Trends in Analytical Chemistry 79 (2016) 80–87

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Electrochemical biosensors for fast detection of food contaminants –

trends and perspective
Lucian Rotariu a,b, Florence Lagarde c, Nicole Jaffrezic-Renault c, Camelia Bala a,b,*
a Department of Analytical Chemistry, University of Bucharest, 4-12 Regina Elisabeta Blvd., 030018 Bucharest, Romania
b LaborQ, University of Bucharest, 4-12 Regina Elisabeta Blvd., 030018 Bucharest, Romania
c
University of Lyon, Lyon 1, Institute of Analytical Sciences, UMR CNRS-UCBL-ENS 5280, 5 rue de la Doua, 69100 Villeurbanne, France

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

Keywords:
Biosensor technology represents an extremely wide field with a great impact to healthcare, environ-
Biosensor
mental and food quality control. The aim of this review is limited to biosensors developed in the very
Food analysis
Food safety
last years specifically for monitoring food contaminants. The review covers the basic principles and types
Contaminants of electrochemical biosensors reported for food-specific applications. Innovation in materials science, nano-
Nanomaterials technology and biomimetic design are reinforcing the biosensor field. This review highlights current and
Carbon nanotubes future trends in materials used for biosensing, miniaturization and development of portable devices in
Graphene order to have on-site detection of the target analytes.
Polymers © 2016 Elsevier B.V. All rights reserved.
Nanoparticles
Enzyme inhibition

Contents

1. Introduction ........................................................................................................................................................................................................................................................... 80
2. Biosensors for food ............................................................................................................................................................................................................................................. 81
2.1. Enzyme-based biosensors ................................................................................................................................................................................................................... 82
2.2. Affinity biosensors ................................................................................................................................................................................................................................. 82
3. Materials for food biosensors .......................................................................................................................................................................................................................... 82
3.1. Carbonaceous materials and nanomaterials ................................................................................................................................................................................. 82
3.1.1. Carbon nanotubes ................................................................................................................................................................................................................. 83
3.1.2. Graphene materials .............................................................................................................................................................................................................. 84
3.2. Metal nanoparticles .............................................................................................................................................................................................................................. 85
3.3. Molecularly imprinted polymers ..................................................................................................................................................................................................... 85
4. Miniaturization and portability ...................................................................................................................................................................................................................... 85
5. Conclusions and perspectives ......................................................................................................................................................................................................................... 86
Acknowledgments ............................................................................................................................................................................................................................................... 86
References .............................................................................................................................................................................................................................................................. 86

1. Introduction The demand for developing simple, rapid, accurate, low-cost and
portable analytical instruments is growing and biosensors fulfill these
The impact of the biosensing technology is increasing in all major requirements. The current review is focused on the very recent ad-
sectors such as pharmaceutical, healthcare, environment and food. vances in biosensing for the food quality control from the last 3 years
Food safety is a global issue in the actual context of intensive de- and will not cover earlier published papers, unless it was consid-
velopment of the agriculture and the food industry. Nutrients ered necessary. Older publications are covered by many review
monitoring and fast screening of contaminants represents some of articles have been published earlier [1–6]. We proposed an over-
the key issues in agrifood field for assessment of the food quality. view of the main types of the electrochemical biosensors with
applications in food analysis and the most recent biosensing con-
figurations with improved performance characteristics based on
* Corresponding author. Tel.: +40 21 4104888; Fax: +40 21 4104888. carbonaceous materials and nanomaterials, metal nanoparticles and
E-mail address: camelia.bala@g.unibuc.ro (C. Bala). molecularly imprinted polymers to understand and evaluate the state

http://dx.doi.org/10.1016/j.trac.2015.12.017
0165-9936/© 2016 Elsevier B.V. All rights reserved.
 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87
of the art of the subject. This review is structured on two parts. First
one is addressing to the type of the biosensors taking into account
the bio-recognition mechanism. Applications to food detection are
discussed and examples of current publications are given. Ad-
vances in materials science, nanotechnology and biomimetic design
are boosting the biosensing field. Therefore, the second part deals
with some of the most used materials and nanomaterials used to
improve the performances of the transducer or the whole biosen-
sor or as immobilization matrix for bioreceptor. The most recent
papers are discussed highlighting the advantages of the proposed
approach. A special emphasis is given to a further step to be done
in this field – from bench to market. For their implementation into
the everyday life, the biosensors must come out from the labora-
tory. Miniaturization, automated analysis, low reagent consumption,
portability, minimal demand on user time or skills and connectiv-
ity represent the demands for passing to commercially available
biosensors.
2. Biosensors for food
Biosensors are analytical devices that integrate a biocomponent/
bioreceptors (isolated enzymes, organelles, whole cells, tissue,
immunosystems, nucleic acids, aptamers, etc.) with a suitable trans-
ducing system to detect chemical compounds. Common transducers
are electrochemical, optical, mass based transducers (piezoelec-
tric, surface acoustic), thermal transducers (thermistors and others.
As a result of the specific interaction between the target molecule
and the biocomponent an electrical signal is usually produced that
can be measured and recorded. A wide range of analytes form in-
organic compounds, small organic molecules to small proteins can
be detected. Compared to the conventional methods used for food
analysis, such as spectrometric or chromatographic methods, the
Fig. 1. Types of biosensors used in food analysis.
81
biosensors have few incontestable advantages: selectivity that allow
direct detection of the analyte without any sample pretreatment
samples or minimal sample pretreatment, fast analysis with results
in few minutes, low costs, perspectives for miniaturization and por-
tability. Not the least, biosensors are very easy to be used and do
not require highly trained personnel and therefore commercially
available devices can be easily launched on the consumers market.
Food quality control requires fast analysis and on the field avail-
able devices for testing different parameters. Biosensors come to meet
these requirements and justify the increased interest of develop-
ing biosensors for food quality control. Basically, there are two types
of compounds that are analyzed: compounds whose concentra-
tion presents interest for nutritional food quality and contaminants
that are not supposed to be found in food products. Some other tests
are performed to find information about the origin, counterfeiting
or adulteration of the food products. Classification of the biosensors
can be realized based on different criteria e.g. type of the bioreceptor
or transducer, analytes or reactions monitored, detection or mea-
surement mode [7]. Biochemical recognition mechanism was
considered in this review to classify the biosensors and the main
types of biosensors used for food analysis are presented in Fig. 1.
Enzyme biosensors represent the main class of electrochemical
biosensors used for food analysis. Two principles are used in this
sense: substrate detection by its conversion in a reaction catalyzed
by an enzyme with consumption or formation of an electroactive
compound and detection of enzyme inhibitors. Substrate detection
uses mainly enzymes from the oxido-reductases class (oxidases, per-
oxidases, dehydrogenases) and the main electroactive compound
detected are hydrogen peroxide or reduced form of nicotinamide
adenine dinucleotide (NADH). Determination of the inhibitors is per-
formed by measuring the enzyme activity in the absence and in the
presence of the inhibitor and correlation of the inhibition degree
82 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87
with the inhibitor concentration. Affinity biosensors are a wide class
of sensors but this review will cover only aspects about electro-
chemical sensors based on molecularly imprinted polymers for food
analysis.
