A dual–function fluorescent probe for Hg (II) and Cu (II) ions with two mutually independent sensing pathways and its logic gate behavior

Article abstract of DOI:10.1016/j.saa.2019.117645

A dual–function fluorescent Probe 1 has been synthesized conveniently by coupling rhodamine hydrazone with O–vinyl protected hydroxyl benzaldehyde. Probe 1 was a highly selective and sensitive chemodosimeter for Hg²⁺ through specific hydrolysis reaction of vinyl ethers with significant fluorescence quenching in CH₃CN–PBS buffer (3:7, v/v) solution. Meanwhile, Probe 1 showed a ratiometric fluorescent detection of Cu²⁺ with a remarkable large Stokes shift (150 nm) by the opening of the spirolactam ring in CH₃CN–PBS buffer (3:7, v/v) solution. Hence, the two recognition mechanisms realized well by using a single fluorescent probe. Moreover, Probe 1 could be efficiently applied to the combinatorial logic circuit of NOR and INHIBIT gates through the procured spectral results, respectively.

Full text of DOI:10.1016/j.saa.2019.117645

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 226 (2020) 117645
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
A dualefunction fluorescent probe for Hg (II) and Cu (II) ions with two
mutually independent sensing pathways and its logic gate behavior
Ming Dong*, Jinyu Tang, Yanfei Lv, Yating Liu, Jinfeng Wang, Tiantian Wang, Jingyi Bian,
Chunju Li**
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of InorganiceOrganic Hybrid Functional Material
Chemistry, College of Chemistry, Tianjin Normal University, Tianjin, 300387, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A dualefunction fluorescent Probe 1 has been synthesized conveniently by coupling rhodamine
hydrazone with Oevinyl protected hydroxyl benzaldehyde. Probe 1 was a highly selective and sensitive
chemodosimeter for Hg2þ through specific hydrolysis reaction of vinyl ethers with significant fluores-
cence quenching in CH3CNePBS buffer (3:7, v/v) solution. Meanwhile, Probe 1 showed a ratiometric
fluorescent detection of Cu2þ with a remarkable large Stokes shift (150 nm) by the opening of the spi-
rolactam ring in CH3CNePBS buffer (3:7, v/v) solution. Hence, the two recognition mechanisms realized
well by using a single fluorescent probe. Moreover, Probe 1 could be efficiently applied to the combi-
natorial logic circuit of NOR and INHIBIT gates through the procured spectral results, respectively.
© 2019 Elsevier B.V. All rights reserved.
Received 12 June 2019
Received in revised form
10 September 2019
Accepted 8 October 2019
Available online 9 October 2019
Keywords:
Dualefunction
Ratiometric
Chemodosimeter
Combinatorial logic circuit
1. Introduction
the U.S. EPA [10]. Thus, developing a highly selective method to
detect Cu2þ is imminently required, and a great number of fluo-
Many metal ion analytes play a vital role in various biological
processes, beyond an optimum limit each of them could potentially
become dangerous to human beings. This makes the sensing and
analysis of such analytes very important. Even at low concentra-
tions, Hg2þ can lead to the dysfunction of the brain, kidney, and
central nervous system because biological ligands, especially for
sulfur-containing proteins, DNA, and enzymes, can coordinate with
mercury cations [1e3]. The permitted limit of Hg2þ ion in water is
only 2 ppb as per the U.S. EPA [4]. Thus, mercury pollution has
sparked interest in the design of new strategies to monitor Hg2þ in
biological and environmental samples. Since Czarnik demonstrated
the first synthetic chemodosimeter for the selective determination
of Hg2þ [5], many new approaches based on the irreversible
chemical reaction have emerged [6,7].
Copper, one of the essential elements for life, is a cofactor of
numerous enzymes and plays a crucial role in many biological
processes [8]. This redox reactivity is potentially harmful to live
organisms, since compromises in homeostatic control of copper
pools may result in oxidative damage to tissue and organ systems
[9]. The permitted limit of Cu2þ ion in water is only 1.3 ppm as per
rescent probes for selective detection of Cu2þ ions [11e19] have
been prepared.
