A pyrene-based dual chemosensor for colorimetric detection of Cu2+ and fluorescent detection of Fe3+

Article abstract of DOI:10.1016/j.tetlet.2017.08.078

A pyrene based chemosensor was designed and synthesized. The pyrene fluorophore was connected with a pyridine unit through a Schiff base structure to give the sensor (L). L was tested with a variety of metal ions and exhibited high colorimetric selectivities for Cu²⁺ and Fe³⁺ over other ions. Upon binding with Cu²⁺ or Fe³⁺, L showed an obvious optical color change from colorless to pink for Cu²⁺ or orange for Fe³⁺ over a wide pH range from 3 to 12. Moreover, the fluorescence of L at 370 nm decreased sharply after bonding with Fe³⁺, while other metal ions including Cu²⁺ had no apparent interference. Thus, using such single chemosensor, Cu²⁺ and Fe³⁺ can be detected independently with high selectivity and sensitivity. The limits of detection toward Cu²⁺ and Fe³⁺ were 8.5 and 2.0 μM, respectively. DFT calculation results also proved the formation of stable coordination complexes and the phenomenon of fluorescence quenching by Fe³⁺. Furthermore, L was also successfully used as a bioimaging reagent for detection of Fe³⁺ in living cells.

Full text of DOI:10.1016/j.tetlet.2017.08.078

Accepted Manuscript
2
+
A pyrene-based dual chemosensor for colorimetric detection of Cu and fluo-
3
+
rescent detection of Fe
Yuxin Guo, Lei Wang, Jiezhen Zhuo, Bo Xu, Xue Li, Jianyu Zhang, Zhiqiang
Zhang, Haijun Chi, Yan Dong, Gonghao Lu
PII:
S0040-4039(17)31081-X
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.08.078
TETL 49268
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Accepted Date:
8 August 2017
25 August 2017
Please cite this article as: Guo, Y., Wang, L., Zhuo, J., Xu, B., Li, X., Zhang, J., Zhang, Z., Chi, H., Dong, Y., Lu,
2
+
3+
G., A pyrene-based dual chemosensor for colorimetric detection of Cu and fluorescent detection of Fe ,
Tetrahedron Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.2017.08.078
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2
A pyrene-based dual chemosensor for colorimetric detection of Cu and fluorescent
+
3
+
detection of Fe
a
a
a
a
b
c
a
a
Yuxin Guo , Lei Wang , Jiezhen Zhuo , Bo Xu , Xue Li *, Jianyu Zhang , Zhiqiang Zhang , Haijun Chi ,
a
a
Yan Dong and Gonghao Lu *
a
School of Chemical Engineering, University of Science and Technology Liaoning, 185 Qianshan Zhong Road, Anshan, Liaoning 114051, PR China
b
School of Material and Metallurgy, University of Science and Technology Liaoning, 185 Qianshan Zhong Road, Anshan, Liaoning 114051, PR China
c
Anshan Tianchang Chemical Co., Ltd, Mayitun Village, Donganshan Town, Tiexi District, Anshan, Liaoning, 114041, PR China
ARTICLE INFO
ABSTRACT
Article history:
Received
A pyrene based chemosensor was designed and synthesized. The pyrene fluorophore was connected
with a pyridine unit through a Schiff base structure to give the sensor (L). L was tested with a variety of
2
metal ions and exhibited high colorimetric selectivities for Cu and Fe over other ions. Upon binding
+
3+
Received in revised form
Accepted
2
with Cu or Fe , L showed an obvious optical color change from colorless to pink for Cu or orange
+
3+
2+
3
+
for Fe over a wide pH range from 3 to 12. Moreover, the fluorescence of L at 370 nm decreased
Available online
3+ 2+
sharply after bonding with Fe , while other metal ions including Cu had no apparent interference.
2
Thus, using such single chemosensor , Cu and Fe can be detected independently with high selectivity
+
3+
Keywords:
2+
3+
and sensitivity. The limits of detection toward Cu and Fe were 8.5 and 2.0 µM, respectively. DFT
calculation results also proved the formation of stable coordination complexes and the phenomenon of
Dual chemosensor
3
