Polymer 177 (2019) 73–83

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Selective 2,4-dichlorophenoxyacetic acid optosensor employing a T

polyethersulfone nanofiber-coated fluorescent molecularly imprinted
polymer
Nargess Yousefi Limaeea, Shohre Rouhanib,c,∗, Mohammad Ebrahim Olyaa, Farhood Najafid
a
Department of Environmental Research, Institute for Color Science and Technology, Tehran, Iran
b
Department of Organic Colorants, Institute for Color Science and Technology, Tehran, Iran
c
Center of Excellence for Color Science and Technology (CECST), Institute for Color Science and Technology, Tehran, Iran
d
Department of Resin and Additives, Institute for Color Science and Technology, Tehran, Iran

H I GH L IG H T S

• Novel MIP based fluorescent optosensor was prepared on the PES nanofiber surface.
• The rapid UV curable fluorescence MIP was prepared via free radical polymerization.
• Magnetic PES nanofiber@FMIP was prepared on the surface of magnetic PES nanofibers.
• The −7 −3
optosensor has linear range of 1 × 10 -10 M and limit of detection 1.01 × 10 M. −8

• Adsorption of 2,4-D on nanofiber@FMIP and nanofiber@FNIP obey Freundlich isotherm.

A R T I C LE I N FO A B S T R A C T

Keywords: In the present study, a fluorescent optosensor containing a molecularly imprinted polymer in combination with
Fluorescent optosensor electrospinning was employed for selective recognition of 2,4-dichlorophenoxyacetic acid (2,4-D). Free radical
Surface fluorescence MIP polymerization was carried out on the surface of polyethersulfone (PES) nanofibers as a substrate using a
1,8-Naphthalimide monomer, initiator, template and a polymerizable 1,8-naphthalimide derivative as the fluorogenic monomer.
Polyethersulfone
PES nanofiber@fluorescent molecularly imprinted polymer (PES nanofiber@FMIP) was produced by means of
2,4-Dichlorophenoxyacetic acid
UV curing. The magnetic PES nanofiber@FMIP was developed in the same manner as the magnetic Fe3O4 na-
noparticles were exerted in the electrospinning of the PES nanofiber. The imprinting factor (IF) was considered
1.97 as a selective character of PES nanofiber@FMIP versus PES nanofiber@FNIP. The developed sensor was
able to selectively determine 2,4-D in a linear range of 1 × 10−7-1 × 10−3 M with limit of detection (LOD) of
1.01 × 10−8 M. The results confirmed that PES nanofiber@FMIP was satisfactorily able to determine trace
concentrations of 2,4-D.

1. Introduction investigated fluorescent MIP sensors [10–14]. Two essential approaches

Molecularly imprinted polymers (MIPs) are a lock-key technique for
specific recognition of molecules in drug delivery, separation, chemical
and bio sensing and purification of pollutants in wastewater [1,2]. MIPs
are produced as nanoparticles in bulk or formed as film, coatings or
fibers [3–7]. In recent years, MIP-based sensors have been applied to
recognize target analytes because of their high selectivity, rapidity, low
cost and strong affinity [8,9]. Fluorescence technique is significant
because of its high sensitivity for trace detection. Few studies have
have been developed for optical detection in MIP-based sensors. Direct
detection that the analyte is essentially fluorescent and its optical
characteristics change upon binding to the polymer base, leading to
qualitative and quantitative detection of shifts in fluorescence intensity
of MIPs [15–19]. Indirect detection includes; a) the application of a
labeled template or use of displacement experiments of analogue de-
rivatives [20–22], b) synthesis and application of a fluorescent func-
tional monomer in MIP preparations to monitor changes in fluorescence
intensity caused when binding to an analyte [10,11,23–27] and c)

∗
Corresponding author. Address: Department of Organic Colorants, Institute for Color Science and Technology, No. 55, Vafamanesh St., Lavizan Exit, Sayad Shirazi
North HWY, Tehran, Iran.
E-mail address: rouhani@icrc.ac.ir (S. Rouhani).

