A hemicyanine-based selective and sensitive colorimetric and fluorescent turn-on probe for Cu2+

Article abstract of DOI:10.1016/j.tetlet.2016.10.056

A hemicyanine-based colorimetric and fluorescent turn-on probe 2 was designed and synthesized. The probe displayed a rapid response time, high sensitivity and high selectivity for Cu²⁺over other metal ions. Moreover, the probe can detect Cu

Full text of DOI:10.1016/j.tetlet.2016.10.056

Accepted Manuscript
A hemicyanine-based selective and sensitive colorimetric and fluorescent turn-
2
on probe for Cu
+
Dongjian Zhu, Yanghe Luo, Liang Shuai, Wei Xie, Xiaowei Yan, Zhenhua
Duan, Wen Cai
PII:
S0040-4039(16)31368-5
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.10.056
TETL 48226
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
2 September 2016
8 October 2016
17 October 2016
Please cite this article as: Zhu, D., Luo, Y., Shuai, L., Xie, W., Yan, X., Duan, Z., Cai, W., A hemicyanine-based
2
selective and sensitive colorimetric and fluorescent turn-on probe for Cu , Tetrahedron Letters (2016), doi: http://
+
dx.doi.org/10.1016/j.tetlet.2016.10.056
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
A hemicyanine-based selective and sensitive
colorimetric and fluorescent turn-on probe
for Cu
Leave this area blank for abstract info.
2
+
Dongjian Zhu,* Yanghe Luo,* Liang Shuai, Wei Xie, Xiaowei Yan, Zhenhua Duan and Wen Cai

1
Tetrahedron Letters
A hemicyanine-based selective and sensitive colorimetric and fluorescent turn-on
2
+
probe for Cu
Dongjian Zhu , Yanghe Luo *, Liang Shuai, Wei Xie, Xiaowei Yan, Zhenhua Duan and Wen Cai
Research Institute of Food Science & Engineering Technology, Hezhou University, Hezhou 542899, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A hemicyanine-based colorimetric and fluorescent turn-on probe 2 was designed and
synthesized. The probe displayed a rapid response time, high sensitivity, and high selectivity for
2+
2+
Cu over other metal ions. Moreover, the probe can detect Cu in the presence of 15 species
metal ions by absorption spectra, fluorescence spectra and naked-eye in aqueous media.
Available online
2
009 Elsevier Ltd. All rights reserved.
Keywords:
Copper ion
Hemicyanine
Colorimetric
Fluorescent
Copper is the third most abundant indispensable trace element
such as low cost, simplicity, visualization and analysis in situ
18 19
(
following iron and zinc) in human body and plays a crucial role
using simple apparatus. So far, only a few rhodamine-based
1
20
in various physiological processes. However, abnormal levels of
copper are implicated in a variety of diseases. Definitely, copper
and BODIPY-based colorimetric and fluorescent turn-on probes
for copper ions have been reported. Nevertheless, some of them
exhibited cross-sensitivities toward other metal ions. Therefore,
developing selective and sensitive colorimetric and fluorescent
2
deficiency may cause coronary heart disease. An excess amount
of copper could lead to harmful effects by causing oxidative
3
2+
stress and disorders,
which are associated with
turn-on probe for Cu detection under physiological conditions
4
5
neurodegenerative diseases including Alzheimer’s, Menke’s,
Parkinson’s, Wilson’s, and prion diseases. In addition, copper
has become an important metal pollutant due to its widespread
is highly demanded.
6
7
8
9
applications. Therefore, development of sensitive and selective
methods for detection of copper ions in biological and
environmental systems is strongly desired.
Although traditional methods such as atomic absorption
11
10
spectrometry (AAS), atomic emission spectrometry (AES),
inductively coupled plasma mass spectrometry (ICP-MS),
12
13
14
voltammetry, and electrochemicalmethods have been used for
detection of copper ions, these methods often require expensive
instruments and tedious sample preparation procedures, which
preclude their application for real-time and in vivo analysis. In
contrast, fluorescence probe because of its specificity, high
2
+
Scheme 1. Synthetic strategy for 2 and proposed reaction mechanism for Cu .
2
1
Based on our previous research, it is necessary to choose an
efficient fluorophore in the design of fluorescent probes.
