A novel turn off fluorescent sensor for Fe(III) and pH environment based on coumarin derivatives: the fluorescence characteristics and theoretical study

Article abstract of DOI:10.1016/j.tet.2016.08.023

In this work, a novel coumarin fluorescent sensor for Fe³⁺and the pH change in DMSO was successfully prepared, and the spectra properties of the sensor a and especially its activity to metal ions, were also investigated This sensor showed an extreme selectivity and sensitivity to Fe³⁺compared with other competing metal ions through fluorescence quenching in DMSO, which formed a 2:1 complex with Fe³⁺and displayed fluorescent quenching. Furthermore, the binding mechanism was studied by the binding stoichiometry and DFT calculation, and the quenching mechanism was also confirmed by Mulliken's charge distribution which was calculated by quantum chemistry.

Full text of DOI:10.1016/j.tet.2016.08.023

Accepted Manuscript
A novel turn off fluorescent sensor for Fe(III) and pH environment based on coumarin
derivatives: the fluorescence characteristics and theoretical study
Chao-jun Hua, Hao Zheng, Kan Zhang, Ming Xin, Jian-rong Gao, Yu-jin Li
PII:
S0040-4020(16)30788-8
10.1016/j.tet.2016.08.023
TET 28004
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 18 May 2016
Revised Date: 6 August 2016
Accepted Date: 9 August 2016
Please cite this article as: Hua C-j, Zheng H, Zhang K, Xin M, Gao J-r, Li Y-j, A novel turn off fluorescent
sensor for Fe(III) and pH environment based on coumarin derivatives: the fluorescence characteristics
and theoretical study, Tetrahedron (2016), doi: 10.1016/j.tet.2016.08.023.
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ACCEPTED MANUSCRIPT
A novel turn off coumarin fluorescent sensor for Fe(ꢀ) and
pH environment
a
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of
Technology, Hangzhou 310014, People’s Republic of China
ABSTRACT
In this work, a novel coumarin fluorescent sensor for Fe3+ and the pH change in DMSO was
successfully prepared, and the spectra properties of the sensor a and especially its activity to metal
ions, were also investigated This sensor showed an extreme selectivity and sensitivity to Fe3+
compared with other competing metal ions through fluorescence quenching in DMSO, which
formed a 2:1 complex with Fe3+ and displayed fluorescent quenching. Furthermore, the binding
mechanism was studied by the binding stoichiometry and DFT calculation, and the quenching
mechanism was also confirmed by Mulliken’s charge distribution which was calculated by
quantum chemistry.
1

ACCEPTED MANUSCRIPT
A novel turn off fluorescent sensor for Fe(ꢀ) and pH
environment based on coumarin derivatives: the fluorescence
characteristics and theoretical study
Chao-jun Hua, Hao Zheng, Kan Zhang, Ming Xin, Jian-rong Gao, Yu-jin Li*
a
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of
Technology, Hangzhou 310014,People's Republic of China
Corresponding authors.
E-mail addresses: lyjzjut@zjut.edu.cn (Y. Li).
Telephone number: +86-0571-88320891 (Y. Li).
ABSTRACT
In this work, a novel coumarin fluorescent sensor for Fe3+ and the pH change in
DMSO was successfully prepared, and the spectra properties of the sensor a and
especially its activity to metal ions, were also investigated This sensor showed an
extreme selectivity and sensitivity to Fe3+ compared with other competing metal ions
through fluorescence quenching in DMSO, which formed a 2:1 complex with Fe3+
and displayed fluorescent quenching. Furthermore, the binding mechanism was
studied by the binding stoichiometry and DFT calculation, and the quenching
mechanism was also confirmed by Mulliken’s charge distribution which was
calculated by quantum chemistry.
