Journal of Food Engineering 296 (2021) 110437

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Journal of Food Engineering

journal homepage: http://www.elsevier.com/locate/jfoodeng

Intensified DES mediated ultrasound extraction of tannic acid from

onion peel
N.F. Sukor, V. Panner Selvam, R. Jusoh *, N.S. Kamarudin, S. Abd Rahim
Faculty of Chemical and Process Engineering Technology, College of Engineering Technology, Universiti Malaysia Pahang, Gambang, Kuantan, Pahang, 26300, Malaysia

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

Keywords: Ultrasound–assisted extraction using deep eutectic solvent (DES) was performed to extract tannic acid from
Deep eutectic solvent onion peel. Notably, DES is an excellent extraction agent, which yielded 641.16 ± 0.01 μg/g of tannic acid
Ultrasound–assisted extraction compared to the extraction using a conventional solvent (368.99 ± 0.02 μg/g). Subsequently, the research was
Tannic acid
conducted based on several exploited parameters and achieved the highest extraction yield (1705.79 ± 0.01 μg/
Onion peel
Antioxidant analysis
g) at the DES ratio of 1:1 (mass ratio of choline chloride to urea), solid to solvent ratio of 1:10 and duty cycle of
Kinetics 10%. The onion sample exhibited higher antioxidant capacity than standard ascorbic acid, which was expressed
in the lower values of the half-maximal inhibitory concentration (IC50) at 7.70 ± 1.12 and 10.14 ± 0.11 mg/ml,
respectively. Moreover, the Fick’s model successfully forecasted that diffusivity is the controlling factor in the
extraction of tannic acid via the DES mediated ultrasound–assisted extraction method.

1. Introduction 2016). In addition, a previous study by Galo et al. (2020) successfully

determined 59.29% of tannic acid from the onion peel. However, to use
Onion (Allium cepa L.) is a versatile vegetable from the Liliaceae onion peel by products as a source that inhibits oxidation, suitable
family that is appreciated worldwide, not only for its taste but also as a extraction methods must be developed to reduce time, cost and envi­
valuable source due to its functional properties of various phenolic ronmental pollution.
compounds in every part of the onion. Global onion production was Ultrasound–assisted extraction is considered as an outstanding
estimated at 400,000 tonnes harvested from 2.40 million ha of land area alternative to conventional methods, as it is equipped with ultrasound
(Sagar et al., 2020). On top of that, Munir et al. (2018) previously re­ energy that focuses on the tip of a probe. The corresponding energy
ported increased of onion production of more than 25% over the past conveys acoustic cavitation to disrupt plant tissues, break down cell
decade and this consequently increased the production of the waste. It is membrane and reduce mass transfer limitations (Sukor et al., 2019). The
reported that more than 550,000 tonnes of onion waste are produced extraction method has also been recognised as an important approach in
annually, mainly generated by human consumption and food processing reducing extraction time, extraction temperature, energy input, con­
industries (Gosi Ruivo de Silva et al., 2020). sumption of organic solvents, and eventually enhancing the chemical
Fortunately, researchers have been aware of the strategy of using kinetics, solubility and experimental reproducibility (Katsampa et al.,
waste as a rich source of natural extracts. Some studies have highlighted 2015). In the past few years, the extensive use of conventional organic
that the tannins from onion peel may be considered as a good source in solvents such as chloroform, glycerol, hexane and ethyl acetate, has
various applications. Hydrolysed tannin has particularly received much restricted the implementation of green chemistry in the field of chemical
interest as the major polyphenol compound dominating the onion peel research. Owing to certain toxicity, volatility and non-degradability,
(Nnaji et al., 2013; Verma et al., 2018), including gallic acid, tannic acid, conventional organic solvents are not in line with the notion of green
vanillic acid, ferulic acid and epigallocatechin (Burri et al., 2017). The chemistry (Gao et al., 2020). To overcome these drawbacks, deep
presence of tannin compounds located primarily in the peel also eutectic solvent (DES) has been evolving as a novel class of green sol­
demonstrated satisfactory results in biological effects, including anti­ vents. DES was introduced by Abbott et al. (2003) by mixing solid
oxidant, antimicrobial and enzyme inhibitory activities (Eldin Hussein quaternary ammonium salts and solid urea to produce eutectics that
Elgailani and Yacoub Ishak, 2016; Fuentes et al., 2020; Patra et al., were liquid at ambient temperature with unusual solvent properties.

* Corresponding author.
E-mail address: [email protected] (R. Jusoh).

https://doi.org/10.1016/j.jfoodeng.2020.110437
Received 25 June 2020; Received in revised form 6 October 2020; Accepted 2 December 2020
Available online 5 December 2020
0260-8774/© 2020 Elsevier Ltd. All rights reserved.
N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

