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Analytica Chimica Acta 998 (2018) 1e27

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Analytica Chimica Acta

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Advances in sensing and biosensing of bisphenols: A review

Dhanjai a, c, Ankita Sinha b, c, Lingxia Wu a, Xianbo Lu a, **, Jiping Chen a, *, Rajeev Jain c
CAS Key Laboratory of Separation Sciences for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), School of Environmental Science and Technology,
Dalian University of Technology, Dalian 116024, PR China
School of Studies in Chemistry, Jiwaji University, Gwalior 474011, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Bisphenols are major environmental

contaminants and endocrine
 State of the art of sensing and bio-
sensing approaches for Bisphenols
(BPs) detection.
 Varied nanomaterials and bio-
receptors based sensors employed for
BPs analysis.
 Sensing strategies for screening of BP
analogs other than BPA are not many.

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

Article history: Bisphenols (BPs) are well known endocrine disrupting chemicals (EDCs) that cause adverse effects on the
Received 24 March 2017 environment, biotic life and human health. BPs have been studied extensively because of an increasing
Received in revised form concern for the safety of the environment and for human health. They are major raw materials for
22 September 2017
manufacturing polycarbonates, thermal papers and epoxy resins and are considered hazardous envi-
Accepted 23 September 2017
Available online 17 October 2017
ronmental contaminants. A vast array of sensors and biosensors have been developed for the sensitive
screening of BPs based on carbon nanomaterials (carbon nanotubes, fullerenes, graphene and graphene
oxide), quantum dots, metal and metal oxide nanocomposites, polymer nanocomposites, metal organic
frameworks, ionic liquids and molecularly imprinted polymers. This review is devoted mainly to a variety
Biosensors of sensitive, selective and reliable sensing and biosensing methods for the detection of BPs using elec-
Electrochemical sensors trochemistry, fluorescence, colorimetry, surface plasmon resonance, luminescence, ELISAs, circular di-
Immunosensors chroism, resonance Rayleigh scattering and adsorption techniques in plastic products, food samples, food
Colorimetry packaging, industrial wastes, pharmaceutical products, human body fluids and many other matrices. It
Fluorescence summarizes the advances in sensing and biosensing methods for the detection of BPs since 2010.
Nanomaterials Furthermore, the article discusses challenges and future perspectives in the development of novel
sensing methods for the detection of BP analogs.
© 2017 Elsevier B.V. All rights reserved.


* Corresponding author.
** Corresponding author.
E-mail addresses: dhanjai83@gmail.com (Dhanjai), xianbolu@dicp.ac.cn (X. Lu),
chenjp@dicp.ac.cn (J. Chen).

0003-2670/© 2017 Elsevier B.V. All rights reserved.
2 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Sensing and biosensing of bisphenols in different matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Electrochemical sensors and biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Nanomaterials based sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Ionic liquids based sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2. Fluorescence based sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3. Chemiluminescence based sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4. Colorimetric sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5. Surface plasmon resonance sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.6. Some significant sensing platforms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.6.1. Microorganisms based sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.6.2. Cell chip based sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.6.3. Other significant sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3. Conclusion, challenges and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

1. Introduction thyroxin, it exhibits a strong affinity towards transthyretin [20e22].

In addition, bisphenol AP (BPAP, 1,1-bis(4-hydroxyphenyl)-1-
The presence of hormone disruptors in the environment and in phenyl-ethane), bisphenol E (BPE, 1,1-bis(4-hydroxyphenyl)
various common consumer goods is an area of concern for human ethane), tetrachlorobisphenol A (TCBPA, 2,20 ,6,60 -tetrachloro-4,40 -
health and biosafety. Endocrine disruptors (EDCs) block the meta- isopropylidenediphenol) and bisphenol Z (BPZ, 1,1-bis(4-
bolism of steroid hormones, as they possess significant potential for hydroxyphenyl)-cyclohexane) are other members of the bisphe-
altering the structure and function of the endocrine system. nol family that have attracted considerable attention due to their
Consequently, exposure to EDCs results in a number of disorders adverse chemical properties [23].
related to obesity, diabetes, cardiovascular diseases, carcinogenicity Various analytical procedures have been reported for the
and neurotoxicity [1]. Bisphenols (BPs) are well-known endocrine routine determination of BPs. Recent developments in the field of
disrupting compounds that contain two hydroxyphenyl groups, materials chemistry offer new possibilities for novel sensor designs
and there are more than fifteen BP analogs. The chemical structures based on advance functional nanostructures [24]. Recent trends in
of various BPs are summarized in Table 1. With the extensive evi- the construction of stable and robust sensors based on different
dence of adverse effects of BPs on human health and the environ- nanomaterials and bio-recognition elements such as aptamers,
ment, numerous studies have been performed to assess their enzymes, antibodies and whole cell have been discussed widely for
toxicity [2]. Various worldwide regulatory bodies and health monitoring environmental toxins [23,25]. Analytical methods for
agencies have reported on various risk assessment studies on the detection of BPs are generally based on various chromato-
bisphenols [3e5]. graphic [26] and hyphenated methods, such as gas
Bisphenol A (BPA), 2, 2-bis (4-hydroxyphenyl) propane, is a very chromatography-mass spectrometry (GC-MS) [27]. However,
popular member of the BP family that has potent endocrine- sensing and biosensing methods have taken a different course
disrupting activity [6]. In addition, BPA has diverse industrial ap- recently toward much more sensitive, selective and convenient
plications as a raw material for manufacturing a wide variety of detection techniques having comparatively low cost, high accuracy
food storage and packaging materials, water pipes, bottle tops, and enhanced user compatibility. Recently, a large number of
tableware and microwave ovenware [6,7]. Routine procedures electrochemical processes have been reported that emphasize the
involving heating and hydrolysis during Pasteurization, canning, catalytic oxidation of BPs. In addition, other sensing strategies
microwave heating, sterilization and washing of the vessels result based on colorimetry, fluorescence, luminescence, optical and im-
in increased leaching of BPA into food products, raising concerns for mune sensing techniques have been proposed for the detection of
food safety [8]. Many studies have been reported on the exposure of BPs in diverse sample compositions. Newly developed methodol-
BPA to human and biotic life, and discuss adverse outcomes such as ogies for the detection of BPs have been validated by analytical
the destruction of basic physiological processes and widespread procedures (e.g., HPLC/GC) for judging the quality, reliability and
environmental contamination [9,10]. consistency of analytical results in terms of specificity, precision,
Apart from BPA, bisphenol B (BPB, 2,2-bis (4-hydroxyphenyl) reproducibility, stability and recovery.
butane) [11,12], bisphenol S (BPS, 4,40 -dihydroxy diphenyl sul- The present article summarizes advancements since 2010 in the
phone) [13], bisphenol AF (BPAF, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- development of various sensors and biosensors for the sensitive
hydroxyphenyl) propane) [14,15] and bisphenol F (BPF, 4, 4 -dihy- detection of bisphenols in different matrices based on electro-
droxydiphenyl-methane) [16] are other members of the bisphenol chemical, fluorescence, luminescence, colorimetry, surface plas-
family that are prominent endocrine disrupters that came to mon resonance and other techniques. The developed sensors have
attention after the onset of strict regulations on the production and been categorized according to their method for detecting BPs.
usage of BPA [17]. Furthermore, tetrabromo bisphenol A (TBBPA, 2,
20 , 6, 60 -tetrabromo-4, 40 -isopropylidenediphenol), is one of the
widely used BPs and is produced by reacting bromine with BPA. It is 2. Sensing and biosensing of bisphenols in different matrices
used as a brominated flame retardant during the manufacturing of
electronic appliances [18,19]. Having a structural similarity to Various strategies have been developed for sensing and bio-
sensing BPs in different media based on the chemical
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 3

Table 1
Chemical structures of different BPs.

Bisphenol (BP) IUPAC name Chemical structure

BPA 2,2-Bis(4-hydroxyphenyl)propane

BPB 2,2-Bis(4-hydroxyphenyl)butane

BPF Bis(4-hydroxyphenyl)methane

BPAF 2,2-Bis(4-hydroxyphenyl)hexafluoropropane

BPE 1,1-Bis(4-hydroxyphenyl)ethane

BPAP 1,1-Bis(4-hydroxyphenyl)-1-phenyl-ethane

BPS Bis(4-hydroxyphenyl)sulfone

TBBPA 2,20 ,6,60 -Tetrabromo-4,40 isopropylidenediphenol

BPZ 1,1-Bis(4-hydroxyphenyl)-cyclohexane

characteristics of the BPs. These detection schemes provide diag- organic frameworks (MOFs). A list of electrochemical sensors and
nostic and mechanistic solutions to many environmental, clinical, biosensors used for the detection of BPs is presented in Table 2.
food and security applications. A systematic and detailed account of
the developed sensors and biosensors is discussed in the following 2.1.1. Nanomaterials based sensors
sections. Carbon nanomaterial based sensors. Carbon based nano-
materials have received considerable attention in the field of
2.1. Electrochemical sensors and biosensors electrochemical sensing and biosensing due to their diverse
morphological, electronic, thermal and chemical properties such as
In recent years, there has been a great deal of interest in the large specific surface area, remarkable conductivity, ease of
development of different electrochemical sensors with increased manipulation and biocompatibility [32,33]. Nanofabrication tech-
sensitivity and selectivity for rapid screening of BPs [24,28]. Elec- nologies have been used to explore the use of carbon based
troanalytical methods offer notable detection characteristics with nanomaterials such as carbon nanotubes (CNTs), graphene (GR),
high reproducibility, stability and ease of miniaturization [29]. The graphene oxide (GO), fullerenes (C60) and their various nano-
enhanced electrochemical performance of sensors is achieved composites as electrode materials to obtain enhanced electro-
mainly by chemical modifications of bare electrode surfaces using catalytic performance [34,35]. Various carbon nanoconjugates have
different nanomaterials and bioreceptors to produce an increased been used extensively by many researchers for electrochemical
response with improved selectivity [30]. A variety of nanomaterials sensing and biosensing of BPs [13,14,16,36e94] (Table 2). For
acts as catalysts to increase the effective electrode surface area and example, the simultaneous detection of BPF and BPAF was per-
electron transfer kinetics between the modified surface and the formed using a carboxylic acid functionalized multi-walled carbon
redox centers of analytes [31]. Significant progress has been made nanotube-modified GCE sensor (MWCNTs-COOH/GCE) that
in designing electrochemical sensors and biosensors based on possessed excellent binding capacity, dispersion quality and pep
carbon nanomaterials, quantum dots (QDs), conducting polymers conjugation, resulting in suitable electrode kinetics for sensing BPF
(CPs), ionic liquids (ILs), metal & metal oxide conjugates and metal and BPAF [14] (Fig. 1a). The fabricated sensor produced well-
4 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Table 2
Electrochemical sensors and biosensors for detection of bisphenols.

