Talanta 269 (2024) 125401

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Novel reusable and switchable deep eutectic solvent for extraction and
determination of curcumin in water and food samples
Qamar Salamat a, Mustafa Soylak a, b, c, *
a
Erciyes University, Faculty of Sciences, Department of Chemistry, 38039 Kayseri, Turkey
b
Technology Research and Application Center (ERU-TAUM), Erciyes University, 38039 Kayseri, Turkey
c
Turkish Academy of Sciences (TUBA), Çankaya, Ankara, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: For the first time, a fast and easy extraction method based on a unique reusable and switchable deep eutectic
Switchable deep eutectic solvent solvent (made of octylamine, succinic acid, and water as precursors) was presented and utilized for the micro­
Curcumin extraction and determination of curcumin as a model analyte. The main factors used to induce a phase transition
Food samples
in the as-prepared deep eutectic solvent were solutions of NaOH and HCl. Among the standout characteristics of
Microextraction
Spectrophotometric analysis
the suggested deep eutectic solvent are the removal of toxic organic solvents like THF, the lack of a need for
centrifugation, and the ability to be reused in subsequent extractions. The influence of effective parameters (i.e.,
proportions of deep eutectic solvent structure components, volume of prepared deep eutectic solvent, volume
and concertation of NaOH, volume of HCl, and salt effect) on the extraction procedure were investigated. The
calibration curve also was linear in the range of 35–500 μg L− 1 with coefficients of determination (R2) of 0.9976.
Limit of detection (S/N = 3) 10.0 μg L− 1, the limit of quantification (LOQ) of 35.0 μg L− 1, the relative standard
deviations (RSDs %) composed of intra-day RSD (4.7) and inter-day RSD (6.4), preconcentration factor of 40.0,
enrichment factor of 38.68, and relative recovery of 92.6%–100.3 % were achieved. The reusable and switchable
deep eutectic solvent based-dispersive liquid-liquid microextraction technique was proficiently employed to
expedite easy and fast extraction of curcumin from water and food samples.

1. Introduction performance liquid chromatography (RP-HPLC) [18], stripping vol­

tammetry (AdSV) [19], and capillary electrophoresis technique coupled
Turmeric’s dried rhizomes, which belong to the Zingiberaceae fam­ with a laser induced native fluorescence detection (CE-LINF) [20] Even
ily, have long been used as a food source, natural coloring agent, while the LC-MS/MS is highly sensitive, it is also quite costly, sophisti­
nutritional spice, and medicinal plant in Asian nations [1,2]. Curcumi­ cated, and needs to be used by experts in the field. Furthermore, whereas
noids are phenolic compounds that are found in abundance in the rhi­ electroanalytical techniques exhibit selectivity, they also incorporate
zomes and range in concentration from 1 to 6 w/w. They are a subjective elements such limited functionality and unstable perfor­
combination of curcumin, demethoxycurcumin, and bisdemethox­ mance. When compared to these methods, the spectrophotometer has
ycurcumin [3]. Among these Curcuminoids, Curcumin is the compound advantages including affordability, ease of use, quick measurement, and
that is most frequently explored for its properties and uses [4]. Antiox­ accessibility in the majority of research labs, despite its low sensitivity.
idant [5], anti-microbial [6], anti-inflammatory [7], anti-allergic [8], Sample preparation, the most crucial step in any analytical proced­
and anticancer actions [9] are just a few of the pharmacological traits ure, is used to preconcentrate traces of chemicals or eliminate matrix-
that Curcumin exhibits. interfering components before measuring them. One sample prepara­
Several methods have been widely developed for the determination tion method that has been recommended is dispersive liquid-liquid
of curcumin and its derivatives in foods, waters, and pharmaceuticals microextraction (DLLME), which is quick, easy to use, flexible, and
such as spectrofluorometric [10], spectrophotometry [11–13], liquid environmentally friendly [21–23]. Depending on the nature of the an­
chromatography tandem mass spectrometry (LC–MS/MS) [14,15], cy­ alyte, a variety of solvent types with different polarity have already been
clic voltammetry (CV) [16,17], reproducible reversed phase high utilized in DLLME, including deep eutectic solvents, supramolecular

* Corresponding author. Erciyes University, Faculty of Sciences, Department of Chemistry, 38039 Kayseri, Turkey.
E-mail address: [email protected] (M. Soylak).

