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Preparation of menthol-based hydrophobic deep

Cite this: Analyst, 2021, 146, 1996
eutectic solvents for the extraction of
triphenylmethane dyes: quantitative properties
and extraction mechanism†
Taotao Fan, Zongcheng Yan, Chanyuan Yang, Shunguo Qiu, Xiong Peng,
Jianwei Zhang, Lihua Hu and Li Chen*

Received 17th September 2020,
Accepted 29th December 2020
DOI: 10.1039/d0an01864c
rsc.li/analyst
A series of natural, environmentally friendly and low-cost menthol-based hydrophobic deep eutectic sol-
vents (DES) were synthesized to extract and concentrate solutes from dilute aqueous solutions, especially
triphenylmethane (TPM) dye micropollutants. The system has excellent extraction performance for TPM.
Density functional theory (DFT) and molecular dynamics (MD) simulation were used to quantitatively
analyze the effect of the DES composition and TPM structure on the distribution of target molecules in
two phases. The solvation free energy of ethyl violet (EV) in DES (−17.128 to −21.681 kcal mol−1) is much
larger than that in water (−0.411 kcal mol−1), and increases with the increase of the HBD chain length,
which is proportional to the extraction rate, indicating that the TPM molecules are more inclined to the
DES environment, especially long-chain DES, than aqueous solution. For the same C12DES, the extraction
efficiency of the TPM dyes follows the order: ethyl violet (EV) (99.9%) > crystal violet (CV) (99.6%) >
methyl violet (MV) (98.8%). EV has the smallest positive charge and the smallest dipole moment (9.109 D),
and the Flory–Huggins parameters of EV (χEV–C12DES 0.053) relative to MV and CV are the smallest in
C12DES, and are also the largest in water (χEV–H2O 0.053), indicating that EV has the largest polarity differ-
ence with H2O and is more easily detached from water and compatible with the long-chain DES phase.
The motion of EV and MV on the phase interface of DES and water was calculated to further analyze from
the molecular level. At the same time, EV tends to move into the DES phase. In summary, the excellent
extraction ability of DES for TPM is verified through experiments and simulations, providing solid theore-
tical support in terms of separation in other fields.

1. Introduction pharmaceuticals and pesticides are all classified as micropol-

At present, the problem of environmental pollution in modern
society is becoming increasingly serious.1 Micropollutants are
new types of pollutants. Although their concentrations are very
low, from ng L−1 to mg L−1, they are almost toxic and difficult
to degrade. After entering the environment, they have direct or
indirect harmful effects on the growth of organisms.2 In par-
ticular, the chemical properties of certain micro-pollutants are
extremely stable. And these micro-pollutants diffuse and
accumulate in the organism through the food chain, and even-
tually lead to chronic tissue poisoning, endocrine destruction
and antibiotic resistance in the biont.3 Dyes, heavy metals,
School of Chemistry and Chemical Engineering, South China University of
Technology, Guangzhou 510640, China. E-mail: celichen@scut.edu.cn;
Fax: +86-20-87111109; Tel: +86-20-87111109
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d0an01864c
lutants.4 A triphenylmethane dye, the third largest dye
after the azo dye and onion ketone dye, is a polyphenyl
ring compound and used extensively in large amounts.
Triphenylmethane (TPM) dyes are widely used in textile, print-
ing and dyeing, leather processing, and ink industries, and in
light industries such as paper, toys and food.5 According to
reports, about 5%−10% of the dyes in the printing and dyeing
industry are discharged into the wastewater due to problems
in the efficiency of the process.6 The dyes themselves and the
intermediates that are formed during their degradation
process can have serious toxic effects on aquatic organisms
and humans. For example, TPM enters the cells through
charge interaction and accumulates in the cytoplasm leading
to the risk of carcinogenesis and mutagenesis.7 Therefore, tri-
phenylmethane dyes need timely content monitoring and
degradation treatment. If the wastewater from the above indus-
tries is discharged directly into the environment without treat-
ment, it will pose a serious threat to the aquatic ecosystem and

