Highly sensitive and selective fluorescent "turn-on" probe for determination of aluminum ion in aqueous solution

Article abstract of DOI:10.1080/00387010.2015.1083586

A novel fluorescent sensor, 1-((2-hydroxynaphthalen-1-yl)methylene) semicarbazide, was synthesized and characterized by infrared spectra, elemental analysis, electrospray ionization mass spectra. The fluorescent sensing behaviors of the sensor toward different metals ions, anions, and amino acids were determined by UV-vis and fluorescence spectroscopy. The fluorescent sensor exhibited obvious changes in its electronic and fluorescent spectral behavior in the visible region of the spectrum in the presence of aluminum ion with the lower detection limit was 8.9 × 10^-9 M.

Full text of DOI:10.1080/00387010.2015.1083586

Spectroscopy Letters
An International Journal for Rapid Communication
ISSN: 0038-7010 (Print) 1532-2289 (Online) Journal homepage: http://www.tandfonline.com/loi/lstl20
Highly Sensitive and Selective Fluorescent ‘turn-
on’ Probe for Determination of Aluminum Ion in
Aqueous Solution
Qing-Ming Wang, Wei Gao, Yang Li, Ting-Ting Yang, Yan Ju & Xin-Hui Tang
To cite this article: Qing-Ming Wang, Wei Gao, Yang Li, Ting-Ting Yang, Yan Ju &
Xin-Hui Tang (2015): Highly Sensitive and Selective Fluorescent ‘turn-on’ Probe for
Determination of Aluminum Ion in Aqueous Solution, Spectroscopy Letters, DOI:
10.1080/00387010.2015.1083586
To link to this article: http://dx.doi.org/10.1080/00387010.2015.1083586
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Date: 22 October 2015, At: 05:37

Highly sensitive and selective fluorescent ‘turn-on’ probe for determination of
aluminum ion in aqueous solution
1
,3
1
1
1
1
2
Qing-Ming Wang , Wei Gao , Yang Li , Ting-Ting Yang , Yan Ju , Xin-Hui Tang
1
School of Pharmacy, Jiangsu Provincial Key Laboratory of Coastal Wetland
Bioresources and Environmental Protection, Yancheng Teachers’ University, Yancheng,
2
Jiangsu, People’s Republic of China School of Pharmacy, Jiangsu University, Zhenjiang,
3
P.R. China State Key Laboratory of Coordination Chemistry, Nanjing University,
Nanjing, People’s Republic of China
Corresponding author: Pro. Xin-Hui Tang School of Pharmacy, Jiangsu University, 301
Xuefu Road, Zhenjiang, 212013, P.R. China E-mail: xinhuitang@sina.com
wang0qingming@163.com (Wang Q)
Abstract
A novel fluorescent sensor, 1-((2-hydroxynaphthalen-1-yl)methylene)semicarbazide was
synthesized and characterized by infrared spectra, elemental analysis, Electrospray
ionization mass spectra. The fluorescent sensing behaviors of the sensor toward different
metals ions, anions and amino acids were determined by UV-vis and fluorescence
spectroscopy. The fluorescent sensor exhibited obvious changes in its electronic and
fluorescent spectral behavior in the visible region of the spectrum in the presence of
-9
aluminum ion with the lower detection limit was 8.9 × 10 M.
KEYWORDS: Aluminum, Fluorescent Sensor, Schiff base, Detection limit
1
. INTRODUCTION
1

3
+
Aluminum(Al ) is a polyvalent cation and the third abundant metal in the earth’s crust,
and it is widly used for water treatment, food additives, medicines and the production of
[
1-8]
light alloys in modern society
. However, the accumulation of aluminum in the human
body can damage normal tissues and cells, resulting in human health problems, such as
[
9-11]
[12]
Alzheimer’s disease
, Parkinson’s disease , lung cancer, breast cancer, and bladder
[
13,14]
cancer
. Besides, the aluminium-containing adjuvants could trigger the cascade of
[15]
immunological events such as chronic fatigue syndrome and macrophagic myofasciitis
.
What’s more, the content of aluminium correlates with the reduction of the
+
+
[16,17]
(
Na /K )ATPase activity
. In ddition, due to the high concentrations of aluminum
[
18-20]
appearing in acidified lakes and acidic soils worldwide
, the fish and the growing
[
21]
crop in these enviroment are also polluted . Therefore, it is very important to determine
and control aluminum ion in environment and the human body.
Recently, a great number of methods have been used for the detection of aluminum
[22-24]
[25-30]
ion
and others
. Of them, the fluorescent detection for aluminum ion and
others have attracted increasing attention, and have been used in a wide range of
[
31-35].
applications because of its operational homeliness
Moreover, a number of
fluorescent sensors based on the schiff bases were used for the detection of aluminum ion
have been reported , but the selectivity over anions and amino acids were not fully
[
36-41]
3+
tested by previous reports
. It is well known that Al prefers a coordination sphere
2