Merocyanine dyes show strong intramolecular charge transfer
ICT) with “push-pull” substituent pairs, when ICT process was
affected by a certain sensing event, both colour and fluorescence
15
sensitivity, real-time detection, and simple instrumentation has
attracted much attention. As a consequence, a number of
fluorescent probes have been developed to detect copper ions in
22
(
16
recent years.
2
3
changes were observed. Thus, merocyanine is an attractive
platform for the design of colorimetric and fluorescent turn-on
probes. With these facts in mind, we develop a selective and
Among the reported probes for copper ions, colorimetric and
17
fluorescent probes have drawn increasing attraction, because
they not only have the advantages of the fluorescent probes, but
also have the characteristics of the colorimetric measurements,
2+
sensitive colorimetric and fluorescent turn-on probe 2 for Cu
(Scheme 1), which employs merocyanine as the fluorophore and
—
——

Corresponding author. Tel.: 86-774-5229756; e-mail: zhudongjian@iccas.ac.cn and 250581250@qq.com

2
Tetrahedron
picolinate as recognition unit. The synthetic strategy for
metal ions, displays the expected pink, but the other metal ions
+ + 2+ 2+ + 2+ 2+ 2+ 2+ 2+
preparing probe 2 is outlined in Scheme 1. For comparison,
compound 3 was also synthesized. The detailed experimental
procedures and H and C NMR spectroscopy and ESI mass
spectrometry are explained in the Supporting Information.
including Na , K , Ca , Mg , Ag , Zn , Cd , Hg , Ba , Pb ,
2+ 2+ 2+ 3+ 3+
Mn , Ni , Co , Fe , Al ions, do not show any colour change,
indicating that 2 exhibits high selectivity to Cu over other metal
ions. It is worth noted that 2 has excellent selectivity to Cu even
1
13
2+
2+
in the presence of 15 species metal ions.
With 2 in hand, we carried out optimizations on experimental
conditions such as pH and solubility. At room temperature (25 C),
o
the fluorescence intensity at 557 nm of 2 in the absence and
2+
presence of Cu at different pH was studied (Fig. S1). It could be
seen that the fluorescence intensity increased slightly in the pH
2+
ranging from 4.0 to 7.0 in the absence of Cu . However, the
fluorescence intensity remarkably increased with pH increasing
2+
in the range of 7.0 - 9.5 in the absence of Cu . On the other hand,
2+
in the presence of Cu , the fluorescence intensity was increased
in the region of pH 6.0 - 8.0. These findings indicated that
alkaline condition (>7.0) could cause the hydrolysis of 2, which
increased background fluorescence. Thus, pH 7.0 is suggested to
Figure 2. Colour change observed before (a) and after (b) the addition of
2
+
Cu (20 µM) to the solution of 2 (10 µM) in HEPES buffer (10 mM,
2+
o
be suitable for Cu detection. In addition, 2 and 3 exhibit good
solubility in HEPES (4-(2-hydroxyethyl)-1-
piperazineethanesulfonic acid) buffer solution containing
acetonitrile as a cosolvent (10 mM, H O/CH CN, 4:1, v/v, pH 7.0)
H
2
O/CH
3
CN, 4:1, v/v, pH 7.0, 25 C) in the presence of different metal ions:
+
+
2+
2+
+
2+
Na (1 mM), K (1 mM), Ca (1 mM), Mg (1 mM), Ag (20 μM), Zn (20
2
+
2+
2+
2+
2+
μM), Cd (20 μM), Hg (20 μM), Ba (20 μM), Pb (20 μM), Mn (20
2
+
2+
3+
3+
2+
2
3
μM), Ni (20 μM), Co (20 μM), Fe (20 μM), Al (20 μM), Cu (20 μM).
at room temperature according to the absorption spectra (Fig. S2).
2
+
The selectivity of 2 for Cu detection was also investigated
by absorption spectra. As shown in Fig. 3, 2 exhibits high
Based on the above observations, buffer solution of HEPES (10
o
mM, H
2
O/CH
3
CN, 4:1, v/v, pH 7.0, 25 C) was selected as the
2+
selectivity to Cu , which is in good agreement with the result of
colour change.
optimized conditions for further spectral investigation.
