 10 −4 to 3.0 × 10 −4 mol∙kg −1 TTDMM). Standard uncer-
tainties u are u(m) = 0.00001 mol∙kg−1, u(ρ) = 5 × 10−3 kg∙m−3,
u(u) = 0.1 m∙s−1 and the expanded uncertainties Uc (0.95 level of
confidence) in viscosity and Isentropic Compressibility are Uc(η) ≤
0.53 × 10−7 kg∙m−1 s−1, Uc(κ) ≤ 0.01 × 1011 m∙s2∙kg−1.
In general, the V0ϕ values for Ln(NO3)3 with WDT and WDRT
(Table S2), increases with increasing TTDMM concentration, as WDT
N WDRT. The V0ϕ values for Ln(NO3)3 with WDT and WDRT are as Nd
(NO3)3 N Sm(NO3)3 N Gd(NO3)3. The Sv values decreases with increasing
TTDMM concentration, supported by the reverse trend observed for the
V0ϕ values.
With increasing TTDMM concentration, the increment in V0ϕ values
for Ln3+ in WDRT is not linear and follows three different rates at
(0.00010–0.00015) mol∙kg−1, (0.00015−0.00020) mol∙kg−1, and
(0.00020−0.00030) mol∙kg−1; depicted by R1, R2 and R3, respectively,
as: R3 b R1 b R2 (Fig. 1).
4.2. Sound velocity (u) and isentropic compressibility (κs)
Sound velocities (u) are illustrated in Tables 3–8. A perusal of
Tables 3–5 illustrate that for Ln(NO3)3 with WDT, on increasing the
TTDMM concentration, the apparent molar isentropic compressibility
(κs, ϕ) value becomes more positive, and are more positive than with
WD. At fixed TTDMM concentration, on increasing the Ln(NO3)3 con-
centration with WDT, the κs, ϕ values become less positive, which other-
wise are more positive with WD. For Ln(NO3)3, the κs, ϕ values with
WDRT are more negative than with WDT (Tables 6–8, Figs. S5–S7). Ad-
ditionally, the κs, ϕ values for Ln(NO3)3 with WDRT b0.00020 mol∙kg−1
TTDMM are more negative than with WDR, which at
N0.00020 mol∙kg−1, become more positive. In WDRT, at
b0.00015 mol∙kg−1 TTDMM, the κs, ϕ values become more positive
330 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

Table 7
Effect of Sm(NO3)3 on Density (ρ/103kg∙m−3), Sound Velocity (u/m∙s−1), Viscosity (η/10−3 kg∙m−1∙s−1), Isentropic Compressibility (κ/1011 m∙s2∙kg−1), Apparent Molar Volume (Vϕ/
10−6 m3·mol−1) and Apparent Molar Isoentropic compressibility (κs, ϕ/1014 m5·N−1∙mol−1) of WDR and WDRT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.

m/mol.kg−1 ρ u η κ Vϕ κs, ϕ

WDR
0.0012 1.054207 1680.98 2.2792 33.570 630.89 ± 11.79 45.202 ± 9.01
0.0024 1.055437 1681.23 2.3079 33.521 14.00 ± 5.87 −6.915 ± 4.61
0.0036 1.056374 1682.39 2.3423 33.445 −118.16 ± 4.28 −28.866 ± 3.20
0.0048 1.057097 1682.77 2.3755 33.407 −144.11 ± 3.27 −31.000 ± 2.51
0.0060 1.057672 1683.19 2.4151 33.372 −137.53 ± 2.60 −31.042 ± 2.11
0.0072 1.058097 1683.72 2.4465 33.338 −114.48 ± 2.13 −30.390 ± 1.86

1.0 × 10−4 mol∙kg−1 WDRT

0.0012 1.055028 1679.29 2.3046 33.611 −985.25 ± 24.02 −111.314 ± 9.38
0.0024 1.056193 1681.37 2.3315 33.491 −769.18 ± 10.47 −112.366 ± 4.82
0.0036 1.056943 1683.25 2.3649 33.393 −593.47 ± 6.16 −103.527 ± 3.32
0.0048 1.057593 1684.19 2.4005 33.335 −486.88 ± 4.27 −90.437 ± 2.59
0.0060 1.058131 1684.51 2.4351 33.305 −406.18 ± 3.21 −77.579 ± 2.16
0.0072 1.058423 1684.75 2.4692 33.287 −321.80 ± 2.50 −66.550 ± 1.90

1.5 × 10−4 mol∙kg−1 WDRT

0.0012 1.055384 1681.76 2.3249 33.501 −537.35 ± 17.67 −4.203 ± 9.01
0.0024 1.056435 1682.35 2.3464 33.444 −502.40 ± 8.63 −32.352 ± 4.63
0.0036 1.057428 1683.55 2.3740 33.365 −476.01 ± 5.63 −47.070 ± 3.21
0.0048 1.058015 1684.62 2.4107 33.305 −386.97 ± 3.95 −48.305 ± 2.52
0.0060 1.058415 1685.04 2.4462 33.275 −305.64 ± 2.96 −43.117 ± 2.12
0.0072 1.058728 1685.12 2.4816 33.262 −240.62 ± 2.35 −37.172 ± 1.86

2.0 × 10−4 mol∙kg-1 WDRT

0.0012 1.055994 1681.79 2.3408 33.481 743.53 ± 12.69 130.525 ± 9.07
0.0024 1.056718 1682.45 2.3544 33.432 260.48 ± 5.30 42.128 ± 4.55
0.0036 1.057538 1683.86 2.3816 33.350 75.69 ± 3.77 3.287 ± 3.15
0.0048 1.058128 1684.77 2.4156 33.295 26.27 ± 2.90 −9.318 ± 2.47
0.0060 1.058494 1685.06 2.4502 33.272 30.02 ± 2.32 −10.778 ± 2.08
0.0072 1.058868 1685.17 2.4904 33.256 31.52 ± 1.93 −10.882 ± 1.83

2.5 × 10−4 mol∙kg−1 WDRT

0.0012 1.056092 1681.84 2.3536 33.476 971.74 ± 15.10 164.73 ± 9.18
0.0024 1.056793 1682.62 2.3628 33.422 383.21 ± 5.31 57.93 ± 4.54
0.0036 1.057789 1684.14 2.3896 33.331 113.78 ± 3.69 9.771 ± 3.14
0.0048 1.058384 1684.83 2.4197 33.285 53.93 ± 2.86 −2.791 ± 2.46
0.0060 1.058698 1685.07 2.4597 33.265 59.91 ± 2.28 −4.727 ± 2.07
0.0072 1.059197 1685.18 2.5001 33.245 40.93 ± 1.92 −6.869 ± 1.83

