A new acetal as a fluorescent probe for highly selective detection of Fe3+ and its application in bioimaging

Article abstract of DOI:10.1016/j.chemphys.2019.110470

A simple fluorescent probe L for Fe³⁺ was easily synthesized based on anthracene. Among the various metal ions including Fe²⁺, this probe exhibited high sensitivity and good selectivity toward Fe³⁺ with turn-off fluorescence mode in DMSO-HEPES buffer solution (20 mM, pH = 7.0, 1:1 (v/v)). When adequate Fe³⁺ ion was added into the solution of probe L, its molecular structure transferred from anthraldehyde dimethyl acetal to anthraldehyde, resulting in fluorescence quenching with a low detection limit of 3.08 μM. ¹H NMR spectra and TLC analysis further supported this concept. Finally, this probe was successfully applied in bioimaging.

Full text of DOI:10.1016/j.chemphys.2019.110470

Journal Pre-Proof
Anthraldehyde dimethyl acetal as a fluorescent probe for highly selective de-
3
+
tection of Fe and its application in bioimaging
Min Wang, Yong-Ming Zhang, Qin-Yi Zhao, Zhen-Hai Fu, Zhi-Hong Zhang
PII:
S0301-0104(19)30730-X
DOI:
https://doi.org/10.1016/j.chemphys.2019.110470
CHEMPH 110470
Reference:
To appear in:
Chemical Physics
Received Date:
Revised Date:
Accepted Date:
27 June 2019
4 August 2019
4 August 2019
Please cite this article as: M. Wang, Y-M. Zhang, Q-Y. Zhao, Z-H. Fu, Z-H. Zhang, Anthraldehyde dimethyl acetal
3
+
as a fluorescent probe for highly selective detection of Fe and its application in bioimaging, Chemical Physics
2019), doi: https://doi.org/10.1016/j.chemphys.2019.110470
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Anthraldehyde dimethyl acetal as a fluorescent probe for highly
3
+
selective detection of Fe and its application in bioimaging
a,b,c
a,b,c
d
*a,b
Min Wang, Yong-Ming Zhang, Qin-Yi Zhao, Zhen-Hai Fu
and
*a,b
Zhi-Hong Zhang
a. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake
Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining,
8
10008, People’s Republic of China. E-mail: fzh@isl.ac.cn, zhangzh@isl.ac.cn
b. Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Xining,
10008, People’s Republic of China.
8
c. University of Chinese Academy of Sciences, Beijing, 100049, People’s Republic of
China.
d. School of Chemical Engineering, Qinghai University, Xining 810016, People’s
Republic of China.
3
+
Abstract: A simple fluorescent probe L for Fe was easily synthesized
2
+
based on anthracene. Among the various metal ions including Fe , this
3
+
probe exhibited high sensitivity and good selectivity toward Fe with
turn-off fluorescence mode in DMSO-HEPES buffer solution (20 mM,
3
+
pH=7.0, 1:1 (v/v)). When adequate Fe ion was added into the solution
of probe L, its molecular structure transferred from anthraldehyde
dimethyl acetal to anthraldehyde, resulting in fluorescence quenching
1
with a low detection limit of 3.08 μM. H NMR spectra and TLC analysis
further supported this concept. Finally, this probe was successfully
applied in bioimaging.
Keywords: Fluorescence, Anthracene, Dimethyl Acetal, Iron(III)

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1
. Introduction
3
+
Fe (Iron(III)) is an essential and indispensable transition metal ion,
which plays an important role in many biological and environmental
[
1-7]
processes.
Importantly, as the most abundant transition metal ion in
3
+
living body, Fe is involved in many physiological processes including
oxygen uptake, enzymatic catalysis, neurotransmission, gene
transcription, electron transport, cellular metabolism and nucleic acid
[
8-11]
3+
synthesis.
Both deficiency and overload of Fe are also associated
with many diseases, such as Parkinson’s disease, liver damage,
hemochromatosis, intelligence decline, cancer, nausea, β-thalassemia,
hypotransferrinemic, abdominal pain, gastric problems, hyperferremic,
[12-16]
disorders and Alzheimer’s disease.
Consequently, development of
3
+
analysis technology for Fe is still significant and highly desirable.
Due to its importance in physiology, a lot of techniques have been
[17]
developed in the past to detect it,
including atomic absorption
spectroscopy, chromatography, inductively coupled plasma mass
spectrometry, optical techniques, and so on. However, compared with
these analytical methods, optical techniques, especially the fluorescence
approach reported in recent years, which is widely used in many fields
such as chemical analysis, environmental monitoring, life science and
biomedicine, have attracted a great deal of attention owing to the

