Journal of Molecular Liquids 215 (2016) 534–540

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Journal of Molecular Liquids

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

Properties and thermal behavior of natural deep eutectic solvents

R. Craveiro a, I. Aroso b,c, V. Flammia a, T. Carvalho a, M.T. Viciosa d, M. Dionísio a, S. Barreiros a, R.L. Reis b,c,
A.R.C. Duarte b,c, A. Paiva a,⁎
a
LAQV—REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
b
3B's Research Group — Biomaterials, Biodegradable and Biomimetic, University of Minho, Headquarters of the European Institute of Excellence on Tissue Engineering and Regenerative Medicine,
Avepark, Barco, 4805-017 Guimarães, Portugal
c
ICVS/3B's PT Government Associated Laboratory, Braga/Guimarães, Portugal
d
Centro de Química-Física Molecular and IN — Institute of Nanoscience and Nanotechnology, Instituto Superior Técnico, Univ. Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

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

Article history: Natural deep eutectic solvents (NADES) have shown to be promising sustainable media for a wide range of
Received 7 August 2015 applications. Nonetheless, very limited data is available on the properties of these solvents. A more compre-
Accepted 11 January 2016 hensive body of data on NADES is required for a deeper understanding of these solvents at molecular level,
Available online 26 January 2016
which will undoubtedly foster the development of new applications. NADES based on choline chloride, organic
acids, amino acids and sugars were prepared, and their density, thermal behavior, conductivity and polarity
Keywords:
Deep eutectic solvents
were assessed, for different NADES compositions. The NADES studied can be stable up to 170 °C, depending on
Physical properties their composition. The thermal characterization revealed that all the NADES are glass formers and some,
Choline chloride after water removal, exhibit crystallinity. The morphological characterization of the crystallizable materials
Thermal analysis was performed using polarized optical microscopy which also provided evidence of homogeneity/phase
Conductivity separation. The conductivity of the NADES was also assessed from 0 to 40 °C. The more polar, organic acid-
based NADES presented the highest conductivities. The conductivity dependence on temperature was well
described by the Vogel–Fulcher–Tammann equation for some of the NADES studied.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction deep eutectic solvents (NADES), based on primary metabolites, such

as organic acids, amino acids, and sugars [3]. Paiva and co-workers
Green technology requires new solvents to replace common organic have recently reported on the cytotoxicity of different NADES, showing
media that present inherent toxicity and have high volatility. Over the that it is much lower than that of commonly used imidazolium-based
past two decades, ionic liquids (ILs) have attracted great attention ILs [4]. Radošević et al. have also studied three ChCl-based DES and sug-
from the scientific community, and the number of articles focusing on gested that they can be classified as readily biodegradable presenting
ILs has grown exponentially. ILs are molten salts, liquid at room temper- low to moderate toxicity [5]. These characteristics have led to growing
ature, whose potential relies on the possibility to tune their properties interest in the research community in replacing ILs with DES, as solvents
through the combination of different cations and anions [1]. Never- for biocatalysis [6,7], extraction [8] and chemical conversion [9] of
theless the “green” character of ILs is often questioned, mainly due to organic compounds, and polymer synthesis. As regards polymer pro-
their poor biodegradability, biocompatibility and sustainability. cessing, DES have been shown to dissolve bioactive materials and bio-
Deep Eutectic solvents (DES) are obtained upon mixing two com- polymers [2]. Bioactive DES with active pharmaceutical ingredients
pounds in such a ratio that the resulting substance has a significantly (APIs), such as ibuprofen [10], can be incorporated in biopolymers
lower melting point than that of each individual component [2]. The through the doping of the biopolymer matrix.
most common DES are based on choline chloride (ChCl), carboxylic A more detailed characterization of DES can lead to further scientific
acids and other hydrogen-bond donors, such as urea, citric acid, succinic developments. Dai et al. have characterized some NADES by nuclear
acid, and glycerol. DES may have similar characteristics to ILs, such as magnetic resonance (NMR) spectroscopy and concluded that water
low vapor pressure, but are cheaper to produce, both due to the lower played an important role in NADES formation [3]. In the case of the
cost of the required raw materials and the simplicity of the synthesis. NADES composed by 1,2-propanediol, ChCl and water, the authors ob-
Furthermore, they are less toxic and often biodegradable [3]. Recently served a strong interaction between the hydroxyl groups of all species.
Dai and co-workers have reported on a large number of stable natural In addition, Dai and co-workers also determined the thermal and phys-
ical characteristics of some of NADES with water in its composition [3].
⁎ Corresponding author. Florindo et al. also reported on the strong influence of water on
E-mail address: [email protected] (A. Paiva). the properties of ChCl:carboxylic acid-based DES [11]. The thermal

http://dx.doi.org/10.1016/j.molliq.2016.01.038
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 R. Craveiro et al. / Journal of Molecular Liquids 215 (2016) 534–540 535

