Tailoring an HSO4-anion hybrid receptor based on a phenazine derivative

Article abstract of DOI:10.1039/d0pp00159g

A catechol-functionalized phenazine imidazole (PD) was tailored with 2,3-diaminophenazine and 3,4-dihydroxy benzaldehyde, and it served as a hybrid acceptor for capturing HSO4- anions. The selectivity and sensitivity of the PD receptor for anion sensing were studied. It was found that the PD receptor could not only display a preferable sensitivity to HSO4- ions with a "turn-off"fluorescence response, but also have a strong anti-interference ability toward other common anions, especially basic anions such as CH3COO-, HPO42-, and H2PO4-. The anion recognition mechanism of PD towards HSO4- is based on multiple hydrogen bond interactions. Finally, the strips for anion detection were prepared, which were verified to be a convenient and high-efficiency test kit for detecting HSO4- ions with the naked eye.

Full text of DOI:10.1039/d0pp00159g

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1
0.1039/D0PP00159G.
Volume 16
Number 12
December 2017
Pages 1737-1846
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Page 1 of 27
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DOI: 10.1039/D0PP00159G
−
Tailoring the HSO anion hybrid receptor based on phenazine
4
derivative
a
a
a
a
a
a
Xiao-Ni Qi , Hong-Qiang Dong , Hai-Long Yang , Wen-Juan Qu , You-Ming Zhang , Hong Yao ,
a
a*
Qi Lin and Tai-Bao Wei
a
Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Key Laboratory of Eco-
environmental Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest
Normal University, Lanzhou, Gansu, PR China
Abstract: A catechol-functionalized phenaziridimidazole (PD) was tailored by 2,3-
diaminophenazine and 3,4-dihydroxy benzaldehyde, which serves as hybrid acceptor for
−
capturing HSO anion. The selectivity and sensitivity of receptor PD for anion sensing were
4
−
studied. It showed that PD can not only display the preferable sensitivity to HSO ions with
4
‘‘turn–off’’ fluorescent response, but also have strong anti-interference toward other common
−
2−
−
anions, especially the basic anions such as CH COO , HPO , and H PO . The anions
3
4
2
4
−
recognition mechanism of PD towards HSO is based on multiple hydrogen bond interaction.
4
Finally, the strips of anions detection are prepared, which is verified to be a convenient and
1
−
high-efficiency test kit for detecting HSO ions by naked-eyes.
4
Key words: phenaziridimidazole; tailored hybrid receptor; hydrogen bond; HSO4−
1*
Corresponding author
Tel: +086 9317973191; E-mail address: weitaibao@126.com.
1

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1
. Introduction
In the past few years, selective detection and targeted recognition of various noxious anions
had attracted substantial attention since they warranted a significant place in the areas of
1
-3
environmental, biological and industrial research . Owning to fluorescence chemosensors
with simplicity, low-cost, and high sensitivity, the designing and tailoring of highly selective
4
-9
optical sensors for detecting anions have aroused a great deal of interests .Among the various
anions, hydrogen sulfate anion is widely used as acid dye additives, metal pretreatment, and
industrial raw materials and regarded as harmful substrate distributed in environment system
owning to its good water solubility10-12. More importantly, it could cause certain harm to the
environment and human body, such as damage skin tissue, eyes and even causing respiratory
tract13-19. Although numerous anions recognition and detection methods have been reported20,21
the development of a sensitive, efficient, reliable, and cost-effective artificial receptor as
,
sensors for hunting HSO ions in aqueous solution is in high demand22-24.
−
4
−
According to the fact that HSO is amphiprotic ion bearing with common traits of the
4
donor and acceptor site of forming the hydrogen bond, which require to tailor the
2
5
corresponding receptor molecules to capture it . To date, merely a handful of selective
−
receptors for HSO have been documented based on the nature of donor-acceptor interaction
4
26,27,
which could be available for detecting the HSO anion by means of fluorescent sensing.
−
4
Recently, the rapid development of phenazine derivatives as outstanding sensing molecules
provided an opportunity for the tailoring and designing of anions receptor. As we all know,
2

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phenazine derivatives have special backbone structure with multiple fused aromatic rings
2
8
(
acceptor sites), the electron-sharing nitrogen atoms (donor groups) , as well as excellent
optical properties (high fluorescence quantum yield, narrow emission band, cross-interaction
2
9
30
of π-π electrons , large stokes displacement , and maximum absorption and emission
wavelength in the visible region) 31-40. These excellent properties make phenazine compound a
−
wonderful candidate for HSO anions receptor.
4
In view of this, as part of our ongoing research interests to phenazine derivatives, we
designed and synthesized corresponding receptor compound PD (Scheme 1) bearing with
−
tailored interaction sites and single selectivity to HSO which can quench the fluorescence
4
emission. Meanwhile, as a controlled experiment, compound D-1 has also been synthesized
according to our previous works41,42. By using the density functional theory (DFT), the
−
quantum chemical calculations and optimal configuration structure of the PD for HSO anions
4
were performed.
2
. Experiment
2
.1 Materials and physical methods
All reactions were carried out under N atmosphere without special instructions. All the
2
materials and chemical reagents were purchased from commercialized approaches and can be
used without further purification procedure. Double distilled water achieving from the fresh
preparation was used in the throughout experiments. All other reagents and solvents that were
analytical grade purchased commercially. Fluorescence spectra were recorded on a Shimadzu
1
RF-5301PC. H NMR spectra with DMSO‑d as solvent were received on a Mercury-600BB
6
3

