Journal of Molecular Liquids 243 (2017) 646–653

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Journal of Molecular Liquids

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

Simultaneous extraction of pesticides of different polarity applying

aqueous biphasic systems based on ionic liquids
Aleksandra Dimitrijević a, Ljubiša Ignjatović b, Aleksandar Tot c, Milan Vraneš c, Nebojša Zec c,
Slobodan Gadžurić c, Tatjana Trtić-Petrović a,⁎
a
Laboratory of Physics, Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia
b
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 16, 11000 Belgrade, Serbia
c
Faculty of Sciences, University of Novi Sad, Department of Chemistry, Biochemistry and Environmental Protection, Trg Dositeja Obradovića 3, 21000 Novi Sad, Serbia

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

Article history: In this paper we report a simultaneous one-step extraction of five pesticides (acetamiprid, imidaclopride, sima-
Received 16 June 2017 zine, linuron and tebufenozide) of different polarity using aqueous biphasic system based on 1-butyl-3(methyl or
Received in revised form 1 August 2017 ethyl) substituted imidazolium or pyrrolidinium ionic liquids with bromide or dicyanamide anion and potassium
Accepted 22 August 2017
carbonate as a salting-out agent. Experimentally data obtained for the ternary system {ionic liquid + K2CO3
Available online 24 August 2017
+ H2O} were fitted and correlated by Merchuk equation with satisfactory high correlation factor. The effect of
Keywords:
the cation alkyl chain length and the variation of anions of the ionic liquid on the aqueous biphasic system for-
Aqueous biphasic system mation and the efficiency of pesticide extraction were investigated. Complete extraction of all studied pesticides
Binding energies was obtained applying aqueous biphasic system based on 1-butyl-3-ethyl imidazolium dicyanamide. It was
Extraction shown that simultaneous extraction of the different polarity pesticides is achieved in a single-step procedure ap-
Ionic liquids plying properly tailored ionic liquids in the aqueous biphasic system formulation. In order to explain excellent
Non-covalent interactions extraction of the polar pesticides in the studied aqueous biphasic systems, molecular dynamics was applied
Pesticides and the binding energies and non-covalent interactions were calculated. It was found that 1-butyl-3-ethyl
imidazolium dicyanamide achieves the strongest interactions with the polar pesticides (acetamiprid and
imidaclopride) leading to the highest partition coefficients. It was shown that combination of experimental
and computational approach can be successfully applied for the selection and design of suitable ionic liquids
for efficient extraction of various polarity pesticides using simple aqueous biphasic ionic liquid based systems.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
It is known that current rates of agricultural production worldwide
strongly depend on the use of pesticides. The presence of pesticides in
the environment (soils, surface water, atmosphere) has been well doc-
umented [1,2]. It becomes an important environmental problem, due to
harmful effects of the pesticides on sensitive non-target organisms such
as humans and animals [3]. In order to analyze the effects of pesticides
on the environment, it is necessary to clean-up and concentrate pesti-
cides from various environmental samples. Also, industrial wastewaters
originated from pesticides production industry before releasing to the
Abbreviations: ABS, aqueous biphasic system; Ace, acetamiprid; Imi, imidacloprid; IL,
ionic liquid; IPBE, ion-pair binding energies; Lin, linuron; NCI, non-covalent interactions;
Sim, simazine; Teb, tebufenozide.
⁎ Corresponding author.
E-mail addresses: daleksandra@vinca.rs (A. Dimitrijević), ljignjatovic@ffh.bg.ac.rs
(L. Ignjatović), aleksandar.tot@dh.uns.ac.rs (A. Tot), milan.vranes@dh.uns.ac.rs
(M. Vraneš), nebojsa.zec@dh.uns.ac.rs (N. Zec), slobodan.gadzuric@dh.uns.ac.rs
(S. Gadžurić), ttrtic@vinca.rs (T. Trtić-Petrović).
receiving water streams have to be pre-treated and cleaned from resid-
ual pesticides. Different separation methods based on extraction have
been applied for both of these purposes [4,5]. Most of the conventionally
applied extraction procedures are based on utilization of the organic
solvents which are highly volatile or semivolatile at room temperature,
flammable and toxic. Additionally, polar pesticides have started to be
frequently applied and to replace the non-polar ones and they cannot
extract in significant rate using classical organic solvents.
The room-temperature ionic liquids (ILs) are favorable alternative of
organic solvents in liquid-liquid extractions, due to their distinctive
tuned properties gained by careful selection of cation and anion, negli-
gible vapor pressure and thus low flammability, broad liquidus range,
high solvation ability, high chemical and thermal stability, good extract-
ability and selectivity for organic and inorganic compounds [6,7]. Water
immiscible ionic liquids with large, highly charge-delocalized anion eas-
ily can form biphasic systems with water and have been used for liquid
phase micro-extraction of different nonpolar, hydrophobic organic
compounds [8]. These systems are useful for extraction of nonpolar pes-
ticides [9–11], but they are unuseful for the extraction of polar

