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Chromatographia (2016) 79:285–291

DOI 10.1007/s10337-016-3022-3


Alternative Liquid–Liquid Microextraction as Cleanup

for Determination of Neonicotinoid Pesticides Prior
HPLC Analysis
Jitlada Vichapong1 · Rodjana Burakham2 · Supalax Srijaranai2 

Received: 14 August 2015 / Revised: 12 November 2015 / Accepted: 21 December 2015 / Published online: 18 January 2016
© Springer-Verlag Berlin Heidelberg 2016

Abstract  A simple microextraction, namely low-density Keywords  Low-toxicity organic solvent-based dispersive
solvent with low-toxicity organic solvent-based dispersive liquid–liquid microextraction · QuEChERS · Extraction ·
liquid–liquid microextraction (LDS-DLLME) and modi- HPLC · Neonicotinoid pesticides
fied QuEChERS sample preparation procedures were opti-
mized and validated for preconcentration of neonicotinoid
pesticides prior to the determination using HPLC. The Introduction
experimental parameters affecting the extraction efficiency,
including salt addition, type of disperser solvent and its Neonicotinoids have been the fastest growing class of
volume, effect of extraction solvent and its volume, and insecticides in modern crop protection [1]. There are seven
extraction time were investigated. Under the selected LDS- commercial neonicotinoids: imidacloprid, acetamiprid,
DLLME and HPLC conditions, separation of seven neonic- nitenpyram, thiacloprid, thiamethoxam, clothianidin and
otinoid pesticides (imidacloprid, acetamiprid, clothianidin, dinotefuran. These insecticides are active against numerous
thiacloprid, thiamethoxam, dinotefuran, and nitenpyram) sucking and biting pests and insects, including whiteflies,
was achieved within 26 min. 1-Octanol (extraction solvent) aphids, beetles and some lepidoptera species [2]. They act
and acetonitrile (disperser solvent) were used for extrac- as agonists at the insect nicotinic acetylcholine receptors
tion of the target analytes. Under the optimum condition, (nAChRs), which play an important role in synaptic trans-
linearity was obtained within the range of 0.1–1000 ng g−1 mission in the central nervous system [3]. They can give
with a correlation coefficient more than 0.999. The high rise to serious risks for the health and safety of the consum-
enrichment factor of the target analytes was 50-fold and ers of the agricultural products due to their distribution over
a low limit of quantitation (0.80–2.50 ng g−1) could be large areas of agricultural land [2]. Many countries have
obtained. The fruit samples (at fortified levels of 10, 30, formulated strict limits for neonicotinoids in various matri-
and 50 ng g−1) were successfully analyzed, and relative ces to ensure that the residues are below the safety limit for
recoveries were obtained in the range of 90.07–112.22 %. maximum residue levels (MRLs). The MRLs of neonicoti-
noids range between 0.1 and 1 mg kg−1 [4].
Due to their low volatility and high polarity, neonicoti-
noid insecticides are unsuitable for direct analysis by gas
* Jitlada Vichapong
chromatography [5]. Nowadays, high-performance liquid;
chromatography (HPLC) coupled with various detection
Creative Chemistry and Innovation Research Unit, systems, including electrochemical (ECD) [6], fluorescence
Department of Chemistry, Center of Excellence (FLD) [7], UV/diode array (DAD) [8, 9] and mass spec-
for Innovation in Chemistry, Faculty of Science,
trometry [10], is the favored technique for multi-analysis of
Mahasarakham University, Mahasarakham 44150, Thailand
neonicotinoid pesticides. Although a MS detector provides
Materials Chemistry Research Center, Department
more sensitivity and selectivity than UV for monitoring tar-
of Chemistry, Center of Excellence for Innovation
in Chemistry, Faculty of Science, Khon Kaen University, get compounds in complex samples, it suffers from being a
Khon Kaen 40002, Thailand very expensive and complex instrument [11]. Due to their

