An OFF–ON–OFF type fluorescent probe based on a naphthalene derivative for Al3+ and F? ions and its biological application

Article abstract of DOI:10.1002/bio.3366

A novel fluorescent probe-based naphthalene Schiff, 1-(C2-glucosyl-ylimino-methyl)-naphthalene-2-ol (L) was synthesized by coupling d-glucosamine hydrochloride with 2-hydroxy-1-naphthaldehyde. It exhibited excellent selectivity and highly sensitivity for Al³⁺ in ethanol with a strong fluorescence response, while other common metal ions such as Pb²⁺, Mg²⁺, Cu²⁺, Co²⁺, Ni²⁺, Cd²⁺, Fe²⁺, Mn²⁺, Hg²⁺, Li⁺, Na⁺, K⁺, Fe³⁺, Cr³⁺, Zn²⁺, Ag⁺, Ba²⁺ and Ca²⁺ did not cause the same fluorescence response. The probe selectively bound Al³⁺ with a binding constant (K_a) of 5.748?×?10³?M^?1 and a lowest detection limit (LOD) of 4.08?nM. Moreover, the study found that the fluorescence of the L???Al³⁺ complex could be quenched after addition of F^? in the same medium, while other anions, including Cl^?, Br^?, I^?, NO₂ ^?, NO₃ ^?, ClO₄ ^?, CO₃ ^2?, HCO₃ ^?, SO₄ ^2?, HSO₄ ^?, CH₃COO^?, PO₄ ^3?, HPO₄ ^2?, S^2? and S₂O₃ ^2? had nearly no influence on probe behaviour. Binding of the [L???Al³⁺] complex to a F^? anion was established by different fluorescence titration studies, with a detection limit of 3.2?nM in ethanol. The fluorescent probe was also successfully applied in the imaging detection of Al³⁺ and F^? in living cells.

Full text of DOI:10.1002/bio.3366

Received: 6 March 2017
DOI: 10.1002/bio.3366
Revised: 26 April 2017
Accepted: 17 May 2017
R E S E A R C H A R T I C L E
An OFF–ON–OFF type fluorescent probe based on a
naphthalene derivative for Al3+ and F− ions and its
biological application
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Yanpeng Ren
Juan Han Yun Wang Xu Tang Lei Wang Liang Ni
School of Chemistry and Chemical
Engineering, Jiangsu University, Zhenjiang,
People's Republic of China
Abstract
A novel fluorescent probe‐based naphthalene Schiff, 1‐(C2‐glucosyl‐ylimino‐methyl)‐naphtha-
lene‐2‐ol (L) was synthesized by coupling D‐glucosamine hydrochloride with 2‐hydroxy‐1‐
naphthaldehyde. It exhibited excellent selectivity and highly sensitivity for Al3+ in ethanol with
a strong fluorescence response, while other common metal ions such as Pb2+, Mg2+, Cu2+, Co2
+, Ni2+, Cd2+, Fe2+, Mn2+, Hg2+, Li+, Na+, K+, Fe3+, Cr3+, Zn2+, Ag+, Ba2+ and Ca2+ did not cause
the same fluorescence response. The probe selectively bound Al3+ with a binding constant (Ka)
of 5.748 × 103 M−1 and a lowest detection limit (LOD) of 4.08 nM. Moreover, the study found
that the fluorescence of the L − Al3+ complex could be quenched after addition of F− in the same
medium, while other anions, including Cl−, Br−, I−, NO2−, NO3−, ClO4−, CO32−, HCO3−, SO4
HSO4−, CH3COO−, PO43−, HPO42−, S2− and S2O32− had nearly no influence on probe behaviour.
Binding of the [L − Al3+] complex to a F− anion was established by different fluorescence titration
studies, with a detection limit of 3.2 nM in ethanol. The fluorescent probe was also successfully
applied in the imaging detection of Al3+ and F− in living cells.