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human health. Due to their large dispersion and trace concen-
tration in the environment, the pretreatment process of enrich-
ment of triphenylmethane dyes is particularly important.8
Methods for enriching micropollutants are constantly evol-
ving. The most commonly used techniques include ultrasonic
extraction (USE),9 solid phase extraction (SPE),10,11 Soxhlet
extraction (SOX),12 semi-permeable membrane dynamic
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sampling (SPMD),13 supercritical fluid extraction (SFE),12 micro-
wave extraction (MWE),2,14 etc. However, these methods
consume a large amount of organic reagents, causing secondary
pollution to the environment, and some operations are cumber-
some and time-consuming, and some require expensive instru-
ments. At the same time, these methods are limited in practical
applications due to their own shortcomings and low dye removal
efficiency. Especially in the dye industry, it is currently discour-
aged to use various conventional physical chemistry and biologi-
cal treatment technologies. Liquid–liquid extraction (LLE) has
been considered as an effective technique for dye separation.15,16
In addition, with the increasing attention to green and sustain-
able technologies, it has gradually been realized that traditional
organic solvents require longer extraction time and their higher
toxicity hinders the development of related applications.17
However, the DES/water two-phase systems for constructing
liquid–liquid microextraction have the characteristics of high
biocompatibility, mild separation environment, low cost and
easy operation with broad application prospects, and have
attracted more attention in various fields.18,19
In recent years, deep eutectic solvents (DESs), first proposed
by Abbott et al., also known as low temperature transition mix-
tures (LTTM), are analogues and alternative solvents to tra-
ditional ionic liquids and are considered as a new type of
green solvent.20,21 DESs have been widely used in the fields of
material synthesis,22 catalysis,23 organic synthesis24 and
electrochemistry.20 DES is a new chemical entity formed by the
interaction of hydrogen bond donor (HBD) and hydrogen
bond acceptor (HBA) through hydrogen bonding, and its
melting point is lower than that of the initial compound.25 At
present, it is not clear how much the melting point of the
initial compound needs to decrease for the mixture to be a
DES. However, most researchers believe that the melting point
of the DES formed by mixing the initial compounds needs to
be below a certain threshold (such as room temperature).26
Compared with traditional organic solvents or ionic liquids,
DESs have many more unique characteristics, such as low tox-
icity, environmental friendliness, low cost of raw materials,
easy manufacturing and biodegradability.27,28 Therefore, the
environmental advantages of DESs provide an excellent plat-
form for green separation.29 DESs can be used as separation
media for the extraction of natural biologically active com-
pounds,30 fuel recoveries19 and purifications of proteins,21
DNA and RNA.31 However, most DESs are currently hydrophilic
and unstable in the water environment, causing the com-
ponents to separate from each other.30 Therefore, it is very
important to search for a new type of hydrophobic DES system.
In recent years, Hadjmohammadi’s group reported that
borneol and decanoic acid can be used to prepare hydrophobic
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DES for the extraction of warfarin from biological samples.30
Kroon et al. also proposed hydrophobic DES based on lido-
caine and decanoic acid for the removal of alkali and tran-
sition metal ions from water.32
In this work, we further develop and understand the behav-
ior of hydrophobic DES in water, so that it can be used to
extract and concentrate solutes from dilute aqueous solutions,
especially triphenylmethane dyes. Therefore, hydrophobic DL-
menthol based DESs are selected as the research target, in
which menthol is used as HBA, and carboxylic acids with
different alkyl chain lengths are used as HBD. In addition,
three typical representative organic molecules with the same
molecular skeleton, methyl violet (MV), crystal violet (CV), and
ethyl violet (EV) with different numbers of methyl groups on
the nitrogen atom, are selected as the target to evaluate the
extraction performance of the system. Subsequently, the effect
of variant hydrogen-bonded donors (HBD) with different
carbon chain lengths is systematically investigated on the
extraction efficiency. The extraction time, temperature, concen-
tration of dyes and ionic strength are comprehensively evalu-
ated in the influence factor experiments. However, the mecha-
nism by which DES can be extracted is not yet clear, so simu-
lation calculations are used for theoretical analysis. Density
functional theory is used to calculate the charge distribution
and dipole distance of the three dye molecules, and kinetic