Compared to singleeanalyte responsive probes, multifunctional
probes [20e33] that can simultaneously detect multiple analytes
exhibit advantages such as analytical time reduction, convenience,
and costeeffectiveness. Though there are several reports based on
rhodamine systems for the detection of Hg2þ or Cu2þ, no effort has
been made to detect both Hg2þ and Cu2þ ion simultaneously.
Herein we report a new dualefunction fluorescent Probe 1
(Scheme 1) for the detection of Hg2þ and Cu2þ using two different
mutually independent sensing pathways. Probe 1 was a highly
selective and sensitive chemodosimeter for Hg2þ through specific
hydrolysis reaction of vinyl ethers with significant fluorescence
quenching in CH3CNePBS buffer (3:7, v/v) solution. Meanwhile,
Probe 1 showed a ratiometric fluorescent detection of Cu2þ with a
remarkable large Stokes shift (160 nm) by the fluorescence reso-
nance energy transfer (FRET) from vinyl protected 4-diethylamino
aryl to rhodamine fluorophore in CH3CNePBS buffer (3:7, v/v) so-
lution. The single fluorescent molecule Probe 1, can respond to
Hg2þ, Cu2þ, and Hg2þ/Cu2þ with three different sets of fluorescence
signals (Table 1). Correspondingly, Probe 1 exhibited NOR and
INHIBIT logic gates with Hg2þ and Cu2þ as chemical inputs by
monitoring the emission mode at 515 and 580 nm, respectively, due
to the two different mutually independent sensing pathways.
* Corresponding author.
** Corresponding author.
E-mail addresses: hxxydongm@tjnu.edu.cn (M. Dong), cjli@shu.edu.cn (C. Li).
https://doi.org/10.1016/j.saa.2019.117645
1386-1425/© 2019 Elsevier B.V. All rights reserved.

2
M. Dong et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 226 (2020) 117645
Scheme 1. Dualefunction fluorescent Probe 1 for the detection of Hg2þ and Cu2þ using two different mutually independent sensing pathways.
Table 1
A unique type of a single fluorescent probe that can report Cu2þ, Hg2þ, and Cu2þ/Hg2þ with three different sets of fluorescence signals: black-yellow-yellow; black-
eblackeblack; and blackeblackeyellow.
Input
Ex. 420 nm
Ex. 530 nm
Em. 580 nm
Fluorescence singal patterns
Em. 515 nm
Em. 580 nm
Free
Cyan-black-black
Cu2þ
Black-yellow-yellow
Black- black - black
Black- black -yellow
Hg2þ
Cu2þ þ Hg2þ
2. Experiment
reflux for 6 h. After the ethanol was evaporated under reduced
pressure, the residue was purified by silica gel column chroma-
tography (CH2Cl2/MeOH ¼ 100:1, v/v) to give 0.52 g of Probe 1
(79%) as a yellow solid (Figs. S1 and S2). 1H NMR (CDCl3, 400 MHz):
2.1. Materials and instruments
Unless otherwise noted, all chemicals and solvents were ob-
tained as the analytical grade by commerce and used without
further purification. Flash chromatography was carried out using
200e300 mesh silica gel. 1H and 13C NMR spectra were recorded in
CDCl3 or DMSO-d6 using a Bruker 400 MHz instrument and spectral
data are reported in ppm relative to tetramethylsilane (TMS) as an
internal standard. Fluorescence emission spectra were recorded on
a Hitachi F4500 fluorescence spectrofluorometer. The pH value was
measured using a Sartorius PBe10 pH meter equipped with a
PYeASI combination glass pH electrode.