Fe
+
3+
fluorescence quenching by Fe . Furthermore, L was also successfully used as a bioimaging reagent for
2
Cu
+
3+
detection of Fe in living cells.
Pyrene derivative
Selectivity
2017 Elsevier Ltd. All rights reserved.
Cell imaging
2
+
2+ 24
analytical time reduction, such as Cu /Hg , Zn /Al ,
2+
3+ 25
The development of chemosensors with high selectivity and
sensitivity for heavy and transition metal ions has attracted
widely attention due to its important application of biological and
3+ 3+ 26 3+ 3+ 27 3+ 3+ 28 2+ 2+ 29 2+ 2+ 30
Al /Fe , Cr /Fe , Cr /Al , Cu /Zn , Zn /Cd ,
+
2+ 31
2+
3+
Ag /Mn . However, single chemosensors for Cu /Fe were
1
2+
32
2+
3+
reported very rare. In particular, Cu and Fe ions give
environment. Among mental ions, copper ion (Cu ) and iron ion
(
3
Fe ) are two of the most important transition metal ions found
+
different colorimetric and fluorescent responses, respectively.
2,3 2+
in both humans and animals. Cu as a component of proteins
and enzymes is an important necessary trace element in
metabolism. Trace amounts of copper help to provide the energy
needed for the biochemical processes, which help to form the
Pyrene, a highly effective fluorophore, and its derivatives
33
have been investigated in many reports for sensing metal ions,
34
35,36
37-
pH, simple inorganic anions,
and small organic molecule.
40
4
,5
3+
In this work, a novel fluorescent sensor {2-[(pyridin-2-
ylimino)methyl]pyren-1-ol, L} based on the pyrene fluorophore
was designed and prepared. In this study, with the introduction of
2-aminopyridine linked by a Schiff base structure, the hydroxy
heme in the blood.
hemoglobin, and plays an important role in cellular metabolism
Fe acts as an oxygen carrier in
6
and enzyme catalysis. The deficiency as well as overload of
,7
2
+
3+
Cu and/or Fe results in various biological disorders.
8-11
group, Schiff base and pyridine structures can selectively
41,42
Therefore, it is highly desirable to develop analytical methods for
the recognition and detection of Cu and Fe ions.
2+
3+
coordinate with different metal ions.
The binding of metal
ions will result in changes in absorption spectra or quench the
fluorescence of pyrene fluorophore. Therefore, it is reasonable to
design a new chemosensor for ions based on ligand to metal
Optical imaging with high selectivity like chemosensors is an
effective and convenient method monitoring the metal change in
the biological and environmental analysis. Chemosensors have
become practical detecting methods because of their real time
43
charge transfer (LMCT).
1
2,13
Sensor L was synthesized in a good yield according to the
synthetic route shown in Scheme 1. The initial fluorophore 4 was
prepared as described previously in the literature from pyrene as
monitoring capability and high selectivity.
So far, while
2+
3+
14-16
various sensors for detecting Cu or Fe have been reported,
and some of them have been successfully applied in biological
44
17-19
analysis.
a starting material. Compound 4 and 2-aminopyridine were
refluxed in ethanol for 12 hours to give sensor L. The structure of
However, most of them could detect only one metal
2
ion (Cu or Fe ), and this certainly limited their practical
+
3+
1
13
2
0-23
L was characterized by FTIR, H NMR, C NMR, and HRMS
Figs. S1-3 in ESI). All of the data in the spectra were in good
accordance with the structure.
application. A single sensor for multiple targets have been
actively developed for the advantages such as potential cost and
(
Corresponding author. Tel.: +86 412 5929931; fax: +86 412 5216902.
E-mail address: xli@ustl.edu.cn (X. Li); ghlu@ustl.edu.cn (G. Lu).
In order to confirm the selectivity of different metal ions with
sensor L, the UV–vis absorption spectra of L (10 µM) was