2.1. Enzyme-based biosensors
First class of biosensors is based on reactions catalyzed by
enzymes. Isolated enzyme, multi-enzyme systems or integrated
enzyme systems such as, organelles, whole cells, and tissues are used
as bioreceptors. Oxidoreductases are the most used enzymes for de-
velopment of the biosensors for detection of substrates. Enzymes
catalyze specific conversion of the substrate and the generated prod-
ucts are directly determined using an appropriate transducer. The
enzyme determines the selectivity of the biosensor but neverthe-
less, the transducer selectivity affects the final analytical performance
of the biosensor. Oxidases were extensively used for developing
enzyme based biosensors. For instance, biogenic amines such as
putresceine, histamine, spemine, spermidine, tyramine, cadaver-
ine, 2-phenylethylamine, tryptamine, which are formed in food
mainly by the microbial decarboxylation of amino acids [8] can be
determined using monoamine oxidase or polyamine oxidase [9]. In
food analysis, the current freshness tests are based on detection of
these biogenic amines. Poor selectivity of these enzymes deter-
mined different research groups to use enzymes with higher
selectivity for a particular amine, such as putrescine oxidase ex-
tracted from Micrococcus rubens [10] characterized by specificity
to putresceine, or spermine oxidase an enzyme specific to sperm-
ine [11]. L-lactic acid detection is used for freshness detection in
tomato or infant food. Different configuration of L-lactate biosensors
based on L-lactate oxidase were reviewed in the literature [12].
Beside the biogenic amines, xanthine is considered an important
biomarker for fish freshness. The increase of the xanthine concen-
tration is a sign of fish spoilage and it was determined by oxidation
with a biosensor based on xanthine oxidase [13]. Lysine oxidase was
reported in the literature as an efficient bioreceptor for detection
of L-lysine with potential application in food quality control [14].
Phenols and poli-phenols, chloro- and alkyl-phenols or aromatic
amines, can be found in food products as anti-oxidants or contami-
nants and can be oxidized by different enzymes. Laccase can oxidize
the substrate using oxygen that is reduced to water and it was used
for detection of mono and poli-phenols [15–20]. Peroxidase uses
hydrogen peroxide to catalyze the oxidation of a large group of
phenol compounds [21–24], chloro-phenols [22], xenoestrogen alkyl-
phenols [25–27]. Tyrosinase has the active site close to the surface
of the protein and it able to catalyze the oxidation of small and large
substrates [28], such as tyramine [29] or bisphenol A [30–32]. Nitrite,
used as preservative on a large scale in food industry, can be de-
termined by using nitrite reductase. This enzyme is capable of a
direct electron transfer with the surface of the electrochemical trans-
ducer as it was recently reported [33]. Dehydrogenases, belonging
to the same group of oxidoreductases, are a huge class of enzymes
based on the NAD+/NADH or NADP+/NADPH redox systems in re-
alization of the electrons transfer from or to the substrate. Histamine
dehydrogenase was used to develop of a selective histamine bio-
sensor [10]. An alternative to lactate oxidase for detection of L-lactate
is the L-lactate dehydrogenase, with numerous advantages for elec-
trochemical detection of NADH [12]. The dehydrogenase-based
biosensors require the addition of a high amount of co-enzyme in
the sample solution. This problem was fixed by incorporating the
glutamate dehydrogenase and NAD+ in the immobilization matrix
of a reagentless glutamate biosensor [34]. A very small number of
enzymes from the hydrolases class are used for electrochemical
biosensors. β-lactamase is the enzyme responsible for the resis-
tance of the bacteria to some class of antibiotics. Actually, there is
an increased concern about the content of antibiotics in different
food products like meat or milk. Penicillin G, a β-lactam antibiot-
ic, was determined using a biosensor based on this enzyme [35].
Enzymes can be used as bioreceptors in biosensors design not
only for determination of substrates but also for detection of their
effectors especially inhibitors [2]. Biosensors based on enzyme in-
hibition are widely reported for detection of toxic compounds
(pesticides, mycotoxins). Acetylcholine esterase (AChE) and
butyrylcholine esterase (BChE) are the most common enzymes used
in detection of organophosphorous and carbamates pesticides [2].
Enzyme activity is measured in the absence and in the presence of
inhibitor and the inhibition degree is correlated with the concen-
tration of the inhibitor [36]. However, there are a consistent number
of papers that use other enzymes like tyrosinase, alkaline phos-
phatase or organophosphate hydrolase as bioreceptors for pesticide
detection [2]. These biosensors lacks of a poor selectivity for a spe-
cific compound that could be sometimes an advantage when this
type of device is intended to be used as a screening method for the
presence of a class of toxic compounds in the sample. An excep-
tion is represented by the methyl parathion hydrolase, which is
specific to methyl parathion [37]. Our group has reported an ap-
proach about use of AChE for detection of mycotoxins like aflatoxin
B1 [38]. A biosensor for cyanide detection was realized by immo-
bilization of peroxidase on different matrices and was based on the
determination of enzyme inhibition [39].
2.2. Affinity biosensors
Affinity biosensors are based on the analytical recognition systems
such as, antigen – antibody, hormone – receptor or interaction
between DNA strands, which do not imply a chemical transforma-
tion of the target analyte. Recently, new classes of recognition
elements were reported. Among them the aptamers, molecularly
imprinted polymers or affibodies attracted attention to the re-
searchers and it was subject of reviewing [40]. The main difference
between the affinity (bio)sensors and enzyme biosensors is the
absence of a biochemical transformation of the analyte after inter-
action with the bioreceptor. The interaction between the analyte
and the affinity partner is reversible, the formation and the de-
composition of the affinity complex being realized in mild conditions
by modifying the physico-chemical parameters like pH or ionic
strength. Molecularly imprinted polymers represent attractive ma-
terials used in bio-mimetic sensors that will be presented in the
next section.
3. Materials for food biosensors
In the recent years, the new functional materials and
nanomaterials were used in the biosensing on two directions: to
improve the response characteristics of the transducer and as the
immobilization matrices for the bioreceptor. Carbonaceous mate-
rials and nanomaterials (e.g. graphene, carbon nanotubes, nanowires,
nanorods), metal and metal oxides nanoparticles, ionic liquids, mag-
netic nanoparticles, quantum dots, molecularly imprinted polymers
are providing an enhancement of the detecting systems, but are also
representing a very attractive and favorable biosensing interface [40].
In this sense, Table 1 presents a selection of the most recent pub-
lications, which were grouped on the type of biosensors presented
in section 2.
3.1. Carbonaceous materials and nanomaterials
A huge number of applications based on carbonaceous materi-
als, nanomaterials and composites are reported in the field of
electrochemical biosensors. These materials are important through
their electrochemical properties, conductivity, high surface area,
 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87 83

Table 1
Recent publications on biosensors for food analysis

Target analytes Bioreceptor Transducer LOD Ref.

