A novel dual-function probe for recognition and differentiation of Zn2+ and Al3+ and its application

Article abstract of DOI:10.1016/j.molliq.2019.112250

A dual-function probe BHMH was synthesized and characterized functioned with benzothiazole as signal unit for the simultaneous detection of Zn²⁺ and Al³⁺ DMF/H₂O (1/1, v/v, 0.01 M HEPES, pH = 6.0). Probe BHMH achieved in the recognition of Zn²⁺ and Al³⁺ both through obvious fluorescence turn-on and absorbance ratiometric response. The limit of detection (LOD) according to the titration of fluorescence for Zn²⁺ and Al³⁺ were 1.27 × 10^{? 7} M and 1.42 × 10^{? 7} M, respectively. Furthermore, the significant color changes could be detected by naked eye whatever under ultraviolet-lamp or daylight. According to Job plot, the binding ratio of BHMH with Zn²⁺ and Al³⁺ were determined as 1:1 and 2:1, respectively. The binging detail was further confirmed by ¹H NMR titration and ESI-MS analysis as well. Moreover, probe BHMH was successfully applied in the detection Zn²⁺ and Al³⁺ in real sample and test stripe.

Full text of DOI:10.1016/j.molliq.2019.112250

Journal Pre-proof
A novel dual-function probe for recognition and differentiation of
Zn2+ and Al3+ and its application
Ting-Ting Liu, Jiao Xu, Cheng-guo Liu, Shuang Zeng, Zhi-Yong
Xing, Xue-Jiao Sun, Jin-Long Li
PII:
S0167-7322(19)35166-9
DOI:
https://doi.org/10.1016/j.molliq.2019.112250
MOLLIQ 112250
Reference:
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
14 September 2019
27 November 2019
30 November 2019
Please cite this article as: T.-T. Liu, J. Xu, C.-g. Liu, et al., A novel dual-function probe for
recognition and differentiation of Zn2+ and Al3+ and its application, Journal of Molecular
Liquids(2018), https://doi.org/10.1016/j.molliq.2019.112250
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2018 Published by Elsevier.

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A novel dual-function probe for recognition and differentiation of
2
+
3+
Zn and Al and its application
a, 1
b, 1
a
a
a,*
a
Ting-Ting Liu , Jiao Xu , Cheng-guo Liu , Shuang Zeng , Zhi-Yong Xing , Xue-Jiao Sun ,
c, *
Jin-Long Li
a
Department of Applied Chemistry, College of Science, Northeast Agricultural University, Harbin
150030, PR China.
b
Jiamusi College, Heilongjiang University of Chinese Medicine, Harbin, China.
School of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, PR China.
Corresponding authors
c
*
E-mail addresses: zyxing@neau.edu.cn; jinlong141@163.com
1
These authors contributed equally to this work.
Abstract: A dual-function probe BHMH was synthesized and characterized functioned with
2
+
3+
benzothiazole as signal unit for the simultaneous detection of Zn and Al DMF/H O (1/1, v/v,
2
2
+
3+
0
.01M HEPES, pH = 6.0). Probe BHMH achieved in the recognition of Zn and Al both
through obvious fluorescence turn-on and absorbance ratiometric response. The limit of detection
2
+
3+
-7
(
LOD) according to the titration of fluorescence for Zn and Al were 1.27×10 M and
-7
1
.42×10 M, respectively. Furthermore, the significant color changes could be detected by naked
eye whatever under ultraviolet-lamp or daylight. According to Job plot, the binding ratio of
2+
3+
BHMH with Zn and Al were determined as 1:1 and 2:1, respectively. The binging detail was
1
further confirmed by H NMR titration and ESI-MS analysis as well. Moreover, probe BHMH
2
+
3+
was successfully applied in the detection Zn and Al in real sample and test stripe.
3
+
2+
Key word: Fluorescence; Dual-function; Al ; Zn
1