Correspondence
Liang Ni and Lei Wang, School of Chemistry
and Chemical Engineering, Jiangsu University,
Zhenjiang, 212013, People's Republic of
China.
Email: niliang@ujs.edu.com;
wanglei86@ujs.edu.cn
Funding information
National Natural Science Foundation of China,
Grant/Award Number: 21507047, 21576124,
21406090 and 31470434
2−
,
KEYWORDS
Al3+ and F−, cell detection, fluorescent probe, OFF–ON–OFF type
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1
INTRODUCTION
approximately 3–10 mg.[11,12] Hence, the design and synthesis of a
sensor for selective detection of Al3+ ions has stimulated a heated dis-
cussion between chemists.[13]
The element aluminium possesses many excellent properties, such as
low density, good thermal conductivity, good ductility and is not sus-
ceptible to air, which makes it widely used in medical devices, food
additives, water purification agents, adsorbents and antacid drugs.[1–
Fluorine is the most electronegative of the elements, the charge
radius ratio of the fluoride ion is the smallest of all ions, giving it unique
chemical properties.[14,15] High concentrations of fluoride intake into
the human body will inhibit protein and DNA synthesis, causing
immune metabolic system disorders, and ultimately reducing the
body's immunity.[16,17] It can also lead to changes in blood pressure
and even anemia, affecting the growth and development of ani-
mals.[18,19] Hence, there is great need to develop receptors that can
combine with and/or detect fluoride in our daily life.[20] The design
and application of a single probe that achieves a discriminating
response for various analytes, however, has been challenging in
recent times.[21]
3]
Such widespread use of aluminium allows entrance into the human
body in the food chain.[4] Aluminium is not an essential element for
the body and long‐term exposure to aluminium can cause obvious
adverse effects in living beings.[5,6] Specifically, aluminium ions can
act as a protein when composited with iron, and can directly damage
the central nervous system after entry into the human brain, leading
to memory loss, mental retardation, aging, and, more seriously, to
Alzheimer's disease.[7–10] The World Health Organization (WHO) has
reported that the daily intake of aluminium for humans is
A fluorescence response would be the best choice for visualization
due to its merits of high sensitivity, high selectivity, simple operation,
real‐time direct visual perception and so on.[22,23] Naphthalene deriva-
tives have been used in a broad range of applications as an ideal
Abbreviations used: CHEF, chelation‐enhanced fluorescence; DMSO, dimethyl
sulphoxide; LOD, limit of detection; PBS, phosphate‐buffered saline; USEPA,
United States Environmental Protection Agency; UV, ultraviolet; WHO, World
Health Organization.
Luminescence. 2017;1–7.
wileyonlinelibrary.com/journal/bio
Copyright © 2017 John Wiley & Sons, Ltd.
1

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REN ET AL.