3.0 × 10−4 mol∙kg−1 WDRT

0.0012 1.056092 1681.62 2.3639 33.484 1134.28 ± 63.88 195.232 ± 9.30
0.0024 1.056793 1682.76 2.3721 33.416 465.23 ± 31.20 67.582 ± 4.53
0.0036 1.057789 1684.48 2.3957 33.320 196.31 ± 90.15 15.987 ± 3.13
0.0048 1.058384 1685.01 2.4267 33.274 79.68 ± 77.26 0.715 ± 2.46
0.0060 1.058698 1685.16 2.4659 33.257 72.62 ± 93.36 −1.886 ± 2.07
0.0072 1.059197 1685.31 2.5108 33.240 69.64 ± 5.64 −3.503 ± 1.82

with increasing Ln(NO3)3 concentration, which otherwise becomes less
positive at N0.00015 mol∙kg−1 TTDMM.
Table S2 illustrates the limiting apparent molar isentropic compress-
ibility (κs,0 ϕ) values of Ln(NO3)3 with WD, WDT, WDR and WDRT. The
κ0s, ϕ value increases with increasing TTDMM concentration, for both
WDT and WDRT, and the κs,0 ϕ values with WDRT are less positive than
with WDT (Fig. 2). The κ0s, ϕ values for [Ln(NO3)3 with WDT] N [Ln
(NO3)3 with WDRT] at all TTDMM concentrations. Furthermore, the κs,
0
ϕ value for Nd(NO3)3 are most positive, while for Gd(NO3)3 are least
positive.
4.3. Viscosity (η)
The plots of [ηr − 1]/m1/2 v/s m1/2 for Ln(NO3)3 are linear for all the
systems. Table 9 illustrates that the B values are negative and with in-
creasing TTDMM concentration, becomes more negative (Fig. S8). For
the Ln(NO3)3, more negative B values were observed with WDR, than
with WD.
Fig. S8 infers that the B values for Ln(NO3)3 with WDRT are more
negative than with WDT at [TTDMM] b 0.00020 mol∙kg−1, whereas
the trend reverses at [TTDMM] N 0.00020 mol∙kg−1. At [TTDMM] =
0.00020 mol∙kg−1, the B values of Ln(NO3)3 with WDRT are nearly the
same as with WDT. Among the Ln(NO3)3, the least negative Bvalues
are observed in presence of Gd(NO3)3.
4.4. Molar conductivity (Λm)
Tables S3 and S4 reports the electrical conductivity (κ) of Ln(NO3)3
with (WD and WDR) and (WDT and WDRT), respectively. Tables 10
and 11 reports the molar conductivities (Λm) of Ln(NO3)3 with (WD
and WDR), and (WDT and WDRT), respectively. Figs. S9–S11 illustrates
the trend observed for Λm values with increasing concentration of Ln
(NO3)3 with WD, WDT, WDR, and WDRT, wherein the Λm value de-
creases with increasing Ln(NO3)3 concentration, reaches a minimum
and then increases. The limiting molar conductivity (Λm) of Ln(NO3)3,
empirical parameters: A(S·cm2·mol−2) and B(S·cm5·mol−3) depicting
the nature of solute-solvent interaction are summarized in Table S5.
Fig. S12 illustrates the impact of increasing TTDMM concentration on
the Λ0m values for Ln(NO3)3 with WDT and WDRT. Fig. S12 illustrates
that the Λ0m values for Ln(NO3)3 with WD, WDT, WDR and WDRT fol-
lows the order: Nd(NO3)3 b Sm(NO3)3 b Gd(NO3)3, a similar trend
was also observed for the viscosities.
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341 331

Table 8
Effect of Nd(NO3)3 on Density (ρ/103kg∙m−3), Sound Velocity (u/m∙s−1), Viscosity (η/10−3 kg∙m−1∙s−1), Isentropic Compressibility (κ/1011 m∙s2∙kg−1), Apparent Molar Volume (Vϕ/
10−6 m3·mol−1) and Apparent Molar Isoentropic compressibility (κs, ϕ/1014 m5·N−1∙mol−1) of WDR and WDRT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.

m/mol.kg−1 ρ u η κ Vϕ κs, ϕ

WDR
0.0012 1.054134 1680.93 2.2746 33.574 679.85 ± 12.21 50.264 ± 9.14
0.0024 1.055109 1681.11 2.3020 33.536 131.03 ± 5.51 3.018 ± 4.92
0.0036 1.056279 1682.3 2.3338 33.451 −100.27 ± 4.20 −26.534 ± 3.65
0.0048 1.056991 1682.68 2.3668 33.414 −130.11 ± 3.23 −29.166 ± 3.06
0.0060 1.057599 1683.12 2.4000 33.377 −132.42 ± 2.58 −30.069 ± 2.73
0.0072 1.058001 1683.66 2.4292 33.343 −108.32 ± 2.11 −29.474 ± 2.54

1.0 × 10−4 mol∙kg−1 WDRT

0.0012 1.054937 1679.15 2.3031 33.620 −922.89 ± 23.02 −102.497 ± 9.58
0.0024 1.056094 1681.03 2.3231 33.508 −737.96 ± 10.20 −104.731 ± 5.17
0.0036 1.056781 1683.06 2.3511 33.405 −558.93 ± 5.98 −99.042 ± 3.79
0.0048 1.057363 1684.07 2.3853 33.347 −449.75 ± 4.13 −86.831 ± 3.15
0.0060 1.057766 1684.34 2.4198 33.324 −357.50 ± 3.07 −73.081 ± 2.79
0.0072 1.058147 1684.61 2.4557 33.301 −293.27 ± 2.43 −63.730 ± 2.58

1.5 × 10−4 mol∙kg−1 WDRT

0.0012 1.055339 1681.56 2.3228 33.511 −509.47 ± 17.24 4.155 ± 9.16
0.0024 1.056405 1682.19 2.3373 33.452 −496.98 ± 8.55 −29.284 ± 4.96
0.0036 1.057398 1683.37 2.3665 33.374 −474.34 ± 5.61 −44.888 ± 3.67
0.0048 1.057923 1684.43 2.3984 33.315 −375.60 ± 3.89 −45.873 ± 3.07
0.0060 1.058091 1684.91 2.4336 33.291 −263.11 ± 2.85 −39.283 ± 2.74
0.0072 1.058412 1685.08 2.4685 33.274 −207.14 ± 2.28 −34.544 ± 2.54

2.0 × 10−4 mol∙kg−1 WDRT

0.0012 1.055896 1681.68 2.3368 33.488 811.00 ± 13.39 138.697 ± 9.17
0.0024 1.056593 1682.24 2.3506 33.444 301.37 ± 5.28 48.351 ± 4.83
0.0036 1.057456 1683.79 2.3756 33.355 90.30 ± 3.72 5.183 ± 3.58
0.0048 1.058013 1684.62 2.4067 33.305 41.92 ± 2.86 −6.914 ± 3.01
0.0060 1.058442 1684.95 2.4409 33.278 31.99 ± 2.31 −9.770 ± 2.70
0.0072 1.058732 1685.12 2.4753 33.262 42.63 ± 1.91 −9.691 ± 2.51

2.5 × 10−4 mol∙kg−1 WDRT

0.0012 1.055952 1681.77 2.3499 33.483 1070.60 ± 16.38 173.745 ± 9.26
0.0024 1.056684 1682.56 2.3577 33.428 418.12 ± 5.35 61.399 ± 4.81
0.0036 1.057319 1684.08 2.3802 33.348 224.86 ± 3.55 17.996 ± 3.56
0.0048 1.057942 1684.75 2.4114 33.302 130.52 ± 2.74 3.125 ± 2.99
0.0060 1.058463 1684.97 2.4459 33.277 89.15 ± 2.24 −1.966 ± 2.69
0.0072 1.058999 1685.15 2.4871 33.253 59.72 ± 1.89 −5.271 ± 2.50