d
8.49 (s, 1H), 7.98 (m, 2H), 7.84 (d, J ¼ 8.8 Hz, 1H), 7.42 (m, 2H), 7.06
(m, 1H), 6.54 (d, J ¼ 8.8 Hz, 2H), 6.41 (dd, J ¼ 13.6, 6.0 Hz, 1H), 6.40
(d, J ¼ 2.4 Hz, 2H), 6.34 (dd, J ¼ 8.8, 2.4 Hz, 1H), 6.21 (dd, J ¼ 8.8,
2.4 Hz, 1H), 6.02 (d, J ¼ 2.4 Hz, 1H), 4.51 (dd, J ¼ 13.6, 1.6 Hz, 1H),
4.20 (dd, J ¼ 6.0, 1.6 Hz, 1H), 3.30 (m, 12H), 1.14 (t, J ¼ 7.2 Hz, 12H),
1.11 (t, J ¼ 7.2 Hz, 6H); 13C NMR (CDCl3, 100 MHz):
d 164.8, 163.9,
152.7 (2C), 152.2, 150.9, 149.5, 148.8 (2C), 142.0, 132.8, 132.1, 129.1,
128.0, 127.9 (2C), 127.8 (2C), 123.4, 123.1, 114.1, 109.5, 108.1 (2C),
106.2, 103.8, 98.0 (2C), 65.6, 44.5 (2C), 44.3 (4C), 12.6 (4C), 12.5 (2C).
ESIꢀMS: m/z ¼ 658.35 [M þ H] þ
.
Stock solutions (10.0 mM) of the perchlorate salts of Mg2þ, Ca2þ
,
Ba2þ, Sr2þ, Ni2þ, Cr3þ, Mn2þ, Co2þ, Zn2þ, Cd2þ, Pb2þ, Fe2þ, Fe3þ, Cu2þ
and Hg2þ were prepared in deionised water. Stock solution
(10.0 mM) of Cuþ ions was generated from CuSO4 (10.0 mM) and
NaAsc (Sodium ascorbate, 100 mM) in situ [34].
3. Results and discussion
3.1. Fluorescent response to Cu2þ and Hg2þ
Stock solutions of the host compounds (10.0 mM) were pre-
pared in CH3CN. Test solutions were prepared by diluting 2.0 mL of
Probe 1 showed good stability in pH ranging from 7.0 to 10.0
(Fig. S3). Upon the addition of Cu2þ, probe 2 exhibited good fluo-
rescence response for Cu2þ in the pH range of 5.0e10.0. Considering
the applications in biological systems, pH 7.40 was selected for the
following experiments.
probe 1 stock solution to 2.0 mL with CH3CNePBS buffer (10.0 mM,
pH ¼ 7.40, 3/7, v/v) solution, followed by the addition of an
appropriate aliquot of each ion stock solution. For all measure-
ments, fluorescence spectra were obtained by excitation at 420 or
530 nm; both the excitation and emission slit widths were 5 nm.
Fluorescence quantum yields were determined by standard
As shown in Fig. 1a, Probe 1 exhibited a weak emission band at
580 nm by excitation of the rhodamine fluorophore at 530 nm.
Then Mg2þ, Ca2þ, Ba2þ, Sr2þ, Ni2þ, Cr3þ, Mn2þ, Co2þ, Zn2þ, Cd2þ
,
methods, using quinine sulfate (
standard.
F
¼ 0.54 in 1 N H2SO4) as a
Pb2þ, Fe2þ, Fe3þ, Cuþ, Cu2þ and Hg2þ ions were used to examine the
selectivity of Probe 1 (10 M) in CH3CNePBS buffer (10.0 mM,
m
pH ¼ 7.40, 3/7, v/v) solution, and Fe, Cle, Bre, Ie, CNe, AcOe, ClO4e,
CF3SOe3 , NO3e, HSOe4 , H2PO4e, BF4e, N3e, and SCNe (as corresponding
tetrabutylammonium salt, respectively) were used to study the
effect of counter anion in the sensing. Fluorescence spectra were
recorded after 5 min upon the addition of 5.0 equiv of each of the
respective ions. Compared to other ions measured, only Cu2þ
2.2. Preparation of probe 1
Compound 1e3 were synthesized according to literature
[35,36], as shown in Scheme 2. A stirred solution of 2 (0.219 g,
1 mmol), 3 (0.456 g, 1 mmol), and 50 mL ethanol was heated to

M. Dong et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 226 (2020) 117645
3
Scheme 2. The synthesis of Probe 1.