fluorescence group due to their low fluorescence quantum yield, short
fluorescence life‐time, and their capability to serve as a dedicator as
well as an receptor.[24]
suspension of D‐glucosamine hydrochloride (1 mmol), at the same time
being subjected to ultrasound and continuous stirring at room temper-
ature while compound 1 (1 mmol) was added. The mixed solution was
incubated for 5–6 h with constant stirring, during which time a yellow
precipitate appeared. The resulting precipitate was filtered and washed
with an appropriate amount of ethanol several times, then dried under
reduced pressure (yield 81%). 1H NMR (400 MHz, dimethyl sulphoxide
(DMSO)‐d6) δ 13.53 (m, 1H), 8.91 (d, J = 11.6 Hz, 1H), 7.95 (d,
J = 8.4 Hz, 1H), 7.67 (d, J = 9.4 Hz, 1H), 7.58 (d, J = 6.9 Hz, 1H),
7.43–7.34 (m, 1H), 7.14 (t, J = 7.0 Hz, 1H), 6.99 (d, J = 3.9 Hz, 1H),
6.62 (d, J = 9.4 Hz, 1H), 5.32 (d, J = 5.7 Hz, 1H), 5.21–5.13 (m, 1H),
5.08 (d, J = 5.9 Hz, 1H), 4.52 (t, J = 5.8 Hz, 1H), 3.73–3.38 (m, 5H),
3.18 (td, J = 8.9, 6.0 Hz, 1H). 13C NMR (100 MHz, DMSO‐d6) δ
179.75 (s, 1H), 158.84 (s, 2H), 137.93 (s, 2H), 135.15 (s, 1H), 129.36
(s, 2H), 128.39 (s, 2H), 126.87 (s, 2H), 125.39 (s, 1H), 122.43 (s, 2H),
118.56 (s, 2H), 105.72 (s, 1H), 91.28 (s, 2H), 72.93 (s, 2H), 71.93 (s,
2H), 70.97 (s, 2H), 65.82 (s, 2H), 61.40 (s, 2H), 40.59 (s, 3H), 40.38 (s,
9H), 40.17 (s, 21H), 39.96 (s, 11H), 39.75 (s, 29H), 39.55 (s, 9H),
39.34 (s, 4H). ESI‐MS m/z ([M + H]+): Calcd 334.27; found: 334.46.
Herein, we describe the design and synthesized of a novel OFF–
ON–OFF fluorescent probe for Al3+ and F− based on a naphthalene
Schiff derivative made by coupling D‐glucosamine hydrochloride with
2‐hydroxy‐1‐naphthaldehyde (Scheme 1). The optical properties of
this fluorescent probe and its selectivity for anions and cations were
studied in a series of ultraviolet–visible (UV–vis) and fluorescence
spectra. LOD and the binding constants of L − Al3+ were obtained
based on measured results. The effect of the probe on imaging of tar-
get ions in living cells was also discussed.
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2
EXPERIMENTAL
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2.1
Chemicals and equipment
All solvents such as chloroform and absolute ethanol were of analytical
grade and used without further purification. All metal perchlorate salts
were purchased from Aldrich (USA), while medicines and chemical
reagents were supplied by Sinopharm Chemical Reagent Co., Ltd
(Shanghai, China). 1H NMR and 13C NMR spectra were measured using
an AVANCE ΙΙ 400 MHz spectrometer (Bruker, Switzerland). Mass
spectra were generated through a liquid chromatography ion trap mass
spectrometer (Thermo LXQ, USA). Photoluminescence spectra were
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2.3
Preparation of solutions for fluorescence
detections
All stock salts solutions including metal cations and the anions were
prepared with distilled water to a 5.0 × 103 μM concentration, while
the stock solution of probe L was prepared in ethyl alcohol at
5.0 × 102 μM. Test solutions were intended via setting 40 μl of the
host stock solution into a 5 ml cuvette with an appropriate amount
of ion solutions added.
obtained using
a DM2500 biological fluorescence microscope
(Leica, Germany). Ultraviolet absorption spectra were obtained
using a UV‐2450 UV–vis spectrophotometer (Shimadzu, Japan) at
25°C, while fluorescence measurements were taken on
a Cary
Fluorescence spectra were obtained by exciting the samples at
360 nm and measuring the emitance, which ranged from 380 nm to
540 nm throughout the experiments. The excitation and emission slit
widths were set at 5 nm.
Eclipse fluorescence spectrophotometer (Variance Ltd, Australia).
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2.2
Procedures for synthesis
Synthesis of compound 1
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2.2.1
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3
RESULTS AND DISCUSSION
Choice of solvent system
Compound 1 was synthesized based on methods in an earlier reported
paper.[25]
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3.1
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2.2.2
Synthesis of compound L
Selective recognition of probe L for metal ions in various solvents (such
as DMSO, ethyl alcohol, acetonitrile, DMF, THF and H2O) was deter-
mined to produce a suitable reaction system. As shown in Figure 1, a
dramatic influence on the fluorescence intensity of L could be
observed after injection of Al3+ and Zn2+ in ethanol and acetonitrile,
while other solvents caused almost no effect on L fluorescence inten-
sity. Ethanol was used as the next reaction solvent, rather than aceto-
nitrile, due to the toxicity of the solvent,. Unfortunately the selectivity
of sensor L to Al3+ was not satisfactory when water was mixed as the
cosolvent, therefore ethanol was used solely as the reaction solvent
rather than the component solvent.