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1
3
spectrometer at 600 MHz, C NMR spectra similarly with DMSO‑d as solvent were collected
6
on a Mercury-600BB spectrometer at 150 MHz. Chemical shifts (δ scale) with
tetramethylsilane (TMS) solvent resonances signal as reference standard were recorded in ppm.
A X-4 digital melting-point apparatus was used to test the melting points. Infrared spectra were
performed on a Digilab FTS-3000. Field emission scanning electron microscopy (FE-SEM,
JSM-6701F) with an accelerating voltage of 8 kV. Mass spectra were performed on a Bruker
Esquire 6000 MS instrument (Bruker-Franzen Analytik GmbH Bremen, America) equipped
with ESI interface and ion trap analyzer. The X-ray diffraction analysis (XRD) was performed
with a Rigaku RINT 2000.
2
.2. Synthesis of receptor PD and controlled compound D-1
,3-diamino phenazine was synthesized according to previous reported methods . 2,3-
4
2
2
diamino-phenazine (0.42 g, 2 mmol), 3,4-dihydroxybenzaldehyde (0.35 g, 2.5 mmol) and
acetic acid (1-2 mL) as catalyst were mixed in hot absolute DMF (20 mL). The solution was
mechanically stirred for 24 hours under continuous refluxing conditions, and then the dark
brown precipitate was achieved by filtrating the mixture after cooling to room temperature,
finally alternately washing with hot absolute ethanol and deionized water for five times. Then
recrystallized with DMF/H O (5:3 v/v) to get dark brown powdery product PD. The controlled
2
compound D-1 was synthesized by the same procedures as shown in Scheme 1.
1
PD: Yield: 78.1%; m.p.>300℃; H NMR (600 MHz, DMSO-d , 293 K) of PD δ13.09 ppm (s
6
1
H, NH), δ 9.87ppm (s 1H, OH), δ 9.47ppm(s 1H OH), δ 8.34-8.12ppm(m 4H ArH), δ 7.83ppm
1
3
(
s 1H ArH), δ 7.78(s 1H, ArH), δ 7.68 (s 1H, ArH), δ 6.92 (d 2H J=30 MHz ArH). C NMR
4

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spectrum
(150
MHz,
DMSO-d6,
293K)
of
PD
δ/ppm
-
1
1
3
60.46,150.16,142.27,140.76,129.80,129.11,116.65,110.33, 109.36,110.02. IR (KBr, cm ) v:
+
101 (N-H),3221(O-H),1649 (C=N). ESI-MS m/z: [M+H ] Calc for C H N O 329.10389;
1
9
12
4
2
Found 329.10326; Anal. Calc For C H N O : C, 71.32; H, 3.52; N, 19.57; O, 5.59; Found C,
1
9
12
4
2
7
1.26; H, 3.55; N,19.56; O, 5.63 as shown in Fig S 4. Compound D-1 was synthesized and
purified according to literature procedures (Yield: 71.2%; m.p.>300℃)
Scheme 1 Synthesis of compound PD and control compound D-1
.3 Preparation of solutions of PD, D-1, anions and cations
2
−
2
−
−
−
−
−
−
−
Sodium salt (1×10 M) of anions (F , Cl , Br , I , CH COO , SCN , CN ) and potassium
3
−
2
−
3−
4−
−
2−
−
2−
2−
salt (1.0×10 M) of anions (H PO , PO , P O , HSO , SO , ClO , S O , HPO ,
2
4
4
2
7
4
3
4
2
3
4
−
−
2−
2−
−2
3+
2+
2+
NO , NO , C O , CO ) and perchlorate metal (1×10 M) of cations (Fe , Hg , Ca ,
3
2
2
4
3
2
+
2+
2+
2+
+
2+
3+
2+
2+
3+
Cu , Co , Ni , Cd , Ag , Zn , Cr , Mg , Ba , Al ) were prepared in deionized water
with HEPES buffer solutions (pH=7.2). While kept the PD and D-1 concentration constant
−
5
(
2.0×10 M) in all experiments. The excitation and emission wavelengths were 450 nm and
5

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5
35 nm, respectively. DMSO/Ethanol/H O (1:8:1 v/v/v) system was selected as the optimal
2
mixed solvent and investigated in the supporting information as shown in Fig.S1-S3.
2
.4 Computational Methods
Density Functional Theory (DFT) was used to optimize the ground state geometries. All
4
3
the computations were operated by Gaussian 09 program by using B3LYP method combined
with 6-311G (d, p) basis sets. Visual configuration model of the structures was presented by
4
4
Gauss View 6.0 program .
3
. Results and discussion
3
.1. Interference studies
+
−
The H originating from the HSO dissociation that may interfere with sensing behavior
4
−
of HSO was investigated. The oxalic acid(H C O ) was selected as the corresponding acid
4
2
2
4
−
2
−2
with similar dissociation constant (Ka =5.9×10 ) relative to hydrogen sulfate (Ka=1.02×10 ).
1
As shown in Fig. 1, the results showed that the oxalic acid (H C O ) could not cause the
2
2
4
−
fluorescence quenching of PD compared with corresponding equiv. HSO , which further
4
+
illustrated the above recognation behavior could not absolutely ascribed to H interference
−
coming from the HSO dissociation. Meanwhile, the different pH value was investigated by
4
gradually adding HCl and NaOH to the PD solution to adjust the system pH, and the
fluorescence responses of the PD solution at different pH pots were measured (pH from 2 to
−
5
1
3). pH-dependent fluorescence responses of PD (2×10 M) upon excitation at 450 nm were
plotted as shown in Fig. S 10. It showed that the fluorescence intensity of PD was not very
6