Enzyme biosensors based on substrate detection

histamine histamine dehydrogenase TTF/SPE 8.1 μM [10]
putrescine oxidase
putresceine TTF/SPE 10 μM [10]
spermine spermine oxidase PB/SPE 2 μM [11]
xanthine xanthine oxidase MWCNTs – poly(GMA-co-VFc)/ PGE 0.12 μM [13]
lysine lysine oxidase MWCNTs-MNPs/Au 0.05 μM [14]
phenols laccase PDA-NiCNFs/MGCE 0.69 μM catechol [16]
phenols laccase RGO-PdCu NCs/GCE 1.5 μM catechol [17]
phenols laccase chitosan/ZnO sol-gel /GCE 0.29 μM catechol [18]
phenols peroxidase SWCNTs/SPE 110 nM catechol [21]
50 nM pyrogallol
phenols peroxidase AuNPs/GCE 74 μM hydroquinone [23]
phenols peroxidase AgNPs-SiSG /poly L-arginine/CPE 0.57 μM hydroquinone [24]
6.2 μM pyrogallol
2-chlorophenol peroxidase Co-Al layered double hydroxide/GCE 2 nM [22]
alkyl-phenols peroxidase MnO2/SPE 0.8 μM TBP [25]
0.7 μM OP
1.7 μM NP
dopamine laccase SiO2-PA NPs/GCE 0.26 μM [19]
bisphenol A tyrosinase TiO2/MWCNTs/PDDA/Nafion/graphite 0.066 μM [30]
bisphenol A tyrosinase RGO-chitosan/ITO 0.74 nM [31]
bisphenol A tyrosinase MWCNTs/BDD 10 pM [32]
nitrite nitrite reducase carbon ink/SPE 0.6 μM [41]
glutamate glutamate dehydrogenase MWCNTs-chitosan/MB-SPE 3 μM [34]
penicillin G β-lactamase CoPC/CPE 0.079 μM [35]
Inhibition-based enzyme biosensors
cyanide HRP Au sonoparticles/sonogel-carbon 0.03 μM [39]
electrode
paraoxon AChE Ni-NTA – GO/GCE 3 μM [42]
organophosphate pesticides AChE AuNPs-PPy-RGO 0.5 nM paraoxon-ethyl [43]
Methyl parathion methyl parathion hydrolase AuNPs/GCE 0.07 ppb [37]
carbamates laccase-tyrosinase AuNPs–chitosan/grahene dopped CPE 1.68 nM [44]
pirimicarb laccase MWCNTs paste electrode 0.18 μM [45]
Affinity sensors – MIP sensors
estradiol MIP (p-aminothiophenol functionalized gold nanoparticles) Au 1.09 fM [46]
aflatoxin B1 MIP (p-aminothiophenol functionalized gold nanoparticles) Au 3 fM [47]
tetracycline MIP (p-aminothiophenol functionalized gold nanoparticles) Au 0.22 fM [48]
quinoxaline-2-carboxylic acid 3-aminopropyl triethoxysilane and tetraethoxysilane MWCNTs-chitosan/GCE 0.44 μM [49]
sulfadimethoxine overoxidized PPy Au 70 μM [50]
isocarbophos poly(o-phenylenediamine-co-gallic GCE 20 nM [51]
acid-co-m-aminobenzoic acid)

TTF – tetrathiafulvalene, PB – Prussian Blue, MWCNTs – multi-walled carbon nanotubes, SWCNTs – single-walled carbon nanotubes, VFc – vinylferrocene, GMA – Glycidyl
methacrylate, PGE – pencil graphite electrode, MNPs – magnetic nanoparticles, GCE – glassy carbon electrode, PDA – ploydopamine, NiCNFs – nickel nanoparticle loaded
carbon nanofibers, RGO – reduced graphene oxide, PdCu NCs – palladium-copper alloyed nanocages, SiO2-PA NPs – phytic acid functionalized silica nanoparticles, TBP –
4-t-butylphenol, OP- 4-t-octylphenol, NP – 4-n-nonylphenol, PDDA – poly(diallyldimethylammonium chloride), BDD – boron dopped diamond electrode, MB – Meldola Blue,
CPE – carbon paste electrode, AgNPs – silver nanoparticles, SiSG – silica sol-gel, CoPC – cobalt phthalocyanine, PPy – polypyrrole, SiO2-PA NPs – silica nanoparticles modi-
fied with phytic acid.

which are the determining factors to attain an unprecedented low
detection limits and high sensitivities.
3.1.1. Carbon nanotubes
Carbon nanotubes have a cylindrical nanostructure and are clas-
sified upon the number of rolled layers of graphene. Both, single
walled carbon nanotubes (SWCNTs) and multi-walled carbon
nanotubes (MWCNTs) were equally used as electrode materials. The
small size and a corresponding large active surface, the easy
functionalization with carboxyl or amino groups represents advan-
tages, which were exploited for electrochemical applications. Anyway,
CNTs are not soluble in hydrophilic solvents and tend to agglom-
erate. Nanocomposites prepared in combination with other materials
e.g. polymers, ionic liquids or metal nanoparticles were designed
to overcome these drawbacks, to improve the electrocatalytical prop-
erties and/or to facilitate the immobilization of the bioreceptor.
Covalent immobilization of hemoglobin (Hb) onto carboxylated
MWCNTs/copper nanoparticle/polyaniline composite was used for
construction of a biosensor for acrylamide [52]. Acrylamide can be
found in a variety of fried and oven-baked foods, in some food pack-
aging and adhesives, presents a high toxicity and cancer risk. The
composite material was electrodeposited onto a pencil graphite elec-
trode and the resulted biosensor exhibited a low detection limit of
0.2 nM acrylamide with a wide linear range (5 nM to 75 mM). A paste
electrode based on MWCNTs and paraffin was used to immobilize
laccase. The biosensor showed an excellent electron transfer kinetic
for detection of 4-aminophenol, used as enzyme substrate, and a
good stability of approx. one month [45]. Pirimicarb was deter-
mined by inhibition of laccase with a low detection limit of
1.8 × 10−7 mol L−1. Tomato and lettuce samples were analyzed and
no interferences from pro-vitamin A, vitamins B1 and C, and glucose
were observed. A biosensor for organophosphate neurotoxins based
on a renewable nanocomposite interface was developed by Kirsch
et al. [53] by using cationic and anionic layers of CNTs modified with
biopolymers in a layer by layer structure with immobilized organo-
phosphorus hydrolase. The biosensor showed a high sensitivity with
a stable electrochemical response. In the last years our group re-
ported the use of nanocomposite materials based on MWCNTs and
imidazolium-based ionic liquids for detection of thiocholine [54],
which was successfully applied for developing AChE biosensors for
organophosphate pesticides [55]. Chlorpyrifos was determined in
the concentration range from 10−8 to10−6 M with a detection limit
84 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87
of 4 nM. A similar nanocomposite based on SWCNTs and 1-butyl-
3-methylimidazolium hexafluorophosphate was published by Gurban
et al. [27] for detection of H2O2 and was further used for estrogen
alkyl-phenols determination in the presence of immobilized HRP.
A fast response time of about 5 s and detection limits of 1.1 μM for
4-t-octylphenol and 0.4 μM for 4-n-nonylphenol was achieved. An
amperometric acetylcholinesterase biosensor was developed
using screen-printed carbon electrodes modified with MWCNTs
and 7,7,8,8-tetracyanoquinodimethane (TCNQ) [36]. The synergis-
tic effect of MWCNTs and TCNQ, due to a specific supramolecular
arrangement resulted from the interaction of the counterparts, was
exploited for biosensing of organophosphates by inhibition of AChE.
A very low detection limit of 30 pM (7 ppt) was achieved for
paraoxon-methyl. A nanocomposite based on polypyrrole (PPy) with
p-phenyl sulfonate-functionalized single-walled carbon nanotubes
was reported by Raicopol et al. [56], which exhibited excellent
electrocatalytic activities towards the reduction or oxidation of H2O2.
The material allows facile enzyme immobilization and can be used
as a platform for developing oxidase-based biosensors. A copoly-
mer based on vinylferrocene and glycidyl methacrylate and MWCNT
were used to incorporate xanthine oxidase, which was used as
bioreceptor for xanthine biosensing, as a marker for fish freshness
[13]. A dramatic increase of the sensitivity was observed in the pres-
ence of MWCNTs compared to the biosensor based only on the
copolymer as the immobilization matrix.