https://doi.org/10.1016/j.talanta.2023.125401
Received 14 September 2023; Received in revised form 16 October 2023; Accepted 7 November 2023
Available online 10 November 2023
0039-9140/© 2023 Elsevier B.V. All rights reserved.
Q. Salamat and M. Soylak Talanta 269 (2024) 125401

solvents, ionic liquids, and switchable solvents [24–26]. 2.2. Instruments and apparatus
In a range of liquid phase microextraction techniques, low-melting-
point ILs [27] have attracted a lot of interest as an efficient extraction The concentration of curcumin was determined using a Hitachi UH
medium. In 2004, the Abbott research group identified Deep eutectic 5300 Double Beam Spectrophotometer (Hitachi, USA) with the quartz
solvents (DESs), a unique subtype of ILs [28]. The melting temperatures cuvette system. The extraction of curcumin from the initial aqueous
of DESs are significantly lower than those of the molecules that make phase to the RS-DES phase was done using an auxiliary apparatus called
them up. A neutral H-bond donor molecule and an H-bond-forming a vortex mixer (VWR international model, Germany).
cation are often found in salts, which is how they are typically created. With a KBr pellet and a scan rate of 20 scans per minute, FT-IR
As with ILs, DESs are non-flammable and offer excellent thermal and spectroscopy was carried out using a PerkinElmer 00 FT-IR spectrom­
chemical stability, a very low vapor pressure, strong conductivity, and eter (Waltham, MA, USA) spanning the wavenumber range of 4000 to
tuning capabilities [29]. Given their potential advantages over 500 cm− 1. At room temperature, 16 scans of the 1H NMR spectra
ILs—such as their simplicity of production, cheap cost of synthesis, (AVANCE 400, Bruker, Switzerland) were performed. After being pre­
chemical inertness toward water, and environmental friendliness pared with CDCl3, the DESs samples were homogenized in a 5 mm NMR
(biodegradable and nontoxic nature)-DESs may prove to be an attractive tube.
substitute for ILs in many applications [30–32]. Although DESs are
sometimes seen as solvents that are beneficial to the environment and 2.3. Real sample preparation
have the ability to be extracted and separated, it is more challenging to
separate them from the target compounds due to their non-volatile na­ The tap water was obtained from the municipal tap water source
ture. Switchable DESs may be able to help with this issue. Changes in located within our laboratory (Department of Chemistry, Faculty of
temperature, light, acidic, and alkaline environments can all lead to the Science, Erciyes University, Turkey). Drinking water was purchased
reversible conversion of switchable solvents [33]. These switchable from a supermarket in Talas, Kayseri, Turkey. These water samples were
solvents may alternate between high and low ionic strengths, hydro­ immediately transferred to the laboratory and stored at 4 ◦ C before
philic and hydrophobic, and polar and non-polar depending on the being used by the proposed method and under optimum conditions.
surrounding conditions [34]. Switchable DESs have been developed Three types of herbal tea samples were bought from a local market.
over the last few years, including CO2-switchable [35], To produce the herbal tea extract, 100 mL of deionized distilled water
thermo-switchable [36], and pH-switchable [37]. and 2.5 g of herbal tea were boiled for 10 min followed by filtration. The
This work aimed to report a fully green DLLME method using a novel filtered solution was then digested with 1.0 mL of concentrated HNO3
reusable and switchable DESs-based dispersive liquid-liquid micro­ solution. To evaluate the extraction recovery of the target analyte, the
extraction (RS-DES/DLLME) for the effective extraction of Curcumin (as extraction technique (section 2.5) was performed on the 40.0 mL of the
a model analyte) from water and food samples prior to its spectropho­ supernatant phase following centrifugation under the optimum extrac­
tometric determination. This method involves first extracting the ana­ tion conditions (after bringing the pH of the solution to the neutral
