Food Chemistry 200 (2016) 1015

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analytical Methods

Magnetic solid phase extraction using ionic liquid-coated coreshell

magnetic nanoparticles followed by high-performance liquid
chromatography for determination of Rhodamine B in food samples
Jieping Chen, Xiashi Zhu
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, PR China

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

Article history: Three hydrophobic ionic liquids (ILs) (1-butyl-3-methylimidazole hexafluorophosphate ([BMIM]PF6),
Received 30 April 2014 1-hexyl-3-methyl-imidazole hexafluoro-phosphate ([HMIM]PF6), and 1-octyl-3-methylimidazole
Received in revised form 17 December 2015 hexafluorophosphate ([OMIM]PF6)) were used to coat Fe3O4@SiO2 nanoparticles (NPs) with coreshell
Accepted 1 January 2016
structures to prepare magnetic solid phase extraction (MSPE) agents (Fe3O4@SiO2@IL). A novel method
Available online 2 January 2016
of MSPE coupled with high-performance liquid chromatography for the separation/analysis of
Rhodamine B was then established. The results showed that Rhodamine B was adsorbed rapidly on
Chemical compounds studied in this article:
Fe3O4@SiO2@[OMIM]PF6 and was released using ethanol. Under optimal conditions, the pre-
Rhodamine B (PubChem CID: 6694)
N-Butyl bromide (PubChem CID: 74236)
concentration factor for the proposed method was 25. The linear range, limit of detection (LOD), correla-
1-Bromohexane (PubChem CID: 8101) tion coefficient (R), and relative standard deviation (RSD) were found to be 0.50150.00 lg L 1,
1-Bromooctane (PubChem CID: 8140) 0.08 lg L 1, 0.9999, and 0.51% (n = 3, c = 10.00 lg L 1), respectively. The Fe3O4@SiO2 NPs could be re-
Tetraethyl orthosilicate (PubChem CID: used up to 10 times. The method was successfully applied to the determination of Rhodamine B in food
6517) samples.
Potassium hexafluorophosphate (PubChem 2016 Published by Elsevier Ltd.
CID: 23688904)
FeCl3 (PubChem CID: 24380)
Methanol (PubChem CID: 887)
Ethanol (PubChem CID: 702)
Methylene chloride (PubChem CID: 6344)

Keywords:
Rhodamine B
Ionic liquid-loaded magnetic nanoparticle
Magnetic solid phase extraction
High-performance liquid chromatography

1. Introduction of a simple method for the determination of RhB in different sam-

ples is necessary. Various techniques have been developed, includ-
Rhodamine B (RhB), a red dye, is used as a colorant in textile, ing ultraviolet spectrophotometry (Sun, Li, Mele, Zhang, & Zhang,
plastic, leather, dyeing, paper, and printing industries (Alesso, 2013), fluorescence spectrophotometry (Chauhan et al., 2014),
Bondioli, Talo, Luconi, & Fernndez, 2012). However, it is harmful capillary chromatography (Desiderio, Marra, & Fanali, 1998), and
to humans and animals, causing irritation to the skin, eyes, and res- high-performance liquid chromatography (HPLC) (Santiago
piratory tract (Roberts, Fletcher, Moore, & Byers, 2010; Xiao, Gong, Valverde, Sanchez Perez, Franceschelli, Martinez Galera, & Gil
& Ledoux, 2007; Xie et al., 2013). The use of RhB as a colorant in Garcia, 2007). However, direct determination using spectropho-
foodstuffs was therefore banned. However, owing to its low price tometry is difficult because of the low concentration of RhB in food
and bright color, some traders continue to use RhB as a food addi- samples. Therefore, it is necessary to develop a separation/
tive (Jain, Mathur, Sikarwar, & Mittal, 2007), endangering the pre-concentration step.
health of consumers (Baldev et al., 2013). Thus, the development Magnetic solid phase extraction (MSPE) is a technique that uses
a magnetic or magnetizable material as a solid absorbent matrix
Corresponding author.
(Ibarra, Miranda, Rodriguez, Nebot, & Cepeda, 2014). In MSPE
E-mail addresses: xszhu@yzu.edu.cn, zhuxiashi@sina.com (X. Zhu).
procedures, magnetic adsorbents can be easily magnetized and