DES has superior properties, such as low vapour pressure, high thermal choline chloride:urea DES solution (Saha et al., 2019), until the mixture
stability and tunable solubility (Kalhor and Ghandi, 2019), which became homogeneous before the extraction process. The DES/water
enabled DES to show extraordinary application values in various fields mixture (aqueous DES) has favourable physicochemical properties, such
(Barbieri et al., 2020; Oktaviyanti et al., 2019; Zhao et al., 2019) and has as lower viscosity. Despite the high level of water mixed into DES so­
received widespread attention in the extraction of various non-polar and lution, the DES nanostructure is retained due to the solvophobic
polar bioactive compounds from plant materials. The synergistic rela­ sequestration of water into nanostructured domains around cholinium
tionship between sonication and DES in facilitating the release of cations (Alonso et al., 2016; Hammond et al., 2017). Moreover, the
phenolic compounds leads to an efficient mass transfer coefficient. choline–urea hydrogen bonding interaction (OH—NH2) will be
Several kinetic models have been postulated in search of the de­ strengthened. Interestingly, the presence of water did not affect the yield
pendency of the extraction process towards effective component diffu­ or selectivity of the process but reduced the viscosity of DES, hence
sion. In engineering, kinetic modelling provides valuable information on allowing an effective stirring of the reaction (Saha et al., 2019). Thus, it
extraction behaviour. Numerous extraction kinetics, such as rate law, can be assumed that the effect of water is insignificant to the extraction
Peleg’s and Fick’s models, have been previously reported (Chiang et al., performance of tannic acid. The preparation of other DES ratios followed
2017; Gomaa et al., 2018). Nevertheless, the data on the comprehensive the same procedures, but the mass of choline chloride and urea was
analysis between the kinetic models and the extraction by ultra­ varied based on the required ratios. For instance, the DES ratio of 1:1
sound–assisted extraction for onion peel extract are scarce. was prepared by mixing 12.50 g of choline chloride and 12.50 g of urea,
Although there are previous findings on extracting phenolic com­ whereas the 2:1 ratio consisted of 16.67 g of choline chloride and 8.22 g
pounds via various methods, the study that emphasizes the extraction of of urea.
tannic acid from onion peel via ultrasound–assisted extraction with the
implementation of DES as a medium has never been reported so far. Past 2.3. Ultrasound–assisted extraction
studies utilised conventional organic solvents as the extraction media in
obtaining the target compounds. However, these solvents are harmful to The experiment with ultrasound application was first carried out in
the environment and do not indicate research priorities for the devel­ diluted DES at different DES ratios by fixing other parameters (i.e., solid
opment of green chemistry technologies. Based on the discussion, in the to solvent ratio of 1:10, duty cycle of 10%, 3 h of extraction time, 60 ◦ C
present study, a green and integrated strategy for enhanced tannic acid of extraction temperature). The extraction was conducted using a high-
extraction from onion peel was developed via DES mediated ultra­ intensity processor model Q700 (700 W, 20 kHz) from QSonica, New­
sound–assisted extraction. The antioxidant activity was also studied to town, USA (Figure S1), with a replaceable flat-tip ultrasonic probe
examine the relationship between the optimum operating conditions. (sonotrode). The probe of the ultrasound–assisted extraction equipment
Moreover, this study also aimed to evaluate several mathematical was equipped with the amplitude setting to fix the temperature and
models to find the controlling factor related to the extraction kinetics. reflect the power level. During sonication, the amplitude was set to 13 to
obtain a fixed temperature of 60 ◦ C, reflecting power of 26 W and
2. Materials and methods sonication intensity of 20.47 W/cm2, whereas the cumulative average
ultrasound dose was varied by adjusting the duty cycle (Sukor et al.,
2.1. Materials and chemicals 2019).
Duty cycle is the fraction of one period in which a signal or system is
Fresh onion (Allium Cepa L.) peel was obtained from shops and res­ active, commonly expressed as a percentage or ratio. A period is the time
taurants. In the preparation of onion peel powder through extraction, required for a signal to complete an on-and-off cycle. In this context,
fresh onion peels were first cleaned, washed, and dried in an oven at ultrasound–assisted extraction works in a pulsating mode. For example,
40 ◦ C until the peels were completely dried, achieving moisture content 10% duty cycle represents a sonication period of 1 s, followed by the rest
at 0.1 kg water/kg dry onion peel. Then, the sample was pulverised in a period of 9 s. Meanwhile, 20% duty cycle represents sonicating period
domestic blender until the sample turned into fine powder (0.50 mm) for 2 s, followed by rest period of 8 s, while 30% duty cycle represents a
before further use in extraction. Different extraction media were tested, sonication period of 3s, followed by the rest period of 7 s. Throughout
namely methanol (Sigma–Aldrich, Germany) and the DES obtained from the experiments, the solid to solvent ratio was examined at 1:8, 1:15 and
the mixing of choline chloride (Sigma–Aldrich, Germany) and urea 1:20, whereas the duty cycles was further studied at 20% and 30%.
(Merck, Germany). Tannic acid (Merck, Germany) was used as a stan­
dard for the quatification of phenolic acids. Acetonitrile (Merck, Ger­ 2.4. Liquid chromatography quadrapole time–of–flight mass spectrometry
many) and orthophosphoric acids, 85% (Fisher Science, UK) were used (LC-QTOF/MS) analysis
as the mobile phase for high performance liquid chromatography
(HPLC) analysis, whereas 2,2-diphenyl-1-picryl-hidrazil (DPPH) reagent The phenolic compounds in the onion peel were identified using the
(Sigma–Aldrich, Germany) was used for scavenging analysis. All re­ method of Tang et al. (2019) with some modifications. The identifica­
agents and standards were purchased from Nano Life Quest Sdn. Bhd. tion of the compounds was performed via Agilent 1200 Series (HPLC)
equipped with an Agilent 6520 Accurate-Mass quadrapole time-of-flight
2.2. Preparation of deep eutectic solvent liquid chromatography/mass spectrometry (Q-TOF LC/MS) using C18
column. Gradient elution was performed by varying the proportion of
Choline chloride is an economical and non-toxic quaternary ammo­ solvent A (water/acetic acid at the ratio 98:2, v/v) to solvent B (aceto­
nium salt that is commonly utilised as a hydrogen bond acceptor (HBA), nitrile/water/acetic acid at the ratio 100:1:99, v/v/v), in the following
which can form homogeneous and stable eutectic solvents with programme: 0–20 min, 10% B; 20–30 min, 25% B; 30–40 min, 35% B;
hydrogen bond donors (HBDs), such as organic acids or polyalcohols. 40–70 min, 40% B; 70–75 min, 55% B; 75–77 min, 80% B; 77–79 min,
The preparation of DES was adapted and modified from Isaifan and 100% B; 79–82 min, 100% B; 82–85 min, 10% B. Each sample was
Anhamed (2018), which consisted of a mixture of choline chloride and filtered with a nylon syringe filter (pore size 0.22 μm) and subsequently
urea at different ratios (1:2, 1:1 and 2:1). The DES ratio of 1:2 (choline transferred into a 2 ml vial. The separation was achieved by fixing the
chloride:urea) was prepared by fixing a total amount of 25 ml of mixed flow rate of 0.8 ml/min and the injection volume was set at 6 μl.
DES solution. The DES ratio of 1:2 (choline chloride:urea) representing Mass spectra acquisition was performed in the m/z range of 50–1300
8.33 g of choline chloride and 16.67 g of urea was mixed, stirred and Da, drying gas (nitrogen) temperature of 300 ◦ C (flow rate: 5 L/min),
heated at 80 ◦ C until a colourless liquid (a total of 25 ml) was formed. sheath gas temperature of 250 ◦ C (flow rate = 11 L/min), capillary
Then, 75 ml of distilled water was mixed with previously prepared voltage of 3500 V, nebuliser gas pressure of 45 psi and nozzle voltage of