https://doi.org/10.1016/j.polymer.2019.05.067
Received 13 March 2019; Received in revised form 20 May 2019; Accepted 26 May 2019
Available online 28 May 2019
0032-3861/ © 2019 Elsevier Ltd. All rights reserved.
N.Y. Limaee, et al.
embedding of organic fluorescent indicators [28] or QDs [29–31] in
MIPs to determine changes in the fluorescence signal.
The use of fluorescent functional monomers is one detection
methods in MIP-based fluorescence sensors. Different fluorescent
functional monomers, including 7-allyloxycoumarin [24], ally fluor-
escein [25], disulfonated pyrenedimethacrylamide [32], 8-hydro-
xyquinoline [33], and 1,8- naphthalimide [10,11] have been applied to
prepare the fluorescent MIP sensors. The 1,8-naphthalimide based
functional monomer is considered as a building block for fluorescent
sensors because it offers good stability, emits strong fluorescence for
analytes, has a high fluorescence quantum yield and is easy to modify
[10,12,34–36].
One challenge to preparing sensors is increasing the accuracy and
speed of response in optical detection. Accordingly, a combination of
nanotechnology and fluorescent MIPs (FMIPs) for use as sensors seems
to be an effective method. Electrospinning is a unique and effective
technique for producing a nanofiber mat. Electrospun nanofiber mats
are used for different applications because of their simplicity and high
performance. Moreover, it offers high porosity, a high specific surface
area and good mechanical strength [37,38].
MIP formation on the surface of a nanofiber offers several ad-
vantages over traditionally imprinted materials, including a high spe-
cific surface area, high localization of molecular recognition sites, high
availability of imprinted sites, high tendency toward and sensitivity to
target analytes, fast absorption, easy template removal, high selectivity,
and rapid response. Because imprinted cavities are situated at or close
to the surface of the fiber, nanofiber@MIP has more accessible binding
sites for target molecules [39,40].
Polyethersulfone (PES) is a biocompatible polymer which has good
environmental endurance, high thermal stability, appropriate chemical
and mechanical resistance, and biological stability [39,41,42]. It per-
forms well as microfiltration and ultrafiltration membranes [43], sup-
porting materials in metal-organic framework bioreactors [44], hemo-
dialysis [45], biomedical applications [46] and tissue engineering
scaffolds [47]. Moreover, it has been used as electrospun nanofibers in
the preparation of MIPs [48].
The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its deri-
vatives are extensively used globally. Different methods have been used
for detection and removal of 2,4-D. Some have used determination
techniques and classic analytical procedures (spectrophotometric
method, HPLC, GC) and others have been examined as removal
methods [49–54]. A literature survey indicates that there are few stu-
dies about the preparation of MIPs for 2,4-D recognition. Of these, some
have attempted MIP production by precipitation polymerization [55],
sol-gel method [56], coating on pencil electrode [57] and electrospun
polymer nanofibers [58]. Very few have been studied for development
of optical sensors for the determination of 2,4-D [59–61]. None of these
have attempted to apply of naphthalimide functional monomers for the
manufacture of optical sensors. Moreover, no studies have reported on
the preparation of UV curable surface MIP or magnetic PES nanofiber@
FMIP as an easy and fast method for preparation of nanostructure MIP
sensors.
In the current study, PES nanofibers and magnetic PES nanofibers
have been used as substrates for a novel FMIP that forms on the surface
of the nanofibers through UV curing. The common phenoxy herbicide
2,4-D was applied as a template. SEM, TEM, optical microscopy, AFM,
EDS, XRD, FTIR, DSC and TGA were used to characterize the synthe-
sized samples. The performance of fluorescence functional monomer
was surveyed in the liquid state and binding conditions in the PES
nanofiber@FMIP and PES nanofiber@FNIP, magnetic PES nanofiber@
FMIP, and magnetic PES nanofiber@FNIP. The Langmuir, Freundlich,
BET adsorption isotherms and Redlich Peterson models were applied to
study the adsorption property of prepared PES nanofiber@FMIP and
PES nanofiber@FNIP using HPLC equipment. The selectivity of the
prepared optosensor was examined for compounds with structures si-
milar to 2,4-D. Moreover, the applicability of the MIP based optosensor
74
Polymer 177 (2019) 73–83
was checked out for the determination of 2,4-D in water samples.
2. Experimental
2.1. Reagents and chemicals
Acenaphthene, allylamine, ethylenediamine, 4-nitrophenyl iso-
thiocyanate (Merck; Germany) were applied for synthesis of the fluor-
escent functional monomer. Methacrylic acid (MAA), ethylene glycol
dimethacrylate (EGDMA) and tetrabutylammonium hydroxide (TBAH)
(Merck; Germany) were used for the preparation of the MIPs and NIPs.
Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure 819) was
employed as the initiator of free radical polymerization (Aldrich;
Germany) and 2,4-D was used as the template (EXIR; Austria). PES was
used to prepare the nanofibers (BASF; Germany). Benzoic acid, Benzyl
acetate and 4-chloro-2-methylphenoxyacetic acid (MCPA) were used as
competitors for selectivity experiments (Aldrich; Germany). All solvents
(ethanol, methanol, acetic acid, acetonitrile, N,N-dimethylacetamide,
dimethylformamide (DMF), and chloroform) were of analytical grade
and were obtained from Merck.
2.2. Equipments
The fluorescence spectra were recorded with a Perkin-Elmer LS55
fluorescence spectrophotometer (USA). The FTIR spectra were recorded
on a Perkin-Elmer Spectrum One spectrometer (USA) using KBr pellets.
A lab-scale electrospinning machine (Fanavaran Nano Meghyas; Iran)
was used to prepare the nanofibers. The surface morphology and
roughness of the fibers were studied by atomic force microscopy (AFM;
DME C-26 dual scope; Denmark). Scanning electron microscopy (SEM;
LEO 1455VP-UK; Germany) was used for morphological studies.
Energy-dispersive x-ray spectroscopy (EDX; Oxford Instruments; X-Max
80; UK) was applied for characterization and analysis of the magnetic
sample. Polarized optical microscope (Bel Photonics; Italy) was used for
morphological and optical studies. Transmission electron microscopy
(TEM) was performed on a Philips CM 120 (the Netherlands).
Thermogravimetric analysis (TGA) was done on a thermogravi-
metric analyzer (Perkins Elmer; Pyris Diamond TG/DTA; USA) under a
nitrogen atmosphere at a heating rate of 10 °C min−1 from room tem-
perature to 800 °C. A differential scanning calorimeter (DSC; 214
Polyma; Netzsch; Germany) was applied at a rate of 5 °C min−1 from
25 °C to 450 °C. X-ray diffractometry (XRD; Philips PW 1730; the
Netherlands) was performed to study the structure of the nano-Fe3O4. A
UV curing system (RW-UV.2BP; China) was applied to perform poly-
merization on the surface of the fiber.
The 2,4-D concentration measurements were performed using HPLC
(Knauer-101896-Germany) with software (ChromGate Client/Server
(version 3.1.7) with a UV detector (UV-2500) and Eclipse XDB C18