Glutamate dehydrogenase and NAD+ were encapsulated in a com-
posite based on chitosan and MWCNT using the layer-by layer
method to develop a reagentless glutamate biosensor [34]. The linear
response range was found to be 7.5–105 μM, with a detection
limit of 3 μM. Food samples were analyzed for detection of mono-
sodium glutamate without any pre-treatment. A disposable
electrochemical immunosensor for simultaneous detection of three
bacteria involved in bacterial food poisoning was published by
Viswanathan et al. [57]. The corresponding antibodies were immo-
bilized on the surface of a MWCNT – polyallylamine modified screen-
printed electrode. After bacteria–Ab interaction, the sandwich
immunoassay was performed with three specific antibodies marked
with nanocrystal of CdS, PbS and CuS. The square wave anodic strip-
ping voltammetry was used to quantify the amount of metal ions
from the “sandwich” structure and correlated with the amount of
bound bacteria cells. The three bacteria cells were determined in
the range of 1 × 103-5 × 105 cells mL−1. Carboxyl functionalized
SWCNTs were successfully used for covalent immobilization of ty-
rosinase and tyramine was determined amperometrically with a
detection limit of 0.62 μM [29]. Recently, Lee et al. [58] reported the
chemical immobilization of olfactory receptors on SWCNTs-field
effect transistors to build a bioelectronics nose for detection of
gaseous trimethylamine. The same enzyme immobilized in a matrix
based on a diazonium-functionalized boron doped diamond elec-
trode modified with MWCNTs was used for highly sensitive detection
of bisphenol A (detection limit of 10 pM) [32].
3.1.2. Graphene materials
Graphene represents a class of carbon materials based on a mono-
layer of carbon atoms arranged in a honeycomb lattice. Graphene
oxide (GO) and reduced graphene oxide (RGO) are the main rep-
resentatives of this class. A surge in interest for graphene
electrochemical applications was observed lately due to their ex-
cellent physico-chemical properties, simple preparation methods
and the presence of functional groups such as hydroxyl, carboxyl
or epoxide. Modification of the glassy carbon electrode (GCE) with
RGO [59] or graphene-Nafion matrix [60] for amperometric detec-
tion of organophosphate pesticides was reported. First approach is
based on the inhibition of AChE, while in the second case methyl-
parathion was determined by stripping voltammetry with detection
limits of 0.5 ng mL−1 and 1.6 ng mL−1, respectively. A versatile strategy
to synthesize functionalized graphene oxide nanomaterials was re-
ported by Zhang et al. [42]. A paraoxon biosensor was constructed
by covalent immobilization of the histidine (His)-tagged acetyl-
cholinesterase (AChE) through the specific binding between Ni-
NTA and His-tag. This approach leads to a great short-term and
long-term stability of the biosensors with a detection limit of
6.5 × 10−10 M paraoxon. A bi-enzymatic biosensor for carbamate pes-
ticides was reported by Oliveira et al. [44]. On the surface of a
graphene doped carbon paste electrode laccase and tyrosinase were
immobilized by electrodeposition in a gold nanoparticles-chitosan
hybrid film. Good recovery was achieved for determination of car-
baryl, formetanate hydrochloride, propoxur and ziram in citrus fruits.
Recently, our research group reported the use of composites based
on electrochemically reduced graphene oxide (ERGO) and poly-
allylamine hydrochloride (PAH) for detection of NADH with potential
application for developing dehydrogenase-based biosensors [61].
Despite the fact that graphene materials are very efficient in the elec-
tron transfer process at the surface of the transducer, the selectivity
of the inhibition-based biosensors is affected by a relatively high
value of the working potential. In order to reduce the applied po-
tential nanocomposites materials based on graphene and gold
nanoparticles [62], platinum nanoparticles [63], gold nanoparticles
and polypyrrole [43], NiO nanoparticles [64], ZnO nanoparticles-
decorated MWCNTs [65] are reported to improve the detector
selectivity. Moreover, a very low detection limit of 5 × 10−14 M methyl
parathion was achieved by using a GCE modified with NiO
nanoparticles, carboxylic graphene and Nafion, which offers a proper
environment for AChE immobilization [64]. A GO platform was used
to immobilize anti-aflatoxin B1 antibody and to fabricate a highly
sensitive label free biosensor for detection of aflatoxin B1 (AFB1)
by electrochemical impedance spectroscopy (EIS) with an im-
proved detection limit of 0.23 ng·mL−1 and a stability of about 5
weeks [66]. Detection limit as low as 1 fM aflatoxin B1 was re-
ported in a paper published by Linting et al. [67]. The enhanced
performances of the immunosensors are based on graphene/
conducting polymer/gold nanoparticles/ionic liquid composite film.
The graphene and gold nanoparticles are responsible for the elec-
trochemical properties of the film, while conducting polymer and
the ionic liquid provide a suitable environment for the antibody. An
extended stability for over 26 weeks was reported in these
conditions.
A comparison between different biosensor architectures based
on graphene, nitrogen doped graphene (NG) and polymer compos-
ites of NG was realized by Barsan et al. [68]. Hypoxanthine enzymatic
detection based on the direct regeneration of FAD at the surface of
NG modified GCE was performed and represents a model for other
oxidase-based biosensors.
Graphene nanoplatelets were used for electrocatalytic detec-
tion of H2O2 and to investigate the kinetic of immobilized HRP [69].
The linear response range was between 2.0 and 28 μM H2O2 with
a detection limit of 0.6 μM. This interface is a promising tool for ap-
plications based on HRP biosensors. An improvement of the H2O2
sensor performances was reported by Chen et al. [70], which use
palladium nanoparticles / graphene nano-sheets film with an en-
hancement of the response range from 0.1 μM to 1000 μM and with
a lower detection limit of 0.05 μM. Moreover, the sensor was se-
lective to H 2 O 2 in the presence of ascorbic acid, glucose and
dopamine. Another composite based on GO decorated with gold
nanoparticles reported by Yu et al. [71] was used as interface to im-
mobilize HRP for sensitive detection of H2O2 with a detection limit
of 7.5 nM. Graphene dots, due to their small size, possess peroxidase-
like catalytic activity much higher than GO [72]. The graphene dots-
based electrochemical system presents similar performances with
HRP-based sensors permitting a detection of H2O2 as low as 10 nM.
It is expected to be applied as enzyme-less H2O2 sensors in differ-
ent fields.
 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87
3.2. Metal nanoparticles
Besides the carbon materials, metal nanoparticles have been
widely used in biosensing for their unique electrochemical prop-
erties and the ability to immobilize bioreceptors without affecting
their bioactivity. Among them gold nanoparticles (AuNPs) have the
most reported applications. Very often, AuNPs are associated with
carbon materials (CNTs and graphene) in a synergetic effect to
enhance the electrocatalytic effect of the working electrode and
some recent papers were already mentioned in the section 3.1
[52,67,70,73,74]. An immobilization matrix based on a hydrogel with
AuNPs was used for immobilization of AChE [75]. High retention
efficiency of the enzyme of about 92% and a long stability of the
enzyme (half-life of 55 days) were achieved. Carbamates, includ-
ing carbofuran, oxamyl, methomyl, and carbaryl were detected by
enzyme inhibition with a detection limit between 2 and 236 nM.
Various fruit and vegetable spiked samples were analyzed with good
testing capabilities. A biosensor for detection of cyanide by inhi-
bition of HRP was reported by Attar et al. [39]. Different HRP
immobilization procedures with and without gold sononanoparticles
were studied. The authors reported an enhancement of the
electron transfer reaction and improvement of the analytical
performances for cyanide detection in the presence of Au
sononanoparticles with a lower LOD than previous published studies
(0.03 μM). An attractive material for its electrochemical proper-
ties and suitable for enzyme immobilization was obtained by
decorating GO with AuNPs, which was used to immobilize HRP for
amperometric detection of H2O2 [71]. A selective and sensitive
L-lactate biosensors was prepared by using a screen-printed elec-
trode modified with AuNPs anchored on RGO and immobilized
L-lactate dehydrogenase [76]. In situ growth of AuNPs on graphene
nanosheets and immobilization of hemoglobin on this composite
material lead to a sensitive and selective biosensor for determina-
tion of nitrite with a wide response range (0.05 to 1000 μM) and a
detection limit of 0.01 μM.
