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A Turn-on and Reversible Schiff base Fluorescence Sensor for Al3+ ion
Chang-Hung Chen†, De-Jhong Liao†, Chin-Feng Wan‡*, An-Tai Wu†*
†Department of Chemistry, National Changhua University of Education, Changhua

Downloaded by Indian Association for the Cultivation of Science on 05 March 2013
50058, Taiwan
Published on 05 March 2013 on http://pubs.rsc.org | doi:10.1039/C3AN00004D
‡ School of Applied Chemistry, Chung Shan Medical University, Taichung City
Analyst Accepted Manuscript

40201, Taiwan
*
Corresponding author. E-mail: antai@cc.ncue.edu.tw; jeanwan02@yahoo.com.tw
1
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Abstract:
A simple Schiff-base receptor 2 was prepared. It exhibits an “off-on-type” mode with
high sensitivity in the presence of Al3+. The receptor 2 exhibited a high association
constant with submicromolar detection for Al3+ in EtOH-H2O (95:5 v/v) solution. The
addition of EDTA quenches the fluorescence of receptor 2·Al3+ complex offers
receptor 2 as a reversible chemosensor.

Keywords: Chemosensor; Fluorescence; Turn-On; Schiff-base
2
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In recent years, fluorescent chemosensors have attracted significant interest because
of their potential application in medicinal and environmental research. Thus, many
fluorescent chemosensors specific for Hg2+, Cu2+, Zn2+ or other transition metals have
been developed. Compared to these transition metal ions, only a few fluorescent
chemosensors have been reported for detection of Al3+.1-22 Al3+ is the most widely
exists in the environment due to acidic rain and human activities. Its toxicity not only

hampers plant growth but also damages the human nervous system to induce
Alzheimer’s disease, Parkinson’s disease, amyotrophic lateral sclerosis, etc.23-28
Therefore, detection of Al3+ is crucial in controlling its concentration levels in the
biosphere and its direct impact on human health. The detection of Al3+ has always
been problematic due to the lack of spectroscopic characteristics and poor
coordination ability.29 In addition, the majority of the reported Al3+ have limitations
such as requiring complicated synthesis and are insoluble in polar solutions. For
practical applications, it is necessary to develop Al3+ sensors that are easily prepared,
and possess selective and sensitive signaling mechanisms.
Herein, we reported a highly sensitive fluorescence turn-on receptor 2 to Al3+. More
importantly, receptor 2 can be readily prepared by three simple steps, as shown in
Scheme 1. The structure of receptor 2 was confirmed by NMR spectra and Mass data
(Fig. S1-S4).
3
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OH OH H
MsO O2N Pd/C
OH
NO2 K2CO3 HO MeOH OH N
O
ethylene glycol EtOH
1 HO
70% O
66%
receptor 2
Scheme 1
The chemosensor behavior of receptor 2 with the following 15 metal ions (as

perchlorate salts): Li+, Na+, K+, Ca2+, Mn2+, Hg2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Pb2+,
Cd2+, Zn2+ and Al3+ in EtOH-H2O (95:5 v/v), was investigated by UV-Vis and
fluorescence measurements. Figure S5 shows significant variations of the absorption
spectrum of receptor 2 in the 300-470 nm range for all the added anions. From the
fluorescence spectra of receptor 2 (Fig. 1), receptor 2 alone and other cations all
displayed very weak single fluorescence emission band at 480 nm when it was excited
at 346 nm except for Al3+. Upon addition of Al3+, receptor 2 exhibited a prominent
fluorescence enhancement with the quantum yield of 0.11 and accompanied by a blue
shift of 30 nm from 510 to 480 nm. Based on the use of a UV lamp, in the presence of
Al3+, the solution of receptor 2 showed a dramatic color change from dark blue to
light blue which could easily be detected by the naked-eye. (Fig. S6). The fluorescent
enhancement efficiency observed at 480 nm was 250-fold greater than the control in
the absence of Al3+ (Fig. S7). The observed fluorescent enhancement may be
4
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attributed to the formation of a rigid system after binding with Al3+, causing the
chelation-enhanced fluorescence (CHEF) effect. This unique selectivity of receptor 2
towards Al3+ could be interpreted in terms of the smaller ionic radius and higher
charge density of the Al3+.