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

500 V. The identified compounds present in the samples from the (Kaderides et al., 2019). The basis for the model can be written as:
METLIN database with more than 30 library identification score were
dc
further selected for characterisation and m/z verification. = k(c − c∞ )2 (3)
dt

2.5. High performance liquid chromatography analysis where, k is the second-order extraction rate constant (g/μg.min), c∞ is
the extraction capacity (μg/g) and c is the concentration of sample
The identification of tannic acid from onion peel extract with DES as constituent in the solution (μg/g) at any time t (h). The integrated rate
solvent was performed according to Md Zain and Ya’akob (2019) with law can be obtained under the boundary conditions of t = 0 to t and c =
some modifications using a reversed–phase HPLC equipped with a 0 to c, as expressed below:
photodiode array (PDA) detector using C18 column via binary gradient
elution. Gradient elution was performed by varying the proportion of c2 kt
c= (4)
solvent A (100% acetonitrile, 10%) to solvent B (3.0% phosphoric acid, 1 + c∞ kt
90%) in an isocratic programme and pumped at a flow rate of 1 ml/min. Eq. (4) is reorganised in its linear form into:
The gradient started with 95% solution A and ended with 5% solution B.
c 1
The column temperature was maintained at 30 ◦ C, with the injection =( ) ( ) (5)
t
volume of 10 μl. The sample peaks were identified by comparing with 1
+ t
kc2∞ c∞
the standard solution of tannic acid at 280 nm (retention time = 4.40
min). A tannic acid standard curve was prepared at concentration
c/t in Eq. (5) signifies the initial extraction rate, which can also be
ranging from 10 to 60 ppm in ultrapure water (Figure S2). Each sample
denoted by h (μg/g.min). As defined by Eq. (6) when the extraction time,
and standard were filtered with a nylon syringe filter (pore size = 0.22
t approaches zero:
μm). The extraction yields were expressed as micrograms per grams of
sample (μg/g) and calculated as follows: h = kc2∞ (6)
(x)(DF)(V) In this study, k and c∞ can be obtained from the gradient and
ExtractionYield = (1)
(W) intercept values, respectively, by plotting a linear curve of c/t vs. 1/t and
the h values can be subsequently computed. Thus, the final equation
where x is the concentration of tannic acid (μg/L), DF is the dilution describing the concentration of the solute in the onion peel at any time
factor, V is the volume of DES (L) and W is the mass of the solid sample can be written as:
(g).
t
c=( ) ( ) (7)
2.6. Scanning electron microscopy 1
h
+ t
c∞

The cellular microstructure of onion peel sample particles before and

after extraction via different extraction methods was examined using a 2.8.2. Peleg’s model
scanning electron microscope (Quanta 450). Upon analysis, the samples An established capacity-dependent kinetic of the Peleg’s model has
were coated with a thin layer of platinum at room temperature and the been extensively enforced to describe the extraction of polyphenols from
images were obtained at 90 V with 3000 × magnification. spent coffee grounds (Pettinato et al., 2019), stevioside from Stevia
rebaudiana (Rouhani, 2019), and phenolic acids from oak galls (Sukor
et al., 2019). The Peleg’s model equation is expressed as follows:
2.7. Antioxidant activity determination using DPPH radical scavenging
assay t
Ct = C0 + (8)
K1 + K2 t
This assay was produced according to the method of Oussaid et al.
(2017) with some modification. 2,2–diphenyl–1–picrylhydrazyl (DPPH) where Ct signifies the concentration of the sample constituent in solution
was dissolved in methanol to the concentration (of 1 mM, 100 ml), using at any time, t (μg/g), and K1 and K2 are the Peleg’s rate constant (min.g/
39.4 mg of DPPH, forming a purple solution. This antioxidant compo­ μg) and Peleg’s capacity constant (g/μg), respectively. Co is the primary
nent can scavenge free radicals, thereby bleaching the purple colour concentration of sample constituent, which is zero due to the use of a
(colourless). Then, 1 ml of extract was added to 1 ml of DPPH meth­ fresh solvent. The Peleg’s model was modified as extraction typically
anolic solution and allowed to stand in the dark for 30 min at room occurs in two stages; the first-order trend in the initial stage and the
temperature. After that, the absorbance was measured at 517 nm using a zero-order trend in the later stage, as presented below:
ultraviolet–visible (UV–Vis) spectrophotometer. The free radical scav­ t
Ct = (9)
enging activity of the sample extract was determined based on the K1 + K2 t
equation as follows:
where the K1 and K2 values can be obtained from the slope and intercept
Acontrol − Asample
Scavengingrate(%) = x100% (2) of the 1/Ct vs 1/t graph, respectively. Moreover, the Ct value can be
Acontrol
further calculated using Eq. (9) at different time points to examine the
where Asample is the absorbance of DPPH with a sample at 517 nm and fitting of this model on the extraction of onion peel.
Acontrol refers to the absorbance of DPPH without the sample at 517 nm.
2.8.3. Fick’s model
According to the Fick’s second law of extraction kinetics, it is
2.8. Experimental set–up for kinetic analysis
assumed that the extraction occurs in two phase; a rapid phase known as
“washing” and a slow diffusion phase, where the concentration of solute
2.8.1. Rate law
remains in effective diffusion and the external mass transfer resistance is
Prominently, the second–order rate law is often employed in the
negligible. This excellent model has been used to perfectly discuss the
solid–liquid extraction modelling due to its compatibility in represent­
nature of the extraction of Glycyrrhiza (Wang et al., 2019), Chinese dark
ing a process. These concentration-dependent kinetics were previously
tea (Cai et al., 2019), and Eucalyptus nitens and Eucalyptus globulus
utilised in examining the phenolic content from Hibiscus sabdariffa
(González et al., 2017). The model can be described as follows:
calyces (Oluwaseun and Nour Hamid, 2019) and pomegranate peels

