Multi-responsive fluorescent probe based on AIE for the determination of Fe3+, total inorganic iron, and CN- in aqueous medium and its application in logic gates

Article abstract of DOI:10.1016/j.jphotochem.2020.112969

A novel and simple probe (denoted LN-1) with AIE property based on malononitrile and 4-diethylaminobenzaldehyde was designed and synthesized. The use of two different mechanisms for the independent detection of Fe³⁺ and CN^? is more c

Full text of DOI:10.1016/j.jphotochem.2020.112969

Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
Contents lists available at ScienceDirect
Journal of Photochemistry & Photobiology, A: Chemistry
journal homepage: www.elsevier.com/locate/jphotochem
Multi-responsive fluorescent probe based on AIE for the determination of
Fe3+, total inorganic iron, and CN- in aqueous medium and its application
in logic gates
Xiaoye Wen, Li Yan, Zhefeng Fan*
Department of Chemistry, Shanxi Normal University, Linfen 041004, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
A novel and simple probe (denoted LN-1) with AIE property based on malononitrile and 4-diethylaminobenzal-
dehyde was designed and synthesized. The use of two different mechanisms for the independent detection of
Fe3+ and CNꢀ is more convenient and efficient than the continuous detection of anions and cations. The
detection mechanism was verified by mass spectrometry (MS), nuclear magnetic resonance (NMR) spectrum, and
particle size distribution. Under optimized experimental conditions, excellent calibration curves were obtained
Aggregation induced emission
Bioimaging
Total inorganic iron
CN-
Fe3+
for the LN-1-Fe3+ and the LN-1-CNꢀ with detection limits of 0.17 and 0.39
μM, respectively. This method was
Logic gate
successfully applied to detect the content of Fe3+ and total inorganic iron in actual samples. Owing to its low
cytotoxicity, good biocompatibility, and enhanced orange emission in aqueous solution, the LN-1 was success-
fully applied for CNꢀ imaging in live cells. In addition, Fe3+ and EDTA incorporation into the LN-1 changed the
fluorescent intensity, which is beneficial in constructing ultrasensitive INHIBIT logic gate.
1. Introduction
that are harmful to the natural environment and human health [26–30]
and present in industrial waste water [31–35]. Therefore, the design of
Iron ions play an essential physiological role in living systems, such
as gene expression, cell metabolism, neurotransmission, electron trans-
fer, and oxygen transport [1–3]. Iron deficiency or excess can lead to
serious biological diseases, such as anemia and neurodegenerative dis-
orders [4–6]. Hence, many methods have been developed to detect iron
ions. Among them, fluorescence technology is favored due to its good
selectivity, sensitivity, and rapid detection [7–9]. Various fluorescence
analysis materials have been used, such as tyloxapol oligomer [10],
spiropyran derivatives [11], benzothiazole derivatives [12], pyrazole
bearing imidazole derivatives [13], polyurethane derivatives [14], tet-
raphenylethene derivatives [15], and Schiff base derivatives [16].
Although many probes have been developed to detect Fe3+ in organic
solvents, most Fe3+ molecules are found in water environment and
biological materials [17–19]. And studies on the detection of inorganic
total iron are relative few [20]. Owing to the positive effect of iron in the
redox process, the total inorganic iron content must be analyzed, and
novel probes must be created to detect iron ions and total inorganic iron
in aqueous solution. In addition to their environmental, biological, and
catalytic applications [21], cations and anions are important sources of
water and food pollution [22–25]. CNꢀ is one of the most toxic anions
novel materials for the sensing of low CNꢀ level in aqueous solution is of
great importance.
Most conventional fluorescent molecules exhibit an aggregation
caused quenching (ACQ) effect [36] and are effectively emitted in dilute
solutions; however, their fluorescence is greatly weakened or even
completely quenched in large concentration or aggregation state. In
addition, these molecules only work in organic solution media, thus
greatly limiting their application in biological and aquatic environments
[37]. The luminous efficiency based on aggregates is high in a diluted
solution. In 2001, Tang et al. proposed the concept of
aggregation-induced emission (AIE) [38–40]. Owing to their advantages
of high photobleaching resistance, large contrast, and long-term and
real-time monitoring methods [38,41], AIE materials can be aroused the
attention and interest of researchers [42–46]. Based on currently re-
ported literature, many probes are used to detect Fe3+ and CNꢀ [10––16,
[47–50]. But there are still many shortcomings and defects for the re-
ported probes, such as organic solvent media, complex synthesis, long
monitoring time, poor biocompatibility, and impossibility for multiple
detection. Therefore, there is still a great challenge to design simple and
effective AIE based multi-probes for rapid detection of Fe3+, total
* Corresponding author.