column (150 × 4.6 mm, 5 μm particle size). A mixture of water/acet-
onitrile was used as the mobile phase (30:70 v/v), (flow rate −1.0 mL/
min) in isocratic elution mode and wavelength of 220 nm was used for
the detection.
2.3. Synthesis of Fe3O4 nanoparticle
Magnetic iron oxide (Fe3O4) nanoparticles were synthesized by an
innovative modified co-precipitation method using oleic acid as a sur-
factant to prevent the growth of nanoparticles [62–64]. For their pre-
paration, FeCl2.4H2O and FeCl3.6H2O with molar ratios of 1:3 with
0.1% v/v oleic acid were added to deionized water and stirred at heater
stirrer at 70 °C. Ammonium hydroxide solution was added dropwise to
the mixture until chemical precipitation occurred at a pH of 10 and the
solution color turned black. After 1 h, the Fe3O4 nanoparticles were
washed several times with ethanol and deionized water followed by
magnetic precipitation. The nanoparticles then were dried at 50 °C for
24 h.
N.Y. Limaee, et al.
2.4. Preparation of nanofiber
A PES nanofiber mat was prepared by electrospinning under optima
conditions as described below. The PES was dissolved in N,N-di-
methylacetamide (29% w/w) using ultrasonic for 15 min followed by
stirring for 24 h until a homogeneous solution was obtained. A 5 mL
syringe was filled with the PES solution and was electrospun on an
aluminum foil wrapper in a cylindrical rotating drum located a distance
of 17 cm from the needle tip. The voltage at 18 kV and a flow rate of
1 ml/h was applied as the optimum condition for preparation of the PES
nanofiber mat.
2.5. Preparation of magnetic nanofiber
In order to prepare the magnetic PES nanofiber mat, PES was dis-
solved in N,N-dimethylacetamide (28% w/w) using ultrasound for
15 min followed by stirring for 24 h until a homogeneous solution was
obtained. Then the Fe3O4 nanoparticles (2% w/v) were added to the
PES solution and stirred for and additional 2 h. A 5 mL syringe was
filled with this solution and electrospinning was carried out on an
aluminum foil wrapper in a cylindrical rotating drum located a distance
of 17 cm from the needle tip. A voltage of 18 kV and a flow rate of 1 ml/
h was applied as the optimum condition for preparation of the magnetic
PES nanofiber mat.
2.6. Preparation of FMIP on the surface of nanofiber
N-allyl-4-amino-substituted 1,8-naphthalimide dye containing
thiourea functional groups was synthesized as a fluorescence monomer
from acenaphthene as the starting material in five steps, as described in
the literature [36,65–67]. The structure of naphthalimide monomer
dye, 2,4-D and three competitor (benzoic acid, benzyl acetate and
MCPA) are shown in schemes 1(a) and 1(b).
For the preparation of PES nanofiber@FMIP, 1 mmol 2,4-D/TBAH
as the template and 0.1 mmol naphthalimide dye were dissolved in a
mixture of 6 mmol MAA and 18 mmol EGDMA by stirring for 2 h. Next,
3% w/w Irgacure 819 was added to the mixture and was stirred for
another 1 h. Then, the prepared mixture was sprayed on 0.2 g of PES
nanofiber and the surface of molecularly imprinted PES nanofiber was
processed by crosslinking in UV curing equipment for 30 s. The free
radicals produced from Irgacure 819 by UV irradiation initiated radical
Scheme 1. Structure of a) fluorescence polymerizable naphtalimide dye and b)
2,4-D, benzoic acid, benzyl acetate and MCPA.
75
Polymer 177 (2019) 73–83
addition polymerization on the acrylate units and created a 3D net-
work. In order to remove remains of the monomers, the template and
the excess dye, the polymers were extracted in a soxhlet apparatus
using a mixture of methanol-acetic acid (9:1, v/v) for 24 h until no
more 2,4-D was detected by HPLC. PES nanofiber@non-imprinted
polymer (PES nanofiber@NIP) was synthesized under the same condi-
tions without the addition of a template.
2.7. Evaluation of binding ability and selectivity
Adsorption experiments were conducted using different concentra-
tions of 2,4-D/TBAH (5, 10, 20, 30, 40 and 50 mg L−1). After attaining
equilibrium, the concentration of the 2,4-D/TBAH solutions were de-
termined and the adsorption capacity of the prepared FMIP and FNIP
(Qe) were acquired using Qe=((C0–Ce)*V)/M, where C0 (mg L−1) and
Ce (mg L−1) are the 2,4-D/TBAH solution concentration at time zero
and equilibrium, respectively. V (L) is the solution volume and M (g) is
the mass of applied FMIP or FNIP in the adsorption experiments
[68,69].
In order to estimate the properties of the selectivity of the prepared
FMIP and FNIP versus 2,4-D/TBAH, three competitor molecules (ben-
zoic acid, benzyl acetate and MCPA) were chosen as compounds having
similar chemical structures. The fluorescence intensity of FMIPs and
FNIPs were determined for 2,4-D, benzyl acetate, benzoic acid and
MCPA. The change in the ratio of fluorescence intensity was determined
as ΔF/F0= ((F0–F)/F0, where F0 and F are the fluorescence intensity of
the samples before and after exposure to the analyte, respectively
[11,12].
The imprinting factor (IF) was attained as IF = QMIP/QNIP to esti-
mate the selective characteristics of the PES nanofiber@FMIP against
PES nanofiber@FNIP, where QMIP and QNIP are the adsorption capacity
of the PES nanofiner@FMIP and PES nanofiber@FNIP, respectively
[10,39].
3. Results and discussion
3.1. Characterization
3.1.1. Surface morphology and structural characteristic
The surface morphologies of the PES nanofiber, PES nanofiber@
FNIP and PES nanofiber@FMIP (before and after template extraction)
were observed by SEM and the results are shown in Fig. 1(a–d).
Fig. 1(a) confirms the preparation of nano-sized PES fiber. Fig. 1(b) and
(c) show that crosslinking was occurred on the surface of the nanofiber
and the morphological differences between PES nanofiber@FNIP and
PES nanofiber@FMIP are evident. Fig. 1(d) shows the PES nanofiber@
FMIP after template extraction. This figure shows the leaching of the
template and apparent extra polymers from the surface of PES nano-
fiber@FMIP. The change in the optical behavior of PES nanofiber@
FMIP was examined under an optical microscope before and after UV
irradiation. The change in fluorescence of the sample was easily per-
ceived in the presence of UV light (Fig. 1(e) and (f)). Fig. 1(g) and (h)
show the TEM images of the PES nanofiber and PES nanofiber@FMIP,
respectively. The figures represent the preparation of nano-sized PES
fibers (Fig. 1(g)) and the formation of an acrylate polymer on the sur-
face of the PES nanofiber after UV curing (Fig. 1(h)). This figure also
confirms polymer crosslinking and MIP formation on the surface of the
PES nanofiber (Fig. 1(h)).
Fig. 2(a) and (b) show SEM images of Fe3O4 magnetic nanoparticles
and magnetic PES nanofibers. Fig. 2(a) shows the uniformly sized and
slightly agglomerated Fe3O4 nanoparticles and the efficient synthesis of
Fe3O4. Fig. 2(b) also shows the suitable distribution of Fe3O4 nano-
particles in the PES nanofiber. TEM images of the magnetic PES na-
nofiber (Fig. 2(c)) confirms the results shown in the SEM images and
indicates the presence and distribution of Fe3O4 nanoparticles on the
PES nanofibers. Fig. 2(d) shows the appropriate distribution of the
N.Y. Limaee, et al. Polymer 177 (2019) 73–83