3.3. Molecularly imprinted polymers
Molecularly imprinted polymers (MIPs) based sensors consist in
use of a cross-linked polymer or co-polymer as synthetic recogni-
tion element for analyte detection. They display high physical,
chemical and thermal stability, short time of synthesis, cost effec-
tiveness and can be adapted to be highly selective. MIPs have a great
potential to replace the natural bio-recognition elements such as
enzymes or antibodies, which are known to have a low stability. The
interaction between MIPs and analyte is based on steric matching,
hydrophobic and electrostatic interactions similar to the Ag-Ab in-
teraction. Therefore, MIPs are considered as the artificial antibodies
or plastic antibodies with real interest in sensing [1,77]. The basic
design, preparation technology and applications was recently re-
viewed [78]. Basically, MIPs are synthesized by electrochemical
polymerization of functional monomers with cross-linkers and in
the presence of the template molecule, which is the target analyte.
After removal of the template molecules, active sites are created in
the structure of the polymer, which are complementary in shape,
size and functional groups to the template molecule. Mimicking the
biological activity of antibodies, MIPs can bind the analyte in the
molecularly imprinted sites. An appropriate transducer will convert
this interaction in a measurable signal.
However, poor signal transduction, lack of stability and selec-
tivity represent the main drawbacks of MIP sensors. In order to
improve the sensitivity of the target analyte detection some re-
searchers proposed different way to amplify the signal. MIP
preparation methods were modified by using some other materi-
als in order to increase the sensors selectivity. Electropolymerization
of p-aminothiophenol functionalized gold nanoparticles in the
85
presence of the template molecule lead to an amplification of the
analytical signal of the MIP sensors [46,47]. Very low detection limits
of 1 fM and 4 fM were reported for detection of estradiol [46] and
aflatoxin B1 [47], respectively. Very recently, the same principle was
applied to develop a MIP sensor for detection of tetracycline in honey
with an even lower detection limit of 0.22 fM [48]. Quinoxaline-2-
carboxylic acid (QCA) is the major metabolite of carbadox veterinary
drug and it is difficult to be measured because it is present in com-
mercial pork meat products at trace level. A MIP-based sensor for
QCA was developed by Yang et al. [49]. A sol-gel molecularly im-
printed polymer was used as bio-recognition element, while
MWNTs-chitosan functional composite was used to modify the
surface of a GCE in order to amplify the electrochemical detection
of QCA. A detection limit of 4.4 × 10−7 mol L−1 was achieved. Good
stability and reproducibility of the MIP sensor permitted an eval-
uation of the QCA content in commercial pork products. An
electrochemical sensor based on molecularly imprinted overoxidized
polypyrrole for detection of sulfadimethoxine from milk samples
was recently reported [50]. The detection limit of 70 μM, the highly
reproducible response and good selectivity in the presence of struc-
turally related molecules are evidences of the sensing performances
of imprinted polypyrrole. Isocarbophos was electrochemically de-
termined using a GCE modified with molecularly imprinted
terpolymer of poly(o-phenylenediamine-co-gallic acid-co-m-
aminobenzoic acid) [51]. DPV measurements in the presence of ferri/
ferrocyanide redox probe pointed out a wide linear range (7.50 × 10−8
to 5.00 × 10−5 M) with a detection limit of 2 × 10−8 M. The MIP sensor
was successfully applied to determine isocarbophos in cabbage and
cowpea samples.
4. Miniaturization and portability
The safety and quality of foods is a global concern that demands
suitable analytical methods for rapid and on-site detection. Food
analysis is focused on analysis of food composition, online process
control in food industry and food security for detection of contami-
nants, allergens, toxins, additives, etc. There are large number of
papers published on biosensors for food, but very few are com-
mercially available or in the phase of implementation for release
on the market. Despite the clear advantages of biosensors, com-
paring classical analysis methods there is a long way to emerge from
the research laboratories to the marketplace [33]. The main ob-
stacles are related to the limited lifetime of the bioreceptor, the
biosensor’s integration into complete system, integrating electron-
ics for data collection/analysis, miniaturization and portability of
the analytical systems [79].
On step forward was done by developing lab-on-a-chip devices
for automation of the analytical process with minimal consump-
tion of reagents and miniaturization [79]. Many microfluidic
strategies, such as the application of droplet-based microfluidics,
paper-based microfluidic devices, handling liquids without
pumps and valves are explored lately. Such a platform was re-
cently reported for detection of electrochemical detection of
organophosphorus pesticides in real food samples by using an AChE
biosensor [80]. It uses a novel AutoDip platform based on the move-
ment of a solid phase through the reagents and sample instead of
transporting the reagents through a fixed solid phase. Chlorpyrifos
was determined in apple samples at concentrations below the
maximum level defined by the European Commission. Not only the
biosensors but also the equipments used for data acquisition/
analysis are engaged in the miniaturization and integration process.
Thus, a wireless potentiostat for mobile chemical sensing and
biosensing was reported recently [81]. Kim et al. [82] reported a por-
table biosensor system for pesticide detection integrated with
wireless communication. Highly topical for food quality control is
the development and implementation of multiplexing tests, which
86 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87
permit determination and discrimination of multiple analytes in one
step analysis. Miniaturized devices with multiplexing capabilities
for detection of mycotoxins in cereals and cereal-based food prod-
ucts is discussed by Meneely and Elliot [83]. Ludwig et al. reported
the potential of a portable protein microarray-based fluorescence
immunoassay system towards simultaneous detection of multiple
biomarkers by an ordinary smartphone [40]. A multiplexed device
that can simultaneously detect chloramphenicol, streptomycin and
desfuroylceftiofur in raw dairy milk, without sample preparation,
has been recently developed [84].
5. Conclusions and perspectives
This overview of the latest reports about biosensors for detec-
tion of food contaminants demonstrates that real progress were
made in improving of their performances such as detection limit,
sensitivity and selectivity. A significant amount of research has gone
on the use of nanomaterials in the preparation of the biosensors
to improve some analytical features. Detection limits at the level
of nM to fM were achieved, which, in general, are below the
maximum level accepted by the European legislation in food prod-
ucts. The low stability of the bioreceptor related to the low long-
term storage stability of the biosensors is still a remaining challenge.
Repeated use in complex sample matrices and environmental con-
ditions are also key factors for biosensors stability.
One potential solution to this problem are the MIPs, which rep-
resent a stable and cheaper alternative to antibodies. Another
solution could be found in developing inexpensive disposable
biosensors, similar to the actual commercially available biosensing
system used in clinical analysis. Deterioration of the biosensor el-
ements in complex matrices such as food samples can be avoided
in this way. The selectivity still represents a weak point of the
biosensors. Lower selectivity, especially in the case of inhibition-
based biosensors, are not limiting the application of these analytical
devices if they are intended as alarm systems for detecting a class
of compounds such as pesticides, mycotoxins or biogenic amines.
These platforms are suitable for fast screening of the food samples
for toxic compounds or in the freshness tests. Another challenge is
the integration of the biosensors in simple, cheap and portable
systems. Some strategies for the implementation of portable devices
are presented in the current review. Multi-analyte detection on mul-
tiplexed systems, development of sensor networks and wireless
signal transmitters for remote sensing will definitively mark the
future of the biosensors for food contaminants analysis.