Figure 3. Absorption spectra of 2 (10 μM) in the absence and presence of
+
+
2+
2+
different metal ions: Na (1 mM), K (1 mM), Ca (1 mM), Mg (1 mM),
+
2+
2+
2+
2+
2+
Ag (20 μM), Zn (20 μM), Cd (20 μM), Hg (20 μM), Ba (20 μM), Pb
2
+
2+
2+
3+
3+
(
20 μM), Mn (20 μM), Ni (20 μM), Co (20 μM), Fe (20 μM), Al (20
2
+
μM), Cu (20 μM). (a): free probe and probe treated with the marked metal
2
+
ions. (b): probe treated with the marked metal ions followed by Cu (20 μM)
and free probe. Data were acquired in HEPES buffer (10 mM, H
2
O/CH
3
CN,
Figure 1. Absorption spectra of 2 (10 μM) (black line) before and (red line)
o
4
:1, v/v, pH 7.0, 25 C).
2
+
after reaction with Cu (20 μM) in HEPES buffer (10 mM, H
2
O/CH
3
CN, 4:1,
o
v/v, pH 7.0, 25 C). The colour change of 2 before and after the reaction are
shown in the insets.
Then, we assessed the photophysical properties of 2 under the
optimized conditions (10 mM, H
2
O/CH
3
CN, 4:1, v/v, pH 7.0,
o
2
5 C). The absorption spectra and colour change of 2 before and
2+
after reaction with Cu are shown in Fig. 1. A solution of 2
2
+
exhibited an absorption band at 388 nm. Upon addition of Cu ,
the band at 388 nm disappeared, while two new absorption bands
centered at 428 nm and 531 nm emerged, which were ascribed to
the fluorescent product 3 enol form and keto form, respectively
Figure 4. (a) Fluorescence spectra of 2 (10 μM) recorded every 12 s within 2
2
+
min after the addition of Cu (20 μM) in HEPES buffer (10 mM,
(Figs. S3 and S4). The colour of the solution dramatically turned
o
H
2
O/CH
3
CN, 4:1, v/v, pH 7.0, 25 C, λex = 500 nm). (b) The fluorescence
from pale yellow to pink, which is similar to the colour of 3 in
intensity at 557 nm changes as a function of time.
HEPES buffer (Fig. S4), thus allowing colorimetric detection of
2+
2+
Cu by the naked eye. Time course studies showed that the
absorbance of 388 nm decreased and the absorbance of 428 nm
and 531 nm reached a plateau within 72 s (Fig. S5), indicating
We next tested fluorescence response of 2 to Cu . A solution
of 2 (10 μM) has almost no fluorescence upon excitation at 500
2+
nm. However, upon addition of Cu (20 μM) for 2 min, the
solution of 2 showed significant fluorescent emission, and the
fluorescence intensity at 557 nm reached a plateau within 72 s
with a 29-fold enhancement (Fig. 4). The fluorescent emission
change clearly demonstrated that the hydrolysis of 2 was
2+
that the probe reacted rapidly with Cu under optimized
conditions.
Based on the colour change of the solution, the colorimetric
analysis of 2 toward various metal ions was studied. As shown in
2+
2+
triggered by Cu and subsequently liberated the fluorescent
Fig. 2, Cu , whether present alone or in the presence of mixed

3
product 3 (Fig. S6). The reaction product of 2 was also checked
probe treated with the marked metal ions. Black bars: probe treated with the
2
+
by ESI analysis to explore the reaction mechanism. The ESI
marked metal ions followed by Cu (20 μM). Data were acquired in HEPES
2+
o
spectrum of the reaction solution of 2 with Cu shows a major
buffer (10 mM, H
2
O/CH
3
CN, 4:1, v/v, pH 7.0, 25 C, λex = 500 nm).
+
peak at m/z = 278.2 [M-I] , which is characteristic of the mass of
We then proceeded to examine the selectivity of 2. As shown
in Fig. 6 and Fig. S10, the fluorescence responses of 2 (10 μM)
3
2
(Fig. S7). All these results clearly demonstrate that reaction of
with Cu causes the hydrolysis of the picolinate moiety, thus
2+
2+
exhibited excellent selectivity toward Cu over other metal ions
validating our proposed mechanism (Scheme 1).