Fig. 1. (a) Fluorescence responses of Probe 1 (10
m
M) in CH3CNePBS buffer (10.0 mM, pH ¼ 7.40, 3/7, v/v) solution (lex ¼ 530 nm). (b) Fluorescent spectra of Probe 1 (10
m
M) upon
addition of Cu2þ (from 0 to 4.0 equiv) in CH3CNePBS buffer (10.0 mM, pH ¼ 7.40, 3/7, v/v) solution (lex ¼ 530 nm). Inset: Plot of the fluorescent intensity of Probe 1 as a function of
Cu2þ concentration at 580 nm. (c) Fluorescent spectra of Probe 1 (10
Fluorescence changes in the CIE diagram of Probe 1 (10
m
M) upon addition of Cu2þ in CH3CNePBS buffer (10.0 mM, pH ¼ 7.40, 3/7, v/v) solution (lex ¼ 420 nm). (d)
m
M) with the increase of Cu2þ in the CH3CNePBS buffer solution. lex ¼ 420 nm.
brought about a prominent fluorescence emission band centered at
580 nm assigned as a characteristic peak of ringeopened rhoda-
mine moiety, which indicated that Probe 1 displayed selective
fluorescence response to Cu2þ. To validate the selectivity of Probe 1
in practice, the competition experiments were also conducted by
addition of 5.0 equiv of Cu2þ to their aqueous solutions in the
presence of 10.0 equiv of other metal ions (Fig. S4). There is no
obvious interference for each of the competitive metal ions, which
indicated that the system of Probe 1eCu2þ was hardly affected by
these coexistent ions. These results suggested that Probe 1
revealed an excellent selectivity toward Cu2þ in CH3CNePBS buffer
at neutral pH.
The fluorescence titrations of Cu2þ were also studied using a
10.0 mM solution of Probe 1 in CH3CNePBS buffer (10.0 mM,
pH ¼ 7.40, 3/7, v/v) solution when excited at 420 and 530 nm,
respectively (Fig. 1b and c). Upon the addition of Cu2þ to the so-
lution of Probe 1 (
cence intensity (
¼ 0.21) at 580 nm with 21efold was observed by
excitation at 530 nm. Further increase in the concentration of Cu2þ
(>30 M) led to no further fluorescence increase (Fig. 1b, inset).
F
¼ 0.08), a remarkable increase of the fluores-
F
m

4
M. Dong et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 226 (2020) 117645
Furthermore, by excitation at 420 nm, Cu2þ caused the change of
the maximum fluorescence emission of Probe 1 from 515 to
580 nm, upon the addition of Cu2þ to the solution, which indicated
a clear ratiometric fluorescence change (Fig. 1c). The ratio of fluo-
rescence intensity at 580 and 515 nm increased linearly with the
detection limit for Hg2þ was calculated to be 1.22
shown in Fig. S12.
mM (244 ppb), as
3.2. Proposed mechanism
concentration of Cu2þ (2.0e25.0
m
M, Fig. S5).
The corresponding detection limit for Cu2þ was calculated to be
0.67 M (42.6 ppb), as shown in Fig. S6. Meanwhile, the solution
The photophysical properties revealed that Probe 1 was a highly
selective and sensitive chemodosimeter for Hg2þ and a ratiometric
fluorescent probe for Cu2þ simultaneously. More direct evidence
was obtained by the 1H NMR titrations (Fig. 3) and the ESI mass
spectrum (Fig. S13) of the system of Probe 1eHg2þ. As shown in
Fig. 3, Ha, Hb, and Hc belong to the proton signals of vinyl ether
moiety in Probe 1 (Fig. 3c). Remarkably, these signals disappeared
after the addition of Hg2þ (Fig. 3b), and instead, the imine moiety
and phenolic hydroxyl group proton signals of the compound 4
were observed. In mass spectrum, a peak at m/z 934.99 was
assigned to oxymercuration intermediate Probe 1eHg2þ (Fig. S13).