To further investigate the chemosensing properties of receptor 2, UV/vis and
fluorescence titration of receptor 2 with Al3+ were performed. As shown in Fig. 2, the

addition of increasing amounts of Al3+ to a solution of receptor 2 in EtOH-H2O (95:5
v/v), the maximum absorbance at 346 nm decreased rapidly, and concomitantly two
rising new absorbance that peaked at 325 and 380 nm appeared. An isosbestic point is
clearly observed at 350 nm, indicating the formation of a new complex between
receptor 2 and Al3+. From the fluorescence titration profiles (Fig. 3), the association
constant for 2-Al3+ in EtOH-H2O (95:5 v/v) was determined as 5.23×105 M-1 by a Hill
plot (Fig. S8). A Job plot indicated a 1:1 stoichiometric complexation of receptor 2
with Al3+ (Fig. 4). In addition, the formation of 1:1 complex between 2 and Al3+ was
further confirmed by the appearance of a peak at m/z 325, assignable to [receptor 2 +
Al3+ + H2O + Na+] in the ESI/MS (Fig. S9). By using above-mentioned fluorescence
titration results, the detection limit for Al3+ was determined as 8.87×10-7 M. The
detection limit was sufficiently low to detect submicromolar concentration of the Al3+,
which belongs the range found in many chemical and biological systems.
5
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The selectivity towards Al3+ was further ascertained by the competition experiment.
As shown in Fig. S10, receptor 2 was treated with 10.0 equiv of Al3+ in the presence
of other metal ions of the same concentration. Relatively low interference was
observed for the detection of Al3+ in the presence of other metal ions except Fe3+. The
receptor 2 responses for Al3+ in the presence of Fe3+ are relatively low but clearly
detectable. Thus receptor 2 can be used as a selective fluorescent sensor for Al3+ in the

presence of most competing metal ions.
To check the pH effect, the fluorescence of receptor 2 under the different pH
conditions was examined. It was found that fluorescence intensity of receptor 2
remained unaffected over a wide pH span of 3-9 (Fig. S11). For practical applications,
the real-time determination was also important. The time evolution of receptor 2 in
the presence of 10.0 equiv of Al3+ in EtOH-H2O (95:5 v/v) was investigated. As
shown in Fig. S12, the recognition interaction was almost completed after addition of
the Al3+. The result showed that receptor 2 was a sensitive sensor and could be
applied in environmental analysis.
Reversibility is a prerequisite in developing novel chemosensors for practical
application. The reversibility of the recognition process of receptor 2 was performed
by adding an Al3+ bonding agent, EDTA (Fig. 5). The binding constant is 1.30×1016
between EDTA and Al+3; however, the binding constant is 3.06×106 between receptor
6
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2 and Al+3. Therefore, the addition of EDTA to a mixture of receptor 2 and Al3+
resulted in diminution of the fluorescence intensity at 480 nm, which indicated the
regeneration of the free receptor 2. The fluorescence was recovered by the addition of
Al3+ again. Such reversibility and regeneration are important for the fabrication of
devices to sense the Al3+.
To better understand the complexation behavior of receptor 2 with Al3+, 1H NMR

titration experiments were carried out in CD3OD. The spectral differences are
depicted in Fig. 6. The imine proton of receptor 2 at around 8.82 ppm was shifted
down-field toward 9.25 ppm upon the addition of Al3+. In addition, the protons of
benzene were all became more complicated. These observations obviously indicated
that the original intramolecular hydrogen bonding interaction between the phenolic
O-H and the nitrogen atom of the imine has been interrupted by the addition of Al3+.
The results also suggested the formation of 1:1 complex between receptor 2 and Al3+.
In summary, we prepared a simple receptor 2 for the detection of selected metal ions.
The receptor 2 displayed dramatic enhanced fluorescence intensity selectively for Al3+
over other ions in EtOH-H2O (95:5 v/v) solution. The addition of EDTA quenches the
fluorescence of receptor 2·Al3+ complex indicated that receptor 2 was a reversible
chemosensor. More importantly, the detection limit was sufficiently low to detect
submicromolar concentration of the Al3+. Thus, we trust receptor 2 has an ability to
7
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serve as a practical sensor for Al3+ detection in biological system and environment.
Acknowledgement. We thank the National Science Council of Taiwan for financial
support.
Supporting Information Available: Supplementary data associated with this article

can be found.
Reference:

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Valentinuzzi Chem. Commun. 2003, 1606.
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10. S. M. Ng, R. Narayanaswamy Anal. Bioanal. Chem. 2006, 386, 1235.
11. D. Mality, T. Govindaraju Chem. Commun., 2012, 48, 1039.
12. A. Sahana, A. Banerjee, S. Das, S. Lohar, D. Karak, B. Sarkar, S. K.

Mukhopadhyay, A. K. Mukherjee, D. Das Org. Biomol. Chem. 2011, 9, 5523.

13. Y. Lu, S. Huang, Y. Liu, S. He, L. Zhao, X. Zeng Org Lett. 2011, 13, 5274.
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Sanceno’n Chem. Commun. 2012, 48, 3000.
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381, 137.
19. T. Han, X. Feng, B. Tong, J. Shi, L. Chen, J. Zhic, Y. Dong Chem. Commun.
2012, 48, 416.
20. X. Sun, Y.-W. Wang, Y. Peng Org. Lett. 2012, 14, 3420.
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21. K. K. Upadhyay, A. Kumar Org. Biomol. Chem. 2010, 8, 4892.
22. J. Y. Jung, S. J. Han, J. Chun, C. Lee, J. Yoon Dyes Pigm. 2012, 94, 423.
23. J. Savory, O. Ghribi, M. S. Forbes, M. M. Herman J. Inorg. Biochem. 2001, 87, 16.
G. D. Fasman, Coord. Chem. Rev., 1996, 149, 125.

24. J. R. Walton, Neuro Toxicol. 2006, 27, 385.
25. J. Croom, I. L. Taylor J. Inorg. Biochem. 2001, 87, 51.

26. J. S. Perlmutter, L. W. Tempel, K. J. Black, D. Parkinson, R. D. Todd Neurology
1997, 49, 1432.
27. Y.W.Wang, M. X. Yu, Y. H. Yu, Z. P. Bai, Z. Shen, F. Y. Li and X. Z. You
Tetrahedron Lett. 2009, 50, 6169
28. S. H. Kim, H. S. Cho, J. Kim, S. J. Lee, D. T. Quang and J. S. Kim, Org. Lett.
2010, 12, 560.
29. K. Soroka, R. S. Vithanage, D. A. Phillips, B. Walker and P. K. Dasgupta, Anal.
Chem. 1987, 59, 629.
10
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600
3+
500 Al
Intensity (a.u.)
400
300
+ + 2+ 2+
host, Li , Na , Mg , Mn ,
2+ 3+ 2+ 2+ 2+
200 Fe , Fe , Co , Ni , Cu ,
2+ 2+ 2+ 2+
Ca , Cd , Pb , Hg
100
2+
Zn

0
400 450 500 550 600 650 700
Wavelength (nm)
Fig. 1 Fluorescence emission spectra (λex. = 346 nm) of receptor 2 (80 µM) in the
presence of 10.0 equiv of various metal ions in EtOH-H2O (95:5 v/v).
1.0
0.8
Wavelength (nm)
host
0.6 40 eq
0.2 eq
0.4
40 eq 0.2 eq
0.2
0.0
300 350 400 450 500
Absorbance (AU)
Fig. 2 UV/vis spectra of receptor 2 (80 µM) in EtOH-H2O (95:5 v/v) upon addition of
increasing concentrations Al3+.
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700
700
600
600 40 eq 500
400
I-I 0
300
Wavelength (nm)
500 200 I=intensity at 480 nm
3+
I0=intensity at 480 nm for [Al ]=0M
100
0
400 0 10 20 30 40
0 eq 3+
[Al ]/[sensor 2]
300
200
100