3.0 × 10−4 mol∙kg−1 WDRT

0.0012 1.056015 1681.54 2.3607 33.490 1203.23 ± 18.11 202.559 ± 9.36
0.0024 1.056787 1682.59 2.3655 33.424 469.52 ± 5.43 70.726 ± 4.81
0.0036 1.057465 1684.35 2.3896 33.333 248.46 ± 3.53 21.008 ± 3.55
0.0048 1.058041 1684.95 2.4231 33.291 157.00 ± 2.71 6.521 ± 2.99
0.0060 1.058578 1685.13 2.4582 33.267 107.96 ± 2.21 0.844 ± 2.68
0.0072 1.058982 1685.21 2.4953 33.251 91.79 ± 1.86 −1.319 ± 2.50

m is the molality (mol∙kg−1) of Nd(NO3)3 in WD and WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM). Standard uncertainties u are u(m) = 0.00001 mol∙kg−1, u(ρ) = 5 × 10−3 kg∙m−3, u
(u) = 0.1 m∙s−1 and the combined uncertainties Uc (0.95 level of confidence) in viscosity and Isentropic Compressibility are Uc(η) ≤ 0.53 × 10−7 kg∙m−1 s−1, Uc(κ) ≤ 0.01 × 1011 m∙s2∙kg−1.

Fig. 1. Limiting apparent molar volume of Gd(NO3)3 ( ), Sm(NO3)3 ( ) and Nd(NO3)3 ( ) with increasing concentrations of TTDMM (0.00010 to 0.00030 mol∙kg−1) in (a) WDT and
(b) WDRT at T = 298.15 K.
332 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

Fig. 2. Limiting apparent molar isentropic compressibility of Gd(NO3)3 ( ), Sm(NO3)3 ( ) and Nd(NO3)3 ( ) with increasing concentrations of TTDMM (0.00010 to 0.00030 mol∙kg−1) in
(a) WDT and (b) WDRT at T = 298.15 K.

m is the molality (mol∙kg−1) of Ln(NO3)3 in WD and WDT (1.0 × 10−4 4.5. Critical aggregation concentration (CAC) of TTDMM
to 3.0 × 10−4 mol∙kg−1 TTDMM). Standard uncertainties u are u(m) =
0.00001 mol∙kg−1 and the combined uncertainties Uc (0.95 level of con- The conductance data were used further for the determination of the
fidence) in Λm are Uc(λm) ≤ 0.28 mS·cm2·mol−1. CAC of TTDMM in WD. The impact of increasing Ln(NO3)3 concentration
on CAC of TTDMM has also been studied, and are tabulated in Table S6,
Table 9 depicted in Fig. 3. The CAC is an important characteristic of dendrimer.
Viscosity B-coefficient (Kg∙mol−1) and A-coefficient (kg1/2·mol−1/2) for Gd(NO3)3, Sm
Before attaining the CAC, the conductance strongly changes with the
(NO3)3, Nd(NO3)3 with WD, WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM), WDR
and WDRT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) at T = 298.15 K.
concentration of TTDMM, while after attaining the CAC, the conduc-
tance changes with a lower slope (Fig. 3). It was observed that the
Gd(NO3)3 Sm(NO3)3 Nd(NO3)3 CAC of TTDMM decreases in presence of Ln(NO3)3 and follows the
WD trend: Nd(NO3)3 N Sm(NO3)3 N Gd(NO3)3. The CAC of TTDMM was
A/kg1/2·mol−1/2 14.429 13.864 13.416 found to be 2.41 × 10−4 M and the CAC values in presence of different
B/Kg∙mol−1 −0.0548 −0.1099 −0.1131
Ln(NO3)3 concentrations are reported in Table S6. Additionally, the
1.0 × 10−4 mol∙kg−1 WDT CAC of TTDMM in presence of nitrate salt of Ln3+ ions with varying fn
A/kg1/2·mol−1/2 19.22 18.295 17.487 electrons (n = 1, 2, 3.0.14) of Ln3+ ions was computed by fitting the
B/Kg∙mol−1 −0.5633 −0.5779 −0.5841
CAC values in presence of different concentrations of Nd(NO3)3 (f3),
1.5 × 10−4 mol∙kg−1 WDT Sm(NO3)3 (f5), and Gd(NO3)3 (f7) to a linear equation (Fig. 4).
A/kg1/2·mol−1/2 21.463 20.011 19.467 For confirming the aggregation of TTDMM in dilute solution, Rhoda-
B/Kg∙mol−1 −0.8373 −0.8824 −0.8946
mine B (RB) may be used as a simple probing system. RB exists as con-
2.0 × 10−4 mol∙kg−1 WDT formations of both pink Z-form and colorless L-form in aprotic solvent.
A/kg1/2·mol−1/2 23.474 22.349 21.686 Since the aggregation of dendrimers becomes a spontaneous process
B/Kg∙mol−1 −1.2593 −1.2763 −1.2791
beyond the CAC, the chemical potential of should TTDMM change.
2.5 × 10−4 mol∙kg−1 WDT This changing chemical potential may contribute to the change of
A/kg1/2·mol−1/2 28.58 27.285 26.639 Gibbs energy, and thus providing the required energy needed for driv-
B/Kg∙mol−1 −1.9384 −1.9415 −1.9597
ing the isomerization equilibrium shift of RB in DMSO [62]. Fig. 5
3.0 × 10−4 mol∙kg−1 WDT shows that the maximum absorbance peak at 555 nm of RB, which de-
B/Kg∙mol-1 32.412 31.313 30.187 creased in presence of upto [TTDMM] = 2.41 × 10−4 M. This confirms
A/kg1/2·mol−1/2 −2.3913 −2.4227 −2.4388
the aggregation of TTDMM, with its CAC at 2.41 × 10−4 M, the same
WDR as observed from the conductometric study.
A/kg1/2·mol−1/2 17.189 16.749 16.089
B/Kg∙mol−1 −0.4122 −0.5132 −0.5393