Receptor (L) was synthesized by one‐step condensation reaction cou-
pling of D‐glucosamine hydrochloride to 2‐hydroxy‐1‐naphthaldehyde.
Triethylamine (1.5 mmol) was added dropwise to an ethanol
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3.2
UV–vis light experiments
The absorbance spectra of L (50 μM) with increasing concentrations of
Al3+ ion from 0 to 10.0 equiv. were recorded to investigate the spec-
troscopic properties of this probe. As shown in Figure 2, the L free
SCHEME 1 Synthesis of the fluorescent probe L

REN ET AL.
3
sensor exhibited two intense absorption bands at 308 nm and 401 nm.
Three new broad peaks at 321 nm, 377 nm and 388 nm appeared,
however, and free ligand peaks disappeared upon increasing addition
of Al3+, with a colour change from yellow to colourless. These prelim-
inary observations indicated that L responds to Al3+ ion in ethanol.
Fluorescence OFF–ON sensing for Al3+
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3.3
Fluorescence spectra were recorded when different metal ions (Pb2+
,
Mg2+, Cu2+, Co2+, Ni2+, Cd2+, Fe2+, Mn2+, Hg2+, Li+, Na+, K+, Fe3+, Cr3
+, Zn2+ Ag+, Ba2+ and Ca2+) were added to determine the selectivity
of the fluorescent probe; 5 μM probe was added to 10 equiv. of metal
ions in all experiments.
FIGURE 1 Effect of the solvent on the fluorescence intensity of L
(5 μM) in the presence of metal ions (5 equiv.). 1: Fe3+; 2: Al3+; 3:
Figure 3(a) summarizes the effect of different metal ions on the
fluorescence spectra of the probe. The addition of Al3+ (10 equiv.) into
L induced a dramatic enhancement (60‐fold change) in fluorescence
intensity at 427 nm, which was ascribed to the combination of probe L
and Al3+. In contrast, there were no significant changes except for some
Zn2+; 4: Cr3+; 5: Mixture of other ions (Pb2+, Mg2+, Cu2+, Co2+, Ni2+
,
Cd2+, Fe2+, Mn2+, Hg2+, li+, Na+, K+, ag+, Ba2+ and Ca2+
)
interference from Zn2+ when other relevant metal ions including Pb2+
Mg2+, Cu2+, Co2+, Ni2+, Cd2+, Fe2+, Mn2+, Hg2+, Li+, Na+, K+, Fe3+, Cr3+
,
,
Ag+, Ba2+ and Ca2+ were added. The selectivity of L for Al3+ in the pres-
ence of additional various anions is plotted as a bar graph in Figure 3(b).
Al3+ brought about a marked colour change from achromatic to blue,
while no obvious colour change following injection of other metal cat-
ions was noticed under UV light (365 nm) (Figure 3c). Al3+ therefore
could be measured exclusively without the use of any other instrument.