286 J. Vichapong et al.

low concentrations and complex matrices in real sample CH3 HN NO2

analysis, sample preparation is another step still required C N
before analysis. CH3
Cl N Cl N
Sample clean-up techniques are the most commonly
Acetamiprid Imidacloprid
employed, which comprise liquid–liquid extraction (LLE)
[12], solid-phase extraction (SPE) [13, 14], combinations
of LLE and SPE [3, 15, 16], accelerated solvent extraction H H
(ASE) [17], quick, easy, cheap, effective, rugged, and safe Cl S NO2
(QuEChERS) [18], and dispersive liquid–liquid microex- N O N N
traction (DLLME) [19, 20]. DLLME is based on the for- Clothianidin Dinotefuran
mation of fine droplets of an extractant in an aqueous sam-
ple solution when a water-immiscible extraction solvent Cl N NO2
(extractant) dissolved in a water-miscible organic dispersive N N
solvent is rapidly injected into the aqueous sample solution NO2
[2]. The analytes in the sample solution are extracted into HN
O N Cl
the fine droplets, which are further separated by centrifu- Nitenpyram Thiamethoxam
gation, and the enriched analytes in the sedimented phase
are then analysised. The main advantages of the DLLME N
include simple operation, low cost, speed, high preconcen-
tration factors, and the use of small volumes of solvents N
[10]. On the other hand, the disadvantages of the DLLME Cl N
are its relatively low selectivity towards target analytes and Thiacloprid

the use of chlorinated solvents (e.g., chloroform, dichlo-

romethane, carbon tetrachloride) which pose a potential Fig. 1  Chemical structures of the studied neonicotinoid pesticides
threat to the environment [20]. In 2008, Leong and Huang
[21] developed a dispersive liquid–liquid microextraction
method based on solidification of floating organic droplets Experimental
(DLLME-SFO). In DLLME-SFO, solvents with densities
lower than water with a low-toxicity organic solvent are Chemicals and Reagents
required. The large contact surface between the sample and
the droplets of the extraction solvent speeds up mass trans- All chemicals used were of at least analytical reagent
fer, as rapidly as DLLME and with a shorter extraction time grade. The chemical structures of the studied neonicoti-
than liquid–liquid microextraction based on solidification of noids evaluated here are shown in Fig. 1. The analytical
floating organic droplets (LLME-SFO). DLLME-SFO was standards of neonicotinoid insecticides including acetami-
developed for the determination of organic pollutant [22], prid, clotianidin, nitenpyram, imidacloprid, and thiameth-
amphetamines [23], triazine herbicides [24], and policyclic oxam were obtained from Dr. Ehren-storfer (Germany),
aromatic hydrocarbons [25]. and dinotefuran and thiacloprid were obtained from
The aim of the present work was to develop a simple Sigma-Aldrich (Germany). The stock solutions of each
low-density solvent with a low-toxicity organic solvent- insecticide were prepared at 1000 mg L−1 by dissolving
based DLLME and modified QuEChERS sample prepa- an appropriate amount in methanol (MeOH). Deionized
ration procedures for the preconcentration and simulta- water obtained from RiOsTM Type I Simplicity 185 (Mil-
neous analysis of neonicotinoid insecticide residues (i.e. lipore Waters, USA) with a resistivity of 18.2 MΩ cm
imidacloprid, acetamiprid, nitenpyram, thiacloprid, thia- was used throughout the experiments. Methanol (MeOH)
methoxam, clothianidin and dinotefuran) prior to HPLC and acetonitrile (ACN) of HPLC grade and acetone were
analysis. The effect of the experimental parameters on the obtained from Merck (Germany). Ethanol was purchased
extraction performance of the target analytes, such as salt from RCI Labscan (Thailand). NaCl and anhydrous
addition, type and volume of extraction solvent, type and Na2SO4 were obtained from Ajax Finechem (New Zea-
volume of disperser solvent and centrifugation time were land), CH3COONa and KI were obtained from Carlo Erba
investigated and optimized. The method was demonstrated (France).
to apply to the analysis of fruit samples.