lyte into a hydrophilic synthetic DES. The hydrophilic DES was state). Turmeric drug as a food supplement and turmeric powder as a
converted to the hydrophobic phase by adding an alkaline solution spice were obtained from different commercial food centers. 50 mg of
containing sodium hydroxide in a certain concentration. After that, this each sample was carefully weighed and added to a beaker. After that,
phase was taken out of the aqueous solution and put into another tube. 40.0 mL of a methanol solution was added to the solid samples. The
In order to recover the synthesized DES, an acidic solution with certain resulting solutions were ultrasonically mixed for 10 min before being
concentration was added. As a results, the extracted analyte was sepa­ centrifuged at 4000 rpm for 5 min. Then, the methanolic supernatant
rated from the DES phase and determined by spectrophotometer. In this was separated and the extraction method (section 2.5) was applied with
process, the synthesized RS-DES was re-produced and utilized for further RS-DES-DLLME under optimum conditions. At the final stage, a UV–vi­
extractions. This novel DES exhibits distinctive characteristics in com­ sible spectrophotometer was used to determine the amount of curcumin
parison to other prepared DES, including removal of hazardous organic in all real samples, both with and without the addition of the standard
solvents like THF, no need for centrifugation, and reusability in analyte solution.
consecutive extractions processes. According to the current literature,
these is no previous report on the preparation and use of this type of 2.4. Preparation of RS-DESs
deep eutectic solvents.
In order to produce the new DES, different mixtures containing
2. Experimental octylamine (OA) as a hydrogen bond acceptor (HBA), succinic acid (SA)
as a hydrogen bond donor (HBD), and also the constant amount of water
2.1. Reagents and materials were combined in the proper proportions (mole ratio of 1:1:5, 2:1:5,
1:2:5, and 3:1:5) in a beaker that were employed in our suggested
All reagents used were of analytical grade. Hydrochloric acid (37 %, technique. On a heating plate, the mixtures were then agitated until a
v/v), and sodium hydroxide (99 %) were purchased from Merck homogenous liquids (hydrophilic DES) were produced. The created
(Darmstadt, Germany) and GmbH (Wuppertal, Germany). Stock stan­ DESs were then gathered, put into different tubes, and kept at room
dard solution of curcumin (100 mg L− 1) was prepared by dissolving temperature for further experiments.
appropriate amounts of analytical grade curcumin powder from Sigma-
Aldrich (St. Louis, MO, USA) in the mixture of methanol/water (50:50 v/ 2.5. RS-DES/LPME procedure
v), and stored at 4 ◦ C. Also, working standard solutions (50 μg L− 1) were
prepared daily by diluting the stock solution. The pH modifications were In the proposed method, 40.0 mL of the sample solution, including
executed utilizing various buffer solutions, including phosphate buffer the target analyte (50 μg L− 1 Curcumin), was poured in a 50 mL
solutions (H2PO−4 /H3PO4), acetate buffer solutions (CH3COO− / centrifuge tube. After that, by injecting 2.0 mL of hydrophilic DES to the
CH3COOH), and ammonium buffer solutions (NH+ 4 /NH3). The working previous solution, the synthesized DES was precipitated at the bottom of
medium was ultra-pure water that has undergone reverse osmosis solution at first. Afterward, the mixture was manually shaken for around
(0.055 μS cm− 1, Millipore). Octylamine (99 %) and succinic acid for 30 s, at which point the homogeneous solution was created. Then, 800
synthesis of RS-DES were procured from Sigma-Aldrich and Merk, μL of a 3 M NaOH solution was added, and the mixture was vortexed for
respectively. The spices and herbal tea real samples were obtained from 1.0 min to convert the synthesized DES from the hydrophilic to the
a local market in Kayseri, Turkey. hydrophobic state and cause phase separation. During the vortex and