theory is used to calculate the solvation free energy in DES and
H2O. The Flory–Huggins parameters are calculated by the solu-
bility parameter to analyze the compatibility between the
solute and solvents, and the selectivity of menthol-based DES
to TPM dyes is verified by molecular dynamics simulation.
2. Experimental section
2.1. Chemicals and apparatus
Methyl violet (indicator level, pH0.1–2.0), crystal violet (AR,
≥90.0%), ethyl violet (AR), (1R,2S,5R)-(−)menthol (99.0%),
acetate (99.5%), butyric acid (99%), hexanoic acid (98%),
n-octanoic acid (99%), decanoic acid (99%), lauric acid (98%)
and NaCl (99.5%) were purchased from Aladdin Reagent Co.,
Ltd. All reagents are analytical reagent grade and can be used
directly without further purification. Milli-Q water was
employed throughout the experiments.
A Bruker AVANCE 400 nuclear magnetic instrument was
used for H NMR. 30 mg DES sample and 0.5 ml deuterated
chloroform (CDCl3) were added to a 5 mm NMR tube, and
then the component solvent was homogenized by vortex
mixing. A QYC200 incubator shaker (Shanghai, China) was
used to shake the sample uniformly and isothermally for
extraction experiments. A Shimadzu UV2450 UV-vis spectro-
photometer was employed to measure UV absorption for
detecting sample concentration.
2.2 Preparation of DESs
(1R,2S,5R)-(−)-Menthol was selected as HBA, and acetic acid,
butyric acid, hexanoic acid, n-octanoic acid, capric acid and
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lauric acid were selected as HBD. First of all, menthol needs to
be dried in a vacuum at 313 K before use. All DESs were pre-
pared by mixing HBA and HBD in a round-bottomed flask with
magnetic stirring at 333.15 K until the solid disappeared and a
uniform colorless liquid with a viscous appearance formed. The
ratio of DES components prepared in this paper is as follows:
(−)-menthol : acetate (1 : 1), (−)-menthol : butyric acid (1 : 1),
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(−)-menthol : hexanoic acid (1 : 1), (−)-menthol : n-octanoic acid
(1 : 1), (−)-menthol : capric acid (1 : 1), and (−)-menthol : lauric
acid (1 : 1) (as shown in Fig. 1). The spectrums obtained by
NMR detection of six kinds of DES are shown in Fig. S1,† and
the results prove that DES prepared by design are correct.
2.3 Extraction experiments
The prepared hydrophobic DESs were subjected to the liquid–
liquid extraction experiment on triphenylmethane dyes. First,
different triphenylmethane dye aqueous solutions were pre-
pared in advance, and the corresponding standard curves were
measured for each dye.33 As shown in Fig. 2, the linear
regression equations for MV, CV, and EV were Y = 0.141X +
0.008 (R2 = 0.999, λmax = 585 nm), Y = 0.192X − 0.002 (R2 =
0.999, λmax = 590 nm), and Y = 0.176X − 0.003 (R2 = 0.999, λmax
= 595 nm), respectively.
The extraction experiment steps were as follows (Scheme 1).
First, triphenylmethane dye aqueous solution was added to a
10 mL centrifuge tube, and then the prepared hydrophobic
DES was instilled in the above solution. Afterwards, the tube
was shaken vigorously at 25 °C for 2 h, and left for 24 h to
make sure that the two phases were completely separated.
Subsequently, when phase equilibrium was reached, the top
Fig. 1 Chemical structures and corresponding abbreviations of the components of the DES prepared in this study.
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layer (DES-rich phase) and the bottom layer (water-rich phase)
were carefully separated using a syringe, and the concentration
of the triphenylmethane dye was measured using a UV-vis
spectrophotometer. Due to the very high dye content in the
DES-rich phase, a mass of dilution was required for UV-vis
analysis, and the presence of DES also affects the determi-
nation of the dye peak intensity. In order to eliminate possible
interference, the water-rich phase was analyzed directly
because it only contains a small quantity of triphenylmethane
dye, so its characteristic peak can be easily tracked.
The formula for the calculation of the extraction efficiency
(EE%) of the dye is as follows: where CIC and CEC were the
initial concentration and equilibrium concentration of the dye
before and after extraction in the water-rich phase,
respectively.
CIC  CEC
%EE ¼ ð1Þ
CIC
2.4 Simulation
The chemical structures of all the studied molecules were
drawn using Material Studio software and geometrically opti-
mized through the Dmol3 module.34,35 The generalized gradi-
ent approximation (GGA) function with the BLYP method was
used as an exchange–correlation function to perform spin-
unrestricted DFT calculations, and all electrons were included
in the nuclear processing, and the convergence criteria for the
tolerance of self-consistent field (SCF), energy, maximum
force, and maximum displacement are 1.0 × 10−6 Ha, 1.0 ×
10−5 Ha, 0.002 Ha Å−1, and 0.005 Å in the geometric optimiz-
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Fig. 2 Standard curves of (A) methyl violet (MV), (B) crystal violet (CV), and (C) ethyl violet (EV), and (D) corresponding UV-vis spectra and chemical
structure.