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1
. Introduction
Aluminum, among the richest elements in earth crust, is closely related to human daily living
due to its widely used in many fields (such as package of foods and drugs, kitchen utensils, and
3
+
water treatment equipment). However, Al which is the most existence ionic style of aluminum in
water and plant body and the unnecessary element for mankind, is inevitable accumulated in
human body through the water and food. However, the upper limitation of daily intake is 10 mg
according to the recommendation of World Health Organization (WHO), and over accumulation
in body will induce neurodegenerative diseases such as Alzheimer’s disease and Parkinson’s
disease [1-6]. On the contrary, as the second most abundant transition metal and a necessary
element for human body, Zinc (Zn), acts as a key role in many functional processes such as signal
transmitters, cellular metabolism, and neural immune function. However, whatever insufficient
2+
intake or excessive ingestion of Zn is detrimental to the health of mankind [7-11]. Hence, it is
3
+
2+
essential to develop an efficient method of trace detection Al and Zn for the health of human
beings and environmental protection as well.
Up to now, it has been a hot topic for researchers that is in the development of fluorescent
probes for the trace detection of various analyte, which mainly due to its unique properties
including high sensitivity, real-time response, facile operation and naked-eye detection [12-14].
Up to now, many excellent fluorescence probes were reported for different metal ions based on
different mechanism and designing idea. Among them, that one probe for simultaneous muti-target
detection, which showed its merits such as high efficiency, time and cost saving, is becoming
popular to researchers in the development of fluorescence probes. Lots of multi-functional
fluorescence probes for multiple targets simultaneous detection were reported with various
2

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3
+
2+
fluorophore [15-55], some of them were Al and Zn fluorescent probes based on various
fluorophore [38-55] such as thiophene [38], diarylethene [39-43], squaraine [44], aza-crown [45],
hydrazine [46], chromone-rhodamine [47], acylhydrazone [48], triphenylamine [49], chromen [50],
naphthalene [51], alicyldehyde [52], biphenyl-anthracene [53] and benzothiazole [54, 55], but
only a few of them were based on benzothiazole fluorophore. Hence, the development of
3
+
2+
benzothiazole-based fluorescent probe for simultaneous detection of Al and Zn is still full of
charming.
2
-(2-hydroxyphenyl)benzothiazole, one of excellent acceptors in D-π-A structures
considering its electron withdrawing ability, is widely used as an idea fluorophore in construction
fluorescent probe through conjugation with proton donating group such as hydroxyl group, which
is characterized as excited state intramolecular proton transfer (ESIPT) mechanism with
significant fluorescence signal change and larger Stokes shift as well. Some previous related
works (Scheme 1) [29, 55, 56] lighted us the idea that the compound synthesized by condensation
of the skeleton molecular (3-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methylbenzaldehyde) with
2-hydroxybenzohydrazide might helpful to achieve in the development of dual functional probe
3
+
2+
for Al and Zn . Hence, (E)-3-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methybenzaldehyde salicyl
acylhydrazone (BHMH) was synthesized (Scheme 2) and its spectrum performance was
3
+
2+
systematic investigated. BHMH showed highly sensitivity to Al and Zn manifested in obvious
3
+
2+
fluorescence turn-on and color change, respectively. Al and Zn could be differentiated by
adding EDTA which is a common reagent be usually used in revisable experiment. Moreover,
3
+
2+
BHMH was achieved in the application in real sample detection of Al and Zn with high
sensitivity and accuracy.
3

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Scheme 1 Designing idea for probe BHMH
2
. Experimental
2.1 Materials and apparatus
All analytical reagent grade chemicals and solvents employed for the synthesis and
characterization were purchased from commercial sources and used as received without any
treatment. Nuclear magnetic resonance spectra (NMR) were recorded on a Bruker 600 MHz
system, and the chemical shifts are reported in ppm with Me Si as the internal standard. High
4
resolution mass spectroscopy (HRMS) was carried out on a Waters Xevo UPLC/G2-SQ Tof MS
spectrometer. The FT-IR spectra were recorded on a Bruker ALPHA-T by dispersing samples in
-1
KBr disks, in the range of 4000-400 cm . The UV–vis absorption and fluorescence spectra of the
samples were measured on Pgeneral TU-255 UV-vis Spectrophotometer and Perkin Elmer LS55
fluorescence spectrometer, respectively.
4