1.0 × 10−4 mol∙kg−1 WDRT

A/kg1/2·mol−1/2 19.001 18.970 18.011
B/Kg∙mol−1 −0.7542 −0.8273 −0.8407
Table 10
1.5 × 10−4 mol∙kg−1 WDRT Molar Conductivity (Λm/mS·cm2·mol−1) of Gd(NO3)3, Sm(NO3)3, Nd(NO3)3 with WD and
A/kg1/2·mol−1/2 21.091 20.511 19.896 WDR at T = 298.15 K.
B/Kg∙mol−1 −1.0833 −1.1123 −1.1349
Λm/mS·cm2·mol−1
2.0 × 10−4 mol∙kg−1 WDRT WD WDR
A/kg1/2·mol−1/2 22.079 21.468 20.950
B/Kg∙mol−1 −1.2744 −1.3212 −1.3390 m/mol∙kg−1 Gd(NO3) Sm(NO3) Nd(NO3) Gd(NO3) Sm(NO3) Nd(NO3)
3 3 3 3 3 3
−4 −1
2.5 × 10 mol∙kg WDRT
A/kg1/2·mol−1/2 25.416 24.864 24.351 0.0012 11.2080 10.6732 9.9811 16.6757 16.7226 15.2766
B/Kg∙mol−1 −1.6972 −1.7709 −1.7949 0.0024 10.6792 10.2668 9.5632 13.2150 12.7293 11.8657
0.0036 10.2178 9.9789 9.1635 11.1652 10.6190 9.4889
3.0 × 10−4 mol∙kg−1 WDRT 0.0048 9.8274 9.7826 8.9806 10.0697 9.6715 8.8523
A/kg1/2·mol−1/2 28.02 27.327 27.03 0.0060 9.9362 9.6145 8.8234 10.1641 9.9831 9.1085
B/Kg∙mol−1 −2.0351 −2.0906 −2.1167 0.0072 9.8923 9.5702 8.7707 11.0949 10.8710 10.1061
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341 333

Table 11 wherein % inhibition increases with increasing Ln(NO3)3 concentration.

Molar Conductivity (Λm/mS·cm2·mol−1) of Gd(NO3)3, Sm(NO3)3, Nd(NO3)3 with WDT The rate of increase in the IC50 value of TTDMM with increasing Ln(NO3)
(1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM) and WDRT (1.0 × 10−4 to 3.0 × 10−-
4
mol∙kg−1 TTDMM) at T = 298.15 K. 3 concentration was found as: Gd(NO3)3 N Sm(NO3)3 N Nd(NO3)3.
Fig. 8a depict the kinetics of antioxidant activity of TTDMM in the
Λm/mS·cm2·mol−1 concentration range: 0.000033 to 0.002657 M, wherein the extent of
WDT DPPH free radical scavenging increases with increasing time and DPPH
Gd 1.0 × 1.5 × 10−4 2.0 × 10−4 2.5 × 10−4 3.0 × 10−4 concentration, and follows a zero order kinetics. Fig. 8b illustrates the
(NO3)3 10−4 mol∙kg−1 mol∙kg−1 mol∙kg−1 mol∙kg−1 rate of DPPH free radical scavenging in presence of different DPPH con-
mol∙kg−1 centration, wherein with increasing TTDMM concentration upto
0.0012 15.0969 15.9041 16.3131 16.9722 17.5477 0.000664 M, the rate decreases, while increases for the next higher
0.0024 10.8836 12.1997 13.0195 13.8089 14.7324 concentrations.
0.0036 8.5226 9.9850 10.6863 11.6202 12.5212
0.0048 7.4186 9.1117 9.8916 10.7576 11.6337
5. Discussion
0.0060 7.7352 9.2354 10.0062 10.6391 11.3401
0.0072 9.1737 10.4579 11.0459 11.2507 11.6626
5.1. Density (ρ) and apparent molar volume (Vϕ)
Sm(NO3)3
0.0012 13.2799 14.1792 14.8806 15.2244 15.7442
0.0024 9.9266 10.9003 11.7178 12.6659 13.4354 The increased density of WD with RB (Table 2) may be due to the
0.0036 8.2194 9.3813 10.1980 11.0378 11.7957 strengthening of hydrophilic-hydrophilic interactions (HHI) prevailing
0.0048 7.2384 8.6867 9.4500 10.0351 10.7876 between the quaternary ammonium cation, carboxyl group of RB and
0.0060 7.6369 8.7763 9.7721 10.2976 10.8565 the dipoles of water and DMSO. The lower ρ values for TTDMM with
0.0072 8.9954 9.9208 10.6987 11.1078 11.5153
WDR as compared to with WD infer the dominance of hydrophobic-
Nd(NO3)3 hydrophobic interaction (HbHbI) between the xanthenylidene system
0.0012 11.6567 12.6850 13.4960 14.2191 14.6823 of RB and the trimesoyl core of TTDMM. With increasing TTDMM con-
0.0024 8.9317 10.3957 11.1419 11.7535 12.7940
0.0036 7.3583 9.0785 9.8415 10.4414 11.2969
centration, the population of (−Cδ+ = Oδ−) dipoles increases, resulting
0.0048 6.5987 8.2276 9.0980 9.6066 10.4825 increased dipole-dipole interactions with the (−Sδ+ = Oδ−) dipole of
0.0060 7.3738 8.3772 9.4248 9.9469 10.4692 DMSO, with higher density. In presence of Ln(NO3)3, the lower ρ values
0.0072 8.8533 9.6792 10.5611 10.8246 11.3067 of WDR than WD (Tables 3–8) may be due to the increased ion-
Gd(NO3)3 hydrophobic interactions between the Ln3+ and the xanthenylidene
0.0012 15.6500 16.4182 16.9059 17.8655 18.7026 moiety of RB. It seems that in presence of Ln(NO3)3, the lower ρ values
0.0024 12.0018 12.9300 13.6665 14.5562 15.3640 of WDT than WDRT (Tables 3–8) may be due to the dominance of ion-
0.0036 9.5662 10.5806 11.2857 12.1598 13.0165
dipole interactions over the ion-hydrophobic interactions in presence
0.0048 8.9757 9.6663 10.1607 11.1047 11.5890
0.0060 9.3471 9.9273 10.3062 10.9457 11.3364 of RB with TTDMM.
0.0072 10.5039 11.0406 11.4017 11.8855 12.7750 In presence of Ln(NO3)3, at [TTDMM] = 0.00010 mol∙kg−1, the IHbI
(prevailing between the Ln3+ and the hydrophobic ester group of
Sm(NO3)3
0.0012 14.8744 15.6655 16.4591 17.0002 18.0131 TTDMM) is dominant over the ion-dipole interaction with the (prevailing
0.0024 11.3570 11.9349 12.5682 14.2925 14.8725 between Ln3+ and (−Cδ+ = Oδ−) dipoles of malonic ester group (MEG)
0.0036 9.0678 9.8062 10.5196 11.6690 12.6932 of TTDMM). At [TTDMM] N 0.00010 mol∙kg−1, due to the higher charge
0.0048 8.3359 9.0738 9.6559 10.5471 11.1905 density (CD) of Gd3+ and Sm3+ over Nd3+, it seems that for Gd3+ and
0.0060 8.6641 9.6114 10.1731 10.5291 11.0416
0.0072 10.2637 10.8368 11.2979 11.4502 12.2588
Sm3+ both, the ion-dipole interaction dominates over IHbI, with ρ values:
WD b WDT. For the Ln(NO3)3, the lower ρ values of WDR than WDRT in-
Nd(NO3)3 fers that inclusion of TTDMM in WDR develops ion-dipole interaction
0.0012 14.0035 15.1317 15.6102 16.3840 17.3261
0.0024 10.6129 11.5486 12.2534 12.9486 14.0087
with the Ln3+ (electrostatic interaction between Ln3+ and (−Cδ+ =
0.0036 8.2984 9.0689 9.8625 10.6532 11.7103 Oδ−) dipoles of MEG), which otherwise was absent in WDR. In all the sol-
0.0048 7.7649 8.4353 9.0704 9.7754 10.8789 vent mixtures, the highest ρ values observed for of Gd(NO3)3 is due to its
0.0060 8.1075 8.6602 9.3991 9.8738 10.8868 highest CD among the studied Ln3+ ions.
0.0072 9.4521 9.8562 10.3181 10.6797 11.3014
For Ln(NO3)3 in WDT, the increased Vϕ values with increasing
m is the molality (mol∙kg−1) of Ln(NO3)3 in WD and WDT (1.0 × 10−4 to 3.0 × 10−4 mol∙kg−1 TTDMM concentration (Tables 3–5) infers increased hydrophilic forces
TTDMM). Standard uncertainties u are u(m) = 0.00001 mol∙kg−1 and the combined prevailing in the system. The decreased Vϕ values with increasing Ln
uncertainties Uc (0.95 level of confidence) in Λm are Uc(λm) ≤ 0.32 mS·cm2·mol−1.
(NO3)3 concentrations in WDT is may be due to the increased IHbI (be-
tween Ln3+ and hydrophobic ester group of TTDMM) with increasing
Ln(NO3)3 concentrations, which otherwise is absent in WD. The lower
4.6. Antioxidant activity Vϕ values for Ln(NO3)3, in WD than in WDT depicts that TTDMM intro-
duces hydrophilicity due to its (−Cδ+ = Oδ−) moiety.
Fig. 6 illustrates the UV–visible absorbance spectra of DPPH free rad- It seems that in WDR, due to the presence of xanthenylidene moiety,
ical in presence of (0.00576−0.06819 mol∙L−1) TTDMM, wherein it is addition of 0.00010 mol∙kg−1 TTDMM may have created a highly
observed that with increasing TTDMM concentration, the absorbance hydrophobic environment due to its hydrophobic ester group. Thus,
of DPPH radical at 520 nm decreases, thus confirming its antioxidant ac- to minimize the increment in hydrophobicity at [TTDMM] =
tivity. Table 12 comprises IC50 values of TTDMM in absence and pres- 0.00015 mol∙kg−1, RB may have induced reorientation of the TTDMM
ence of Gd(NO3)3, Sm(NO3)3 and Nd(NO3)3. The IC50 value for molecules (Fig. 9). The drastic increase in the Vϕ values for Ln(NO3)3
TTDMM were found to increase with increasing Ln(NO3)3 concentra- with WDRT (0.00015 mol∙kg−1 TTDMM) than with WDRT
tion, and was least in absence of Ln(NO3)3. Fig. 7a depicts the % scaveng- (0.00020 mol∙kg−1 TTDMM), followed by lesser increment in the Vϕ
ing of DPPH free radical by TTDMM in absence and presence of Ln(NO3)3 values for further TTDMM concentrations, supports our proposed RB in-
at varied concentration. The IC50 value for TTDMM in absence of Ln duced TTDMM reorientation (Figs. S2–S4). Thus, for Ln(NO3)3 with
(NO3)3 was 2 × 10−4 M, and is in range to that of ascorbic acid (1.51 WDRT, as compared to WDT, due to the RB induced compact TTDMM
× 10−4 M), used as a standard antioxidant (Fig. 7b). Table S7 reports rearrangement, the IHbI between the Ln3+ and the hydrophobic ester
the % inhibition of scavenging activity at IC50 of TTDMM by Ln(NO3)3, group of TTDMM is minimized. Figs. S2-S4 illustrate that in WDR and
334 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