Scheme 1 Schematic diagram of the liquid–liquid extraction of TPM dyes by various deep eutectic solvents/H2O two-phase system.

ation simulation, respectively. The frequency, electron density
and electrostatics of optimized structures were further calcu-
lated to determine the stability and the charge distribution of
the molecular structure.
The Amorphous Cell Tool module was used to build a
series of amorphous three-dimensional periodic cells, and the
simulation cells contain various dye molecules and DES mole-
cules. Ab initio COMPASSII force field was chosen to perform
geometric optimization with ultra-fine-precision by the Forcite
Module 50 000 max. The iterative calculation was performed to
avoid possible bad contacts. NPT ensemble (maintaining the
number of particles, pressure and temperature by adjusting
cellular parameters) was used to perform 100 ps dynamics
simulation to calculate the average density. The NVT ensemble

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Fig. 3 Vacuum cell of EV and C12DES molecules.
was employed to perform another 100 ps dynamics simulation
controlled using an Andersen thermostat. The time step is 1
fs, and the electrostatic interactions and van der Waals forces
were calculated by the Ewald method. Subsequently, the
Cohesive Energy Density task was used to calculate the cohe-
sive energy per unit volume for a material to obtain the cohe-
sive energy density and solubility parameters for evaluating
the compatibility of solvents and solutes.
Solvation free energy is the energy required to transfer the
solute from the vacuum state into the solvent and can be
obtained directly from the simulation using the thermo-
dynamic integration method. Fig. 3 shows the cell containing
EV and C12DES molecules. A dye molecule and 50 DES mole-
cules were constructed in an amorphous cubic cell
50 000 max. iterative geometric optimization calculation was
Fig. 4 (A) Three-dimensional columnar distribution diagram of extraction efficiency with different compositions of DES. Red, green, and blue rep-
resent MV, CV, and EV, respectively. (B) Six types of hydrophilic DESs (C2, C4, C6, C8, C10, and C12) to form the DES aqueous two-phase system for
MV, CV, and EV partitioning, respectively.
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performed to rationalize the distribution of molecules.
Afterwards, the dye molecule was selected as the “solute atom”
set, and the Forcite module was used to calculate the solvation
free energy. The NVT ensemble was applied for dynamics
simulation using the Andersen thermostat.36
3. Results and discussion
3.1 Liquid–liquid extraction of TPM dyes from menthol-
based hydrophobic DES
Six different hydrophobic DESs were successfully prefabricated
for liquid–liquid extraction experiments, in which menthol
was used as HBA, and six carboxylic acids with different
carbon chain lengths were used as HBD. The DES aqueous
two-phase system was formed using 2 mmol of hydrophobic
DES and 200 mmol of H2O. MV, CV and EV (60 mg L−1) were
added to the above systems as target dye molecules to test
their extraction behavior. The mixed system was separated into
a two-phase system after being stirred and extracted and UV
analysis was used to analyze the change in the dye content
before and after extraction. The extraction efficiency of the
selected triphenylmethane-based dyes is plotted in Fig. 4(A).
Fig. 4(B) shows that the six selected hydrophobic DES are
used as extraction agents for extracting dye molecules in
aqueous solution, and the extracted dyes are mainly distribu-
ted in the upper phase. It can be observed that the extraction
rate of the dyes gradually increases with the increase of the
alkyl chain length of HBD. When the carbon chain length is
greater than 4, the extraction rates of the three dyes are all
greater than 97.83%. When the carbon chain length is 4 or
less the extraction rate decreases rapidly. In particular, when
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the carbon chain length is 2, there is almost no extraction
effect on methyl violet and crystal violet. The driving force gov-
erning the distribution behavior of the dye is the hydrophobi-
city of the eutectic solvent and the Coulomb interaction
between the DES and the dye molecule. Many studies have
confirmed that an increase in the length of the alkyl chain
usually leads to a decrease in the Coulomb force and the polar
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Based on the above qualitative experiments, optimization
analysis was conducted to further explore the effects of extrac-
tion time, temperature, mass of dye, and amount of NaCl
added to the extraction experiment, as shown in Fig. 5. In this
section, MV, CV and EV (1.38 g L−1) are selected as the target
molecule, and C12DES was selected as the extractant.
3.1.1 Effect of the extraction time. The changes in the

force, and at the same time the dispersion interaction between
molecules increases.37 Obviously, when the polarities of the
top and bottom phases are close, the extraction efficiency
tends to decrease continuously. In other words, the greater the
relative hydrophobicity between the two-phase systems, the
more obvious the difference in the distribution of triphenyl-
methane dyes in the two phases, and the stronger the extrac-
tion ability. In addition, for the same DES, the extraction
efficiency of the three dyes follows the order: EV > CV > MV, in
which the extraction rates of EV, CV and MV for C12DES are
99.9%, 99.6% and 98.8%. For ethyl violet, six eutectic solvents
show good extraction effects, with extraction rates greater than
92.23%, among which C12DES exhibits the highest extraction
rate of ethyl violet at 99.9%. The extraction efficiency value
obtained by the experiment is comparable to or even better
than that reported in the previous literature (Table 1). In
addition, for better comparison, other methods for dye
removal, and their corresponding reaction conditions and
extraction capacity or extraction efficiency are listed in
Table S1,† and append the synthesis steps of these materials
after the table.
extraction efficiency at 10 min, 30 min, 2 h, 4 h, 8 h, and 16 h
were considered (Fig. 5(A)). After comparison, it was found
that the C12DES system has a good extraction effect on triphe-
nylmethane dyes. The extraction efficiency increases with the
increase of extraction time. A higher extraction efficiency is
achieved in 10 minutes. During 10 minutes of extraction time,
the extraction efficiencies of EV, CV and MV were 99.6%, 92%
and 73%, respectively. In addition, the extraction efficiency
slowly increased and stabilized after 30 minutes. When the
extraction time of EV, CV and MV is 16 h, it shows the highest
extraction efficiency, which are 99.7%, 95.6% and 78.5%,
respectively.
3.1.2 Effect of the extraction temperature. It is obvious that
temperature plays an essential role in the actual separation
process and needs to be considered mainly. The experimental
results were obtained in a commonly used temperature range
from 30 to 70 °C, as shown in Fig. 5(B). The change of the
extraction temperature had little effect on the extraction
efficiency of EV and CV but a great effect on that of MV. It is
possible that the increase of temperature causes the viscosity
of the top phase to decrease, increasing the molecular move-