http://dx.doi.org/10.1016/j.molliq.2017.08.077
0167-7322/© 2017 Elsevier B.V. All rights reserved.
 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653
compounds due to a low partition coefficient. Contrary, water miscible
ILs with small and low charge-delocalized anion are able to form aque-
ous biphasic systems (ABS) due to a salting out effect upon addition of
inorganic or organic salts, polymers, carbohydrates [12]. ABS based on
water miscible ILs are recognized as alternatives for extraction of
more polar organic compounds such as bioactive alkaloid S-(+)-
glaucine from plant material [13], 1,3-propanediol [14], estrogens [15],
pharmaceuticals [16], β-carotene [17], textile dyes [18,19] etc. Up to
now, there was only one attempt to apply formation of aqueous biphas-
ic systems based on ionic liquids for the extraction of the only one pes-
ticide (pentachlorophenol) [20].
The purpose of this work was simultaneous one-step extraction of
selected pesticides of different polarity (acetamiprid, imidaclopride, si-
mazine, linuron and tebufenozide) applying ABS based on ionic liquids.
The targeted pesticides were chosen as a model system to cover wide
range of polarity from nonpolar to polar e.g. from hydrophobic to hydro-
philic compounds. The influence of ILs cation and anion on the
partitioning and extraction efficiency of the pesticide was investigated
using the following ILs: 1-butyl-3-methylimidazolium dicyanamide,
[bmim][DCA], 1-butyl-3-ethylimidazolium dicyanamide, [beim][DCA],
1-butyl-3-ethylimidazolium bromide, [beim][Br] and 1-butyl-1-
methylpyrrolidinium dicyanamide, [bmpyr][DCA]. Additionally, molec-
ular dynamic simulations were applied to describe main interactions of
polar pesticides and the ILs in the ABSs which are important for their
successful extraction.
2. Experimental
2.1. Materials
The pesticides investigated in this work were: acetamiprid (Ace, N-
[(6-chloro-3-pyridyl)methyl]-N′-cyano-N-methyl-acetamidine),
imidacloprid (Imi, N-[1-[(6-chloro-3-pyridyl)methyl]-4,5-
dihydroimidazol-2-yl]nitramide), simazine (Sim, 6-Chloro-N,N′-diethyl-
1,3,5-triazine-2,4-diamine), linuron (Lin, 3-(3,4-dichlorophenyl)-1-
methoxy-1-methylureum), and tebufenozide (Teb, N-tert-butyl-N′-(4-
ethylbenzoyl)-3,5 dimethylbenzohydrazide). The main properties of the
selected pesticides are presented in Table 1. All pesticides (mass fraction
purity ω ≥ 95%) were purchased from Galenika-Fitofarmacija A.D.
Zemun, Serbia. Stock solutions of individual pesticides (1000 mg dm−3,
except for Sim 100 mg dm−3) were prepared in methanol and stored at
−20 °C. Aqueous solutions containing 100 mg dm−3 of each pesticide ex-
cept 10 mg dm−3 of Sim were prepared daily by diluting the stock solu-
tions with Milli-Q water. Potassium carbonate (ω ≥ 99%) and methanol
(for HPLC ω ≥ 99.9%) were supplied from Sigma Aldrich (St. Louis, MO,
USA).
The ionic liquids: [bmim][DCA] and [bmpyr][DCA] were supplied by
Iolitec GmbH (Denylingen, Germany) and Sigma Aldrich (St. Louis, MO,
Table 1
The chemical structure and the properties which influence the extraction of the selected pesticides.
Pesticide Structure
Imi
Ace
Sim
Lin
Teb
b
Calculated by ACD/Labs PhysChem program.
a
LogP in octanol/water system at pH 6 and pH 11 calculated by ACD/Labs PhysChem program.
647
USA), respectively. Other two ionic liquids, [beim][Br] and [beim][DCA],
were synthesized by the procedures published elsewhere [21]. Briefly,
the equimolar amounts of 1-ethylimidazole and 1-bromobutane were
mixed and stirred under nitrogen atmosphere for 72 h at low tempera-
ture (the mixture was cooled using the ice). Obtained [beim][Br] was
purified by liquid-liquid extraction using ethyl acetate. Ethyl acetate
was removed from the samples by heating for 45 min at 343.15 K
under the vacuum. When achieving a constant mass, the ionic liquid
was additionally dried under the vacuum for the next 72 h. For synthesis
of [beim][DCA], the equimolar amounts of [beim][Br] and sodium
dicyanamide were mixed in the acetone. Precipitated sodium bromide
was removed by filtration and obtained filtrate was dried at 343.15 K
under the vacuum. Structure of the ionic liquids and the water content
is confirmed by the NMR spectroscopy and Karl Fischer titration, respec-
tively. The provenance and purity of the applied ILs are given in Table 2.
2.2. Phase diagrams and tie-lines
The ternary phase diagrams were determined applying the cloud
point titration method at (296.15 ± 1) K and atmospheric pressure (p
= 0.1 MPa) [21–23]. The aqueous solution of K2CO3 (ωsalt = 50%) was
added drop by drop to the aqueous solution of IL (ωIL = 60%) until
the mixture become cloudy, and the amount of the added salt solution
was recorded using an analytical balance (CP224S, Sartorius) with an
uncertainty of ±10−4 g. Then, water was added into the mixture until
the mixture gets clear and the amount of added water was measured
using the analytical balance. After each addition, the mixture was shak-
en using a vortex agitator (Reax Top, Heidolph, Germany) at 2500 rpm.
This procedure was repeated until enough points for the construction of
binodal curve were obtained. The experimental data of the ternary
phase diagrams were fitted by Merchuk equation [24]:


Y ¼ Aexp BX 0:5 −CX 3 ð1Þ
where Y and X correspond to IL and salt mass fractions, respectively, and
A, B and C, are constants obtained by least-squares regression.
The tie-lines (TL) which connect two nodes on the binodal curve
were determined by a gravimetric method originally proposed by
Merchuk [24]. The solution of predetermined quantity of IL and K2CO3
was prepared, vigorously stirred for 2 min and left for at least 3 h at
296.15 K to reach equilibrium. The phases were carefully separated
and weighed. The mass fractions of IL (Y) and salt (X) in IL-rich (YIL
and XIL) and salt-rich phases (YS and XS) were calculated applying
MathCad 15.0 program [19,21] and using following equations:
h i
Y IL ¼ Aexp BX 0:5 3
IL −CX IL ð2Þ
pKaa LogPowb
11.2 0.46
0.7 1.55
1.62 2.28
12.13 3.12/3.09
10.89 4.38/3.97
648 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653

Table 2
The provenance and purity of the applied ionic liquids.

Ionic liquid Chemical structure Provenance Final mass fraction Purification method Water (ppm)

[bmim][DCA] Iolitec GmbH ω N 0.98a None 189

[bmpyr][DCA] Sigma Aldrich ω N 0.99a None 145

b
[beim][DCA] Synthesis ω N 0.96 Evaporation and drying under vacuum 98

b
[beim][Br] Synthesis ω N 0.99 Extraction and drying under vacuum 89

a
Specified by supplier.
b
Confirmed by NMR spectroscopy.

h i 2.5. Computational details

Y S ¼ Aexp BX 0:5 3
S −CX S ð3Þ
All simulations were obtained using Macro Model and Jaguar 8.5
program, as implemented in Schrödinger Material Suite 2015-1. Pre-op-
Y M 1−α
Y IL ¼ − YS ð4Þ timization of pesticides and ionic liquids were performed using Macro
α α
Model Conformation Search, using force field OPLS_3. After initial opti-
X M 1−α mization DFT geometrical optimization was performed employing
X IL ¼ − YS ð5Þ B3LYP exchange-correlation functional with empirical correction for
α α
dispersion (B3LYP-D3) together with 6–31 + G(d,p) basis set [26,27].
where subscript M denotes the mixture and α is determined mass ratio Ion-pair binding energies (IPBE) have been calculated including coun-
of the top phase and the mixture. Coefficients A, B and C were taken terpoise correction for BSSE error according to the approach by Boys
from the fitting parameters of binodal curve (Eq. 1). The tie line lengths and Bernardi [28]. Intermolecular non-covalent interactions (NCI)
(TLL) and slope of TLs (STL) were calculated using the lever arm rule [25] have been investigated using the method of Johnson et al. [29].
to determine the mass relationship between the top phase and the over-
all system composition according following equations:
3. Results and discussion
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
TLL ¼ ðY IL −Y S Þ2 þ ðX IL −X s Þ2 ð6Þ 3.1. Phase diagrams and tie-line lengths of the aqueous biphasic systems