Keywords:
Fluorescent sensor, selectivity and sensitivity, coumarin, fluorescence quenching,
DFT calculation
1. Introduction
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With great potential of environmental1 and physiological applications, the
chemosensors for the selective detection of transition and heavy metal ions are very
important in various fields of chemical and biological science.2,3 Fluorescent
chemosensor for metal ions has received unprecedented attention4 because it is a
method that detects fluorescent signal with low cost and desirable real-time response
remains desirable. The response reflects a cumulative exposure to analyte.5,6
Fe3+ is an important transition metal ion in biological systems, and it plays
performs a major role in the growth and development of living systems as well as in
many biochemical processes at the cellular level.7,8 Its deficiency or overload will not
only induce some dysfunction of certain organs like the heart, pancreas, and liver, but
also lead to anemia, hemochromatosis, liver damage, diabetes, and Parkinson’s
disease.7 Therefore, the careful control of Fe3+ is of great importance.9 The traditional
techniques used to detect Fe3+ include FAAS (Flame Atomic Absorption
Spectrometry),10 CE (Capillary Electrophores).11 as well as ICP-AES (Inductively
Coupled Plasma-Atomic Emission Spectroscopy).12 However, fluorescent sensors
possess have more distinct advantages, which are easy operation, rapid response, low
cost, and real-time monitoring.9 In 2014 Li’s group7 reported a new fluorescence
chemosensor of “turn on” type for Fe3+ based on naphthalimide and coumarin. This
chemosensor exhibited high selectivity to Fe3+ compared with other ions with
fluorescence-enhancement in THF-H2O solution. Then in 2015, Han’s group13
proposed a new rhodamine-based chemosensor for the turn-on fluorescent detection
of Fe3+ with high sensitivity and selectivity in a H2O-CH3CN solution. This
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chemosensor was designed and synthesized using a double Schiff base condensation
between rhodamine B and 2-naphthylamine. In addition, Fan et al14 reported two
novel cell-permeable colorimetric and fluorescent off-on enantiomers based on the
rhodamine derivatives with selectivity and sensitively to Fe3+. However, the
literatures of Fe3+-selective “turn-off” chemosensors were scarcely reported.15
It is well known that intracellular pH plays an important role in modulating cell
growth16 and differentiation,17 enzyme18 and tissue functions,19 such as cell cycle
control,20 cellular proliferation21 and apoptosis,22 membrane potential23 and ion
regulation,24 muscle contraction23 and multidrug resistance (MDR).4 Abnormal pH
values are associated with inappropriate cell functions, growth, and division, which
can result in many serious human diseases.4 Therefore, a fluorescence sensor with
high selectivity and sensitivity, decreased response time as well as convenient local
observation fluorescence sensor is badly needed.25
To the best of our work, there were really few probes with two functions for both
metal ions and pH changes. In this paper we report a novel fluorescence “turn-off”
type sensor for not only Fe3+, but also the detection of pH environment was reported.
This sensor was synthesized by an efficient one-pot,and three-component synthesis
method based on the literature from Ahmed’ s group.26,27 There was a high quantum
yield fluorescence sensor21 that was quenched in alkaline environment or in Fe3+
environment. The fluorescence sensor showed three notable features: (1) the structure
was simple and the sensor was easy to be synthesized; (2) the detection of Fe3+ and
pH environment could be carried out in DMSO; (3) the selectivity and sensitivity
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compared to other competing metal ions were remarkable. Besides, the DFT and
TDDFT calculations were used to confirm the experimental results.
2. Experimental
2.1 Materials
4-aminocoumarins and 7-(2-hydroxyphenyl)-9,10,11,12-tetrahydro-6H-
chromeno[4,3-b]quinoline-6,8(7H)-dione was synthesized according to literature
procedures. All of the chemicals used in the current study were purchased from
commercial vendors and used as received without further purification, unless
otherwise noted. All solvents were purified and dried using standard methods prior to
use. The salts used in stock solutions of metal ions were AlCl3, FeCl3, CuCl2, CrCl2,
MgCl2, NiCl2, AgNO3, Zn(NO3)2 and HgCl2.
2.2 Instrumentation
Nuclear magnetic resonance (1H, 13C ) spectra were recorded on a Bruker AM 500
spectrometer (Bruker) with chemical shifts reported as ppm at 500, 125 MHz,
respectively (in DMSO and TMS as the internal standard). Fluorescence spectra were
obtained with a F-7000 Fluorescence Spectrophotometer in a solution of 100 µM.
UV-Vis absorption spectra were measured on a UV-2550.