Table 1 Separation of various dyes using various solvents reported in the literature. (C = dye concentration, Cini = initial concentration, Cfin = final
concentration, D = distribution coefficient, EE% = percentage of dye extraction)

Solvent Extraction application Reaction conditions C D EE% Ref.

a −1
ChCl-GA DES Eriochrome 6 ml dye solution Cini: 200 mg l 271.81 90% 38
Black T 0.2 ml DESs
Glycolic acid Methyl violet 25 ml xylene; 25 ml aqueous solution Cini: 50 mg l−1 24.0 96% 39
0.0125 g glycolic acid Cfin: 2 mg l−1
HTABb Methylene blue 100 ml aqueous phase Cini: 200 mg l−1 80% 40
SDBS Methyl orange 30 mg surfactant 65%
50 ml amyl alcohol
[p14][Tf2N]c Acid blue dye 1 ml aqueous solution; 0.7 ml ILs Cini: 16.6 mg l−1 2.02 58.5% 41
(Navy 5RE) Cfin: 6.89 mg l−1
[Hmim][Tf2N] d
Congo red 10 ml aqueous solution; Cini: 40 mg l−1 80–90% 42
70 mg ILs; 0.5 ml acetone
[Omim][PF6]e Brilliant green 10 ml aqueous solution Cini: 0.1 mg l−1 80% 43
Crystal violet 0.1 M Phosphate buffer 60%
100 μl [Omim][PF6]
Salicylic acid Methylene blue 10 ml H2O; 10 ml Benzene Cini: 20 mg l−1 93% 44
7.24 × 10−2 M extractant; 3 min
[N1888][SCN] f Methyl orange 5 ml dye solution Cini: 20 mg l−1 2.9 89.09% 45
Methylene blue 1 ml IL 64.14%
SDBS Methylene blue A/O phase ratio = 1 : 1 Cini: 30 mg l−1 95% 46
Diluent: C2H4Cl2
0.06 M extractant; pH = 11; 20 °C
Menthol-based DES Methyl violet 3.6 ml H2O; Cini: 200 mg l−1 4496 98.8% This work
Crystal violet 0.8 ml C12DES Cfin:0.2 mg l−1 99.6%
Ethyl violet 99.9%
a
ChCl-GA DES: Choline chloride–glycolic acid DES (1 : 1). b HTAB: Hexadecyltrimethylammonium bromide. SDBS: sodium dodecyl benzene sulfo-
nate. c [p14][Tf2N]: Pyrrolic ionic liquid, N-methyl pyrrole bis(trifluoromethylsulfonyl)imide. d [Hmim][Tf2N]: 1-Hexyl-3-methylimidazolium bis
(trifluoromethylsulfonyl)imide. e [Omim][PF6]: 1-Methyl-3-octylimidazolium hexafluorophosphate. f [N1888][SCN]: Tricaprylmethylammonium
thiocyanate (quaternary ammonium-based ionic liquids).