containing N and O as hard-base donor sites. Schiff bases are known to be good ligands
3
+ [33,35,42]
which provide a hard-base environment for the hard-acid Al
.
In the present study, we attempted to design and synthesize an optical chemosensor for
3
+
Al . 1-((2-hydroxynaphthalen-1-yl)methylene)semicarbazide (NS) was chosen as the
signaling subunit and its binding properties with other cation, antion and amino acid by
the means of UV–vis and fluorescence spectroscopy. As expected, the chemosensor(NS)
3
+
could recognize Al over other cation, antion and amino acid.
2
. EXPERIMENTAL
2
.1 Materials And Methods
-1
FT-IR spectra (4,000 - 400 cm ) were obtained on NICOLET380 FT-IR spectrometer in
KBr disks (USA). Melting point was determined on a WRX-4 apparatus in a sealed
capillary (China). UV - vis spectra were measured with Hewlett Packard
1
13
HP-8453(China). H and C NMR spectra were recorded at room temperature on a
Varian 400MHz spectrometer in CD3OD(USA). The fluorescence spectra were
obtained on Varian Cary ESe-NipSe-N fluorescence spectrometer with the excitation and
emission slits are 2.5 nm (USA). Elemental analyses (EAs) were carried out with a
VARI-EL elemental analyzer. Electrospray ionization mass spectra (ESI-MS) were
measured on a Finnigan LCQ system in methanol/water solution(USA). pH values of
buffer solutions were measured using a PHS-3TC pH meter(China). All chemicals used
3

were of analytical grade and were used as received without any further purification and
were obtained from Sigma–Aldrich (USA)and Alfa Aesar (USA)Chemical Reagent Co.
All metal salts were introduced as their chlorate salts. Anions were purchased as sodium
salts.
2
.2 Synthesis Of 1-((2-Hydroxynaphthalen-1-Yl)Methylene)Semicarbazide (NS)
0
.344 g(0.002 mo1) 2-hydroxy naphthalene formaldehyde was added to 6.00 mL ethanol
with heating until it was dissolved. Then 0.150 g(0.002 mol) of semicarbazide in 7.00 mL
water and 0.4 mL acetic acid was added drop-wise into the mentioned solution above.
After the resulting solution was refluxed for 15 min with a constant stirring, light yellow
solid was obtained and washed with ethanol and ether, respectively, recrystallized from
dimethylbenzene, dried in vacuo. Yield, 67.8%. mp.:111-113℃. Elemental Analysis
Calcd for C H N O : C: 62.87; H: 4.84; N: 18.33. Found: C: 62.86; H: 4.86; N: 18.33.
1
2
11
3
2
-
1
IR(cm , s strong, m medium, w weak): 3442m, ν(O-H); 3346m, ν(N-H); 1675s, ν(C-H);
1
1
625m, ν(C=N). H NMR (400 MHz, CD OD): 9.04 (1H, s), 7.19-7.89 (6H, s), 2.50
3
1
(
4H, s). C NMR (400 MHz, CD OD): 163.43, 162.12, 158.31, 152.64, 137.62, 133.72,
3
1
30.21, 126.91, 123.83, 120.44, 119.45, 117.25. Exact mass for NS: 229.09, ESI-MS:
+
[
NS+H] (m/z, 230.2473).
3
. RESULTS AND DISCUSSION
3
.1 Absorption Spectra Studies
4

3
+
Uv-vis titration experiments were conducted for evaluation of the formation of NS-Al
in solution. As shown in Figure 1, two main absorption peaks at 316 and 357 nm were
3
+
observed in the absorption spectra of NS(25μM). Upon addition of Al , the two peaks
show obvious red-shift and their intensities decrease gradually. Meanwhile, two new
absorption peaks at 336 nm and 385nm appear and their intensities increase gradually.
Moreover, there were three isosbestic points at 322, 352, 368 nm in the Uv-vis titration
3
+
spectra. The results suggested the formation of a new compound between Al and NS,
which extends the conjugated system and leads to new absorption in the long wavelength
[
42,43]
region
. The absorbance peaks have been hardly changed when the concentration of
3
+
Al was increased to 13 μM.
3
.2 Effect Of Ph On The Fluorescence Spectra
To evaluate the optimal determinations conditions, it is necessary to investigate pH effect
3
+
on NS in the absence and presence of Al . As shown in Figure 2, there is hardly change
3
+
in the fluorescence spectra of NS with the addition of Al at pH 1.0-12.0, while the
remarkable change was found at pH range 4.0–6.0. The results showed the combination
3
+
of protons and N atoms in –C=N– groups inhibits the coordination of Al with NS at pH
3
+
range 1.0–3.0, On the other hand, the fluorescence of NS has no response to Al at high
3
+[44]
pH values because the hydrolysis happens between OH and Al
. The optimal pH
corresponding to the highest intensity is 6.0, which is within the biologically relevant pH
5