http://dx.doi.org/10.1016/j.foodchem.2016.01.002
0308-8146/ 2016 Published by Elsevier Ltd.
 J. Chen, X. Zhu / Food Chemistry 200 (2016) 1015 11

gathered together in the presence of an external magnetic field and using a procedure previously described in the literature (Dang,
redispersed immediately once the magnetic field is removed, Ma, & Zhou, 2012).
which greatly simplifies the SPE procedure and enhances the
extraction efficiency (Jiang, Yang, Wang, Lian, & Hu, 2013). Most 2.3. MSPE procedure
MSPE sorbents contain Fe3O4 nanoparticles (NPs) with specific
chemical functional group modifications on their surface to The MSPE procedure is shown in Fig. 1. First, 0.10 g Fe3O4@-
achieve concentration of the target analytes. Numerous organic SiO2@IL MNPs were added to 100 mL sample solution (pH 3.0),
and inorganic polymers have been used to modify Fe3O4 NPs. and the mixture was placed on a slow-moving platform shaker
Gao et al. used polyaniline-loaded Fe3O4 (PANI/Fe3O4) as an adsor- and allowed to equilibrate for 10 min at 30 C. Then, the RhB-
bent for the magnetic solid-phase extraction of fluoroquinolones in adsorbed Fe3O4@SiO2@IL MNPs were separated from the solution
honey samples (Gao, Zheng, Luo, Ding, & Feng, 2012) and Cao et al. using an external magnetic field. Once the suspension became lim-
used ionic liquid-coated Fe3O4@graphene (Fe3O4@grapheme/IL) as pid, the supernatant was decanted and the isolated MNPs were
an adsorbent for the magnetic solid-phase extraction of nitroben- eluted with 4.0 mL ethanol to desorb the pre-concentrated target
zene compounds in environmental water samples (Cao et al., analytes. The eluted solution was collected and then dried under
2014). Magnetic core-mesoporous shell microspheres with C18- a mild nitrogen stream. Finally, the residue was re-dissolved in
functionalized interior pore-walls (CFe3O4@mSiO2/C18) were used 150 lL ethanol, of which 20.0 lL was injected into the HPLC sys-
as adsorbents for the analysis of cephalosporin residues in milk tem for detection of the target analytes.
(Liu, Yu, et al., 2014). However, this approach has not been
reported for the determination of RhB using Fe3O4@SiO2@IL. 2.4. Sample preparation
In this study, Fe3O4@SiO2@IL were prepared via self-assembly
and used as MSPE agents, combining the advantages of the ILs Chili powder/hot pepper (5.0 g) was accurately weighed out,
and the magnetic nanoparticles (MNPs). Compared with previous poured into a beaker, and dissolved in 80.0 mL ethanol. The resul-
reports (Cao et al., 2014; Gao et al., 2012), the MSPE method tant clear solution was evaporated to dryness at 60 C. The residue
reported herein provided a rapid and efficient sample preparation was diluted with distilled water to 100 mL and stored in the dark
process, which enabled the treatment of a large volume of samples for future analysis.
in a short period of time. A novel MSPE method coupled with HPLC
was therefore established for the separation/analysis of RhB in food
2.5. Chromatographic conditions
samples.
Separations were performed on a C18 reversed-phase column
(250 mm  4.6 mm I.D., 5 lm, Shimadzu Corporation, Japan) at
2. Experimental 35 C. The injections were carried out through a 10.0 lL loop. The
detection was at 554.0 nm. The mobile phase was methanolwater
2.1. Equipment and reagents (75:25). The flow rate was 1.0 mL min 1.