Accordingly, upon the addition of Hg2þ to the solution of Probe 1,
the Hg2þepromoted hydrolysis reaction of aryl vinyl ether
occurred, followed by the generation of phenol hydroxyl, which is a
weaker electron-donating group than vinyl ether group [37]. Then
the decrease of the fluorescence intensity at 515 nm may be due to
breaking the ICT process (Intramolecular Charge Transfer) from 4-
diethylamino group to imine moiety.
m
containing Cu2þ exhibited a change of fluorescence color from cyan
to yellow under irradiation by a 365 nm UV lamp (as shown in
Fig. 1c), which were also marked in the CIE diagram. It is worth
mentioning that the CIE color coordinates of Probe 1 were located
at the boundary between the green light and yellow light. The Job’s
plots and nonlinear fitting of the titration curve (Figs. S7 and S8)
confirmed a 1:1 stoichiometry between Probe 1 and Cu2þ with the
association constants of 1.4 ꢁ 106 Me1. Reversible titration using
EDTA/Cu2þ (Fig. S9) demonstrated that the above fluorescent re-
sponses were also reversible. These results indicated that Probe1
could be a fluorescent ratiometric probe for the Cu2þ ion in the
CH3CNePBS buffer solution.
We surmised that the response of Probe 1 to Hg2þ is feasible
owing to specific hydrolysis reaction of vinyl ethers. Upon the
addition of various metal ions to the CH3CNePBS buffer (10.0 mM,
pH ¼ 7.40, 3/7, v/v) solution of Probe 1, a significant decrease of the
A plausible mechanism of Probe 1 for detecting Cu2þ is pro-
posed in Fig. 4, in which Cu2þ is coordinated cooperatively with
carbonyl O, imino N, and the ortho-phenol O, and induced
ringeopening of the spirolactam moiety.
This mechanism has been researched in detail by Tong’s work
[38]. That suggests Probe 1 could be served as a ratiometric fluo-
rescent chemosensor with the FRET from the 4-diethylamino aryl
(donor) to the ringeopened form of rhodamine (acceptor), which is
consistent with the photophysical properties (Fig. S14).
fluorescence intensity (
F
¼ 0.005) at 515 nm was observed (Fig. 2a).
The fluorescence intensity of Probe 1 at 515 nm decreased to 24%
when 10.0 equiv of Hg2þ was present. The fluorescence quench
could be due to the hydrolysis reaction of aryl vinyl ethers pro-
moted by Hg2þ, which may result in the inhibition of intra-
molecular charge transfer (ICT). The competition experiments were
also conducted by addition of 4.0 equiv of Hg2þ to the aqueous
solutions in the presence of 10.0 equiv of other metal ions (Fig. S10).
There is no obvious interference for each of the competitive metal
ion. When the fluorescence spectra were recorded after 60 min
(Fig. S11), upon the addition of Hg2þ to the solution of Probe 1, the
titration of Probe 1 with Hg2þ (from 0 to 2.5 equiv.) showed
saturation behavior at 0.5 equiv. of Hg2þ, and suggested that Probe
1 could be a chemodosimeter for Hg2þ with the 1:1 stoichiometry
3.3. Logic behavior of probe 1 with Cu2þ and Hg2þ as inputs
Due to the distinguishing fluorescence responses of Probe 1
(10.0 m m mM), it
M) in the presence of Cu2þ (20.0 M) and Hg2þ (20.0
would be able to act as a two output combinatorial logic circuit. The
combination of Cu2þ and Hg2þ as input signals on Probe 1 led to a
logic operation characteristic for a twoeinput INHIBIT gate on the
emission at 580 nm and NOR gate on emission at 515 nm. As shown
in Fig. 5, the fluorescence of Probe 1 at 515 nm (output 1) is the
strongest in the absence of any input, while the remaining com-
binations lead to a much weaker signal. Defining positive logic for
the output 1 channel (binary encoding: high signal ¼ 1, low
signal ¼ 0), the truth table of a NOR gate was gained. On the other
between Probe 1 and Hg2þ
The fluorescence titrations of Hg2þ were also studied using a
10.0 M solution of Probe 1 in CH3CNePBS buffer (10.0 mM,
.