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2.2. General information
3
+
3+
3+
2+
2+
2+
2+
2+
2+
2+
Stock solutions of the metal ions (Al , Fe , Cr , Ca , Pb ,Cd , Cu , Co , Zn , Fe ,
2
+
2+
2+
2+
+
+
+
Mn , Mg , Ni , Hg , Na , K , Ag ) from the nitrate, chloride or perchlorate salts were prepared
with ultrapure water. BHMH (0.1 mM) was dissolved in DMF, which was then diluted by adding
HEPES buffer (10 mM, pH 6.0) to 10 μM. The diluted solution DMF/H O (1/1, v/v, 0.01M
2
HEPES, pH = 6.0) was used for the measurement of UV-Vis spectra and fluorescence spectra. The
excitation wavelength (E = 420 nm) was used for fluorescence experiments and the slits
x
including excitation and the emission all were set to 10 nm.
2
2
3
.3. Synthesis
.3.1 Synthesis
-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methylbenzaldehyde (2)
Compounds 1 and 2 were synthesized according to reported methods [29], respectively.
.3.2 Synthesis of (E)-3-(benzo[d]thiazol-2-yl)-2-hydroxy-5-methybenzaldehyde salicyl
of
2-(benzo[d]thiazol-2-yl)-4-methylphenol
(1)
and
2
acylhydrazone (BHMH)
Compound 2 (199 mg, 0.74 mmol) and 2-Hydroxybenzohydrazide (116 mg, 0.76 mmol)
were dissolved in ethanol (30 mL), then the solution was refluxed until the completion of reaction
(monitored by TLC). After cooling to room temperature, the solid was filtered and washed with
ethanol (3 x 5 mL), then dried under vacuum to get yellow product BHMH (363 mg, yield 82%).
1
m.p.: 278.4-280.2 °C. H NMR (600 MHz, DMSO-d ) (Fig. S1) δ (ppm): 13.25 (s, 1H), 12.25 (s,
6
1
7
8
H), 11.68 (s, 1H), 8.75 (s, 1H), 8.21 (s, 1H), 8.18 (d, J = 7.8 Hz, 1H), 8.09 (d, J = 7.8 Hz, 1H),
.91 (d, J = 7.8 Hz, 1H), 7.61 (s, 1H), 7.56 (t, J =8.4 Hz, 1H), 7.48 (t, J = 7.2 Hz, 2H), 7.02 (d, J =
1
3
.4 Hz, 1H), 7.00 (t, J = 7.8 Hz, 1H), 2.41 (s, 3H). C NMR (151 MHz, DMSO-d ) (Fig. S2) δ
6
5

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(ppm) 164.99, 163.95, 159.29, 154.54, 151.81, 148.99, 135.24, 134.57, 133.53, 131.08, 129.26,
129.21, 126.99, 125.66, 122.76, 122.53, 119.99, 119.87, 119.59, 117.78, 116.25, 20.41. HRMS
+
+
(
m/z) (TOF MS ES ) (Fig. S3): calcd for C H N O S: 404.1069 [M+H] , found: 404.1061.
22 17 3 3
Scheme 2 Synthetic route of probe BHMH
3
. Results and discussion
3
.1. Sensing ability of BHMH to metal ions
Fluorescence selectivity of BHMH (Fig. 1a) in sensing different metal ions (Na , K , Ca ,
+
+
2+
2
+
2+
2+
2+
2+
3+
2+
3+
2+
+
2+
2+
2+
3+
2+
Fe , Ba , Mg , Mn , Ni , Cr , Cu , Fe , Co , Ag , Cd , Zn , Hg , Al and Pb ) were
firstly carried out in DMF/H O (1/1, v/v, 0.01M HEPES, pH = 6.0). The result showed that
2
3
+
2+
BHMH was highly selectivity to Al and Zn through significant fluorescent enhancement
response accompanied with color change from yellow to deep green and light green, respectively.
3
+
2+
Consideration its specifical fluorescent response to Al and Zn , the UV-vis absorbance
3
+
2+
spectrum of BHMH were measured before and after addition of Al and Zn (Fig. 1b),
3
+
2+
respectively. Compared with BHMH itself, the addition of Al and Zn were all caused a
significant change, respectively. The probe BHMH alone displayed two shoulder absorption peaks
at 362 nm and 430 nm, which attributed to the π-π* transition derived from the
2-(2’-hydroxyphenyl) benzothiazole chromophore during the ESIPT process of enol-keto
3
+
2+
automerization in the excited state [57, 58]. However, the addition of Al and Zn to the solution
6