FT-IR spectra were measured on a Bruker Tensor 27 spectrom-

eter (Bruker Company, Germany). Samples were pressed into KBr 3. Results and discussion
pellets and spectra were recorded from 4000 to 400 cm 1 with a
resolution of 4 cm 1. A Tecnai 12 transmission electron microscope 3.1. Characterization of the Fe3O4@SiO2@IL MNPs
(Philips, Netherlands) was used to obtain micrographs of the
MNPs. Chromatographic separation of the analytes was achieved The Fe3O4@SiO2@IL MNPs were characterized using FT-IR spec-
using an Agilent 1200 HPLC system (Agilent Corporation, Japan). troscopy, thermogravimetric analysis (TGA), and magnetic
All chemicals and reagents were at least of analytical grade characterization.
unless otherwise stated. RhB standards were all obtained from Fig. 2A shows the FT-IR spectra of Fe3O4, Fe3O4@SiO2, Fe3O4@-
Shanghai, Chemical Reagent Co., Ltd, China. A standard stock solu- SiO2@[BMIM]PF6, Fe3O4@SiO2@[HMIM]PF6, and Fe3O4@SiO2@
tion was prepared by dissolving 10.0 mg RhB in 100.0 mL ethanol. [OMIM]PF6 (curves ae, respectively). Comparing curves a and b,
This was then stored in the dark at 4 C. N-Methylimidazole (Darui
Fine Chemicals, Shanghai, China), N-butyl bromide, 1-
bromohexane, 1-bromooctane, tetraethyl orthosilicate (TEOS),
KPF6, FeCl3, (NH4)2Fe(SO4)2, methanol, ethanol, acetone, and
methylene chloride were all obtained from Sinopharm Chemical
Reagent Co., Ltd., Shanghai, China.

2.2. Preparation of Fe3O4@SiO2@IL MNPs

A series of ionic liquids (1-alkyl-3-methylimidazolium hexaflu-

orophosphate) were synthesized using a two-step method
described in previous reports (Chun, Dzyuba, & Bartsch, 2001;
Dzyuba & Bartsch, 2001; Holbrey & Seddon, 1999; Tokuda,
Hayamizu, Ishii, Abu Bin Hasan Susan, & Watanabe, 2004).
Fe3O4 NPs were prepared by chemical coprecipitation (Hong
et al., 2006; Huang, Fang, Yan, & Cheng, 2012).
For the preparation of Fe3O4@SiO2, a previously reported pro-
cess was followed (Hou et al., 2013; Hu et al., 2014).
Fe3O4@SiO2@IL MNPs (Fe3O4@SiO2@[BMIM]PF6, Fe3O4@SiO2@ Fig. 1. Schematic of the MSPE method. Procedure for the MSPE of RhB using
[HMIM]PF6, and Fe3O4@SiO2@[OMIM]PF6) were also synthesized Fe3O4@SiO2@IL MNPs.
12 J. Chen, X. Zhu / Food Chemistry 200 (2016) 1015

Fig. 2. FT-IR spectra and magnetic hysteresis loops. (A) FT-IR spectra of Fe3O4 (a), Fe3O4@SiO2 (b), Fe3O4@SiO2@[BMIM]PF6 (c), Fe3O4@SiO2@[HMIM]PF6 (d), and Fe3O4@SiO2@
[OMIM]PF6 (e); (B) magnetic hysteresis loops of Fe3O4, Fe3O4@SiO2, and Fe3O4@SiO2@IL.