2
Tetrahedron Letters
4
3
8% HBr
0% H
3
CH ONa
CuI
2
O
2
CH OH
3
THF
CH
Br Reflux
3
OH
OCH
3
2
Pyrene
1
1
) n-butyllithium
TMEDA
AlCl
CH Cl
rt
3
CHO
OCH3
CHO
OH
2) DMF
2
2
3
4
N
NH
OH
2
H
C
N
N
OH
2 5
C H
Reflux
L
Scheme 1. Synthesis for sensor L
studied in DMF–HEPES buffer (2:8, v/v, pH = 7.4), a simulated
physiological condition. As shown in Fig. 1, free L showed two
characteristic peaks on absorption spectrum at 285 nm and 352
3+
Fig. 3. Emission spectra of sensor L (10 µM) with various ions (40
equiv.) in DMF–HEPES (2:8, v/v, pH = 7.4) at λex = 305 nm. The inset
image shows the photo images of L under irradiated by 365 nm light
2
+
nm, assigned to the pyrene moiety. When 40 equiv. Cu or Fe
was added into the solution of L, the absorbance intensity for
3
+
3+
2+
Fe increased at all bands above those of free L with distinct
color change from colorless to orange, while a red shift (21nm)
before and after added Fe or Cu .
2+
from 352nm to 373 nm was observed for Cu , accompanied by a
color change from colorless to pink. However, equal
concentrations of other metal cations caused negligible changes
on absorption spectrum and colors (Fig. S4 in ESI). These results
3
+
2+
indicate the formation of L-Fe and L-Cu complexes.
3
+
Considering that the intrinsic color of Fe is also orange, the
3
color change of L binding with Fe was compared with the
+
3
+
colors of Fe solutions in DMF–HEPES buffer (2:8, v/v, pH =
.4), as shown in Fig. 2. It was found that the color of L with 40
7
3+
3+
µM Fe was lightly darker than that of 160 µM Fe , indicating
the color change of L with Fe should be mainly attributed to the
3+
3
+
interaction between L and Fe instead of the intrinsic color of
2+
Fe . The color change features make L possible to detect Cu
3+
3
+
and trace amount of Fe by the naked eye without using any
other instrumental technique.
Fig. 4. Relative fluorescence intensities of L (10 µM) in DMF–HEPES
The selectivity of L (10µM) to different metal ions was also
3+
(2:8, v/v, pH = 7.4) with Fe (40 equiv.) in the presence of other
competition metal ions (40 equiv.).
investigated by fluorescent spectra in DMF–HEPES buffer (2:8,
v/v, pH = 7.4) solution. As shown in Fig. 3, free L exhibited
strong fluorescence intensity at 370 nm under excitation
wavelength of 305 nm. The fluorescence of L quenched
3
+
significantly on addition of 40 equiv. Fe , while only slightly
2
+
partial quenching was observed in presence of Cu (see photo
images for all ions in Fig. S5 in ESI). The ratios of the final
fluorescence intensity to the initial fluorescence intensity were
3
+
2+
found to be 0.26 for Fe and 0.79 for Cu , respectively. The
fluorescent quantum yield of L decreased from 25.5% to 0.43%
3
+
in the presence of Fe (40 equiv) with reference to (details in
3
+
ESI). The quenching property of Fe can be attributed to its
4
strong paramagnetic nature with unfilled d-shell.
5
3
+
The fluorescent selectivity of sensor L for Fe was further
examined in the presence of competing species. The competitive
3
studies of L with Fe were carried out in the presence of 40
+
Fig. 1. Absorption spectra of sensor L (10 µM) with various metal ions
2
+
(
40 equiv.) in DMF–HEPES (2:8, v/v, pH=7.4). The inset image shows
equiv. other metal ions, as shown in Fig. 4. Only Cu partially
quenched the fluorescence emission while all the other metal ions
3
color changes for the addition of Fe or Cu into the solution of L.
+
2+
3
+
did not interfere with the quenching of Fe . Therefore, the sensor
3
+
L showed a highly fluorescent selectivity toward Fe over other
metal ions.
2
+
The sensing behavior of L toward Cu was evaluated by the
2
+
absorption spectral titration of L with Cu in DMF–HEPES
buffer (2:8, v/v, pH = 7.4). As shown in Fig. 5, free sensor L
exhibited a miximum absorbance at 352 nm. Upon addition of
2
+
Cu , the absorption band at 352 nm decreased and a new
2+
absorption band at 373 nm increased gradually till 17 equiv. Cu
3
Fig. 2. Color changes of Fe solutions in DMF–HEPES buffer (2:8,
+
v/v, pH=7.4) with or without L.
addition. The ratios of the absorbance at 352 nm and 373 nm