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of probe BHMH was all caused significant change which mainly reflected in the disappearance of
absorption peak centered at 362 nm and obvious enhancement of that at 430 nm. Meanwhile, the
solution color of probe BHMH was turned from colorless to pale green and green, respectively.
3
+
2+
This result displayed the existence of interaction between probe BHMH and Al and Zn .
Fig. 1. Selectivity of BHMH to metal ions by spectra measurement of fluorescence (a) and UV-Vis absorbance
(b).
3
+
2+
In order to investigate the sensitivity of BHMH (10 µM) to Al and Zn , the titration of
fluorescence (Fig. 2) and UV-Vis absorbance(Fig. 3) were carried out in DMF/H O (1/1, v/v,
2
0.01M HEPES, pH = 6.0), respectively. BHMH itself displayed weak fluorescent emission which
might due to ESIPT process from hydroxyl group to its conjugated benzothiazole fluorophore.
3
+
2+
However, whatever the addition of metal ion was Al or Zn , fluorescence titration results of
BHMH (10 µM) were all showed a gradually enhancement in emission intensity attributed to the
3
+
2+
vanishment of ESIPT process after coordination of BHMH with Al /Zn . Moreover, based on
3+
2+
the good relationship between BHMH (10 µM) with Al (0-5 µM) (Fig. S4) and Zn (0-10 µM)
3
+
2+
(
Fig. S5), the detection limit (LOD) of BHMH to Al and Zn which were calculated according
to the reported equation (LOD=3σ/S, where σ is the standard deviation of the blank solution and S
-7
-7
is slope of calibration curve) [59-61] was 1.42×10 M and 1.27×10 M, respectively. Moreover,
the comparative analysis between BHMH and some previously reported sensors were summarized
in Table 1.
7

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Table 1. Comparison of different properties of BHMH with recently reported probes.
Ref.
Selectivity
Detection Medium
LOD
Binding Constants
Application
3
+
-9
4
-1
-1
Al
3.7 × 10 M
1.16×10 M
Water sample
Cell imaging
Water sample
Logic circuit
[
[
[
[
[
[
38]
39]
40]
41]
42]
43]
DMSO/H O (1:1)
2
2
+
-8
4
Zn
3.0 × 10 M
2.08×10 M
3
+
-7
4
-1
Al
2.7 × 10 M
1.5×10 M
CH OH
3
2
+
-8
4
-1
Zn
4.0 × 10 M
6.4×10 M
3
+
-9
4
-1
-1
-1
-1
Al
2.97 × 10 M
1.27×10 M
CH OH
Logic circuit
Logic circuit
Logic circuit
3
2
+
-9
5
Zn
5.98 × 10 M
1.73×10 M
3
+
-7
5
Al
1.15 × 10 M
1.24×10 M
DMSO
2
+
-7
4
Zn
5.27 × 10 M
9.70×10 M
3
+
Al
CH OH
NR
NR
NR
NR
3
2
+
Zn
CH CN
3
3
+
-9
4
-1
-1
-1
-1
-1
Al
CH OH
6.72 × 10 M
4.61×10 M
Water sample
Logic circuit
3
2
+
-8
4
Zn
THF
7.02 × 10 M
2.06×10 M
3
+
-7
9
Al
Zn
Cd
1.77 × 10 M
5.40×10 M
Biological
application
2
+
-8
5
[44]
EtOH/H O (9:1)
2.13 × 10 M
2.67×10 M
2
2
+
-8
3
5.76 × 10 M
1.37×10 M
3
+
-6
3
-1
Al
1.20 × 10 M
2.5×10 M
Logic circuit
Cell imaging
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
DMSO/H O (3:2)
2
2
+
-6
3
-1
Zn
0.02 × 10 M
3.0×10 M
3
+
-8
5
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
Al
1.56 × 10 M
5.77×10 M
DMSO
Cell imaging
Solid State
2
+
-8
5
Zn
1.62× 10 M
3.87×10 M
3
+
-6
4
Al
3.18 × 10 M
1.61×10 M
EtOH/H O (3:1)
2
2
+
-7
4
Zn
1.25 × 10 M
3.85×10 M
3
+
-6
4
Al
3.66 × 10 M
2.66×10 M
DMSO/H O (9:1)
Cell imaging
2
2
+
-6
5
Zn
1.01× 10 M
1.08×10 M
3
+
-6
3
Al
2.13 × 10 M
6.65×10 M
Biological
application
CH OH
3
2
+
-8
4
Zn
3.81 × 10 M
7.70×10 M
3
+
-7
4
Al
0.62 × 10 M
2.62×10 M
Water sample
Membrane sensing
CH OH/H O (9:1)
3
2
2
+
-7
4
Zn
1.67 × 10 M
1.92×10 M
3
+
-9
3
-1/2
Al
5.70 × 10 M
1.5×10 M
CH OH/H O (7:3)
Water sample
3
2
2
+
-6
5
-1
Zn
1.09× 10 M
5.0×10 M
3
+
-7
4
-1
-1
-1
Al
8.04 × 10 M
1.66×10 M
Real sample
Cell imaging
Water sample
Test paper
CH OH/H O (1:9)
3
2
2
+
-7
4
Zn
7.95 × 10 M
0.60×10 M
3
+
-8
6
Al
5.22 × 10 M
1.74×10 M
EtOH/H O (95:5)
2
2
+
-8
2
-1/2
-1
Zn
7.88 × 10 M
6.45×10 M
3
+
-8
6
Al
2.70 × 10 M
4.86×10 M
DMF/H O (96:4)
Cell imaging
NR
2
2
+
-8
7
-1
-2
-1
Zn
3.30× 10 M
3.10×10 M
3
+
-6
8
Al
0.11 × 10 M
2.25×10 M
DMF/H O (9:1)
2
2
+
-6
2
Zn
0.21 × 10 M
3.42×10 M
3
+
-7
2
-1/2
This
Al
1.42×10 M
2.79×10 M
Water sample
Test paper
DMF/H O (1:1)
2
2
+
-7
4
-1
work
Zn
1.27×10 M
3.19×10 M
LOD: The limit of detection; NR: Not reported in the corresponding paper.
8

