A Simple Fluorescence Probe Based on Aggregation-Induced Emission (AIE) Property for the Detection of Mg2+ Ions

Article abstract of DOI:10.1007/s10895-015-1717-8

A simple aggregation-induced emission-based fluorescence probe (1) for Mg²⁺ was synthesized by condensation of benzene-1, 2-diamine with 5-bromo-2-hydroxybenzaldehyde, This compound shows favourable character of the AIE-active molecules. More i

Full text of DOI:10.1007/s10895-015-1717-8

J Fluoresc
DOI 10.1007/s10895-015-1717-8
SHORT COMMUNICATION
A Simple Fluorescence Probe Based on Aggregation-Induced
2+
Emission (AIE) Property for the Detection of Mg Ions
1
1
1
1
Yan-Jiang Bian & Lu-Qiong Wang & Fu-Xiang Cao & Li-Jun Tang
Received: 21 August 2015 /Accepted: 28 October 2015
#
Springer Science+Business Media New York 2015
Abstract A simple aggregation-induced emission-based
material in organic light emission diodes (OLEDs),
2
+
fluorescence probe (1) for Mg was synthesized by
condensation of benzene-1, 2-diamine with 5-bromo-2-
hydroxybenzaldehyde, This compound shows favourable
character of the AIE-active molecules. More important-
bioprobes, and so forth [2–6].
2
+
The Mg ion is one of the most abundant divalent ions and
plays an important role in biology, such as in cell proliferation,
DNA synthesis, protein phosphorylation, and various trans-
porters [7–11]. Therefore, it is significant that effectively and
selectively detecting the magnesium ion for biochemistry, en-
vironmental science and medicine [12]. Within the last several
2
+
ly, after addition of Mg to probe (1) in acetonitrile,
the solution changed from colorless to yellow colour
solution under ultraviolet (UV) radiation obtained from
hand-held UV lamp, this finding suggested that probe
2
+
years, various fluorescent probe for the detection of the Mg
2
+
(
1) can be used to detect Mg by colorimetric detec-
ion have been synthesized [13, 14], However, some of the
used reductants are complicated, time consuming, expensive
or the detection conditions are critical [15].
−
5
−1
tion. Detection limit can reach 2.31 × 10 M . The
practical value of the selective and sensitive fluores-
cence indicators was confirmed by its application to
detection of magnesium ion in acetonitrile.
In this paper, we report an efficient and convenient proce-
2
+
dure for detecting Mg with an AIE-active fluorescence
probe (1) in acetonitrile. The receptor shows sensitive re-
2
+
sponse to the addition of Mg with fluorescence aggregation
enhancement by colorimetric detection.
.
Keywords Aggregation-induced emission Fluorescence
.
.
probe Colorimetric detection Magnesium ion
Traditional photonic materials suffer from the aggregation-
caused quenching (ACQ) effect in their aggregation or
solid phase, differently, the AIE-active molecules, first
reported by Tang and co-workers in 2001 [1], display
no obvious emission in solution, but an intense emission
when aggregated or in the solid state. The AIE-active
molecules have the potential to be used as fluorescent
Experimental
Reagent and apparatus: Unless otherwise specified, solvents and
reagents were of analytical grade from commercial suppliers and
were used without further purification. HNMR spectra were
performed on an Agilent 400NMR spectrometer. Fluorescence
measurements were carried out on a Sanco 970-CRT spectroflu-
orometer (Shanghai, China). The pH measurements were made
with a Model PHS-25B meter (Shanghai, China).
1
*
*
Yan-Jiang Bian
bianyanjiang@126.com
Synthesis of Probe (1) To a solution of benzene-1,2-diamine
(4 mmol) in ethanol (35 mL) was added 5-bromo-2-
hydroxybenzaldehyde (8 mmol). Then the mixture was
refluxed for 4 h. The solution was concentrated to give crude
solid, which was recrystallized with ethanol and dried to get
probe (1) as a yellow solid, yield is 87.5 %.
Li-Jun Tang
bhutang@126.com
1
College of Chemistry and Chemical Engineering, Bohai University,
Jinzhou 121013, China