E-mail address: zhefengfan@126.com (Z. Fan).
https://doi.org/10.1016/j.jphotochem.2020.112969
Received 24 July 2020; Received in revised form 18 September 2020; Accepted 4 October 2020
Available online 10 October 2020
1010-6030/© 2020 Elsevier B.V. All rights reserved.

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
(Leica microsystems).
2.2. Synthesis and characterization
As shown in scheme S1, the synthesis method was simple and
feasible. Malononitrile (2.0 mmol) and 4-diethylaminobenzaldehyde
(2.0 mmol) were slowly added to anhydrous ethanol (15 mL). The
mixture refluxed for 24 h, then cooled to room temperature. The solvent
was removed by vacuum distillation and purified by column chroma-
tography with ethyl acetate and n-hexane as eluent, precipitated. After
vacuum drying, the orange-yellow solid as target was obtained (364.9
mg, yield: 81 %). 1H NMR (600 MHz, DMSO) δ 8.02 (s, 1 H), 7.84 (d, J
=9.1 Hz, 2 H), 6.86 (d, J =9.3 Hz, 2 H), 3.79ꢀ 3.37 (m, 4 H), 1.14 (t, J =
7.1 Hz, 6 H) (Fig. S1). 13C NMR (150 MHz, DMSO) δ 153.13, 134.67,
118.89, 115.68, 81.04, 68.33, 56.75, 44.74, 12.86 (Fig. S2). HRMS (ESI)
m/z: [M+H]+: Calculated for C14H15N3: 225.300, found: 225.116
(Fig. S3) (Scheme 1).
2.3. General method of spectral measurement
The solvent of the LN-1 stock solution (1 mM) was dimethyl sulfoxide
(DMSO), and the concentration of other anion and cation stock solution
was 10 mM. In fluorescence spectrometry, the excitation wavelength
was 390 nm, the slit width was 5/20 nm, and all tests were performed at
room temperature. The AIE properties of the LN-1 were determined by
measuring the fluorescence and absorption spectra in different mixed
Scheme 1. Proposed mechanism of the detection of Fe3+, total inorganic iron,
and CNꢀ with the LN-1.
inorganic iron, and CN- in aqueous solution and biological system with
high selectivity and good reversibility.
With the long-term interest in AIE fluorescent molecular for ion
recognition [51–54], a novel and simple probe (LN-1) exhibiting good
AIE properties was designed based on malononitrile and 4-diethylami-
nobenzaldehyde. Under the conditions of DMSO/H2O (1:99, v/v, pH
= 7.0), the LN-1 emits strong orange-red light, and the two cyano groups
in its molecule can selectively bind Fe3+ to form a complex and change
the fluorescence. When CNꢀ was added to the LN-1, the fluorescence
was quenched because the CN- nucleophilic groups were added to the
alpha position of the dicyanovinyl group, resulting in the free rotation of
the dicyano group. The LN-1 can be used for the rapid and sensitive
solvents (the volume fraction of water is 0 %–99 %). The LN-1’s (2 μM)
response to Fe3+/CNꢀ was measured under the conditions of DMSO/
H2O (1:99, v/v), pH = 7.0, and fluorescence quenching.
2.4. Determination of total inorganic iron in actual samples
The LN-1 can be used to measure the total amount of trace iron in
actual samples. Each group of experiments was measured in triplicate.
The recovery rate was determined by the addition of the standard
product. The measured fluorescence value and the standard curve
equation were used to calculate the added Fe3+ concentration in the
actual sample. After the same concentrations of Fe3+ and Fe2+ were
added to the sample, H2O2 (1.5 equiv.) was incorporated to completely
oxidize the spiked Fe2+. The total amount of iron in the solution was also
calculated by measuring the fluorescence value. Fe2+ concentration was
denoted as the difference in fluorescence intensity before and after the
oxidant was added.
detection of Fe3+ and CN- ions with detection limits of 0.17 and 0.39
μM,
respectively. In particular, the LN-1 has
a
highly selective
anti-interference effect on Fe3+, can effectively distinguish Fe3+ from
Fe2+, and was successfully applied to detect Fe3+ and total iron ions in
actual samples. Owing to its good biocompatibility, the LN-1 was also
successfully applied for CN- bioimaging. Incorporating Fe3+ and EDTA
into the probe changed the fluorescent intensity, which is beneficial in
constructing an ultrasensitive INHIBIT logic gate.