properties of DES were also presented by those authors, with special at- To assess the thermal behavior of the NADES, calorimetric experi-
tention to the glass transition temperature (Tg) and decomposition tem- ments were carried out with a DSC Q2000 from TA Instruments Inc.
perature (Td). Rengstl and co-workers have recently reported on the (Tzero™ DSC Technology) operating in the Heat Flow T4P option [13].
thermal behavior of DES based on different choline ILs [12]. Measurements were performed under dry high purity helium, at a
Following the work of Dai et al. [3], we prepared NADES composed of flow rate of 50 mL∙min−1. Less than 5 mg of each sample were encap-
different sugars, organic acids and ChCl, in the ratios reported and ac- sulated in Tzero aluminum pans. The set was not hermetically sealed
cording to the procedures described by those authors. We measured a to allow free water evaporation. At least two scans at cooling and
number of properties of these NADES. We also used polarized optical heating rates of 20 °C ∙min−1 were performed, covering the tempera-
microscopy measurements coupled with differential scanning calorim- ture range from −90 °C to 120 °C. Each sample was kept for one addi-
etry analysis to better understand the thermal behavior of NADES, tional minute at 120 °C at the end of the scan, to ensure water
e.g., the influence of water on the glass transition and melting tempera- removal. Also each sample was kept for 10 min at −90 °C in order to ob-
ture. Density, polarity and conductivity measurements were also tain a better signal of the glass transition temperature, when present.
performed.
ChCl can form NADES with almost any kind of primary metabolites 2.4. Polarized optical microscopy measurements
and has been used to prepare most of the DES reported in the literature.
Therefore ChCl is present in most of the NADES we selected for our Polarized optical microscopy was performed on an Olympus Bx51
study. In addition, three sugar based NADES are also studied in this optical microscope equipped with a Linkam LTS360 liquid nitrogen-
work. cooled cryostage. The microstructure of the samples was monitored
by taking microphotographs at appropriate temperatures, using an
2. Material and methods Olympus C5060 wide zoom camera. A drop of each sample was posi-
tioned on a microscope slide and inserted in the hot stage. Before each
2.1. Materials measurement, the samples were heated to 120 °C and kept at least
10 min at this temperature to allow water removal; after this thermal
Choline chloride (ChCl) (N 98% purity, CAS number 67-48-1), D-(+)- treatment a cover slip was placed on the top of the sample. Cooling
xylose (99% purity, CAS number 58-86-6), citric acid monohydrate (CAS and heating thermal treatments were carried out at a rate of
number 5949-29-1), D-(+)-glucose (99% purity, CAS number 50-99-7), 20 °C ∙ min− 1.
Nile red (N98% purity, CAS number 7385-67-3), and Hydranal Coulomat
AG were obtained from Sigma-Aldrich. D-(+)-sucrose (98% purity, CAS 2.5. Water content determination
number 57-50-1) were obtained from Fluka. L-(+)-tartaric acid (N99%
purity, CAS number 87-69-4) was obtained from Fisher scientific. All The water content of the NADES was determined after drying under
chemicals were used without further purification. vacuum for 24 h upon preparation. A 831 KF Coulometer with generator
electrode and without diaphragm was used. The water content values
2.2. Preparation of NADES given are an average of at least three measurements.

NADES were prepared according to Table 1. Weighed amounts of 2.6. Density measurements
each component, as required to achieve the molar ratios indicated in
the table, were dissolved in water. The two solutions were mixed, and The density of the NADES was measured following a simple gravi-
water was removed in a rotary evaporator at 50 °C under vacuum, metric procedure, using a calibrated volume at 23 °C.
until a clear viscous liquid was obtained. NADES were then kept under
vacuum for 24 h, after which they were stored in a desiccator. 2.7. Conductivity measurements

2.3. Differential scanning calorimetry analysis (DSC) The conductivity of the different NADES was assessed by dielectric
relaxation spectroscopy (DRS). For the DRS measurements, samples
To determine the degradation temperature of the NADES (Td), ex- were placed between two stainless steel electrodes (10 mm diameter)
periments were performed using a DSC Q100 equipment (TA Instru- in a BDS 1200 parallel plate capacitor, using two 50 μm silicon spacers
ments — ELNOR). The experiments were conducted under a nitrogen to maintain sample thickness. The sample cell was mounted on a BDS
atmosphere, with samples of 5–10 mg packed in aluminum pans. The 1100 cryostat, and exposed to a gas stream resulting from the evapora-
samples were heated at a constant heating rate of 20 °C min−1, from tion of liquid nitrogen in a Dewar. Temperature control was ensured by
−40 °C up to 250 °C. The results presented are the average of at least a Quatro Cryosystem controller and performed to within ± 0.5 °C (all
three measurements. modules supplied by Novocontrol). Measurements were carried out

Table 1
NADES prepared in this study, respective abbreviations and water content.