Acknowledgments
This work was supported by the Romanian National Authority
for Scientific Research, CNDI– UEFISCDI, projects no 107/2012 and
177/2014. The Marie Curie International Research Staff Exchange
Scheme, grant no. PIRSES GA 2012-318053 is acknowledged.
References
[1] C. Algieri, E. Drioli, L. Guzzo, L. Donato, Bio-mimetic sensors based on
molecularly imprinted membranes, Sensors (Basel) 14 (2014) 13863–13912.
[2] A. Amine, F. Arduini, D. Moscone, G. Palleschi, Recent advances in biosensors
based on enzyme inhibition, Biosens. Bioelectron. 76 (2016) 180–194.
[3] S. Kumar, N. Dilbaghi, M. Barnela, G. Bhanjana, R. Kumar, Biosensors as novel
platforms for detection of food pathogens and allergens, BioNanoScience 2
(2012) 196–217.
[4] B.D. Malhotra, S. Srivastava, S. Augustine, Biosensors for food toxin detection:
carbon nanotubes and graphene, in: V. Renugopalakrishnan, M.R. McDevitt, P.M.
Ajayan, S.J. Koester (Editors), 2014 MRS Fall Meeting, Materials Research Society,
2015, pp. 33–43.
[5] V. Scognamiglio, F. Arduini, G. Palleschi, G. Rea, Biosensing technology for
sustainable food safety, Trends Anal. Chem. 62 (2014) 1–10.
[6] J.C. Vidal, L. Bonel, A. Ezquerra, S. Hernández, J.R. Bertolín, C. Cubel, et al.,
Electrochemical affinity biosensors for detection of mycotoxins: a review,
Biosens. Bioelectron. 49 (2013) 146–158.
[7] A. Turner, G. Wilson, I. Karube, Biosensors: Fundamentals and Applications,
Oxford University Press., Oxford, UK, 1987.
[8] A. Naila, S. Flint, G. Fletcher, P. Bremer, G. Meerdink, Control of biogenic amines
in food – existing and emerging approaches, J. Food Sci. 75 (2010) R139–
R150.
[9] K. Kivirand, T. Rinken, Biosensors for biogenic amines: the present state of art
mini-review, Anal. Lett. 44 (2011) 2821–2833.
[10] W. Henao-Escobar, L. Del Torno-De Román, O. Domínguez-Renedo, M.A.
Alonso-Lomillo, M.J. Arcos-Martínez, Dual enzymatic biosensor for simultaneous
amperometric determination of histamine and putrescine, Food Chem. 190
(2016) 818–823.
[11] A. Boffi, G. Favero, R. Federico, A. Macone, R. Antiochia, C. Tortolini, et al., Amine
oxidase-based biosensors for spermine and spermidine determination, Anal.
Bioanal. Chem. 407 (2015) 1131–1137.
[12] L. Rassaei, W. Olthuis, S. Tsujimura, E.J.R. Sudhölter, A. Van Den Berg, Lactate
biosensors: current status and outlook, Anal. Bioanal. Chem. 406 (2013)
123–137.
[13] M. Dervisevic, E. Custiuc, E. Çevik, M. Şenel, Construction of novel xanthine
biosensor by using polymeric mediator/MWCNT nanocomposite layer for fish
freshness detection, Food Chem. 181 (2015) 277–283.
[14] J. Narang, U. Jain, N. Malhotra, S. Singh, N. Chauhan, Development of lysine
biosensor based on core shell magnetic nanoparticle and multiwalled carbon
nanotube composite, Adv. Mater. Lett. 6 (2015) 407–413.
[15] J.H. Kim, S.G. Hong, H.J. Sun, S. Ha, J. Kim, Precipitated and chemically-
crosslinked laccase over polyaniline nanofiber for high performance phenol
sensing, Chemosphere 143 (2016) 142–147.
[16] D. Li, L. Luo, Z. Pang, L. Ding, Q. Wang, H. Ke, et al., Novel phenolic biosensor
based on a magnetic polydopamine-laccase-nickel nanoparticle loaded carbon
nanofiber composite, ACS Appl. Mater. Interfaces 6 (2014) 5144–5151.
[17] L.P. Mei, J.J. Feng, L. Wu, J.Y. Zhou, J.R. Chen, A.J. Wang, Novel phenol biosensor
based on laccase immobilized on reduced graphene oxide supported palladium-
copper alloyed nanocages, Biosens. Bioelectron. 74 (2015) 347–352.
[18] J. Qu, T. Lou, Y. Wang, Y. Dong, H. Xing, Determination of catechol by a novel
laccase biosensor based on zinc-oxide sol-Gel, Anal. Lett. 48 (2015) 1842–
1853.
[19] K. Wang, P. Liu, Y. Ye, J. Li, W. Zhao, X. Huang, Fabrication of a novel laccase
biosensor based on silica nanoparticles modified with phytic acid for sensitive
detection of dopamine, Sens. Actuators B Chem. 197 (2014) 292–299.
[20] W. Zhao, K. Wang, Y. Wei, Y. Ma, L. Liu, X. Huang, Laccase biosensor based on
phytic acid modification of nanostructured SiO2 surface for sensitive detection
of dopamine, Langmuir 30 (2014) 11131–11137.
[21] F. Chekin, L. Gorton, I. Tapsobea, Direct and mediated electrochemistry of
peroxidase and its electrocatalysis on a variety of screen-printed carbon
electrodes: amperometric hydrogen peroxide and phenols biosensor, Anal.
Bioanal. Chem. 407 (2015) 439–446.
[22] L. Fernández, I. Ledezma, C. Borrás, L.A. Martínez, H. Carrero, Horseradish
peroxidase modified electrode based on a film of Co-Al layered double hydroxide
modified with sodium dodecylbenzenesulfonate for determination of
2-chlorophenol, Sens. Actuators B Chem. 182 (2013) 625–632.
[23] G. Hernández-Cancel, D. Suazo-Dávila, J. Medina-Guzmán, M. Rosado-González,
L.M. Díaz-Vázquez, K. Griebenow, Chemically glycosylation improves the
stability of an amperometric horseradish peroxidase biosensor, Anal. Chim. Acta
854 (2015) 129–139.
[24] P. Raghu, T. Madhusudana Reddy, K. Reddaiah, L.R. Jaidev, G. Narasimha, A novel
electrochemical biosensor based on horseradish peroxidase immobilized on
Ag-nanoparticles/poly(l-arginine) modified carbon paste electrode toward the
determination of pyrogallol/hydroquinone, Enzyme Microb. Technol. 52 (2013)
377–385.
[25] A.M. Gurban, D. Burtan, L. Rotariu, C. Bala, Manganese oxide based screen-
printed sensor for xenoestrogens detection, Sens. Actuators B Chem. 210 (2015)
273–280.
[26] A.M. Gurban, L. Rotariu, V.E. Marinescu, C. Bala, Determination of xenoestrogenic
compounds using a nanostructured biosensing device, Electroanalysis 24 (2012)
2371–2379.
[27] A.M. Gurban, L. Rotariu, M. Baibarac, I. Baltog, C. Bala, Sensitive detection of
endocrine disrupters using ionic liquid – single walled carbon nanotubes
modified screen-printed based biosensors, Talanta 85 (2011) 2007–2013.
[28] S. Tembe, S.F. D’Souza, Immobilisation strategies for construction of tyrosinase-
based biosensors, Mater. Technol. 30 (2015) B190–B195.
[29] I.M. Apetrei, C. Apetrei, The biocomposite screen-printed biosensor based on
immobilization of tyrosinase onto the carboxyl functionalised carbon nanotube
for assaying tyramine in fish products, J. Food Eng. 149 (2015) 1–8.