2. Experimental
2.5. Cell viability and cell imaging
2.1. Reagents and instruments
Cell viability was measured using different concentrations of the LN-
1. HeLa cells were cultured overnight at 37 ◦C in CO2 incubator. A series
All chemical reagents used in the experiments were purchased
directly without additional purification. HeLa cells were provided by
Bingxin Biotechnology (Shanghai) Co., Ltd. Other medicines were pur-
chased from Aladdin Co., Ltd. (Shanghai). The water used in the ex-
periments was ultrapure water with a resistivity of 18.2 MΩꢀ 1. The
fluorescence spectrum was collected on Cary eclipse spectrophotometer
(Agilent), The UV–vis absorption spectrum was recorded by TU-1901
of the LN-1 with different concentrations (0ꢀ 60 μM) was used to prepare
a reserve solution of culture medium (90 % DMEM).The LN-1 with
different concentrations (100 u L, three repeats for each concentration)
were added to each well of the cell culture plate. The supernatant was
removed after 6 h of incubation. CCK-8 was then added to each well, and
incubation was continued for additional 3 h. Absorbance was measured
with a microplate reader. Cell survival percentage was also calculated (A
is the absorbance of the experimental group, A0 is the absorbance of the
control group):
spectrophotometer (Purkinje General Instrument Co Ltd.), 1H NMR,13
C
NMR and HRMS spectra were collected on 600 MHz AVANCE IIIHD
NMR spectrometer (Bruker) and high-resolution mass spectrometry
(Ultraflex TOF/TOF; Bruker), the surface morphology of the probe was
observed by scanning electron microscope (SEM)(JSM-7500 F). The
particle size distribution of the probe was measured by Zetasizer Nano
ZS90 particle analyzer (Malvern Panalytical). The preparation of buffer
solution was realized by pH meter (Jinpeng Analytical Instrument Co.
Ltd.). Fluorescence images of cells were taken by confocal microscopy
VR = A/A0×100 %
The LN-1 (10 μM) was added to the medium inoculated with HeLa
cells, incubated at 37 ◦C for 30 min, washed with PBS three times (10
mM, pH = 7.4), and immediately observed under a confocal fluores-
cence microscope. The cells were then incubated with different con-
centrations (50 and 100
μ
M) of CNꢀ for 10 min, and fluorescence
imaging was performed again.
2

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
Fig. 1. (a) AIE characteristics of the LN-1 (10
μ
M) : emission intensity changes with water volume; inset: the fluorescent photo of the LN-1 with different water
fraction under UV lamp (365 nm); (b) Particle size determination of the LN-1 (10 μM): the water content was fw = 0% and the water content was fw = 99 %.
Fig. 2. (a) Fluorescence spectrum response of the LN-1 (10 μM) to different metal ions (50 μM) in H2O/DMSO (1:99, v/v); (b) metal ion competition experiments.
3. Results and discussion
the fluorescence intensity was substantially enhanced at 11 times higher
than the original intensity. Similarly, AIE properties can be verified by
UV–vis spectra (Fig. S4). With the increase in water content, the
maximum absorption peak shows a weakening trend, and the UV ab-
sorption peak was remarkably decreased when the water content was fw
= 99 %. The dispersed particle size of the LN-1 in different solvents was
determined by DLS spectra (Figs. 1b and S5). The dispersed particle size
of the LN-1 increased substantially when the solvent was DMSO/H2O
(1:99, v/v). And the quantum yield of the LN-1 in DMSO solution and in
DMSO/H2O (1:99, v/v) mixtures has been calculated to be approxi-
mately 12.79 % and 62.76 %. The above results indicated that the LN-1
3.1. LN-1’s response to metal cations
First, the fluorescence properties of the LN-1 were studied. A series of
experiments was conducted to investigate the AIE properties of the LN-1.
The LN-1 in pure DMSO had almost no fluorescence under the ultraviolet
lamp. Given that water is a poor solvent for the LN-1, its aggregation
state can be changed by increasing the water content. According to the
fluorescence spectrum (Fig. 1a), the water content was fw = 99 % in the
mixed solvent of the LN-1, the emission peak red shifted to 590 nm, and
Fig. 3. (a) Fluorescence spectra of LN-1-Fe3+; (b) Calibration plot of fluorescence intensity changes of the LN-1 (10
μ
M) with of Fe3+ (0-16
μM).