m
pH ¼ 7.40, 3/7, v/v) solution when excited at 420 nm (Fig. 2b). Upon
the addition of Hg2þ to the solution for 5 min, a remarkable
decrease of the fluorescence intensity at 515 nm was observed.
Further increase in the concentration of Hg2þ (>40
mM) led to no
further fluorescence increase (Fig. 2b, inset). The corresponding
Fig. 2. (a) Fluorescence responses of Probe 1 (10
m
M) in CH3CNePBS buffer (10.0 mM, pH ¼ 7.40, 3/7, v/v) solution (lex ¼ 420 nm). (b) Fluorescent spectra of Probe 1 (10
mM) upon
addition of Hg2þ (from 0 to 10.0 equiv) in CH3CNePBS buffer (10.0 mM, pH ¼ 7.40, 3/7, v/v) solution (lex ¼ 420 nm). Inset: Plot of the fluorescent intensity of Probe 1 as a function of
Hg2þ concentration at 515 nm.

M. Dong et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 226 (2020) 117645
5
Fig. 3. Proposed mechanism of Probe 1 with Hg2þ and Partial 1H NMR spectra in DMSO-d6/D2O (10:1, v/v): (a) compound 4, (b) Probe 1 þ Hg2þ, (c) probe 2 only.
Fig. 4. Proposed binding mode between Probe 1 and Cu2þ
.
Fig. 5. (a) Inputedependent changes of fluorescence spectra of Probe 1 with excitation at 420 nm. (b) The changes in fluorescence intensity of Probe 1 (20.0
with Cu2þ (20.0 M) and Hg2þ (20.0 M) as chemical inputs. (c) Truth table of Probe 1. Input 1 and Input 2 represent Hg2þ ions and Cu2þ ions (20.0
Output 2 are the fluorescence intensity at 515 and 580 nm, respectively. (d) Scheme of the logic gate for Probe 1.
m
M) at 515 and 580 nm
m
m
mM), respectively; Output 1 and

6
M. Dong et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 226 (2020) 117645
Flatbedescannerebased colorimetric Cu2þ signaling system derived from a
hand, the output 2 channel (emission at 580 nm) realizes an
INHIBIT gate (binary encoding: high signal ¼ 1, low signal ¼ 0) with
input 1 holding a veto. The strongest signal for the output 2 channel
is observed in the presence of Cu2þ, and it is due to the FRET
occurring within Probe 1eCu2þ complex.
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In summary, dualefunction fluorescent Probe 1 for the detec-
tion of Hg2þ and Cu2þ using two different mutually independent
sensing pathways with excellent high selectivity has been suc-
cessfully designed and synthesized. It exhibited a typical FRET
process induced by Cu2þ and exhibited a significant change in the
intensity ratio of the two emission bands of 4-diethylamino aryl
and rhodamine, which is due to Cuechelating spirolactam
ringeopen and efficiently transfer the energy from 4-diethylamino
aryl to rhodamine. However, Probe 1 employed Hg2þepromoted
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Declaration of competing interest
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There are no conflicts of interest to declare.
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A fluorescein-based chemosensor for relay fluorescence recognition of Cu (II)
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Acknowledgment
This work was financially supported by the Doctoral Fund
Project of Tianjin Normal University (52XB1407), and the Founda-
tion of Development Program of Future Expert in Tianjin Normal
University (WLQR201710).
Appendix A. Supplementary data
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