Reference Sensor Bisphenol LOD Linear range Real Sample Matrix Recovery % References

Carbon based sensors

GO-C60/GCE BPS 0.50 mM L1 1.0e100.0 mM L1 Milk 84.2e91.7% [13]
MWCNTs-COOH/GCE BPF 5.49  1010 ML1 5.92  1010-3.0  108ML1 Water, milk, juice packing 93.8e105.3% [16]
MWCNTs-COOH/GCE BPF 0.12 mM L1 0.6e1.60 mM L1 Waste water, rubber gloves 97.5e102.5% [14]
MWCNTs-COOH/GCE BPAF 0.17 mM L1 0.60e1.60 mM L1 Waste water, rubber gloves 97.5e102.5% [14]
MWCNTs-COOH/GCE BPAF 7.70 nM L1 0.02e8.0 mM L1 Water samples, rubber gloves 95.0e108.6% [45]
CTAB-NGR-TPA/GCE TBBPA 9.0 nM L1 0.01e1.0 mM L1 Water sample 95.3e109.8% [72]
MWCNTs-PTh-Pt/GCE BPA 3.0  109 M L1 5.0  108-4.0  107 M L1 Water sample 96.0e105.0% [36]
C60/GCE BPA 3.70 nM L1 74.0 nM L1-0.23 mM L1 Waste water 94.0e104.0% [37]
MWCNTs/GCE BPA 0.08 mM L1 4.50e82.50 mM L1 e e [38]
dsDNA modified dcells BPA 100.0 cells mL1 100.0e700.0 cells mL1 Milk 93.0e101.0% [39]
Tyr/TiO2-MWCNTs-PDDA-Nafion/ BPA 0.66 mM L1 0.28e45.0 mM L1 Leaches of plastic products e [40]
MWCNTs-GO-Chi/GCE BPA 4.38  1012 ML1 2.19  1011-6.57  107 ML1 Water 94.3e106.7% [41]
PGA/MWCNTs-NH2/GCE BPA 0.02 mM L1 0.1e10 mM L1 Plastic products 95.0e108.0% [42]
f-SWCNTs/PC4/GCE BPA 0.32 mM L1 0.09e5.79 mM L1 Mineral water 99.6e103.35% [43]
Tyr-diazonium MWCNTs/BDD BPA 10.0 pM L1 0.1e100.0 nM L1 Waste water 95.0e103.0% [44]
Tyr/CFP BPA 5.0 nM L1 1.0  108 -1.0  106 M L1 e e [46]
MWCNTs-COOH/GCE BPA 5.0 nM L1 10.0  104 nM L1 Food packaging 98.4e102.8% [47]
Solgel-MWCNTs-AuNP/GCE BPA 3.6  109 M L1 1.13  107-8.21  103ML1 Honey, tap water, grape juice 92.7e97.8% [48]
ssDNA-SWCNTs/Au BPA 11.0 nM L1 0.50e3.80 mM L1 e e [49]
Tyr-SF-MWCNTs-COPC/GCE BPA 0.03 mM L1 0.05e3.0 mM L1 Plastic samples 95.36 [50]
TaPC/SWCNTs/CPE BPA 1.16  1010 M L1 1.0e8.0 M L1 Feeding bottles 98.0% [51]
Laccase-CB-thionine-nafion/SPE BPA 0.20 mM L1 0.50e50.0 mM L1 Tomato juice 92.0e120.0% [52]
Tyr-thionine-CPE BPA 0.15 mM L1 0.15e75.0 mM L1 e e [53]
NiTPPS/MWCNTs/GCE BPA 15.0 mM L1 0.05e50.0 mM L1 Water samples 96.0e104.0% [54]
Tyr-MWCNTs/GCE BPA 5.0  107 M L1 2.0  106-1.0  104 M L1 Water samples 94.3e105.5% [55]
Catholically pretreated BDD BPA 0.21 mM L1 0.44e5.20 mM L1 Water samples 95.0e107.0% [56]
MWCNTs-SbNPs/GCE BPA 5.24 nM L1 0.5e5.0 mM L1 e e [57]
SWCNTs-bCD/GCE BPA 1.0 nM L1 10.80 nM L1-18.50 mML1 Plastic samples 95.0e103.0% [58]
MWCNTs-MAM/GCE BPA 5.0 mM L1 10.0 nM L1-40.8 mM L1 Plastic samples 96.0e102.0% [59]
SPCE BPA 5.10  108M L1 1.0  106-1.05  106M L1 River water, sewage 97.90% [60]
MWCNTs-titania-nafion/GCE BPA 9.0  1010 M L1 1.0  108-5.0  106 M L1 Food packaging 99.57% [61]
MWCNT-Li4Ti5O12/GCE BPA 7.8  108 M L1 1.0  107 -1.0  105 M L1 Food packaging, edible oils 97.8e106.3% [62]
ct-DNA-SWCNTs-nafion/GCE BPA 5.0 nM L1 1.0  108 -2.0  105 M L1 Plastic baby bottles 94.0e106.0% [63]
Polylysine-SWCNTs-Tyr/GCE BPA 0.97 nM L1 4.0 nM L1-11.5 mM L1 Plastic spoons e [64]
Tyr-AuNPs/SPCE BPA 1.0  108 M L1 4.20  108 -3.6  105 M L1 e e [65]
Tyr-NiNPs/SPCE BPA 7.10  109 M L1 9.10  107-4.80  105ML1 e e [65]
Tyr-Fe3O4/SPCE BPA 8.30  109 M L1 2.20  108-4.0  105 M L1 e e [65]
Tyr-MWCNTs-Chi/GCE BPA 0.10 mM L1 0.30e2.50 mM L1 Plastic products 93.8e103.1% [66]
NSGR-NiTPPc/GCE BPA 25.50 nM L1 0.20e12.0 mM L1 Plastic samples 96.33e98.67% [73]
Tyr-GR-Chi/GCE BPA 33.0 nM L1 100.0e2000.0 nM L1 Water samples e [74]
GR-SP-Tyr/GCE BPA 0.72 mM L1 2.0 nM L1-5.48 mM L1 Plastic bottles e [75]
GR-AuNP-Tyr-Chi/GCE BPA 1.0 nM L1 0.02e3.0 mM L1 Plastic, milk carton samples 98.0e110.3% [76]
Arg-GR/GCE BPA 1.10 nM L1 5.0e40.0 nM L1 Plastic products 98.9e102.2% [77]
rGO-MAM/GCE BPA 4.0  109 M L1 1.0  108 -2.0  104 M L1 Food, water samples 97.0e100.96% [78]
Lacl-BPA/rGO BPA 5.0 fM L1 100.0 fM L1-10.0 nM L1 Plastic extracts 94.0e106.0% [79]
TA-NGR/GCE BPA 4.0 nM L1 0.50e13 mM L1 Food package 95.0e103.0% [80]
ZnTsPc-fGR/GCE BPA 2.0  108 M L1 5.0  108 -4.0  106 M L1 Plastic samples 96.8e103.6% [81]
pb-CD-EGR/GCE BPA 52.0 pM L1 1.0e6000.0 nM L1 Water samples 95.0e101.0% [82]
rGO-Fc-NH2-AuNPs/GCE BPA 2.0 nM L1 0.005e10.0 mM L1 Milk samples 96.0e103.0% [83]
Tyr-rGO-Chi/ITO BPA 0.74 nM L1 0.01e50.0 mM L1 Plastic bottles 97.83 [84]
GR/GCE BPA 20.0 nM L1 0.08e5.0 mM L1 e e [85]
AuNPs-SGRNF/GCE BPA 35.0 nM L1 0.08e250.0 mM L1 Plastic bottles 98.4e102.1% [86]
GR/ABPE BPA 0.60 nM L1 0.80 nM L1-0.1 mM L1 Plastic products 97.6e103.8% [87]
GRS-Fe2O3/GCE BPA 2.50 nM L1 5.0 nM L1-1.0 mM L1 Water samples 97.6e105.0% [88]
Chi-MNPs/GCE BPA 1.7  108 M L1 6.0  108 -1.10  105 M L1 Plastic products 97.0e109.2% [89]
SiO2-rGO-AuNPs/GCE BPA 5.0  109 M L1 3.0  108 -1.2  104 M L1 Printing papers 96.39e108.3% [90]
EG BPA 0.76 mM L1 1.56e50.0 mM L1 Plastic products 98.0e104.0% [91]
GR/GCE BPA 4.6  108 M L1 5.0  108 -1.0  106 M L1 Plastic bottle 90.0% [92]
N-GRS-Chi/GCE BPA 5.0  109 M L1 1.0  108 -1.30  106 M L1 River water 95.8e106.5% [93]
b-CD-rGO-AuNPs/GCE BPA 3.0 nM L1 0.01e50.0 mM L1 Water, milk, plastic samples 98.2e105.3% [94]
Metal nanocomposites based sensors
CuMOFs-Tyr-Chi/GCE BPB 56.0 nM L1 1.25  107 -8.0  106 M L1 Waste water e [23]
CuMOFs-Tyr-Chi/GCE BPE 15.0 nM L1 5.0  108 -3.0  106 M L1 Waste water e [23]
CuMOFs-Tyr-Chi/GCE BPF 16.0 nM L1 5.0  108 -3.0  106 M L1 Waste water e [23]
CuMOFs-Tyr-Chi/GCE BPZ 33.0 nM L1 2.50  107 -5.0  106 M L1 Waste water e [23]
CuMOFs-Tyr-Chi/GCE BPA 13.0 nM L1 5.0  108 -3.0  106 M L1 Waste water e [23]
MoS2-Chi-AuNPs/GCE BPA 5.0 mM L1 0.05e100.0 mM L1 Plastic, food & water samples 94.2e105.2% [99]
AuNPs/Ceramic sensor BPA 2.90 nM L1 1.0e35.0 nM L1 Water samples 94.7e109.8% [100]
4MBA-Au nano dendrites/GCE BPA 1.20 nM L1 0.05e55.0 mM L1 Plastic samples 96.9e104.3% [101]
PAMAM-AuNPs-SF/GCE BPA 0.50 nM L1 1.0 nM-1.30 mM L1 Water samples 97.0e105.0% [102]
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 5

Table 2 (continued )

Reference Sensor Bisphenol LOD Linear range Real Sample Matrix Recovery % References