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Q. Salamat and M. Soylak Talanta 269 (2024) 125401

forming the cloudy solution, the analyte was adsorbed on the surface of analyte (curcumin) was also assessed by utilizing Equation (3):
the DES. Afterward, in order to separate the DES layer from the bulk of
ER% = EF/PF×100 (3)
the sample solution, the mixture was placed for 1.0 min at room tem­
perature (complete phase separation was done without using centrifu­ All experiments were conducted on aqueous samples and were
gation). Then, by using the syringe, the upper layer comprising the replicated three times.
target analyte and DES was collected and transferred to another tube. In
the next step, to separate the extracted analyte from the DES phase and 3. Result and discussion
form two separate phases, a 900 μL aliquot of a 3 M HCl solution was
incrementally introduced to the mixture containing the DES and analyte, 3.1. Characterization of pH-induced RS-DES
followed by manually shaking for 30 s (to facilitate the desorption of the
analyte). Finally, the supernatant (analyte phase) was collected with a The novel RS-DESs, which were synthesized using succinic acid and
micro-syringe, put into an Eppendorf tube, and diluted with methanol octylamine in varying mole ratios, exhibited hydrophilic properties and
until 1.0 mL followed by spectrophotometric analysis. On the other were found to be miscible in water under neutral conditions. In contrast,
hand, lower phase (DES phase) was reused for another extraction pro­ upon adjusting the aqueous environment to an alkaline state through the
cesses. The optimization of the affecting parameters on the extraction addition of NaOH, the aforementioned synthesized DESs exhibited
recovery (such as the ratio of hydrogen bond acceptors to donors in the immiscibility with water, leading to the formation of heterogeneous
structure of DES, the volume of the DES, the concentration and volume solutions. The unique phase behavior that was observed as a result of pH
of the sodium hydroxide (NaOH) solution, the concentration and volume can be attributed to the distinct characteristics of the hydrogen bond
of the hydrochloric acid (HCl) solution, and the salt effect) was done by donors (HBDs) and hydrogen bond acceptors (HBAs). The chosen small
using the one variable at a time (OVAT) method. The schematic of pH- straight-chain fatty acids (HBD) that possess carbon chains of four
induced RS-DES-based DLLME technique for the extraction of curcumin lengths exhibited hydrophilic properties. Simultaneously, it is impera­
is depicted in Fig. 1. tive for the HBA to maintain regular interactions with the HBD subse­
quent to alterations in the pH levels of the surrounding aqueous
medium. Regarding octylamine, by increasing the size of the hydro­
2.6. Calculation of enrichment factor, preconcentration factor, and phobic alkyl part in amines, the molar mass of amines will be increased
extraction recovery which results in a decrease in its solubility in water. But, once it com­
bines with succinic acid and forms a DES, the resulting product will be
The enrichment factor (EF) of the target analyte was determined soluble in water in a natural environment, and by adjusting the pH to
using Equation (1). alkaline media, its behavior switches to hydrophobic. The present
M2 investigation involved the preparation of DESs using varying molar ra­
EF = (1) tios of HBA and HBD, specifically at ratios of 1:1:5, 2:1:5, 1:2:5, and
M1
1:3:5. Initially, it was observed that four ratios of DESs exhibited the
The variable of M2 denotes the slope of the calibration equation ability to achieve solubility with water through pH modulation of the
obtained after extraction process, while M1 demonstrates the slope of environment. This characteristic renders them suitable for use as an
the calibration equation obtained prior to apply the extraction proced­ extractant in the DLLME technique. During the experimental period at
ure. Two calibration curves were also derived by utilizing the extracted room temperature, it was observed that only three DESs (namely, 1:1:5,
sample solutions and the initial sample solutions of the analyte at 1:2:5, and 1:3:5) exhibited stability in their liquid state without any solid
different concentrations, respectively [38]. separation. It is worth mentioning that one type of DES having a ratio of
The preconcentration factor (PF) of the studied analyte was calcu­ 2:1:5 exhibited a semi-solid state at room temperature and required
lated by using Equation (2). heating for its efficient utilization as an extractant. The DES that was
V1 initially prepared and the one that was recovered after applying the
PF = (2)
V2 extraction process were characterized by using FT-IR spectroscopy and
1
H NMR to investigate and compare their chemical structure.
The parameters of V1 and V2 indicate the respective volumes of the
By analyzing the IR spectrum of the compound, the state of the bonds
sample solution at the beginning and the DES phase at the final stage of
in the structure, the functional groups, and its aromatic or aliphatic
the experiment.
structure were determined (Fig. 2a). The primary factor responsible for
In the present study the extraction recovery (ER%) of the target

Fig. 1. Schematic of the RS-DES-DLLME/UV-VIS procedure for extraction and determination of Curcumin.

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Q. Salamat and M. Soylak Talanta 269 (2024) 125401

Fig. 2. (a) FT-IR spectrum of succinic acid (SA), octylamine (OA), and prepared hydrophilic DES, (b) 1HNMR spectra of SA, OA, and prepared hydrophilic DES before
using (pre-DES), and after using (post-DES) in the developed method.