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sensitive to a varied range of pH between 4 to 9. Such broad pH range in an aqueous
environment can afford a great opportunity in several applications.
−
Fig. 1 Fluorescence response of the PD (20uM), PD+HSO (25 equiv.), PD+H C O (25
4
2
2
4
equiv.).
.2 Exploring the spectral competition properties of PD against HSO4−
The influence of different anions on PD was carefully investigated through the addition
3
−
−
−
−
−
−
–
and diffusion of water solutions of various ions (F , Cl , Br , I , SCN , ClO , H PO ,
4
2
4
3
−
4−
2−
2−
2−
−
−
2−
2−
−
−
PO , P O , SO , S O ,HPO , NO , NO , C O , CO , CH COO , HSO ) into the
4
2
7
3
2
3
4
3
2
2
4
3
3
4
PD solution, respectively. As shown in Fig. 2, the results revealed that the maximum
fluorescence emission band showed no change after adding the hydrogen sulfate to PD, while
the fluorescence intensity of PD rapidly decreased, meanwhile other various anions showed
tiny change in maximum fluorescence emission intensity. The results powerfully manifested
−
that the PD receptor has a single selectivity to HSO over other anions.
4
7

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Fig 2. Fluorescence response of the PD (20 μM) in the presence of various anions (25 equiv.,
E = 450 nm) in three solvent system DMSO/Ethanol/H O (1:8:1, v/v/v). From 1 to 20: PD,
X
2
−
−
−
−
−
−
−
−
−
−
−
2−
−
4−
HSO , ClO , F , Cl , Br , I , CH COO , H PO , CN , SCN , NO , SO , NO , P O ,
4
4
3
2
4
3
3
2
2
7
3
−
2−
2−
2−
2−
PO , C O , S O , CO , HPO .
4
2
4
2
3
3
4
3
.3 Sensitivity studies
Furthermore, fluorescence titration experiments were carried out at room temperature
−
according to incremental addition of the standard solution of HSO (0-25 equiv. in
4
−
DMSO/Ethanol/H O (1:8:1v/v/v)). As shown in Fig 3, the increasing amount of HSO resulted
2
4
in a gradual decrease in the fluorescence emission intensity at 535 nm. Strikingly, a desirable
2
−
linear dependence (R = 0.9852) of the concentrations of HSO was achieved. The lowest
4
−
7
29
detection (LOD) was estimated as 5.49 ×10 M according to the equation LOD = K×σ/S,
where K=3. The linearity range of PD towards HSO4− in the fluorescent spectra was
−
7
−4
determined to be 2.3×10 -5×10 M (Fig. S11), which suggested that the PD has high
−
sensitivity to bind HSO . Furthermore, the Job's plot was conducted by varying the
4
8

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−
−
concentration of PD and HSO to explore the stoichiometry between PD and HSO (Fig. 3).
4
4
−
Upon addition of HSO (0–25equiv.), stable emission intensity was arrived when the molar
4
−
fraction of PD and HSO was 0.5. The binding ratio was evaluated by Job’s plot experiment,
4
−
45
which specified a 1:1 binding of PD with HSO ions. From the Benesi−Hildebrand plot , the
4
4
−1
binding constant (Ka) was estimated to be 6.48×10 M . Those results were also convincingly
−
−
supported by the ESI-MS. As show in Fig. S8, the ESI-MS [M ]of PD-HSO complex was
4
found at 425.05635, Calcd for C H N O S 425.05558.
1
9
13
4
6
-5
Fig 3. Fluorescence titration of PD (2.0×10 M) in DMSO/Ethanol/H O (1:8:1, v/v/v) solution)
2
−
upon addition of increasing with HSO . Inset: A plot of fluorescent intensity depending on the
4
concentration of hydrogen sulfate in the range from 0 to 25 equivalent.
¯
A simple comparison of some reported receptors for HSO were made in terms of the
4
interfering ions, bonding constant (Ks) and the LOD in recent 5 years as shown in Table 1.
After carefully collecting, suggested that the Ks and LOD of the present receptors molecules
¯
for detecting HSO were acceptable, but most of the selectivity and LOD needed to immensely
4
9

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enhance. In this work, we tailored and developed the receptor PD based on the nature of donor-
acceptor has high selectivity and desired LOD according to the related literature.
¯
Table 1 A Comparison of HSO chemosensors
4
Bonding
Ref
Lowest detection
Sensing Ions
constant
[
[
[
[
1]
2]
6]
9]
_
_
-
2+
HSO , Hg
4
-
4
−1
−6
HSO4
5
1
3
6
.437×10 M
5 ×10 M
_
_
_
-
3+
HSO , Fe
4
-
3
−1
HSO4
.42×10 M
[10]
[20]
[21]
[22]
[23]
_
-
2+
−
8
HSO , Zn
4
×10 M
4
_
-
3+
4
−1
HSO , NB, Fe
.69 ×10 M
4
_
_
-
-
HSO , F
4
-
5
−1
−5
HSO4
.13 ×10 M
4.427 ×10 M
-
1
10
1
−9
HSO4
4
.19×
7.5 ×10 M
−
M
2
[
24]
26]
_
-
2+
−
−
6
HSO , Zn , H PO
3
.84ꢀ×ꢀ10 ꢀM
4
2
4
[
-
3+
4
-1
−6
HSO , Fe
1
.55× 10 M
1.3ꢀ×ꢀ10 M
4
1
0