AuNPs-MWCNTs/GCE BPA 3.0  109 M L1 8.0  108 -1.0  105 M L1 Water samples 96.0e103.4% [103]
AgNPs@C/GCE BPA 8.80 nM L1 0.05e1.0 mM L1 Water & plastic samples 94.60e106.5% [104]
Pt-GR-CNTs/GCE BPA 0.04 mM L1 0.06e10.0 mM L1 Thermal printing paper 96.09e106.7% [105]
Ni(II)TAPc/Au BPA 3.6  102 M L1 7.0  104 -3.0  102 M L1 Plastic samples 72.0% [106]
FeOx- bCD/GCE BPA 5.0  107 M L1 1.0  107 -50.0  106 M L1 Ginger beer e [107]
Poly zircon/GCE BPA 9.0  106 M L1 21.0e292.0 mM L1 Oilfield waste water 98.8e100.8% [108]
Mg-Al-CO3 LDH/GCE BPA 5.0  109M L1 1.0  108 -1.05  106 M L1 Plastic products 96.06e104.9% [109]
Mg-Al-SDS LDH/GCE BPA 2.0  109M L1 8.0  109 -2.80  106 M L1 Lake, river, tap, & waste water 96.42e102.6% [110]
CuMOF-Tyr-Chi/GCE BPA 13.0 nM L1 0.05e3.0 mM L1 Plastic products 94.0e101.6% [111]
Tyr-nano Au-TNH2/Au BPA 3.99  107M L1 3.99  107 -2.34  104 M L1 e e [112]
aptamer-NPAu/GCE BPA 0.05 nM L1 0.01e100.0 nM L1 Human serum 98.9e102.3% [113]
aptamer-cDNA/Au BPA 0.28 pM L1 0.5e5.0 nM L1 Water samples 93.7e102.9% [115]
antiBPA-MCH-AuNPs-GR/GCE BPA 5.0 nM L1 0.01e10.0 mM L1 Milk samples 90.0e116.0% [116]
Peptide(CKSLENSYC)/Au BPA 0.7 nM L1 1.0e5000.0 nM L1 Plastic products 92.0e107.0% [117]
Metal oxide nanocomposite based sensors
Chi-Fe3O4/GCE BPA 8.0  109 M L1 5.0  108 -3.0  105 M L1 PC nursing bottles 92.0e106.2% [118]
Fe3O4 NPs-CB/GCE BPA 0.03 nM L1 0.1 nM-50.0 mM L1 Plastic bottles &food samples 93.2e104.1% [119]
PAMAM- Fe3O4/GCE BPA 5.0 nM L1 0.01e3.07 mM L1 Milk 95.3e104.0% [120]
TiO2-Au NTAs BPA 6.20  109 M L1 1.0  107-3.80  105 M L1 Water samples 95.0e107.0% [121]
Pd@ TiO2-SiC BPA 4.30 nM L1 0.01e200.0 mM L1 Water samples 97.4e103.6% [122]
ITO electrode BPA 290.0 nM L1 5.0  106 -1.20  104 M L1 e e [123]
Bi2WO6/CPE BPA 15.0 nM L1 70.0e1300.0 nM L1 Milk 87.0e99.9% [124]
Tyr-APTES-nTiO2/Ti BPA 0.01 mM L1 0.01e1.0 mM L1 e e [125]
Polymer nanocomposite based sensor
AuNPs-poly-cys/GCE TBBPA 3.20 nM L1 10.0 nMe10.0 mM L1 Water samples e [19]
MoS2-SPAN/GCE BPA 0.60 nM L1 1.0 nM-1.0 mM L1 PC water &infant bottle 95.0e105.6% [127]
PAM-MWCNTs/GCE BPA 1.70 nM L1 5.0 nMe20.0 mM L1 Milk 95.7e105% [128]
PANI nanorod MWCNTs/PEG BPA 10.0 nM L1 1.0e400.0 mM L1 Baby bottles 86.0e102.0% [129]
PEDOT/GCE BPA 22.0 mM L1 40.0e410.0 mM L1 Mineral water 100.0 ± 10% [130]
A-M-CPPyNPs/FET BPA 1.0 fM L1 e e e [131]
Poly (Jug-co-JugBPA)/GCE BPA 0.01 nM L1 0.05e5.0 nM L1 e e [132]
CYP2C9-PAM/GCE BPA 0.58 mM L1 1.25e10.0 mM L1 e e [133]
Tyr-PEDOT-PSS/SPE BPA 19.0 nM L1 0.02e9.0 mM L1 Lake water e [134]
MIP-GR-NBD/CE TBBPA 0.23 nM L1 0.50e4.50 nM L1 Water samples 100.2e100.3% [20]
MIPPy-GR-CNTs/GCE TBBPA 3.70  1012M L1 1.0  1011 -1.0  108 M L1 Catfish, chub, carp 93.3e107.7% [21]
MIPPy-Ni-GR/CE TBBPA 1.30  1010 M L1 5.0  1010 -1.0  105 M L1 Water samples 96.0e105.0% [22]
MIPPy-GRQDs/GCE BPA 0.04 mM L1 0.01e50.0 mM L1 Water samples 94.5e93.7% [137]
MIPPy-SnO2/ITO BPA 1.20 nM L1 2.0e500.0 nM L1 Water samples 89.0e108.0% [138]
MIPPy-GR-Ag/CE BPA 3.20  1012 M L1 1.0  1011 -1.0  108 M L1 Plastic samples 93.3e103.0% [139]
MIPPy-TiO2NTs BPA 2.0 nM L1 4.50e108.0 nM L1 Water samples 95.75 [140]
GO-APTES-MIP/GCE BPA 3.0 nM L1 0.006e0.1 mM L1 Milk & mineral water 96.8e106.2% [141]
SBA-MIP-APTES/CPE BPA 3.20  108 M L1 1.0  107 -5.0  104 M L1 Water samples 97.23e101.6% [142]
MIP-AB-Chi/GCE BPA 2.0 nM L1 5.0 nM L1-10.0 mM L1 Water samples 94.1e105.7% [143]
MIP-Chi-GR/ABPE BPA 6.0 nM L1 8.0 nM L1-1.0 mM L1 Plastic bottles & canned beverages 92.0e106.0% [144]
MIP-Chi/ABPE BPA 60.0 nM L1 80.0 nM-10.0 mM L1 Plastic samples 98.6e104.4% [145]
MIP-PVP-MWNPE BPA 22.0 nM L1 0.80e100.0 mM L1 Water samples 92.8e105.0% [146]
MIP-PVC membrane electrode BPA 0.02 mM L1 0.10e1.0 mM L1 Plastic bottle 90.0e103.0% [147]
MIP- 2aminothiophenol-NGR/GCE BPA 1.38  107 M L1 8.0  106 -6.0  102 M L1 Plastic bottle e [148]
EMIP-terthiophene-carbazole/ITO BPA 0.42 mM L1 0.0e12.0 mM L1 e e [149]
MMIP NP-CTAB/CPE BPA 1.0  107 M L1 6.0  107 -1.0  104 M L1 Drinking bottle & lake water 95.0e112.0% [150]
Quantum dots based sensor
CoTeQDs-PAMAM/GCE BPA 1.0  109 M L1 1.30  106 -9.8  106 M L1 Water samples 97.0e107.2% [151]
Ionic liquids based sensors
1 1
CMK-3/nCILPE BPA 0.05 mM L 0.20e150.0 mM L Plastic samples 98.9e101.8% [154]
SWCNT-IL/GCE BPA 1.0  109 M L1 5.0  109 -3.0  105 M L1 Plastic products e [155]
8 1
Chi-GR/CILE BPA 2.60  10 M L 0.10e800.0 mM L1 Plastic products 94.36 [156]
ZnO-CNTs-IL/CPE BPA 9.0 nM L1 2.0 nM L1-700.0 mM L1 Food samples e [157]
GR-IL/GCE BPA 8.0 nM L1 20.0 nM L1-2.0 mM L1 Milk, soda 90.0e95.0% [158]
ILGRCPE BPA 55.0 nM L1 9.0  108 -2.5  104 M L1 Water samples 96.0e102.7% [159]
ILs-LDH/GCE BPA 4.60 nM L1 0.02e3.0 mM L1 Water samples 94.9e102.0% [160]
CdO-IL-CPE BPA 0.10 mM L1 0.30e650.0 mM L1 Food samples e [161]
PEDOT-BMIMBr/SPCE BPA 0.02 mM L1 0.10e500.0 mM L1 Water, plastic bottles 97.6e105.7% [162]
1,10-PhenanNTf2/AgE sensor BPA 0.09 nM L1 0.10 nM L1-1.0 mM L1 e e [163]
PBPIDS/GCE BPA 8.0 nM L1 10.0 nM L1-10.0 mM L1 Plastic bottle e [164]
Poly-IL/GCE BPA 4.0  109 M L1 1.0  108 -1.0  105 M L1 Plastic bottle e [165]
b CD/IL/CPE BPA 83.0 nM L1 1.0  107 -1.1  105 M L1 Food, plastic, water samples 96.3e103.2% [166]
Tyr-DAPPT-rGO/GCE BPA 3.5  1010 M L1 1.0  109 -3.8  105 M L1 Plastic bottles 104.0% [167]
6 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 1. (a) Electro-oxidation of BPAF and BPF at MWCNTs-COOH/GCE sensor, (b) CVs of 1.0 mM L1 BPF and BPAF in a mixture solution at MWCNT-COOH/GCE (curve red) and bare
GCE (curve black), (c) simultaneous determination of BPF and BPAF at MWCNT-COOH/GCE, linearity curves keeping the concentration of BPF constant and BPAF changed and (d)
keeping the concentration of BPAF constant and BPF changed; Inset: the related calibration plots [14]. Reprinted with the permission from Ref. [14]. Copyright 2014, Elsevier B.V. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

separated oxidation peaks by cyclic voltammetry (CV) (Fig. 1b) for a electrostatic interactions, which accelerates electron transfer be-
sample mixture of BPF & BPAF and exhibited a linear current tween the modified sensor surface and TBBPA. The study suggested
response with increasing concentrations of BPF and BPAF using that the use of less hazardous aqueous surfactant media in elec-
differential pulse voltammetry (DPV), as shown in Fig. 1c and d, troanalysis would promote the green chemistry concept. Moreover,
respectively. Insignificant interference by hydroquinone, hydrox- nitrogen and sulfur co-doped GR (NSGR) hybrids of nickel tetra-
yphenol, pyrocatechol, BPAP, BPA and some inorganic ions sug- pyridyloxyphthalo cyanine (NiTPPc) were prepared for BPA oxida-
gested that there was no influence on the determination of BPF and tion using a solvothermal method taking GO, 5-amino-1, 3, 4-
BPAF. However, structural characterization of the sensor was not thiadiazole-2-thiol (ATT) and NiTPPc as precursors [73]. The
evaluated, and this could facilitate studying interactions of BPF and NSGR-NiTPPc/GCE sensor exhibited a higher surface area of
BPAF with MWCNTs-COOH. 0.12 cm2 compared to bare GCE (0.05 cm2), with the high catalytic
To evaluate the potential of CNT-bioreceptor hybrid sensors, calf activity of the sensor being attributed to the synergistic effects of
thymus DNA (ctDNA) was immobilized on SWCNTs-nafion/GCE to NSGR and NiTPPc. To evaluate selectivity and specificity, the per-
enable the selective detection of BPA [63]. The addition of ctDNA to formance of the NSGR-NiTPPc/GCE sensor requires further analysis
BPA caused a decrease in the current and a large positive potential of BPA in the presence of other phenolic compounds to further
shift was observed indicating the formation of BPA-ctDNA hybrids. justify its sensing characteristics.
Furthermore, the electrochemical measurments were validated by Several other GR-based enzymatic biosensors have been fabri-
HPLC and compared using the t-test. Despite the high activity of the cated for the detection of BPs [74e77]. A GR-based tyrosinase
biosensor, the electrode fabrication step involved functionalization biosensor was developed by our group and systematically
of SWCNTs with concentrated nitric acid, which is very hazardous. compared with a MWCNTs-tyrosinase biosensor for the rapid
Due to the large working surface area, high catalytic activity and detection of BPA [74]. A typical design for tyrosinase immobilized
excellent accumulation ability, graphene (GR) is a novel electrode GR and MWCNTs composites is shown in Fig. 2a and b, respectively.
material for sensing applications [67e70]. Various desirable aspects The electrocatalytic oxidation mechanism for BPA with the Tyr-GR-
of GR for use in sensors have been reported by many researchers Chi/GCE biosensor is illustrated in Fig. 2c. The study revealed sig-
[71]. For example, nitrogen-doped GR (NGR) was modified with the nificant advantages of the Tyr-GR-Chi/GCE in terms of sensitivity
cationic surfactant Cetyltrimethylammonium bromide (CTAB) and and surface area, which were much higher than for the Tyr-
1, 3, 6, 8-pyrene tetrasulfonic acid tetrasodium salt (TPA) hydrate to MWCNTs-Chi/GCE. The fabricated sensor provides a promising
form a unique CTAB-NGR-TPA/GCE nanosensor for voltammetric tool for screening environmental contaminants that leach from
detection of TBBPA [72]. Below the critical micelle concentration plastic and resin products. Furthermore, the anti-interference
(CMC) of CTAB, the long positively charged alkyl chain is absorbed ability of the sensor suggests that it can be used effectively for
by the negatively charged NGReTPA composite through typical investigations of the environmental effect of BPs and other
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 7