0
400 450 500 550 600 650 700
Intensity (a.u.)
Fig. 3 Fluorescence spectra of receptor 2 (80 µM) in EtOH-H2O (95:5 v/v) upon
addition of increasing concentrations Al3+; Inset is a plot of intensity change vs equiv.
of Al3+ added.
4
(I-I0)*X
0
0.0 0.2 0.4 0.6 0.8 1.0
3+
X=[receptor 2]/([receptor 2]+[Al ])
Fig. 4 Job plot

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700
600 Host
3+
Host+Al
500
Wavelength (nm)
3+
Host+Al +EDTA
400
300
200
100

400 450 500 550 600 650 700
Intensity (a.u.)
Fig. 5 Fluorescence emission spectra of receptor 2 in the presence of Al3+ (10.0 equiv)
or EDTA disodium (10.0 equiv) in EtOH-H2O (95:5 v/v) solution. λex = 346 nm.
Fig. 6 1H NMR titration plot of receptor 2 with Al3+ in CD3OD.

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Chang-Hung Chen, De-Jhong Liao, Chin-Feng Wan, An-Tai Wu
Supplementary Data
2-(2-nitrophenoxy)ethanol (1)
To a solution of 2-nitrophenol (3.02 g, 21.7 mmol) in ethylene glycol (30 mL)

was added K2CO3 (2.99 g, 21.6 mmol). The reaction mixture was refluxing for 10 h
and extracted by CH2Cl2 and water. The organic layer was then dried over MgSO4,

filtered, and concentrated. The resulting residue was purified by silica column
chromatography (Hexanes/EtOAc 10:1) to give 1 (2.78 g, 70%) as a brown oil; Rf
0.55 (EtOAc/ Hexane = 1：1); 1H NMR (300 MHz, CDCl3) δ: 7.61 (dd, J =1.8, 8.1 Hz,
1H), 7.36 (td, m, 1H), 6.93 (dd, J = 8.1 Hz, 1H), 6.85 (td, J = 0.6, 7.8 Hz, 1H), 4.031
13
(t, J = 4.5, 4.6 Hz, 2H), 3.777 (t, J = 4.5, 4.6 Hz, 2H), 3.423 (s, 1H) ; C NMR
(75MHz, MeOD) δ: 155.9, 139.2, 134.3, 125.2, 120.3, 114.7, 70.9, 60.2
(E)-2-(((2-(2-hydroxyethoxy)phenyl)imino)methyl)phenol (2)
A mixture of 8 (2.00 g, 11.0 mmol) and 10% Pd–C (0.14 g) in methanol (20 mL)
was stirred under H2 atmosphere (balloon pressure) for 12 h when the starting
material was completely consumed. The reaction mixture was filtered and the filtrate
was concentrated to get the crude amine product. The crude amine product was added
to a solution of 2-hydroxybenzaldehyde (1.37 g, 11.2 mmol) in dry EtOH. The
reaction mixture was stirred at the room temperature for 4 h and the EtOH was
removed. The resulting residue was purified by silica column chromatography

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(Hexanes/EtOAc 10:1) to give 2 (1.98 g, 66%) as a yellow solid; m.p = 94℃; Rf 0.43
(EtOAc/ Hexane = 1：1); 1H NMR (300 MHz, MeOD) δ: 8.72 (s, 1H), 7.35 (dd, J =
1.5, 4.5 Hz, 1H), 7.25 – 7.20 (m, 2H), 7.14 (td , J = 1.5, 7.4 Hz, 1H), 6.98 (d, J = 8.0
Hz, 1H), 6.95 (td , J = 1.2, 7.0 Hz, 1H), 6.79 – 6.73 (m, 2H), 4.50 (s, 1H), 4.01 (t, J =
13
4.8 Hz, 2H), 3.82 (t, J = 4.8 Hz, 2H); C NMR (75 MHz, MeOD) δ: 164.4, 163.1,
153.7, 137.5, 134.7, 133.8, 129.4, 122.8, 120.8, 120.5, 119.8, 118.7, 114.9, 71.7, 61.9;

HRMS (EI): Calcd for C15H16NO3 (M+H), m/z 258.1130; found m/z 258.1135.
Fig. S1 1H NMR Spectra of 1.
Fig. S2 13C NMR Spectra of 1.