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significant advantages of real-time application, high sensitivity and
selectivity, simplicity, low detection limit, low cost, and the ability to be
[18-20]
applied in bioimaging.
Therefore, increasing efforts have been
devoted to the development of fluorescence probe for the detection of
3
+ [21,22]
[23]
[24]
Fe ,
including polymers, organic nanoparticles, metal-organic
[
25,26]
[27,28]
frameworks (MOFs),
quantum dots (QDs)
and small
[29-31]
molecule-based sensors.
Among them, fluorescence quenching
3
+ [32,33]
mechanism is often adopted due to the paramagnetic nature of Fe ,
which limits their practical application. In addition, the detection of Fe
3
+
2
+
is easily affected in the presence of other bivalent cations (such as Fe ,
2
+
2+ [34-37]
3+
3+ [38-44]
Zn and Cu )
and trivalent cations (such as Al and Cr ),
3
+
resulting in the inaccuracy of Fe detection. Consequently, it is still a
3
+
challenge to discriminate Fe from other commonly coexistent metal
ions.
It is well known that the aromatic acetals have been used as
[
45,46]
protecting groups in synthetic organic chemistry,
few of them was
3
+
used as fluorescence probe for the detection of Fe . Therefore, to further
investigate into the acetals as fluorescent probe for the detection of metal
ions, and reduce the amount of organic solvent in use, we herein report a
very simple anthracene-based probe L with blue fluorescent, which was
reported as a selective protecting group for selective protection of diols
[
47]
before.
Notably, it demonstrated very fast, highly selectivity toward

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3
+
Fe over other commonly metal ions in DMSO-HEPES buffer solution
(20 mM, pH=7.0, 1:1 (v/v)).
2
. Experimental section
2
.1 General information
The commercially available chemicals in experiments were used
without further purification. All of solvents used in experiments were
1
13
analytical-reagent grade. H, C NMR spectra were measured on the
JEOL JNM-ECS 400 MHz instruments using TMS as an internal standard.
The single-crystal X-ray was performed on a Bruker smart CCD area
detector diffractometer using graphite-monochromated Mo K radiation
α
(
λ= 0.71072 Å). Lorentz-polarization and absorption corrections were
applied for the compounds. The structures were solved with direct
2
methods and refined by full-matrix least-squares on F using the
SHELXL-97 program package. Fluorescence spectra were recorded on a
Hitachi F-7000 spectrophotometer equipped with quartz cuvettes of 1 cm
path length. All pH measurements were made with a pH-10C digital pH
meter.
+
+
3+
Various stock solutions (100.0 mM) of metal ions (Ag , Na , Al ,
2
+
2+
+
2+
2+
2+
3+
2+
3+
2+
+
2+
2+
Ca , Ba , K , Co , Mg , Cu , Fe , Ni , Cr , Fe , Li , Cd , Sr ,
2
+
2+
Mn and Zn ) were prepared in deionized water. Stock solutions of
probe L (10.0 mM) were prepared in DMSO. Test solutions were
prepared by placing 2.0 μL of the probe stock solution into a test tube,

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and then diluting to 2.0 mL with DMSO-HEPES buffer solution (20 mM,
pH=7.0, 1:1 (v/v)), followed by the addition of an appropriate aliquot of
each stock solution of metal ions.
2
.2 Synthesis of L
-Anthraldehyde (412.5 mg, 2.0 mmol) was dissolved in methanol
9
o
(
10 mL), then the solution was heated to reflux for 12 h at 70 C. Cooling
the solution resulted in crystallization. The resulting solid was filtered
and washed with methanol, dried over vacuum to obtain L (185.5 mg,
o
1
3
2
6.8 %). Mp: 144-147 C. H NMR (DMSO-d , 400 MHz): δ 8.75-8.73 (m,
6
H), 8.62 (s, 1H), 8.08 (dd, J = 12, 4.0 Hz, 2H), 7.55-7.49 (m, 4H), 6.63
1
3
(
s, 1H), 3.46 (s, 6H) ppm. C NMR (DMSO-d , 100 MHz): δ 131.0,
6
1
2
29.5, 129.2, 128.7, 128.6, 125.8, 125.2, 125.0, 103.3, 55.5 ppm.
.3 Calculation of detection limit
The limit of detection was calculated based on the following
Equation:
Detection Limit (DL) = 3σ/k
Where σ is the standard deviation of a blank measurement and k is
the slope of a plot of fluorescence intensity versus different metal ion
concentration.
2
.4 Determination of the Stern–Volmer constant KSV
The fluorescence quenching efficiency can be evaluated using the
Stern–Volmer equation：