Y IL −Y S The new phase diagrams of the ABSs based on the targeted ILs com-
STL ¼ ð7Þ
X IL −X S bined with inorganic salt (K2CO3) at (296.15 ± 1) K and atmospheric
pressure (p = 0.1 MPa) were determined in this work. The experimen-
tal binodal data for the ternary mixtures of the studied ILs are reported
2.3. Extraction of the pesticides by ABS in Table S1 in the Supporting information of this manuscript. The phase
diagrams (Fig. 1) are shown in molality units, moles of solute (IL or salt)
A ternary mixture within the biphasic region was prepared contain- per kilogram of solvent, which allow comparison of diagrams obtained
ing approximately 22% of IL, 17% of K2CO3 and 61% of the mixture of pes- for different ILs. The experimental data were fitted by empirical relation
ticides and shaken for 2 min using a vortex agitator at 2500 rpm and left of Merchuk (Eq. 1) [24] and the regression parameters for this equation
to equilibrate for 2 h. The final volume of the ternary system was 0.6 cm3 were estimated by a least-squares regression. The calculated coeffi-
with the concentration of each pesticide of 33.3 mg dm−3, except in the cients of Merchuk equation (A, B and C) for the investigated ABS, corre-
case of simazine which was 10 mg dm−3. The phases were separated sponding standard deviations (σ) and correlations coefficients (R2) are
and the concentration of the pesticides was quantified by HPLC-DAD
method.
The HPLC analysis of the samples was performed using Agilent 1100
liquid chromatograph with Zorbax XDB-C18 column (4.6 mm
× 250 mm, 3.5 μm particle size) and DAD detector at 220 nm (Sim
and Teb), 254 nm (Ace and Lin) and 270 nm (Imi). The flow rate was
0.7 cm3 min−1 and an aliquot of 20 μL of the sample was injected into
HPLC system. The mobile phase was a mixture of methanol (A) and de-
ionized water (B) and the following gradient profile was run: 0.0 min
43% A and 57% B, then 7 min 70% A and 30% B, and 20 min the initial
composition. The system was controlled by the Chemstation software.

2.4. Partition coefficient and extraction efficiency

Partition coefficients of the pesticides in ABS based on ILs (PIL) were

calculated as the ratio of the equilibrium concentration of the pesticides
in the IL-rich and in the salt-rich phases. The extraction efficiency (E)
was defined as the fraction of the initial amount of the pesticides
which was extracted into the IL-rich phase.
The dissociation constants, pKa, and n-octanol – water partition coef-
Fig. 1. Ternary phase diagrams of the studied {IL + K2CO3 + H2O} systems at T = 296.15 K
ficients, Po/w, were calculated using the computer software ACD/Labs
and atmospheric pressure (p = 0.1 MPa). Legend: [beim][DCA], [bmpyr][DCA], ■
PhysChem Suite v12 (Advanced Chemistry Development Inc.). [bmim][DCA], [beim][Br].
 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653 649

Table 3
Experimental tie-lines data as mass fraction for the ternary system composed of {IL(Y)
+ K2CO3(X) + H2O} ABS at 296.15 K and pressure p = 0.1 MPa.

IL Total IL-rich phase Salt-rich 100 TLL Slope

composition phase

100 X 100 Y 100 X 100 Y 100 X 100 Y

[bmim][DCA] 17.08 22.48 1.30 57.45 27.08 0.29 62.71 −2.22

[bmpyr][DCA] 17.16 22.29 0.83 57.04 27.62 0.02 62.99 −2.13
[beim][DCA] 16.99 22.66 0.56 58.76 27.23 0.02 60.01 −2.32
[beim][Br] 16.69 23.76 5.27 42.09 28.06 5.51 43.10 −1.60