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

[( ) ( )]
c∞ − c 6 π 2 D1 t π 2 D2 t quantification by the UV spectrometry, and the results revealed that
= 2 f1 exp − + f exp − (10)
c∞ π r2
2
r2 tannic acid occupied the highest yield in the sample. Hence, tannic acid
quantification was highlighted in this study and further investigation on
where f1 and f2 represent the fractions of the solute, extracted from the several extraction parameters was conducted using HPLC to evaluate the
washing or fast and slow diffusion stages, respectively, along with the process intensification of the amount of extraction yield from the onion
diffusion coefficients, D1 and D2. C∞ is the concentration in equilibrium, peel.
C is the concentration in time t and r is the particle radius.
The equation above was applied upon considering several estab­ 3.2. Effect of different operating conditions
lished conditions by Shafaei et al. (2016). In this study, the onion peel
sample powder was assumed to be spherical with 0.25 mm radius. In the 3.2.1. Effect of solvent
later stages of extraction, only the second term on the right-hand side of In this study, aqueous DES was used to extract tannic acid from onion
Eq. (8) remained significant. The parameters of diffusion, D and fraction peel, and methanol was used for comparison purposes. Fig. 2A indicates
[ ]
of solute, f can be obtained from the slope and the intercept of ln C∞C∞− C that DES yielded a higher amount of tannic acid at 641.16 ± 0.01 μg/g
compared to methanol at 368.88 ± 0.02 μg/g. An almost two-fold
vs. time graph, respectively. greater extraction efficiency of DES-based extraction suggests that the
polyalcohol DES implemented in this study is easy to synthesise and
2.9. Statistical analysis possesses low viscosity, hence offerring better ability to dissolve the
sample matrix and generate a higher yield (Shafie et al., 2019). Besides,
The mean values and standard deviations of all replicates were the polarity of DES is close to those of the target compounds in the onion
calculated using Microsoft Excel. The values were displayed as mean ± peel, which is in favour of extracting the target phenolics (Skarpalezos
standard deviation (SD) while P < 0.05 was considered statistically and Detsi, 2019).
significant. All determinations were measured in triplicate and the This is in agreement with a previous study by Barbieri et al. (2020) in
confidence interval is represented by an error bar. the extraction of rosemary (Rosmarinus officinalis L.), which obtained a
higher total phenolic compound using choline chloride derivative-based
3. Results and discussion DES with propanediol compared to ethanol at 62.21 mg/g and 49.14
mg/g, respectively. Another finding by Alanon et al. (2020) also
3.1. Identification of phenolic compounds in the sample using LC–QTOF/ confirmed that choline chloride derivative–based DES was an excellent
MS solvent for the extraction of phenolic compounds from olive leaf.
Accordingly, DES was selected for further intensification of the extrac­
A full–spectrum analysis of onion peel extract was performed using tion of onion peel extract.
LC–QTOF/MS as illustrated in Fig. 1. Meanwhile, Table 1 shows the
theoretical and observed m/z based on one plant sample for each 3.2.2. Effect of DES choline chloride:urea ratio
phenolic compound with mass errors within ±5 ppm. A total of 34 As shown Fig. 2B, different DES ratios of choline chloride:urea at 1:1,
different phenolic compounds were identified in the onion peel extract 1:2 and 2:1 were applied in evaluating its reliance towards the extrac­
sample based on the records from the METLIN database, including 22 tion yield of tannic acid from the onion peel extract. The 1:1 ratio of
flavonoids, nine phenolic acids, one stilbenes and two polyphenols. choline chloride:urea demonstrated a significant increase in the
Phenolic compounds, namely, tellimagrandin, nobergenin, 3,4,5-O-tri­ extraction yield of 1705.79 ± 0.01 μg/g of tannic acid compared to the
caffeoyl-quinic acid, pedunculagin and tannic acid revealed higher ratios of 1:2 and 2:1 with the yields of tannic acid of 516.91 ± 0.02 and
peaks, detected at the retention time of 0.47, 2.45, 16.54, 16.64 and 422.15 ± 0.04 μg/g, respectively. The same type of DES with different
15.56 min, respectively. These compounds are a form of tannins, which HBD/HBA ratios showed a great difference in extraction yield due to its
are widely found in the onion peel as previously reported by Burri et al. different viscosity, surface tension and polarity.
(2017) and Rodrigues et al. (2017). Firstly, the LC–QTOF/MS analysis The increasing amount of HBA (choline chloride) ratio in DES might
was conducted in this study to confirm the availability of these tannin increase the surface tension, whereas excess HBD (urea) may result in
compounds on MS basis. Upon the confirmation, HPLC analysis was stronger steric hindrance that weakens the interactions between the
used, combined with a diode array detector (DAD) and the target compounds and chloride anion (Gao et al., 2020). The appropriate

Fig. 1. LC–QTOF/MS chromatogram showing main phenolic compounds in the onion peel extract.