Alternative Liquid–Liquid Microextraction as Cleanup… 287

Apparatus the isocratic elution using 25 % (v/v) acetonitrile in water

at a flow rate of 1.0 mL min−1. The injection volume was
The HPLC system comprised of a Waters 600 multisolvent 20 µL. The detection of the target analytes was set at the
delivery system (USA), a Rheodyne injector with a sample maximum absorption wavelength of 254 nm. Seven neo-
loop of 20 µL, and a Waters 996 photodiode array detector. nicotinoid insecticides were separated within 25 min with
The Millennium software was used was utilized to control. the elution order of dinotefuran (tR = 2.74 min), nitenpyran
An Atlantis dC18 (4.6 × 150 mm, 5.0 µm) column (Waters, (tR = 2.98 min), thiamethoxam (tR = 6.81 min), clothiani-
USA) was used for separation of the target neonicotinoids. din (tR = 9.51 min), imidacloprid (tR = 11.45 min), aceta-
miprid (tR = 14.01 min) and thiacloprid (tR = 24.31 min).
Fruit Samples Analysis
Optimization of LDS‑DLLME Procedure
Fruit samples including watermelon, longan and grape were
randomly purchased from local markets in Mahasarakham In order to obtain the high extraction efficiency of the pro-
province, northeast Thailand. The edible parts of the fruit posed LDS-DLLME method, several factors were investi-
samples (500 g) were cut and blended using a commercial gated including salt addition, the type of disperser solvent
food mixer. A modified QuEChERS method [26, 27] was and its volume, the type of extraction solvent and its vol-
applied for sample preparation of the studied fruit sam- ume, and the extraction time. The optimization was car-
ples. Briefly, the procedure was as follows: 10 g of sample ried out on the aqueous solution (10.00 mL) containing
was placed in a 50-mL centrifugation tube and mixed with 500 ng g−1 of each analyte. All the experiments were per-
20 mL of 1 % (v/v) acetic acid in ACN, and the mixture formed in triplicate and the mean of the results were used
vortexed for 1 min. After that, anhydrous Na2SO4 (15 g) for optimization.
and sodium acetate (1 g) were added and the mixture was Generally, the addition of salt decreases the solubility of
immediately shaken manually. The solution was then cen- analytes in aqueous samples and enhances their distribution
trifuged at 3000 rpm for 5 min. The supernatant was sub- into the organic phase [28]. In this experiment, 1 g of NaCl,
sequently evaporated to dryness using a rotary evaporator Na2SO4, CH3COONa were investigated and the results were
(40 °C water bath). The resulting residue was re-dissolved compared with that obtained from the process without salt
with 10.00 mL of water before extraction by a low-density addition (data not shown). It was found that the addition
solvent with low-toxicity organic solvent-based dispersive of Na2SO4 provided higher extraction efficiency in term of
liquid–liquid microextraction procedure. peak area of neonicotinoids. Therefore, the concentration
of Na2SO4 on the extraction efficiency of the target neoni-
Low Density Solvent with Low‑Toxicity Organic cotinoid analytes were also studied within the range of 0.5–
Solvent‑Based Dispersive Liquid–Liquid 4.0 g. The results in Fig. 2 show an enhancement of extrac-
Microextraction Procedure (LDS‑DLLME Procedure) tion efficiency for all neonicotinoids when 2.5 g Na2SO4 was
added. Salt solutions reached or exceeded their solubility
A 10-mL aliquot of sample (or standard solution) was mixed
with 2.5 g of Na2SO4 and then subsequently transferring to
a 10-mL screwcap test tube. After that, a mixture of 100 µL 900000 Dinotefuran
extraction solvent (1-octanol) and 50 µL dispersive solvent Thiamethoxam
(acetonitrile) were injected rapidly into the sample solution. 750000 Clothianidin
A cloudy solution because of the dispersion of 1-octanol in Acetamiprid
the solution was obtained. After that, the resulting emulsion 600000 Thiacloprid
Peak area

was completely separated by centrifugation at 3500 rpm for

10 min. The reconstituted solution floated on the top of the
tube. The upper extraction solvent was collected by a 1-mL 300000
syringe and then injected into the HPLC for analysis.