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Page 16 of 22

Published on 05 March 2013 on http://pubs.rsc.org | doi:10.1039/C3AN00004D Page 17 of 22
HO
OH N
O
2
Fig. S3 1H NMR Spectra of 2.
Fig. S4. 13C NMR Spectra of 2.

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Host
3+
2.0 Al
Li+
+
Na
+
K
2+
Mg
1.5 2+
Mn
Absorbance (AU)
2+
Fe
3+
Fe
2+
Co
1.0 2+
Ni

2+
Cu
2+
Zn
2+
Ca
0.5 2+
Cd
2+
Hg
2+
Pb
0.0
300 350 400 450 500
Wavelength (nm)
Fig. S5 UV/vis spectra of 1 (80 µM) recorded in EtOH-H2O (95:5 v/v) after addition
of 10 equiv of various metal ions.
Fig. S6 Fluorescence changes excited by UV lamp (λex. = 346 nm) of receptor 2 upon
addition of 10 equiv of various metal cations in EtOH-H2O (95:5 v/v).
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480 nm
250
200
(I-I0)/I0 150
100
50

0
3+ + + + 2+ 2+ 2+ 3+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+
Al Li Na K Mg Mn Fe Fe Co Ni Cu Zn Ca Cd Hg Pb
Fig. S7 Variation of the fluorescence intensity at 480 nm (λex. = 346 nm) of receptor 2
(80 µM) in the presence of 10.0 equiv of various metal ions in EtOH-H2O (95:5 v/v).
1.0 Y=5.71866+1.74086X
2
R =0.996
0.5 5
Ka=5.23*10
log((I-I0)/(Imax-I))
0.0
-0.5
-1.0
-1.5
-2.0
-2.5
-5.0 -4.5 -4.0 -3.5 -3.0 -2.5
log[Al(III)]
Fig. S8 Hill plot

(I-I )/(I -I )
0 Al 0
0 .0
0 .2
0 .4
0 .6
0 .8
1 .0
H
os
H t+
os A
t+ l 3+
H A
os l 3+
t+ +
A Li +
l 3+
H
os +N
H t+ a +
os A
l 3+
t+
A +K +
H l 3+
os
t+ + C
A a2
l 3+ +
H
EtOH-H2O (95:5 v/v). λex = 346 nm.

os +
t+ M
A n 2+
H l 3+
os
t+ + F
A e 2+
H l 3+
os
t+ + F
A e 3+
H l 3+
os +
Analyst
t+ C o
H A 2+
o s l 3+
t+ + N
A
H l 3 i 2+
o s ++
t+ C
A u 2+
H l 3+
os
t+ + Z
A n 2+
H l 3+
os
t+ + C
A a 2+
H l 3+
os
t+ + C
A d 2+
H l 3+
os
t+ + P
A d 2+
l 3+
+H
g 2+
480 nm
equiv of other cations. [2] = 80 µM, [Al3+] = 800 µM, and [Xn+] = 800 µM in
Fig. S9 ESI Mass spectrum for [ receptor 2-Al3++H2O+ Na+] complex
Figure S10. Competition experiment of receptor 2 towards Al3+ in the presence of 10

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Page 20 of 22

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200
150
Intensity (a.u.) at 510 nm

100
50

2 3 4 5 6 7 8 9 10 11
pH
Fig. S11 Variation of fluorescence spectra of receptor 2 in EtOH-H2O (95:5 v/v) as a

function of pH at 510 nm; λex= 346 nm
480
440
Intensity (a.u.)
400
360
320
0 5 10 15 20 25 30 35 40 45
Time (min)
Fig. S12 Time evolution of receptor 2 in EtOH-H2O (95:5 v/v) in the presence of 10
equiv of Al3+ ion.
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Graphic Abstract
Chang-Hung Chen, De-Jhong Liao, Chin-Feng Wan, An-Tai Wu
A simple Schiff-base receptor 2 was prepared. It exhibits an “off-on-type” mode with
high sensitivity in the presence of Al3+.