2.3 Preparation of raw materials and product
(a) Synthesis of 4-aminocoumarins26
A mixture of well powdered 4-hydroxycoumarin (1.07 g, 0.0066 mol) and ammonium
acetate (7.87 g, 0.100 mol) was melted in an oil bath (max. 130 ºС ) and stirred for 3 h.
After cooling to ambient temperature, water was added and the crude product was
isolated as yellow crystals by simple filtration. 4-aminocoumarin was obtained by
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recrystallized from EtOH and water as yellow crystals (0.98 g, 92.2%). General
Procedure for the Synthesis of compound sensor a.
(b)7-(2-hydroxyphenyl)-9,10,11,12-tetrahydro-6H-chromeno[4,3-b]quinoline-6,8(
7H)-dione26
A mixture of salicylaldehyde (0.12gꢁ1 mmol), 1,3-cyclohexanedione (0.112 g , 1
mmol) and 4-aminocoumarin(0.161g, 1 mmol) in acetic acid (6 mL) was stirred for
2-3 h at 110 ꢂand complete reaction was detected by TLC analysis and then cooled
to room temperature. Then, The reaction mixture was washed with H2O (20 ml) and
the crude product was recrystallized from DMSO to give product 0.873 mmol (0.231
g, 87.3%) as light yellow solid.
2.4 Characterization of probes
Yellow solid. Yield 87.3%. Mp 338-340 ꢂ.1H-NMR (DMSO,500 MHz) δ (ppm):
9.87 (s, 1H), 9.29 (s, 1H), 8.35 (dd, J1=1 Hz, J2=8 Hz, 1H), 7.63-7.67 (m, 1H),
7.44-7.48 (m, 1H), 7.40 (dd, J1=1 Hz, J2=8.5 Hz, 1H), 6.94-7.00 (m,2H), 6.65-6.69 (m,
2H), 5.04 (s, 1H), 2.78-2.83 (m,1H), 2.65-2.72 (m,1H), 2.27-2.39 (m,2H), 1.96-2.01
(m, 1H), 1.79-1.83 (m,1H). 13C NMR (DMSO, 125 MHz) δ (ppm): 196.75 (1C),
160.40 (1C), 154.39 (1C), 153.19 (1C),151.99 (1C), 142.65 (1C), 132.12 (1C), 131.89
(1C), 129.76 (1C), 127.42 (1C), 123.98 (1C), 122.89 (1C), 119.35 (1C), 116.85 (1C),
116.73 (1C), 112.97 (1C), 111.23 (1C), 101.27 (1C), 36.36 (1C), 30.15 (1C), 26.47
(1C), 20.49 (1C). HRMS (ESI-TOF) m/z Calcd for C22H17O4N, [M + H]+ 360.1231, found
360.1241ꢁ[M + Na]+ 382.1050, found 382.1063.
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2.5 Computational methodology
All the structure optimization were based on density functional theory (DFT) with
B3LYP functional and 6-31G basis set. It was calculated with the time-dependent
density functional theory (TDDFT) for the fluorescence emission wavelength and the
excitation wavelength of the compounds. All these calculations were performed with
Gaussian 09W.28
3. Results and discussion
3.1 Synthesis
As shown in Scheme 1, the coumarin fused dihydropyridine derivatives sensor a was
synthesized
by
the
efficient
three-component
reaction
of
1,3-cyclohexadione , salicylaldehyde and 4-Aminocoumarin.
1
This compound was characterized by H-NMR , 13C-NMR and HRMS. Pure
product was obtained in 87.3% yield after crystallization.
Scheme 1. Synthesis of sensor a.
3.2 Fluorescence detection
3.2.1 The solvent selection of sensor a
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The solvent effect on the absorption and fluorescence properties of sensor a was
examined (Fig. 1). As displayed in Fig. 1, sensor a showed a maximum sharp
absorption peak at approximately 275 nm along with a shoulder peak at about 308 and
375 nm, and it was barely affected by the solvent polarity. Meanwhile, the molar
absorption coefficient (ε) of sensor a did not have any obvious changes in different
organic solvents.
The maximum absorption peak (λmax) of sensor a emerged at about 375 nm.