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F /F −1= K [Q]
0
SV
Where F is the emission intensity in the absence of quencher, F is
0
the emission intensity in the presence of quencher [Q] and K is the
SV
Stern–Volmer constant.
2
.5 Cell imaging
HeLa cells were cultured in DMEM (Dulbecco's Modified Eagle
Medium) subjoined with 10% FBS (fetal bovine serum), and kept in a
moist atmosphere containing 5% CO at 37°C. one group of cells were
2
incubated with probe L (10 μM) in 1.0 mL of a PBS buffer solution
(containing 50% DMSO, pH=7.0) for 20 min; while another group was
3
+
treated with Fe for 30 min first, then probe L was added and incubated
for another 20 min. Cells were incubated and rinsed with PBS buffer
solution three times to remove free compound before imaging. Confocal
fluorescence images of HeLa cells were carried out on an Olympus
FV1000-IX81 laser confocal microscope.
3
. Results and discussion
3
.1 Design and syntheses of probe L
Scheme 1 Synthesis of probe L

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As shown in Scheme 1, a fluorescent probe L was synthesized from
-anthraldehyde by simply refluxing it at 70℃. Its structure was
9
confirmed by nuclear magnetic resonance (Fig. S1–S2, ESI†) and X-ray
crystal structure (Table S1).
3
.2 Fluorescence performance of probe L toward metal ions
Fig. 1 (a) The fluorescence spectra of probe L (10.0 μM) toward different metal ions
1500.0 μM) in DMSO-HEPES buffer solution (20.0 mM, pH=7.0, 1/1, (v/v)). (b) The
(
images of probe L (10.0 μM) with different metal ions (1500.0 μM) in DMSO-HEPES
buffer solution (20.0 mM, pH=7.0, 1/1, (v/v)) under visible light and UV light. From
+
+
3+
2+
2+
+
2+
2+
2+
3+
2+
3+
2+
0
to 18: none, Ag , Na , Al , Ca , Ba , K , Co , Mg , Cu , Fe , Ni , Cr , Fe ,
+
2+
2+
2+
2+
Li , Cd , Sr , Mn and Zn . Irradiated at 365 nm by use of a UV-lamp.
First, the fluorescence responses of probe L toward different metal
ions were investigated in DMSO-HEPES buffer solution (20 mM,

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pH=7.0, 1:1 (v/v)). As shown in Fig. 1, probe L showed a strong
fluorescence emission peak at 420 nm when excited by a wavelength at
3
60 nm, which is attributed to the characteristic peak of anthracene.
+
+
3+
2+
2+
+
Subsequently, various metal ions such as Ag , Na , Al , Ca , Ba , K ,
2
+
2+
2+
3+
2+
3+
2+
+
2+
2+
2+
2+
Co , Mg , Cu , Fe , Ni , Cr , Fe , Li , Cd , Sr , Mn and Zn
were added into the solution of L, it was interesting to note that the
3
+
fluorescence quenching occurred only upon the addition of Fe into the
solution, accompanying with the appearance color changed from
colorless to tawny (Fig. 1), which could be distinguished by naked eye.
These changes in the fluorescence intensity suggested that probe L
showed “turn-off” fluorescence mode for highly selective detection of
3
+
Fe over other metal ions.
Fig.2 The selectivity of L (λ = 420 nm). Black bars: fluorescence intensity of L with
em
+
+
3+
2+
2+
+
2+
2+
2+
other cations (From 1 to 18: none, Ag , Na , Al , Ca , Ba , K , Co , Mg , Cu ,
Ni , Cr , Fe , Li , Cd , Sr , Mn and Zn .). Red bars: fluorescence intensity
2
+
3+
2+
+
2+
2+
2+
2+