given in Table S2 in the Supporting information of this manuscript. The

high values of the regression parameters (R2 ≥ 0.9949) and low values of
the standard deviations prove that Merchuk equation is suitable to fit
the experimental data. The biphasic region is localized on the right
side of binodal curves in all phase diagrams. The effect of cation on abil-
ity of the targeted ILs with the same anion to form ABS follows the
order: [beim][DCA] ~ [bmpyr][DCA] N [bmim][DCA]. Similar as we Fig. 3. Partition coefficient of the targeted pesticides in the ABSs based on ILs: (blue)
shown in our previous paper [19] IL with ethyl group in the imidazolium [bmim][DCA], (orange) [beim][DCA], (olive) [beim][Br] and (purple) [bmpyrr][DCA].
ion has higher ability to form ABS comparing to IL with the methyl Experimental conditions: 22% of IL, 17% of K2CO3, total volume of ABS 0.6 cm3,
temperature (296.15 ± 1) K. The error bars represent the standard deviation of the
group at the same position, due to higher hydrophobicity of the cation
experimental results.
and lower affinity for water molecules. The ability of [beim][DCA] to
form ABS is slightly higher than [bmpyr][DCA]. Also, Fig. 1 shows that
[beim][DCA] has better ability to form ABS than [beim][Br] due to a
lower affinity of DCA to bound hydrogen ion comparing to bromide ion. and K2CO3 are approximately equal for all investigated systems (Fig. S1
In order to compare extraction ability of the investigated ABS based in the Supporting information of this manuscript). The parameters of
on the selected ILs, TLs were determined so that the concentrations of IL TLs such as total composition, IL-rich and salt-rich phases, TLL and