NADES Water content Density

Mole ratio Sample name
Component 1 Component 2 /wt.% /g∙mL−1

Choline chloride D-(+)-glucose 1:1 ChCl:gluc (1:1) 5.5 1.27

Choline chloride Citric acid 1:1 ChCl:ca (1:1) 0.2 1.30
Choline chloride D-(+)-sucrose 4:1 ChCl:suc (4:1) 0.2 1.22
Choline chloride D-(+)-sucrose 1:1 ChCl:suc (1:1) 0.2 1.35
Choline chloride L-(+)-tartaric acid 2:1 ChCl:ta (2:1) 1.9 1.26
Choline chloride D-(+)-xylose 2:1 ChCl:xyl (2:1) 3.8 1.23
Choline chloride D-(+)-xylose 3:1 ChCl:xyl (3:1) 0.2 1.22
Citric acid D-(+)-sucrose 1:1 ca:suc (1:1) 1.2 1.43
Citric acid D-(+)-glucose 1:1 ca:gluc (1:1) 0.5 1.45
D-(+)-glucose L-(+)-tartaric acid 1:1 gluc:ta (1:1) 0.4 1.46
536 R. Craveiro et al. / Journal of Molecular Liquids 215 (2016) 534–540

using an Alpha-N analyzer also from Novocontrol, covering a frequency the effect of water in the glass transition, water was added to the
range from 10− 1 Hz to 1 MHz. After a first cooling ramp from room ChCl:xyl (2:1) NADES. As can be observed in Table 3, up to 5 wt.% of
temperature to 0 °C, isothermal spectra were collected from 0 °C to water added Tg decreases about 4 °C, thus confirming the plasticizing ef-
40 °C, in steps of 5 °C. fect of water in NADES.
Table 3 also shows the effect of water on Tm of the NADES. NADES are
2.8. Polarity measurements obtained by the complexation of a hydrogen-bond acceptor and a
hydrogen-bond donor. Therefore, water will have a significant influence
Polarity measurements were carried out using Nile red as on the complex, altering the properties of the NADES and interfering in
solvatochromic probe. A stock solution was prepared by dissolving the liquidus and solidus lines of the eutectic phase diagram. As for
1 g ∙ L−1 of Nile red in ethanol, and stored at 4 °C. The NADES sample ChCl:xyl (2:1), with the addition of water only one thermal event corre-
was placed in a 1 cm2 quartz cuvette, and a blank was recorded. After sponding to melting is observed. At 4 wt.% water added to the NADES,
that 50–100 μL of Nile red stock solution were added to the NADES sam- Tm suffers a depression of 1 °C, while at higher water contents the oppo-
ple. The cuvette was placed under a gentle high-purity nitrogen gas site effect occurs and an increase in the melting temperature is ob-
stream to evaporate the solvent, and the UV spectra were immediately served. In fact, Dai and co-workers observed a strong interaction
acquired, at 23 °C. Spectra of Nile red solutions with different amounts between the hydroxyl groups of water and the hydroxyl groups of xy-
of water were also recorded in order to study the influence of the lose and choline, and with the chloride anion [3]. The destabilization
water amount on the wavelength of maximum absorbance (λmax) of of the supramolecular structure of NADES by water increases the mobil-
Nile red. ity of both components of the NADES, which translates into a decrease
in Tg. This agrees with Dai et al. who reported a Tg of − 81.8 °C for
3. Results and discussion ChCl:xyl (2:1) with 7.74% water content. The impact of the water con-
tent on Tg observed for NADES is not observed with the pure compo-
3.1. Thermal characterization and polarized light microscopy (POM) nents, for which almost no variation occurs in the respective Tg
(Table 2). E.g. after the addition of 12.8 wt.% water to glucose, only a
The thermal stability of NADES was evaluated by DSC up to 250 °C. small change in Tg occurs.
All NADES present a single degradation peak at temperatures above For gluc:ta (1:1), illustrated in Fig. 1 (a), and most of the NADES
ca. 120 °C (decomposition temperatures presented in Table 2). DSC studied, the glass transition is the only thermal event detected
was further used to probe thermally induced transformations over sev- (Table 2). Polarized optical microscopy (POM) was also used to observe
eral scans; the individual components of the NADES were also analyzed. the phase transformations detected by DSC. Fig. 1 (a) includes a micro-
For all the NADES studied in the present work, a discontinuity in the photograph taken by POM at 0 °C. It illustrates the micro-cracks that