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[30]
_
-
-
−
8
HSO , CN
2
× 10 M
4
[
47]
53]
-
2+
2
−1
−5
HSO , Zn
2
6
.65 ×10 M
1.3 × 10 ꢀM
4
[
-
2+
2-
−
6
HSO , Cu , S
8
.89 ×10 M
4
_
This work
-
4
−1
−7
HSO4
.48×10 M
5.49×10 M
3
.4 Selectivity studies
The selectivity of PD to HSO was investigated by adding a variety of anions (ClO , F ,
−
−
−
4
4
−
−
−
−
2−
−
−
−
−
2−
−
4−
3−
2−
Cl , Br , I , CH COO , HPO ,H PO , CN , SCN , NO , SO , NO , P O ,PO , C O ,
3
4
2
4
3
3
2
2
7
4
2
4
2
−
2−
2+
+
2+
2+
2+
2+
3+
3+
2+
2+
S O , CO ) and various cations (Zn , Ag , Cd , Hg , Co , Ni , Al , Fe , Cu ,Pb ,
2
3
3
2
+
2+
3+
−
Mg , Ba , Cr ) and then we monitored the fluorescence intensity of PD-HSO system
4
appeared in multifarious analytical substrates. As shown in Fig. 4, Fig. S6, and Fig. S7, the
fluorescence emission showed puny variation compared with intensity of the PD-HSO4−
complex after adding all kinds of interfering ions to PD-HSO4− system. The competition
−
experiments also elucidated that other analytes hardly had effect on PD detection for HSO .
4
−
Meanwhile, it also explained that the PD had unique selectivity to HSO recognition.
4
1
1

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-5
Fig 4. Fluorescence response of the PD (2.0 ×10 M) in the presence of various anions (25
equiv., Ex = 450 nm) in three solvent system DMSO/Ethanol/H O (1:8:1, v/v/v) solution.
2
−
−
−
−
−
−
−
2−
−
−
−
From 1to 20: PD, ClO , HSO , F , Cl , Br , I , CH COO , HPO , H PO , CN , SCN ,
4
4
3
4
2
4
−
2−
−
4−
3−
2−
2−
2−
NO , SO , NO , P O , PO , C O , S O , CO .
3
3
2
2
7
4
2
4
2
3
3
3
.5 Self-assembly study of free PD
In view of our previous works, the free PD might contain various self-assembly driving
forces among intermolecular46,47. In order to gain the comprehensive understanding of the
interaction mechanism of PD molecule hunting targeted anions, we explored the possible self-
assembly courses of the free PD molecules. Herein, we carried out a series of experiments.
1
Firstly, the concentration-dependent H NMR results of PD provided important insights into
the self-assembly behaviors (Fig.5), with the concentrations of PD gradually increasing, the
resonance signal of Hc on the imidazole group (donor) and the H proton of phenol hydroxy
(acceptor) distinctly shifted downfield. These observations clearly manifested that the π–π
stacking and intermolecular hydrogen bond interaction existed in free PD molecules. In
addition, the above proposed self-assembly behaviors were further verified by XRD patterns.
As shown in Fig. 8, the XRD patterns of the PD powder (treated with the mixed solvent in
advance) appeared two peaks at 2θ =23.76°and 27.34° (d = 3.74 Å and 3.26 Å), respectively,
which suggested a long-range ordering of the molecules self-assembly appeared in the free PD
47.
Interestingly, in the SEM (Fig. 6 A), the morphology of the PD (treated with the mixed
solvent in advance) showing the network structures with the peculiarity of porous surface
displaying a regular micropore structure about 1-2 μm, suggested that PD molecules might
1
2

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4
8
self-assemble into porous structures by π–π stacking interaction . According to these results,
the proposed self-assembly mechanism of the PD was illustrated in scheme 2.
1
Fig. 5 Partial H NMR spectra in DMSO-d with different concentration of PD: (a) 0.1 mg,
6
(b) 0.3 mg, (c) 0.5 mg, (d) 1.0 mg, (e) 5 mg, (f) 10 mg, (g) 30 mg
−
Fig. 6 The SEM images of PD(A) and PD-HSO (B)
4
3
.6 Sensing mechanism
The anions sensing mechanisms of PD were adequately investigated by controlled
1
experiments, H NMR titration, IR spectra, X-ray powder diffraction, and SEM. For instance,
the D-1 without O-H corresponding to PD molecule as the controlled compound was
1
3

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−
synthesized and investigated (Fig. 7). After adding the HSO anions with equivalent molar to
4
the PD and D-1, respectively, no marked change of the fluorescence intensity of D-1 was
monitored compared with fluorescence quenching of the PD. Therefore, we speculated the
−
1
phenolic groups played a key role in HSO anions sensing mechanism. According to the H
4
−
NMR titration spectrum of HSO for PD (Fig. 8), the shift of the phenolic H(a) and H(b)
4
showed an obvious down-field shift and imidazole proton H(c) nearly disappeared upon adding
−
HSO . These observations manifested that the original intermolecular hydrogen bonding was
4
−
−
interrupted by the coordination of HSO and the PD-HSO complex were formed after adding
4
4
various equiv. HSO (0.1-0.5 equiv.)49-52. Moreover, in corresponding FT-IR spectra (Fig. S9),
−
4
the stretching vibration absorption bands of N-H and O-H became a broad peak compared with
-1
-1
the free PD with a couple of sharp peaks appearing in 3101cm (N-H) and 3221 cm (O-H),
−
which also showed complexing between the PD and HSO . What’s more, the X-ray peak of
4
−
the PD-HSO complex (Fig. 9) showed four strong new peaks, indicating that a new stacking
4
mode was formed in PD-HSO4− complex. Meanwhile the image of SEM provided
−
supplementary evidence to the above stacking mode based on PD-HSO complex as show in
4
Fig.6 B (coating film obviously cover with holes structures and a regular micropore structure
nearly vanish). Therefore, a possible interaction mechanism was illustrated in Scheme 2.
1
4