3

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
Fig. 4. 1H NMR spectrum (DMSO-d6): (a) the LN-1 (10
μ
M), (b) LN-1-Fe3+(0.5 eq.), and (c) LN-1-Fe3+(1eq.).
has good AIE characteristics, which may be attributed to the restriction
of intramolecular rotation (RIR) [40]. In further experiments, 1% DMSO
aqueous solution was used as the detection medium to improve the
biocompatibility of the LN-1.
weakened and moved slightly to the low field. With the increase in Fe3+
concentration, the proton peak became plate-like, and the shielding ef-
fect was enhanced. In addition, Fe3+ was successfully coordinated to the
LN-1 and detected by a high-resolution mass spectrometer (HRMS),
Mprobe-Fe3+ = 283.094 (Fig. S3). In addition, the scanning electron mi-
croscope (SEM) analysis was performed for studying the binding
mechanism of the probe-Fe3+ as solid evidence. As shown in Fig. S7, the
LN-1 displayed the spherical aggregates topography, larger aggregates
with irregular topography were observed with addition of Fe3+
(Fig. S7b). 1H NMR spectrum, SEM and HRMS characterization revealed
that the LN-1-Fe3+ formed a complex that changed the fluorescence
intensity. We speculated that the conjugated structure formed by the
benzene ring, vinyl group, and cyano group in the LN-1 was destroyed
due to its coordination with Fe3+. And electron was transferred from the
LUMO of excited LN-1 to the “d” orbitals of the Fe3+. The electron is then
transferred to the HOMO of the another LN-1. The electron exchange
process blocked the fluorophore to its ground state following a non-
radiative process and results in fluorescence quenching. The possible
binding mode between the LN-1 and Fe3+ is shown in Fig. 4.
The performance of the LN-1 to detect metal ions in aqueous solution
was investigated. Fig. 2a shows that when metal ions (5 equiv.) were
added, almost no change of fluorescence intensity was observed for the
LN-1. Only Fe3+ with the same amount can induce a response to the LN-
1, and its fluorescence intensity was significantly quenched with the
fluorescent color changed from orange to colorless. On the basis of the
fluorescence spectrum, a competitive experiment was performed to
investigate the interference. When Fe3+ was added to the LN-1 with
other ions (10 equiv.), the fluorescence of the LN-1 was also quenched
(Fig. 2b). This result indicated that the LN-1 displays excellent selec-
tivity and anti-interference to Fe3+
.
The effect of pH for the LN-1 and LN-1-Fe3+ was also investigated. As
shown in Fig. S6, the fluorescence intensity of the LN-1 was basically
unchanged at the pH range of 3ꢀ 8. This phenomenon occurred because
as an electron-withdrawing group, the cyano group in the LN-1 can
reduce the electron cloud density of the double bond and improve the
stability of the LN-1 under acidic conditions. The optimal pH condition
for the LN-1-Fe3+ was pH = 7.
AIE probes have been used for Fe3+ detection, but most of them
worked in organic solvent media, and only a few can determine the total
inorganic iron. Compared with other probes [10–16] [47], (Table 1), the
proposed the LN-1 has the advantages of low raw material cost, simple
synthesis process, applicability to an aqueous medium, high selectivity,
and low detection limit and therefore can be used to detect and distin-
guish the iron ions of different valence states.
The association constant and detection limit of the LN-1-Fe3+ were
determined by fluorescence titration. As shown in the Fig. 3, the fluo-
rescence quenching degree of the LN-1 increased with the Fe3+ con-
centration. In the range of 0ꢀ 16 μM, the LN-1 exhibited good linearity,
and the linear equation was Y=-14.80X + 391.67, R2 = 0.99. The
detection limit was estimated to be 0.17 μM by using the equation 3σ/k
3.3. Determination of Fe3+ and total inorganic iron in actual samples
(k is the slope of the analysis curve, and
blank samples).
σ is the standard deviation of 11
Satisfactory results were obtained for the detection of Fe3+ and total
inorganic iron in water samples (Tables 1 and 2). The water samples
were collected from rivers and lakes in LinFen, Shanxi, centrifuged, and
diluted appropriately, and the recovery rate was studied by adding a
known amount of Fe3+ to the samples. The LN-1’s ability to determine
the total iron ions in the environment was studied by adding iron ions of
different valence states and H2O2 in the samples. Each experiment was
conducted three times, and a good recovery rate was obtained Table 3.