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Fig. 5 Factors influencing the experiments: (A) extraction time; (B) temperature; (C) mass of dyes; and (D) ionic strength.
ment rate of the two phases, and reducing the interaction
between the two phases. As a result, the partition coefficient of
the target extraction molecule in two phases is reduced, which
reduces the extraction effect.
3.1.3 Effect of the mass of dyes. Different concentrations
of the dye were employed to explore the effect of TPM quality
on the extraction efficiency of DES. As shown in Fig. 5(C), the
extraction efficiency of EV is the highest and is almost
unchanged at around 99.7% with the increase in the EV
content. The EE% of CV and MV demonstrates a rapid decreas-
ing tendency with the increase of the mass of dyes from 99.6%
to 67.2% and 98.8% to 25.8%, respectively. This may be due to
the limited extraction capacity of menthol-based DES.
3.1.4 Effect of the ionic strength. The trend curves of the
extraction efficiency are depicted in Fig. 5(D), and the results
show that the extraction efficiency increased rapidly when the
amount of NaCl added increased from 0 to 200 mg (CTPM
9.72 g L−1). Effio’s group found that NaCl changes the DNA
distribution of the upper and lower phases through changes in
the electrostatic interactions.47 These results can be explained
by the following reasons. First, the salting-out effect reduces
the solubility of the dyes in water and forces them into the
hydrophobic phase. Second, the addition of NaCl to the DES
aqueous two-phase system improves the hydrocarbon solubil-
ization capacity of hydrophobic DES. However, the hydrogen
bonding structure of DES was destroyed by the addition of
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NaCl. With the increase in the amount of NaCl added, the two-
phase system gradually becomes unstable.
In order to better compare the environmental friendliness
and experimental hazards of the materials used in DES and
previous work, we should also consider whether our method is
green and its corresponding toxicity. We list the effects and
capabilities of different methods to remove dyes in Table 1
and Table S1.† And the corresponding toxicity data and GHS
Hazard Statements are listed in Tables S2–S4.† The results
show that our synthesis method is relatively greener, with a
100% atomic utilization rate (atom economy) and zero dis-
charge of waste water and exhaust gas, and it has a very out-
standing use efficiency. Moreover, we can find from the table
that most of the DES components used have low toxicity, some
of which are even practically nontoxic, less irritating to the
human body, and safe chemicals. At the same time, these com-
ponent raw materials are derived from nature, are renewable
raw materials, widely exist in various oils, etc., and are widely
used in human life, at the same time, they are safe for the
environment and easily degraded.
3.2 Simulation
At present, the mechanism by which DES can be extracted is
not clear, so we conduct theoretical analysis from the following
aspects: solvation free energy is used for calculating the inter-
action, polarity is determined for considering similar dis-
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solution, Flory–Huggins parameter is employed for analyzing
compatibility and molecular dynamics is introduced for study-
ing the movement of TPM at the phase interface.
In order to analyze the trends imported by systematically
increasing the side chain length in the hydrogen bond donor,
EV was used as the target molecule and extracted using
different DESs with diverse carbon chain lengths, and the
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corresponding extraction efficiency was calculated, these
results are graphically shown in Fig. 6(A). This demonstrates
that the extraction efficiency can be increased by increasing
the length of the carbon chain. As the alkyl chain length of
HBD increases, the hydrophobicity of DES gradually strength-
ens, resulting in changes in interfacial tension and the poten-
tial difference between phases and lesser DES migrates to
water, and the interactions and the difference in properties
between the two phases increase gradually. Then, the solvation
free energy of EV molecules in DES was calculated to analyze
the reason.
The solvation free energy of a molecule refers to the energy
required to transfer the solute from the vacuum state to the
solvent at a constant temperature and isopiestic pressure. The
solvation free energy, ΔE, can be obtained directly by using
thermodynamic integration in MD simulation, as shown in
Fig. 6 (A) Extraction efficiency curves of EV on 6 kinds of hydrophobic DES. (B) Calculation of solvation free energy of EV in C2DES, C4DES, C10DES
and C12DES.
Fig. 7 Schematic diagram for calculating the solvation free energy of TPM molecules in DES.
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Fig. 7. First, the charges of the EV molecule gradually reduce
to zero in a vacuum, then the uncharged EV molecules are
added to the menthol-based DES through van der Waals inter-
action, and finally, the charges are re-added to the EV
molecule.48
ΔE ¼ ΔEid þ ΔEvdW þ ΔEelec ð2Þ
where ΔEid is the free energy generated by the removal of
charge by the solute molecules, ΔEvdW is the free energy of
adding solute molecules to the solvent, and ΔEelec is the free
energy of the solute interacting with the solvent after the
charge is reintroduced again.48
The solvation free energies of EV under different DES
(Fig. 6(B–E)) and H2O (Fig. S2†) are listed in Table 2. The sol-
vation free energy of EV in water is very low, only −0.411 kcal
mol−1, while the solvation free energies of EV in C2DES,
C4DES, C10DES and C12DES are −17.128, −18.392, −19.096
and −21.681 kcal mol−1, respectively.
Higher solvation free energy of EV in DES molecules indi-
cates that the interaction between them is stronger than that
of H2O molecules, indicating that the TPM molecules are more
inclined to the DES environment. This may be the main
Analyst, 2021, 146, 1996–2008 | 2003