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3
+
after inclusion of Fe .
To further get insight into the influence of other metal ions on the
3
+
interaction between L and Fe , we also carried out the competitive
experiments in the presence of other tested metal ions in DMSO-HEPES
buffer solution (20 mM, pH=7.0, 1:1 (v/v)). As shown in Fig. 2, upon the
3
+
addition of Fe into the mixture of probe L and 1.5 mM other interfering
+
3+
2+
2+
2+
2+
3+
2+
+
+
metal ions such as Ag , Al , Ba , Ca , Cd , Co , Cr , Cu , K , Li ,
2
+
2+
+
2+
2+
2+
2+
Mg , Mn , Na , Ni , Sr , Zn and Fe , it was clear that fluorescence
quenching occurred and all of them have no apparent disturbance, which
indicated that these coexistent metal cations almost had no remarkable
3
+
influence on the fluorescence intensity of probe L toward Fe , and it
3
+
could act as an good on-off fluorescent probe for the detection of Fe in
DMSO-HEPES buffer solutions (20 mM, pH=7.0, 1:1 (v/v)).
3
+
3
.3 Fluorescence titration of probe L with Fe
3
+
To better understand the sensitivity of L toward Fe , the
3
+
fluorescence titrations of probe L with Fe were carried out in
DMSO-HEPES buffer solution (20 mM, pH=7.0, 1:1 (v/v)). As shown in
3
+
Fig. 3, with the increase addition of Fe into the solution of L,
fluorescence emission intensity at 420 nm decreased gradually with no
obvious shift in wavelength, and fluorescence quenched when the
3
+
concentration of Fe ran up to 1.5 mM.
Noticeably, according to the fluorescence intensity at 420 nm, a good
3
+
linear response was observed in the Fe concentration range of 0-100 μM

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2
(
R =0.9966) (Fig. 4), and the corresponding LOD (limit of detection) was
determined as 3.08 μM using the equation DL= 3σ/k (S/N=3), which is
lower than those reported previously, and also lower than 0.3 ppm (～5.4
μM, a limit of iron in drinking water and food settled by the U.S.
[
48]
Environmental Protection Agency (EPA)). Furthermore, the quenching
efficiency was also evaluated, the Stern-Volmer constant K of L with
sv
3
+
Fe had been established using the Stern-Volmer equation based on the
fluorescence titration results. As shown in Fig. S3, there is a good linear
3
+
dependence of the fluorescence intensity (F/F ) on Fe concentration in
0
the range from 0 to 90 μM, and the corresponding constant K for the
sv
3
+
3
-1
probe L with Fe was calculated as 2.89 × 10 M . These results showed
3
+
that L can sensitively and selectively detect Fe in DMSO-HEPES buffer
solution (20 mM, pH=7.0, 1:1 (v/v)).

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3
+
Fig.3 Fluorescent responses of L (10.0 μM) with variable Fe [0, 10, 20, 30, 40, 50,
6
5
1
0, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 350, 400, 450,
00, 550, 600, 650, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700,
800, 1900, 2000, 2100, 2200, 2300 μM] (λ = 360 nm). Inset: Plot of the intensity of
ex
3
+
L as a function of [Fe ] at 420 nm.

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3
+
Fig.4 Plot of the intensity a mixture of Probe L and Fe . (λ = 420 nm).
em
3
.4 pH effect
It is well known that pH is an important parameter for the
application of probe L. Therefore, to investigate the effect of pH on the
fluorescence intensity, the fluorescence emission intensity of L at 420 nm
3
+
in the absence and presence of Fe were examined and recorded at
different pH values. As depicted in Fig. 5, Free probe L exhibited good
stability in the pH range of 5-10, while fluorescence emission intensity of
3
+
L decreased clearly at lower pH values. Nevertheless, when Fe was
added into solution of L at various pH values, marked fluorescence
quenching was observed in the pH range from 3 to 12, which suggested
3
+
that L showed good fluorescence response to Fe under these pH