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More information about Accepted Manuscripts can be found in the

Chang-Hung Chen†, De-Jhong Liao†, Chin-Feng Wan‡*, An-Tai Wu†*

†Department of Chemistry, National Changhua University of Education, Changhua

‡ School of Applied Chemistry, Chung Shan Medical University, Taichung City

Analyst Accepted Manuscript

A simple Schiff-base receptor 2 was prepared. It exhibits an “off-on-type” mode with

addition of EDTA quenches the fluorescence of receptor 2·Al3+ complex offers

receptor 2 as a reversible chemosensor.

Analyst Accepted Manuscript

In recent years, fluorescent chemosensors have attracted significant interest because

of their potential application in medicinal and environmental research. Thus, many

Analyst Accepted Manuscript

Alzheimer’s disease, Parkinson’s disease, amyotrophic lateral sclerosis, etc.23-28

Therefore, detection of Al3+ is crucial in controlling its concentration levels in the

been problematic due to the lack of spectroscopic characteristics and poor

and possess selective and sensitive signaling mechanisms.

Herein, we reported a highly sensitive fluorescence turn-on receptor 2 to Al3+. More

importantly, receptor 2 can be readily prepared by three simple steps, as shown in

Analyst Accepted Manuscript

fluorescence measurements. Figure S5 shows significant variations of the absorption

chelation-enhanced fluorescence (CHEF) effect. This unique selectivity of receptor 2

charge density of the Al3+.

To further investigate the chemosensing properties of receptor 2, UV/vis and

Analyst Accepted Manuscript

further confirmed by the appearance of a peak at m/z 325, assignable to [receptor 2 +

Analyst Accepted Manuscript

To check the pH effect, the fluorescence of receptor 2 under the different pH

conditions was examined. It was found that fluorescence intensity of receptor 2

applied in environmental analysis.

Reversibility is a prerequisite in developing novel chemosensors for practical

application. The reversibility of the recognition process of receptor 2 was performed

devices to sense the Al3+.

To better understand the complexation behavior of receptor 2 with Al3+, 1H NMR

Analyst Accepted Manuscript

fluorescence of receptor 2·Al3+ complex indicated that receptor 2 was a reversible

submicromolar concentration of the Al3+. Thus, we trust receptor 2 has an ability to

Acknowledgement. We thank the National Science Council of Taiwan for financial

Supporting Information Available: Supplementary data associated with this article

Analyst Accepted Manuscript

2. A. B. Othman, J. W Lee, Y. D. Huh, R. Abidi, J. S. Kim, J. Vicens Tetrahedron

2007, 63, 10793.

3. D. Maity, T. Govindaraju, Chem. Commun. 2010, 46, 4499.

Tetrahedron Lett. 2009, 50, 6169.

5. W. Lin, L. Yuan, J. Feng Eur. J. Org.Chem. 2008, 3821.

6. M. Arduini, F. Felluga, F. Mancin, P. Rossi, P. Tecilla, U. Tonellato, N.

Valentinuzzi Chem. Commun. 2003, 1606.

7. D. Maity, T. Govindaraju Inorg. Chem. 2010, 49, 7229.

8. K. K. Upadhyay, A. Kumar, Org. Biomol. Chem. 2010, 8, 4892.

10. S. M. Ng, R. Narayanaswamy Anal. Bioanal. Chem. 2006, 386, 1235.

11. D. Mality, T. Govindaraju Chem. Commun., 2012, 48, 1039.

12. A. Sahana, A. Banerjee, S. Das, S. Lohar, D. Karak, B. Sarkar, S. K.

Mukhopadhyay, A. K. Mukherjee, D. Das Org. Biomol. Chem. 2011, 9, 5523.

Analyst Accepted Manuscript

17. A. Barba-Bon, A. M. Costero, S. Gil, M. Parra, J.Soto, R. M. Mñez; F.

Sanceno’n Chem. Commun. 2012, 48, 3000.

2012, 48, 416.

21. K. K. Upadhyay, A. Kumar Org. Biomol. Chem. 2010, 8, 4892.

G. D. Fasman, Coord. Chem. Rev., 1996, 149, 125.

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Analyst Accepted Manuscript

1997, 49, 1432.

Chang-Hung Chen†, De-Jhong Liao†, Chin-Feng Wan‡, An-Tai Wu†