[30] J. Kochana, K. Wapiennik, J. Kozak, P. Knihnicki, A. Pollap, M. Woźniakiewicz,
et al., Tyrosinase-based biosensor for determination of bisphenol A in a
flow-batch system, Talanta 144 (2015) 163–170.
[31] K.K. Reza, M.A. Ali, S. Srivastava, V.V. Agrawal, A.M. Biradar, Tyrosinase
conjugated reduced graphene oxide based biointerface for bisphenol A sensor,
Biosens. Bioelectron. 74 (2015) 644–651.
[32] N. Zehani, P. Fortgang, M. Saddek Lachgar, A. Baraket, M. Arab, S.V. Dzyadevych,
et al., Highly sensitive electrochemical biosensor for bisphenol A detection based
on a diazonium-functionalized boron-doped diamond electrode modified with
a multi-walled carbon nanotube-tyrosinase hybrid film, Biosens. Bioelectron.
74 (2015) 830–835.
 L. Rotariu et al. / Trends in Analytical Chemistry 79 (2016) 80–87
[33] D.P. Nikolelis, T. Varzakas, A. Erdem, G.-P. Nikoleli, Portable Biosensing of
Food Toxicants and Environmental Pollutants, CRC Press Taylor & Francis Group,
2013.
[34] G. Hughes, R.M. Pemberton, P.R. Fielden, J.P. Hart, Development of a novel
reagentless, screen-printed amperometric biosensor based on glutamate
dehydrogenase and NAD+, integrated with multi-walled carbon nanotubes for
the determination of glutamate in food and clinical applications, Sens. Actuators
B Chem. 216 (2015) 614–621.
[35] T.M.D. Prado, M.V. Foguel, L.M. Gonçalves, M.D.P.T. Sotomayor, β-Lactamase-
based biosensor for the electrochemical determination of benzylpenicillin in
milk, Sens. Actuators B Chem. 210 (2015) 254–258.
[36] L. Rotariu, L.G. Zamfir, C. Bala, A rational design of the multiwalled carbon
nanotube-7,7,8,8-tetracyanoquinodimethan sensor for sensitive detection of
acetylcholinesterase inhibitors, Anal. Chim. Acta 748 (2012) 81–88.
[37] G. Liu, W. Guo, Z. Yin, Covalent fabrication of methyl parathion hydrolase on
gold nanoparticles modified carbon substrates for designing a methyl parathion
biosensor, Biosens. Bioelectron. 53 (2014) 440–446.
[38] M. Puiu, O. Istrate, L. Rotariu, C. Bala, Kinetic approach of aflatoxin B1-
acetylcholinesterase interaction: a tool for developing surface plasmon
resonance biosensors, Anal. Biochem. 421 (2012) 587–594.
[39] A. Attar, L. Cubillana-Aguilera, I. Naranjo-Rodríguez, J.L.H.H. de Cisneros, J.M.
Palacios-Santander, A. Amine, Amperometric inhibition biosensors based on
horseradish peroxidase and gold sononanoparticles immobilized onto different
electrodes for cyanide measurements, Bioelectrochemistry 101 (2015) 84–91.
[40] A. Tiwari, A.P.F. Turner, Biosensors Nanotechnology, Wiley-Scrivener, 2014.
[41] T. Monteiro, P.R. Rodrigues, A.L. Gonçalves, J.J.G. Moura, E. Jubete, L. Añorga,
et al., Construction of effective disposable biosensors for point of care testing
of nitrite, Talanta 142 (2015) 246–251.
[42] H. Zhang, Z.F. Li, A. Snyder, J. Xie, L.A. Stanciu, Functionalized graphene oxide
for the fabrication of paraoxon biosensors, Anal. Chim. Acta 827 (2014) 86–94.
[43] Y. Yang, A.M. Asiri, D. Du, Y. Lin, Acetylcholinesterase biosensor based on a gold
nanoparticle-polypyrrole-reduced graphene oxide nanocomposite modified
electrode for the amperometric detection of organophosphorus pesticides,
Analyst 139 (2014) 3055–3060.
[44] T.M.B.F. Oliveira, M.F. Barroso, S. Morais, M. Araújo, C. Freire, P. de Lima-Neto,
et al., Sensitive bi-enzymatic biosensor based on polyphenoloxidases–gold
nanoparticles–chitosan hybrid film–graphene doped carbon paste electrode for
carbamates detection, Bioelectrochemistry 98 (2014) 20–29.
[45] T.M.B.F. Oliveira, M. Fátima Barroso, S. Morais, P. De Lima-Neto, A.N. Correia,
M.B.P.P. Oliveira, et al., Biosensor based on multi-walled carbon nanotubes paste
electrode modified with laccase for pirimicarb pesticide quantification, Talanta
106 (2013) 137–143.
[46] A. Florea, C. Cristea, F. Vocanson, R. Səndulescu, N. Jaffrezic-Renault,
Electrochemical sensor for the detection of estradiol based on
electropolymerized molecularly imprinted polythioaniline film with signal
amplification using gold nanoparticles, Electrochem. Commun. 59 (2015) 36–39.
[47] M. Jiang, M. Braiek, A. Florea, A. Chrouda, C. Farre, A. Bonhomme, et al., Aflatoxin
B1 detection using a highly-sensitive molecularly-imprinted electrochemical
sensor based on an electropolymerized metal organic framework, Toxins 7
(2015) 3540–3553.
[48] M. Bougrini, A. Florea, C. Cristea, R. Sandulescu, F. Vocanson, A. Errachid, et al.,
Development of a novel sensitive molecularly imprinted polymer sensor based
on electropolymerization of a microporous-metal-organic framework for
tetracycline detection in honey, Food Control 59 (2016) 424–429.
[49] Y. Yang, G. Fang, G. Liu, M. Pan, X. Wang, L. Kong, et al., Electrochemical sensor
based on molecularly imprinted polymer film via sol-gel technology and
multi-walled carbon nanotubes-chitosan functional layer for sensitive
determination of quinoxaline-2-carboxylic acid, Biosens. Bioelectron. 47 (2013)
475–481.
[50] A. Turco, S. Corvaglia, E. Mazzotta, Electrochemical sensor for sulfadimethoxine
based on molecularly imprinted polypyrrole: study of imprinting parameters,
Biosens. Bioelectron. 63 (2015) 240–247.
[51] X. Yan, J. Deng, J. Xu, H. Li, L. Wang, D. Chen, et al., A novel electrochemical sensor
for isocarbophos based on a glassy carbon electrode modified with
electropolymerized molecularly imprinted terpolymer, Sens. Actuators B Chem.
171-172 (2012) 1087–1094.
[52] B. Batra, S. Lata, M. Sharma, C.S. Pundir, An acrylamide biosensor based on
immobilization of hemoglobin onto multiwalled carbon nanotube/copper
nanoparticles/polyaniline hybrid film, Anal. Biochem. 433 (2013) 210–217.
[53] J. Kirsch, V.A. Davis, A.L. Simonian, Direct and discriminative detection of
organophosphate neurotoxins for food and agriculture products, Proceedings
of IEEE Sensors, 2012.
[54] L. Rotariu, L.G. Zamfir, C. Bala, Low potential thiocholine oxidation at carbon
nanotube-ionic liquid gel sensor, Sens. Actuators B Chem. 150 (2010) 73–79.
[55] L.G. Zamfir, L. Rotariu, C. Bala, A novel, sensitive, reusable and low potential
acetylcholinesterase biosensor for chlorpyrifos based on 1-butyl-3-
methylimidazolium tetrafluoroborate/multiwalled carbon nanotubes gel,
Biosens. Bioelectron. 26 (2011) 3692–3695.