[
45-47]
3+
range (5.5–7.5)
, indicating that NS could be applied as an Al sensor in biological
organisms potentially.
3
.3 Fluorescence Titration
On the basis of the above evaluation of optimal pH, fluorescence titration was performed
3
+
to study the stoichiometric ratio of the NS–Al complex in pH 6.0 buffer solution. The
3
+
fluorescence enhancement of the NS in the presence of various concentrations of Al
was shown in Figure 3. The receptor NS do not show remarkable emission at 450 nm
3
+
when the excitation wavelength is at 390 nm. However, upon the addition of Al (2.5μM),
the fluorescence intensity at 450 nm increases accordingly, but when the concentration of
3
+
Al was up to 10 μM, the rising tendency slowed down gradually until stable.
The binding constant was calculated from the emission intensity - titration curve
[
48]
according to the equations (1) and (2)
:
2
2
3
1/ 2
I I f
(
b (b 2k C [Al ]/ s) )
t
Ib I f
2kCt
(
1)
2)
3
b 1 kC k[Al ]/2s
t
(
3
+
where I is the emission intensity observed at a given Al concentration, I is the emission
f
intensity of free NS in solution, I is the emission intensity of NS when fully bound to
b
3
+
3+
Al (it is assumed that when further addition of Al does not change the emission
3
+
intensity, K is the equilibrium binding constant, C is the total NS concentration, [Al ] is
t
6

3
+
the Al concentration, and s is the binding site. Both K and s are obtained from the best
fit line. From Figure 4, we can obtained the equilibrium binding constant K between
3
+
7
-1
3+
Al with NS is 1.3×10 M and the binding site(s= [Al ]/[NS]) is 0.43.
[
49,50]
The limit of detection (LOD)
was calculated based on the fluorescence titration. The
3
+
emission intensity of NS without Al was measured 10 times and the standard deviation
of blank measurements was determined. A good linear relationship between the
3
+
fluorescence intensity and the Al concentration could be obtained in the 1.25 - 8.75 µM
2
concentration range (R = 0.996). LOD was then calculated with the equation: LOD =
3
σ /m, where σ is the standard deviation of blank measurements, m is the slope between
bi bi
-9
intensity versus sample concentration. LOD was measured to be 8.9 × 10 M, nearly the
[
38]
3+
same capacity compared with other compounds . In general, the concentration of Al
-3
should be lower than (1.85×10 M) in drinking water, which means that our proposed
fluorescent method based on probe NS is sensitive enough to monitor the water quality of
drinking water.
3
.4 Selectivity Experiment
2
+
2+
2+
2+
+
2+
+
The selectivity of NS for various common cations (Zn , Sr ,Pb , Ni , Na , Mg , K ,
2
+
3+
2+
3+
2+
2+
2+
3+
2+
3+
+
Hg , Fe , Cu , Cr , Co , Cd , Ca , Bi , Ba , Al , Ag ) were investigated in
3
+
Tris-HCl buffered aqueous solution (25mM, pH=6.0). As shown in Figure 5, Al
treatment induces a large increase for the fluorescence intensity at 450 nm, whereas other
7

+
+
2+
physiologically important metal ions, not only exist in living cells, such as Na , K , Mg ,
2
+
2+
3+
Ca , but also most heavy and transition metal ions such as Mn , Cr or some
3
+
2+
2+
2+
2+
paramagnetic metal ions, such as Fe , Cu , Co , Ni , Zn , cause a slight fluorescence
increasment at a 20-fold excess concentration.
3
+
In order to prove that the sensor was highly selective for Al , other species existing in
2
-
2-
3-
4
-
-
-
-
-
-
-
cells such as anions(SO , SO , PO , NS , NO , MnO , IO , HPO , HCO , H PO ,
4
3
3
4
3
4
3
2
4
-
2-
2-
7
2-
3
-
-
-
2-
-
2-
F , CrO , Cr O , CO , CNS , ClO , Cl , C O , Br , B O ) and amino acids (Ile, Val,
4
2
3
2
4
4
7
Asp, Ser, Pro, Tyr, Lys, Arg, Met, Gln, Glu, Gly, Ala, Phe, Leu) were determinated. The
3
+
results show that both the anions and the amino acids have no interference on Al
3
+
determination, indicating that NS can be applied to detect Al effectively(Figure 6-7).
3
.5 The Preliminary Application Of The Sensor
3
+
The recovery of Al from river water was studied with the proposed fluorescent sensor.
First, the sample was concentrated by rotary evaporator. The fluorescence intensity of NS
for the concentrated river water was investigated in Tris-HCl buffered aqueous solution
-4
(
25mM, pH=6.0). The results demonstrated that the average amount was 1.21×10 M by
fluorescence for 3 times, which was more or less the same as the result of the traditional
-4
flame atomic absorption spectrophotometry, 1. 38×10 M. The experiment suggested that
it was a convenient, accurate and reliable way to calculate the amount of Al3+ by the
fluorescence sensor way.
8