Results and Discussion 0
0.0 0.5 1.0 1.5 2.0 2.5

Chromatographic Analysis Concentration of Na2SO4 (g)

The simultaneous separation of the studied neonicotinoids Fig. 2  Effect of concentration of salt on the extraction of neonicoti-
was carried out on a reversed-phase HPLC system with noids

288 J. Vichapong et al.

limits when the amount of salt was more than 2.5 g. There- because 1-octanol has a lowrt density than other extraction
fore, 2.5 g Na2SO4 was selected for further studies. solvents (data not shown). Consequently, 1-octanol was
In LDS-DLLME, the dispersive solvent is one of the selected as the extraction solvent for further study.
most important factors that accelerates the emulsification of The effect of extraction solvent volume was studied for
water-immiscible extraction solvent affecting the extraction 1-octanol volume in the range from 50 to 750 µL. It was
efficiency. For the investigation, various types of disperser found that when the extraction solvent volume is 50 µL, the
solvent (50 µL) including acetonitrile, methanol and etha- solution cannot complete phase separation. Moreover, the
nol were studied. As shown in Fig. 3a, the results showed extraction solvent volume of more than 100 µL decreased
that acetonitrile gave a higher extraction efficiency in term the peak area of neonicotinoids. As can be seen from Fig. 4,
of peak area compared to ethanol and methanol; therefore, the highest extraction efficiency was obtained using 100 µL
it was selected as the disperser solvent. of 1-octanol. Therefore, 100 µL of 1-octanol was selected
To investigate the effect of the disperser solvent (ace- for further study.
tonitrile) volume on the extraction efficiency, several vol- Centrifugation time is another important step in LDS-
umes of acetonitrile in the range of 25–250 µL were studied DLLME for achieving phase separation. Therefore, the
(Fig. 3b). It was found that, if the disperser solvent volume effect of centrifugation time was studied in the range of
is 25 µL, the solution cannot complete phase separation. It 1–15 min at 3500 rpm. It was found that the peak areas
was noted that a disperser solvent volume of 50 µL provide of all analytes increased by applying centrifugation up to

Dinotefuran Dinotefuran
a 1200000
b 900000 Thiamethoxam
Clothianidin Clothianidin
1000000 Imidacloprid 750000 Imidacloprid
Acetamiprid Acetamiprid
Thiacloprid Thiacloprid
800000 600000
Peak area

Peak area

600000 450000

400000 300000

200000 150000

0 0
Ethanol Acetonitrile Methanol 0 50 100 150 200 250
Kind of disperser solvent Volume of acetonitrile (µL)

Fig. 3  Effect of a the kind of disperser solvent and b the volume of extraction solvent on the extraction of neonicotinoids

the highest peak area. Therefore, acetonitrile 50 µL was Dinotefuran

selected for further study. Nitenpyram
In the LDS-DLLME method, extraction solvents have 1200000
to be low-toxicity solvents and these solvents have to fulfill Imidacloprid
some requirements such as low density compared to water, Acetamiprid
Peak area

low solubility in water and have a proper melting point as 800000

well as the other requirements that are available in each
solvent, such as high extraction capability for target com-
pounds, good chromatographic behavior, cheap, low vola- 400000
tility to minimize solvent losses during extraction and high
purity [24]. Based on these requirements for the extraction 200000

solvent, four types of low-density organic solvent were 0

investigated (data not shown) including 1-octanol [density 100 125 150 175 200 225 250
(d) = 0.8240 g mL−1], 1-dodecanol (d = 0.8309 g mL−1), Volume of 1-octanol (µL)
toluene (d  = 0.8700 g mL−1), and ethyl acetate
(d = 0.8970 g mL−1). It is clearly seen that 1-octanol pro- Fig. 4  Effect of volume of 1-octanol on the extraction of neonicoti-
vided a high extraction efficiency in terms of peak area noids

Alternative Liquid–Liquid Microextraction as Cleanup… 289

10 min, and then gradually decreased. Consequently, a cen- 0.999. The enrichment factors, defined as the concentration
trifugation time of 10 min was selected. ratio of the analytes in the settled phase (Cset) and in the
aqueous sample (Co), were 50 for all compounds. The chro-
Analytical Performance of the Method matograms obtained from the separation of standard neo-
nicotinoids by HPLC without and with the LDS-DLLME
Under the above-mentioned conditions, the proposed LDS- procedure are compared in Fig. 5a and b, respectively. The
DLLME combined with the HPLC method for the determi- LOD and LOQ were determined based on the concentra-
nation of neonicotinoid pesticides was validated by deter- tion giving a signal-to-noise ratio of 3 (S/N  = 3) and 10
mining its analytical characteristics, i.e. linearity, precision, (S/N  = 10), respectively. LOD were found to be in the
limit of detection (LOD), limit of quantitation (LOQ) and range of 0.25–0.80 ng g−1 and LOQ in the range of 0.80–
enrichment factor. The analytical performances of the pro- 2.50 ng g−1. The RSDs of five consecutive extractions of
posed method are summarized in Table 1. The calibration the standard solution containing 50 µg kg−1 nenonicoti-
curves of all the analytes were linear in the range from 0.1 noids were in the ranges of 0.52–1.97 and 2.59–6.38 % for
to 1000 ng g−1 with a correlation coefficient (R2) more than retention time and peak area, respectively.