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3
+
Fig. 2. (a) Fluorescence titration of BHMH to Al . Inset: the ratio of fluorescence intensity of BHMH as a
3
+
2+
function of Al concentration; (b) Fluorescence titration of BHMH to Zn . Inset: the ratio of fluorescence
2
+
intensity of BHMH as a function of Zn concentration.
3
+
On the other hand, titration of UV-Vis absorbance for Al (Fig. 3a) illustrated that the
absorbance centered at 367 nm gradually disappeared while the shoulder absorbance peak at 435
nm was gradually increased with an obvious isobestic point at 388 nm, these findings indicated the
3
+
complex formation of BHMH with Al . In addition, the satisfied relationship was reached
3
+
between the ratio of absorbance intensity (A435/A367) versus the Al concentration (0-5 μM) (Fig.
3
+
S6), indicated the achievement in ratiometric detection for Al with the limit of detection (LOD)
-8
as 3.99×10 M which calculated according the reported method [29]. Similarly, upon the gradual
2+
addition of Zn (0-10 µM), the absorbance at 366 nm decreased gradually and peak at 440 nm
gradually enhanced accompanied with the formation of isobestic point at 392 nm at the same time
2
+
(
Fig. 3b), all of these supported the existence of interaction between BHMH and Zn . The LOD
2
+
-8
for Zn calculated as 3.32×10 M was satisfied based on the ratio of absorbance intensity
2+
(
A440/A366) versus the Zn concentration (0-5 μM) (Fig. S7), which also proved that BHMH was
2
+
capable of used as ratiometric probe of Zn .
9

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3
+
Fig. 3. (a) UV-Vis absorbance titration of BHMH to Al . Inset: the ratio of absorbance (A435/A367) of BHMH as a
3
+
2+
function of Al concentration; (b) Fluorescence titration of BHMH to Zn . Inset: the ratio of absorbance
2
+
(
A440/A366) of BHMH as a function of Zn concentration.
To further verify the anti-disturbance from other co-existence metal ions, the competition
3+
2+
experiments (Fig. 4) for Al and Zn were carried out through measurement of fluorescence
2
+
intensity (recorded E =494 nm for Al, and E =508 nm for Zn ) after adding other competition
m
m
3
+
2+
metal ions, respectively. The result showed that BHMH was sensitive enough to Al and Zn
3
+
2+
and could be used in the detection of Al and Zn in the existence of other tested ions.
3
+
2+
Fig. 4. Competition experiments of BHMH to Al (a) and Zn (b) in the presence of other metal ions.
3
+
2+
Consideration the similarity response of BHMH to Al and Zn in the facet of color change
either in daylight or UV-lamp, which was unfavorable in fast determination by naked-eye for one
3+
2+
analyte containing Al or Zn . So, some efficient method should be found that which could be
3+
2+
used to differentiate Al from Zn . EDTA, a valuable reagent which is usually used in
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0