the peak at 580 cm 1 in curve a was assigned to FeOFe stretch- Fe3O4@SiO2@IL, which revealed that ERhB% largely depended on
ing vibrations and the strong peaks at 12001000 cm 1 in curve b the hydrophobicity of the ILs; (3) ERhB% gradually increased with
correspond to SiOH and SiOSi stretching vibrations, which increasing length of the loaded IL cationic alkyl chain; and (4)
indicated that SiO2 had been successfully loaded onto the surface ERhB% on Fe3O4@SiO2@[OMIM]PF6 showed the highest extraction
of Fe3O4. In curves c, d, and e, the peaks at 2920 cm 1 and efficiency, perhaps because the hydrophobicity of the ILs increased
2850 cm 1 correspond to CH stretching vibrations, and the peaks with increasing cationic alkyl chain length (Deng et al., 2011).
at 1575 cm 1 correspond to the characteristic absorption of imida- Therefore, Fe3O4@SiO2@[OMIM]PF6 was employed in subsequent
zole groups in Fe3O4@SiO2@IL. In addition, the peaks at 840 cm 1 experiments.
were attributed to PF stretching vibrations (Galan-Cano,
Alcudia-Leon, Lucena, Cardenas, & Valcarcel, 2013), which indi- 3.3. Optimization of extraction
cated that the ILs had been successfully immobilized on the surface
of Fe3O4@SiO2 to form Fe3O4@SiO2@IL. The factors affecting the extraction process of RhB: pH, temper-
TGA revealed the weight loss of the materials, which demon- ature, ionic strength, solution volume, and extraction time, are dis-
strated differences between Fe3O4@SiO2 and Fe3O4@SiO2@ cussed (Fig. 3).
[OMIM]PF6. In this study, TGA was conducted in a nitrogen atmo-
sphere, and the heating rate employed was 5 C min 1 in all cases 3.3.1. Effect of pH
from 25 to 1000 C. From the experimental results, it can be con- pH is a crucial factor in the extraction process because it affects
cluded that: (1) Fe3O4@SiO2 showed a mass loss of approximately the form of RhB. In this work, the effect of pH was investigated over
1.7% after heating to 200 C, corresponding to water content; and the pH range 2.013.0. As shown in Fig. 3A, ERhB% increased over
(2) for Fe3O4@SiO2@[OMIM]PF6, an additional weight loss of 5.6% pH 2.03.0, reached a maximum value at a pH of 3.0, and subse-
was observed from 200 to 650 C due to the decomposition of quently decreased. It may be that RhB was mainly present as the
the ILs. This observation suggests that [OMIM]PF6 was located on neutral molecule at a pH of 3.0 (pKa = 3.2) and in the ionic form
the surface of Fe3O4@SiO2. at pH > 3.2. The hydrophobicity of the neutral molecule was stron-
Fig. 2B shows the magnetic hysteresis loops of the three types of ger than that of the ionic form, which was favorable for RhB
MNPs. It is apparent that all of the NPs showed superparamagnetic adsorption by Fe3O4@SiO2@[OMIM]PF6 MNPs (Ping, Zhu, & Wang,
properties due to the core magnetite particles. Magnetic character- 2014). Therefore, pH 3.0 was selected for the subsequent assays.
ization using a magnetometer at 27 C indicated that the maximal
saturation magnetizations of the Fe3O4, Fe3O4@SiO2, and Fe3O4@- 3.3.2. Effect of extraction temperature
SiO2@[OMIM]PF6 MNPs were 97.0, 85.3, and 61.1 emu g 1, respec- The effect of extraction temperature was studied by varying the
tively. The lower maximal saturation magnetization of the temperature from 20 to 60 C (Fig. 3B). ERhB% increased with tem-
Fe3O4@SiO2@[OMIM]PF6 MNPs resulted from the non-magnetic IL perature up to 30 C, after which it decreased. It could be eluci-
shell. Fe3O4@SiO2@[OMIM]PF6 MNPs could be rapidly separated dated that increasing the temperature increased the transition of
from the solution using a magnet on account of their superparam- the analytes to the solid phase extraction sorbent (adsorbent),
agnetism and large saturation magnetization. but the analytes may also be desorbed from the adsorbent at
higher temperature due to an exothermic extraction process (Liu,
3.2. Extraction efficiency of different MNPs Lu, Huang, Liu, & Zhao, 2014). The maximum extraction efficiency
for RhB was obtained at 30 C. Hence, all adsorption experiments
In this work, the extraction efficiencies of Fe3O4, SiO2, Fe3O4@- were carried out at 30 C.
SiO2, Fe3O4@SiO2@[BMIM]PF6, Fe3O4@SiO2@[HMIM]PF6, and Fe3-
O4@SiO2@ [OMIM]PF6 for RhB (ERhB%) were evaluated. The results 3.3.3. Effect of ionic strength
were as follows: (1) the order of ERhB% was Fe3O4 < SiO2 < Fe3O4@- The effect of ionic strength was evaluated using NaCl as a model
SiO2 < Fe3O4@SiO2@[BMIM]PF6 < Fe3O4@SiO2@[HMIM]PF6 < Fe3- electrolyte within a concentration interval of 030% (w/v) (Fig. 3C).
O4@SiO2@[OMIM]PF6 under the same experimental conditions; (2) ERhB% increased with NaCl concentration up to 20% for two rea-
ERhB% on Fe3O4@SiO2 was far less than that of the three kinds of sons: (1) the extraction efficiency increased due to the salting
 J. Chen, X. Zhu / Food Chemistry 200 (2016) 1015 13