3.2. Mechanism underlying the Fe3+ detection of the LN-1
The 1H NMR spectrum (DMSO-d6) of LN-1-Fe3+ was investigated to
study the interaction between the LN-1 and Fe3+. Fig. 4 shows that after
the combination of Cyano group in the LN-1 and Fe3+, the chemical shift
of hydrogen at the Ha was affected, and the proton peak of Ha was
4

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
Table 1
Comparison of Fe3+ probes with AIE characteristics.
Probe
Medium
(V/V)
Ions
LOD (
μ
M)
Total iron ion
no
Biological
study
Ref
H2O
Fe3+, DA
2.2
no
[10]
DMF/H2O
(9:1)
Fe3+
Fe3+
0.19
8.43
no
no
no
[11]
[12]
CH3CN/H2O
(4:1)
yes
DMF/H2O
(1:1)
Fe3+
5.86
0.49
no
no
yes
no
[12]
[13]
DMSO/H2O (1:9)
Fe3+
buffered/MeOH (9:1)
Fe2+, Fe3+
2.19,
0.56,
15.80
yes
yes
[14]
DMF/H2O (8:2)
EtOH/H2O(9:1)
Fe3+, Al3+
Fe3+, Cu2+
–
–
no
no
no
no
[15]
[16]
ACN/H2O (7:3)
Fe3+, Al3+
1.73
0.17
no
yes
yes
[47]
DMSO/H2O (1:99)
Fe3+, CNꢀ
yes
This work
3.4. LN-1 response to anions
Table 2
Analysis results of detection Fe3+ in water (mean ± S, n = 3).
Twelve anions including CNꢀ , Fꢀ , Clꢀ , Brꢀ , Iꢀ , CO23-, NO3ꢀ , HCOꢀ3 , S2-,
H2POꢀ4 , HPO42-, and CH3COOꢀ were evaluated selectively to further
study the role of the LN-1 in anion detection. Fig. 5 shows that among
these anions, only the addition of CNꢀ under an ultraviolet lamp (365
nm) successfully quenched the fluorescence of the LN-1. Anion compe-
tition experiments confirmed the above finding and showed that the
fluorescence intensity did not change significantly when other anions
were added in the system. This result proved that the LN-1 was more
selective to CNꢀ compared with other competitive metal ions. Moreover,
the fluorescence changes of the LN-1 were examined with CNꢀ additions
under different pH conditions (Fig. S8). The change in pH almost had no
samples
Found
Spiked (μM)
Found (
μM)
Recovery
(%)
5
5.54 ± 0.35
9.80 ± 0.21
5.46 ± 0.36
10.10 ± 0.13
110.94
98.07
Lake water
River water
No detected
No detected
Fe3+
Fe3+
10
5
109.27
100.96
10
effect on the fluorescence of the LN-1. With regard to its application in
biological systems, the LN-1 can detect CN- at the medium condition of
pH = 7.
Fluorescence titration was also conducted to determine the linear
5

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
Table 3
Analysis results of detection total iron ion in water (mean ± S, n = 3).
samples
Found
Spiked (
μ
M)
Found (
μM)
Recovery
(%)
5
No detected
No detected
5.42 ± 0.30
9.80 ± 0.28
No detected
No detected
5.17 ± 0.19
9.60 ± 0.06
–
Fe2+
10
–
Lake water
River water
No detected
No detected
Fe3+, Fe2+
5, 5
108.41
98.01
–
Fe3+, Fe2+, H2O2
5, 5, 7.5
5
Fe2+
10
–
Fe3+, Fe2+
5, 5
103.47
96.00
Fe3+, Fe2+, H2O2
5, 5, 7.5
equation and detection limit of the LN-1-CNꢀ . As shown in Fig. 6, the
fluorescence intensity of the LN-1 decreased with the increase in CNꢀ
excellent AIE effect. Prior to cell imaging (Fig. S9), cell toxicity was
evaluated by co-incubating the LN-1 of different concentrations (0, 10,
concentration. When the concentration of CNꢀ reached 40
μM, the
20, 30, 40, 50, and 60 μM) with live HeLa cells. After culture for 6/10 h,
fluorescence of the LN-1 was almost completely quenched. In the range
the cell viability was not almost affected. After 6and 10 h of incubation,
the survival rate of the cells was 98.58 %–92.63 %, 98.22 %–89.17 %,
respectively. This finding proved that the LN-1 has low toxicity and good
biocompatibility and thus can be applied in cell imaging.
of 4ꢀ 40
μ
M CNꢀ concentration, the fluorescent quenching of the LN-1
displayed good linearity with the linear equation of Y= -6.55X +
389.60 (R2 = 0.99) and detection limit of 0.39
μM.