Fig.5. Absorption spectra of sensor L (10 µM) in DMF–HEPES (2:8,
Fig.7. Fluorescent titration spectra of sensor
3+
DMF/HEPES (2:8, v/v, pH=7.4) upon addition of Fe (0 - 40 equiv.)
L (10 µM) in
2
+
v/v, pH=7.4) upon addition of 0 - 17 equiv. Cu
.
2
+
at λex = 305 nm.
(
A
373/A352) were calculated with increasing Cu concentration
from 0 – 20 µM (Fig. S6 in ESI). The A373/A352 ratio increased
along with increasing Cu concentration and was linearly
47
0
expression, the measured fluorescence intensity 1/(F −F) at 370
2
+
3+
nm showed a linear relationship with 1/[Fe ] upon the
2+
proportional to the Cu concentration in the range of 0 – 10 µM
3+
concentration of Fe increased from 0 to 40 equiv. (Fig. 8a). The
2
R =0.995), as shown in Fig. 6a. The limit of detection (LOD)
(
and limit of quantification (LOQ) toward Cu was calculated to
3+
binding constant of L-Fe complex was found to be 4.4×10 M
5
−1
2+
2
R = 0.9878) by the Benesi–Hildebrand plot, and the LOD was
(
4
6
be 8.5 µM (3σ/k) and 28.3 µM 2+(10σ/k), respectively,
demonstrating its sensitivity toward Cu . Furthermore, the ratio
46
calculated to be 2.0 µM (3σ/k) and 6.7 µM (10σ/k),
respectively. Through the detection of Job’s Plot (Fig. 8b), the
2
+
between Cu and L was confirmed by the Job’s Plot (Fig.6b).
3+
change happened at [Fe ]/([Fe ] + [L]) equal to about 0.5,
3+
2
+
2+
The change of Job’s Plot happened at [Cu ]/([Cu ] + [L]) equal
3+
indicating a 1:1 stoichiometry of the L-Fe complex.
2
+
to 0.5, which meant that the binding mode between L and Cu
was a 1:1 stoichiometry. A ratiomertic measurement employing
the ratio of two emissions at different wavelengths as the
detecting signal, could provide accurate analysis.
Sensor L exhibited a stable absorption or fluorescence
intensity in a wide range of pH from 3 to 12 (Figs. S7 and S8 in
2+
ESI). Both the absorption intensity of L-Cu
3
and the
fluorescence intensity of L-Fe complex were relatively stable at
+
Fig. 7 showed the fluorescence emission intensity of L in
DMF–HEPES buffer (2:8, v/v, pH = 7.4) solution with increasing
the corresponding pH range. The results indicated that the
2+
sensing process of L-Cu or L-Fe was not affected at pH value
3+
3+
3+
Fe concentration. When different concentrations of Fe were
added into the solution of L, a drastic decrease in the
fluorescence emission was observed, indicating the formation of
from 3 to 12.
2
+
3+
Although the LODs of L toward Cu (8.5 µM) and Fe (2.0
3
+
L-Fe complex. According to the linear Benesi–Hildebrand
Fig. 8. a) Benesi–Hildebrand plot of L by plotting 1/(F − F
0
) as a
3
function of 1/[Fe ] (emission at 370 nm). b) Job’s plot for the
+
3
+
L and Fe in the complexation.
stoichiometry determination of
2
+
Fig. 6. a) The A373/A352 ratio of sensor L as a function of the Cu
Fluorescence at 370 nm was plotted as a function of the molar ratio of
3+ 3+
Fe ]/([Fe ] + [L]).
2
concentration. b) Job’s Plot for L- Cu complex by UV-vis spectra.
+
[