Table 1  Analytical performances of the proposed method

Insecticide Linear equation Linearity (ng g−1) r2 LOD (ng g−1) LOQ (ng g−1) %RSD EF
tR Peak area

Dinotefuran y = 167,991x − 516 0.1–1000 0.9998 0.80 (100)a 2.50 0.52 5.30 50

Nitenpyram y = 169,284x − 612 0.1–1000 0.9998 0.80 (100)a 2.50 0.83 4.18 50
Thiamethoxam y = 469,542x − 2324 0.1–1000 0.9994 0.40 (60) 1.20 1.45 2.59 50
Clothianidin y = 1,000,000x − 1001 0.1–1000 0.9995 0.25 (50)a 0.80 1.62 3.06 50
Imidacloprid y = 891,512x − 5835 0.1–1000 0.9997 0.30 (60)a 1.00 1.35 2.85 50
Acetamiprid y = 2,000,000x − 43,547 0.1–1000 0.9997 0.25 (50)a 0.80 1.58 5.15 50
Thiacloprid y = 2,000,000x + 20,910 0.1–1000 0.9997 0.25 (50)a 0.80 1.97 6.38 50

LOD limit of detection in ng g−1, LOQ limit of quantitation in ng g−1, RSD relative standard deviation (n = 5), EF enrichment factor
  Values reported in parentheses obtained from the standard neonicotinoids without preconcentration (direct injection)

Fig. 5  Chromatograms of 6
standard neonicotinoids: a 0.040
without LDS-DLLME and b
with LDS-DLLME; concen- 0.035
tration of all standards was 5
500 ng g−1. Peak assignments: 7
1 dinotefuran, 2 nitenpyran, 3 0.030
thiamethoxam, 4 clothianidin, 5 3
Voltage (mV)

imidacloprid, 6 acetamiprid and 0.025

7 thiacloprid


0.005 1
2 4 5 6
7 (a)

0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 21.00 22.00 24.00 26.00 28.00
Time (min)

290 J. Vichapong et al.

Table 2  Recovery of the studied neonicotinoids spiked in fruit samples obtained by the proposed method
Analyte Spiked (ng g−1) Watermelon (n = 3) Longan (n = 3) Grape (n = 3)
Recovery (%) RSD (%) Recovery (%) RSD (%) Recovery (%) RSD (%)

Dinotefuran 0 – – – – – –
10 102.78 2.02 98.93 2.54 92.60 3.66
30 98.82 0.78 97.82 2.54 98.93 1.82
50 110.53 0.81 95.28 0.67 90.07 0.10
Nitenpyram 0 – – – – – –
10 94.90 0.75 93.47 2.35 92.97 2.26
30 98.89 2.26 97.72 1.51 100.64 3.21
50 93.79 0.90 99.32 1.79 101.52 0.34
Thiamethoxam 0 – – – – – –
10 97.60 1.42 93.27 2.61 105.60 3.34
30 96.78 0.84 91.78 1.50 104.89 1.73
50 99.25 1.03 100.49 1.12 102.69 1.08
Clothianidin 0 – – – – – –
10 104.75 0.45 100.03 1.30 99.70 1.40
30 97.78 1.49 97.78 1.49 107.78 2.12
50 99.69 2.13 101.02 1.10 105.35 1.20
Imidacloprid 0 – – – – – –
10 104.03 1.25 102.37 3.46 103.37 3.73
30 112.22 2.38 100.22 2.93 102.11 1.50
50 110.69 2.09 99.82 0.33 100.62 1.00
Acetamiprid 0 – – – – – –
10 107.75 2.83 97.70 2.33 97.03 3.03
30 93.22 1.79 99.78 0.33 102.33 2.11
50 91.69 1.95 100.22 0.43 100.09 0.09
Thiacloprid 0 – – – – – –
10 101.7 2.53 105.7 1.82 100.37 4.26
30 93.67 0.51 101.11 0.77 102.33 1.92
50 99.42 1.16 108.69 1.12 100.22 0.63