Fig. 3. CAC of TTDMM with (a) Gd(NO3)3, (b) Sm(NO3)3 and (c) Nd(NO3)3 (d) in absence of Ln(NO3)3 at their varying concentrations [0.0012 ( ), 0.0024 ( ), 0.0036 ( ), 0.0048 ( ),
0.0060 ( ), 0.0072 ( ) mol∙L−1] at T = 298.15 K.

WDRT (except b0.00020 mol∙kg−1 TTDMM), the Vϕ value decreases
with increasing Ln(NO3)3 concentration. This may be due to the domi-
nance of IHbI and repulsive forces (Ln3+ and the ammonium ion of
RB) over the ion-dipole interaction with increasing Ln(NO3)3 concen-
tration. At b0.00020 mol∙kg−1 TTDMM, it seems that the electrostatic in-
teraction between Ln3+ and (−Cδ+ = Oδ−) dipoles of MEG dominates
over the IHbI and repulsive forces.
The increased V0ϕ values with increasing TTDMM concentration in
WDT (Table S2) is may be due to the increased solute-solvent interac-
tions (SLSOI) prevailing in the system. With increasing TTDMM concen-
tration, there may be the development of intermolecular forces like
dipole-dipole interaction between the carbonyl oxygen of malonate
ester groups (MEG) of TTDMM and the sulphur atom of DMSO. The hy-
dration shell of DMSO is due to the formation of hydrogen bonds be-
tween the DMSO methyl hydrogen and water oxygen atoms. On
increasing the TTDMM concentration in WDT, the hydrogen bonds
existing between DMSO and water may have disrupted. In addition to
the dipole-dipole interactions between TTDMM and DMSO, a new set
of hydrogen bonds may have formed between the DMSO methyl hydro-
gen and carbonyl oxygen of MEG of TTDMM. The disruption of hydrogen
bonds between DMSO and water may have thus resulted in the release
of some water molecules from the hydration shell of DMSO to the bulk,
and gets engaged in the Ln3+ ion hydration sphere, with increased V0ϕ
values. The linear increase in V0ϕ values for Ln3+ with increasing
TTDMM concentration in WDT depicts formation of cation-π interaction
between the Ln3+ and the delocalized π electronic core of TTDMM, thus
resulting in increased SOSLI. The lower V0ϕ values for Ln(NO3)3 in WDRT
than with WDT illustrates that RB engages water molecules which oth-
erwise is released to the bulk due to the development of increased
dipole-dipole interaction between TTDMM and DMSO. Thus, in compar-
ison to WDT, lesser water molecules are now available in the bulk to in-
teract with the Ln3+ in case of WDRT, resulting in weaker SLSOI.
Furthermore, in WDRT, the chances of Ln3+ to develop cation-π interac-
tions are less due to pre-existing cation−π between the = N+ = moi-
ety of RB and the delocalized π electronic core of TTDMM. Thus in
WDRT, lesser cation-π interactions exists between the Ln3+ and
TTDMM, with reduced SOSLI. The Sv values shows that SLSLI decreases
with increasing TTDMM concentration in WDT and WDRT both, with
Gd(NO3)3 having the highest SLSLI and Nd(NO3)3, having the least. The
obtained trends for Sv values are supported by V0ϕ values with reverse

Fig. 4. CAC of TTDMM with fn electrons of Ln3+ at their varying concentrations [0.0012 ( ), 0.0024 ( ), 0.0036 ( ), 0.0048 ( ), 0.0060 ( ), 0.0072 ( ) mol∙L−1] at T = 298.15 K.
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341 335

Fig. 5. UV–visible absorbance spectra of Rhodamine B with increasing concentration of TTDMM, inset: Absorbance of Rhodamine B at 555 nm with increasing TTDMM concentration.