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−
Fig. 7 Fluorescence response of the PD (20uM), PD+ HSO (25 equiv.), D-1(20uM), D-1+
4
−
HSO (25 equiv.)
4
1
−
Fig. 8 Partial H NMR spectra of PD in DMSO-d with different equivalents of HSO : (a)
6
4
0
, (b) 0.1, (c) 0.2, (d) 0.3, (e) 0.
1
5

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Figure 9 XRD diagrams of PD and PD-HSO4−
−
Scheme 2. Chemical structures and cartoon representations of PD and HSO and the
4
interaction mechanism.
3
.6 DFT study
1
6

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Quantum mechanical calculations was carried out to determine the relaxed geometries and
their HOMO-LUMO orbital energies by using Gaussian 09 program package [43,44]. As we
expected, the original O–H distance (0.9976 Å) (Fig. 10) has increased after forming of PD-
−
HSO complex, which illustrated the hydrogen bond might been formed. The energy gap of
4
−
−
the HOMO and LUMO of the PD-HSO complex manifested that the PD can bind the HSO
4
4
5
3
to obtain the optimal configuration according to model 2 (∆E <∆E ) as shown in Fig.11. The
2
1
electron density distribution diagram (Fig. S12) also indicated that model 2 was much more
beneficial to electron dispersion. The optimization results of practical and standard orientation
−
for the molecular structure (PD-HSO and free PD) in spatial distribution as shown in Table
4
S1-S6.
−
Fig. 10 Structure optimization of bonding mode of PD-HSO by using Gaussian 09 program
4
(DFT/B3LYP/6-311G method; Color codes; blue: N, red: O, yellow :S, gray: C, White: H)
1
7

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−
Fig. 11 The HOMO-LUMO of the frontier orbitals gap for free PD, and PD-HSO complex
4
(model 1 and model 2)
3
.6 Visual detection of HSO4−
Test strips were prepared with filter paper as a rectangle to investigate the visual detection
−
of receptor PD to HSO .The PD-based test strips were also prepared by immerging processed
4
filter paper strips into the PD in DMSO/Ethanol/H O (1:8:1, v/v/v) solution and dried in the
2
−
air. As shown in Fig. 12, when theHSO and other anions were sprinkled on the surface of the
4
test strips, no color change were observed under the visible light to all the test strips, however,
−
the test strip stained with HSO sharply appeared color change (the color change from the
4
yellow to deep purple) in few seconds compared with other test strips under the UV lamp. This
observation suggested that the PD have the high selectivity and could detect HSO4−
conveniently and instantaneously as a low cost and high-efficiency test kits.
1
8

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−
−
Fig. 12 Naked eye detection of HSO at presence of the others anions (from 1 to 18: ClO ,
4
4
−
−
−
−
−
2−
−
−
−
−
2−
−
4−
3−
F , Cl , Br , I , CH COO , HPO , H PO , CN , SCN , NO , SO , NO , P O , PO ,
3
4
2
4
3
3
2
2
7
4
2
−
2−
2−
C O , S O , CO ).
2
4
2
3
3
4
.0 Conclusion
To date, merely a few receptor molecules have been tailored and synthesized based on the
−
nature of donor-acceptor to capture the amphoteric HSO ions. In this work, the receptor PD
4
with the dual functional groups (donor-acceptor sites) was developed, which could pick out the
HSO4− with high selectivity and sensitivity over a series of anions. The receptor–anion
1
complexes has been definitely verified by H NMR titration spectroscopy, ESI-MS, XRD, IR,
SEM and supported by DFT calculations. As we expected, the PD with the imidazole motifs
connected with phenolic hydroxyl group as the HSO4− anion selective recognition site by
−
forming the multiple hydrogen bond. The detection limit of the receptors towards HSO was
4
-7
5
.49×10 M and other anions had no obvious effect on this behavior. As a result, we prepared
−
the strips of visual anions detection which verified to be feasible to detect HSO anions as a
4
low cost and high-efficiency test kits.
1
9

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Conflicts of interest
There are no conflicts to declare
Acknowledgment
This work was supported by the National Natural Science Foundation of China (NSFC) (Nos.
1574104; 21662031; 21661028), the Natural Science Foundation of Gansu
2
Province(1506RJZA273) and the Program for Changjiang Scholars and Innovative Research
Team in University of Ministry of Education of China (IRT15R56). The Program for doctoral
students of Northwest Normal University.
Supplementary data These data include the spectral data, MS data and others date of the
compounds described in this article. Supplementary data associated with this article can be
found in the online version.
Reference:
1
N. Choudhury, B. Saha, B. Ruidas, and P. De, Dual-Action polymeric probe: turn-on sensing
2
+
−
and removal of Hg : chemosensor for HSO , ACS Appl. Poly. Mater., 2019, 1, 461-471.
4
2
D. Bains, G. Singh and N. Singh, Pyridoanthrone-based chromo-fluorogenic amphiphiles for
−
selective CN detection and their bioimaging application, Tetrahedron Lett., 2019, 60, 1457-
1
462.
3
4
A. Kumar, V. Vanita, A. Walia, P. S. Chae and S. Kumar, Pyridoanthrone-based chromo-
−
fluorogenic amphiphiles for selective CN detection and their bioimaging application, Sens.
Actuators B, 2020, 304, 1273-1296.
J. H. Oh, J. H. Kim, D. S. Kim, H. J. Han, V. M. Lynch, J. L. Sessler and S. K. Kim, Synthesis
and anion recognition features of a molecular cage containing both hydrogen bond donors and
acceptors, Org. Lett., 2019, 21, 4336-4339.
2
0