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3
+
2+
reversibility evaluation for one probe, was qualified to make a distinction between Al and Zn
through adding it into the analyte solution. The phenomena was that the recognization process
2
+
(
Fluorescence spectrum and UV-Vis absorbance spectrum) (Fig. 5) for Zn was reversible by
2+
alternate adding EDTA and Zn , and which could be done at least 5 cycles assessed by
fluorescence intensity (recorded at E = 508 nm) (Fig. 6a) and color change (Fig. 6b). However,
m
3
+
the above experimental method was out of validation for Al that was the addition of EDTA
3
+
could not recover the complex system of BHMH-Al into BHMH itself (Fig. S8). Hence, this
3
+
2+
result supplied an efficient method in the fast estimation of Al from Zn .
2
+
Fig. 5. Reversible experiments of BHMH to Zn in fluorescence spectrum (a) and UV-Vis absorbance spectrum
2
+
(
b) by alternate adding EDTA and Zn .
2
+
Fig. 6. Reversibility assessment of BHMH to Zn by (a) fluorescence intensity (E = 508 nm) and (b) color
m
change under daylight (top) and UV-light (bottom).
3
+
2+
3
.2. Sensing mechanism of BHMH to Al and Zn
11

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The Job’s plot analysis (Fig. 7) was employed to determine the stoichiometry of BHMH with
3
+
2+
Al and Zn , respectively. The results showed that when the molar fraction was 0.3, the
3
+
2+
fluorescence intensity recorded at 494 nm for Al reached maximum (Fig. 7a). While for Zn
recorded at 508 nm, the maximum molar fraction was 0.5 (Fig. 7b), all of these indicated that the
3
+
2+
binding ratio of BHMH was 2:1 for Al while 1:1 for Zn , respectively. According to the
3
+
2+
Benesi–Hildebrand plot [32, 62], the binding constants of Al and Zn with probe BHMH were
2
-1/2
4
-1
2
.79×10 M (Fig. S9) and 3.19×10 M (Fig. S10), respectively.
3
+
2+
Fig. 7. Job plot for binding ratio between BHMH with Al (a) and Zn (b).
Furthermore, ESI-MS analyses were carried out to investigate the coordination detail of
3+
2+
BHMH with Al and Zn in DMF solution (Fig. 8), respectively. Peaks at m/z 831.1631 and
+
3+ +
4
04.1054 were designated to [2(BHMH - H ) + Al ] (Calcd: 831.1640) which was a
+
+
supplementary proof for the 2:1 binding ratio concluded by job plot, and [BHMH + H ] (Calcd:
3
+
4
04.1061) illustrated in the spectra of BHMH + Al (Fig. 8a). As for the spectra of BHMH +
2
+
Zn (Fig. 8b), peaks at m/z 404.1056, 539.0719 and 612.1244 were respectively attributed to
+
+
+
2+
+
[
BHMH + H ] (Calcd: 404.1061), [BHMH - H + Zn + DMF] (Calcd: 539.0731) and
+
2+
+
[
BHMH - H + Zn + 2DMF] (Calcd: 612.1259) which also to some extent indicated the 1:1
2
+
complex formation between BHMH and Zn . These results further confirmed the formation of
1
2

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3
+
2+
stable complexes between probe BHMH and Al /Zn , respectively.
3
+
2+
Fig. 8. ESI–MS spectrum of BHMH (10 μM) upon addition of Al (a) and Zn (b) in DMF.
3
+
2+
To precisely master the binding detail of BHMH with Al /Zn , FT-IR spectra were firstly
3
+
2+
measured in the absence and presence of Al /Zn (Fig. S11), respectively. The result showed that
the FT-IR spectrum of BHMH itself had its characteristic peaks including the stretching frequency
of amide group (-NH), phenolic hydroxyl group (-OH), carbonyl group (C=O) and imide group
-1
-1
-1
-1
(
C=N) , which were located at 3444 cm , 3260 cm , 1624 cm and 1539 cm , respectively. As
3
+
for the FT-IR spectrum of BHMH-Al (Fig. S11a), the stretching bands of phenolic hydroxyl
group (-OH) of BHMH was disappeared, indicated the deprotonation of phenolic hydroxyl group
1
3

