Analytica Chimica Acta 650 (2009) 195–201
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Analytica Chimica Acta
journal homepage: www.elsevier.com/locate/aca
Use of a bisphenol-A imprinted polymer as a selective sorbent for the
determination of phenols and phenoxyacids in honey by liquid chromatography
with diode array and tandem mass spectrometric detection
E. Herrero-Hernández
1
, R. Carabias-Martínez, E. Rodríguez-Gonzalo
∗
Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Química, Universidad de Salamanca, Plaza de la Merced s/n, 37008 Salamanca, Spain
article info
Article history:
Received 26 May 2009
Received in revised form 15 July 2009
Accepted 15 July 2009
Available online 21 July 2009
Keywords:
Molecularly imprinted polymer
Bisphenol-A
Phenols
Phenoxyacids
Molecularly imprinted solid phase
extraction
Honey
abstract
An extraction-preconcentration procedure based on the use of a molecularly imprinted polymer (MIP) as
selective sorbent has been developed for the determination of several phenolic compounds (bisphenol-
A, bisphenol-F and 4-nitrophenol) and phenoxyacid herbicides (2,4-D, 2,4,5-T and 2,4,5-TP) in honey
samples. Liquid chromatography with diode array detection (LC–DAD) and electrospray ionisation-ion
trap mass spectrometry (LC–IT-MS) were used for the separation, identification and quantification of
these analytes.
The molecularly imprinted polymer was obtained by precipitation polymerisation with bisphenol-A
(BPA) as template and 4-vinylpyridine as the functional monomer. The behaviour of this sorbent was
compared with those of other materials frequently used in SPE. The selectivity of the BPA–MIP for the
target analytes was tested in samples containing other pesticides in common use. The recoveries achieved
for all six compounds were in the 81–96% range.
By applying the proposed procedure prior to LC–IT-MS, the limits of detection achieved in commercial
honey samples were in the 0.1–3.8 ng g
-1
range, with relative standard deviations of 12–24%.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction
Honey is a wholesome natural product consumed all over the
world. The nutritional and quality aspects of honey are important
since they determine consumer acceptance. The safety of honey
is also critical because it affects human health and hence there is
increasing interest in monitoring honey for the presence of pesti-
cides and other chemical compounds. According to European Union
(EU) regulations, honey as a natural product must be free of chem-
icals [1].
The global evaluation of honey requires the study of possi-
ble contamination by harmful substances. According to EC norm
2001/110/EC (2002), honey must be free of antibiotics, pesticides,
atmospheric pollutants and heavy metals [2]. European Union (EU)
legislation has established a level of 0.01 mg kg
-1
as the general
limit applicable “by default” as the maximum pesticide residue
level in food products for human consumption [Regulations EC no
396/2005 and no 178/2006].
∗
Corresponding author. Tel.: +34 923 294 483; fax: +34 923 294 483.
E-mail address: erg@usal.es (E. Rodríguez-Gonzalo).
1
Present address: Institute of Natural Resources and Agrobiology (IRNASA-CSIC),
Salamanca 37008, Spain.
Owing to the complex nature of the matrices in which the
target compounds are present, efficient sample preparation and
trace-level detection and identification are important aspects of
analytical methods. At present, solid-phase extraction (SPE) rep-
resents a suitable way to extract, clean and preconcentrate target
analytes from environmental or food samples. However, one prob-
lem associated with ordinary SPE is its low selectivity, due to
many unwanted interfering substances of similar hydrophobic-
ity/hydrophilicity.
Molecularly imprinted polymers (MIPs) are extensively cross-
linked polymers containing specific recognition sites with a
predetermined selectivity for analytes of interest. In recent years,
molecularly imprinted polymers have been successfully used as
selective sorbents in solid-phase extraction; the so called molec-
ularly imprinted solid phase extraction (MISPE). Besides their
selectivity, some qualities of MIPs, such as tolerance to extreme pH
values and organic environments, have brought MIPs to the fore-
front in contemporary chemical research. Owing to the inherent
selectivity provided by these materials, MIPs have been considered
as powerful sorbents for the extraction and clean-up of target ana-
lytes in complex samples. Accordingly, the use of MISPE seems to
represent an appropriate alternative to circumvent the drawback
of more traditional SPE techniques, and it is particularly suitable
for extractive applications where analyte selectivity represents the
main problem.
0003-2670/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2009.07.043