trend. Fig. 10 illustrates a mechanistic representation of the possible
pathways for the intermolecular interaction of Ln(NO3)3 prevailing in
different solvent systems.
The order for increment in V0ϕ values: R3 b R1 b R2 (Fig. 1) depicts
strongest SLSOI with TTDMM = (0.00015–0.00020) mol∙kg−1, while
least with TTDMM = (0.00020–0.00030) mol∙kg−1. The Gd3+ with
highest CD, may have resulted in the dominance of IHbI over the IHI,
while the Nd3+ ions having lowest CD, may have caused the dominance
of IHI over IHbI. This may have resulted in highest V0ϕ values for Nd(NO3)
3, while least for Gd(NO3)3 with WDT and WDRT.
5.2. Sound velocity (u) and isentropic compressibility (κs)
The κ0s, ϕ values are a product of two effects: (a) positive effect insti-
gated by the compression of the 3D network structure of aq. DMSO and
(b) negative effect instigated by the isentropic compressibility due to
the compression of the solvation sphere of ions and interionic distance
[52,53]. A positive κs,0 ϕ value can be interpreted in terms of an increase
in the compressibility of the solution compared to the pure solvent,
while a negative κ0s, ϕ value can be interpreted in terms of close packed
structure of solution compared to the pure solvent [54]. The positive κs,
0
ϕ values indicate that the solute acts as a solvent structure breaker [55].
The more positive κs, ϕ values with WDT than with WD hints that
TTDMM may have acted as aq. DMSO structure breaker, thereby releas-
ing water molecules to the bulk (Table 3). With increasing Ln(NO3)3
concentration in WDT (Tables 3–5), the less positive κs, ϕ value infers
that Ln3+ act as structure maker with WDT, while structure breaker
with WD. For the Ln(NO3)3, the more negative κs, ϕ values with WDRT
than with WDT (Tables 6–8), infers that inclusion of RB to WDT, de-
creases the solute-solvent interaction. In WDRT, at [TTDMM] b
0.00020 mol∙kg−1, the solute–solvent interaction are weaker than at
[TTDMM] b 0.00020 mol∙kg−1, as proposed in the RB induced reorienta-
tion of TTDMM (Fig. 9). In WDRT (b0.00015 mol∙kg−1 TTDMM), with in-
creasing Ln(NO3)3 concentration, the κs, ϕ values become more positive,
which otherwise becomes less positive at [TTDMM] N 0.00015 mol∙kg−
1
. Probably in WDRT, at b0.00015 mol∙kg−1 TTDMM and with increasing
Ln(NO3)3 concentration, the solvation sphere of Ln3+ becomes more
compressible due to increasing IHbI [56]. As shown earlier in case of
Vϕ, at 0.00015 mol∙kg−1 TTDMM, RB may have induced a compact
TTDMM reorientation of the molecules, thereby reducing the hydropho-
bicity (Fig. 9). This may thus, have resulted in a more compact Ln3+ sol-
vation sphere due to increased cation−π and ion-dipole interaction
with the MEG dipoles of TTDMM. The negative and positive κ0s, ϕ values
for Ln(NO3)3 with WD and WDR (Table S2), respectively, illustrate that
RB induces a positive effect on the intrinsic compressibility of aq. DMSO,
which otherwise is of lesser magnitude in WD.
The positive κs,0 ϕ values with both solvents (WDT and WDRT) can be
interpreted in terms of an increase in the compressibility of the solution.
The positive κs,0 ϕ values for [Ln(NO3)3 with WDT/WDRT)], is due to the
solvent intrinsic compressibility N the solute intrinsic compressibility.
The κ0s, ϕ values for [Ln(NO3)3 with WDT] N [Ln(NO3)3 with WDRT)] at
all TTDMM concentrations indicates greater (ion + solvent) interac-
tions in case of [Ln(NO3)3 with WDT], well supported by the trend ob-
served for the V0ϕ values. The negative κ0s, ϕ values for [Ln(NO3)3 with
WDRT)] at 0.00010 mol∙kg−1 TTDMM illustrate that the solvent intrin-
sic compressibility b he solute intrinsic compressibility. The most posi-
tive κ0s, ϕ value for Nd(NO3)3, while least for Gd(NO3)3 infers highest
solute-solvent interaction for Nd(NO3)3.
5.3. Viscosity (η)
The viscosity A-coefficient (Table 9) values quantitatively manifest
long-range interionic forces (electrostatic attraction) i.e. SLSLI, which
decrease when SOSLI, reflected by viscosity B-coefficient values
(Table 9), are dominating over SLSLI. The B values can be exploited for
defining the extent of solvent structuring in terms of its positive and
negative magnitude. The B values are positive for structure maker
(kosmotropes) and negative for structure breaker (chaotropes). In our
previous study, the Ln3+ due to their high CD, acted as kosmotropes

0.936
0.819 Table 12
0.702
Absorbance of DPPH

IC50 value (mg∙L−1) of TTDMM in Absence and Presence of Different Concentrations

0.585 (0.0013−0.0076 mol∙L−1) of Gd(NO3)3 Sm(NO3)3 and Nd(NO3)3 Obtained from DPPH
0.468 Free Radical Scavenging Assay.
radical

0.351
0.234 M (mol∙L−1) Gd(NO3)3 Sm(NO3)3 Nd(NO3)3
0.117 0 110.80 ± 1.32 110.80 ± 1.32 110.80 ± 1.32
0.000 0.0013 182.82 ± 2.07 171.74 ± 2.04 166.20 ± 1.78
400 450 500 550 600 650 0.0025 321.32 ± 3.12 299.16 ± 3.55 271.46 ± 3.03
wavelength (nm) 0.0038 470.90 ± 5.09 432.12 ± 5.21 393.34 ± 4.17
0.0051 598.32 ± 7.11 526.30 ± 6.03 520.76 ± 5.81
0.0063 692.50 ± 8.12 609.40 ± 7.24 603.86 ± 6.87
Fig. 6. UV–visible absorbance spectra of DPPH radical in presence of (0.00576−
0.0076 764.52 ± 9.08 714.66 ± 8.19 681.42 ± 7.53
0.06819 mol∙L−1) TTDMM.
336 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

Fig. 7. (a) Scavenging of DPPH radical by TTDMM in absence of Gd(NO3)3 ( ) and in presence of Gd(NO3)3: 0.0013 mol∙L−1 ( ),0.0025 mol∙L−1 ( ),0.0038 mol∙L−1 ( ),0.0051 mol∙L−1 ( ),
0.0063 mol∙L−1 ( ), and 0.0076 mol∙L−1 ( ) (b) Calibration curve of ascorbic acid to DPPH assay.