100 100
A B

Extraction Efficiency%
Extraction Efficiency%
80 80

60 60

40 40

20 20

0 0
2 4 6 8 10 12 14 20 30 40 50 60
pH Temperature/( )
100 100
C D

Extraction Efficiency%
Extraction Efficiency%

80 80

60 60

40 40

20 20

0 0
5 10 15 20 25 30 5 10 15 20 25 30
NaCl (w/v %) Time/min
Fig. 3. Factors affecting the extraction efficiency. Effect of pH (A), temperature (B), ionic strength (C), and adsorption time (D) on extraction efficiency.

out effect; (2) electrostatic attractions increased with increasing ied by varying the concentration of RhB in aqueous samples before
ionic strength, also increasing the extraction efficiency (Hu et al., the MSPE procedure. The maximum ERhB% was obtained when the
2013). The extraction efficiency decreased when the concentration concentration of RhB was 70.0 lg mL 1. The adsorption capacity of
of NaCl was above 20%. The reason for this phenomenon was that Fe3O4@SiO2@[OMIM]PF6 for RhB was calculated as 6.71 mg g 1.
higher ionic strength induced an increase in sample viscosity, mak-
ing it difficult for the analytes to transfer from the bulk samples to 3.5. Optimization of desorption
the adsorbent (Ho, Cole, Augusto, & Anderson, 2013). Based on this,
20% (w/v) NaCl was used for subsequent experiments. 3.5.1. Selection of eluent and its volume
In this study, different eluents were investigated. The order of
3.3.4. Effect of sample volume elution efficiency of RhB was ethanol > methanol > cetyltrimethyl
The effect of sample volume was studied using different vol- ammonium bromide (CTAB) > sodium dodecyl sulfonate (SDS)
umes of sample solution (20.0120.0 mL) for a fixed amount of > NaOH (0.1 M) > HCl (0.1 M). Ethanol was therefore adopted as
RhB. The experimental results show that ERhB% decreased when the eluent.
the sample volume was greater than 100.0 mL. Therefore, the sam- The effect of the volume of ethanol on the elution efficiency of
ple volume was set as 100.0 mL. RhB was evaluated in detail. The results show that quantitative
elution (above 98.0%) was observed when the volume of ethanol
3.3.5. Effect of extraction time was higher than 4.0 mL. The pre-concentration factor was 25 (the
To evaluate the effect of extraction time on ERhB%, different quotient of volume before absorption and after elution). The opti-
extraction times ranging from 5 to 25 min were tested (Fig. 3D). mum volume of ethanol was therefore 4.0 mL.
ERhB% gradually increased up to 10 min, after which it remained
almost constant. Thus, 10 min was selected as the optimal extrac- 3.5.2. Elution time
tion time. The experimental results show that the elution efficiency of RhB
increased up to 98.0% after 5.0 min stripping time. Thus, 5.0 min
3.4. Adsorption capacity was selected as the optimal elution time.

Adsorption capacity is defined as the maximum amount of RhB 3.5.3. Reusability of the Fe3O4@SiO2 MNPs
adsorbed per gram of Fe3O4@SiO2@[OMIM]PF6. In this work, the Fe3O4@SiO2 MNPs were washed twice with 2.0 mL ethanol after
adsorption capacity of Fe3O4@SiO2@[OMIM]PF6 for RhB was stud- the MSPE procedure and subsequently assembled with the ILs.
14 J. Chen, X. Zhu / Food Chemistry 200 (2016) 1015