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Table 2 The solvation free energy ΔE in menthol-based DES
EV in menthol-based DES or H2O Solvation free energy (kcal mol−1)
C2DES −17.128
C4DES −18.392
C10DES −19.096
C12DES −21.681
H2O −0.411
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reason that DES has excellent extraction performance for TPM
molecules. Additionally, the solvation free energy value of EV
in DES gradually increases as the HBD chain length increases,
which is positively correlated with the extraction rate. This
shows that the force of EV and DES is greater, and EV is more
inclined to enter the DES with long chain HBD. This may be
the most important reason why EV shows a higher extraction
rate in long-chain DES.
Fig. 8(A) demonstrates the distribution images of MV, CV
and EV molecules in a DES aqueous two-phase system and the
corresponding extraction efficiency values. It is obviously
found that the lower phase of the centrifuge tube that extracts
EV is the cleanest, almost colorless, and the corresponding
extraction efficiency is also the highest. Molecular simulation
is used to analyze why such a result is obtained. Three dye
molecules were first geometrically optimized at an advanced
theoretical level using the DMol3 program. The partial charges
on the atoms are determined using density functional theory
to calculate the electrostatic potential-derived atomic charges.
Fig. 8 (A) Extraction efficiency and extraction results of MV, CV, and EV by the C4 DES aqueous two-phase system, respectively. The electrostatic
potential field of various dyes calculated by DFT. ((B) MV, (C) CV, (D) EV).
2004 | Analyst, 2021, 146, 1996–2008
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Analyst
Fig. 8 reveals the electrostatic potential field around the (B)
MV, (C) CV and (D) EV, as exhibited by the result of the above
DFT calculations. It can be clearly seen from the structure that
as the chain length of the alkyl substituent on the N atom
increases, the positive charge density on the organic molecule
decreases. The variation in the electrostatic potential distri-
bution also exhibits that there are obvious differences in many
physicochemical properties of these triphenylmethane dye
molecules, including melting point, density, polarity and so
on.49 These structurally optimized organic molecules are used
in subsequent molecular dynamics simulations.
The dipole moment is the product of the distance between
the positive and negative charge centers and the amount of
charge in the charge centers, and the unit is D (Debye). The
direction of the dipole moment is specified from the positive
electric center to the negative electric center. The dipole
moment was used to analyze the spatial configuration and
determine the polarity of the molecule, and a greater the
dipole moment, the greater the polarity of the molecule. The
dipole moments of EV, CV, and MV calculated by the
Dmol3 module are 9.109 D, 9.159 D, and 9.984 D, respectively,
with the values gradually increasing in the same order. That is,
EV has the smallest polarity and the MV has the largest
polarity. With reference to the principle of similar polarity, the
closer the solute and solvent polarities are, the easier it is to
dissolve the solute in the solvent. The polarity of water is the
largest. According to the comparison, it can be found that the
polarity difference between EV and water is the largest. It
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Analyst Paper

reveals that EV is more easily detached from the water and dis-
solved into the DES phase.
To evaluate the compatibility of solvents and solutes, solu-
bility parameters are usually calculated to predict solubility.
The cohesive energy is the mean energy required to separate
all molecules in this system from each other at an infinite
distance.
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χ12 is the Flory–Huggins parameter between components 1
and 2, The volume fractions of components 1 and 2 in the
mixture are represented by φ1 and φ2, δ1 and δ2, and refer to
the solubility parameters of the two substances, respectively,
and v is the reference volume.
The dissolution process is a process in which solute mole-
cules and solvent molecules are mixed with each other. From

the perspective of thermodynamics, the dissolution must

Ecoh ¼ Einter ¼ Eintra  Etotal
where Ecoh is the cohesive energy, Einter is the intermolecular
energy, which is the difference between the total energy of the
system, Etotal, and all intramolecular energy, Eintra.
The cohesive energy density (CED) is calculated by the cohe-
sive energy per unit of volume and is often expressed in MPa
(equal to J cm−3). Moreover, the solubility parameter, δ, is the
square root of the CED and is often expressed in (J cm−3)0.5,
which plays an important part in the mixture theory.
C¼
Ecoh
V the better the compatibility is.
pffiffiffiffiffiffiffiffiffiffi
δ ¼ CED
δ ¼ ðδvdw 2 þ δES 2 Þ1=2
The solubility parameter is mainly composed of two parts,
van der Waals dvdW and electrostatic dES forces, including
Coulomb and H bond components.
The solubility parameter of three TPM molecules, C12DES
and H2O was calculated using the cohesive energy density task
in the Forcite module (Fig. S3†). As shown in Table 3, the solu-
bility parameters of MV, CV, EV, C12DES and H2O are 20.540,
20.363, 19.000, 19.552 and 48.157 (J cm−3)0.5, respectively.
Most of the changes in the solubility parameters are attributed
to the variation in the polar component, while changes in the
TPM molecules reduces with the increasing number of methyl
molecules on the N atom in the molecular backbone, which is
likely related to the charge density shown in Fig. 8.
ΔGmix ¼ ΔH mix  TΔSmix
ΔSmix ¼ RðnA ln φA þ nB ln φB Þ
ΔH mix ¼ RTχ 12 n1 φ2
Vðδ1  δ2 Þ2
χ 12 ¼
RT
Table 3 Cohesive energy density and corresponding solubility para-
meters of MV, CV, EV, C12DES and H2O
ð3Þ satisfy the conditions of ΔGmix < 0. Among them, the value of
TΔSmix is positive. However, in order to make the value of
ΔGmix less than 0, it is mainly required to change the value of
enthalpy (ΔHmix). According to the formula, the mixing
enthalpy ΔH is always positive, which means that mixing two
substances requires energy, which is equivalent to endother-
mic mixing. In order to ensure that the value of ΔG is less
than 0, the value of ΔH should be as small as possible. At the
same time, ΔHmix is proportional to the Flory–Huggins para-
meter value. That is, the closer the values of δ1 and δ2 are, the
ð4Þ smaller the difference is, the smaller the ΔHmix value is and
As shown in Table 4, Flory–Huggins parameters of MV, CV
ð5Þ
and EV are 0.148, 0.101 and 0.053 in C12DES, and 55.581,
58.072 and 81.235 in H2O, respectively.
ð6Þ
The change in the value of the interaction energy of TPM
with DES is much smaller than that with water, indicating that
TPM is more likely to be miscible in the DES phase in this
extraction system, which may be an important reason why DES
has excellent extraction ability for TPM. At the same time, the
change in the value of the interaction energy of EV is the smal-
lest with C12DES relative to MV and CV, and is also the largest
with water, indicating that EV is more easily detached from
water and compatible with long-chain DES. This may be the
reason why C12DES has the best extraction efficiency for EV.
The solubility of the solvent is the ability of the solute to
disperse and dissolve, often manifested as the rate of solution
formation at a certain concentration. A space cell was built to
construct the two phases of C12DES and water molecules. The
EV and MV molecules were placed on the phase interface of
ð7Þ the two phases, respectively, and 1000 ps molecular dynamics
calculation was performed using the Forcite module. For the
ð8Þ
simulation calculation results, the frame pictures at 5 ps,
ð9Þ 50 ps, 100 ps, 250 ps, 500 ps, and 1000 ps were selected to
analyze the EV and MV molecular motion trajectories, respect-
ively (Fig. 9). It can be found that the MV has been moving at
ð10Þ the two-phase phase interface during the 1000 ps simulation
calculation. At 100 ps, the EV obviously enters the upper
phase. The EV molecule has a stronger force on the DES upper