Fig. 2. Chromatograms of IL-rich (up) and salt-rich (down) phases after extraction of the selected pesticides in the ABS based on following ILs: (a) [bmim][DCA]; (b) [bmpyrr][DCA]; (c)
[beim][DCA] and (d) [beim][Br].
650 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653
Fig. 4. Partition coefficient of the selected pesticides in {[beim][Br] + K2CO3 + H2O} ABS at
296.15 K, with 22% of [beim][Br] and different mass fraction of salt: (cyan) 14% of K2CO3,
(violet) 17% of K2CO3 and (blue) 21% of K2CO3. The error bars represent the standard
deviation of the experimental results.
slope are given in Table 3. TLs were chosen so that IL was dominantly
presented in IL-rich phase, for example ABS based on [bmpyr][DCA]
and [beim][DCA] mass fraction of IL in salt-rich phase is negligible
(0.02%). Higher mass fraction of IL in salt-rich phase was found for
ABS based on [beim][Br] due to poorer ability of this IL to form ABS.
3.2. Extraction of the pesticides
Five pesticides of different polarity and chemical classes (Imi and
Ace are neonicotinoid insecticides; Sim is triazine herbicide; Lin is
phenylurea herbicide and Teb is diacylhydrazine insecticide) were se-
lected for extraction using ABS based on the studied ILs. The main prop-
erties of the pesticides are shown in Table 1. The chosen pesticides cover
wide range of polarity from nonpolar to polar e.g. from hydrophobic to
hydrophilic compounds. In order to compare extraction of the pesti-
cides applying ABS based on ILs with classical liquid-liquid extraction
based on immiscible liquids, the properties of the pesticides such as dis-
sociation constants (given as logKa) and n-octanol/water distribution
coefficients (express as logPo/w) which may influence the extraction,
were calculated using the computer software ACD/Labs PhysChem
Suite v12. Distribution coefficient were calculate at two pH values, at
pH = 6 which is usually pH of laboratory and tap water, and at pH =
11 which is pH of the applying ABS based on the ILs and K2CO3. The
slightly negative influence of pH on logPo/w was observed for Lin and
Teb at pH = 11 due to their dissociation constants which are close to
this pH. Based on the values of logPo/w, the pesticides can be divided
into three groups: polar (Imi) with LogPo/w ˂ 1, medium polar (Ace)
with 1 ˂ LogPo/w ˂ 2 and low polar pesticides with log Po/w N 2 (Sim,
Lin and Teb).
The capability of the selected ILs [bmim][DCA], [beim][DCA],
[beim][Br] and [bmpyrr][DCA] to extract pesticides of different polarity
Table 4
The experimentally determined partition coefficients in the investigated ABSs based on the studied ILs.
Pesticide LogPIL
[bmim][DCA] [beim][DCA] [bmpyr][DCA]
Imi 2.36 ∞ 2.84
Ace 2.54 ∞ 2.55
Sim 2.85 ∞ 2.86
Lin 3.07 ∞ 3.15
Teb ∞ ∞ ∞ 2.63
a
[11].
in ABS with K2CO3 as salting-out agent were studied. The ILs are chosen
to allow investigation of effect of cation on extraction of the pesticides
such as [bmim]+ and [bmpyrr]+ or effect of alkyl group in imidazolium
ring ([bmim]+ and [beim]+). Also, the influence of anion of the ILs
(dicyanamide or bromide) on the extraction of the pesticides was
studied.
In regard to a working solution of the pesticides in this study con-
tents 50% of methanol, the influence of methanol on building ABS
based on IL was examined (Fig. S2). [beim][Br] was chosen for this
study due to the lowest capability to build ABS comparing to other ILs
applied in this work. Methanol was added in aqueous solution of IL
and K2CO3 so that the concentration was fixed at 16% of methanol. Fig.
S2 shows that with addition of methanol decrease the quantity of
K2CO3 which is necessary for ABS formation. Also Gutowski et al. [30]
described extraction of methanol in ABS based on [bmim][Cl] and
K3PO4 with partition coefficient ranging from 4 to 12 at TLL from 43 to
83. Based on these results, methanol has a favorable influence on build-
ing ABS (higher biphasic region) and its co-extraction with pesticides in
IL-rich phase should be expected.
Extraction of the targeted pesticides was performed at the point
marked in Fig. S1 which corresponds to 22% of IL, 17% of K2CO3 and
61% of the pesticide mixture. This composition of ABS was chosen in re-
gard to the properties of all investigated ABS. Namely, Fig. S1 shows that
for all studied ABSs based on the targeted ILs and K2CO3, the content of
22% of IL and 17% of K2CO3 guarantied formation of biphasic system and
IL will be dominantly presented in IL-rich phase. The mixture of all com-
ponents was stirring for 2 min, and left to phase separation for 3 h. IL-
rich and salt-rich phases were separated and the pesticides were quan-
tified by HPLC in both phases (Fig. 2). Fig. 2 shows that after extraction
of the selected pesticides in the investigated ABS, all pesticides were
dominantly presented in IL-rich phase. In order to check possible inter-
ference of pesticides and ILs in HPLC analysis, chromatograms of
[beim][DCA] and the pesticides mixture were shown in Fig. S3 in
Supporting information file of this manuscript. The retention time of
the IL was about 2.5 min and no interference with the ionic liquid was
observed during the quantification of the targeted pesticides using
HPLC. The similar chromatograms and retention times of other investi-
gated ILs were obtained.
The partition coefficients of the targeted pesticides in the ABS con-
taining the studied ILs, K2CO3 and water are depicted in Fig. 3. All exper-
iments were performed in triplicate and the mean concentrations were
used for further calculation. It should be noted that when the complete
extraction was reached (no detection of pesticides in the salt-rich
phase) then PIL equals ∞ [18]. The results show that highest values of
PIL were obtained in the ABS based on [beim][DCA], and four out of
five studied pesticides were completely extracted in IL-rich phase.
Partition coefficients higher than 200 were obtained for the ABSs
based on [bmim][DCA] and [bmpyrr][DCA]. Lower partition coeffi-
cients for all targeted pesticides except Teb were obtained in ABS
based on [beim][Br] due to significantly higher quantity of this IL
presented in the salt-rich phase at applied ratio of IL and K2CO3. It
is clear that extraction of the pesticides is achieved in a single-step
procedure by a proper tailoring of the ionic liquid applied in the
ABS formulation.
[beim][Br] [hmim][NTf2]a [hmim][NTf2] + K2CO3
1.65 1.58 1.55
1.79 1.60 1.56
1.81 – 2.05
1.88 3.25 3.08
4.60 ∞
 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653
Table 5
Calculated binding energies (Ebin) and number of the non-covalent interactions between the studied pesticides and ILs.
Pesticides [bmim][DCA] [beim][DCA]
Ebin (kJ·mol−1)
Imi −50.61 −85.36
Ace −57.04 −129.66
Number of non-covalent interactions
Imi 9 10
Ace 8 13
In order to enhance partitioning of the selected pesticides in ABS
based on [beim][Br], the effect of increasing the salt mass fraction was