the creation of DES is the hydrogen bonding that occurs between the Considering to octylamine, the bands at 1074 cm− 1 and 3370 cm− 1 are
succinic acid (SA) and octylamine (OA) compounds in the presence of resulted from C–N stretching vibration and N–H bending vibration in its
water. Additionally, based on the findings, it was confirmed that the structure, respectively. Also, the stretching vibration of the Csp3–H
structure of the synthesized DES was almost unchanged both before and bonds are confirmed by two sharp peaks at around 2850 cm− 1- 3000
after the extraction process. Regarding succinic acid spectra, the cm− 1.
observed peaks around 1682 cm− 1, 1302 cm− 1, and 887 cm− 1 indicate In addition, the structures of octylamine, succinic acid, and synthe­
C–– O, C–O, and O–H stretching vibrations, respectively. Furthermore, sized DES both before and after applying the extraction method were
the broad peak around 2600-3300 cm− 1 is attributed to stretching vi­ verified through 1H NMR spectroscopy (Fig. 2b). These spectra
brations of O–H in carboxylic acid group in the molecule. Succinic acid’s demonstrate that the chemical composition of synthesized DES was
broad O–H stretching band is undoubtedly caused by the fact that car­ derived from SA and OA. It should also be noted that the chemical
boxylic acids typically exist as dimers with hydrogen bonds. This peak in composition of synthesized DES before (pre-DES) and after (post-DES)
the synthesized DES is broader, which may indicate that there is more the transformation of miscibility and phase transition remained almost
hydrogen bonding in the product than in the initial compound. unchanged, which means that the newly produced DES can be fully

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Q. Salamat and M. Soylak Talanta 269 (2024) 125401

recovered and used in subsequent experiments. mL on the extraction recovery of curcumin was assessed in order to
determine the optimal volume of DES. Fig. 3b illustrates that the
extraction efficiency exhibited an upward trend solely within the range
3.2. Optimization of the DLLME conditions of 0.5 mL–2.0 mL of DES volume, followed by a gradual decline as the
DES volume was increased to 2.5 mL. Consequently, the optimal volume
3.2.1. Effect of different mole ratios of DES for further experiments was determined to be 2.0 mL of DES.
The physical characteristics of the synthesized DES and its effec­
tiveness for the analyte extraction would be influenced by the molar 3.2.3. Effect of the concentration and volume of NaOH solution
ratio of HBA to HBD. Therefore, an assessment was performed on the After adding the appropriate amount of hydrophilic DES to the
different molar ratios of SA (HBD) and OA (HBA) in the formation of sample solution containing the target analyte (curcumin) and adsorption
new DES, and subsequently, their efficiencies were evaluated for the of the analyte to the surface of DES, in order to separate the DES phase
extraction of curcumin. As per the findings depicted in Fig. 3a, a change from the bulk of the solution, NaOH solution was added. The volume and
in the molar ratio of OA: SA: W from 1:1:5 to 1:2:5 resulted in elevated concentration of the NaOH solution determine the amount of conversion
extraction recoveries. In contrast, the extraction recoveries of curcumin of water-miscible DES into a water-immiscible, which leads to the pro­
exhibited a decrease upon the application of a mole ratio from 1:2:5 to duction of the two separate phases in the solution. Since the produced
1:3:5. Thus, the utilization of RS-DES with a 1:2:5 (SA: OA: W) ratio as DES phase directly affected the extraction efficiency of the analyte. As a
an extractant was deemed optimal for the extraction of curcumin in the result, the volume and concentration of the applied NaOH solution have
aforementioned DLLME methodology and was consequently chosen for also an impact on the extraction efficiency and should be optimized. For
subsequent investigations. this reason, NaOH solutions in concentrations between 1.0 M and 8.0 M
along with different volumes in the range of 200 μL–1200 μL were
3.2.2. Effect of DES volume evaluated. As can be seen in Fig. 3c and in relation to the optimization of
The volume of prepared DES (as the extraction phase) is an NaOH concentration, by increasing the NaOH concentration up to 3.0 M,
impressive factor in the extraction recovery of the studied analyte. The a rising trend in the extraction efficiency is created due to the
investigated analyte (curcumin) will interact with the DES phase more improvement in the phase separation between the DES and sample so­
when the DES volume is increased, which will boost the extraction re­ lution and by utilizing 3 M of NaOH solution, a complete phase sepa­
covery. Conversely, using an overabundance volume of DES probably ration, as well as maximum extraction recovery, will be observed.
causes dilution resulting in a reduction of the extraction recovery of the Conversely, it has been demonstrated that concentrations greater than
analyte. Therefore, the effect of various volumes in the range of 0.5–2.5

Fig. 3. The effect of (a) DES ratio, (b) Volume of DES (mL), (c) Concentration (mol L− 1) and volume of NaOH (μL), (d) Volume of HCl solution (μL), and (e)
Concentration of NaCl (%v/v) on the extraction recovery of Curcumin by on-variable-at the-time (OVAT) method (f) The degree of Greenness of the pro­
posed method.