Fig. 2. SEM images of a) Fe3O4 magnetic nanoparticles and b) magnetic PES

nanofiber, c) TEM images of magnetic PES nanofiber, and d, e) EDS analysis of
magnetic PES nanofiber.
Fig. 1. SEM images of a) PES nanofiber, b) PES nanofiber@FNIP, c, d) PES
nanofiber@FMIP (before and after 2,4-D extracting), e, f) Optical microscopy
images of nanfiber@FMIP (before and after UV light irradiation, g, h) TEM
images of PES nanofiber and PES nanofiber@FMIP.

Fe3O4 nanoparticles on the surface of the nanofibers using EDS and

confirms the observations in the TEM images. Fig. 2(e) shows the re-
sults of EDS and the presence of the Fe element along with C, O, and S.
Fig. 3 shows the results of XRD analysis, which supports the results
attained by EDS, as all the diffraction peaks agreed well with the pat-
tern of Fe3O4 (JCPDS-01-079-0417). The XRD pattern of the magnetic
PES nanofiber@FMIP resembles amorphous material which includes
some crystalline phases. The XRD pattern of the synthesized Fe3O4
nanoparticles is shown in Fig. 3(c) in which all the diffraction peaks fit
the JCPDS-01-079-0417 pattern. This analysis confirms successful
synthesis of Fe3O4.
The surface morphologies of the PES nanofiber, PES nanofiber@
FNIP, and PES nanofiber@FMIP are shown in the 3-D AFM images.
Fig. 4 reveals that the roughness of the PES nanofiber@FNIP and PES
nanofiber@FMIP increased in comparison with the PES nanofiber. As
the FNIP formed on the surface of the PES nanofiber, the surface
roughness increased from 438 nm to 798 nm. Immobilization of FMIP
on the surface of the PES nanofiber produced a rougher surface
(846 nm).
The FTIR spectra of the materials (2,4-D, PES nanofiber, PES na-
nofiber@FMIP, extracted (PES nanofiber@FMIP) and PES nanofiber@
FNIP) were obtained to provide proof of imprinting of 2,4-D/TBAH
onto the PES nanofiber (Fig. 5). The FTIR spectrum of 2,4-D (Fig. 5(a))
indicates an aromatic C–H stretching vibration at 3070 cm−1 and ether
C–O stretching vibration at 1091 cm−1. The broadening of the band Fig. 3. The XRD pattern of a) magnetic PES nanofiber@FMIP, b) JCPDS-01-
from 2500 cm−1 to 3400 cm−1 is due to the carboxylic acid OH. When 079-0417 and c) Fe3O4 nanoparticles.
compared to the PES nanofiber (Fig. 5(b)), it can be seen in Fig. 5(c)
that new bands appear at 1724, 2960 and 3436 cm−1. The band at 819. Also, the band at 2960 cm−1 is caused by the C–H stretching vi-
1724 cm−1 corresponds to the stretching vibration of the carbonyl bration. The band at 3436 cm−1 is for the hydroxyl group of MAA. It is
group in the 2,4-D, naphthalimide dye, MAA, EGDMA and Irgacure interesting to note that the peak intensity of these three bands on