– not detected

Application to Real Fruit Samples Conclusions

The proposed LDS-DLLME procedure was applied for the A simple miniaturized extraction method, namely low-
determination of neonicotinoid pesticides in fruit samples to density solvent with a low-toxicity organic solvent-based
elucidate the applicability and reliability of this method. In dispersive liquid–liquid microextraction (LDS-DLLME)
this study, no residues of the neonicotinoids were detected and a modified QuEChERS method was developed for the
in the samples (Table 2). In order to validate the accuracy extraction and preconcentration of seven neonicotinoid pes-
of the established method, fruit samples were spiked with ticides in fruit samples before their analysis by HPLC. The
neonicotinoid pesticides at concentration levels of 10, 30, proposed extraction method is simple, fast and effective
and 50 ng g−1. As indicated in Table 2, the recoveries of the and convenient in operation. The developed method shows
studied neonicotinoid pesticides were between 90.07 and good analytical features providing low limits of detection
112.22 % with RSDs of less than 4.26 %. Good recoveries at the level of 0.25–0.80 ng g−1 which is below the accept-
were obtained, indicating that the performance of the method able MRLs for neonicotinoids. High preconcentration fac-
was not affected by the sample co-extractives, at least for the tors, good recoveries and high reproducibility were also
matrices studied in this work. Figure 6 shows a typical chro- obtained. The proposed method has the potential to be used
matogram of watermelon and spiked watermelon samples as an alternative green extraction method for the determina-
using the LDS-DLLME procedure and HPLC analysis. tion of neonicotinoids in fruit samples.

Alternative Liquid–Liquid Microextraction as Cleanup… 291

Fig. 6  Chromatograms of a
watermelon and b watermelon
spiked with 100 ng g−1 of each
neonicotinoid. Peak assign-
ments are described in Fig. 5 0.08


Voltage (mV)

1 3 4
0.02 2 6 7

- 0.02 (a)

0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 21.00 22.00 24.00 26.00 28.00

Time (min)

Acknowledgments  This article is dedicated to Professor Dr. Kate 10. Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M,

Grudpan (Chiang Mai University, Thailand) in celebration of his 60th Milovanović I, Nedeljković N (2014) Food Res Int 55:11–19
birthday. The authors gratefully acknowledge the financial supports 11. Vichapong J, Burakham R, Srijaranai S (2013) Talanta

of this research by the Thailand Research Fund (TRF) and Mahasara- 117:221–228
kham University, through the TRF Grant for New Scholars (Grant no. 12. Jansson C, Pihlstrom T, Öterdahl BG, Markides KE (2004) J
TRG5780060). The authors also gratefully acknowledge the partial Chromatogr A 1023:93–104
supports for this research from the Center for Innovation in Chem- 13. Zhou Q, Ding Y, Xiao J (2006) Anal Bioanal Chem

istry (PERCH-CIC), Commission on Higher Education, Ministry of 385:1520–1525
Education, and Materials Chemistry Research Center, Khon Kaen 14. Štajnbaher D, Zupančič-Kralj L (2003) J Chromatogr A

University. 1015:185–198
15. Cazorla-Reyes R, Fernandez-Moreno JL, Romero-Gonzalez R,
Compliance with Ethical Standards  Frenich AG, Vidal JL (2011) Talanta 85:183–196
16. Liu S, Zheng Z, Wei F, Ren Y, Gui W, Wu H, Zhu G (2010) J
Conflict of Interest  The authors declare that they have no conflict Agric Food Chem 58:3271–3278
of interest. 17. Chitescu CL, Oosterink E, de Jong J, Stolker AAML (2012) Tal-
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18. Yáñez KP, Bernal JL, Nozal MJ, Martín MT, Bernal J (2013) J
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