The interaction between the fluorescence probe L and Al3+ was
investigated by recording the fluorescence response of L (5 μM) to a
range of Al3+ concentrations from 0 to 50 μM. As displayed in
Figure 4, a significant increase in monomer emission at 427 nm was
observed upon progressive addition of Al3+, which induced a 60‐fold
enhancement in the fluorescence intensity in which the fluorescence
quantum yield increased from 0.02 to 0.71[26], due to chelation‐
enhanced fluorescence (CHEF). Figure 4 (inset) shows no obvious
FIGURE 2 Absorption spectra of L (50 μM) with injection of Al3+ in
ethanol. [Al3+] = 0, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450
and 500 μM. Inset: Visible colour change of L and L + Al3+
FIGURE 3 (a) fluorescence spectra of L (5 μM) under the injection of different metal cations (10 equiv.), λex = 360 nm. (b) fluorescence selectivity
of L (5 μM) for Al3+ (10 equiv.) in the presence of various metal ions (10 equiv.) added to the same medium. (c) colour change of L under UV light
(365 nm) upon injection of different metal cations (10 equiv.)

4
REN ET AL.
prepared in ethanol by adding 10 equiv. of Al3+ to the sensor L
(5 μM). Afterwards, the influence of common anions on the fluores-
cence spectral of [L − Al3+] complex in the solvent was determined.
Figure 5(a) exhibited that the emission intensity was quenched with
addition of F− to the [L − Al3+] ensemble, while the addition of other
anions, for example, Cl−, Br−, I−, NO2−, NO3−, ClO4−, CO32−, HCO3
,
−
SO42−, HSO4−, CH3COO−, PO43−, HPO42−, S2− and S2O3 produced
almost no change. Interference from competitive anions was also mea-
sured to further verify the fluorescence ON–OFF switching properties
of the [L − Al3+] complex. As shown Figure 5(b), there was no signifi-
cant interference in F− recognition in the presence of equal amounts
of other anions. Consequently, the [L–Al3+] complex was shown to
have great selectivity towards F−. Figure 5(c) shows the observable col-
our change of the [L − Al3+] system under UV light when treated with
various anions (10 equiv.). These experimental results show that the
[L − Al3+] complex is potentially applicable for quantitative analysis of
the F− ion.
2−
FIGURE 4 Fluorescence spectra of L (5 μM) after addition of different
concentrations of Al3+ (0–10 equiv.) in ethanol. Inset: Fluorescence
emission intensity changes due to increasing Al3+ (λex = 360 nm)
further increase in fluorescence intensity of this system after a five‐
fold [Al3+] was added. Al3+ concentration could be determined through
this geometrical relationship (Figure S1).
To understand the interaction between sensor L and Al3+, the
reverse experiment was conducted. L solution (5 μM) with Al3+
(50 μM) exhibited a strong fluorescence emission peak at 427 nm,
while the fluorescence intensity was almost quenched after injection
of F− (50 μM). Figure 6(a) indicates that Al3+ addition can give rise to
fluorescence emission (OFF–ON), while further addition of F− resulted
in spectral quenching (ON–OFF), with the fluorescence quantum yield
of the system decreased from 0.71 to 0.023. This change is due to the
formation of a new stable complex [AlF]2+. This process was duplicated
at least three times without obvious signal lost, which demonstrated
that this OFF–ON–OFF fluorescent probe could be regenerated
(Figure 6b).
The detection limit could also be calculated from the fluorescence
titration experiment. The detection limit of sensor L towards Al3+ was
calculated as 4.08 × 10−9 M, in the range 0.5–25 μM based on 3σblank
/
k[27], in which σblank is the standard deviation of the blank solution, k is
the slope of the calibration curve (Figure S1), which was much lower
than most previously reported assays for Al3+ detection.[28–30] The
combined relationship between L and Al3+ in ethanol was calculated
using the Benesi–Hildebrand equation[31], for which the association
constant Ka was evaluated as 5.748 × 103 M−1 (Fig. S2).