Fig. 2. Schematic representation of tyrosinase immobilized on (a) nanographene, (b) MWCNTs, (c) electro-oxidation mechanism of BPA at Tyr-GR-Chi/GCE [74]. Reprinted with the
permission from Ref. [74]. Copyright 2012, Elsevier B.V.

contaminants. rGO surface containing the denatured Lacl-BPA hybrid offered

In another case, an amino acid functionalized GR nano- numerous probes that are readily available on the electrode surface
composite was prepared for the determination of BPA [77]. The to capture BPA. The LacI-BPA-rGO showed minimal cross reactivity
standard heterogeneous rate constant (ks) for the irreversible with other BPA analogs such as BPS, BPF and other potentially
oxidation process for an arginine (Arg) GR-modified sensor (Arg- interfering species that may be extracted from plastic products. In
GR/GCE) was calculated to be 1.21  102 cm s1, which demon- addition, the method demonstrated the interaction of proteins with
strates a higher adsorption capacity and conductivity for the hydrophobic rGO, thereby providing a biocompatible sensing
modified sensor. The study suggested a promising approach for platform for direct interactions between probes and sensor sur-
designing amino acid functionalized advanced carbon sensors for faces. Various other GR and GO based sensors have also been re-
the detection of contaminants in biological fluids and their in vivo ported for the detection of BPs in different matrices [80e94].
interactions with various essential and non-essential amino acids. A fullerene based sensor was recently reported for the detection
Graphene oxide (GO) with its extraordinary catalytic properties of BPS [13]. The electrochemically co-reduced GO-C60 nano-
has been reported to be useful in electrochemical sensing appli- assembly was prepared by simple grinding followed by electro-
cations. Recently, a reduced graphene oxide-melamine nano- chemical reduction in 0.1 M KCl (Fig. 3a and b). Electrochemical
particle-modified glassy carbon electrode (rGO-MAM/GCE) was reduction in KCl led to the formation of a K3C60 network which was
described for the detection of BPA [78]. A nitrogen-rich conjugated responsible for the high electrocatalytic activity of the nano-
MAM was noncovalently attached to GO through strong p-p assembly. The rC60 nanoparticles were deeply embedded into the
stacking interactions. Upon excitation of rGO-MAM, the fluores- rGO with a larger surface-to-volume ratio, thereby providing
cence signal increased with increasing rGO content, which was additional binding sites for BPS. The electrochemical reduction of
attributed to the interaction of rGO carboxyl and hydroxyl groups GO-C60 was confirmed by X-ray photoelectron spectroscopic (XPS)
with MAM amino groups. The high ks for totally irreversible studies that clearly demonstrated the presence of K in the reduced
oxidation process at the modified electrode was due to the high state (Fig. 3c). The rGO-rC60 nanoassembly exhibited characteristic
adsorption capacity and conductivity of the rGO-MAM hybrid voltammetric responses for the detection of BPS, as shown in
sensor and fast electron transfer between BPA and the electrode Fig. 3d. The study presented a green and simple technique for the
surface. fabrication of 3D nanoassemblies with high catalytic performance
Demonstrating further advancements, a novel recombinant toward BPS in the presence of other phenolic compounds.
binding protein probe (Lacl-BPA) was fabricated based on an rGO
thin film-modified electrode for the selective detection of BPA [79]. Metal nanocomposites based sensors. Metal nanomaterials
In a typical fabrication process, a cysteine-containing peptide
(MNPs) with fascinating chemical and electronic properties have
(CKSLENSYC) was linked to the C terminal of the Lacl protein and
been considered as interesting materials for the preparation of
then adsorbed to a rGO electrode in denatured form. The uniform
effective electrochemical sensors and biosensors [95e98]. A variety
8 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 3. (a) Fabrication of 3D GO-C60 nanoassembly by simple grinding followed by electrochemical reduction in 0.1 M KCl for BPS oxidation (b) Cyclic voltammetric curves showing
electrochemical reduction of GO to rGO, (c) comparison of XPS spectra of GO-C60 and rGO-rC60, (d) DPV responses of rGO-rC60/GCE for BPS oxidation at different concentrations
[13], Reprinted with the permission from Ref. [13]. Copyright 2016, Elsevier Ltd.

of electrochemical sensors based on MNPs such as Au [99e103], Ag AgNPs@C/GCE for BPA oxidation studies. The oxygen containing
[104], Pt [105], Ni [106], Fe [107], Zr [108] and Mg [109,110] are functional groups on the carbon shell acted as electron transfer
discussed in this section. Furthermore, Cu-based enzymatic mediators by forming hydrogen bonds with BPA hydroxyl groups.
[23,111], Au-based enzymatic [112], aptamer [113e116] and peptide This activity decreased the hydroxyl bond energies and stimulated
[117] biosensors have been reported for the sensitive and rapid the electron transfer process through OeHeO bonding. The
determination of BPs in different media (Table 2). For example, a method was validated for its accuracy by high-performance liquid
novel electrochemical sensor based on molybdenum disulfide chromatography (HPLC), and the results were found to be in good
nanoflower (MoS2), chitosan (Chi) and AuNPs was constructed for agreement with the electrochemical method.
detecting BPA [99]. The study revealed the synergistic action of Recently, our group reported a notable Cu-centered metal
AuNPs and MoS2 nanoflowers in which the negative potential shift organic framework (Cu MOFs)-based tyrosinase biosensor for the
enhanced the conductive area and electron transfer rate between detection of BPA, BPB, BPF, BPAF, BPS, BPE, BPZ, BPAP and TBBPA
BPA and the electrode surface. However, the overall detection [23,111]. Fig. 4a shows a typical chemical design for CuMOFs. The
involved tedious synthesis procedures of AuNPs and MoS2 nano- fabricated CuMOF-Tyr-Chi biosensor was employed to study the
flowers. As another example, AgNPs with carbon shells were syn- current response characteristics of different BPs by amperometry
thesized by a hydrothermal process [104] and fabricated as (Fig. 4b) and cyclic voltammetry (CV) (Fig. 4cef). p-p stacking
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 9

Fig. 4. (a) Typical design of CuMOF; Cu-green, O-red, N-blue, C-gray, (b) linear amperometric current-time curve for detection of BPE at CuMOF-Tyr-Chi/GCE in the concentration
range 50.0 nM L-1-3.0 mM L-1, cyclic voltammograms of the CuMOF-Tyr-Chi/GCE biosensor for responsive (c) BPF, (d) BPE and unresponsive BPs (e) BPS and (f) TBBPA, red curve red
solid line: before BPs addition, curve black dashed line: after BPs addition [23]. Reprinted with permission from Ref. [23]. Copyright 2016, American Chemical Society. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

interactions were established between the aromatic rings of BPs tyrosinase biosensor was demonstrated to be a promising bio-
and benzenedicarboxylate ligands of CuMOF, which improved the sensing platform for the detection of five BPs (BPA, BPB, BPF, BPE
biosensor sensitivity. The oxidation of BPs by the enzyme tyrosi- and BPZ) and exhibited no interference by heavy metal ions [23].
nase was highly dependent on the availability of ortho-positions of An aptamer functionalized nano porous Au film modified elec-
phenolic hydroxyl groups and electron accepting or donating trode (aptamer-NPAu/GCE) has been described for direct electro-
groups within the BPs framework. For example, in BPA, BPB, BPF, screening of BPA [113]. Fig. 5 shows the systematic fabrication
BPE and BPZ, the strong electron donating methyl/methylene scheme for an NPAu-aptamer sensor for the oxidation of BPA. The
groups at the 4, 40 -position led to ortho-hydroxylation of BPs by NPAu was adhered to GCE and functionalized with a BPA-specific
tyrosinase. Alternatively, the presence of strong electron accepting aptamer by Au-S bond. Furthermore, the fabricated sensor exhibi-
sulfonyl group in BPS, trifluoromethyl group in BPAF, and weak ted high specificity for BPA in the presence of hydroquinone,
electron acceptor phenyl group in BPAP inhibited the enzymatic phenol, 4, 4 dihydroxybiphenyl and BPB. However, the AuNPs
oxidation of BPs to the corresponding o-quinones. Tyrosinase preparation method involved the use of highly hazardous
stimulated and nonstimulated CV curves for the oxidation of BPs at concentrated HNO3 that can be replaced by green methods that use
CuMOF-Tyr-Chi/GCE are shown in Fig. 4cef. The Cu-MOF-based aqueous solutions of plant extracts such as Swietenia mahogani
10 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 5. Schematic illustration of the NPAu-based aptasensor for direct electroanalysis of BPA [113]. Reprinted with the permission from Ref. [113]. Copyright 2015, Elsevier B.V.