+
+
2+
2+
+
2+
2+
2+
2+
2+
such as Na , K , Ca , Mg , Ag , Zn , Cd , Hg , Ba , Pb ,
2+
2+
2+
3+
3+
Mn , Ni , Co , Fe , Al ions. Competition experiments
revealed that the Cu -induced fluorescence was almost
unaffected in the presence of the metal ions mentioned above.
2+
2+
Moreover, the fluorescence response of 2 to Cu was almost
unaffected even in the presence of 15 species metal ions (Fig. 6
2+
1
7). The probe has high selectivity for Cu over the other metal
ions, which can be ascribed to the specific hydrolysis of the
2+ 26
picolinate moiety by Cu .
Figure 5. (a) Plot of fluorescence intensity at 557 nm vs. the reaction time in
In summary, we designed, synthesized and characterized a
hemicyanine-based colorimetric and fluorescent turn-on probe 2.
The probe displayed a rapid response time (within 72 s), high
sensitivity (detection limit of 0.2 μM), and high selectivity for
2
+
the presence of varied concentrations of Cu . (b) The fluorescence intensity
2
+
at 557 nm as a function of the concentrations of Cu in the range of 0 - 5 μM.
Data were acquired in HEPES buffer (10 mM, H
2
O/CH
3
CN, 4:1, v/v, pH 7.0,
o
2+
2+
2
5 C, λex = 500 nm).
Cu over other metal ions. Moreover, the probe can detect Cu
in the presence of 15 species metal ions by absorption spectra,
fluorescence spectra and an obvious colour change which was
observed easily by naked-eye in aqueous media.
To test sensitivity, the time-dependent fluorescence spectra of
in the presence of varied concentrations of Cu were studied
and the hydrolysis was traced by measuring the fluorescence at
2+
2
5
5
57 nm (Fig. 5a). It can be seen that the fluorescence intensity at
Acknowledgments
57 nm of 2 (10 μM) increased gradually with the increasing of
2+
the concentration of Cu from 0 μM to 30 μM and then reached
a plateau. The fluorescence at 557 nm was stable at about 20 μM
of Cu (Fig. S8). However, negligible changes in fluorescence
were detected in the absence of Cu for the same interval of time.
Moreover, a good linearity between the fluorescence intensity at
5
observed, as depicted in Fig. 5b. The detection limit of the probe
for Cu was thus calculated to be 0.2 μM (Fig. S9), which is
much lower than the limit of copper in drinking water (～20 μM)
We thank the Scientific Research and Technological
Development Program of Guangxi (GKH14251003), the Middle-
aged and Young Teachers' Basic Ability Promotion Project of
Guangxi (KY2016YB452), the Doctor's scientific research
foundation of Hezhou University (HZUBS201509) and Key
Laboratory of Food and Agricultural Products Quality and Safety
in Guangxi Colleges and Universities for financial support.
2+
2+
2+
57 nm and the Cu concentration in the range of 0 - 5 μM is
2+
24
25
Supplementary Material
set by the U. S. Environmental Protection Agency.
The fluorescence intensity at 557 nm reached a plateau within
2 s in the presence of Cu (20 μM), which is in accordance with
Supplementary materials including synthetic procedures and
characterization of compounds 1, 2, and 3, and additional
spectroscopic data.
2+
7
that in the above absorption spectra studies. The above findings
2+
indicated that the hydrolysis reaction of 2 by Cu was very fast
within 72 s) under optimized conditions with fluorescence
(
References and notes
enhancement. Therefore, this reaction time of 72 s and the safety
limit of copper (20 μM) in drinking water were used for the
following experiments.
1 (a) Uauy, R.; Olivares, M.; Gonzalez, M. Am. J. Clin. Nutr. 1998, 67, 952S;
(b) Que, E. L.; Domaille, D. W.; Chang, C. J. Chem. Rev. 2008, 108, 1517;
(c) Robinson, N. J.; Winge, D. R. Annu. Rev. Biochem. 2010, 79, 537; (d)
Okamoto, S.; Eltis, L. D. Metallomics 2011, 3, 963.
2
3
Torrado, A.; Walkup, G. K.; Imperiali, B. J. Am. Chem. Soc. 1998, 120, 609.
(a) Multhaup, G. ; Schlicksupp, A.; Hesse, L.; Beher, D.; Ruppert, T.;
Masters, C. L.; Beyreuther, K. Science 1996, 271, 1406; (b) Lovstad, R. A.