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

Table 1
Qualitative characterization of phenolic compounds in onion peel extract by LC–QTOF/MS.
Proposed compounds Molecular Mass error Retention time Molecular Theoretical (m/ Observed (m/ Mode of
formula (ppm) (min) weight z) z) ionization

Flavonoids
Pedunculagin C34H24O22 − 4.1 16.64 784.08 785.07 785.08 [M+H]+
Casuarictin C41H28O26 5.2 16.33 936.09 937.08 937.09 [M+H]+
Norbergenin C13H14O9 − 4.0 2.45 314.06 353.06 353.03 [M+K]+
1,2,3,4,6-Penta-O-galloyl-β-D- C41H32O26 − 1.4 16.53 940.12 963.13 963.11 [M+Na]+
glucopyranoside
Arecatannin B1 C45H38O18 − 0.6 16.61 866.21 867.21 867.21 [M+H]+
Laevigatin A C34H26O23 2.8 16.52 802.09 825.09 825.08 [M+Na]+
Phenolic acids
Corilagin 1 C27H22O18 5.4 16.64 634.08 657.08 657.07 [M+Na]+
6′ -O-Galloyl-homoarbutin C20H22O11 − 0.2 5.64 438.12 439.12 439.12 [M+H]+
3,4,5-O-Tricaffeoyl-quinic acid C34H30O15 − 0.9 16.54 678.16 679.13 679.17 [M+K]+
1,3,6-Trigalloyl-β-D-glucose C27H24O18 5.3 16.55 636.10 675.10 675.06 [M+K]+
1-O-Galloylpedun-culagin C41H28O26 5.2 16.55 936.09 937.09 937.10 [M+H]+
Polyphenols
Tellimagrandin II C41H30O26 3.0 0.47 938.10 961.11 961.10 [M+K]+
Stilbenes
4,4′ ,5,6-Tetrahydroxystilbene C14H12O4 − 9.1 16.34 244.07 245.07 245.08 [M+H]+

Fig. 2. Extraction yield of tannic acid under different (A) type of solvents and (B) DES ratio.

ratios of HBD/HBA should be carefully examined in reducing the vis­ decrease in the extraction yield beyond the critical ratio may be
cosity and surface tension of DES for accelerating the diffusion and mass attributed to the formation of liquid film at the interfacial surface of the
transfer of the reaction system, hence leading to a higher extraction sample. These phenomena will hinder the mobility of solvent molecules
yield (Isaifan and Amhamed, 2018). Pal and Jadeja (2019) previously into the interior pores, promoting resistance to the diffusion mass
discussed similar results for the extraction of onion peel-mediated DES transfer of the solute particles (Anbalagan et al., 2019). This may be due
(choline chloride:urea) with varied ratios from 1:1 to 1:3, and the to the inadequate solvent concentration to extract from the substance
highest total phenolic content of 222.97 mg/g was obtained (at the ratio matrix. However, no significant difference was observed, the best con­
of 1:2) compared to other ratios of DES. Therefore, the DES ratio of 1:1 dition for the solid-to-solvent ratio is 1:10, which was used to study
with suitable physio–chemical properties and polarity was selected for another effect in enhancing the extraction yield of tannic acid.
the subsequent experiments. A past study by Kankara et al. (2014) stated that 1:10 appeared to be
the best solid-to-solvent ratio using hot water extraction for extracting
3.2.3. Effect of solid to solvent ratio phenolic antioxidants from Guirea senegalensis (Combratecae) leaves.
The effect of solid-to-solvent ratio of 1:8, 1:10, 1:15 and 1:20 was Another successful finding by Durdun et al. (2016) also suggested
investigated, as demonstrated in Fig. 3A. The extraction yield increased solid-to-solvent ratio of 1:10 positively influenced the total phenolic and
from 1001.15 ± 0.01 to 1705.79 ± 0.01 μg/g as the solid-to-solvent ratio flavonoid contents of the dried fruits of dog-rose, sea buckthorn and
increased from 1:8 to 1:10. An increase in the DES volume fraction hawthorn via ultrasound–assisted extraction using ethanol as a solvent.
positively influenced the extraction efficiency and the yield of tannic
acid that was maximised at 1:10. Nonetheless, with a further increase of 3.2.4. Effect of duty cycle
DES volume, the extraction yields insignificantly dropped to 1623.05 ± The duty cycle of ultrasound–assisted extraction is another critical
0.03 and 1523.76 ± 0.02 μg/g at 1:15 and 1:20, respectively. The slight parameter for an efficient extraction process that will maximise the

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

Fig. 3. Extraction yield of tannic acid under different (A) solid to solvent ratio and (B) duty cycles.