in aq. systems [57]. In this study, the negative B values illustrate that the
Ln3+ still acts as solvent structure maker but is not able to compensate
the solvent structure breaking effect by TTDMM. With increasing
TTDMM concentration, the solvent structure breaking effect becomes
more dominant over the kosmotropic effect by the Ln3+, with greater
negative B values. For the Ln(NO3)3, the more negative B values with
WDR than with WD (Table 9) illustrate that the structure making effect
of Ln3+ is further supressed by RB.
The more negative B values for Ln(NO3)3 with WDRT at TTDMM
b0.00020 mol∙kg−1, than with WDT and the reversed trend at TTDMM
N0.00020 mol∙kg−1 (Table 9) further supports the RB induced TTDMM
reorientation. May be, [TTDMM] = 0.00020 mol∙kg−1 is the transition
concentration where RB induces rearrangement of the TTDMM mole-
cules to decrease the surface area, thereby decreasing the hydrophobic-
ity at higher TTDMM concentrations. Thus at TTDMM N0.00020 mol∙kg−
1
, the decreased hydrophobicity induced by RB results in the dominance
of the Ln3+ induced kosmotropic effect, thus B values with WDRT N
WDT. Among the Ln(NO3)3, the least negative viscosity B-coefficient
values observed for Gd(NO3)3 in all the solvent systems is due to its
highest CD, with strongest solvent structure making ability
(kosmotropic effect).
5.4. Molar conductivity (Λm)
The decreased Λm values with increasing Ln(NO3)3 concentration
(Tables 10 and 11) is may be due to (i) increased microscopic viscosity
of the medium (ii) increased hydrodynamic radii of Ln3+ due to en-
hanced electrostatic attractions, thus retarding the Ln3+ and NO− 3 mo-
bility at lower concentrations [58], while the increased Λm values at
higher Ln(NO3)3 concentrations may be due to dominance of SLSLI
over SOSLI. With WD, a linear decrease in the Λm values with increasing
Ln(NO3)3 concentration (Figs. S9–S11) depicts that at higher Ln(NO3)3
concentrations, the SLSLI dominates over SOSLI in presence of TTDMM
and RB due to enhanced IHbI.
Due to the presence of MEG dipoles in TTDMM and the dipoles in
DMSO, the dielectric constant of WD may increase on TTDMM addition.
Similarly, inclusion of RB in WD may decrease the dielectric constant of
WD, which then may have increased on TTDMM addition. Thus, possi-
bly the dielectric constant of WDRT may have been lower than of
WDT. With increasing TTDMM concentration, the dielectric constant
of the solvent mixture further increases, but could reach a saturation
stage. Similar behaviour was also observed with amino acids and pro-
teins in water with increased dielectric constant [59]. The limiting
molar conductivity (Λ0m) values for ionic salts in molecular solvents in-
creases with an increase in the dielectric constant of the solvent. This
suggests that Ln3+ and NO− 3 are less associated in the solvent possessing
a high dielectric constant (WDT) due to independent ionic solvation
[60]. Thus, both Ln3+ and NO− 3 remain very less associated in WDT
and hence higher Λ0m values are seen in WDT, while in WDRT the ion re-
mains more associated and hence shows lower Λ0m values (Table S5).
The decreased rate of increase in the Λ0m values for Ln(NO3)3 with in-
creasing TTDMM concentration with WDT and WDRT (Fig. S12) thus

Fig. 8. Kinetics of DPPH free radical scavenging by TTDMM of different concentrations.

 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341
Development of electrostatic
interactions
Compact TTDMM arrangement
with reduced hydrophobicity
Fig. 9. RB induced reorientation of TTDMM.
validates the concept of TTDMM saturation stage attainment, wherein
the rate of increment in the dielectric constant of the solvent mixtures
saturates. The trend observed for Λ0m values for Ln(NO3)3 with all the
solvent mixtures suggests the greater predominance of dielectric con-
stant of the solvent mixtures in presence of Gd3+ due to its highest CD
over the viscosity in affecting the conductance in these solutions.
5.5. Critical aggregation concentration (CAC) of TTDMM
In case of critical micellar concentration (CMC), the micelles start to
form much above the CAC, wherein the CAC may be of several orders
magnitude below the CMC. TTDMM is a hydrophobic-branched mole-
cule because it has a trimesoyl core with malonate ester branching
units. Because of the hydrophobic nature of TTDMM, it has a tendency
to form aggregates at a very low concentration (2.41 × 10−4 M) in pres-
ence of a mixture of polar solvents like (water + DMSO). In case of CMC,
with TTDMM increasing concentration much above the CAC, its surface
coverage will increase in the solvent medium, and to minimize the sys-
tems free energy, at a particular concentration much higher than its
337
RB induced reorientation
of TTDMM
CAC, it will tend to form bulk complexes called micelles, thereby de-
creasing the surface free energy. The observed CAC of TTDMM could
be a combined effect of the dielectric constant of the medium, the hy-
drogen bonding and interacting sites present in TTDMM [61]. The de-
creased CAC values (Table S6, Fig. 3) with increasing Ln(NO3)3
concentration may be due to the increased dielectric constant of solvent.
Also, the stronger SOSLI with increasing Ln(NO3)3 concentration may
cause an earlier aggregation of TTDMM. The least CAC in presence of
Gd3+ ions may be due to the dominance of dielectric constant of the sol-
vent mixtures and development of strongest SOSLI in presence of Gd3+
due to its highest CD, than in presence of Nd3+ ions, with least CD.
Fig. 4 depicts that CAC decreases with increasing number of electrons
in the f orbital of Ln3+ for all the Ln(NO3)3 concentration. The difference
between two successive CAC on increasing Ln(NO3)3 concentration de-
creases as the number of electrons in the f orbital of Ln3+ increases. For
the highest number of electrons (f14) the impact of concentration of Ln
(NO3)3 on CAC is very less.
The decline in the absorbance of RB as depicted in Fig. 5 with in-
creasing TTDMM concentration causes the shifting of zwitterion-
338 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341

WD

H-bonding between
water and DMSO WDR
H ion-dipole interaction
HH
between water & RB
TTDMM
TTDMM WDT

ion-dipole interaction WDRT ion-dipole interaction between

between TTDMM & RB and TTDMM leading to
DMSO Ln3+
RB induced compact
Ln3+ release of water from DMSO Ln3+
TTDMM arrangement Ln3+
hydration sphere release of water less availability of water
to bulk
due engagement
by RB

less cation-π interaction

between Ln3+ and TTDMM
Vφ0 WDT > Vφ0WDRT
due to presence of RB
ion-dipole & cation-π interaction between Ln3+ forming hydration sphere with
TTDMM-Ln3+ bulk water
Ln3+hydration sphere with bulk water

O O
S DMSO H H Wa Ln3+ Gd3+/Sm3+ /Nd3+
ter

Rhodamine B TTDMM
RB

Fig. 10. Mechanistic representation of possible pathways for the intermolecular interaction of Ln(NO3)3 with different solvent systems.