J Fluoresc
Scheme 1 Synthesis of probe (1)
1
H NMR (400 MHz, CDCl ) δ: 13.03 (s, 2 H), 8.56 (s,
ratio of ethanediol and ethanol. In a good solvent of
9:1 ethanol/ethanediol, probe (1) was well dispersed in
its Bsolution^ state with a structured absorption spectra,
and displayed weak fluorescence emission. However,
when probe (1) was dispersed in 1 : 9 ethanol/
ethanediol, the fluorescence intensity of probe (1) in-
crease accordingly (Fig. 2).
3
2
2
(
H), 7.50 (d, J = 2.5 Hz, 2 H), 7.44 (dd, J = 8.8, 2.5 Hz,
H), 7.41–7.35 (m, 2 H), 7.24 (dd, J = 5.9, 3.4 Hz, 2 H), 6.96
d, J = 8.8 Hz, 2 H) (Scheme 1).
General Procedure for Metal Ions Detection A stock solu-
tion of probe (1) (10 μM) was prepared by dissolving the
This phenomenon strongly suggested the formation of
a poor-solvent Baggregate^ state that the fluorescence of
probe (1) increased because of restricted intramolecular
rotation [2, 3]. As aggregation state, the Bhexatomic
ring^ structure (Fig. 3) appeared enlarge the conjugated
system, therefore the fluorescence intensity of probe (1)
gradually raised. Based on the above facts, we found
that the probe (1) has the property of AIE. Therefore,
it has the potential to be photochemical material.
requisite amount of probe (1) in CH CN, and solution of var-
3
+
3+
2+
2+
2+
2+
ious metal ions, such as Ag , Al , Ba , Ca , Cd , Co ,
3
+
+
2+
+
2+
2+
2+
2+
3+
2+
Cr , K , Mg , Na , Ni , Pb , Zn , Fe , Fe , Hg and
2
+
Cu , were prepared by dissolving as their salts in water.
Results and Discussion
AIE characteristics of probe (1): The AIE feature of
probe (1) was confirmed in the mixture solution that
constituted with water and ethanol with different vol-
ume. As shown in Fig. 1, there is no obvious emission
when the water percentage is 10 %-60 %, while the
volume fraction of water more than 60 %, an intense
fluorescence arise at 514 nm. When the volume fraction
of water reaches 80 %, the fluorescence intensity attains
the highest.
Selectivity of Probe (1) To gain an insight into the fluo-
rescent properties of probe (1) toward metal ions, the
emission changes were measured with various metal
ions in CH CN solution. In the absence of metal ions
3
probe (1) has weak fluorescence. Upon addition of
2
+
Mg , a prominent fluorescence spectra at 514 nm is
observed (Fig. 4). what is more import, only after addi-
2
+
tion of Mg , the color of solution has changed from
colorless to yellow in under hand-held ultraviolet lamp,
In order to further confirm the AIE properties of probe
(
1),we also do experiment in the mixture solution of
+
3+
2+
while the addition of other metal ions(Ag , Al , Ba ,
different viscosities that content with different volume
2
+
2+
2+
3+
+
+
2+
2+
2+
Ca , Cd , Co , Cr , K , Na , Ni , Pb , Zn ,
9
7
6
4
3
1
00
50
00
50
00
50
0
8
6
4
2
00
00
00
00
0
1050
1
000
800
600
400
900
7
50
600
4
50
0
2
4
6
8
10
0.0
0.2
0.4
0.6
0.8
1.0
Ethanediol Volumn Fraction
Water Volumn Fraction
f
ethanediol
200
4
50
500
550
600
650
700
750
800
0
450
500
550
600
650
700
750
Wavelength(nm)
Wavelength(nm)
Fig. 1 The change of fluorescence of probe (1) in different mixture
solvent that water/ethanol (from 1:9 to 9:1, v:v) buffer with 10 mM
HEPES at pH 7.4
Fig. 2 Fluorescence spectra changes of probe (1) (100 μM) in the
mixture solution with ethanediol/ethanol (from 1:9 to 9:1.v:v)

J Fluoresc
Fig. 3 a The Bhexatomic ring^
structure of the state of
aggregation. b The photographs
of solution(dissolved in pure
3
CH CN) and aggregation(fw is
8
0 %) under hand-held ultraviolet
lamp
(a)
(b)
9
7
6
4
3
1
00
50
00
50
00
50
0
-
5 -1
M
Detection Limit=2.31*10
Y=7.44215+1.60536X
R=0.99713
0.90
0.75
0.60
0.45
2
+
Mg
-4.4
-4.3
-4.2
-4.1
-4.0
2
+
]
Log[Mg
4
50
500
550
600
650
700
Wavelength(nm)
Fig. 4 Fluorescence intensity of addition metal ions into the solution of
Fig. 6 Fluorescence spectra changes of 1(10 M) in the presence of
different concentrations of Mg ions in pure CH CN solution
3
probe (1) in CH
Photographs of probe (1) in CH
under hand-held ultraviolet lamp)
3
CN with the excite wavelength of 400 nm (Inset:
2+
2+
3
CN treated with Mg ions at 10 μM
2+
Fig. 5 Competition selectivity of 1(10 μM) toward Mg (10 equiv) in
the presence of other metal ions (10 equiv) with an excitation of 400 nm
2+
in CH
3
CN solution
Fig. 7 Job plot of probe (1) with Mg

J Fluoresc
Scheme 2 Proposed binding
2
+
mode of probe (1) with Mg
2
+
3+
2+
2+
2+
Fe , Fe , Hg and Cu ) did not show any detectable
Mg , the solution of indicators 1 exhibited an obvious color
changed from colorless to yellow in under hand-held ultravi-
olet lamp by naked-eye detection. The compound 1 can be
2
+
color change. This phenomenon confirmed that Mg
could be recognized by probe (1) by color change.
We carried out competition experiments to further check
the practical applicability of probe (1) as Mg selective
fluorescent sensor. Probe (1) was treated with 10 equiv.
of Mg in the presence of other metal ions with the
same concentration. As shown in Fig. 5, there is no
obvious interference with the detection of Mg ion
from other background metal ions.
2
+
used a sensitive probe to detect Mg ion in acetonitrile and
other common ions have no obvious interference. So, we de-
veloped a simple, rapid and portable sensor for magnesium
ion in acetonitrile.
2
+
2
+
2
+
Acknowledgments The project was supported by the national natural
science funds projects (No. 21176029, 21476029) and BLNET
No.LR2015001)^.
(
Sensitivity of Probe (1) To further investigate the
chemosensing properties of probe (1), a fluorimetric titration
of probe (1) with Mg ion was performed. As shown in
Fig. 6, the emission intensity of indicator 1 centered at
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