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Q. Salamat and M. Soylak Talanta 269 (2024) 125401

3.0 M have a negative impact on the extraction recovery of analyte. This Table 1
is explained by the fact that the HCl concentration (in the next step) Influence of matrix ions on % recovery of Curcumin using the proposed method
required to neutralize this alkaline medium will not be sufficient. As a (The amount of curcumin: 0.2 μg mL− 1, N = 3).
result, 3.0 M of NaOH solution was selected for further experiments. Coexisting Ions Added as Concentration (μg mL− 1) Recovery, %
Additionally, scanning the NaOH volume reveals that 800 μL of the Na +
NaCl 5000 95 ±2
alkaline solution was sufficient to attain maximum extraction recovery K+ KCl 5000 98 ±4
along with complete phase separation. Ba2+ BaCl2.2H2O 1000 96 ±3
Mg2+ MgCl2.6H2O 1500 91 ±2
Zn2+ Zn(NO3)2.6H2O 10 97 ±4
3.2.4. Effect of the volume of HCl solution
Fe3+ Fe(NO3)3.9H2O 5 99 ±2
After the extraction of the target analyte into the DES phase followed Cl− NaCl 5000 96 ±3
by its separation from the bulk of the solution, the DES phase was NO−3 NaNO3 5000 98 ±2
transferred to another tube. Afterward, to neutralize the alkalinity SO2-4 CaSO4.2H2O 1500 99 ±3
property of the DES phase that was created in the phase transition Tartrazine Tartrazine 10 95 ±4
Amaranth Amaranth 10 98 ±2
process by using NaOH solution, different volumes of 3.0 M HCl solu­ Carmoisine Carmoisine 5 93 ±3
tions within the range of 300–1500 μL were utilized. By increasing the Rhodamine B Rhodamine B 10 95 ±3
volume of the HCl solution up to 800 μL, the alkalinity of the solution is Brilliant Black Brilliant Black 5 96 ±4
gradually reduced, the separation of the extracted analyte from the DES
phase is facilitated, and also better regeneration of the DES phase is
the RS-DES-DLLME of curcumin was not significantly affected from the
observed. According to the result shown in Figs. 3d. 800 μL of 3.0 M HCl
coexistence of other ions and molecules.
is required to completely neutralize the 800 μL of 3.0 M NaOH which
was applied in the previous step. On the other hand, since in the acidic
media, the curcumin is protonated and can be easily separated from the 3.4. Method validation
DES phase, by means of 900 μL of HCl complete phase separation and
formation of two distinct phases between the DES phase and target The performance of the proposed method (RS-DES/DLLME) was
analyte was achieved and also the DES phase was completely recovered. examined by investigating parameters such as linear dynamic range
Then, with the addition of HCl concentration up to a volume of 1500 μL, (LDR), limit of quantification (LOQ), limit of detection (LOD), extraction
the extraction recovery exhibited constancy, while the preconcentration recovery (ER%), and relative standard deviation (RSD) for the extraction
factor experienced a decline owing to the process of dilution. Thus, a of Curcumin from water and food products under optimized conditions.
volume of 900 μL of HCl with a concentration of 3.0 M was chosen for The aforementioned parameters were evaluated through the introduc­
subsequent experimental procedures. tion of standard solutions containing the target analyte (curcumin) into
water samples at eight distinct concentrations. The outcomes presented
3.2.5. Effect of the ionic strength in Table 2 indicate that LDR, LODs (S/N = 3), LOQ, and R2 were ac­
During the phase transition process, the suggested method required quired within the 35.0–500 μg L− 1 range, 10.0 μg L− 1, 35.0 μg L− 1, and
the addition of alkaline and acidic solutions. This makes it clear that 0.9976, respectively. Intra-day and inter-day relative standard de­
NaCl would be produced as a result of the neutralization of NaOH and viations (%RSDs) were obtained at 4.7 % and 6.4 %, respectively.