Cell imaging experiments were performed. Fig. 7 shows that under
confocal microscopy, the HeLa cells remained active after co-incubation
with the LN-1, and almost all cells were fluorescently stained with the
3.5. Application in bioimaging
LN-1. When CNꢀ (50
μM) was co-incubated with these cells, fluores-
CNꢀ is widely used in the industry but is highly toxic. Hence,
monitoring CN- concentration in biological systems is necessary. CN- can
be used as a biological probe for cell imaging applications due to its
cence quenching occurred in the live cells. Consistent with the cell
viability assay, cell imaging assay revealed that the LN-1 has excellent
Fig. 5. (a) Fluorescence spectrum response of the LN-1 (10
μM) to different anion ions in aqueous solution; (b) anion ion competition experiments; inset: fluorescent
photo of the LN-1 (10 M) with different anion ions under UV lamp (365 nm).
μ
Fig. 6. (a) Fluorescence spectra of the LN-1-CNꢀ ; (b) the calibration plot of fluorescence intensity changes of the LN-1 (10
μ
M) with of CNꢀ (0-40
μM).
6

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
strong and the signal of output is 1. If the input is “1, 0”, then the
fluorescence intensity is quenched and the signal of output is 0. If the
input becomes “0, 1”, then the fluorescence intensity is enhanced. If the
two inputs are “1, 1” at the same time, then the signal of output is 1.
Therefore, the LN-1 works as an INHIBIT logic gate behavior.
4. Conclusions
A novel and highly sensitive the LN-1 with AIE was designed and
synthesized to detect Fe3+ and CNꢀ in aqueous solution through
different mechanisms. Based on the principle of the specific complexa-
tion of dicyano group with Fe3+, the LN-1 can determine Fe3+ but does
not respond to Fe2+. Its excellent selectivity and anti-interference to
Fe3+ allows the LN-1 to effectively distinguish the iron ions of different
valence states. The Fe3+ detection limit was 0.17
μM, and a good re-
covery rate was obtained in the standard determination of total inor-
ganic iron in the actual sample. Through the nucleophilic addition of
cyano group and vinyl group, CNꢀ detection was realized with detection
Fig. 7. Confocal fluorescence images of live HeLa cells treated with the LN-1
μ
M) and CNꢀ (50
limit of 0.39 μM. Owing to the low cytotoxicity and good membrane
for 30 min (the first line); Cells treated with the LN-1(10
permeability of the LN-1, its applicability for CNꢀ bioimaging in live
cells was successfully completed. With its reversible emission behavior,
an INHIBIT logic gate was assembled with EDTA and Fe3+ as the two
inputs.
μ
M) for 30 min (the second line).
membrane penetration and low toxicity. Its strong fluorescence char-
acteristics are beneficial to eliminate background interference, verifying
that the LN-1 could be used to monitor CNꢀ in living cells.
Author statement
3.6. Logic gate behavior
The manuscript entitled “” by Xiaoye Wen, Li Yan, Zhefeng Fan*,
which is original and has not been published previously All authors are
aware of the submission and agree to its publication. If accepted, it will
not be published elsewhere in the same form, in English or in any other
language, including electronically without the written consent of the
copyright-holde. Signed by all authors as follows:
To build the molecular logic gate behavior of the present system, the
fluorescence “on–off” process of the LN-1 was examined using fluores-
cence intensity as output and EDTA and Fe3+ as two inputs. The easy
molecular system of the LN-1 associates was in good agreement with an
INHIBIT logic gate behavior (Fig. 8). According to the INHIBIT logic gate
features of the LN-1, EDTA and Fe3+ were labeled as the behavior inputs,
and the intensity of fluorescence peak at 590 nm was the output (Fig. 8).
Four different settings appeared, namely, in the presence of EDTA, the
presence of Fe3+; the presence of EDTA and Fe3+, and the absence of
EDTA and Fe3+. If the input is “0, 0”, then the fluorescence intensity is
Xiaoye Wen wenxiaoye84@163.com
Li Yan 1203055687@qq.com
Zhefeng Fan zhefengfan@126.com
Fig. 8. (a) Logic gate behavior of the LN-1 with Fe3+/EDTA; (b) truth table for the INHIBIT logic gate; (c) Fl spectra of the LN-1 (10
inset: the diagram for reversible logic operations through “write-read-erase-read” functions.
μM) with adding different inputs,
7

X. Wen et al.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112969
[20] S. Rattanopas, P. Piyanuch, K. Wisansin, A. Charoenpanich, J. Sirirak,
W. Phutdhawong, N. Wanichacheva, J. Photochem. Photobiol. A: Chem. 377
(2019) 138–148.