JACQ [114]. environmental stability [126]. This section discusses polymer based
chemical sensors [19,127e130] and biosensors [131e134] for the
detection of BPs (Table 2). Carbon based nanomaterials, metal and Metal oxide nanocomposites based sensors. In addition to
metal-oxide nanoparticles have been conjugated extensively with
metal nanocomposites, metal oxides provide a new approach for
conducting polymers to enhance electrocatalytic sensing towards
constructing novel electrochemical sensing [118e124] and bio-
BPs. In a typical study, thin layered MoS2 was intercalated into self-
sensing platforms [125] for detecting BPs (Table 2). Electrochemical
doped PANI composites (SPAN) by a simple ultrasonic exfoliation
sensors based on Fe3O4 NPs [118e120], TiO2 NPs [121,122] and
method and used for the detection of BPA [127]. The effect of
Bi2WO6 NPs [124] have been utilized for the detection of BPA
ultrasonication time of MoS2-SPAN nanocomposite on electro-
because of their ease of preparation, low toxicity, good biocom-
chemical detection of BPA was studied by DPV. MoS2-SPAN hybrids
patibility and high surface area. With regard to metal oxides based
prepared by ultrasonication of 5H, exhibited a high level of per-
sensors, a photoassisted electrochemical sensing platform was
formance for the detection of BPA with no interference by other
developed for the detection of BPA based on AuNPs decorated
phenolic compounds. The high electroactivity of MoS2-SPAN hy-
carbon doped TiO2 nanotube arrays [121]. BPA was detected elec-
brids was attributed to their high anionic exchange and adsorption
trochemically on a freshly prepared electrode surface of TiO2-
capacity along with their large electroactive surface area. The
AuNTAs under UV irradiation. The oxidation current increased due
developed nanopolymer sensor exhibited a great ability for moni-
to the improved separation efficiency of electron-hole pairs.
toring complex and conjugated aromatic compounds.
Furthermore, a new sensor based on bismuth tungstate nanoplates
Electrochemical immunoassays involving polymer nano-
modified carbon paste electrode (Bi2WO6/CPE) was developed for
composites have also been reported for biospecific recognition
the simultaneous detection of BPA and diethylstilbestrol (DES)
processes. For example, 3-carboxylate polypyrrole was functional-
[124]. Fig. 6a and b show the respective XRD and SEM images of
ized with an aptamer to fabricate a field effect transistor (A-M-
crystalline Bi2WO6 nanoplates. The Bi2WO6/CPE sensor exhibited
CPPyNPs/FET) sensor for BPA sensing [131]. The strong interaction
well defined DPV oxidation peaks for BPA without DES (Fig. 6c), and
between aptamer and BPA provided a suitable environment for
in the presence of DES (Fig. 6d). Although the developed sensor
enhancing the BPA kinetics. The selectivity and specificity studies of
produced high recoveries for BPA in milk samples, the procedures
the sensor were performed using other BPA analogs, including BPB,
required tedious pretreatments of milk samples prior to the elec-
4, 4 biphenol and 6F-BPA. In addition, another electrochemical
trochemical measurements.
immunosensor modified electrode (poly(Jug-co-JugBPA)-a-BPA/
A new TiO2 based enzymatic biosensor was developed for the
GCE) based on the multifunctional conducting copolymer [N-(3-(4-
analysis of BPA [125]. In a typical fabrication process, surface
(2-(4-hydroxyphenyl) propan-2-yl) phenoxy) propyl) 3-(5-
functionalization of nanocrystalline TiO2 (nTiO2) with 3-
hydroxy-1,4-dihydro-1,4-dioxonaphthalen-2 (3)yl) propionamide]
aminopropyltriethoxy silane (APTES) and glutaraldehyde (GA)
(Jug-BPA) was prepared for the detection of BPA [132]. The Jug-BPA
was followed by Tyr immobilization. The covalent interaction be-
polymer was linked to BPA covalently and steric hindrance was
tween APTES and Tyr resulted in improved sensing activity of the
observed due to antibodies in the a-BPA-Jug-BPA complex, which
biosensor for BPA oxidation with a sensitivity of 361.90 kU mM1.
enhanced the charge transfer rate at the polymer solution interface
The high activity of the sensor was attributed to point defects in the
and thus the redox kinetics. However, the analytical utility of A-M-
nTiO2 which increased the loading capacity of Tyr molecules on the
CPPyNPs/FET and poly (Jug-co-JugBPA)/GCE sensors must be justi-
APTES-nTiO2/Ti surface.
fied by the detection of BPA in real samples. Polymer nanocomposites based sensors. Polymer nano-

composites (PNCs) offer great possibilities for fast, sensitive and Molecularly imprinted sensors. Molecular imprinting tech-
reliable electrochemical analysis due to their outstanding con- niques have gotten much attention in recent years for introducing
ducting properties, rapid electrode kinetics, biocompatibility and recognition properties into synthetic polymers [135,136].
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 11

Fig. 6. (a) XRD pattern (b) SEM image of Bi2WO6 nanoplates inset; SEM at high magnification, (c) DPV curves of BPA upto 1300 nM L1 without DES (d) in presence of 500.0 nM L1
DES insets; linear calibration plots [124]. Reprinted with the permission from Ref. [124]. Copyright 2014, Elsevier B.V.

Functional monomers along with template and cross linkers are generated a current density which was proportional to the TBBPA
polymerized together, and templates are later removed from the concentration (Fig. 7c). Furthermore, the sensor exhibited negli-
polymer matrix to form molecularly imprinted polymers (MIPs). In gible interference for the detection of TBBPA in the presence of
general, MIPs are conjugated with different types of nano- TBBPS and BPA as shown in Fig. 7d.
structured materials to enhance the sensitivity and specificity of In another development, an electropolymerized molecularly
the detection method owing to their large surface area and high imprinted polymer (E-MIP) film comprising different ratios of BPA-
conducting properties. Various MIPs such as pyrrole terthiophene and carbazole monomer complex was fabricated onto
[20e22,137e140], APTES [141,142], chitosan [143e145], pyridine an ITO electrode for the electrochemical impedance sensing of BPA
[146], polyvinyl chloride [147], 2 aminothiophenol [148], electro- [149]. Magnetic molecularly imprinted polymers (MMIPs) possess
polymerised [149] and magnetically imprinted MIP nanoparticles high encapsulation capability for magnetic NPs under an applied
[150] for the sensitive detection of bisphenols using electro- magnetic field. Using this principle, a novel magnetic electro-
chemical methods are listed in Table 2. chemical sensor based on core shell MMIPsNPs was prepared using
A polypyrrole based tin oxide MIP sensor was developed for the a coprecipitation method and was imprinted onto the surface of
photoelectrochemical determination of BPA [138]. MIP films were CTAB/CPE. The fabricated oleic acid-Fe2O3NPs sensor demonstrated
prepared by the electropolymerization of pyrrole on SnO2 electrode specificity for BPA in spiked plastic bottle samples and in lake
using BPA as the template. Cavities complementary in size and water.
shape with the binding sites of BPA molecules promoted the se-
lective recognition of BPA. Introduction of an excited electron to the
conduction band of SnO2 resulted in the production of Ru3þ species Quantum dot based sensors. Quantum dots (QDs) are well
which were reduced back to Ru2þ by oxidation of BPA, and an known nanostructured semiconductor materials which have
enhancement in the photocurrent was observed. In another study, a attracted substantial attention in recent times for sensing appli-
surface imprinted sensor based on NiNPs and GR was developed for cations due to their unique optical properties. For example, an
the electrochemical detection of TBBPA [22]. Electrochemically amperometric sensor was prepared by immobilizing cobalt tellu-
reduced GO sheets were immobilized onto carbon electrode, as rium QDs and the amine-terminated G4 poly (amidoamine) den-
shown in Fig. 7a. Fig. 7b shows the SEM image of an electro- drimer PAMAM on GCE (CoTeQDs-PAMAM/GCE) for trace detection
deposited imprinted layer on NiNPs-GR/CE surface. TBBPA mole- of BPA [151]. The protonated primary amine groups of PAMAM
cules diffused to the electrode through the imprinted cavities and adsorbed the negatively charged BPA, which resulted in high ac-
tivity of the sensor. The performance of CoTe-PAMAM was
12 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 7. (a) Fabrication scheme of Ppy-MIP-Ni-GR/CE sensor, (b) SEM image of Ppy-MIP-Ni-GR/CE surface, (c) DPV curves of imprinted Ppy-MIP-Ni-GR/CE sensor towards TBBPA
oxidation, (d) interference performance of imprinted sensor for TBBPA oxidation in presence of TBBPS and BPA [22]. Reprinted with the permission from Ref. [22]. Copyright 2014,
Elsevier B.V.

attributed to small dimension effect, quantum size effect and large enzyme [167] for the electrochemical determination of BPs are
specific surface area. The fabricated sensor was successfully applied discussed in this section (Table 2).
to water samples for the detection of BPA. A unique electrochemical sensor based on 1-aminopropyl-3-
methyl imidzaolium tetra fluoroborate (APMIMBF4) IL and Zn-Al
2.1.2. Ionic liquids based sensors layerd double hydroxides (LDH) was used for screening of BPA
Having various excellent properties such as high viscosity, [160]. The specific layered structure of LDH with its desirable ion-
thermal stability, ionic conductivity, tunable solvent properties and exchange capability, unique biocompatibility, high surface area
a wide electrochemical potential window, ionic liquids (ILs) have and catalytic activity accelerated the electrode transfer process. In
become one of the greatest achievements in modern sensor addition, the presence of positively charged IL amino groups pro-
designing technology [152,153]. Different ionic liquids and their moted the immobilization on negatively charged BPA and thus
conjugates based on carbon nanomaterials [154e159], metal hy- enhanced the oxidation kinetics. Although LDH were used as
droxide [160], metal oxide [157,161], polymer [162], conducting attractive sensor materials, their propensity for cracking and ag-
binder [163], polymerized ILs [164,165], cyclodextrin [166] and gregation greatly affected the performance of LDH sensors and limit
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 13

their use in practical applications. fluorescence techniques (Table 3). BPA itself can produce a fluo-
Further development of IL-based sensors was reported with the rescence signal, as it possesses a conjugated cyclic structure;
fabrication of PEDOT and 1-butyl-3-methylimidazolium bromide however, in aqueous solutions, the signal is too weak to be detec-
(BMIMBr) IL modified screen printed carbon electrodes (SPCE) by ted. In this regard, various fluorescent probes have been synthe-
electropolymerization [162]. The PEDOT-BMIMBr/SPCE sensor sized. As an example, chitosan-capped zinc sulfide quantum dots
inhibited effective adsorption of the oxidation products of BPA at (Chit-ZnSQD) were prepared for the sensitive fluorescence detec-
the sensing surface which minimized surface fouling. The fabri- tion of BPA as shown in Fig. 9a [169]. Hydrogen bonding between
cated sensor exhibited insignificant interference during the eOH groups of BPA and eNH2/eOH groups of chitosan led chitosan
detection of BPA in the presence of inorganic salts such as NaNO3, molecules to partly peel off from the ZnS QDs surface, resulting in
Na2SO4, Na2CO3, KCl, CoCl2, ZnCl2 and sodium citrate; however, fluorescence quenching (Fig. 9b). The decrease in fluorescence in-
other salts, such as MgCl2, CaCl2, Cu(NO3)2, FeCl3 and some easily tensity was proportional to the increasing concentrations of BPA
oxidizable compounds such as sodium nitrite, ferrous sulfite, (Fig. 9c). The method was applied to the fluorescence detection of
catechol, hydroquinone and 2-aminophenol produced significant BPA in water and plastic samples for practical applications.
interference in the detection of BPA. This restricted the use of the In addition, MIPs based novel fluorescent probes have been
developed sensor for BPA analysis; however, separation techniques fabricated for the rapid detection of BPA. The target analyte can
such as HPLC and electrophoresis could be applied to overcome this bind specifically to the molecularly imprinted surface, resulting in
problem. fluorescence quenching that is proportional to the concentration of
A b-cyclodextrin and 1-butyl-3-methylimidazolium tetra- the target analyte. For example, based on an APTES-imprinted MIP,
fluoroborate (BMIMBF4) IL hybrid modified carbon paste electrode a Mn-doped ZnS QD fluorescent sensor was developed for the
(b-CD-IL/CPE) was reported for detection of BPA in various water detection of BPA [176]. In the absence of BPA, an orange fluores-
and plastic samples. The high ionic conductivity and non-covalent cence spectrum was generated by Mn-doped ZnS QDs entrapped
interaction of BMIMBF4 and b-CD resulted in an enhanced vol- MIPs, which on the addition of BPA resulted in signal quenching.
tammetric response of BPA at the surface. The a-1,4 glucopyranose Moreover, no significant quenching was observed for molecularly
of cyclodextrins, containing a lipophilic central cavity and hydro- imprinted membranes by BPA analogs such as 1, 1-bis (4-
phobic outer surface, promoted the formation of a supramolecular hydroxyphenyl) cyclohexane, 4-tert-butylphenol and hydroqui-
complex with BPA molecules and improved the sensitivity of the none, suggesting a high selectivity of the sensor for BPA. The study
transducer system for their analysis as shown in Fig. 8 [166]. demonstrated the simple and rapid screening of BPA with less
sample pretreatment.
Furthermore, a portable planar waveguide evanescent wave
2.2. Fluorescence based sensors biosensor was developed for the fluorescence immunoassay of BPA
[181]. The fluorophore tagged anti-BPA antibodies were attached to
Various fluorescent chemical sensors [168e176], enzymes the surface of a planar optical waveguide chip coated with bovine
[177,178] and immunoassay based biosensors [179e186] have been serum albumin (BSA)-BPA antigen. The amount of antibody that
discussed in this section for the sensitive detection of BPs using was immobilized on the chip was proportional to the fluorescence
intensities excited by the evanescent wave field. This method
suggested the design of sensitive biosensing platforms which can
significantly be applied to various quality monitoring procedures
and biochemical applications. Other fluorescence based immuno-
assays for the detection of BPs are listed in Table 3 [181e186].