Biometals 2004, 17, 111; (c) Madsen, E.; Gitlin, J. D. Annu. Rev. Neurosci.
2
007, 30, 317.
(a) Barnham, K. J.; Masters, C. L.; Bush, A. I. Nat. Rev. Drug Discovery
004, 3, 205; (b) Gaggelli, E.; Kozlowski, H.; Valensin, D.; Valensin, G.
4
2
Chem. Rev. 2006, 106, 1995; (c) Karr, J. W.; Szalai, V. A. J. Am. Chem.
Soc. 2007, 129, 3796.
5
(a) Bertini, I.; Rosato, A. Cell Mol. Life Sci. 2008, 65, 89; (b) Kaler, S. G.
Nat. Rev. Neurol. 2011, 7, 15.
6
7
Li, J.; Uversky, V. N.; Fink, A. L. Biochemistry 2001, 40, 11604.
(a) Lutsenko, S.; Gupta, A.; Burkhead, J. L.; Zuzel, V. Arch. Biochem.
Biophys. 2008, 476, 22; (b) Zhang, L.; Lichtmannegger, J.; Summer, K. H.;
Webb, S.; Pickering, I. J.; George, G. N. Biochemistry 2009, 48, 891.
(a) Brown, D. R.; Qin, K.; Herms, J. W.; Madlung, A.; Manson, J.; Strome,
R.; Fraser, P. E.; Kruck, T.; von Bohlen, A.; Schulz-Schaeffer, W.; Giese,
A.; Westaway, D.; Kretzschmar, H. Nature 1997, 390, 684; (b) Brown, D.
R.; Kozlowski, H. Dalton Trans. 2004, 1907.
8
Figure 6. Fluorescence intensity at 557 nm for 2 determined in the absence
+
+
and presence of different metal ions: 1, none; 2, Na (1 mM); 3, K (1 mM); 4,
2
+
2+
+
2+
2+
Ca (1 mM); 5, Mg (1 mM); 6, Ag (20 μM); 7, Zn (20 μM); 8, Cd (20
9
Krämer, R. Angew. Chem. Int. Ed. 1998, 37, 772.
2
+
2+
2+
2+
μM); 9, Hg (20 μM); 10, Ba (20 μM); 11, Pb (20 μM); 12, Mn (20 μM);
10 (a) Freedman, E. Y. E.; Ronen, D.; Long, G. L. Environ. Sci. Technol.
1996, 30, 2270; (b) Gonzáles, A. P.; Firmino, M. A.; Nomura, C. S.; Rocha,
F. R.; Oliveira, P. V.; Gaubeur, I. Anal. Chim. Acta. 2009, 636, 198.
2
+
2+
3+
3+
1
3, Ni (20 μM); 14, Co (20 μM); 15, Fe (20 μM); 16, Al (20 μM); 17,
2
+
all mentioned above metal ions; 18, Cu (20 μM). Gray bars: free probe and

4
Tetrahedron
1
1 Liu, Y.; Liang, P. ; Guo, L. Talanta 2005, 68, 25.
S.-K. Sens. Actuators B 2015, 220, 376; (d) Kumbhar, H. S.; Gadilohar, B.
L.; Shankarling, G. S. Sens. Actuators B 2016, 222, 35; (e) Kim, H.-S.;
Angupillai, S.; Son, Y.-A. Sens. Actuators B 2016, 222, 447.
19 (a) Xiang, Y.; Tong, A.; Jin, P.; Ju, Y. Org. Lett. 2006, 8, 2863; (b) Zhang,
X.; Shiraishi, Y.; Hirai, T. Org. Lett. 2007, 9, 5039; (c) Yu, C.; Zhang, J.;
Wang, R.; Chen, L. Org. Biomol. Chem. 2010, 8, 5277; (d) Weerasinghe, A.
J.; Abebe, F. A.; Sinn, E. Tetrahedron Lett. 2011, 52, 5648; (e) Xu, L.; Xu,
Y.; Zhu, W.; Zeng, B.; Yang, C.; Wu, B.; Qian, X. Org. Biomol. Chem.
2011, 9, 8284; (f) Liu, Y.; Sun, Y.; Du, J.; Lv, X.; Zhao, Y.; Chen, M.;
Wang, P.; Guo, W. Org. Biomol. Chem. 2011, 9, 432; (g) Yang, Y.; Gao, W.;
Sheng, R.; Wang, W.; Liu, H.; Yang, W.; Zhang, T.; Zhang, X.