Obviously, the sensor a showed the fluorescence emission wavelength at 438 nm with
375 nm as the excitation wavelength in the different organic solvent, excepted the
slight red shift in DMSO (448 nm). It is noteworthy that the fluorescence intensity of
the sensor a was much higher in DMSO than in other solvent because sensor a was
more soluble in DMSO. Thus, the high fluorescence quantum yields in DMSO could
be anticipated, and DMSO was selected as its best solvent. Therefore, the Stokes shift
was 63 nm in DMSO.
Fig. 1. Left: Absorption spectra of compound sensor a (1.0×10-6 mol/L) in different Solution
(PMT Voltage: 900 V). Right: Fluorescence emission spectra of sensor a (1.0×10-6 mol/L) in
different Solution (PMT Voltage: 400 V).
3.2.2 Fluorescence spectral properties of detecting Fe3+
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The photophysical characteristics of sensor a were investigated in DMSO after
several metal cations (Al3+, Fe3+, Cu2+, Zn2+, Cr3+, Ag+, Mg2+, Ni2+and Hg2+) were
added by UV-vis and fluorescence spectroscopy. Fig. 2 illustrated the absorption and
fluorescence response of sensor a to the above mentioned metal cations(1.0×10-6
mol/L). It should be noted that the absorption spectrum of sensor a displayed a red
shift from 375 nm to 465nm in the presence of Fe3+, while the absorption spectrum
(λabs=375 nm) did not show any obvious changes in the presence of other metal
cations . More interestingly, the fluorescence of sensor a was quenched due to the
presence of Fe3+ (see Fig. 2 and Fig. 3). which could be attributed to the formation of
metal-organic coordination clathrate between sensor a and Fe3+. In addition, by
confirming this phenomenon with the ions titration method and theoretical
calculations, it was found that both the theoretical and experimental results verified
the possible mode of interaction between sensor a and Fe3+. However, there was no
significant change in the fluorescence spectrum (λ FL = 450 nm) of sensor a with the
addition of other metal cations. With the addition of other metal cations the
fluorescence intensity of sensor a become a little weaker without fluorescence
quenching, because the addition of water made a few samples dissolve out. These
observations indicated that sensor a could be used as a turn-off chemosensor for Fe3+.
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Fig. 2. Left: the absorption spectra of sensor a (1.0×10-5 mol/L) in the presence of different metal
ions in the DMSO (PMT Voltage: 900 V). Right: The Fluorescence spectra of sensor a (1.0×10-5
mol/L) in the presence of different metal ions in the DMSO (PMT Voltage: 500 V).
Fig. 3. The sensor a (1.0×10-5 mol/L) under the UV lamp (365 nm) in the presence of different
metal ions in the DMSO.
3.2.3 Fluorescence spectral properties of detecting pH
As shown in Fig. 4, the UV-vis spectra of sensor a (1.0×10-5 mol/L, DMSO) exhibited
a maximum sharp absorption peak at approximately 308 nm as well as a shoulder
peak at about 375 nm, and they were barely affected by the solvent polarity when
pH≤7. As the pH value gradually increased from 7 to 14 in the solution, the maximum
absorption peak showed an obvious red shift which reached 466 nm. Meanwhile, it
was also observed that the color of the solution changed distinctly from colorlessness
to faint yellow with the change of the pH value, indicating that the color change could
be detected by naked eyes under visible light (see Fig. 4). Furthermore, the
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fluorescence spectra of the sensor a showed the maximum emission at 460 nm, and as
the pH value gradually increased from 1 to 7 in the solution, the fluorescence intensity
was obviously enhanced when pH≤7.However, it can be seen from Fig. 4 that with
the increase of the pH (pH>7), the fluorescence intensity decreased quickly until
quenching was achieved. Therefore, the absorption and emission properties could be
used to judge the pH value.
Fig. 4. Left: The absorption spectra of sensor a with different pH (1.0×10-5 mol/L) in DMSO
(PMT Voltage: 900 V). Right: Fluorescence emission spectra of sensor a (1.0×10-5 mol/L) with
different pH in DMSO (PMT Voltage: 500 V).
Fig. 5. Left: Sensor a (1.0×10-5 mol/L) under the visible light with different pH in DMSO. Right:
Sensor a (1.0×10-5 mol/L) under the UV lamp (365 nm) with different pH in DMSO.