Declaration of Competing Interest
The authors report no declarations of interest.
[21] P.A. Gale, Chem. Commun. 47 (2011) 82–86.
[22] D. Banerjee, D. Kim, M.J. Schweiger, A.A. Kruger, P.K. Thallapally, Chem. Soc.
Rev. 45 (2016) 2724–2739.
Acknowledgements
[23] J. Li, X. Wang, G. Zhao, C. Chen, Z. Chai, A. Alsaedi, Chem. Soc. Rev. 47 (2018)
2322–2356.
This work was supported by the Doctor Fund of Shanxi Normal
University (0505/02070481)Science Foundation for Youths Fund of
Shanxi Province of China (0502/02010163) and the 1331 Engineering
of Shanxi Province.
[24] J.H. Jung, J.H. Lee, S. Shinkai, Chem. Soc. Rev. 40 (2011) 4464–4474.
[25] A.P. Esser-Kahn, A.T. Iavarone, M.B. Francis, J. Am. Chem. Soc. 130 (2008)
15820–15822.
[26] X. Zhou, J. Kim, Z. Liu, S. Jo, Y.L. Pak, K.M.K. Swamy, J. Yoon, Dye. Pigment. 128
(2016) 256–262.
[27] M. Lee, S. Jo, D. Lee, Z. Xu, Dye. Pigment. 120 (2015) 288–292.
[28] L. Nelson, J. Emerg. Nurs. 32 (2006) 8–11.
Appendix A. Supplementary data
[29] X. Cheng, H. Li, F. Zheng, Q. Lin, Y. Zhang, H. Yao, T. Wei, Dye. Pigment. 127
(2016) 59–66.
[30] D. Shan, C. Mousty, S. Cosnier, Anal. Chem. 76 (2004) 178–183.
[31] B. Yu, C.Y. Li, Y.X. Sun, H.R. Jia, J. Li, Spectrochim. Acta A. Mol. Biomol.
Spectrosc. 184 (2017) 249–254.
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jphotochem.2020.
112969.
[32] P.X. Pei, J.H. Hu, P.W. Ni, C. Long, J.X. Su, Y. Sun, RSC Adv. 7 (2017)
46832–46837.
[33] Y. Zhuge, D. Xu, C. Zheng, S. Pu, Anal. Chim. Acta 1079 (2019) 153–163.
[34] S. Suganya, E. Ravindran, M.K. Mahato, E. Prasad, Sens. Actuators B Chem. 291
(2019) 426–432.
References
[1] M. Shamsipur, M. Sadeghi, A. Garau, V. Lippolis, Anal. Chim. Acta 761 (2013)
169–177.
[35] O.J. Achadu, T. Nyokong, Dye. Pigment. 160 (2019) 328–335.
[36] J. Qi, X. Hu, X. Dong, Y. Lu, H. Lu, W. Zhao, W. Wu, Adv. Drug Deliv. Rev. 143
(2019) 206–225.
[2] S. Virtanen, A. Simojoki, H. Hartikainen, M. Yli-Halla, Sci. Total Environ. 486
(2014) 130–142.
[37] S. Kagatikar, D. Sunil, J. Mol. Liq. 292 (2019).
[38] L. Mao, Y. Liu, S. Yang, Y. Li, X. Zhang, Y. Wei, Dye. Pigment. 162 (2019) 611–623.
[39] M. Gao, B.Z. Tang, ACS Sens. 2 (2017) 1382–1399.
[40] Y.Q. Dong, J.W. Lam, B.Z. Tang, J. Phys. Chem. Lett. 6 (2015) 3429–3436.
[41] X. Chen, L. Wang, X. Yang, L. Tang, Y. Zhou, R. Liu, J. Qu, Sens. Actuators B Chem.
241 (2017) 1043–1049.
[3] J.W. Oh, T.H. Kim, S.W. Yoo, Y.O. Lee, Y. Lee, H. Kim, J. Kim, J.S. Kim, Sens.
Actuators B Chem. 177 (2013) 813–817.
[4] R.J. Ward, F.A. Zucca, J.H. Duyn, R.R. Crichton, L. Zecca, Lancet Neurol. 13 (2014)
1045–1060.
[5] T. Kurz, A. Terman, B. Gustafsson, U.T. Brunk, Histochem. Cell Biol. 129 (2008)
389–406.