HCl. On the other hand, the ionic strength of the sample solution also Additionally, the PF, EF, and ER% of the analyte were achieved at 40.0,
affects how well the sample is extracted because of the salting-out effect, 38.68, and 96.7 %, respectively.
which can alter the solubility of the analytes and the viscosity of the
aqueous phase. Consequently, by applying the different amounts of 3.5. Greenness evaluation of the proposed method
NaCl, ranging from 0 to 15 % (w/v), an investigation was carried out to
determine the impact of the sample solution’s ionic strength. The results AGREE (Analytical GREEnness), a novel and recently developed in­
illustrated in Fig. 3e indicate that using the different concentrations of strument, was used to assess the suggested microextraction method’s
NaCl did not result in any significant changes to the extraction re­ level of greenness [39]. Green, yellow, and red color schemes represent
coveries of the target analyte. Consequently, further experiments were the various aspects’ states. Furthermore, a total score ranging from 0 to 1
carried out without the addition of salt. is awarded. Greener is indicated by a score that is closer to 1, and it is
lowered by deducting points for violations of the 12 green analytical
3.2.6. Reusability of the prepared switchable DES chemistry principles. The result is a graph that resembles a clock that
The evaluation of prepared DES efficacy can be done through an displays the overall score and the color in the middle (Fig. 3f). The
analysis of its stability, or, in other words, its reusability. For this pur­ proposed method has a total score of 0.68 and a predominant color of
pose, after the separation and recovery of the DES phase in the last step green, which means that it has a low environmental impact and can be
of the extraction procedure, the recovered DES was transferred to deemed a green method. Principles 1 and 3 (yellow and red) correspond
another tube and then used again for the extraction of curcumin at to the sampling procedure and positioning of the analytical device,
optimal conditions without any pretreatment. The results indicated that respectively, which are based on the external sample pretreatment
the recovered DES was able to extract the model analyte (curcumin) required and offline measurement of the analyte by injection into a
successfully up to 5 times with minimal change in extraction recovery. UV-VIS instrument, respectively. Principle 9 states that the selection of
instrument results in a green color for the use of UV-VIS. The sampling
3.3. Effect of interfering matrix on the extraction recovery of target procedure requires only a few steps and no derivatization step is needed
analyte (Principles 4 and 6). Furthermore, low sample volume and moderate
solvent consumption are employed in the microextraction process,
Most common matrix ions in real samples can cause a decrease on the which reduces waste generation (Principles 2, 5, and 7) as well as
extraction efficiency of the studied analyte. In order to assess the effi­ toxicity and user dangers (Principles 11 and 12). Due to the large
cacy of the proposed technique for microextraction of curcumin, the number of samples analyzed in 1 h, the proposed method in relation to
selectivity of the method in extraction of target analyte in the presence principle 8 is considered completely compatible with the environment.
of various ions and molecules was evaluated. An ion was considered to Since no solvent in the reagents comes from a bio-based source and
be interfering when it causes deviation greater than 5 % in the extraction acquiring reagents from renewable sources is preferable, Principle 10
recovery of target analyte. As indicated by the data presented in Table 1, was chosen in red color.