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conditions. These results indicated that probe L can be employed to
3
+
detect Fe in a wide range of pH.
Fig.5 Fluorescence intensity of L (10 μM) at various pH values (λ = 420 nm), in the
em
3
+
absence and presence of Fe (1500 μM).
3
.5 Proposed mechanism
To get insight into the interaction between probe L and Fe , the
3
+
3
+
reaction between probe L and Fe was also carried out, and the
1
corresponding product was obtained. Then H NMR spectra were
employed to account for the behaviour of probe L upon the addition of
3
+
Fe in DMSO-d solution. As shown in Fig. 6, By comparing, the proton
6
signals of product are the same with the characteristics of the
9
-Anthraldehyde, which suggested that the fluorescence quenching of
probe L was attributed to the formation of 9-Anthraldehyde after the

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3
+
addition of Fe . This is further identified by TLC analysis. As can be
seen from Fig. 6, there are four lanes from left to right, corresponded to
3
+
3+
probe L, L+Fe (2.0 equiv), L+Fe (adequate) and 9-Anthraldehyde,
respectively. The blue fluorescence spot of probe L disappeared, and a
3
+
new clear spot was observed in the presence of adequate Fe , which is
consistent with the spot of 9-Anthraldehyde. Accordingly, the detection
3
+
mechanism can be described as follows: when Fe was added into the
solution of probe L, the reaction occurred, and then followed by the
[49]
transformation from probe L to 9-Anthraldehyde .
3
+
1
Fig. 6 Proposed mechanism of probe L with Fe , TLC analysis and H NMR spectra
in DMSO-d : (a) probe L, (b) obtained product and (c) 9-Anthraldehyde.
6
3
.6 Bioimaging of probe L

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Based on the above results, it was further applied in bioimaging by
3
+
using HeLa cells due to its highly selectivity to Fe . We first evaluated
the cytotoxicity of probe L by the MTT assay at different concentrations
of L. As shown in Fig. S4, the results showed probe L almost has no
influence on the cells and could be applied in bioimaging. Next, the
fluorescence imaging of probe L in HeLa cells was performed and the
corresponding cell images are shown in Fig. 7. Cells incubated with
3
+
probe L exhibited strong blue fluorescence. However, when Fe was
added and cultured for 30 min first, then these cells were further
incubated with probe L for 20 min, it is can be seen that the fluorescence
quenched. Therefore, through the comparison of fluorescence in the
3
+
absence and in the presence of Fe , it can be concluded that probe L can
3
+
detect intercellular Fe in living cells.
Fig. 7 HeLa cell images: (a) bright field and (c) fluorescence images of HeLa cells

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with probe L (10.0 μM) for 20 min; (b) bright field and (d)fluorescence images of
3
+
HeLa cells incubated with Fe (150.0 μM) for 30 min, and then incubated with probe
L (10.0 μM) for 20 min.
4
. Conclusion
In summary, a simple turn off fluorescent probe L for Fe has been
constructed based on anthracene. Among the commonly metal ions
3
+
2
+
3+
including Fe , this probe showed highly selective detection of Fe in
DMSO-HEPES buffer solution (20 mM, pH=7.0, 1:1 (v/v)). Upon the
3
+
addition of excessive Fe , this probe’s molecular structure transferred
from anthraldehyde dimethyl acetal to anthraldehyde, resulting in the
1
fluorescence quenching with tawny color. H NMR spectra and TLC
analysis further supported this concept. In addition, this probe showed
low cytotoxicity to HeLa cells and was successfully applied in
bioimaging. To the end, we hope this strategy can be employed to
develop probes for other metal ions.
Acknowledgement
We thank the Natural Science Foundation of Qinghai (Grant Nos.
2
019-ZJ-954Q), the Youth Innovation Promotion Association CAS
2018466) and the CAS “Light of West China” Program.
Appendix A. Supplementary data
(
1
13
Supplementary data available: Spectral data, copies of H/ C NMR
and other materials can be found online at http://doi.org/*******.
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Graphical abstract

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Highlights
•
A simple anthracene-based fluorescent “on-off” probe was developed for highly
selective detection of Fe .
3
+
3
+
•
A turn “on-off” fluorescent detection of Fe was achieved via the
transformation of molecular structure from anthraldehyde dimethyl acetal to
anthraldehyde.
•
The probe displayed good performance on living cell imaging.