amount of target compounds. The experimental results of the effect of and other plant sources for comparing the extraction methods, operating
duty cycle ranging from 10% to 30% are presented in Fig. 3B. The 10% conditions and extraction yields. Similar observations by Mohd Abdul
duty cycle yielded the highest amount of tannic acid of 1705.79 ± 0.01 Alim et al. (2016) declared that 10% duty cycle appeared to be the ideal
μg/g, compared to 20% and 30% duty cycles that obtained 935.37 ± condition to extract vitexin from Ficus deltoidea leaves. Moreover, Sukor
0.01 μg/g and 431.83 ± 0.01 μg/g of tannic acid, respectively. The in­ et al. (2019) also maintained 10% duty cycle in the entire process of
tensity level provided by the duty cycle adjuster creates ultrasonic ultrasound–assisted extraction for extracting gallic acid and tannic acid
waves, which generate stable bubbles in the solvent through diffusion from oak galls. The extraction of phenolic compounds from the onion
(Mahindrakar and Rathod, 2020). The adequate intensity level at 10% peel has been done in the past studies; however no effort has been use
duty cycle facilitates the disruption of the plant cell wall of the onion the greener solvent of DES as the extraction medium along with ultra­
peel and consequently enhances the release rate of target components sound–assisted extraction (Chia et al., 2019; de et al., 2017; Katsampa
from the sample matrix to the solvent. However, the higher intensity et al., 2015). The onion peel was previously extracted either by using
supplied up to 20% and 30% duty cycle may damage the target phenolic conventional organic solvents (i.e., ethanol, glycerol) or water. In this
compounds, minimizing the amount of extraction yield (Sulaiman et al., study, the optimum condition of ultrasound–assisted extraction for
2011). onion peel was achieved under the utilisation of DES as the medium at
Table 2 tabulates previous findings on the extraction of onion peel the DES ratio of 1:1, solid-to-solvent ratio of 1:10 and duty cycle of 10%.

Table 2
Table of comparison on the various extraction method, operating condition and extraction yield from several plants.
Source Active compounds Extraction method Operating condition Extraction References
yield
Solvent Duty
cycle
(%)

Onion peel Tannic acid Ultrasound–assisted DES (Choline chloride:Urea) 10 1705.80 μg/g This study
extraction
Oak galls Gallic acid (GA) and tannic Ultrasound–assisted Ionic liquid, 1-Butyl-3-methylimidazolium bis 10 497.34 mg/g [6]
acid (TA) extraction (trifluoromethylsulfonyl)imide, [Bmim][Tf2N] (GA)
2430.48 mg/g
(TA)
Mulberry Phenolic compounds Microwave assisted DES (Choline chloride:Glycerol) N/A 8.35 mg/g [8]
(Morus alba extraction
L.)
Quercus Gallic acid (GA) and tannic Ultrasound–assisted Hexadecyltrimethylammonium bromide, CTAB 40 2155.77 mg/ [18]
infectoria acid (TA) extraction kg (GA)
galls 15236.83 mg/
kg (TA)
Ficus deltoidei Vitexin Ultrasound–assisted Water 10 0.74% w/w [41]
leaves extraction
Red onion skin Phenolic compound Aqueous extraction 80% ethanol N/A 757.38 mg/g [42]
Onion solid Polyphenols and pigments Ultrasonic bath Glycerol N/A 490 μmol/g [43]
wastes
Onion peel Bisindolylmenthanes Aqueous extraction Water N/A 90% [44]
Waste onion Quercetin Aqueous extraction DES (Choline chloride:Urea) N/A 2.80 mg/ml [45]
Ginger Gingerols Ultrasonic bath alcohol–based DES N/A 3.82 mg/g [67]
Ethanol (L–cartinine:1,3–butanediol)

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

3.3. Microscopic observation using SEM

At the desired operating condition, the scanning electron microscopy

(SEM) images of the outer surface of the onion peel powder sample were
captured and compared before and after extraction, as depicted in
Fig. 4A and B, respectively, at 3000 × magnification. From the micro­
scopic morphology, it is determined that the intensity of the cell wall
integrity depends on the sonication treatment. The obtained results
illustrated that the ultrasound–assisted extraction procedures damaged
cell tissues, as exemplified in Fig. 4B. Meanwhile, a smoother surface
could be observed on the exterior side in Fig. 4A (control). This profile
may support the previous results in attaining a high extraction yield of
tannic acid upon sonication. The damaged cell walls subsequently in­
crease the solvent penetration into the plant sample, thus encourages the
diffusivity of the target compounds from the onion peel matrix sample.
Fonteles et al. (2016) also previously claimed that sonication promotes
diffusivity as many bioactive compounds were obtained from cashew
apple bagasse puree.

3.4. Antioxidant analysis

The antioxidant activity of the onion peel extract was measured to

identify its ability to trap an unpaired electron of the DPPH radical,
which was expressed as the percentage of inhibition of DPPH in the
solution. In Fig. 5, it can be observed that the onion peel sample
exhibited better performance in scavenging the DPPH radical than the
standard ascorbic acid. The onion peel sample displayed 97.51 ± 1.12% Fig. 5. Antioxidant activity of onion peel extract.
antioxidant activity compared to standard ascorbic acid (94.476 ±
0.11%). The highest scavenging activity is reflected by a smaller value of Kenari (2016) for the extraction of onion peel obtained 61.11%–84.68%
the IC50, which indicates how much of a specific pharmacologic agent is inhibition via various extraction methods.
required to inhibit a given biological activity by half. The onion peel
sample extract exhibited a lower IC50 value at 7.70 ± 1.12 mg ascorbic 3.5. Kinetic analysis
acid/ml than standard ascorbic acid (10.14 ± 0.11 mg ascorbic acid/
ml). The results of experimental data, calculated data, coefficient of
Tannic acid is a potent antioxidant that donates two hydrogen atoms determination (R2) and percentage error (%) at the optimum condition
to DPPH radical, which transforms it into a quinone intermediate of DES as a solvent, the DES ratio of 1:1, solid-to-solvent ratio of 1:10
(Ghatak and Iyyaswami, 2019). Apak et al. (2016) also declared that and varied duty cycles (10%–30%) were analysed to evaluate different
tannic acid has the highest antioxidant capacity than other antioxidant kinetic models (rate law, Peleg’s model and Fick’s model) in explaining
compounds. These statements supported the obtained results in this the extraction nature of onion peel. R2 is a statistical measure that sig­
study, which agreed that tannic acid possesses high antioxidant activity. nifies the goodness-of-fit of a model, whereas the percentage error is the
Also, Lee et al. (2014) reported a comparable result of the antioxidant difference between the experimental and calculated values, divided by
activity from the onion peel extract of 89.72%. A study by Razavi and the calculated value and multiplied by 100%. The value of R2 near to 1

Fig. 4. SEM microscopic observation (magnitude 3000 × ) of onion peel surface (control), (B) after ultrasound–assisted extraction method.