investigated and presented in Fig. 4. With increasing the salt concentra-
tion, the partition coefficients of the pesticides significantly increase. It
should be noted that at the concentration of 21% K2CO3, the partition co-
efficients are still lower than the partition coefficient obtained in ABS
based on [beim][DCA] and 17% of K2CO3.
The comparison of determined logPIL for the targeted pesticides is
given in Table 4. Table 4 also contents experimentally obtained
distribution coefficient in the two-phase extraction system based
on previously published water immiscible ILs [11]. The polar and
medium polar compound (Imi and Ace) show significantly higher
partitioning in the ABSs based on the studied ILs comparing to n-
octanol/water system and liquid-liquid extraction based on water
immiscible IL. Low polar pesticides (Lin and Teb) exhibit the similar
partitioning in the ABS as in both classical liquid-liquid extraction
systems based on n-octanol or water immiscible IL ([hmim][NTf2])
as extractant. In order to investigate the influence of salt addition
on partition of the pesticides in the extraction system with
[hmim][NTf2], the extraction was performed under the same condi-
tions as in the ABS: 22% of [hmim][NTf2] and 17% of K2CO3. The ob-
tained results of logP of the studied pesticides (Table 3) show that
the addition of salt in this extraction system has no influence on
partitioning of the pesticides.
Fig. S4 in the Supporting information file of this manuscript shows
the effect of ILs on the extraction efficiency of the investigated pesticides
under the same extraction conditions (22% of IL and 17% of K2CO3). The
complete extraction (E = 100%) was not achieved only for partition co-
efficient lower than 100.
The obtained results in Table 4 show similar trend of increasing
logPIL for the targeted pesticides with increasing logPo/w, e.g. more hy-
drophobic pesticides are extracted easier from aqueous phase than
more hydrophilic pesticides. Compounds with low values of logPo/w
(Ace and Imi) were extracted quantitatively in ABS based on
[beim][DCA] (logPIL = ∞), while their logPIL in the ABS based on other
targeted ILs were significantly lower. It should be emphasized that
ABS based on the studied IL, especially [beim][DCA], completely extract-
ed both hydrophilic and hydrophobic pesticides in one-step. These re-
sults imply that one-step extraction applying ABS based on the
selected ILs can be successfully applied for easy and fast removal of var-
ious polarity pesticides (from highly hydrophilic to hydrophobic) either
from natural samples in order to quantify them or from manufacturing
waste waters in order to purify them. The recovery of the used ILs will
be the subject of future research due to very low quantity of IL which
used in these studies.
To explain extraction of the polar pesticides in the ABSs, the relation-
ship between pesticide's polarity, ionic liquid ability to form ABS and ex-
traction efficiency, the binding energies and non-covalent interactions
(NCI) between pesticides and ILs were calculated and presented in
Table 5. It is clear that [beim][DCA] achieves the strongest interactions
with Imi and Ace, which is certainly one of the reasons for their efficient
extraction from the aqueous media. However, structurally similar ionic
liquid [bmim][DCA], with the only difference of one\\CH2 group in the
alkyl substituent of the imidazolium ring, has significantly lower logPIL
value. This can be explained from the calculated % of the hydrophilic
651
[bmpyr][DCA] [beim][Br] [hmim][NTf2]
−46.23 −28.33 −51.35
−52.04 −29.59 −55.23
20 14 15
10 14 14
surface of the pesticide molecules before and upon addition of IL
(Table 6).
If the ionic liquid efficiently binds to the hydrophilic surface of the
pesticide, its extraction from an aqueous medium will be facilitated. In
the case of Ace and Imi, both molecules have in their structure the p-
substituted chloropyridil group which is linked to the rest of the mole-
cule through benzylic carbon atom. This carbon is sp3 hybridized and
prevents complete delocalization of the π-electrons, separating thus dif-
ferent delocalized systems of the molecule (Fig. S5 in the Supporting in-
formation of this manuscript). In the case of Imi, the benzylic carbon is
associated through imidazolidine ring and the imino group with highly
polar NO− 2 group, while in the structure of Ace benzylic carbon is con-
nected to nitrilo group through the amino and imino groups. These
groups are the most hydrophilic parts of two pesticides. The second cen-
ter of the hydrophilicity of both molecules is Cl and N atoms of
chloropyridyl group.
From Figs. 5(b and c) and 6(b and c) it can be seen that ethyl group
from [beim]+ forms NCI with nitrilo group in Ace and with NO− 2 group
in Imi, but also with N and Cl from chloropyrydil group in both mole-
cules. In contrast, [bmim]+ cation (Figs. 5d and 6d) does not form any
NCI with N and Cl in the case of Ace, and only one interaction with N
in the case of Imi. Such interactions of hydrophobic alkyl substituents
with chloropyridyl group reduce the ILs hydrophilicity and provide
greater extraction ability of [beim]+ based ionic liquids.
From the quantitative values of hydrophilic area presented in Table
5, it can be observed that in the case of [beim][DCA] after addition of
Imi and Ace, the percentage of the available hydrophilic area is equal
to zero, while in the case of [bmim][DCA] approximately 1% of hydro-
philic area remains available. However, if DCA anion is replaced with
Br−, the extraction efficiency using [beim]+ based ionic liquid signifi-
cantly decreases, although [beim]+ in the case of both pesticides
forms NCI with Cl and N atoms of the chloropyridyl group. Also, it is ev-
ident from Table 4 that percentage of the hydrophilic area upon addition
of [beim][Br] remains almost the same in the case of Ace, or slightly in-
creases in the case of Imi compared to pure pesticides, resulting in the
low logPIL values. Similarly, the substitution of DCA with Br− ion de-
creases the value of binding energy (Table 4), indicating that the extrac-
tion efficiency of hydrophilic molecules from water strongly depends on
the choice of both, cation and anion of the IL. It confirms that values ob-
tained by DFT calculations (binding energy and the percentage of avail-
able hydrophilic area) can be used as a guidelines for the choice of ionic
liquids in the purpose of extraction.
4. Conclusions
1-Butyl-3(methyl or ethyl) substituted imidazolium or
pyrrolidinium based ionic liquids with bromide and dicyanamide
Table 6
Calculated hydrophilic surface area (%) of two pesticides (Imi and Ace) with or without ad-
dition of the ILs.
Pesticides without IL added [bmim][DCA] [beim][DCA] [beim][Br]
Imi 6.20 1.71 0 8.95
Ace 7.55 1.28 0 7.48
652 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653