Page 21 of 27
Photochemical & Photobiological Sciences
View Article Online
DOI: 10.1039/D0PP00159G
5
6
A. Mohammadia, Z. Dehghana, M. Rassa and N. Chaibakhsh, Colorimetric probes based on
bioactive organic dyes for selective sensing of cyanide and fluoride ions, Sens. Actuators B,
2
016, 230, 388-397.
L. Y. Wang, L. L. Yang, L. B. Huang and D. R. Cao, Diketopyrrolopyrrole-derived Schiff base
−
3+
as colorimetric and fluorometric probe for sequential detection of HSO and Fe with “off-on-
4
off” response, Sens. Actuators B, 2015, 209, 536-544.
7
8
A. K. Mahapatra, G. Hazra, N. K. Das and S. Goswami, Optical waveguide biosensor based on
modal interference between surface plasmon modes, Sens. Actuators, B, 2016, 156, 456-462.
L. T. Wang, X. M. He, Y. Guo, J. Xu and S. J. Shao, Anion binding and sensing properties of
bis(3-indolyl) methane derivatives based on proton transfer process, Lett. Org. Chem., 2011, 8,
6
0-65.
9
C. L. Deng, J. P. Bard, J. A. Lohrman, J. E. Barker, L. N. Zakharov, D. W. Johnson and M. M.
Haley, Exploiting the hydrogen bond donor/acceptor properties of PN-heterocycles: selective
anion receptors for hydrogen sulfate, Angew. Chem. Int. Ed., 2019, 131, 3974-3978.
1
0 U. Fegade, J. Bhosale, H. Sharma, N. Singh, R. Bendre and A. Kuwar, Fluorescence
−
2+
chemosensor for HSO ion based on pyrrole-substituted salicylamide Zn complex: nanomolar
4
detection, J. Fluoresc, 2015, 25, 819-824.
1
1
1
1 S. T. Yang, D. J. Liao, S. J. Chen, C. H. Hua, and A. T. Wu, A fluorescence enhancement-based
sensor for hydrogen sulfate ion, Analyst, 2012, 137, 1553-1555.
2 W. J. Xue, L. Li, Q. Li and A. X. Wu, Novel furor[2,3-d] pyrimidine derivative as fluorescent
−
chemosensor for HSO , Talanta, 2012, 88, 734-738.
4
3 S. Bayindir and N. Saracoglu, A facile one-pot method to synthesize 2-alkylated indole and 2,2′-
bis(indolyl)methane derivatives using ketones as electrophiles and their anion sensing ability,
RSC Adv., 2016, 6, 72959-72967.
1
4 U. Fegade, S. K. Sahoo, A. Singh, P. Mahulikar, S. Attarde, N. Singh and A. Kuwar, A selective
−
and discriminating noncyclic receptor for HSO ion recognition, RSC Adv., 2014, 4, 15288-
4
1
5292.
2
1

Photochemical & Photobiological Sciences
Page 22 of 27
View Article Online
DOI: 10.1039/D0PP00159G
1
5 Y. Upadhyay, S. Bothra, R. Kumar, H. J. Choi and S. K Sahoo, Optical sensing of hydrogen
sulphate using rhodamine 6G hydrazide from aqueous medium. Spectro. Acta. Part A, 2017,
1
80, 44-50.
1
6 C. Tan, Q. Wang and L.J. Ma, Fluorescent‑ based solid sensor for hydrogen sulfate in water,
Photochemistry, 2010, 86, 1191-1196.
1
7 K. C. Tayade, B. Bondhopadhyay, K. Keshav, S. K. Sahoo, A. Basu, J. Singh, N. Singh, D.
Nehete and A. Kuwar, A novel Zinc (II) and hydrogen sulphate selective fluorescent "turn-on"
chemosensor based on isonicotiamide: INHIBIT type's logic gate and application in cancer cell
imaging, Analyst, 2016, 141, 1814-1821.
1
8 G. X. Huang, G. X. Zhang and D. Q. Zhang, Turn-on of the fluorescence of tetra(4-
pyridylphenyl) ethylene by the synergistic interactions of mercury cation and hydrogen sulfate
anion, Chem. Commun., 2012, 48, 7504-7506.
1
2
9 M. C. C. Ribeiro, High viscosity of imidazolium ionic liquids with the hydrogen sulfate anion:
araman spectroscopy study, J. Phys. Chem. B, 2012, 116, 7281-7290.
0 X. Wang, J. Feng, Y. D. Zhao, X. F. Zhao, T. Yan, Q. Wang, L. Du and Q. H. Zhao, Flexible
coordination polymers based on zwitterion ligands and d10 metal ions for selective sensing of
3
+
−
nitrobenzene, Fe and HSO , Chem. Commun., 2018, 98, 80-86.
4
2
2
2
2
1 Q. Li, Y. Yue, Y. Guo and S. J. Shao, Fluoride anions triggered “OFF–ON” fluorescent sensor
for hydrogen sulfate anions based on a BODIPY scaffold that works as a molecular keypad
lock, Sens. Actuators B, 2012, 173, 797-801.
2 G. Keşan, B. Topaloğlu, E. Özcan, H. H. Kazan, E. T. Ecik, E. Şenkuytu, I. F. Sengul, H.
Kandemir and B. Çoşut, Azaindole-BODIPYs: Synthesis, fluorescent recognition of hydrogen
sulfate anion and biological evaluation, Spectro. Acta. Part A, 2019, 213, 73-82.
3 Q. X. Liu, H. Wu, Z. X. Zhao and D. C. Wei, Macro metallocycle binuclear NHC silver (I)
complex with bridging azobenzene: synthesis, structure and recognition for hydrogen sulfate,
Tetrahedron, 2019, 75, 3128-3134.
4 X. J. Feng, Y. L. Fu, J. Jin and J. X. Wu, A highly selective and sensitive fluorescent sensor for
2
2