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

and a small percentage error show a good correlation between the Peleg’s model in describing the solid-liquid extraction of mangiferin
experimental and calculated data. In this study, three kinetic models from Mangifera indica leaves.
were compared and evaluated in determining the best kinetic curve that The slope of the curve in Fig. 6B proposed a less scattered experi­
can best explain the extraction of onion peel. mental data than the previous rate law model; nevertheless, the tabu­
lated data of the high percentage error (1.41 ± 0.01% - 7.36 ± 0.02%)
3.5.1. Rate law seemed unfit to elucidate the extraction process. Although satisfactory
The model parameters of extraction rate constant, k1, initial extrac­ R2 between 0.88 ± 0.03 and 0.99 ± 0.01 were obtained at all duty cy­
tion rate, h, R2 and percentage error were determined numerically using cles, it is still insufficient to fully describe the nature of the extraction of
the rate law nonlinear regression algorithm at different duty cycles, as onion peel extract. This is in agreement with past findings by Segovia
tabulated in Table 3. At the optimum extraction condition using DES as a et al. (2016) and Balyan and Sarkar (2017) which revealed that the
solvent, the DES ratio of 1:1 and solid-to-solvent ratio of 1:10, the duty Peleg’s model could not justify the avocado and Syzygium cumini L. seed
cycle of 10% recorded the highest k1 value at 6.36 ± 0.03 g/μg min and extraction, respectively. Therefore, another kinetic model was further
subsequently dropped to 3.07 ± 0.06 and 1.70 ± 0.01 g/μg min at 20% established to adequately fit the experimental data with lower per­
and 30% duty cycles, respectively. High k1 indicates a relatively faster centage error values.
reaction in extracting the target compounds. The result shows a good
correlation between the optimum condition of 10% duty cycle, resulting 3.5.3. Fick’s model
in the maximum yield with the highest k1 value compared to other duty The diffusivity elements promoted by the Fick’s model are tabulated
cycles (“The Rate Law: Concentration and Time | Boundless Chemistry,” in Table 5, comprising the diffusion coefficients, D1 and D2; fraction of
2020). A similar trend was observed on the initial extraction rate values solutes, f1 and f2; R2; and percentage error between the experimental and
with the highest h of 26.32 ± 0.04 ( × 105) μg/g min for 10% duty cycle. calculated data among different duty cycles. The extraction of onion
As the duty cycle was further intensified to 20% and 30%, the h value peel employed under 10% duty cycle (optimum extraction condition
abruptly reduced to 4.71 ± 0.01 ( × 105) and 1.09 ± 0.06 ( × 105) μg/g using DES as a solvent, the DES ratio of 1:1 and solid-to-solvent ratio of
min, respectively. Even though the rate law kinetics showed high R2, 1:10) revealed 2.19 ± 0.01 ( × 10− 2) m2/min and 22.34 ± 0.01 ( × 10− 2)
values ranging from 0.95 ± 0.01 to 0.99 ± 0.01, the findings contra­ m2/min of D1 and D2, respectively. A further increment in the duty cycle
dicted with the high percentage errors between the experimental and intensity to 20% and 30% significantly produced lower diffusion co­
calculated values of 28.83 ± 0.03%, 33.37 ± 0.01% and 11.28 ± 0.01% efficients of D1 and D2. As 10% duty cycle recorded the highest D1 and D2
at the duty cycles of 10%, 20% and 30%, respectively. coefficients, this finding suggests a rapid initial mass transfer from onion
Fig. 6A shows an imprecise fit of the experimental and calculated peel extract. The acoustic cavitation from ultrasound–assisted extraction
data, hence explaining a disagreeable kinetic curve of the rate law model provides sufficient disruption towards the plant tissues to easily diffuse
of onion peel. Furthermore, the underestimation of the calculated out tannic acid from the sample (Ghitescu et al., 2015; Rashed et al.,
extraction yield and the high value of percentage error imply the in­ 2016). Nonetheless, prolonged and intense duty cycles up to 20% and
efficiency of this concentration-dependent kinetic model as proposed by 30% may eventually damage the plant cells, which leads to a slow
the rate law for the extraction of tannic acid from onion peel via DES diffusion process.
mediated ultrasound–assisted extraction. This is in accordance with Fig. 6C shows the precisely adjusted calculated data to the experi­
previous study by Chua et al. (2018), which argued that the rate law mental data curve corresponding to the diffusivity factor in explaining
could not justify the extraction of pectin from dragon fruit peels. the extraction process. This finding was further supported by the high,
Another finding by Abugabr Elhag et al. (2019) also agreed with this R2 (>0.99 ± 0.05) and low percentage error values (<0.05) obtained at
study that the kinetic modelling of rate law was less successful repre­ all duty cycles. The difference between the calculated and experimental
senting the extraction behaviour of proteins from the root extracts of values of the model is significant; therefore, it is suitable to consider the
Tongkat Ali (Eurycoma apiculata). Fick’s model as the prominent kinetics in describing this diffusion-
dependent extraction of onion peel extract. The applicability of this
3.5.2. Peleg’s model model in explaining extraction behaviour was supported by other pre­
Table 4 presents the Peleg’s model parameters, including the rate vious findings from Oluwaseun and Nour Hamid (2019), Louati et al.
constant, K1; capacity constant, K2; R2 and percentage error of the tannic (2019) and Setford et al. (2017) for extracting phenolic compounds from
acid extraction yield from onion peel at various duty cycles. At the op­ Hibiscus sabdariffa calyces, Citrus sinensis L. and red grapes, respectively.
timum extraction condition using DES as a solvent, the DES ratio of 1:1 A perfectly fit curve of the Fick’s model obtained from previous studies,
and solid-to-solvent ratio of 1:10, the K1 values increased with elevated and with high R2 (0.99) are the evidences that diffusivity magnitude is
duty cycle, which obtained 1.84 ± 0.07 ( × 10− 2), 3.87 ± 0.02 ( × 10− 2) the factor in controlling the process. Thus, it can be concluded that the
and 4.64 ± 0.02 ( × 10− 2) min g/μg for 10%, 20% and 30% duty cycles, diffusivity factor is the core value in the extraction of tannic acid from
respectively. This gradually increasing pattern with elevated duty cycle the onion peel via synergistic DES mediated ultrasound–assisted
was also observed on the K2 values that attained 0.05 ± 0.05 ( × 10− 2) extraction.
g/μg at 10% duty cycles, followed by 0.07 ± 0.01 ( × 10− 2) and 0.21 ±
0.01 ( × 10− 2) g/μg for 20% and 30% duty cycles, respectively. Both K1 4. Conclusion
and K2 that refer to the rate of mass transfer and the maximum con­
centration of the desired compound during extraction, respectively, are This study was carried out to determine the performance of the DES
in concordance with a past study by Anbalagan et al. (2019), which mediated ultrasound–assisted extraction in extracting tannic acid from
stated that lower values of K1 and K2 ascertained the accuracy of the onion peel. The extraction using DES significantly yielded higher tannic