[42] J. Mei, N.L.C. Leung, R.T.K. Kwok, J.W.Y. Lam, B.Z. Tang, Chem. Rev. 115 (2015)
11718–11940.
[6] M. Zheng, Z. Xie, Mater. Today Chem. 13 (2019) 121–127.
[7] Y. Luo, C. Zhu, D. Du, Y. Lin, Anal. Chim. Acta 1061 (2019) 1–12.
[8] N. Bhardwaj, S.K. Bhardwaj, D. Bhatt, D.K. Lim, K.-H. Kim, A. Deep, TrAC Trends
Anal. Chem. 113 (2019) 280–300.
[43] Y. Wang, Y. Zhang, J. Wang, X.J. Liang, Adv. Drug Deliv. Rev. 143 (2019)
161–176.
[44] Q. Xia, Z. Chen, Z. Yu, L. Wang, J. Qu, R. Liu, ACS Appl. Mater. Interfaces 10
(2018) 17081–17088.
[9] J. Li, N. Kwon, Y. Jeong, S. Lee, G. Kim, J. Yoon, ACS Appl. Mater. Interfaces 10
(2018) 12150–12154.
[45] Z. Zhao, Z. Wang, P. Lu, C. Chan, D. Liu, J. Lam, B. Z. Tang, (2009) 1345.
[46] M. Jiang, R.T.K. Kwok, X. Li, C. Gui, J.W.Y. Lam, J. Qu, B.Z. Tang, J. Mater. Chem.
B 6 (2018) 2557–2565.
[10] L. Zhao, X. Xin, P. Ding, A. Song, Z. Xie, J. Shen, G. Xu, Anal. Chim. Acta 926
(2016) 99–106.
[11] R. Zhang, L. Hu, Z. Xu, Y. Song, H. Li, X. Zhang, X. Gao, M. Wang, C. Xian, J. Mol.
Struct. 1204 (2020), 127418.
[47] S. Rattanopas, P. Piyanuch, K. Wisansin, A. Charoenpanich, J. Sirirak,
W. Phutdhawong, N. Wanichacheva, J. Photochem. Photobiol. A: Chem. 377
(2019) 138–148.
[12] X. Gong, X. Ding, N. Jiang, T. Zhong, G. Wang, Microchem. J. 152 (2020), 104351.
[13] J.S. Ganesan, M. Sepperumal, A. Balasubramaniem, S. Ayyanar, Spectrochim. Acta
A. Mol. Biomol. Spectrosc. 230 (2020), 117993.
[48] X. Cheng, R. Tang, H. Jia, J. Feng, J. Qin, Z. Li, ACS Appl. Mater. Interfaces 4
(2012) 4387–4392.
[14] K. Wang, H. Lu, B. Liu, J. Yang, Tetrahedron Lett. 59 (2018) 4191–4195.
[15] Y. Yang, C.Y. Gao, N. Zhang, D. Dong, Sens. Actuators B Chem. 222 (2016).
[16] Z.Y. Yin, J.H. Hu, K. Gui, Q.Q. Fu, Y. Yao, F.L. Zhou, L.L. Ma, Z.P. Zhang,
J. Photochem. Photobiol. A: Chem. (2020), 112542.
[49] Y. Li, Z. Gu, T. He, X. Yuan, Y. Zhang, Z. Xu, H. Qiu, Q. Zhang, S. Yin, Dye. Pigment.
173 (2020), 107969.
[50] S. Erdemir, S. Malkondu, Talanta 207 (2020), 120278.
[51] Q. Wang, X.Y. Wen, Z.F. Fan, Anal. Chim. Acta 1013 (2018) 79–86.
[52] X.Y. Wen, Z.F. Fan, Sensors and Actuators B：chemical 247 (2017) 655–663.
[53] X.Y. Wen, Q. Wang, Z.F. Fan, J. Lumin. 194 (2017) 366–373.
[54] Q. Wang, X.Y. Wen, Z.F. Fan, Physiology, J. Photochem. Photobiol. A: Chem. 358
(2018) 92–99.
[17] T. Gunnlaugsson, M. Glynn, G.M.T. Hussey, P.E. Kruger, F.M. Pfeffer, Coord. Chem.
Rev. 250 (2006) 3094–3117.
[18] S.K. Sahoo, D. Sharma, R.K. Bera, G. Crisponi, J.F. Callan, Chem. Soc. Rev. 41
(2012) 7195–7227.
[19] K. Shah, N. Ain, F. Ahmed, I. Anis, M.R. Shah, Sens. Actuators B Chem. 249 (2017)
515–522.
8