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3
+
of BHMH during the binding process with Al . Furthermore, the stretching bands intensity of the
carbonyl group (C=O) and imide group (C=N) were all significant decreased, indicated the
3
+
2+
interaction between the carbonyl group (C=O) and Al . While the FT-IR spectra of BHMH-Zn
(Fig. S11b), the characteristic stretching bands of amide group (-NH) and phenolic hydroxyl
-1
-1
group (-OH) were obviously shifted to 3161cm and 3056 cm , indicating the interaction of
2+
BHMH with Zn through the phenolic hydroxyl group (-OH) and carbonyl group (C=O).
1
H NMR titrations were measured to further investigate the interaction between BHMH and
3
+
2+
Al /Zn through compared with BHMH itself. The proton signals located at 13.26 ppm, 12.26
ppm and 11.68 ppm were designated to the phenolic hydroxyl (H ) and (H ), and the amide (H )
g
k
b
groups of BHMH in the (E)-configuration (Fig. 9) which was the dominated configuration in
3
+
Schiff-base molecular, respectively. Upon gradual addition of Al , the signal of H was almost
g
disappeared and its integral area was obviously decreased according to the integral area ratio (Hg:
H : H ) (Fig. S12), indicating the deprotonation on hydroxyl group during the combination of
k
j
3+
BHMH with Al , while the intensity of the other two signals (H and H ) were gradual weakened
k
j
and their corresponding signals in (Z)-configuration were gradual appeared at 10.34 ppm (H ) and
k’
9
.24 ppm (H ), respectively. This result indicated the configuration changed from
j’
3
+
(
Z)-configuration to (E)-configuration after coordination with Al which coordinated with oxygen
2
+
atom came from the deprotonation of phenolic hydroxyl (H ). As for the titration of Zn (Fig. 10),
g
the proton signal of the phenolic hydroxyl (H ) was decreased and its integral area was also
g
2
+
reduced upon the gradual addition of Zn (Fig. S13), and the proton signal of the phenolic
hydroxyl (H ) and amide (H ) were all weakened gradually, indicating the deprotonation of the
k
j
2
+
phenolic hydroxyl (H ) on probe BHMH upon the coordination with Zn .
g
1
4

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1
3+
Fig. 9. H NMR spectra of BHMH with Al in DMSO-d6.
1
2+
Fig. 10. H NMR spectra of BHMH with Zn in DMSO-d6.
According to the above launched experimental results containing job’ plot, FT-IR, HRMS,
1
3+
2+
and HNMR titration, the probable sensing mechanism of both BHMH-Al and BHMH-Zn
was illustrated in Scheme 3.
1
5

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3
+
2+
Scheme 3 Plausible sensing mechanism of BHMH to Al and Zn .
3+
2+
3
.3. pH effect on BHMH with Al and Zn
3
+
In order to estimate the effect caused by pH change on BHMH for the detection of Al and
2
+
3+
2+
Zn , the fluorescence spectra of BHMH upon addition of Al and Zn were measured in
different pH condition (Fig. 11), respectively. The result indicated that the idea pH ranges for
3+
2+
BHMH in the detection of Al (Fig. 11a) and Zn (Fig. 11b) were 4-7 and 5-7, respectively.
3
+
2+
Fig. 11. The fluorescent response of BHMB (10 μM) in the absence and prescence of Al (a) and Zn (b) in
DMF/H O (1/1, v/v) at different pH medium, respectively.
2
3
3
.4. Application of BHMH
3+
2+
.4.1 Detection Al and Zn in water samples
3
+
2+
Probe BHMH for the determination of Al and Zn were firstly carried out in real water
1
6