heat flux is observed at lower temperatures in the first scan, due to the emerged on heating at −57 °C (well below the Tg), covering all the sam-
glass transition. This is a second order transition, with no latent heat as- ple. Observation of the cracks confirms the vitreous state of the sample,
sociated, and in DSC it appears as a step transition. It corresponds to a as reported for amorphous polymers [15]. The cracks start to disappear
change in the structure of the material from a glass-like state to a when the sample is further heated slightly above the glass transition,
rubber-like state, or vice-versa, reflected in a jump in heat capacity. giving rise to a homogeneous dark image, characteristic of the super-
The detection of a glass transition from which a glass transition temper- cooled and isotropic liquid.
ature (Tg) value can be determined allows us to classify all the NADES The ca:gluc (1:1) NADES has a different behavior, exhibiting two
tested as glass formers; this is also true for all the pure components, glass transitions (Fig. 1 (b)). This suggests that two glasses were formed
with the exception of ChCl. In most cases, Tg was lowest in the first on cooling. The phase separation is clearly shown in the POM micro-
scan, and shifted to higher temperatures in following scans, until it be- graphs of Fig. 1 (b), where two phases are observed in both the vitreous
came constant. This effect can be attributed to water evaporation. The state and supercooled state. Nevertheless, cracks only emerge in one of
glass transition temperature decreases upon hydration due to a plasti- the sample phases in the sub-glass region. The microphotograph taken
cizing effect of water, as already observed [14]. In order to determine by POM near −55 °C, a temperature below the two calorimetric glass
transitions, reveals the coexistence of two different glasses by the ob-
Table 2 servation of micro-cracks that only emerge in a definite region of the
Thermal properties obtained from DSC data for the NADES under study, namely degrada- sample (inset of Fig. 1 (b)). Crack formation was also detected by DSC
tion temperature (Td), melt and cold crystallization temperatures (Tc,melt and Tc,cold), melt- through a sharp discontinuity in the heat flux near − 50 °C, deep in
ing temperature (Tm), and the temperature of the onset of the glass transition (Tg),
obtained in the last DSC cycle.
the glassy state (blue line in Fig. 1 (b)). A similar behavior was found
for other low molecular weight glass formers [16,17]. The two domains
Td Tc,melt Tc,cold Tm Tg are still observed at a temperature above the two glass transitions de-
NADES
/°C /°C /°C /°C /°C
tected by DSC, evidencing that phase separation persists when the
ChCl:gluc (1:1) 129.8 – – −28.4 whole sample is in the supercooled liquid state.
ChCl:ca (1:1) 171.3 −9.7 76.0 −21.4
In the case of ChCl:ca (1:1), ChCl:suc (4:1), ChCl:xyl (2:1) and
ChCl:suc (4:1) 141.7 −33.9 51.8 79.2 −42.0
ChCl:suc (1:1) 126.8 – – −15.8 ChCl:xyl (3:1), a more complex thermal behavior is observed. In addi-
ChCl:ta (2:1) 130.8 – – −41.6 tion to the glass transition, these NADES exhibit exo and endothermic
ChCl:xyl (3:1) 165.2 20.1 59.9 78.5 −46.4 event peaks due to crystallization and melting. Upon thermal treatment
ChCl:xyl (2:1) 172.7 – 56.9 78.3 −51.2 to 120 °C, ChCl:ca (1:1) undergoes partial crystallization on cooling
ca:suc (1:1) 121.2 – – −14.0
ca:gluc (1:1) 130.1 – – 9.8/48.7a
gluc:ta (1:1) 117.5 – – −18.3
Glucose −39.2b/−37.0c Table 3
Sucrose −39.1b Influence of the amount of water on the Tg and Tm values, measured by DSC. Data for
Xylose −43.8b ChCl:xyl (2:1) NADES.
Citric acid 64.2 −38.2
Water content (wt.%) Tg first scan (°C) Tm (°C)
Tartaric acid −40.1b
Choline chloride 46.5–33.2 90.8 – 2.2 −58.5 77.1
a 3.8 −59.1 76.2
Two Tg values are observed in the thermogram for this sample.
b 5.0 −61.3 77.0
The flux discontinuity across the glass transition is ill-defined.
c 7.74 [3] −81.8 [3] –
Sample with 12.8 wt.% of water.
 R. Craveiro et al. / Journal of Molecular Liquids 215 (2016) 534–540 537