76
N.Y. Limaee, et al.
Fig. 4. AFM images of PES nanofiber, PES nanofiber@FNIP, and PES nanofiber@FMIP.
Fig. 5. FT-IR spectrum of a) 2,4-D, b) PES nanofiber, c) PES nanofiber@FMIP,
d) extracted (PES nanofiber@FMIP), e) PES nanofiber@FNIP.
nanofiber@FMIP (Fig. 5(c)) is higher than on extracted (PES nano-
fiber@FMIP) (Fig. 5(d)) and PES nanofiber@FNIP (Fig. 5(e)). More-
over, the peaks for the extracted (PES nanofiber@FMIP) and PES na-
nofiber@FNIP approximately fit each other. The results provide
evidence of MIP formation on the PES nanofiber surface and successful
removal of 2,4-D after extraction with methanol and acetic acid solu-
tion.
3.1.2. Thermal analysis
TGA was performed to estimate the thermal stability of the samples.
Fig. 6 shows that the PES nanofiber has a decrease at 100 °C that can be
attributed to the sample moisture and the weight loss of 2–3% is oc-
curred at 100–400 °C. Thermal degradation occurred at nearly 480 °C,
which can be ascribed to the decomposition of the polymeric main
chain of the PES nanofiber. The results indicate that the thermal sta-
bility of PES nanofiber@FNIP, PES nanofiber@FMIP and extracted PES
nanofiber@FMIP decreased after the addition of the weak structure of
the acrylate to the polyethersulfone structure having high thermal
stability. For PES nanofiber@FMIP, there is insignificant weight loss at
about 50–150 °C that can be attributed to free unreacted acrylate
monomers. Additional slight weight loss can be observed at about
150–320 °C because of slight structural decomposition and 2,4-D de-
gradation. Major degradation was observed at 320–450 °C. In the ex-
tracted PES nanofiber@FMIP, minor degradation was not observed due
77
Polymer 177 (2019) 73–83
Fig. 6. Thermogravimetric analysis (TGA) of PES nanofiber, PES nanofiber@
FMIP, extracted (PES nanofiber@FMIP) and PES nanofiber@FNIP.
to absence of 2,4-D. These results indicate that 2,4-D was successfully
removed by the methanol and acetic acid solution. In the PES nano-
fiber@FNIP sample, slight decomposition was observed up to 150 °C
that can be attributed to the destruction of free unreacted acrylate
monomers. The decrease at 320–450 °C is caused by structural de-
gradation.
The DSC thermograms of PES nanofibers (Fig. 7(a)) were compared
with those of PES nanofiber@FNIP (Fig. 7(b)) and PES nanofiber@FMIP
(Fig. 7(c)). The glass transition temperature (Tg) at 249.2 °C (Fig. 7(a))
can be attributed to PES nanofibers. For the PES nanofiber@FNIP, the
Tg at 156.2 °C is from the presence of naphthalimide monomer in
combination with MAA/EGDMA polymer. When 2,4-D entered the
polymer structure of PES nanofiber@FMIP, the strength of the polymer
increased in response to intermolecular interactions and hydrogen
bonding between the 2,4-D and polymer. The Tg at 325.8 °C can be
ascribed to changes in the polymer structure in the presence of 2,4-D.
3.2. Spectroscopic properties
One common mechanism for designing a probe is based on photo-
induced electron transfer (PET) which occurs by means of a fluor-
ophore-spacer-receptor format. N-substituted 1,8-naphthalimides is one
of the best chromophores for electron donor-acceptor interaction. The
interaction occurs between the electron donating substituent at position
C-4 and the carbonyl groups from the chromophoric section [70,71].
In this case, N-allyl-4-amino-substituted 1,8-naphthalimide dye
containing the thiourea functional group was chosen as a fluorescence
monomer. The N-allyl group operated as the reactive linker for the PES
nanofiber@FMIP matrix and 2-aminoethylene and thiourea at C4-po-
sition of the naphthalimde ring was responsible for the binding of the
analyte and fluorescence signaling. It is proposed that fluorescence
emission by the dye could be affected by hydrogen bond formation
between the hydrogen from the amino groups of the C-4 position of
naphthalimide and the oxygen from the carboxyl and hydroxyl groups
of the 2,4-D molecule (Scheme 2). We previously demonstrated the use
N.Y. Limaee, et al.
Fig. 7. DSC thermograms of a) PES nanofiber, b) PES nanofiber@FNIP and c) PES nanofiber@FMIP.
of the photoinduced electron transfer (PET) principle for the sensing of
anions using charge neutral anion receptors. These sensors comprised of
a fluorophore–spacer–receptor model where the fluorescence emission
was quenched upon anion recognition, due to enhanced PET from the
anion complexed receptor to the excited state of the fluorophore
[10,36,65,67].
It seems that the hydrogen band formation between 2,4-D molecule
and amino groups of dye pumped the electrons to naphthalimide ring.
We propose that this quenching process is due to the formation of the
anion-receptor hydrogen bonding complex resulted an increase in re-