Cohesive energy density Solubility parameter

(J m−3) (J cm−3)1/2 Table 4 Flory–Huggins parameters (χ12)

EV 3.610 × 108 19.000 C12DES H2O

CV 4.146 × 108 20.363
MV 4.219 × 108 20.540 EV 0.053 81.235
C12DES 3.827 × 108 19.552 CV 0.101 58.072
H2O 2.321 × 109 48.157 MV 0.148 55.581

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Paper
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Fig. 9 Molecular motion diagram of EV and MV at 5 ps, 50 ps, 100 ps, 250 ps, 500 ps, and 1000 ps on the two-phase interface of C12DES and
water, respectively.
phases than MV molecule and is more inclined to enter the
C12DES upper phase.
4. Conclusions
In this work, a series of natural and environmentally friendly
menthol-based hydrophobic DESs composed of HBA and HBD
with different chain lengths were synthesized for extraction
experiments and theoretical research on the TPM micropollu-
tants. The extraction efficiency of EV, CV and MV increases
with the increase of the chain length of HBD. According to the
calculation result of the solvation free energy, the solvation
free energy of EV in DESs (−17.128 to −21.681 kcal mol−1) is
much larger than that in water (−0.411 kcal mol−1), and
increases with the increase of HBD chain length, which is pro-
portional to the extraction rate. The greater solvation free
energy of EV in DES molecules indicates that the interaction
between them is stronger than that of H2O molecules, indicat-
ing that the TPM molecules are more inclined to the DES
environment. EV has the largest solvation free energy value
(−21.681 kcal mol−1) in C12DES, which indicates that the inter-
action between EV and long-chain DES is the strongest. DFT
calculation was performed to study intermolecular interactions
and it was found that EV has the smallest positive charge and
the smallest dipole moment (9.109 D). It can be found that the
polarity difference between EV and water is the largest, indicat-
ing that EV is more easily detached from water and dissolves
into the DES phase. Through simulation calculation of Flory–
Huggins parameters, it can be found that the change in the
value of the interaction energy of TPM with DES is much
smaller than that with water, indicating that TPM is more
likely to be miscible in the DES phase in this extraction
system. Among these, the change in the value of the inter-
action energy of EV (χEV–C12DES 0.053) is the smallest with
C12DES relative to MV and CV, and is also the largest with
water (χEV–H2O 0.053), indicating that EV is more easily
detached from water and compatible with long-chain DES. The
motion of EV and MV at the phase interface of DES and water
2006 | Analyst, 2021, 146, 1996–2008
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Analyst
is calculated to further analyze from the molecular level by the
Forcite module. At the same time, EV tends to move into the
DES phase. In summary, the excellent extraction ability of the
DES for TPM was verified through experiments and simu-
lations. At the same time, DFT calculation and MD simulation
were used to quantitatively analyze the effect of the DES com-
position and TPM structure on the distribution of target mole-
cules in the two phases, providing sufficient theoretical
support for the application of this system in other fields.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by National Natural Science
Foundation of China (No. 21676095, No. 21376088), the
Science and Technology Program of Guangdong, China
(2016B020243005), and the Science and Technology Program
of Guangzhou, China (201804020014). The authors would also
gratefully acknowledge the support from the Guangdong
Provincial Laboratory of Green Chemical Technology.
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