2.3. Chemiluminescence based sensors

Due to its excellent sensitivity and negligible interference by

background scattering light, chemiluminescence (CL) has proved to
be a promising and reliable technique for the detection of BPs
[187e189]. Several MIPs [18,190], metal nanoparticles, viz., AuNPs
[191], CuNCs [192] and AgNPs [193] based luminescent and elec-
trochemiluminescent [194,195] sensors have been developed for
the sensitive detection of BPs (Table 3). As an example, a sensitive
CL method was developed based on a luminol-KMnO4-CuNCs
(copper nanoclusters) system [192]. The CL intensity for luminol-
KMnO4 was greatly improved by CuNCs, which again decreased
upon incorporation of BPA into the system (Fig. 10a). The decrease
in CL intensity was attributed to the oxidation of BPA hydroxyl
groups by KMnO4. River water produced interference in the anal-
ysis due to metal ions; however, this was resolved by the addition
of ethylenediaminetetraacetic acid (EDTA). Recently, electro-
chemiluminescence (ECL) has received attention as a detection
technique due to the combined principles of CL and electrochem-
istry [194,195]. In a typical example, the addition of N-C dots
increased the sensitivity and stability of Ru[bpy]þ2
3 ECL signal due to
the reaction between N-C dots and electrogenerated Ru[bpy]þ2 3 .
However, introduction of BPA into the N-C dots-Ru[bpy]þ2 3 system
Fig. 8. Schematic mechanism of the electrode reaction of BPA at b-CD/ILCPE [166]. decreased the intensity due to the transfer of an electron from
Reprinted with the permission from Ref. [166]. Copyright 2013, Elsevier B.V. exited Ru[bpy]þ23 to the BPA oxidation intermediate 2, 2-bis (4-
14 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Table 3
Fluorescence, Luminescence, Colorimetric and Surface plasmon resonance based sensors and biosensors for bisphenols detection.

Reference Sensor Bisphenol LOD Linear range Real Sample Matrix Recovery % References

Fluorescence based sensors and biosensors

BPO BPA 5.0 mM L1 5.0e100.0 mM L1 Water samples 95.9e105.8% [168]
Chi-ZnSQD BPA 1.31  1010 M L1 2.19  109-1.31  106 M L1 Water & plastic samples e [169]
SPS-AFS BPA 2.62  1013 M L1 8.76  1013-2.19  1011 M L1 Milk samples e [170]
MIP-APTES-SiO2@AuNPs BPA 0.10 mM L1 0.0e13.1 mM L1 Sea water 91.3e96.2% [172]
MIP-APTES-CD BPA 30.0 nM L1 100.0e4200.0 nM L1 River water 97.5e102.5% [173]
MIP-APTES-GSH-AgNCs BPA 8.76  1011 M L1 8.76  1010 -8.76  106 M L1 Milk, juice samples 92.5e108.5% [174]
MIP-APTES-Mn2þ ZnS BPA 8.03 nM L1 10.0e700.0 nM L1 Water, plastic cup 98.7e105.5% [175]
MIP-APTES-Mn2þ ZnS BPA 1.9 nM L1 5.0e0.10 mM L1 Plastic & water samples 92.0e108.0% [176]
PPESO3-HRP-H2O2 BPA 4.0  107 M L1 1.0e100.0 mM L1 Food packaging 95.0e105.0% [177]
DNA Y junction BPA 5.0 fM L1 10.0 fM L1-10.0 nM L1 Water samples 90.0e118.0% [178]
EWI BPA 1.31  1010 M L1 5.25  1013-4.20  105 M L1 Water samples 88.3e103.7% [181]
EWMI BPA 1.09  1010 M L1 5.25  1013-4.20  105 M L1 Water samples e [182]
EWFOA BPA 1.86 nM L1 2.0e100.0 nM L1 Waste water 91.7e110.4% [184]
FAM-ssDNA-GO BPA 2.19  1013 M L1 4.38  1013-4.38  1011 M L1 Water samples 96.0e104.5% [185]
QD immnoprobe BPA 1.31  1011 M L1 4.38  1011-4.38  108 M L1 Water samples 80.0e117.0% [186]
Chemiluminescence based sensors and biosensors
DPA-MIP-QDs TBBPA 0.015 mM L1 0.1e100.0 mM L1 Water & soil 80.2e96.5% [18]
FI-CL oil acid@Fe3O4 BPA 3.11  1012 M L1 4.38  1012-8.76  1011 M L1 Plastic products 98.2e102.0% [190]
Au (III) HCO4 BPA 0.08 mM L1 0.30e80.0 mM L1 Plastic containers 96.0e108.0% [191]
Lumilol-KMnO4-CuNCs BPA 1.2  1010 M L1 2.1  109-2.5  107 M L1 Water samples 97.6e102.5% [192]
Lumilol-KMnO4-AgNPs BPA 4.38  1012 4.38  1012-2.19  107 M L1 Water samples 93.0e106.0% [193]
Lucigenin-GO BPA 3.0  109 M L1 1.0  109-1.0  104 M L1 Biological & environ. samples e [194]
N-Carbon dots BPA 10.0 nM L1 0.03e1.0 mM L1 Baby bottles 90.0e120.0% [195]
Colorimetric sensors and biosensors
Tyr-Chi-LBL biosensor BPA 3.76  109 M L1 4.38  109-8.76  107 M L1 Water samples 94.0e98.0% [196]
Tyr-Chi-LBL biosensor BPA 0.28 mggg1 0.05e3.87 mggg1 Dust samples e [197]
Aptamer-cysteamine AuNPs BPA 4.81  1011 M L1 1.53  1010-6.13  1010 M L1 Tap water 91.0e106.0% [198]
Anti-BPA aptamer-AuNPs BPA 4.38  1013 M L1 4.38  1011-4.38  1010 M L1 Water samples 95.6e103.8% [199]
Surface plasmon resonance based sensors
poly (EGDMA-MAPA-VI) BPA 8.76  1011 M L1 3.50  1010-4.38  108 M L1 Milli Q water e [201]
poly (EGDMA-MAPA-VI) BPA 2.62  1010 M L1 3.50  1010-4.38  108 M L1 Tap water e [201]
poly (EGDMA-MAPA-VI) BPA 3.50  1010 M L1 3.50  1010-4.38  108 M L1 Waste water e [201]
MIP-SPR BPA 6.15  109 M L1 1.0  108-1.0  106 M L1 Water & plastic samples 86.6e95.5% [202]
SRSPP BPA 2.19  1013 M L1 2.19  1013-2.19  1011 M L1 e e [203]
SPRCD BPA 3.50  1013 M L1 2.19  1013-4.38  1011 M L1 Waste water e [204]
SPRCD BPA 1.75  1013 M L1 2.19  1013-4.38  1011 M L1 Drinking water e [205]

phenylquinone) propane. An illustration of the mechanism for N-C successfully applied to spiked water samples for the detection of
dots enhanced and BPA-quenched ECL is shown in Fig. 10b. BPA and was further validated by an HPLC method.

2.4. Colorimetric sensors 2.5. Surface plasmon resonance sensors

Colorimetric sensors, with their simple detection methodology, Surface plasmon resonance (SPR) is a novel optical reflection
have been employed for the quantification of phenolic compounds technique that has been applied to the sensing of BPs with
[196e199] (Table 3). Various biosensors based on enzymes demonstrated simplicity and high sensitivity [200e205] (Table 3).
[196,197] and aptamers [198,199] for the screening of BPs are dis- A slab type optical wave guide (s-OWG) microfluidic SPR mea-
cussed in this section. Detection schemes involve monitoring of surement system was developed that contained consecutive par-
various changes in optical characteristics, the redox state or in allel gold and silver deposition bands in the line of plasmon flow
physicochemical properties of targets accompanied by a visible [200]. Fig. 12a shows the procedure for immobilization of MIP
color change. For example, a paper based colorimetric enzymatic nanoparticles and BPA-AuNp on the sensor chip for label-free
biosensor was developed for the detection of BPA in dust samples detection of BPA. The Ag deposition band showed a red-shift
[197]. Tyrosinase induced oxidation of BPA resulted in the forma- when free BPA was passed over the BPA-AuNp/immobilized MIP-
tion of a quinone-imine complex between quinone carbonyl groups Np complexes that formed over the s-OWG, as shown in Fig. 12b.
and nucleophilic amino groups of chitosan, leading to a distinct Excess BPA induced a blue-shift that was due to the competitive
color change from blue to green with a strong absorption band at desorption of BPA-AuNps from the immobilized MIP-Np on the s-
610 nm (Fig. 11a). Validation of the colorimetric biosensing method OWG (Fig. 12c).
for the detection of BPA was performed using conventional GC and
GC-MS techniques. A comparison of GC and developed colorimetric 2.6. Some significant sensing platforms
methods demonstrated a good correlation between the two
methods (Fig. 11b). 2.6.1. Microorganisms based sensors
In another study, an aptamer based colorimetric sensor was In recent years, various microbial strains based sensors have
prepared for the selective determination of BPA [198]. Cysteamine been developed for the rapid and routine screening of BPs
modified positively charged AuNP hybrids were modified with [206e208]. For example, a ligand-receptor binding approach was
negatively charged anti-BPA aptamers through electrostatic inter- developed for detection of BPA using Escherichia coli (E. coli) strains
action. The attchment of aptamers led to aggregation and resulted Solea solea (sole) and Sus scrofa (pig). The ligand-binding domains
in a distinct color change from wine red to blue. The method was (LBDs) for the estrogen receptors (ERb) present in E. coli exhibited a
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 15