4
. CONCLUSION
In conclusion, a structurally characterized 1-((2-hydroxynaphthalen-1-yl)methylene)
3
+
-
semicarbazide (NS) demonstrates as a new sensor toward Al in pH 6.0 Tris-HCl buffer
3
+
solution. The sensor NS exhibited high selectivity for Al over other important metal
2
+
2+
2+
2+
+
2+
+
2+
3+
2+
3+
2+
2+
2+
3+
ions(Zn , Sr ,Pb , Ni , Na , Mg , k , Hg , Fe , Cu , Cr , Co , Cd , Ca , Bi ,
2
+
3+
+
2-
2-
3
3-
4
-
-
-
-
-
-
Ba , Al , Ag ), anions(SO , SO , PO , NS , NO , MnO , IO , HPO , HCO ,
4
3
4
3
4
3
-
-
2-
2-
7
2-
3
-
-
-
2-
4
-
2-
H PO , F , CrO , Cr O , CO , CNS , ClO , Cl , C O , Br , B O ) and amino
2
4
4
2
3
2
4
7
acids(Ile, Val, Asp, Ser, Pro, Tyr, Lys, Arg, Met, Gln, Glu, Gly, Ala, Phe, Leu) with the
-9
lower detection limit is 8.9 × 10 M. So this sensor may play an important role for
3
+
detecting Al in the biological and environmental system.
ACKNOWLEDGMENT
This work were financially supported by the National Natural Science Foundation for
Young Scientists of china(21301150), the Natural Science Foundation of the Jiangsu
Higher Education Institutions of China (13KJB150037), the Foundation of Jiangsu
Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental
Protection (JLCBE14007, JLCBE10006), the Foundation of Jiangsu Provincial Key
Laboratory of Solonchak (JKLBS2012022), the practice inovation trainng program
projects for the Jiangsu College students (201310324034Y).
9

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6

Scheme 1. Synthesis the sensor of 2-hydroxy naphthalene formaldehyde.
1
7

Figure 1. UV−vis spectra changes of the sensor (2.5μM) after addition of aluminum ion
0, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 μM) at room temperature. Inset.
Graph of the absorbance at 385 nm as a function of aluminum ion concentration.
(
1
8

Figure 2. Effect of pH on the fluorescence intensity of the sensor 2-hydroxy
naphthalene formaldehyde (2.5μM) at 450 nm with (Black) and without (Red) 1 equiv
aluminum ion in water. λ = 390 nm.
ex
1
9

Figure 3. The fluorescence spectra of the sensor (2.5μM) after addition of aluminum ion
0, 1.25, 2.5, 3.75, 5, 6.25, 7.5, 8.75, 10, 11.25, 12.5, 13.75 μM) at room temperature.
(
2
0

Figure 4. Plot of (I- I )/(I - I ) vs. [Aluminum ion] for the sensor 2-hydroxy naphthalene
f
b
f
2
formaldehyde. λ = 390 nm. The best fit line (R =0.996), superimposed on the data,
ex
7
-1
according to 2 eq yields K=1.3×10 M and S = 0.43.
2
1

Figure 5. The fluorescence responses (I450nm) of sensor 2-hydroxy naphthalene
formaldehyde (2.5μM) with various cations (50μM) in Tris-HCl buffer (pH=6.0)( λex =
3
90 nm).
2
2

Figure 6. The fluorescence responses (I450nm) of the sensor 2-hydroxy naphthalene
formaldehyde (2.5μM) with various anions (50μM) in Tris-HCl buffer (pH=6.0)( λex =
3
90 nm).
2
3

Figure 7. The fluorescence responses (I450nm) of the sensor 2-hydroxy naphthalene
formaldehyde (2.5μM) with various amino acids (50μM) in Tris-HCl buffer
(pH=6.0)( λex = 390 nm).
2
4