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sample to verify its practical application. These water samples were collected from campus of our
3
+
2+
university and Songhua River in Heilongjiang Province, and Al and Zn at different levels (1-10
μM) were spiked by those water samples, respectively. The fluorescence responses of Probe
3+
2+
BHMH were recorded for sensing Al at 494 nm and Zn at 508 nm (Fig. 12), respectively. The
3
+
2+
results showed that with the increase of concentration of either Al (Fig. 12a) or Zn (Fig. 12b)
in tested samples (including ultrapure water, tap water and Songhua water), the fluorescence
intensity were all increased gradually, and the good linearity was found between fluorescence
3+
2+
intensity and Al /Zn over the concentration range of 1-10 μM (Fig. S14-19), respectively. The
desirable recovery and relative standard deviations (R.S.D) values (Table S1 and S2) indicated
that Probe BHMH could be applied in quantitative analysis in real water sample for the detection
3
+
2+
of Al and Zn .
Fig. 12. Fluorescent detection of BHMH (10 μM) in “ultrapure water”, “tap water”, and “Songhua River” upon
3
+
2+
addition of different concentration of (a) Al (E = 494 nm) and (b) Zn (E = 508 nm), respectively.
m
m
3+
2+
3
.4.2 Detection Al and Zn on test paper
Fast and portable detection for one analyte was one important factor to evaluate a probe’s
3
+
2+
application property. Hence, the test paper experiments for sensing Al and Zn were
investigated through fluorescence color change (Fig. 13), respectively. Test papers were obtained
3
+
by which was immersed in BHMH solution containing different concentrations of Al (0, 1, 2, 3,
1
7

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2+
4
and 5 μM) and Zn (0, 2, 4, 6, 8 and 10 μM), respectively. After dried in air, accompanied with
3+
2+
the increasing concentration of Al (Fig. 13, top) and Zn (Fig. 13, bottom) under 365 nm
ultraviolet light, the color of the test papers were gradually changed from ivory to light blue and
3
+
2+
light green, respectively. Moreover, the differentiate Al from Zn on test paper was further
investigated by adding EDTA, and the procedure was recorded as Video S1. The first step was
that the dried test papers which had been immersed in BHMH (50 μM) solution containing the
3+
2+
same concentrations of Al (50 μM) and Zn (50 μM) were put on the watch glass, respectively.
The second step was that the same quality EDTA (50 μL) was added onto the test papers. The
2
+
result showed that the color of test paper (containing Zn ) turned from blackish green into the
bright orange similar as the color of the solid of BHMH under the under 365 nm ultraviolet light,
3
+
indicated the regeneration of BHMH. However, the test paper (containing Al ) almost showed no
color change after the addition of EDTA, which was similar to the result of differentiation
3+
2+
experiments of Al from Zn in BHM solution by adding EDTA. The above results indicated
3+
2+
that the probe BHMH can detect Al or Zn conveniently in the actual sample through the test
paper.
3
+
2+
Fig. 13. The image of probe BHMB on test strips with different concentrations of Al (top) and Zn (bottom)
nunder 365 nm UV light, respectively.
1
8

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4
. Conclusion
In conclusion, a simple ESIPT-based dual-functional probe BHMH was designed and
3
+
synthesized which displayed fluorescence turn-on and absorbance ratiometric detection for Al
2
+
3+
2+
and Zn . The 1:1 stoichiometry concerning the complex of BHMH -Al and BHMH -Zn were
confirmed by Job’s plot, respectively. Especially, BHMH was achieved in making a distinction
2+
3+
between Zn and Al by adding the EDTA reagent through either fluorescence or absorbance
3
+
2+
response. Moreover, probe BHMH was successfully achieved in the detection Al and Zn in
real water samples as well as fast and portable detection by test strips.
Declaration of competing interest
The authors declare no competing financial interest
Acknowledgements
This work was supported by the Postdoctoral Scientific Research Developmental Fund of
Heilongjiang Province (No. LBH-Q14023), and Students' Innovation and Entrepreneurship
Training Program of Northeast Agricultural University (No. 201910224325).
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CRediT author statement
Liu Ting-Ting: Data curation, Writing-original draft; Xu Jiao: Formal analysis; Liu Cheng-guo:
Investigation; Zeng Shuang: Validation; Xing Zhi-Yong: Conceptualization, Methodology,
Writing-review & editing; Sun Xue-Jiao: Visualization; Li Jin-Long: Supervision.
Declaration of interests
☒
The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which
may be considered as potential competing interests:
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