3.7. Analytical performance of the method

Under the optimum conditions, a linear calibration curve was

obtained in the concentration range 0.50150.00 lg L 1. The equa-
tion of the calibration graph is I (peak area) = 11.97c + 12.11
(lg L 1), with a correlation coefficient of 0.9993. The limit of detec-
tion (LOD), defined as LOD = 3r/k (where r is the standard devia-
tion of the blank sample and k is the slope of the calibration
graph), was 0.08 lg L 1. The relative standard deviation was
b 0.51% (n = 3, c = 10.00 lg L 1). The pre-concentration factor,
defined as the quotient of volume before absorption and after elu-
a
tion, is 25-fold.
d
3.8. Sample analysis
c
Fig. 4 shows the chromatographic peak of RhB standard solu-
0 1 2 3 4 5 6 7
tion/chili powder before and after separation. It can be seen that:
t/min (1) the retention time of RhB was 6.4 min (curve a); (2) the concen-
tration of RhB increased significantly after pre-concentration
Fig. 4. HPLC results. Chromatograms of RhB: (a) RhB standard solution
(10.00 lg L 1); (b) RhB standard solution after separation (60.00 lg L 1); (c) chili (curves a and b); and (3) RhB could only be determined in chili
powder sample; (d) chili powder after separation. powder after separation/concentration (curves c and d).
The proposed method was applied to determine the content of
RhB in chili powder and Chinese prickly ash. The results show that
the amount and recovery rate of RhB in chili powder were
Table 1 5.46 lg kg 1 and 99.0100.9%, respectively. RhB was not detected
Determination results of the samples (n = 3). in Chinese prickly ash with a sample added recovery rate of
Sample Added (lg kg 1
) Found (lg kg 1
) Recovery (%) 100.4101.2% (see Table 1).
Chili powder 0 5.46 0.01
5.00 10.47 0.02 100.2 0.6 3.9. Comparison with other methods
50.00 54.96 0.04 99.0 0.1
100.00 106.36 0.02 100.9 0.3 Comparison of the presented method with some other proce-
Chinese prickly ash 0 NDa dures for the determination of RhB (Table 2) revealed that the
5.00 5.02 0.02 100.4 0.4 method described herein had higher sensitivity, a wider linear
50.00 50.4 0.04 100.8 0.3
range, and easier operation.
100.00 101.2 0.03 101.2 0.6
a
Not determined.
4. Conclusion

In summary, Fe3O4@SiO2@IL were successfully prepared and

Each re-prepared adsorbent was used for MSPE. The extraction effi- applied as magnetic adsorbents to pre-concentrate and separate
ciency of the newly prepared Fe3O4@SiO2@[OMIM]PF6 MNPs for RhB. MSPE was coupled with HPLC for the analysis of RhB. This
RhB was greater than 90.0% after being re-used 10 times. Thus, MSPE method based on Fe3O4@SiO2@IL MNPs was faster than tra-
the Fe3O4@SiO2 MNPs could be used repeatedly 10 times. ditional SPE, thus saving time, and the adsorbent could be easily
separated from the sample solution. The hydrocarbon chains of
3.6. Effect of foreign substances the ILs on the surface of Fe3O4@SiO2@IL provided good adsorption
sites for RhB (higher extraction capacity and larger enrichment fac-
The effects of different foreign substrates were investigated in tors). The proposed method was satisfactory for the analysis of RhB
the determination of 10.00 lg L 1 RhB. With a relative error of less in food samples.
than 5%, the tolerance limits for various foreign ions were as fol-
lows (tolerance ratio in mass): SO24 , Br (500); citrate, glucose Acknowledgments
(250); NO3 (100); Zn2+, Cu2+, phenol, safranin, bright yellow, sun-
set yellow (20); allura red, congo red (10); rhodamine 6G (2). The authors acknowledge the financial support from the
The results indicate that the majority of these substances showed National Natural Science Foundation of China (21375117) and
no remarkable interference in the determination of RhB.

Table 2
Comparison of the results with those from the literature.

Method LRa (lg L 1

) LODb (lg L 1
) RSDc (%) Refs.
MSPE-fluorescence 0.355.00 0.10 2.108.20 Bagheri, Daliri, and Roostaie (2013)
SPE-UV 3.14 5.0 Soylak, Unsal, Yilmaz, and Tuzen (2011)
SPE-HPLC 1.0  1031.0  104 250 2.87 Li, Zhang, and Lu (2011)
HPLC-CL 1.582.1 1.50 4.0 Zhang, Cui, Myint, Lian, and Liu (2005)
MSPE-HPLC 0.50150.00 0.08 0.51 (n = 3) This method
a
Linear range.
b
Limit of detection.
c
Relative standard deviation.
 J. Chen, X. Zhu / Food Chemistry 200 (2016) 1015 15

the Priority Academic Program Development of Jiangsu Higher polymer coating for the selective solid phase extraction of dimetridazole. Food
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