The emission titration of the [L − Al3+] complex with F− reflected
that the fluorescence intensity of [L − Al3+] system progressively weak-
ened upon the increasing addition of F− ion (Figure 7). Any unknown
amounts of F− in a system, therefore, could be determined from the
geometrical relationship of [L − Al3+] towards F− (Fig. S3), in which
Fluorescence ON–OFF sensing for F−
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3.4
Due to the high stability of [AlF]2+, the [L − Al3+] complex could serve
as a possible means to detect fluoride. The probe [L − Al3+] was
FIGURE 5 (a) fluorescence spectra of [L − Al3+] (5 μM) upon addition of different anions (50 μM), λex = 360 nm. (b) fluorescence response of probe
[L − Al3+] (5 μM) towards F− (50 μM) in the presence of various anions (50 μM) in ethanol. (c) the observable colour change in the [L − Al3+] system
under UV light (365 nm) when treated with various anions (10 equiv.)

REN ET AL.
5
FIGURE 6 (a) fluorescence titration spectra of L − Al3+ (5 μM) upon addition of 10 equiv. of F−. (b) reversibility of L (5 μM) estimated by injecting
Al3+ and F− (F− and Al3+ are also 10 equiv. to L) alternately into the sensor solution
probe L with Al3+ as shown in Scheme 2, in which the hydroxyl group
on glucose and naphthalene and the imine nitrogen were used for Al3+
binding.
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3.6
Time course
Figure 8(a) and (b) demonstrates the sensor L response to Al3+ and the
[L − Al3+] complex towards F− with time. Upon treatment with 2, 5, or
10 equiv. Al3+, fluorescence intensity enhanced quickly and remained
unchanged after 20 min, indicating that binding to the lactam structure
of probe L with Al3+ was accomplished. Alternatively, the emission
intensity of the [L − Al3+] complex reverted to a relatively balanced
state after the addition of F− (2, 5, or 10 equiv.,) after only 4 min.
FIGURE 7 Fluorescence response of complex [L − Al3+] (5 μM) upon
addition of F− in ethanol. Inset: Variation in the fluorescence
intensity of [L − Al3+] recorded at 427 nm as a function of [F−] injected
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3.7
Application
As well as understanding the fluorescence turn‐off response mecha-
nism, based on its marked fluorescence properties, we explored using
L for recognition of Al3+ in living cells. The human B lymphocyte
tumour cell line Ramos was pre‐exposed to L (5 μM) for 30 min at
37°C, then washed with phosphate‐buffered saline (PBS) to eliminate
any residual compound. The treated Ramos cells were divided into
two groups, one incubated with Al3+ (10 equiv.), and the other incu-
bated with Al3+ and F− simultaneously (10 equiv.) in the same medium
for 0.5 h. Treated cells were washed with PBS buffer and imaged
using an inverted fluorescence microscope. The results are shown in
Figure 9. The cells incubated without Al3+ exhibited nearly no fluores-
cence (Figure 9b), but those with Al3+ displayed a significant increase
in intracellular fluorescence (Figure 9c), and those with Al3+ and F−
displayed signs of fluorescence quenching (Figure 9d). These results
suggested that sensor L is cell membrane permeable and could be a
suitable fluorescence probe for detection of Al3+ and F− in
biological systems.
100 μM of F− could lead to complete quenching (Figure 7 inset). The
LOD for F− was calculated to be 0.0032 μM based on the results of
fluorescence titrations, this value is lower than the specified minimum
detection limit (4.0 mg L−1, 211 μM) of drinking water, standardized by
the United States Environmental Protection Agency.[32] Thus trace
levels of [F−] in water samples could be determined using the above‐
mentioned method.
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3.5
Investigation of mechanism
The structure of L was characterized by 1H NMR, 13C NMR and
EI − MS, and experimental data were all in line with the structure
exhibited in Scheme 1 (Figs. S4−S6). Job's plot also exhibited a 1:1
stoichiometric complex of probe L with Al3+ (Fig. S7). Fluorescence
probe L itself has no fluorescence emission but the addition of Al3+
induced blue fluorescence emission. Both the phenomena of charge
transfer from hydroxyl group to naphthalene moiety (ICT) and
cis − trans interconversion around the C = N bond in L relies on the
presence of Al3+, which is the trigger of the switch ON response in
the fluorescence spectra following the CHEF mechanism.[27] The addi-
tion of F− to the [L − Al3+] complex constituted a reversible monitoring
process as fluorescence was quenched due to the high stability
of [AlF]2+. This fluorescence probe can be described as an ‘OFF–
ON–OFF’ type, therefore and allows possible complex formation for
SCHEME 2 Fluorescence switch OFF–ON–OFF of probe L

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REN ET AL.