Fig. 1. (a) Thermogram obtained at 20 °C min−1 for gluc:ta (1:1). The microphotograph included was taken by POM at 0 °C during a heating cycle. (b) Thermogram obtained at 20 °C min−1
for ca:gluc (1:1). The microphotographs included were taken by POM at −70 °C during a cooling cycle (top left), and at 95 °C during a heating cycle (bottom right). Cooling and heating
rates of 20 °C min−1. Degree of magnification of POM microphotographs: 40×.

from the liquid state, which is called melt crystallization [13], and the containing ChCl exhibit both melt and cold crystallizations, and these
respective melting is observed in the following heating scan. On the processes occur at temperatures quite different than for pure ChCl.
other hand, ChCl:xyl (2:1) fails to crystallize on cooling, but crystallizes The differences found for the crystallization phenomenon vs. melting
upon heating from the glass, i.e., it exhibits cold-crystallization. This is a are not completely unexpected since while melting is purely thermody-
type of crystallization undergone by an amorphous material upon namic in nature, crystallization is also controlled by kinetic factors that
reheating above its glass transition [13]. Fig. 2 illustrates all the phase influence nuclei formation and crystal growth [18]. Using transmitted
transformations for ChCl:xyl (3:1). Interestingly, ChCl:suc (4:1) and light microscopy with cross polarizers, it is possible to obtain informa-
ChCl:xyl (3:1) undergo both melt and cold crystallizations, in addition tion on the isotropy of the NADES at different experimental conditions.
to the glass transition.
The temperatures of melting and crystallization, in the cases where 3.2. Density
such processes were observed, are given in Table 2. All the NADES that
undergo crystallization present a sharp endothermic melting peak at All the NADES have densities over 20% higher than that of water,
temperatures close to 80 °C. Only the NADES with ChCl in their compo- NADES containing ChCl having comparatively lower densities, as
sition exhibit crystallization. This can be an indication that the compo- shown in Table 2.
nent that determines crystallization is ChCl. Pure ChCl melts between
85.2 °C and 90.8 °C, meaning that mixing with the second component 3.3. Conductivity
influences melting by slightly decreasing Tm. The effect is more dramatic
in the case of crystallization. For pure ChCl, only melt crystallization is The NADES were studied over a range of temperatures and frequen-
observed between 46.5 and 33.2 °C. On the other hand, NADES cies by dielectric relaxation spectroscopy (DRS) which, for a sample
under the influence of an oscillating electrical field, mainly probes
reorientational movements of dipoles and propagation of mobile charge
carriers. The migration of charge carriers is due to translational diffusion
through hopping movements of electrons, holes and ions, giving rise to
conductivity. The conductivity of each sample was measured from
10−1 Hz to 106 Hz, in a range of temperatures from 0 to 40 °C, in steps
of 5 °C. The property under measurement is the complex dielectric
function, ε*:
0
ε
ðωÞ ¼ ε ðωÞ  iε ″ ðωÞ ð1Þ

where Ω is the angular frequency. The real part of ε* is related with

energy stored by the system, while the imaginary part accounts for the
energy dissipated inside the material. Ω is given by:

ω ¼ 2πf ð2Þ

where f is the frequency of the outer electrical field. One of the

alternative representations of the dielectric response is the complex
conductivity, σ⁎ [19]:

σ
ðωÞ ¼ iωε0 ε
ðωÞ ð3Þ

Fig. 2. Thermogram obtained at 20 °C∙min−1 for ChCl:xyl (3:1) after water removal at
100 °C. The microphotographs included were taken by POM at −10 °C during a cooling
cycle (top left), and at 30 °C during a heating cycle (bottom right). Cooling and heating where ε0 is the vacuum permittivity. Since the propagation of mobile