3.3 Binding stoichiometry and sensing mechanism
A Job’s Plot was constructed to estimate the binding stoichiometry of sensor a and
Fe3+. The fluorescence spectra of sensor a with Fe3+ showed an emission maximum
peak nearly at 457 nm, and as the Fe3+ (1.0×10-6-1.0×10-5 mol/L) was gradually added
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to the solutions of sensor a the fluorescence spectra displayed a little red shift. Then
with the gradual titration of Fe3+ ion, the fluorescence intensity of sensor a decreased
quickly, and it was quenched completely with 5.0×10-6 mol/L Fe3+. When more Fe3+
was titrated, the fluorescence intensity showed negligible changes (see Fig. 6).
Moreover, a Job’s Plot showed a maximum at 0.66~0.67 M fraction of sensor a,
which indicated that only a 2:1 metal-ligand complex was formed between sensor a
and Fe3+ in DMSO (see Fig. 7). As result, it can be concluded that the formation of
the coordination between Fe3+ and sensor a resulted from the hydroxyl group in the
phenyl ring and the carbonyl group in the cyclohexane ring, suggesting that the
hydroxyl group and the carbonyl group were the binding sites. (see Scheme 2).
In addition, the sensing mechanism of pH was ascribed to the sensor a with
pH-sensitive functional group existing in two forms of different pH solutions: one was
the weak-fluorescent base form, and the other was the acid form. The equilibrium
between these two forms could be adjusted by changing the pH, which could be
attributed to the ionization of sensor a. (see Scheme 2). To further investigate the
1
sensing mechanism of pHꢁa comparison was made on the HNMR spectroscopy
between the sensor a in the neutral environment and that in the alkaline environment
1
(DMSO/D2O=9:1).( see Fig. 8). According to the HNMR spectroscopy, the sensor a
in the neutral environment showed the proton signals of hydroxide radical at 9.87 ppm
but disappeared in the alkaline environment. These observations indicated the
ionization of hydroxide radical, and generally support proposed sensing mechanism.
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Fig. 6. Fluorescence response of sensor a (1×10-5 mol/L) exposed to Fe3+ of various
concentrations: 1.0 ×10-6, 2.0 ×10-6, 3.0 ×10-6, 4.0 ×10-6, 5.0 ×10-6, 6.0 ×10-6, 7.0 ×10-6, 8.0
×10-6, 9.0×10-6, 1.0 ×10-5mol/L (from top to bottom). Inset shows fluorescence titration curve of
sensor a with Fe3+. These spectra were measured in DMSO solution. (PMT Voltage: 700 V)
Fig. 7. Job’s plot for determining the stoichiometry for sensor a ( λmax=457 nm) and Fe3+ in
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DMSO/water (9:1, v/v).Total concentration=1.0×10-5 M.
Scheme 2. The response mechanism of sensor a to Fe3+ and pH.
HN
O
O
O-
O
HN
O
O
OH
O
Fig. 8. 1H NMR spectra of sensor a and after addition of NaOH in DMSO/D2O (9:1, v/v)
An important property of the chemosensor is its high selectivity to the analyte
compared with other competing metal ions. Therefore, the fluorescence intensity of
sensor a at 455 nm was determined in the presence of various metal ions, including
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Al2+, Cu2+, Zn2+, Cr3+, Ag+, Mg2+, Ni2+, Hg2+ as well as Fe3+ 1.0×10-6 mol/L,
(
respectively).When Fe3+(1.0×10-6 mol/L) was introduced into sensor a in DMSO, the
bars exhibited fluorescence quenching.(see Fig. 8). These studies clearly suggested
that the chemosensor could be utilized for the selective detection of Fe3+ without the
interference from other metal ions.
Fig. 9. Fluorescence intensities of sensor a (1×10-5 mol/L) in the presence of various metal ions
and Fe3+ mixtures in DMSO. The red bars represent the emission intensities of sensor a in the
presence of different metal ions, the blue bars represent the emission intensities of sensor a in the
presence of different metal ions and Fe3+ (1 ꢀM) (λex=375 nm, λem=455 nm).