FIGURE 8 (a) time course of probe L (5 μM) after injection of Al3+ (2, 5, or 10 equiv.) in ethanol. (b) time course of complex [L − Al3+] (5 μM) after
addition of F− (2, 5, or 10 equiv.) in ethanol
FIGURE 9 Fluorescence microscopic
photographs of Ramos cells: (a) bright field
image of Ramos cells treated with L (5 μM); (b)
fluorescence microscopy image of (a); (c)
fluorescence microscopy image of Ramos cells
pre‐exposed to 5 μM L for 30 min and then
incubated with Al3+ (50 μM) for 30 min; (d)
fluorescence microscopy image of Ramos cells
pre‐exposed to 5 μM L and then incubated
with Al3+ and F− (50 μM, individually) for
60 min. Cells were incubated at 37°C
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Protection Agency (USEPA). In addition, we successfully applied this
technique for the detection of biological cells.
4
CONCLUSION
A novel naphthalene Schiff based fluorescent sensor (L) that exhibited
marked fluorescence towards Al3+ was synthesized. Upon binding to
Al3+, obvious detectable change in the fluorescence was observed
due to the CHEF effect. The detection limit was very low and was cal-
culated to be 4.08 nM, indicating that the probe had high recognition
ability and selectivity towards aluminium ions. The binding constant
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science Foundation
of China (Nos. 31470434, 21406090, 21576124 and 21507047).
and the Job curve revealed that the probe is a 1:1 complex with Al3+
.
REFERENCES
Moreover, the addition of F− could quench the emission intensity of
the L − Al3+ complex, indicating good reversibility of probe L. The
low detection limit for the L − Al3+ complex is in full accord with the
standard for drinking water set by the United States Environmental
[1] R. Ali, S. S. Razi, P. Srivastava, M. Shahid, A. Misra, RSC Adv. 2015, 5,
61513.
[2] R. Azadbakht, T. Almasi, H. Keypour, M. Rezaeivala, Inorg. Chem.
Commun. 2013, 33, 63.

REN ET AL.
7
[3] A. Banerjee, A. Sahana, S. Das, S. Lohar, S. Guha, B. Sarkar, S. K.
[21] X. Yang, L. Zheng, L. Xie, Z. Liu, Y. Li, R. Ning, G. Zhang, X. Gong, B.
Gao, C. Liu, Y. Cui, G. Sun, G. Zhang, Sensors Actuat. B Chem. 2015,
207, 9.
Mukhopadhyay, A. K. Mukherjee, D. Das, Analyst 2012, 137, 2166.
[4] K. Boonkitpatarakul, J. Wang, N. Niamnont, B. Liu, L. McDonald, Y.
[22] K. Kaur, V. K. Bhardwaj, N. Kaur, N. Singh, Inorg. Chem. Commun. 2012,
18, 79.
Pang, M. Sukwattanasinitt, ACS Sensors 2016, 1, 144.
[5] L. Cao, C. Jia, Q. Zhang, D. Chen, C. Zhang, Y. Qian, Chem. Res. Chinese
U. 2014, 30, 362.
[23] C. R. Li, J. C. Qin, B. D. Wang, L. Fan, J. Yan, Z. Y. Yang, J. Fluoresc.
2016, 26, 345.
[6] N. Chatterjee, S. B. Maity, A. Samadder, P. Mukherjee, A. R. Khuda‐
Bukhsh, P. K. Bharadwaj, RSC Adv. 2016, 6, 17995.