rates of 10 °C min−1. Degree of magnification of POM microphotographs: 40×. charge carriers also contributes to the complex function, it can be
538 R. Craveiro et al. / Journal of Molecular Liquids 215 (2016) 534–540

Table 4
Fitting parameters obtained by applying the VFT equation (Eq. 5).

σ∞ B T0
NADES
/S∙cm−1 /K /K

ChCl:xyl (3:1) 1063 ± 812 1107 ± 301 136 ± 2

ca:suc (1:1) 556 ± 333 1556 ± 223 127 ± 1
ca:gluc (1:1) 1.3 ± 0.7 397 ± 84 227 ± 6

NOTE: The uncertainties are the statistical errors given by the fitting program. For each
material, the similarity between B and T0 estimated through σdc (T) indicates a parallelism
between these two quantities.

An important feature in the σ′(ν) plot, where ν is the frequency of

the applied oscillating electrical field, is the occurrence of a plateau, as
shown in Fig. 3 for ca:suc (1:1).
This plateau gives σdc, the direct conductivity. At lower tem-
peratures, or higher frequencies, the conductivity becomes frequency
dependent and the σ′(ν) plot presents a pronounced increase. The con-
ductivities of the NADES studied, are an average of the values at the
plateau. ChCl:suc (1:1) and ChCl:suc (4:1) were found to exhibit the
highest conductivities with values of 1.35 S∙cm−1 and 1.28 S ∙cm−1 at
Fig. 3. Conductivity as a function of frequency for the sample ca:suc (1:1). 25 °C respectively. The conductivities of these two NADES are of
the same order of magnitude as those of some ionic liquids (e.g.
[BMIM][BF4] has a conductivity of 3.55 S∙cm−1 at room temperature)
advantageous to analyze the dielectric response through the complex [21]. All other NADES have conductivities of at least one order of magni-
conductivity function: tude lower (see supplementary material) and the amplitude of the var-
iation of σdc is relatively small within the studied temperature range.
0 However for the NADES ca:suc (1:1), ca:gluc (1:1) and ChCl:xyl
σ
ðωÞ ¼ σ ðωÞ þ iσ ″ ðωÞ ð4Þ
(3:1) it is possible to simulate the temperature dependence of the direct
conductivity by the Vogel–Fulcher–Tammann (VFT) equation. The VFT
Conductivity data can elucidate the charge transport mechanism of equation usually describes the temperature dependence of the relaxa-
the material [19]. In the present study, the analysis was based mainly tion time associated with the dynamic glass transition, but it was
on the real part of the conductivity, which has a universal behavior for found to describe quite well σdc (1/T) for a variety of materials, in-
a variety of disordered conductive materials, exhibiting a plateau at cluding ionic liquids [18,22,23]. The VFT equation was fitted to σdc
the lowest frequencies and highest temperatures. At this plateau, the (1/T), according to:
conductivity is frequency independent and by extrapolating to Ω → 0,
the dc conductivity, σdc, can be determined. At higher frequencies, the  
TT
B
conductivity bends off into a frequency dependent regime, with a pro- σ dc ¼ σ ∞ ∙ exp 0
ð5Þ
nounced increase of the conductivity with increasing frequency [20].
Conductivity data were taken from this plateau for each isotherm,
i.e., a set of very similar data points were extracted from the plateau, where B is an empirical parameter accounting for the plot curvature,
for which an average value along with respective standard deviation σ∞ is the high temperature limit of the conductivity, and T0 is the Vogel
were calculated. temperature at which the conductivity goes to zero. When the VFT
equation is used to simulate the glassy dynamics relaxation time, T0 is
interpreted as the glass transition temperature of an ideal glass, i.e., a
glass obtained with an infinitely slow cooling rate [24]. The fitting is rep-
resented in Fig. 4 as solid lines, evidencing that the temperature depen-
dence of the conductivity is adequately described by the VFT equation.
The VFT fitting parameters are given in Table 4.