lactone equilibrium effectively towards the L-form, a neutral mole-
cule contributing to much lower conductivity than the Z-form, on ad-
dition of TTDMM. This may be due to the TTDMM aggregation which
contributes to the increased hydrophobicity of the system, which re-
sulted in the shift of RB equilibrium. This phenomenon is further
confirmed by least absorption of RB at CAC (2.41 × 10−4 mol∙L−1)
at 555 nm (Fig. 5).
5.6. Antioxidant activity
1,1-diphenyl-2-picryl hydrazyl (DPPH) free radical scavenging assay
has been employed to study the antioxidant property of TTDMM be-
cause DPPH is a stable free radical source. The methanolic solution of
DPPH has a violet colour with absorption maxima at 520 nm. The
DPPH radical can easily accept an electron or proton (H+) to become a
stable diamagnetic molecule [63]. Antioxidants easily donate protons
to DPPH, which in this study is played by the donation of protons by
the MEG of TTDMM. Thus, the decrease in the DPPH absorbance peak
at 520 nm in the presence of TTDMM is a clearly indication of its antiox-
idant activity (Fig. 6). Table 12 reports the IC50 value of TTDMM in
absence and presence of different concentrations of Ln(NO3)3, wherein
it increases with increasing Ln(NO3)3 concentration, and highest inhibi-
tion in the antioxidant activity of TTDMM is observed in presence of Gd
(NO3)3. Fig. 7a illustrates the antioxidant activity of TTDMM in absence
and presence of Gd(NO3)3. It is apparent from Fig. 7a, that the free rad-
ical scavenging activity of TTDMM is suppressed with increasing Gd
(NO3)3 concentration. Interestingly, the impact of increasing Gd(NO3)3
concentration on inhibition of the scavenging activity decreases with in-
creasing TTDMM concentration, and at [TTDMM] = 0.00465 M disap-
pears. This is further reflected by the increased rate observed for the
free radical scavenging by TTDMM in presence of the chosen Gd(NO3)
3 concentrations (Fig. 7a). The decreased scavenging activity of
TTDMM in presence of Gd(NO3)3 may be due to the development of
electrostatic interaction between the Gd3+ ions and the electron rich
malonate ester groups of TTDMM. This results in the inhibition of the
electron donating activity of the malonate ester groups, thereby
inhibiting the scavenging activity. With increasing Gd(NO3)3 concentra-
tion, the extent of inhibition increases due to more number of MEG
being involved in electrostatic interaction with the Gd3+ ions. At
TTDMM concentrations below CAC (2.41 × 10−4 M), more malonate
 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341
Fig. 11. Working mechanism of Scavenging of DPPH radical by TTDMM in absence of Gd(NO3)3.
ester groups are available to interact with the Gd3+ ions, whereas with
increasing TTDMM concentration and at concentrations above the CAC,
the number of malonate ester groups which can interact with the Gd3+
ion decreases due to the development of hydrophobicity around the
TTDMM aggregates. This causes the Gd3+ ions to move away from the
electron rich malonate ester groups, and as a consequence, the impact
of Gd(NO3)3 on inhibiting the scavenging activity, decreases. At
≈[TTDMM] = 46.50 × 10−4 M, no impact of Gd(NO3)3 concentration
on the scavenging activity by TTDMM infers development of strongest
hydrophobicity around the TTDMM aggregates. Due to the develop-
ment of such robust hydrophobic environment, Gd3+ ions are able to in-
teract with the malonate ester head, and hence no impact of increasing
Gd(NO3)3 concentration is observed. Similar trend was also observed
with Sm(NO3)3 and Nd(NO3)3. Fig. 11 illustrates the working mecha-
nism of the results portrayed in Fig. 7a.
The lowest IC50 value and maximum scavenging activity (Table 12)
observed for TTDMM in absence of Ln(NO3)3 may be due to the
malonate ester head, which serves as the electron rich centre with elec-
tron donating nature, might be the source of scavenging ability. In pres-
ence of Ln(NO3)3, these electron rich sites may got engaged by Ln3+ ion
via ion-dipole interactions, which in turn results into decreased scav-
enging efficiency of TTDMM. The rate of increase in the IC50 value of
TTDMM with increasing Ln(NO3)3 concentration was found as: Gd
(NO3)3 N Sm(NO3)3 N Nd(NO3)3 (Table S7). Gd3+ due to its highest CD
interacts more strongly with the electron rich malonate ester head of
TTDMM leading to unavailability of electrons to scavenge the free
radical.
6. Conclusion
The increased V0ϕ values for Ln(NO3)3 with TTDMM found as WDT
N WDRT as ion-dipole interactions are dominant over ion-
hydrophobic interactions. The weaker SLSOI in WDRT than in WDT has
proven the role of RB induced reorientation of TTDMM. The as proposed
RB induced reorientation of TTDMM is further supported by similar
339
trend observed inK0s, ϕ. The positive K0s, ϕ for [Ln(NO3)3 with WDT/
WDRT] inferred the solvent intrinsic compressibility N the solute intrin-
sic compressibility with SLSOI for WDT N WDRT. The V0ϕ and K0s, ϕ values
are affected by CD of the Ln3+ as Gd(NO3)3 b Sm(NO3)3 b Nd(NO3)3,
which confirmed the prevalence of strongest IHI between TTDMM and
Nd3+ in the absence and presence of RB. These findings are in close
agreements with the B values where the more negative B values with
WDRT than with WDT at TTDMM b0.00020 mol∙kg−1, whereas the
trend reversed at TTDMM N0.00020 mol∙kg−1. This further supported
the RB induced TTDMM reorientation, where TTDMM =
0.00020 mol∙kg−1 is noted as the transition concentration. The more
negative B values with increasing TTDMM concentration indicated the
dominance of solvent structure breaking effect by TTDMM over the
kosmotropic effect by the Ln3+. The Gd(NO3)3 with least negative
value is due to its highest CD, displays strongest solvent structure mak-
ing ability.
The Λ0m values for Ln(NO3)3 with all the solvent systems are as Nd
(NO3)3 b Sm(NO3)3 b Gd(NO3)3, a trend similar for the viscosities sug-
gests the predominance of dielectric constant of the solvent over the
viscosity. The conductivity measurements inferred the TTDMM aggre-
gation in the solution. The CAC of TTDMM decreases with Ln(NO3)3
and their increasing concentrations as Nd(NO3)3 N Sm(NO3)3 N Gd
(NO3)3. The Gd3+ with least CAC for TTDMM may be due to dominance
of dielectric constant of the solvent and stronger SOSLI. The absorption
spectra of RB in WD in presence of TTDMM confirmed aggregation of
TTDMM in WD, established through the conversion of the Z-form to
the L-form of RB due to the increased hydrophobicity at higher
TTDMM concentrations. TTDMM in absence of Ln(NO3)3 exhibited
higher antioxidant property, with IC50 value in range of standard antiox-
idant (ascorbic acid). The Ln(NO3)3 were found to inhibit the antioxi-
dant activity of TTDMM, wherein their inhibition followed the order:
Gd(NO3)3 N Sm(NO3)3 N Nd(NO3)3. The inhibition of TTDMM antioxi-
dant activity by Ln(NO3)3 disappeared at higher TTDMM concentration
(0.00465 M). Thus, TTDMM could have a potential in the treatment of
diseases in which oxidative stress is a major component.
340 N. Vashistha et al. / Journal of Molecular Liquids 260 (2018) 323–341
Notes
The authors declare no competing financial interest.
Acknowledgments
Authors gratefully acknowledge Defence Research and Development
Organization (DRDO), Government of India (Research project No. ERIP/
ER/1203062/M/01/1586), for financial assistance. Abhishek Chandra
thanks DRDO for providing financial assistance in the form of Senior
Research Fellowship (SRF). The authors are thankful to the Central
University of Gujarat, Gandhinagar for providing infrastructure and in-
strumentation facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2018.03.056.
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