[24] A. Shokrollahi, R. Aghaei, Environ. Monit. Assess. 2014, 186, 1113.
[25] K. Wu, H. Xiao, L. Wang, G. Yin, Y. Quan, RSC Adv. 2014, 75, 39984.
[26] A. Liu, L. Yang, Z. Zhang, Z. Zhang, D. Xu, Dyes Pigm. 2013, 99, 472.
[7] Y. Chen, Y. Mi, Q. Xie, J. Xiang, H. Fan, X. Luo, S. Xia, Anal. Methods‐UK
2013, 5, 4818.
[27] B. K. Datta, D. Thiyagarajan, A. Ramesh, G. Das, Dalton T. 2015,
44, 13093.
[8] X. Y. Cheng, R. Fang, Z. Y. Yang, M. F. Wang, Q. X. Zhou, T. R. Li, Y. Li,
J. Coord. Chem. 2014, 67, 737.
[28] T. J. Jia, W. Cao, X. J. Zheng, L. P. Jin, Tetrahedron Lett. 2013, 54, 3471.
[29] N. Mergu, A. K. Singh, V. K. Gupta, Sensors Basel 2015, 15, 9097.
[9] S. Das, M. Dutta, D. Das, Anal. Methods‐UK 2013, 5, 6262.
[10] A. Dhara, A. Jana, S. Konar, S. K. Ghatak, S. Ray, K. Das, A.
Bandyopadhyay, N. Guchhait, S. K. Kar, Tetrahedron Lett. 2013,
54, 3630.
[30] R. Patil, A. Moirangthem, R. Butcher, N. Singh, A. Basu, K. Tayade, U.
Fegade, D. Hundiwale, A. Kuwar, Dalton T. 2014, 43, 2895.
[11] T. Han, X. Feng, B. Tong, J. Shi, L. Chen, J. Zhi, Y. Dong, Chem.
Commun. 2012, 48, 416.
[31] R. Bhowmick, M. Dolai, R. Alam, T. Mistri, A. Katarkar, K. Chaudhuri,
M. Ali, RSC Adv. 2014, 4, 41784.
[32] S. Rochat, K. Severin, Chem. Commun. 2011, 47, 43.
[12] Y. Jiang, L. L. Sun, G. Z. Ren, X. Niu, W. Z. Hu, Z. Q. Hu, Chem. Open
2015, 4, 378.
[13] W. H. Ding, W. Cao, X. J. Zheng, D. C. Fang, W. T. Wong, L. P. Jin,
SUPPORTING INFORMATION
Inorg. Chem. 2013, 52, 7320.
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[14] S. Erdemir, O. Kocyigit, S. Malkondu, J. Fluoresc. 2015, 25, 719.
[15] K. Ghosh, S. Panja, T. Sarkar, Supramol. Chem. 2015, 27, 490.
[16] Y. Deng, Y. Chen, D. Cao, Z. Liu, G. Li, Sensor. Actuat. B‐Chem. 2010,
149, 165.
How to cite this article: Ren Y, Han J, Wang Y, Tang X, Wang
L, Ni L. An OFF–ON–OFF type fluorescent probe based on a
naphthalene derivative for Al3+ and F− ions and its biological
application. Luminescence. 2017;1–7. https://doi.org/10.1002/
bio.3366
[17] Y. W. Liu, M. X. Kao, A. T. Wu, Sensor. Actuat. B‐Chem. 2015, 208, 429.
[18] R. Sakai, A. Nagai, Y. Tago, S. I. Sato, Y. Nishimura, T. Arai, T. Satoh, T.
Kakuchi, Macromolecules 2012, 45, 4122.
[19] C. Saravanan, S. Easwaramoorthi, C. Y. Hsiow, K. Wang, M. Hayashi, L.
Wang, Org. Lett. 2014, 16, 354.
[20] P. C. Swamy, S. Mukherjee, P. Thilagar, Anal. Chem. 2014, 86, 3616.