Fig. 4. Temperature dependence of the pure conductivity, σdc, of NADES. • ChCl:xyl (3:1),
✮ ca:suc (1:1), ✰ ca:gluc (1:1). The solid lines were obtained by fitting with the VFT Fig. 5. ENR values obtained for NADES in this study. The [BMIM][BF4] IL was included in the
equation. study for comparison.
 R. Craveiro et al. / Journal of Molecular Liquids 215 (2016) 534–540 539

slightly higher polarity of gluc:ta (1:1) relative to gluc:ca (1:1) can be

due to its shorter alkyl chain length. Also, tartaric acid is a stronger
acid (pKa = 2.98) than citric acid (pKa = 3.14). As expected, a higher
proportion of organic acid brings about an increase in polarity.
Another factor that needs to be taken into account is the water con-
tent of the sample. Dai and co-workers have shown the influence of the
amount of water of the NADES on their polarity [3]. In this work, to ac-
count for that effect, measurements with Nile red solutions with differ-
ent amounts of water from 0.1% to 15% were performed. A bathocromic
shift is visible, since increasing water content shifts λmax to higher
wavelengths. The deviation of Nile red's λmax was under 1.2% and the
changes in ENR values are small (Fig. 6).
Lower ENR values imply higher polarity. The same is observed in
Table 5 for the case of ChCl:xyl (2:1) and ChCl:ca (1:1), where the var-
iation of water content results in small variations in the ENR value. Nev-
ertheless, these small changes in the ENR values can alter the relative
polarity scale, meaning that the control of the water content in these
Fig. 6. Effect of the amount of water on λmax of Nile red.
NADES is of extreme importance.
Dai and co-workers have reported an ENR value of 49.72 kcal mol−1
The fact that the VFT equation gives an adequate representation of for the NADES with 7.74 wt.% water already referred. In Table 5, it can be
the experimental data can be taken as an indication that the ion observed that increasing the water content increases the polarity of the
conducting motions are governed by the glassy dynamics, as found for NADES. A decrease in water content of about 4 wt.% results in an in-
related systems [18,22,23]. The comparison between the Vogel temper- crease of ca. 0.9 kcal∙mol−1 in the ENR value.
ature and the glass transition temperature gives the same variation, i.e., This trend was also observed and reported for 1,2-
the highest T0 values are found for ca:suc (1:1) and ca:glu (1:1), while propanediol:ChCl:water (1:1:1) NADES [3]. The authors of that
the lowest value is found for ChCl:xyl (3:1); the Tg values observe the study suggested that the dilution of the NADES (up to water content
same order for NADES. This seems to corroborate the coupling between of 50%) caused a dramatic change in the structure of the NADES, due
the charge transport mechanism and the structural relaxation associat- to the rupture of the hydrogen bonding network formed between the
ed with the dynamic glass transition. two components. A careful control of the water content is necessary
when polarity measurements are being performed, and also its effect
3.4. Polarity in the overall relative polarity scale can be dependent on the NADES
composition.
The polarity of the NADES under study was measured with the
solvatochromic dye Nile red, which has been used for weak acids and
4. Conclusions
protic molecular solvents [25] and ILs [26].
For each sample λmax was determined, and the related parameter
In this work we present a study of the thermophysical properties of
ENR was calculated, using the following equation [27]:
different NADES. The determination of properties such as density, vis-
cosity, thermal behavior, polarity, and conductivity are essential for a
ENR ¼ 28; 591=λ max ð6Þ
better understanding of these solvents and for unveiling potential appli-
cations of what is now considered to be the new generation of ILs. Un-
with ENR in kcal mol−1 and λmax in nm.
derstanding the mechanisms leading to NADES formation is essential
Solvents with higher polarity shift λmax of the dye to higher
for the production of tailor-made NADES. The knowledge of thermo-
wavelength values, yielding lower ENR values, according to Eq. (6). By
physical data is essential for further developments in modeling and mo-
measuring changes in λmax of Nile red relative to the value it exhibits
lecular simulation, which will undoubtedly provide new cues on the
in a reference solvent, it is possible to calculate the relative polarity of
possible combinations of compounds to prepare NADES with specific
the solvent of interest [28]. Fig. 5 gives the polarity of the NADES stud-
properties.
ied. The polarity of the [BMIM][BF4] IL was included for the sake of
comparison.
According to Eq. (6), our experimental value of ENR for [BMIM][BF4] Acknowledgments
yields a λmax of 556.0 nm, which differs by less than 1% from the value
reported in the literature [26]. Our data indicates that NADES composed Rita Craveiro, Tânia Carvalho and Alexandre Paiva are grateful for
of ChCl and organic acids are more polar than those combining ChCl the financial support from Fundação para a Ciência e a Tecnologia
with a sugar, in agreement with results previously reported [3]. The (FCT/MEC) through the grants PTDC/EQUEPR/12191/2010/ENIGMA,
SFRH/BD/47088/2008 and SFRH / BPD / 44946 / 2008. We further ac-
knowledge the financial support of FCT/MEC through the project
Table 5
Influence of the water content of ChCl:xyl (2:1) and ChCl:ca (1:1) on λmax and ENR of Nile
ENIGMA — PTDC/EQU-EPR/121491/2010, and the project PEst-C/
red value. EQB/LA0006/2013 and FCOMP-01-0124-FEDER-020646. We also ac-
knowledge the funding from the European Union Seventh Frame-
NADES Water content λmax ENR
work Programme (FP7/2007–2013) under grant agreement no.
(wt.%) (nm) (kcal mol−1)
REGPOT-CT2012-316331-POLARIS, and from the Project “Novel
2.2 563 50,78
smart and biomimetic materials for innovative regenerative medi-
3.8 564 50,69
ChCl:xyl (2:1)
6.0 570 50,16 cine approaches (Ref.: RL1 — ABMR — NORTE-01-0124-FEDER-
7.74 [3] – 49.72 [3] 000016)” co-financed by the North Portugal Regional Operational
4.8 592 48.30 Programme (ON.2 — O Novo Norte), under the National Strategic
ChCl:ca (1:1) 5.2 596 47.94 Reference Framework (NSRF), through the European Regional De-
5.9 597 47.89
velopment Fund (ERDF).
540 R. Craveiro et al. / Journal of Molecular Liquids 215 (2016) 534–540