[56] M. Raicopol, A. Prunǎ, C. Damian, L. Pilan, Functionalized single-walled carbon
nanotubes/polypyrrole composites for amperometric glucose biosensors,
Nanoscale Res. Lett. 8 (2013) 1–8.
[57] S. Viswanathan, C. Rani, J.A.A. Ho, Electrochemical immunosensor for
multiplexed detection of food-borne pathogens using nanocrystal bioconjugates
and MWCNT screen-printed electrode, Talanta 94 (2012) 315–319.
87
[58] S.H. Lee, J.H. Lim, J. Park, S. Hong, T.H. Park, Bioelectronic nose combined with
a microfluidic system for the detection of gaseous trimethylamine, Biosens.
Bioelectron. 71 (2015) 179–185.
[59] Y. Li, Y. Bai, G. Han, M. Li, Porous-reduced graphene oxide for fabricating an
amperometric acetylcholinesterase biosensor, Sens. Actuators B Chem. 185
(2013) 706–712.
[60] R. Xue, T.-F. Kang, L.-P. Lu, S.-Y. Cheng, Electrochemical sensor based on the
graphene-nafion matrix for sensitive determination of organophosphorus
pesticides, Anal. Lett. 46 (2013) 131–141.
[61] O.-M. Istrate, L. Rotariu, C. Bala, Electrochemical determination of NADH using
screen printed carbon electrodes modified with reduced graphene oxide and
poly(allylamine hydrochloride), Microchim Acta (2015) 1–9.
[62] L. Zhang, L. Long, W. Zhang, D. Du, Y. Lin, Study of inhibition, reactivation and
aging processes of pesticides using graphene nanosheets/gold nanoparticles-
based acetylcholinesterase biosensor, Electroanalysis 24 (2012) 1745–1750.
[63] L. Yang, G. Wang, Y. Liu, An acetylcholinesterase biosensor based on platinum
nanoparticles–carboxylic graphene–nafion-modified electrode for detection of
pesticides, Anal. Biochem. 437 (2013) 144–149.
[64] L. Yang, G. Wang, Y. Liu, M. Wang, Development of a biosensor based on
immobilization of acetylcholinesterase on NiO nanoparticles–carboxylic
graphene–nafion modified electrode for detection of pesticides, Talanta 113
(2013) 135–141.
[65] P. Nayak, B. Anbarasan, S. Ramaprabhu, Fabrication of organophosphorus
biosensor using ZnO nanoparticle-decorated carbon nanotube–graphene hybrid
composite prepared by a novel green technique, J. Phys. Chem. C 117 (2013)
13202–13209.
[66] S. Srivastava, M.A. Ali, S. Umrao, U.K. Parashar, A. Srivastava, G. Sumana, et al.,
Graphene oxide-based biosensor for food toxin detection, Appl. Biochem.
Biotechnol. 174 (2014) 960–970.
[67] Z. Linting, L. Ruiyi, L. Zaijun, X. Qianfang, F. Yinjun, L. Junkang, An immunosensor
for ultrasensitive detection of aflatoxin B 1 with an enhanced electrochemical
performance based on graphene/conducting polymer/gold nanoparticles/the
ionic liquid composite film on modified gold electrode with electrodeposition,
Sens. Actuators B Chem. 174 (2012) 359–365.
[68] M.M. Barsan, K.P. Prathish, X. Sun, C.M.A. Brett, Nitrogen doped graphene and
its derivatives as sensors and efficient direct electron transfer platform for
enzyme biosensors, Sens. Actuators B Chem. 203 (2014) 579–587.
[69] X. Luo, Z. Qiu, Q. Wan, H. Shu, N. Yang, Graphene nanoplatelets and horseradish
peroxidase based biosensor, Phys. Status Solidi A 211 (2014) 2795–2800.
[70] X. Chen, Z. Cai, Z. Huang, M. Oyama, Y. Jiang, X. Chen, Ultrafine palladium
nanoparticles grown on graphene nanosheets for enhanced electrochemical
sensing of hydrogen peroxide, Electrochim. Acta 97 (2013) 398–403.
[71] C. Yu, L. Wang, W. Li, C. Zhu, N. Bao, H. Gu, Detection of cellular H2O2 in living
cells based on horseradish peroxidase at the interface of Au nanoparticles
decorated graphene oxide, Sens. Actuators B Chem. 211 (2015) 17–24.
[72] A.-X. Zheng, Z.-X. Cong, J.-R. Wang, J. Li, H.-H. Yang, G.-N. Chen, Highly-efficient
peroxidase-like catalytic activity of graphene dots for biosensing, Biosens.
Bioelectron. 49 (2013) 519–524.
[73] J. Jiang, W. Fan, X. Du, Nitrite electrochemical biosensing based on coupled
graphene and gold nanoparticles, Biosens. Bioelectron. 51 (2014) 343–348.
[74] Y. Wang, H. Ma, X. Wang, X. Pang, D. Wu, B. Du, et al., Novel signal amplification
strategy for ultrasensitive sandwich-type electrochemical immunosensor
employing Pd-Fe3O4-GS as the matrix and SiO2 as the label, Biosens. Bioelectron.
74 (2015) 59–65.
[75] R.M. Kestwal, D. Bagal-Kestwal, B.H. Chiang, Fenugreek hydrogel-agarose
composite entrapped gold nanoparticles for acetylcholinesterase based
biosensor for carbamates detection, Anal. Chim. Acta 886 (2015) 143–150.
[76] S. Azzouzi, L. Rotariu, A.M. Benito, W.K. Maser, M. Ben Ali, C. Bala, A novel
amperometric biosensor based on gold nanoparticles anchored on reduced
graphene oxide for sensitive detection of l-lactate tumor biomarker, Biosens.
Bioelectron. 69 (2015) 280–286.
[77] A.A. Volkert, A.J. Haes, Advancements in nanosensors using plastic antibodies,
Analyst 139 (2013) 21–31.
[78] L. Chen, S. Xu, J. Li, Recent advances in molecular imprinting technology: current
status, challenges and highlighted applications, Chem. Soc. Rev. 40 (2011)
2922–2942.
[79] X. Ding, B. Srinivasan, S. Tung, Development and applications of portable
biosensors, J. Lab. Autom. 20 (2015) 365–389.
[80] L. Drechsel, M. Schulz, F. Von Stetten, C. Moldovan, R. Zengerle, N. Paust,
Electrochemical pesticide detection with AutoDip – a portable platform for
automation of crude sample analyses, Lab Chip 15 (2015) 704–710.
[81] M.D. Steinberg, P. Kassal, I. Kerekovic, I.M. Steinberg, A wireless potentiostat
for mobile chemical sensing and biosensing, Talanta 143 (2015) 178–183.
[82] B.S. Kim, G.W. Kim, N.S. Heo, M.S. Kim, K.S. Yang, S.Y. Lee, et al., Development
of a portable biosensor system for pesticide detection on a metal chip surface
integrated with wireless communication, Food Sci. Biotechnol. 24 (2015)
743–750.
[83] J.P. Meneely, C.T. Elliott, Rapid surface plasmon resonance immunoassays for
the determination of mycotoxins in cereals and cereal-based food products,
World Mycotoxin J. 7 (2014) 491–505.
[84] T.F. McGrath, L. McClintock, J.S. Dunn, G.M. Husar, M.J. Lochhead, R.W. Sarver,
et al., Development of a rapid multiplexed assay for the direct screening of
antimicrobial residues in raw milk, Anal. Bioanal. Chem. 407 (2015) 4459–
4472.