Table 3
The kinetic parameters of Rate law at different duty cycles [Extraction temperature 60 ◦ C; solvent DES; DES ratio 1:1; solid to solvent ratio 1:10].
Condition Experimental (μg/g) k1 (g/μg min) h (μg/g min) Calculated (μg/g) R2 % Error

Duty cycle (%) 10 1705.79 ± 0.02 3.07 ± 0.06 26.32 ± 0.04 1323.31 ± 0.06 0.99 ± 0.01 28.83 ± 0.03
20 935.35 ± 0.03 6.36 ± 0.03 4.71 ± 0.01 701.30 ± 0.06 0.95 ± 0.01 33.37 ± 0.01
30 431.84 ± 0.03 1.70 ± 0.01 1.09 ± 0.06 388.06 ± 0.02 0.99 ± 0.01 11.28 ± 0.01

h (x105).

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

Fig. 6. Extraction kinetics of (A) Rate law, (B) Peleg’s model and (C) Fick’s model at different duty cycles.

Table 4
The kinetic parameters of Peleg’s model at different duty cycles [Extraction temperature 60 ◦ C; solvent DES; DES ratio 1:1; solid to solvent ratio 1:10].
Condition Experimental (μg/g) K1 (min g/μg) K2 (g/μg) Calculated (μg/g) R2 % Error

Duty cycle (%) 10 1705.79 ± 0.02 1.84 ± 0.07 0.05 ± 0.05 1840.49 ± 0.02 0.98 ± 0.03 7.36 ± 0.02
20 935.35 ± 0.03 4.64 ± 0.02 0.07 ± 0.01 922.37 ± 0.01 0.99 ± 0.01 1.41 ± 0.01
30 431.84 ± 0.03 3.87 ± 0.02 0.21 ± 0.01 412.93 ± 0.04 0.88 ± 0.03 4.57 ± 0.01

K1 (x10− 2); K2 (x10− 2).

Table 5
The kinetic parameters of Fick’s model at different duty cycles [Extraction temperature 60 ◦ C; solvent DES; DES ratio 1:1; solid to solvent ratio 1:10].
Condition Experimental (μg/g) D1 (m2/min) D2 (m2/min) f1 f2 Calculated (μg/g) R2 % Error

Duty cycle (%) 10 1705.79 ± 0.02 2.19 ± 0.01 22.34 ± 0.01 30.77 ± 0.06 1746.43 ± 0.03 1705.80 ± 0.02 0.99 ± 0.05 <0.05
20 935.35 ± 0.03 1.97 ± 0.06 23.01 ± 0.01 3.93 ± 0.01 1716.73 ± 0.03 935.36 ± 0.03 0.99 ± 0.05 <0.05
30 431.84 ± 0.03 0.27 ± 0.02 0.32 ± 0.01 0.56 ± 0.01 4.33 ± 0.002 431.85 ± 0.03 0.99 ± 0.05 <0.05

D1 (x10− 2); D2 (x10− 2); f1 (x10− 2); f2 (x10− 2).

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N.F. Sukor et al. Journal of Food Engineering 296 (2021) 110437

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Galo, G.T., Morandim-Giannetti, A.A., Cotting, F., Aoki, I.V., Aquino, I.P., 2020.
The authors declare that they have no known competing financial Evaluation of purple onion (Allium cepa L.) extract as a natural corrosion inhibitor for
carbon steel in acidic media. Met. Mater. Int. https://doi.org/10.1007/s12540-020-
interests or personal relationships that could have appeared to influence 00679-9.
the work reported in this paper. Gao, M.Z., Cui, Q., Wang, L.T., Meng, Y., Yu, L., Li, Y.Y., Fu, Y.J., 2020. A green and
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Acknowledgement doi.org/10.1016/j.microc.2020.104598.
Ghatak, D., Iyyaswami, R., 2019. Selective encapsulation of quercetin from dry onion
The authors are grateful for the support from Jabatan Pertanian peel crude extract in reassembled casein particles. Food Bioprod. Process. 115,
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Negeri and the internal university grant by Universiti Malaysia Pahang Ghitescu, R.E., Volf, I., Carausu, C., Bühlmann, A.M., Gilca, I.A., Popa, V.I., 2015.
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