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Table 2
Analytical performance of the RS-DES-DLLME of Curcumin from spiked water samples (N = 8: the number of concentration levels used for calibration).
Analyte Linearity LODc %ERd Precisione (RSD%, n = 3) PFf EFg Calibration curve
a 2b
LDR R Intra-day Inter-day
h
Curcumin 35.0–500 0.9976 10.0 96.7 4.7 6.4 40.0 38.68 Y = 4.7808 (Cur, μg mL− 1) + 0.0631
i
Y = 0.1236 (Cur, μg mL− 1) + 0.0083
a
Linear dynamic range (μg L− 1).
b
Coefficient of determination.
c
Limit of detection (S/N = 3) (μg L− 1).
d
Extraction recovery.
e 1
Relative standard deviation for intra– (n = 5) and inter–day (n = 5) precisions at a concentration of 100 μg L− of analyte.
f
Preconcentration factor (n = 3).
g
Enrichment factor (n = 3).
h
Obtained from the calibration curve of extracted sample solutions.
i
Obtained from the calibration curve of initial sample solutions.

3.6. Comparison of proposed method with other reported techniques for

Cfound − Creal
the extraction of curcumin RR% = ×100 (4)
Cadded
Table 3 presents a comparative analysis between the RS-DES/DLLME Where Cfound represents the concentrations of analyte after addition of a
method proposed in this study and several previously published tech­ known amount of standard, Creal refers the concentration of analyte in
niques for the extraction and determination of curcumin. According to the real sample, and Cadded denotes the concentration of a known
the findings, the developed approach exhibits limit of detection (LOD) amount of standard that was spiked into the real sample, respectively.
and limit of quantification (LOQ) values that are comparable to those
described in previous methodologies that have been published. The
preconcentration factor of the method is equivalent to or higher than Table 4
that of some previously documented techniques in comparison to Application of the presented RS-DES-DLLME technique for Curcumin in various
alternative preconcentration methodologies. The proposed study has foodstuff samples (N = 3).
many desirable features, including simplicity, high efficiency, rapidity, Sample Added (μg L− 1) Found (μg L − 1
) Recovery (%)
high recovery, and the use of much fewer reagents and solvents. The Tap water 0.0 N.D. –
results demonstrated that the method could be used to extract curcumin 150 145 ± 3.1 96.6
from water and food products with complicated matrices. 300 301 ± 2.8 100.3
Drinking water 0.0 N.D. –
150 143 ± 3.6 95.3
3.7. Application of the suggested method in the analysis of real samples 300 287 ± 4.2 95.6

Sample Added (μg kg¡1) Found (μg kg ¡1

) Recovery (%)
The extraction and quantification of curcumin in a number of food
and water samples under optimal conditions were examined in order to Herbal tea 1 0.0 52.0 ± 3.8 –
150 198 ± 4.2 97.3
assess the applicability of the proposed method. The experimental
300 342 ± 3.5 96.6
conditions were fixed, and the extraction procedures were carried out in Herbal tea 2 0.0 62.0 ± 1.8 –
accordance with the ‘RS-DES/DLLME procedure’. The real samples were 150 209 ± 3.7 98.0
spiked with standard curcumin solutions in suitable concentrations to 300 359 ± 4.1 99.0
evaluate the matrix effects, and the recoveries were calculated taking Herbal tea 3 0.0 42 ± 1.6 –
150 188 ± 4.4 97.3
into account the additional amounts. Water and food samples were
300 328 ± 3.8 95.3
spiked at two concentration levels of 150 and 300 μg L− 1, and then they Turmeric powder 0.0 159 ± 2.7 –
were extracted under optimal extraction conditions to evaluate the 150 298 ± 3.4 92.6
relative recoveries. The following equation was used to compute the 300 446 ± 4.2 95.6
Turmeric drug 0.0 117 ± 3.8
relative recovery (RR): –
150 259 ± 3.3 94.6
300 409 ± 2.8 97.3

Table 3
Comparison of the figures of merit of the proposed method with other reported methods for extraction and determination of Curcumin.
Method Detection system LDR (μg L− 1) PF LOD (μg L− 1) RSD Ref.

VA-DES-ME Spectrophotometry 5.0–300 100/120 1.5 1.7–3.3 [40]

VA-DES-ELLME Spectrophotometry 9.0–920 12.5 2.86 1.0–6.0 [41]
DLLME Spectrophotometry 10–2000 66.67 0.23 1.16–2.31 [42]
4 1
SPE CE-AD (0.03–7) × 10− mol L− 9.0 30.0 4.5–6.3 [43]
TAIL-DLPME Spectrophotometry 18.4–494 – 6.0–0.003 0.57–3.23 [44]
– HPLC-ITMS/MS/MS 1.0–3000 – 0.1 5.11 [45]
RSM-CCT-CPE HPLC 220–10000 9.5 66.0 2.77 [46]
RS-DES-DLLME Spectrophotometry 35.0–500 40 10.0 4.7–6.4 This Work

Vortex assisted deep eutectic solvent-microextraction (VA-DES-ME), Vortex assisted deep eutectic solvent-emulsification liquid-liquid microextraction (VA-DES-
ELLME), Dispersive liquid-liquid microextraction (DLLME), Solid phase extraction (SPE), Temperature-assisted ionic liquid dispersive liquid phase microextraction
(TAIL-DLPME), Response surface methodology-Cold column trapping-Cloud point extraction (RSM-CCT-CPE). Reusable and switchable deep eutectic solvent-
dispersive liquid-liquid microextraction (RS-DES-DLLME), Capillary electrophoresis with amperometric detection (CE-AD), High performance liquid
chromatography-ion trap triple stage mass spectrometry (HPLC-ITMS/MS/MS), High performance liquid chromatography (HPLC).

7
Q. Salamat and M. Soylak Talanta 269 (2024) 125401

The experimental procedure was conducted in triplicate for each treat­ cellulose-based microcapsules for targeted drug delivery, J. Ind. Eng. Chem. 105
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