Fig. 9. (a) Synthesis procedure of ZnS QDs, (b) fluorescence quenching of ZnS QDs by BPA (c) fluorescence emission spectra of ZnS QDs in the presence of increasing concentrations
of BPA (aeo); inset: corresponding calibration plot [169]. Reprinted with the permission from Ref. [169]. Copyright 2014, The Royal Society of Chemistry.
16 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 10. (a) Kinetic curves of chemiluminescence systems: luminoleKMnO4 (green curve), luminoleKMnO4eCu NCs (red curve), luminoleKMnO4eCuNCseBPA (blue curve) [192],
(b) The possible enhancement mechanism by N-C dots and the quench mechanism by BPA of the electroluminescence system [195]. Reprinted with the permission from
Refs. [192,195]. Copyright 2014, The Royal Society of Chemistry & Copyright 2015, Elsevier B.V. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

significant alteration in their phenotype during the detection of the attachment of neuroblastoma cells to the electrode surface.
BPA [206]. Furthermore, a bioluminescence technique was also Cyclic voltammetry was performed for BPA detection with an
utilized as a sensitive tool for the detection of BPA that involved increasing dose of neural cells (Fig. 13b) [210]. In another example,
emission of light from bioluminescent protein that were derived human embryo kidney cells (HEK-293) were immobilized on a
from microorganisms. As an example, a yeast-based biolumines- cysteine terminated C(RGD)4 peptide modified Au electrode for the
cent sensor was fabricated for the detection of BPA in surface and detection of BPA [213]. The electrochemical properties of the
drinking water. BPA activated the human estrogen receptor (hER) biosensor were studied to determine the effect of BPA on the
agonist complex, which expressed the light emitting reporter gene viability of HEK-293 cells. The CV studies of BPA sensing with an
and resulted in the production of light proportional to the BPA HEK-293 immobilized RGD peptide/Au electrode demonstrated
concentration [208]. negative correlations between the signal intensity of the redox
peaks and the concentrations of BPA. The study suggested a
2.6.2. Cell chip based sensors beneficial role for the use of chip sensors for monitoring the toxicity
Electrochemical cell chip sensors provide a novel strategy for of chemicals on the viability of living cells.
sensitive onsite monitoring of toxicants using voltammetry and
amperometry. Various neural cancer cell-based chip biosensors for 2.6.3. Other significant sensors
the detection of BPA are presented in this section [209e212]. In a A large number of other immunosensors, aptamers and MIPs
typical example of a chip-based sensor, an electrode was fabricated based sensors with detection methods based on circular dichroism
with Si, Ti and Au layers as shown in Fig. 13a. The Au surface was (CD) [214], resonance Rayleigh scattering (RRS) [215], capacitance
modified with cysteine, which served as a bio-ligand and facilitated [216], photoelectrochemistry (PEC) [217], adsorptions isotherms
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 17

Fig. 11. (a) Design of the colorimetric paper-based biosensing device for detection of BPA in household dust specimens; (A) Air-sampling cassette with the paper-based sensor; (B)
compact device included the test zone and the hose extension; (C) sensing device connected to the air-sampling pump by a rubber tube; (D) accumulation of BPA-dust particles on
the test zone; (E) color change after the exposure to BPA-dust sample; (F) scanned image of the test zone clearly showed the formation of greenish color, (b) linear correlation
between the paper based colorimetric and GC methods for the detection of BPA in household dust specimens [197]. Reprinted with the permission from Ref. [197]. Copyright 2015,
American Chemical Society. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

[218e220], photonics [221e223], electrophoresis (EP) [224] and in capacitance with BPA concentration.
immunochromatography [225e229] have been reported as sensi- In other development, an opal photonic crystal sensor (OPCS)
tive assays for BPs as shown in Table 4. A plasmonic chirality based that was based on the combined principles of molecular imprinting
aptasensor for BPA analysis using CD was fabricated [214]. The CD and photonic crystal technology was developed for the detection of
signals generated by AuNPs dimers were inversely proportional to BPA. BPA-imprinted polymethyl methacrylate (BPA-PMAA) pho-
the concentration of BPA. A systematic illustration of the determi- tonic crystals with diameter of 220 nm produced a high optical
nation of BPA based on asymmetric plasmonic dimer using CD is response toward BPA using reflection spectroscopy [221].
shown in Fig. 14. The anti-BPA aptamer combined with target BPA Many other immune-assay sensors that are based on ELISAs,
to form a complementary oligo-nucleotide. Consequently, the Au- optofluidics and immunochromatographic techniques have been
NPs dimers were disassembled into discrete nanoparticles. A cor- developed [225e229]. After the successful application of dual-
relation between the number of dimers and the intensisty of the CD labeling lateral flow strip sensors on AuNPs (Duo-LFS) for the
signal in the reaction system was observed, suggesting that the detection of BPA [226], other LFS nano immunosensor based on
increase in the concentration of BPA corresponded to fewer AuNPs anti-BPA antibody-AuNPs conjugates was developed and applied
dimers and thus weaker signal intensity. for BPA detection in water samples [227].
Furthermore, an aptamer-nanogold (apt-nanoAu) conjugate
sensor was developed which in the presence of BPA produced a 3. Conclusion, challenges and future perspectives
decreased RRS signal and strong catalytic activity for HAuCl4-
Vitamic C particle reaction [215]. A capacitive sensor was developed With the knowledge that BPs possesses endocrine disrupting
to detect BPA using anodized aluminum oxide (AAO) [216]. BPA was properties, BPs have been detected in various household samples,
recognized by its biospecific binding to anti-BPA aptamers that industrial wastes, plastic products, food items and other matrices.
were immobilized on the Au-AAO surface, which exerted a change The removal of BPA from consumer products has been promoted
18 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 12. (a) Schematic of preparative and immobilization procedure of MIPNp and BPA-AuNp on the sensor chip for the binding of free BPA, peak shifts of SPR spectra by the addition
of free BPA into MIPNp-immobilized s-OWG (b) red shift at low concentration, (c) blue shift at high concentration [200]. Reprinted with the permission from Ref. [200]. Copyright
2012, American Chemical Society. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

worldwide and has led to an increased production of BPA analogs as materials to form charge-transfer complexes with electron donor
substitutes in a variety of industrial processes. Various analytical groups results in Van der Waals interactions between different
strategies have been developed for the detection of BPA in a variety carbon particles, which significantly lower their solubility and
of samples; however, no such investigations have been conducted dispersion in polar solvents. This can be overcome by covalent and
on its analogs. Reports of such sensors and biosensors for the noncovalent functionalization of the surface to improve the overall
determination of BPA analogs are very rare [13,14,19,22,23,45]. The performance of the sensor [230e232]. Molecular imprinting tech-
main challenge focuses on the synthesis and design of other niques introduce recognition sites of templates on polymer surfaces
chemical substituents of BPs with no or less toxic, biological or that are complementary to template molecules in size and shape
endocrine disrupting activities or hazardous effects on the envi- and can rebind with them even after their removal. The rebinding
ronment. In addition, analysis of the additives and synergistic ef- capacity is limited by the low surface area to volume ratio of the
fects of BPs with other endocrine disrupting compounds should be polymer surfaces, rendering the process of removal of template
taken into consideration to elaborate on their adverse outcomes. A from the conventional binding sites of MIPs very difficult, which
comprehensive understanding of endocrine pathways that respond restricts their use in sensor fabrication [171,173]. Many QDs have
to BPs would be of great interest. In this regard, designing living toxic effects on the environment; therefore, a reliable eco-friendly
cells immobilized biosensing platforms for studying in vivo in- approach for developing fluorometric and optical sensors is war-
teractions of BPs in a living organism by evaluating the effect of BPs ranted. Designing low-cost, portable paper based bioanalytical
dose on the viability of cells would be of great value. sensing platforms with flexible and compatible design for the
Despite great advancements, certain factors interfere with the colorimetric detection of analytes, such as aerosols and dust con-
novel design of sensors and biosensors. The ability of carbon taminants, remains a major challenge [196,197]. The detection
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 19

sensitivity can be increased by the use of digital image scanners,

high-resolution cameras and color readers. The concept of a smart
phone app that can be interfaced with the sensor to enable direct
onsite image quantification based on a pre-calibrated color scheme
could be used to establish a sensitive and accurate detection
scheme for contaminants [199]. Furthermore, molecular modeling
of sensor materials is requisite to study structure-function re-
lationships and to support experimental efforts for the synthesis of
promising structures for enhanced sensing qualities.
Advancements in technology and materials engineering have
proposed high-performance sensors for the effective detection of
BPs. However, commercialization of these sensors is still a chal-
lenging issue. A number of factors work towards the commercial-
ization of sensors such as stricter controls and legislation,
remediation programs, environmental awareness and reliable
methods with low detection limits. As far as the legislation is
concerned, there is a great conflict between industries and gov-
ernment federal agencies regarding safe exposure levels of
bisphenols [2] which restricts the commercialization and market-
ing of sensors. For example, the Food and Drug Administration
(FDA), the federal agency which regulates BPA, reported no
observed adverse effect of BPA for a toxicity level of 5 mg kg1 per
body weight per day (Federal Drug Administration, 2008, 1) [2,233].
However, this level was significantly higher than that reported by
NTP scientists (Environmental Working Group, August 15, 2008) to
be safe [2,234]. Furthermore, a report released by the FDA in May
2008 indicates that marketed foods containing BPA are safe for
infants & children and contain less BPA than levels that may cause
health effects (U.S. Federal Drug Administration, May 14, 2008)
[2,235]. However, the NTP Center for the Evaluation of Risks to
Human Reproduction (CERHR) reported in contradiction to this and
stated that human exposure to BPA is not safe for infants and
children [2,236]. Also, a six-month Canadian review of 150 research
studies resulted in findings contradictory to the FDA (Schmidt,
October 16, 2008, 1) [2,237]. The regulatory agreements between
industry and federal agencies on the safety issue of BPs should be
clearly defined. This would help researchers to set the standards
required for the detection of bisphenols at an appropriate level and
enhance the marketing of sensors. The understanding of trans-
duction systems, their physico-chemical properties and engineer-
Fig. 13. (a) Typical design of an electrochemical-cell chip sensor for BPA detection, (b)
CV curves for BPA detection with increasing dose of neural cells, inset; calibration plot
ing aspects will help researchers to monitor the commercial
[210] Reprinted with the permission from Ref. [210]. Copyright 2011, Elsevier B.V. viability of the sensors and will improve experimental efforts to
create such sensors. Moreover, another challenge involves the
integration of sensing and biosensing assay procedures in fully

Table 4
Aptamers, MIPs, immunosensors and biosensors for bisphenols detection.