Appendix A. Supplementary data [14] B. Carvalho, T.,. Augusto, V.,. Brás, A.R.,. Lourenço, N.M.T.,. Afonso, C.A.M.,. Barreiros,
S.,. Correia, N.T.,. Vidinha, P.,. Cabrita, E.J.,. Dias, C.J.,. Dionísio, M.,. Roling, T.
Carvalho, V. Augusto, a.R. Brás, N.M.T. Lourenço, C.a.M. Afonso, et al., Understanding
Supplementary data to this article can be found online at http://dx. the ion jelly conductivity mechanism, J. Phys. Chem. B 116 (2012) 2664–2676,
doi.org/10.1016/j.molliq.2016.01.038. http://dx.doi.org/10.1021/jp2108768.
[15] R. Ramani, G. Shariff, Influence of gamma irradiation on the formation of methanol
induced micro-cracks in polycarbonate, J. Mater.Sci. 8 (2003) 1431–1438.
References [16] V. Legrand, M. Descamps, C. Alba-Simionesco, Glass-forming meta-toluidine: a ther-
mal and structural analysis of its crystalline polymorphism and devitrification,
[1] C. Chiappe, D. Pieraccini, Ionic liquids: solvent properties and organic reactivity, J. Thermochim. Acta 307 (1997) 77–83, http://dx.doi.org/10.1016/S0040-
Phys. Org. Chem. 18 (2005) 275–297, http://dx.doi.org/10.1002/poc.863. 6031(97)00271-2.
[2] M. Zdanowicz, T. Spychaj, Ionic liquids as starch plasticizers or solvents, Polimery 56 [17] E. Dudognon, F. Danède, M. Descamps, N.T. Correia, Evidence for a new crystalline
(2011) 861–864. phase of racemic ibuprofen, Pharm. Res. 25 (2008) 2853–2858, http://dx.doi.org/
[3] Y. Dai, J. van Spronsen, G.-J. Witkamp, R. Verpoorte, Y.H. Choi, Natural deep eutectic 10.1007/s11095-008-9655-7.
solvents as new potential media for green technology, Anal. Chim. Acta 766 (2013) [18] J.J. Diogo, H.P.;.M. Ramos, Are the crystallization and the melting the reverse of each
61–68, http://dx.doi.org/10.1016/j.aca.2012.12.019. other? J. Chem. Educ. 83 (2006) 1389–1392.
[4] A. Paiva, R. Craveiro, I. Aroso, M. Martins, R.L. Reis, A.R.C. Duarte, et al., Natural deep [19] A. Kremer, F. Schönals, Broadband dielectric spectroscopy, in: A. Kremer, F. Schönals
eutectic solvents — solvents for the 21st century, Sustain. Chem. Eng. (2014)http:// (Eds.), Broadband Dielectr, Spectrosc., Springer Verlag, Berlin, 2003.
dx.doi.org/10.1021/sc500096j (ASAP). [20] C.J. Bowlas, D.W. Bruceb, K.R. Seddon, Liquid-crystalline ionic liquids, Chem.
[5] K. Rado, M. Cvjetko, D. Grgas, T. Landeka, I. Radoj, Ecotoxicology and environmental Commun. (Camb.) (1996) 1625–1626.
safety evaluation of toxicity and biodegradability of choline chloride based deep eu- [21] X. Fu, Polymer Electrolytes, Elsevier, 2010http://dx.doi.org/10.1533/
tectic solvents, 112 (2015) 46–53, http://dx.doi.org/10.1016/j.ecoenv.2014.09.034. 9781845699772.2.471.
[6] H. Zhao, G.a. Baker, S. Holmes, New eutectic ionic liquids for lipase activation and [22] J.R. Sangoro, C. Iacob, A. Serghei, C. Friedrich, F. Kremer, Universal scaling of charge
enzymatic preparation of biodiesel, Org. Biomol. Chem. 9 (2011) 1908–1916, transport in glass-forming ionic liquids, Phys. Chem. Chem. Phys. 11 (2009)
http://dx.doi.org/10.1039/c0ob01011a. 913–916, http://dx.doi.org/10.1039/b816106b.
[7] D. Carriazo, M.C. Serrano, M.C. Gutiérrez, M.L. Ferrer, F. del Monte, Deep-eutectic sol- [23] J. Leys, M. Wübbenhorst, C. Preethy Menon, R. Rajesh, J. Thoen, C. Glorieux, et al.,
vents playing multiple roles in the synthesis of polymers and related materials, Temperature dependence of the electrical conductivity of imidazolium ionic liquids,
Chem. Soc. Rev. 41 (2012) 4996–5014, http://dx.doi.org/10.1039/c2cs15353j. J. Chem. Phys. 128 (2008) 064509, http://dx.doi.org/10.1063/1.2827462.
[8] P.S. Kulkarni, L.C. Branco, J.G. Crespo, M.C. Nunes, A. Raymundo, C.a.M. Afonso, Com- [24] J.F. Mano, M. Dionísio, Handbook of Thermal Analysis and Calorimetry, Elsevier,
parison of physicochemical properties of new ionic liquids based on imidazolium, 2008.
quaternary ammonium, and guanidinium cations, Chemistry 13 (2007) [25] W. Ogihara, T. Aoyama, H. Ohno, Polarity measurement for ionic liquids containing
8478–8488, http://dx.doi.org/10.1002/chem.200700965. dissociable protons, Chem. Lett. 33 (2004) 1414–1415.
[9] S. Gore, S. Baskaran, B. Koenig, Efficient synthesis of 3,4-dihydropyrimidin-2-ones in [26] A.J. Carmichael, K.R. Seddon, Polarity study of some 1-alkyl-3-methylimidazolium
low melting tartaric acid–urea mixtures, Green Chem. 13 (2011) 1009–1013, http:// ambient-temperature ionic liquids with the solvatochromic dye, Nile Red, J. Phys.
dx.doi.org/10.1039/c1gc00009h. Org. Chem. 13 (2000) 591–595, http://dx.doi.org/10.1002/1099-1395(200010)13:
[10] S. Tuntarawongsa, T. Phaechamud, Polymeric eutectic drug delivery system, J. Met. 10b591::AID-POC305N3.0.CO;2-2.
Mater. Miner. 22 (2012) 27–32. [27] P.G. Jessop, D.a. Jessop, D. Fu, L. Phan, Solvatochromic parameters for solvents of in-
[11] C. Florindo, F.S. Oliveira, L.P.N. Rebelo, A.M. Fernandes, I.M. Marrucho, Insights into terest in green chemistry, Green Chem. 14 (2012) 1245, http://dx.doi.org/10.1039/
the synthesis and properties of deep eutectic solvents based on cholinium chloride c2gc16670d.
and carboxylic acids, ACS Sustain. Chem. Eng. 2 (2014) 2416–2425, http://dx.doi. [28] Y. Chen, Y. Cao, X. Lu, C. Zhao, C. Yan, T. Mu, Water sorption in protic ionic liquids:
org/10.1021/sc500439w. correlation between hygroscopicity and polarity, New J. Chem. 37 (2013) 1959,
[12] D. Rengstl, V. Fischer, W. Kunz, Low-melting mixtures based on choline ionic liquids, http://dx.doi.org/10.1039/c3nj00213f.
Phys. Chem. Chem. Phys. 16 (2014) 22815–22822, http://dx.doi.org/10.1039/
C4CP02860K.
[13] M., R.B. Prime, Thermal Analysis of Polymers, Fundamentals and Applications, Hobo-
ken, New Jersey, 2009.