duction potential of the receptor, making the electron transfer more
feasible. This subsequently gave rise to enhanced fluorescence
quenching.
3.2.1. Spectral characteristics of naphthalimide monomer against 2,4-D
The spectroscopic characterization of naphthalimide dye (10−5 M in
chloroform) shows the maximum excitation wavelength at 401 nm and
Scheme 2. Proposed mechanism for hydrogen bond interaction between fluorescence dye and 2,4-D.
78
Polymer 177 (2019) 73–83
a maximum emission wavelength at 498 nm.
In order to study the sensing behavior, changes in the fluorescence
emission of the naphthalimide monomer (10−5 M) were studied after
the addition of 2,4-D/TBAH (0–1 M). The fluorescence titration spectra
of the dye for different concentrations of 2,4-D/TBAH are presented in
Fig. 8(a). The results show that fluorescence emission by the dye is
quenched by the addition of 2,4-D/TBAH. The linear range for changes
in naphthalimide monomer fluorescence with the addition of 2,4-D/
TBAH is shown in Fig. 8(b). The limit of detection (LOD) was calculated
as 3.3 σ/S, where σ is the standard deviation of the y-intercept and S is
the slope of the calibration line. The results show that the naphthali-
mide monomer probe exhibited a linear range of 1 × 10−6-10−3 M
with a LOD of 5.11 × 10−8 M.
3.2.2. Spectral characteristics of PES nanofiber@FMIP against 2,4-D
The excitation and emission spectrum of PES nanofiber@FMIP is
compared with magnetic PES nanofiber@FMIP in Fig. 9. As seen, the
N.Y. Limaee, et al.
Fig. 8. a) Fluorescence changes of naphthalimide monomer (10−5 M) towards
2,4-D/TBAH (0–1 M), b) The fluorescence changes at λmax against the addition
of 2,4-D/TBAH (0-10−2 M) and linear range of the fluorescence change at
498 nm (maximum emission wavelength) in the presence of 2,4-D/TBAH.
Fig. 9. Excitation (ex) and emission (em) of PES nanofiber@FMIP (FMIP) and
magnetic PES nanofiber@FMIP (MFMIP).
maximum excitation and emission wavelength for PES nanofiber@
FMIP are 437 nm and 512 nm, respectively. While, the absorption and
emission spectra for magnetic PES nanofiber@FMIP took place at
417 nm and 511 nm, respectively.
In order to study the spectroscopic properties of the PES nanofiber@
FMIP against 2,4-D/TBAH, changes in the fluorescence spectra of the
PES nanofiber@FMIP were studied after the addition of 2,4-D/TBAH
(0–10−2 M).
Fig. 10(a) shows the quenching of fluorescence emission of PES
nanofiber@FMIP after the addition of 2,4-D/TBAH. Figs. 10(a) and 8(a)
can be used to compare the fluorescence intensity change ratio (ΔF/F0)
as the criterion of comparison of the ability of PES nanofiber@FMIP to
79
Polymer 177 (2019) 73–83
Fig. 10. a) Fluorescence changes of PES nanofiber@FMIP towards 2,4-D/TBAH
(0-10−2 M), b) The fluorescence changes at λmax against the addition of 2,4-D/
TBAH (0-10−2 M) and linear range of the fluorescence change at 512 nm
(maximum emission wavelength) in the presence of 2,4-D/TBAH.
recognize 2,4-D versus its liquid state in the fluorescent functional
monomer. The results show that the value of ΔF/F0 increased for PES
nanofiber@FMIP to 0.8276 as the surface area in the nano-sized surface
MIP increased compared to 0.6933 for the fluorescent functional
monomer. The fluorescence changes of PES nanofiber@FMIP at λmax
against the addition of 2,4-D/TBAH and the linear range for changes in
fluorescence of the FMIP after 2,4-D/TBAH addition is presented in
Fig. 10(b). Moreover, the fluorescence dependence of PES nanofiber@
FMIP to 2,4-D/TBAH addition was studied by Stern-Volmer equation,
(F0/F)-1 = KSV[Q], where F0 and F are the fluorescence intensity at
time 0 and after exposure to the analyte, respectively. Also, [Q] is the
concentration of 2,4-D/TBAH as the quencher and KSV is the Stern-
Volmer constant. By plotting ((F0/F)-1) against [2,4-D/TBAH], a
straight line with the slop of 1900.8 M-1 was obtained which is equal to
KSV. The probe exhibited a linear range of 1 × 10−7-10−3 M with a
LOD of 1.01 × 10−8 M.
To determine the PES nanofiber@FMIP regeneration behavior, the
MIP was exposed to the template by shaking for 15 min. Next, the
template was extracted with methanol/acetic acid (9:1) by shaking for
15 min and the fluorescence intensity was recorded at all stages. As
shown in Fig. 11, the fluorescence of the PES nanofiber@FMIP de-
creased after the template exposure. After washing the 2,4-D from the
FMIP, the fluorescence intensity increased. In other words, the fluor-
escence intensity was restored approximately to that of the FMIP, which
indicates that the templates were removed from the recognition sites of
the FMIP. This was the result of the rapid adsorption and desorption
process that simplifies the application of FMIP in actual samples.
N.Y. Limaee, et al. Polymer 177 (2019) 73–83