Reference Sensor Bisphenol LOD Linear range Real Sample Matrix Recovery % References
10 1 14 11 1
Plsmonic chiral aptasensor BPA 3.50  10 ML 8.76  10 -2.19  10 ML Tap water 93.0e98.4% [214]
RRS (Apt-nanoAu) BPA 3.63  1013 ML1 1.45  1010 -1.45  109 ML1 Plastic samples e [215]
AAO capasitve sensor BPA 8.76  10 ML1 13
8.76  10 -1.0  10 11
ML1 e e [216]
PEC-TiO2-Fe2O3 BPA 1.75  1014 ML1 1.75  1014-3.06  1012 ML1 Water samples 90.4e107.0% [217]
SMIP BPA 2.19  109 ML1 8.76  1010-1.31  108 ML1 Water samples e [218]
OPCS BPA e 4.38  1012-4.38  109 ML1 e e [221]
FOEWS BPA 7.44  1012 ML1 1.75  1014-3.06  1012 ML1 Plastic products 92.0e104.0% [223]
MIP-CE-UV BPA 2.36  108 ML1 8.76  108-4.38  107 ML1 Waste water 77.5e80.2% [224]
MIP-CE-UV BPA 1.31  108 ML1 8.76  108-4.38  107 ML1 Tap water 81.2e90.2% [224]
MIP-CE-UV BPA 3.02  108 ML1 8.76  108-4.38  107 ML1 River water 76.7e88.5% [224]
MIP-CE-UV BPA 9.19  109 ML1 2.19  106-4.38  106 ML1 Soil 65.2e74.2% [224]
MIP-CE-UV BPA 7.88  109 ML1 2.19  106-4.38  106 ML1 Shrimp 73.5e80.5% [224]
MIP-CE-UV BPA 3.67  107 ML1 2.19  106-4.38  106 ML1 Human urine 76.2e82.3% [224]
Mab-ELISA BPA 0.22  109 ML1 e Canned food e [225]
Duo-LFS BPA 3.32  1013 ML1 2.19  1013-4.38  1011 ML1 Water samples e [226]
Immunochromatographic LFS BPA 4.02  1010 ML1 0e8.76  1011 ML1 Water samples 98.9e106.8% [227]
AFOB BPA 2.62  1010 ML1 2.19  109-4.38  107 ML1 Water, tea samples 92.5e113.0% [228]
CLIO-OVA BPA 1.75  1012 ML1 e Tap water 86.0e109.0% [229]
20 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

Fig. 14. (a) Scheme of BPA detection based on asymmetric plasmonic dimer, (b) CD spectra of BPA in concentrations range from 5.0 to 0.02 ng mL1, (c) calibration curve of the
different concentrations of BPA [214]. Reprinted with the permission from Ref. [214]. Copyright 2014, American Chemical Society.

automatic systems that will result in accurate, precise and error free BPZ Bisphenol Z
testing. TBBPA Tetrabromo bisphenol A
TCBPA Tetrachloro bisphenol A
Notes MOFs Metal organic frameworks
QDs Quantum dots
The authors declare no competing financial interest. CPs Conducting polymers
ILs Ionic liquids
CNTs Carbon nanotubes
GR Graphene
GO Graphene oxide
This work was supported by the National Natural Science
rGO Reduced graphene oxide
Foundation of China (No. 21577139), the Chinese Academy of Sci-
C60 Fullerenes
ences President's International Fellowship Initiative for Post-
GCE Glassy carbon electrode
doctoral Researcher (2015PM002), the Science and Technology
SCE Screen printed electrode
Service Network Program, CAS (KFJ-EW-STS-099).
MWNPE Multiwalled carbon paste electrode
PEG Pencil graphite electrode
Abbreviations CE Carbon electrode
CPE Carbon paste electrode
BPs Bisphenols ITO Indium tin oxide
EDCs Endocrine disrupting chemicals SPCE Screen printed carbon electrode
BPA Bisphenol A PEG Pencil graphite electrode
BPB Bisphenol B BDD Boron doped diamond electrode
BPC Bisphenol C CV Cyclic voltammetry
BPE Bisphenol E DPV Differential pulse voltammetry
BPF Bisphenol F Chi Chitosan
BPS Bisphenol S Tyr Tyrosinase
BPAF Bisphenol AF Arg Arginine
BPAP Bisphenol AP
Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 21

LacI Laccase CB Carbon black

AuNPs Gold nanoparticles NiTPPS Nickel tetrapyridyloxyphthalo cyanine
AuNCs Gold nanoclustures SbNPs Antimony nanoparticles
CuNCs Copper nanoclustures bCD Beta cyclodextrin
AgNPs Silver nanoparticles MAM Melamine
AgNCs Silver nanoclustures SPCE Screen printed carbon electrode
NiNPs Nickel nanoparticles Li4Ti5O12 Lithium titanate
NMNs Novel metal nanoparticles ct DNA Calf thymus DNA
TiO2 Titanium dioxide SP Silk peptide
Fe3O4 Ferric Chloride TA Tannic acid
SnO2 Tin oxide ZnTsPc-fGR zinc phthalocyanine tetrasulfonic acid functionalized
NGR Nitrogen doped graphene graphene
NSGR Nitrogen-Sulpher doped graphene pb-CD-EGR Polybeta cyclodextrin electro reduced graphene
MNPs Metal nanoparticles rGO-FcNH2-AuNPs Reduced graphene oxide ferrocene hybrid gold
Bi2WO6 Bismuth tungstate nanoparticles
MoS2 Molybdenum disulphide SGRNF Stacked nano graphene fiber
PNCs Polymer nanocomposites ABPE Acetylene black paste electrode
MIP Molecularly imprinted polymer GRS Graphene nanosheets
MIPPy Molecularly imprinted pyrrole imprinted EG Exfoliated grahite
ELISA Enzyme linked immune sorbent assay N-GRS Nitrogen doped graphene sheets
FLISA Fluorescence linked immunoassay 4MBA 4 Mercapto benzoic acid
ZnO Zinc oxide PAMAM Poly amidoamine dendrimer
CdO Cadmium oxide NPAu nano porous gold film
CTAB Cetyl trimethyl ammnonium bromide Ni(II)TAPc Ni (II) tetraamino metallophthalocyanine
PAM Polyacrylamide FeOx Hydroxy iron
PANI Polyaniline LDH Layered double hydroxide
CoTe QDsCobalt tellurium quantum dots SDS Sodium dodecyl sulphate
PVC Polyvinyl chloride T-NH2 Thioctic acid amide
DES diethylstilbestrol MCH 6 Mercaptohexanol
E2 17 b-estradiol CB Carbon black
MbCD methyl b cyclodextrin AuNTAs Gold nanotube arrays
CD Carbon dots SiC Silicon carbide
ZnS Zinc sulphide APTES 3-aminopropyltriethoxysilane
IG Immunoglobulin poly-cys Polycystein
HRP Horse raddish peroxidase SPAN Self doped polyaniline
H2O2 Hydrogen peroxide Poly(Jug-co-JugBPA) N-(3-(4-(2-(4-hydroxyphenyl) propan-2-yl)
EEFS Excitation emission fluorescence spectroscopy phe-noxy) propyl) 3- (5-hydroxy-1, 4-
CL Chemiluminescence dihydro-1, 4-dioxonaphthalen-2 (3) -yl)
HCO 4 peroxymonocarbonate propionamide
KMnO4 Potatium permagnate A-M-CPPyNPs/FET aptamer-polymer (3-carboxylate polypyrrole)
FI-CL Flow injection chemiluminescence nanoparticles-field effect transistor
ECL Electroluminescence PEDOT poly (3,4-ethylenedioxythiophene)
SPR Surface plasmon resonance CYP2C9 cytochrome P450 2C9
LBDs Ligand binding domains PSS poly styrenesulfonate
ERb Estrogen receptors NBD Amine benzenediazonium
CD Circular dichroism PPy Polypyrrole
RRS Resonance rayleigh's scattering (RRS) GRQDs Graphene quantum dots
PEC Photoelectrochemistry TiO2NTs Titanium dioxide nanotubes
EP Electrophoresis SBA-MIP Mesoporous silica molecularly imprinted polymer
LBL Layer by layer AB Acetylene black
MWCNTs-COOH Carbxy functionalized multiwalled carbon PVP poly 4vinyl pyridine
nanotubes EMIP Electropolymerized molecularly imprinted electrode
TPA 1, 3, 6, 8-pyrene tetrasulfonic acid tetrasodium salt CMK 3 Mesoporous carbon
hydrate nano-CILPE Nano carbon ionic liquid paste electrode
PTh Polythiophene ILGRCPE Reduced graphene oxide ionic liquid carbon paste
dsDNA Double strandard DNA electrode
PDDA Poly diallyl dimethyl ammonium chloride PBPIDS 1-butyl -3-[3-(N- pyrrole)- propyl] imidazolium
PGA Polyglutamic acid tetrafluoroborate
f-SWCNTs carboxyl functionalized single walled carbon nanotubes Poly-IL 1-[3-(tert-butoxycarbonylamino) propyl]- 3-[3-(N-
PC4 Poly 3, 4 dioxythiophene pyrrole) propyl] imidazolium tetrafluoroborate
CFP Carbon fiber paper 1,10-PhenanNTf2 1,10-Phenanthroline monohydrate hydrochloride
ssDNA Single strandard DNA with lithium-bis (trifluoromethane) sulfonamide
SF Silk fibroin BMIMBr 1-butyl-3-methyl imidazolium bromide
CoPC Cobalt pthalocyanin DAPPT 1,3-di(4-amino-1-pyridinium) propane tetrafluoroborate
TaPC Tanthalum complex ionic liquid
22 Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27

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Ankita Sinha is currently working as a Postdoctoral fellow
at Dalian University of Technology, Dalian, China. She
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determination, Anal. Bioanal. Chem. 406 (2014) 2411e2420. in Dalian Institute of Chemical Physics, Chinese Academy
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Dhanjai et al. / Analytica Chimica Acta 998 (2018) 1e27 27

Prof. Xianbo Lu received his Ph.D. in 2007 from University recognised and respected leader in environmental
of Science and Technology of China (USTC). He worked at analytical chemistry, especially persistent organic pollut-
University of California, Los Angeles (UCLA) as a visiting ants (POPs). Professor Chen is a member of several aca-
scholar during 2013e2014. His current research interests demic organizations such as Analytical Toxicology
focus on environmental analysis and detection technology Committee of Chinese Society of Toxicology and Microbial
such as biosensors and analytical nanomaterials for rapid Ecology Committee of Ecological Society of China. He was
screening and detection of environmental pollutants, awarded Liaoning Hundred Talents Program in 2009 and
environmental mass spectrometry for trace analysis, etc. selected as the first batch of Leading Talents of Dalian in
Prof. Lu has published more than 50 peer-reviewed papers 2012. He has published more than 200 peer-reviewed pa-
and holds 10 invention patents. He also participated in the pers and holds 17 accredited invention patents.
fabrication of four kinds of environmental monitoring
commercial equipment prototype. Prof. Lu has received
several awards, including the First prize of Natural Science
from the Ministry of Education in 2013, Environmental Prof. Rajeev Jain is the director of Institute of Engineering,
Protection Science and Technology Award from the Na- head of Environmental Chemistry and Professor of
tional Environmental Protection Administration in 2014, Chemistry at Jiwaji University Gwalior, India. He
Lu Jiaxi Young Talent Award from the Chinese Academy completed his B.Sc. and M.Sc. from C.C.S. University,
of Science (CAS) in 2013. https://www.researchgate.net/ Meerut and Ph.D. in Chemistry from the University of
profile/Xb_Lu/publications Roorkee (now Indian Institute of Technology, Roorkee),
India, in 1978. He worked as Post-Doctoral Fellow and
Research Associate at the same institute. He was awarded
Prof. Jiping Chen is the director of Modern Analysis Center D.Sc. degree by Jiwaji University, Gwalior, India in 1990. He
of Dalian Institute of Chemical Physics (DICP), CAS and the has published more than 350 research papers and has
leader of Environmental Assessment and Analysis Group, worked over on 17 research projects sanctioned by CSIR,
DICP, CAS since 2003. Prof. Chen received his B.S. degree in UGC, MOEF, DRDO etc. His research interests include
Analytical Chemistry from China West Normal University analytical chemistry, electroanalysis of pharmaceuticals,
in 1985 and Ph.D. in Analytical Chemistry from Dalian environmental contaminants and natural antioxidants,
Institute of Chemical Physics, CAS in 1997. During micellar catalysis, electrocatalysed reactions, method
2004e2005 he was a visiting scholar at Max Planck development and validation, environmental engineering
Institute for Chemical Ecology in Germany. He is a world chemistry and wastewater treatment