Fig. 5. Non-covalent interactions of: a) Ace; b) [beim][Br] + Ace; c) [beim][DCA] + Ace; d) [bmim][DCA] + Ace; e) [bmpyr][DCA] + Ace; f) [hmim][NTf2] + Ace.

anions suitable for ABS formation were applied for simultaneous extrac- [beim][DCA] ~ [bmpyr][DCA] N [bmim][DCA]. Ionic liquids with ethyl
tion of five pesticides of different polarity. The effect of cation on ability group in the imidazolium ion have higher ability to form ABS, due to a
of the targeted ILs with the same anion to form ABS follows the order: higher hydrophobicity of the cation and lower affinity for water

Fig. 6. Non-covalent interactions of: a) Imi; b) [beim][Br] + Imi; c) [beim][DCA] + Imi; d) [bmim][DCA] + Imi; e) [bmpyr][DCA] + Imi; f) [hmim][NTf2] + Imi.
 A. Dimitrijević et al. / Journal of Molecular Liquids 243 (2017) 646–653
molecules. The results of the pesticides extraction in the studies ABSs
show that highest values of partition coefficient were obtained in the
ABS based on [beim][DCA]. The low and medium polar compound
(Imi, Ace and Sim) show significantly higher partitioning in the ABSs
based on the studied ILs comparing to n-octanol/water system and liq-
uid-liquid extraction based on water immiscible IL. Low polar pesticides
(Lin and Teb) exhibit the similar partitioning in the ABS as in both clas-
sical liquid-liquid extraction systems based on n-octanol or water im-
miscible IL as extractant. Also, the binding energies and non-covalent
interactions between studied pesticides and ILs were calculated apply-
ing DFT approach. The main interaction between ILs and the polar pes-
ticides which lead to their complete extraction were explained based on
molecular simulation results. This study shows that ABS based on prop-
erly selected ILs give excellent opportunity for one-step simultaneous
extraction of various polarity pesticides. It was also presented that com-
putational approach together with the experimental results can be effi-
ciently applied for the selection of suitable ionic liquids for efficient
extraction of polar pesticides which can be extended to other
compounds.
Funding
This work was supported by the Ministry of Education, Science and
Technological Development of Serbia under project contracts III 45006
and ON 172012.
The authors have declared no conflict of interest.
Acknowledgements
The authors would like to acknowledge the contribution of the COST
Action CM1206 – Exchange on Ionic Liquids.
Conflicts of interest
None.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.molliq.2017.08.077.
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