FMIP. Evaluation of the fluorescence intensity change ratio (ΔF/F0) for

magnetic PES nanofiber@FMIP (0.7844) and PES nanofiber@FMIP
(0.8276) shows comparable values. The fluorescence changes of mag-
netic PES nanofiber@FMIP at λmax against the addition of 2,4-D/TBAH
and the linear range of fluorescence change for magnetic PES nano-
fiber@FMIP after addition of 2,4-D/TBAH is shown in Fig. 12(b).
Moreover, the Stern-Volmer constant (KSV) was obtained 1972 M−1 by
plotting ((F0/F)-1) against [2,4-D/TBAH]. As seen, the magnetic probe
exhibited a linear range of 5 × 10−7-10−3 M with a LOD of
1.27 × 10−8 M.

3.3. Selectivity

Fig. 11. Fluorescence changes of PES nanofiber@FMIP after 2,4-D/TBAH ex- The selectivity of PES nanofiber@FMIP and magnetic PES nano-
posure (10−3 M) and 2,4-D/TBAH removal. fiber@FMIP in the presence of benzoic acid, benzyl acetate and MCPA
was determined because the compounds have chemical structures si-
milar to 2,4-D. For this purpose, the fluorescence intensity of PES na-
3.2.3. Spectral characteristics of magnetic PES nanofiber@FMIP against
nofiber@FMIP, PES nanofiber@FNIP, magnetic PES nanofiber@FMIP
2,4-D
and magnetic PES nanofiber@FNIP were determined towards 2,4-D/
In order to investigate the effect of nano-Fe3O4 on the spectroscopic
TBAH, benzyl acetate, benzoic acid and MCPA (10−2 M). The change in
properties of magnetic PES nanofiber@FMIP in comparison to PES
the ratio of fluorescence intensity (ΔF/F0) was applied as a criterion for
nanofiber@FMIP, changes in the fluorescence spectra of the magnetic
the quenching value of the prepared FMIP. Fig. 13 showed the highest
PES nanofiber@FMIP were studied after the addition of 2,4-D/TBAH
value of ΔF/F0 was recorded by PES nanofiber@FMIP for 2,4-D/TBAH.
(0–10−2 M). Fig. 12(a) shows the quenching of fluorescence emissions
The value of ΔF/F0 for PES nanofiber@FMIP was 0.8276 for 2,4-D/
of magnetic PES nanofiber@FMIP as well as PES nanofiber@FMIP with
TBAH, versus 0.0696, 0.032 and 0.1027 for benzoic acid, benzyl acetate
the addition of 2,4-D/TBAH. As seen, there was a slight decrease in
and MCPA, respectively. Whereas, the value of ΔF/F0 for magnetic PES
fluorescence intensity of magnetic PES nanofiber@FMIP in comparison
nanofiber@FMIP was 0.7844 for 2,4-D/TBAH versus 0.0353, 0.1106
with PES nanofiber@FMIP (Fig. 10(a)) that can be attributed to the
and 0.1161 for benzoic acid, benzyl acetate and MCPA, respectively.
distribution of Fe3O4 nanoparticles in the magnetic PES nanofiber@

3.4. Binding characteristics and isotherm studies

To study the isotherm adsorption of 2,4-D/TBAH onto the PES na-

nofiber@FMIP and PES nanofiber@FNIP, different concentrations of
2,4-D/TBAH (5–50 ppm) was incubated for 2 h with 0.04 g of FMIP and
FNIP at room temperature. Afterwards, the adsorbent was filtered
through filter paper and the filtrate was analyzed by HPLC to determine
the isotherm constants. Accordingly, the Langmuir, Freundlich,
Brunauer, Emmett and Teller (BET), and Redlich–Petersen (R–P) ad-
sorption isotherms were fitted to the adsorption equilibrium data
[68,69]. Fig. 14 shows the adsorption isotherms of 2,4-D/TBAH onto
PES nanofiber@FMIP and PES nanofiber@FNIP. Besides, Table 1 lists
the adsorption constants. Table 1 shows the isotherm equations and
constants when adsorption of 2,4-D/TBAH onto FMIP and FNIP is fitted
to the Freundlich adsorption isotherm and expresses a heterogeneous
adsorbent surface with correlation coefficients of 0.9446 and 0.9399,

Fig. 12. a) Fluorescence changes of magnetic PES nanofiber@FMIP towards Fig. 13. The fluorescence intensity change ratio (ΔF/F0) of PES nanofiber@
2,4-D/TBAH (0-10−2 M), b) The fluorescence changes at λmax against the ad- FMIP (FMIP), PES nanofiber@FNIP (FNIP), magnetic PES nanofiber@FMIP
dition of 2,4-D/TBAH (0-10−2 M) and linear range of the fluorescence change (MFMIP), and magnetic PES nanofiber@FNIP (MFNIP) against different com-
at 511 nm (maximum emission wavelength) in the presence of 2,4-D/TBAH. pounds (10−2 M).

80
N.Y. Limaee, et al. Polymer 177 (2019) 73–83

Table 2
Results for the analysis of water samples.
Sample nanofiber@FMIP HPLC

Measured R (%) RSD (%) Measured R (%) RSD (%)

(ppm)a (ppm)a

Well water 20.72 103.6 3.1 19.31 96.55 4.1

Tap water 19.65 98.25 3.8 20.44 102.2 4.2
River water 21.13 105.65 4.4 20.86 104.3 3.6

a
Average (n = 5).

While, for the lower affinity site, Kd and Qmax were attained
19.92 mg L−1 and 0.851 mg g−1, respectively. By comparison, for FNIP,
Kd and Qmax at higher affinity site, were calculated 29.94 mg L−1 and
0.566 mg g−1, respectively. Besides, for lower affinity site, Kd and Qmax
were 24.272 mg L−1 and 0.449 mg g−1, respectively. The results in-
dicate a higher affinity for PES nanofiber@FMIP than PES nanofiber@
NIP.