Spectrochimica Acta. Part A 2011, 81, 14; (h) Ghosh, K.; Sarkar, T.;
Samadder, A.; Khuda-Bukhsh, A. R. New J. Chem. 2012, 36, 2121; (i)
Kumar, M.; Kumar, N.; Bhalla, V. ; Sharma, P. R.; Kaur, T. Org. Lett. 2012,
14, 406.
1
2 (a) Becker, J. S.; Matusch, A.; Depboylu, C.; Dobrowolska, J.; Zoriy, M.
V. Anal. Chem. 2007, 79, 6074; (b) Zhu, Y. B.; Inagaki, K.; Chiba, K. J.
Anal. At. Spectrom. 2009, 24, 891.
1
3 Luther, G. W.; Rickard, D. T.; Theberge, S.; Olroyd, A. Environ. Sci.
Technol. 1996, 30, 3640.
1
1
4 Singh, L. P.; Bhatnagar, J. M. Talanta 2004, 64, 313.
5 (a) de Silva, A. P.; Gunaratne, H. Q.; Gunnlaugsson, T.; Huxley, A. J.;
McCoy, C. P.; Rademacher, J. T.; Rice, T. E. Chem. Rev. 1997, 97, 1515;
(
b) Valeur, B.; Leray, I. Coord. Chem. Rev. 2000, 205, 3; (c) Kim, H. N.;
Lee, M. H.; Kim, H. J.; Kim, J. S.; Yoon, J. Chem. Soc. Rev. 2008, 37,
465; (d) McRae, R.; Bagchi, P.; Sumalekshmy, S.; Fahrni, C. J. Chem.
Rev. 2009, 109, 4780; (e) Xu, Z.; Yoon, J.; Spring, D. R. Chem. Soc. Rev.
010, 39, 1996.
1
2
1
6 (a) Yu, M.; Shi, M.; Chen, Z.; Li, F.; Li, X.; Gao, Y.; Xu, J.; Yang, H.;
Zhou, Z.; Yi, T.; Huang, C. Chem. Eur. J. 2008, 14, 6892; (b) Xu, Z.; Han,
S. J.; Lee, C.; Yoon, J.; Spring, D. R. Chem. Commun. 2010, 46, 1679; (c)
Li, P.; Duan, X.; Chen, Z.; Liu, Y.; Xie, T.; Fang, L.; Li, X.; Yin, M.; Tang,
B. Chem. Commun. 2011, 47, 7755; (d) Zhu, W.; Huang, X.; Guo, Z.; Wu,
X.; Yu, H.; Tian, H. Chem. Commun. 2012, 48, 1784; (e) Yuan, L.; Lin, W.;
Chen, B.; Xie, Y. Org. Lett. 2012, 14, 432; (f) Wang, X.; Ma, X.; Yang, Z.;
Zhang, Z.; Wen, J.; Geng, Z.; Wang, Z. Chem. Commun. 2013, 49, 11263;
20 Zhang, J.; Zhao, B.; Li, C.; Zhu, X.; Qiao, R. Sens. Actuators B 2014, 196,
117.
21 (a) Zhu, D.; Li, G.; Xue, L.; Jiang, H. Org. Biomol. Chem. 2013, 11, 4577;
(b) Li, G.; Zhu, D.; Liu, Q.; Xue, L.; Jiang, H. Org. Lett. 2013, 15, 2002;
(c) Zhu, D.; Xue, L.; Li, G.; Che, Y.; Jiang, H. Org. Chem. Front. 2014, 1,
501; (d) Zhu, D.; Xue, L.; Li, G. ; Jiang, H. Sens. Actuators B 2016, 222,
419.
(
4
g) Wen, H.; Huang, Q.; Yang, X. F.; Li, H. Chem. Commun. 2013, 49,
956; (h) Satriano, C.; Sfrazzetto, G. T.; Amato, M. E.; Ballistreri, F. P.;
22 (a) Wang, S. P.; Deng, W. J.; Sun, D.; Yan, M.; Zheng, H.; Xu, J. G. Org.
Biomol. Chem. 2009, 7, 4017; (b) Chang, J.; Lu, Y.; He, S.; Liu, C.; Zhao,
L.; Zeng, X. Chem. Commun. 2013, 49, 6259.