4
Tetrahedron Letters
L. The result was consistent with the partial quenching of copper
Fig. 11. Fluorescence images and their corresponding bright-field
Fig. 9. Frontier molecular orbital profiles and HOMO-LUMO energy
+
−
levels of L, L -[CuNO
−
and L -[Fe(NO
+
]
transmission images of MCF-7 cells treated with L (10 µM) in the
3
]
3
)
2
based on DFT
3
absence or presence of Fe or Cu . (a, b, I and j) MCF-7 cells
+
2+
calculations.
incubated with L (10 µM) for 30mins; MCF-7 cells treated with L
3+
incubated with 400 µM Fe for 5 mins (c), 10 mins (d), 15 mins (e), 20
mins (f), 25 mins (g) and 30 mins (h); (k, l) MCF-7 cells incubated with
2+
400 µM Cu for 5 mins (k) and 30mins (l).
2
+
µM) are inferior to those of some sensors for single ion Cu or
3+ 14-16,26,27
Fe ,
2+ 3+
a dual chemosensor for Cu and Fe is still
2+
3+
desirable because single chemosensors for both Cu and Fe are
rarely reported. To the best of our knowledge, this is the first
3+
ions. In contrast, after binding with Fe , the LUMO was fully
2+
3+
demonstration of single sensor for Cu and Fe as a dual-
channel colorimetric and fluorescent signaling system, which will
localized on Fe, C=N and pyridine units. Upon excitation, the
48
fluorescence quenching would occur due to LMCT.
2
+
3+
provide a basis for a new strategy for Cu and Fe dual sensing
over other competing metal ions.
To demonstrate the potential application of this pyrene-based
fluorescent sensor in biological systems, we applied L to MCF-7
cells. The cytotoxicity of sensor L was firstly performed by MTT
cell toxicity assays. As shown in Fig. 10, when the concentration
of L was below 20 µM, over 90% cells survived. When 30 µM L
was used, nearly 80% percent of cells still survived. Thus, 10 µM
of L exhibited little toxicity to MCF-cells, and then 10 µM of L
was used in following cells imaging experiments. Ligand treated
2+
3+
Cu and Fe are paramagnetic with an unfilled d shell and
strongly quench the emission of fluorophore near it through
electron and/or energy transfer processes. Based on the results of
absorption and fluorescence titration experiments and the HRMS
spectra of complexes (Figs. S9 and S10 in ESI), we proposed a
−
+
−
+
plausible binding mode for L -[CuNO
3 3 2
] or L -Fe(NO ) ] , as
shown in Fig. 9. In order to further understand the difference of
2+
3+
2+
3+
the fluorescence quenching between the L-Cu /Fe complexes,
cells were incubated with Cu or Fe ions and observed under a
fluorescence microscope as described in supporting information.
A significant blue fluorescence was produced when the MCF-7
cells were incubated with L (10 µM) at 37ºC for 30 mins in the
serum-free MEM, as shown in Fig. 11b and 11j. These results
indicate that the ligand L is easily permeable to the tested living
cells causing no harm as the cells remained alive even after 30
minutes of exposure to the ligand at 10 µM. The cells were
2+
3+
we carried out DFT calculations for L and L-Cu /Fe
complexes. The optimized structures and the relevant frontier
molecular orbitals of L and L-Cu /Fe complexe are shown in
Fig. 9. The energy gaps between highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital
2
+
3+
2+
(
eV for L-Fe , respectively. It is obvious that the energy gaps of
LUMO) were 2.9551 eV for L, 2.2615eV for L-Cu and 1.9102
3+
3+
2+
2
L-Cu /Fe complexes were significantly reduced than that of
+
3+
subsequently treated with Fe or Cu (400 µM) for 30 minutes.
Figs. 11c-h show noteworthy fluorescence quenching after
2
+
3+
free L, which clearly indicates that the L-Cu /Fe complexes
can be stably formed. For all structures, DFT optimizations
showed that the HOMOs were similarly distributed from the
pyrene fluorophore (maximum probability density) to the C=N
structure, while the distributions of the LUMOs were completely
different. For L, the LUMO was distributed over the whole
molecule, resulting in the strong fluorescence, although the
LUMO lightly transferred to C=N bond and receptor. After
3+
incubation for different times upon addition of Fe . However,
only weak fluorescence quenching was observed when the same
amount of Cu was added, as showed in Fig.11k and 11l. These
results suggest that the sensor L is capable of permeating into
2+
3+
cells and reacting with the Fe to quench fluorescence.
2
In summary, a pyrene-based dual chemosensor L for Cu and
+
3
+
Fe detection was described in aqueous DMF medium. The
2+
sensor showed high selectivity toward Cu in colorimetric
2
+
binding with Cu , the LUMO transferred more to C=N bond and
receptor, resulting in relatively weaker fluorescence than that of
3
detection and Fe in fluorescent detection over a wide pH range
+
2
from 3 to 12. Upon binding with Cu or Fe , L showed an
+
3+
2
+
obvious optical color change from colorless to pink for Cu ,
3
+
while the strong fluorescence of L was quenched by Fe . DFT
studies supported the experimental findings very well.
Fluorescence microscopy results showed the applicability of
3
+
sensor L as an imaging reagent for detection of Fe , which
demonstrated its practical applications in biological systems.
High sensitivity, selectivity and detectable color change make the
2
+
ligand suitable for an excellent naked-eye dual sensor for Cu
3
+
3+
and Fe as well as a fluorescent probe for Fe .
Acknowledgments
This research was supported by Natural Science Foundation of
Liaoning Province of China (2015020246), Foundation of
University of Science and Technology Liaoning (2015TD02) and
Fig. 10. Cell viability of MCF-7 cell treated with different
concentrations of L.

the Engineering Research Center of Advanced Coal & Coking
Technology and Efficient Utilization of Coal Resources, the
Education Department of Liaoning Province (USTLKFZD
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Graphical Abstract
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A pyrene-based dual chemosensor for
Leave this area blank for abstract info.
2
+
colorimetric detection of
Cu
and
3
+
fluorescent detection of Fe
Yuxin Guo, Lei Wang, Jiezhen Zhuo, Bo Xu, Xue Li*, Jianyu Zhang, Zhiqiang Zhang, Haijun Chi,
Yan Dong and Gonghao Lu*

2
+

A pyrene-based dual chemosensor is reported for the selective detection of Cu
3
+
and Fe ions in aqueous medium and biological samples.
The sensor can be used as a naked-eye colorimetric sensor for Fe and Cu .
3
+
2+



2+
3+
Through selective interactions, Cu and Fe form a 1:1 complex with the sensor.
The sensor is stable at biologically relevant pH range, membrane permeable, and
3
+
useful for imaging intracellular Fe levels in live cells.