3.5. Analysis of water samples

In order to assess the ability of PES nanofiber@FMIP to detect 2,4-D,

Fig. 14. a) Isotherm and b) scatchard plot for the adsorption of 2,4-D/TBAH on
PES nanofiber@FMIP and PES nanofiber@FNIP.
respectively [10]. The value of 1/n for PES nanofiber@FMIP and PES
nanofiber@FNIP was 0.9263 and 0.7174, respectively, indicating fa-
vorable adsorption. The adsorption capacities of FMIP and FNIP were
24.752 and 12.547 mg/g, respectively. The imprinting factor (PES na-
nofiber@FMIP/PES nanofiber@FNIP) was acquired 1.97, indicating
that FMIP possesses higher affinity to 2,4-D/TBAH than FNIP.
Scatchard plots were created to estimate binding affinity for PES
nanofiber@FMIP and PES nanofiber@FNIP. Fig. 14(b) reveals two
straight lines with different slopes for FMIP and FNIP that represent
heterogeneous affinity for high affinity and low affinity sites. The
equilibrium dissociation constant (Kd) and Qmax (maximum number of
binding sites) were calculated using the Scatchard equation as qe/Ce=
(Qmax/Kd)-(qe/Kd) [73,74]. For the higher affinity site of FMIP, Kd and
Qmax were obtained 40.984 mg L−1 and 1.213 mg g−1, respectively.
the water samples including well water, tap water and river water were
spiked with appropriate concentrations of 2,4-D/TBAH. The fluores-
cence intensity of PES nanofiber@FMIP and PES nanofiber@FNIP was
determined by adding 2,4-D/TBAH (20 ppm) as the average of five
replications and by HPLC analysis. The method was validated by de-
termining the recovery (%R) and relative standard deviation (RSD %).
As shown in Table 2, the results obtained by HPLC measurements were
in good agreement with the results of fluorescence measurements. Ac-
cording to the results, the values of recovery ± RSD for well water
were obtained 96.55 ± 4.1% and 103.6 ± 3.1% for HPLC and fluor-
escent measurement, respectively. This amount was attained
102.2 ± 4.2% and 98.25 ± 3.8% for tap water as well as
104.3 ± 3.6% and 105.65 ± 4.4% for river water (for HPLC and
fluorescent analysis), respectively. The results represented that the PES
nanofiber@FMIP could potentially applied for the determination of 2,4-
D in water samples.
4. Conclusions
The novel fluorescent molecularly imprinted polymer optosensor
was prepared by means of UV curing on the surface of polyethersulfone
nanofiber and was compared with its magnetic species. The magnetic
PES nanofiber@FMIP were obtained by inserting magnetic Fe3O4 na-
noparticles into the nanofiber by electrospinning. A polymerizable 1,8-
naphthalimide derivative was used as the indicator for selective re-
cognition of 2,4-D/TBAH. Morphological studies revealed the suc-
cessful synthesis of Fe3O4, PES nanofiber@FMIP and PES nanofiber@

Table 1
Linearised isotherm constants for the adsorption of 2,4-D/TBAH on PES nanofiber@FMIP and PES nanofiber@FNIP
Isotherms Adsorbent Parameters

Langmuir Ce
=
1
+
Ce Q0 (mg g−1) KL (L mg−1) RL R2
qe KL Q0 Q0
FMIP 24.752 9.16 × 10−4 0.956 0.8927
FNIP 12.547 5.89 × 10−4 0.971 0.8998
Freundlich log qe = log KF +
1
log Ce KF (mg g−1) (L mg−1)1/n 1/n R2
n
FMIP 0.0286 0.9263 0.9446
FNIP 0.0225 0.7174 0.9399
BET Ce
=
1
+
Kb − 1 Ce Kb qm (mg g−1) R2
(Cs − Ce ) q Kb qm Kb qm Cs FMIP 5.663 0.285 0.824
FNIP 5.207 0.284 0.6688
Redlich-Peterson C KR (L g −1) aR (L mg−1) β β R2
ln ⎡KR e − 1⎤ = ln aR + β ln Ce
⎣ qe ⎦ FMIP 0.038169 1.053798 1 0.7317
FNIP 0.014568 1.067838 1 0.8804

81
N.Y. Limaee, et al.
FNIP and its magnetic composition. The results obtained by FTIR, TGA
and DSC confirm the successful preparation of PES nanofiber@FMIP
and PES nanofiber@FNIP. The sensing behavior of PES nanofiber@
FMIP and magnetic PES nanofiber@FMIP was studied as well as
fluorescent monomer-dye indicating switch off in fluorescence emission
for all of them. In addition, the fluorescence intensity change ratio (ΔF/
F0) was determined to compare the ability of PES nanofiber@FMIP and
magnetic PES nanofiber@FMIP for the recognition of 2,4-D/TBAH in
comparison to fluorescent functional monomer. The results showed that
the amount of ΔF/F0 was obtained 0.8276 for PES nanofiber@FMIP
comparing to 0.7844 and 0.6933 for magnetic PES nanofiber@FMIP
and fluorescent functional monomer, respectively. The linear range of
PES nanofiber@FMIP and magnetic PES nanofiber@FMIP for the de-
termination of 2,4-D/TBAH was 1 × 10−7-10−3 M and 5 × 10−7-
10−3 M with LOD of 1.01 × 10−8 M and 1.27 × 10−8 M, respectively.
The selectivity of PES nanofiber@FMIP and magnetic PES nanofiber@
FMIP was investigated in the presence of benzoic acid, benzyl acetate
and MCPA as the compounds with similar chemical structure to 2,4-D.
The values of ΔF/F0 was represented the appropriate selectivity against
2,4-D/TBAH. Moreover, the adsorption of 2,4-D/TBAH onto PES na-
nofiber@FMIP and PES nanofiber@FNIP was ascertained and indicated
that the results were in a good fit to the Freundlich adsorption isotherm.
The sensing principles of PES nanofiber@FMIP optosensor was suc-
cessfully performed using different water samples.
Acknowledgements
We would like to appreciate the of Center for Excellence for Color
Science and Technology and Institute for Color Science and Technology
for providing us a good environment and facilities.
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