3.4 Theoretical calculation
3.4.1 Mechanism of detecting Fe3+
In order to get a deep insight into the mechanism of the “turn off” system for sensing
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“Fe3+”, the density functional theory (DFT) calculations as implemented in Gaussian
09W suits of the program employed the basis sets B3LYP/6-31G. Theoptimized
configuration of sensor a was displayed in Fig. 8, which showed that the Fe3+ion was
chelated through four coordination sites, which formed an energy minimized structure
of metal-organic coordination clathrate .
Fig. 10. Calculated energy-minimized structure of sensor a with Fe3+ by B3LYP/6-31G method
Moreover, the mechanism of the fluorescence quenching by the energy and the
charge transfer model were explained to further support our assumptions. Table 1 and
Fig. 9 presented the change of the mulliken charge distribution about the sensor from
sensor a to sensor a-Fe. It can be seen clearly that the charge distribution of the
pyridine ring changed obviously, with the center of positive charge(e = -0.3)
translating to the center of negative charge( e = 0.06)(see Fig. 9). Therefore, it
revealed that fluorescence quenching in the presence of Fe3+ was due to the
intramolecular charge transfer( ICT) reaction.
Table 1 Mulliken charge distribution before and after proton transfer
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C1
Charge before proton transfer/e 0.248 -0.890 0.469 -0.095 0.129 -0.161
Charge after proton transfer/e 0.339 -0.790 0.251 0.226 0.019 0.015
N2
C3
C4
C5
C6
Fig.11. The mulliken charge distribution change of sensor a (a) to metal-organic coordination
clathrate (b).
3.4.2 Mechanism of detecting pH environment
The charge distribution of the pyridine ring about the sensor a in the alkaline
environment was also listed, with the center of the charge changing from -0.3 to
-0.634 (see Table 2). These data effectively indicated that the electronegativity of the
pyridine ring was increased due to the intramolecular charge transfer ( ICT) reaction,
which was caused by the fluorescence quenching in the alkaline environment.
Table 2 Mulliken charge distribution before and after proton transfer
C1
N2
C3
C4
C5
C6
Charge before proton transfer/e 0.248 -0.890 0.469 -0.095 0.129 -0.161
Charge after proton transfer/e
0.054 -0.570 0.304 -0.191 -0.09 -0.141
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4. Conclusion
In summary, a novel fluorescence sensor was synthesized by an efficient one-pot and
three-component synthesis method. The sensor a displayed excellent selectivity and
sensitivity to Fe3+ as well as high sensitivity to pH compared with other competing
metal ions. With the addition of the Fe3+, an obvious fluorescence quenching was also
determined. Besides, as the pH value increased from 7 to 14, the fluorescence was
quenched quickly. From this, it was believed that the fluorescence sensor a would be
applied to the biomedical and environmental detection.
Acknowledgement
We gratefully acknowledge the finance supported by the Natural Science
Foundation of China (21176223) and the National Natural Science Foundation of
Zhejiang (LY13B020016) and the Key Innovation Team of Science and Technology
in Zhejiang Province (2010R50018).
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References
(1) Chen, S.; Jiang, F.; Cao, Z.; Wang, G.; Dang, Z.-M. Chem. Commun. 2015, 51, 12633.
(2) Hu, S.; Zhang, S.; Hu, Y.; Tao, Q.; Wu, A. Dyes Pigments. 2013, 96, 509.
(3) Bozkurt, E.; Arık, M.; Onganer, Y. Sensors Actuat B-Chem.. 2015, 221, 136.
(4) Liu, M. Q.; Hu, M. S.; Jiang, Q.; Lu, Z. Y.; Huang, Y.; Tan, Y. F.; Jiang, Q. Rsc Adv.
2015,
5, 15778.
(5) Chen, F.; Hou, F.; Huang, L.; Cheng, J.; Liu, H.; Xi, P.; Bai, D.; Zeng, Z. Dyes
Pigments. 2013, 98, 146.
(6) Wu, X.; Xu, B.; Tong, H.; Wang, L. Macromolecules 2010, 43, 8917.
(7) Li, Z.; Zhou, Y.; Yin, K.; Yu, Z.; Li, Y.; Ren, J. Dyes Pigments. 2014, 105, 7.
(8)
Li, P.; Zhang, M.; Sun, X.; Guan, S.; Zhang, G.; Baumgarten, M.; Mullen, K.
Biosensors &bioelectronics. 2016, 85, 785.