23 (a) Wang, S.-P. ; Deng, W.-J.; Sun, D.; Yan, M.; Zheng, H.; Xu, J.-G. Org.
Biomol. Chem. 2009, 7, 4017; (b) Yang, S.; Liu, Y.; Feng, G. RSC Adv.
2013, 3, 20171; (c) Han, Q.; Shi, Z.; Tang, X.; Yang, L.; Mou, Z.; Li, J.;
Shi, J.; Chen, C.; Liu, W.; Yang, H.; Liu, W. Org. Biomol. Chem. 2014, 12,
5023.
Copani, A.; Giuffrida, M. L.; Grasso, G.; Pappalardo, A.; Rizzarelli, E.;
Tomaselli, G. A.; Toscano, R. M. Chem. Commun. 2013, 49, 5565; (i) Lee,
Y. H.; Park, N.; Park, Y. B.; Hwang, Y. J.; Kang, C.; Kim, J. S. Chem.
Commun. 2014, 50, 3197; (j) Zhou, L.; Zhang, X.; Wang, Q.; Lv, Y.; Mao,
G.; Luo, A.; Wu, Y.; Wu, Y.; Zhang, J.; Tan, W. J. Am. Chem. Soc. 2014,
1
5
2
36, 9838; (k) Liu, Z.; He, W.; Pei, M.; Zhang, G. Chem. Commun. 2015,
1, 14227; (l) Li, Z.; Zhang, Y. ; Xia, H.; Mu, Y.; Liu, X. Chem. Commun.
016, 52, 6613; (m) Wang, B.; Cui, X.; Zhang, Z.; Chai, X.; Ding, H.; Wu,
24 Chen, Y.; Zhu, C.; Yang, Z.; Chen, J.; He, Y.; Jiao, Y.; He, W.; Qiu, L.;
Cen, J.; Guo, Z. Angew. Chem. Int. Ed. 2013, 52, 1688.
Q.; Guo, Z.; Wang, T. Org. Biomol. Chem. 2016, 14, 6720; (n) Guan, J.;
Zhang, P.; Wei, T.; Lin, Q.; Yao, H.; Zhang, Y. Chem. Res. Chin. Univ.
25 Edition of the Drinking Water Standards and Health Advisories (EPA 822-
S-12−001); U.S. EPA Office of Science and Technology: Washington, D.C.
2012.
26 (a) Zhou, Z.; Li, N.; Tong, A. Anal. Chim. Acta 2011, 702, 81; (b) Li, H.;
Zhang, P.; Smaga, L. P.; Hoffman, R. A.; Chan, J. J. Am. Chem. Soc. 2015,
137, 15628; (c) An, R.; Zhang, D.; Chen, Y.; Cui, Y. Sens. Actuators B
2016, 222, 48; (d) Wang, J.; Zong, Q. Sens. Actuators B 2015, 216, 572.
2
015, 31, 347.
7 (a) Wang, H.-H.; Xue, L.; Fang, Z.-J.; Li, G.-P.; Jiang, H. New J. Chem.
010, 34, 1239; (b) Lin, W.; Long, L.; Chen, B.; Tan, W.; Gao, W. Chem.
1
1
2
Commun. 2010, 46, 1311; (c) Cheng, J.; Zhang, Y. ; Ma, X.; Zhou, X.;
Xiang, H. Chem. Commun. 2013, 49, 11791; (d) Yin, C.-X.; Qu, L.-J.; Huo,
F.-J. Chin. Chem. Lett. 2014, 25, 1230.
8 (a) Kaur, K.; Kumar, S. Tetrahedron 2010, 66, 6990; (b) Ma, Y.; Niu, H.;
Zhang, X.; Cai, Y. Chem. Commun. 2011, 47, 12643; (c) Park, H.; Chang,
Click here to remove instruction text...

5
Highlights


A novel hemicyanine-based colorimetric and
fluorescent turn-on probe 2 for Cu was
2+
developed.
2
+
The probe can detect Cu in the presence of 15
species metal ions by absorption spectra,
fluorescence spectra and naked-eye.
2
+


The probe exhibited a rapid response of Cu
within 72 s.
2
+
The detection limit of 2 for Cu was found to
be 0.2 μM.