Page 23 of 27
Photochemical & Photobiological Sciences
View Article Online
DOI: 10.1039/D0PP00159G
2
+
−
−
relay recognition of Zn and HSO /H PO with “on-off” fluorescent responses, Analytical
4
2
4
Biochemistry. 2018, 563, 20-24.
2
2
5 E. Han, D. H. Sohn, S. J. Cho and J. M. Kang, Differential recognition of various anions utilizing
aromatic C-H hydrogen bonding, Bull. Korean Chem. Soc., 2019, 40, 301-305.
−
6 M. Orojloo and S. Amani, Colorimetric detection of pollutant trivalent cations and HSO in
4
aqueous media using a new Schiff-base probe: An experimental and DFT studies, Polycyclic
Aromatic Compounds, DOI: 10.1080/10406638.2019.1567561.
−
2
2
2
3
3
7 S. M. Hezaveh, H. Khanmohammadi, M. Zendehdel, Rapid detection of HSO in water: Novel
4
immobilized azo-azomethine colorimetric anion receptors on solid supports, Spectro. Acta. Part
A, 2018, 199, 21-31.
8 J. L. Sessler, E. Katayev, G. D. Pantos and Y. A. Ustynyuk, Synthesis and study of a new
diamidodipyrromethane macrocycle. An anion receptor with a high sulfate-to-nitrate binding
selectivity, Chem. Commun., 2004, 11, 1276-1277.
9 M. R. Gill, D. Cecchin, M. G. Walker, R. S. Mulla, G. Battaglia, C. Smythe and J. A Thomas,
Targeting the endoplasmic reticulum with a membrane-interactive luminescent Ruthenium (II)
polypyridyl complex, Chem. Sci., 2013, 4, 4512-4519.
0 L. Yang, X. Li, J. B Yang, Y. Qu and J. L Hua, Colorimetric and ratiometric near-infrared
fluorescent cyanide chemo dosimeter based on phenazine derivatives, ACS Appl. Mater.
Interfaces, 2013, 5, 1317-1326.
1 M. Krishnaiah, N. R. Almeida, V. Udumula, Z. Song, Y. S. Chhonker, M. M. Abdelmoaty, V.
A. Nascimento, D. J. Murry and C. M. Sheridan, Synthesis, biological evaluation, and metabolic
stability of phenazine derivatives as antibacterial agents, Eur. J. Med. Chem.,2018, 143, 936-
9
47.
3
3
2 N. Guttenberger, W. Blankenfeldt, and R. Breinbauer, Recent developments in the isolation,
biological function, biosynthesis, and synthesis of phenazine natural products, Bioorg. Med.
Chem., 2017, 25, 6149-6166.
3 Z. Q. Lin, J. Xie, B. W. Zhang, J. W. Li, J. Weng, R. B. Song, X. Huang, H. Zhang, H. Li, Y.
2
3

Photochemical & Photobiological Sciences
Page 24 of 27
View Article Online
DOI: 10.1039/D0PP00159G
Liu, Z. C. J. Xu, W. Huang and Q. C. Zhang, Solution-processed nitrogen-rich graphene-like
holey conjugated polymer for efficient lithium ion storage, Nano. Energy, 2017, 41,117-127.
4 G. Li, J. Gao, F. Hu and Q. C. Zhang, Synthesis, characterization, and physical properties of
two novel nonaheteroacene derivatives, Tetrahedron Lett., 2014, 55, 282-285.
3
3
5 Y. Li, Z. L. Wang, C. Zhang, P. Y. Gu. W. Q. Chen, H. Li, J. M. Liu and Q. C. Zhang, Thiadizolo
quinoxaline-based N-heteroacenes as active elements for high-density data-storage device, ACS
Appl. Mater. Interfaces., 2018, 10, 15971-15979.
3
3
6 X. Y. Song, J. Zhao, W. D. Zhang and L. Chen, Novel n-channel organic semiconductor based
on pyrene-phenazine fused monoimide and bisimides, Chin. Chem. Lett., 2018, 29, 331-335.
7 K. Y. Sun, Z. S. Cai, J. F. Jiang, W. W. Tian, W. Guo, J. L. Shao, W. Jiang, Y. M. Sun, Multi-
substituted dibenzo[a,c] phenazine derivatives as solution-processable thermally activated
delayed fluorescence materials for orange–red organic light-emitting diodes, Dyes Pigments,
2
020, 173, 107958.
3
3
8 T. B. Wei, B. R. Yong, L. R. Dang, Y. M. Zhang, H. Yao and Q. Lin, A simple water-soluble
2
+
phenazine dye for colorimetric/fluorogenic dual-mode detection and removal of Cu in natural
water and plant samples, Dyes Pigments, 2019, 171,107707.
9 S. H. Lee, A. J. Matula, G. F. Hu, J. L. Troiano, C. J. Karpovich, R. H. Crabtree, V. S. Batista,
G. W. Brudvig and G. W. Brudvig, Strongly coupled phenazine–porphyrin dyads: Light-
harvesting molecular assemblies with broad absorption coverage, ACS Appl. Mater. Interfaces.,
2
019, 11, 8000-8008.
4
4
4
0 Y. Wang and Y. Hasebe, Phenazine-dye and enzyme-modified plastic formed carbon electrode
for amperometric dihydronicotinamide adenine dinucleotide and glucose sensing, Sens. Mater.,
2
019, 31, 1181-1190.
1 A. M Amer, A. A. El-Bahnasawi, M. R. H. Mahran and M. Lapib, On the synthesis of
pyrazino[2,3-b] phenazine and 1H-imidazo[4,5-b] phenazine derivatives, Monat. Fur. Chem,
1
999, 130, 1217-1225.
2 G. Y. Gao, W. J. Qu, B. B. Shi, P. Zhang, Q. Lin, H. Yao, Y. M. Zhang and T. B. Wei, A highly
2
4