(9) Yang, L.; Yang, W.; Xu, D.; Zhang, Z.; Liu, A. Dyes Pigments. 2013, 97, 168.
(10) Kim, H. J.; Park, J. E.; Choi, M. G.; Ahn, S.; Chang, S.-K. Dyes Pigments. 2010, 84, 54.
(11) Panchenko, P. A.; Fedorov, Y. V.; Fedorova, O. A.; Jonusauskas, G. Dyes Pigments.
2013, 98, 347.
(12) Yang, Y.; Huo, F.; Yin, C.; Chao, J.; Zhang, Y. Dyes Pigments. 2015, 114, 105.
(13) Han, X.; Wang, D.-E.; Chen, S.; Zhang, L.; Guo, Y.; Wang, J. Anal. Methods. 2015, 7,
4231.
(14) Fan, C.; Huang, X.; Han, L.; Lu, Z.; Wang, Z.; Yi, Y. Sensors Actuat B-Chem. 2016,
224, 592.
(15) Skowronski, L.; Krupka, O.; Smokal, V.; Grabowski, A.; Naparty, M.;
Derkowska-Zielinska, B. Opt. Mater. 2015, 47, 18.
(16) Chang, M. L.; Lu, S. S.; Zhang, F.; Zuo, T. T.; Guan, Y. Y.; Wei, T.; Shao, W.; Lin, G.
M. Colloid Surface B. 2015, 129, 175.
(17) Li, H. Q.; Guo, J.; Zhang, X. B.; Chen, Z. Heteroatom Chem. 2012, 23, 551.
(18) Liu, X. D.; Xu, Y.; Sun, R.; Xu, Y. J.; Lu, J. M.; Ge, J. F. Analyst. 2013, 138, 6542.
(19) Sadhu, K. K.; Mizukami, S.; Yoshimura, A.; Kikuchi, K. Org Biomol Chem. 2013, 11,
563.
(20) Suzuki, K.; Ubukata, T.; Yokoyama, Y. Chem. Commun. 2012, 48, 765.
(21) Xu, Y.; Jiang, Z.; Xiao, Y.; Bi, F. Z.; Miao, J. Y.; Zhao, B. X. Anal Chim Acta. 2014,
820, 146.
(22) Yin, H. J.; Zhang, B. C.; Yu, H. Z.; Zhu, L.; Feng, Y.; Zhu, M. Z.; Guo, Q. X.; Meng, X.
M. J. Org. Chem. 2015, 80, 4306.
(23) Zheng, X. X.; Wang, S. Q.; Wang, H. Y.; Zhang, R. R.; Liu, J. T.; Zhao, B. X.
Spectrochimi Acta A. 2015, 138, 247.
(24) Zhu, S. S.; Lin, W. Y.; Yuan, L. Dyes Pigments. 2013, 99, 465.
(25) Guo, Y.-Y.; Yang, L.-Z.; Ru, J.-X.; Yao, X.; Wu, J.; Dou, W.; Qin, W.-W.; Zhang,
G.-L.; Tang, X.-L.; Liu, W.-S. Dyes Pigments. 2013, 99, 693.
(26) Ahmed, N.; Babu, B. V.; Singh, S.; Mitrasinovic, P. M. Heterocycles. 2012, 85, 1629.
(27) Li, J.; Zhang, C. F.; Ming, Z. Z.; Hao, G. F.; Yang, W. C.; Yang, G. F. Tetrahedron.
2013, 69, 4743.
(28) Jara, G. E.; Solis, C. A.; Gsponer, N. S.; Torres, J. J.; Glusko, C. A.; Previtali, C. M.;
18

ACCEPTED MANUSCRIPT
Pierini, A. B.; Vera, D. M. A.; Chesta, C. A.; Montejano, H. A. Dyes Pigments. 2015, 112, 341.
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Highlights:
ꢀ
Novel coumarin-based fluorescence sensor for Fe3+ and pH.
ꢀ
This fluorescence sensor exhibit selectivity and sensitivity not only to Fe3+ by fluorescence
quenching in DMSO but also to pH.
ꢀ
The binding mechanism was studied binding stoichiometry and DFT calculation, and the
quenching mechanism was confirm by Mulliken charge distribution which calculated by
quantum chemistry.
1