Page 25 of 27
Photochemical & Photobiological Sciences
View Article Online
DOI: 10.1039/D0PP00159G
selective fluorescent chemosensor for iron ion based on 1H-imidazo [4,5-b] phenazine
derivative, Spectro. Acta. Part A, 2014, 121, 514-519.
4
3 G.E.S.M.J. Frisch, G.W. Trucks, H.B. Schlegel, B.M.M.A. Robb, J.R. Cheeseman, G.Scalmani,
V. Barone, H.P.H.G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, M.H.A.F. Izmaylov, J.
Bloino, G. Zheng, J.L. Sonnenberg, T.N.M. Ehara, K. Toyota, R. Fukuda, J.Hasegawa, M.
Ishida, J.Y.Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery,E.B.J.E. Peralta, F.
Ogliaro, M. Bearpark, J.J. Heyd, J.N.K.N. Kudin, V.N. Staroverov, T.Keith, R. Kobayashi,
J.T.K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J.B.C.M. Cossi, N. Rega, J.M.
Millam, M. Klene, J.E. Knox, R.E.S.V. Bakken, C. Adamo, J.Jaramillo, R. Gomperts, J.W.O.O.
Yazyev, A.J. Austin, R. Cammi, C. Pomelli, G.A.V.R.L. Martin, K. Morokuma, V.G.
Zakrzewski, A.D.D.P. Salvador, J.J.Dannenberg, S.Dapprich, J.C.O. Farkas, J.B. Foresman,
J.V. Ortiz, D.J. Fox, Gaussian 09, RevisionD.01, 2013.
4
4
4 A. D. Becke, Density-functional thermochemistry III: The role of exact exchange, J. Chem.
Phys., 1993, 98, 5648-5652.
5 Y. M. Zhang, H. Fang, W. Zhu, J. X. He, H. Yao, Q. Lin and T. B. Wei, Ratiometric fluorescent
sensor based oxazolo-phenazine derivatives for detect hypochlorite via oxidation reaction and
its application in environmental samples, Dyes Pigments, 2019, 172,107765.
4
6 W. Huang, M. Bender, K. Seehafer, I. Wacker, R. R. Schröder and U. H. F. Bunz, Novel
functional TPE polymers: aggregation‑induced emission, pH response, and solvatochromic
behavior, Macron. Rapid Commun., 2019, 40, 1800774.
2
+
4
4
7 S. Q. Cui, S. Y. Qiu, R. M. Lu and S. Z. Pu, A multi-functional fluorescent sensor for Zn and
−
HSO based on a new diarylethene derivative, Tetrahedron Lett., 2018, 59, 3365-3372.
4
8 Q. Lin, K. P Zhong, J. H. Zhu, L. Ding, J. X. Su, H. Yao, T. B. Wei and Y. M. Zhang, Iodine
controlled Pillar[5] arene-based multiple responsive supramolecular polymer for fluorescence
detection of cyanide, mercury, and cysteine, Macromolecules, 2017, 50, 7863-7871.
4
9 Y. Ma, J. Zhang and H. Qu, Synthesis and properties of novel fluorescence probe based on 1,
8
-naphthalimide for detection of hydrogen sulfide, Chem. Res. Chin. Univ., 2019, 35, 1-5.
2
5

Photochemical & Photobiological Sciences
Page 26 of 27
View Article Online
DOI: 10.1039/D0PP00159G
5
5
5
5
0 T. S. Pandian, V. Srinivasadesikan, M. C. Lin and J. Kang, A selective acetate anion binding
receptor: participation via cationic CH donors, Tetrahedron Lett., 2015, 71, 7782-7788.
3
1 E. Han, D. H. Sohn, S. J. Cho and J. Kang, Differential recognition of various anions utilizing
aromatic C-H hydrogen bonding, Bull. Korean Chem. Soc., 2019, 40, 293-392.
2 T. S. Pandian and J. Kang, Participation of aliphatic C–H hydrogen bonding in anion recognition,
Tetrahedron Lett., 2015, 56, 4191-4194.
3 S. Erdemir, B. Tabakci and M. Tabakci,A highly selective fluorescent sensor based on calix
2
+
2−
−
[
4] arene appended benzothiazole units for Cu , S and HSO ions in aqueous solution, Sens.
4
Actuators B, 2016, 228, 109-116.
2
6

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Graphical Abstract
−
The hybrid acceptor PD was tailored for hunting HSO , which could not
4
only display the preferable sensitivity with ‘‘turn–off’’ fluorescent
response, but also have strong anti-interference toward other common
anions.