A Highly Selective and Sensitive Fluorescent Probe Recognition for Co2+in Aqueous Media Based on 8-Hydroxyquinolin-2-carbaldehyde-2-pyridylformylhydrazone Derivative

Article abstract of DOI:10.1002/cjoc.201600555

A new (8-hydroxyquinolin-2-yl)methylene picolinohydrazide derivative (L) has been successfully synthesized and characterized. The probe L displays high selectivity to Co²⁺in CH₃CN/HEPES (1:1, Ｖ/Ｖ, 10 mmol·L^?1, pH=7.4) with a fluorescence "ON-OFF" response. The Co²⁺ion recognition event possesses some distinct features including rapid response, high selectivity and sensitivity, good anti-interference ability and being applicable within a wide pH range. Based on job's plot and ESI-MS studies, the 1:1 binding mode was proposed. The binding constant of L and Co²⁺is 1.63×10⁸L·mol^?1and the detection limit is 1.15 μmol·L^?1. Natural water samples experiments revealed that probe L can be potentially applied to the detection of Co²⁺in real environment.

Full text of DOI:10.1002/cjoc.201600555

FULL PAPER
DOI: 10.1002/cjoc.201600555
A Highly Selective and Sensitive Fluorescent Probe Recogni-
＋
tion for Co2 in Aqueous Media Based on 8-Hydroxyquinolin-2-
carbaldehyde-2-pyridylformylhydrazone Derivative
Keli Zhong,a,b Jie Zhao,a Xue Zhou,a Shuhua Hou,a Yanjiang Bian,a
Jianrong Li,*,a,b and Lijun Tang*,a
a College of Chemistry and Chemical Engineering, College of Food Science and Technology, Bohai University,
Jinzhou, Liaoning 121013, China
b National & Local Joint Engineering Research Center of Storage, Processing and Safety Control Technology for
Fresh Agricultural and Aquatic Products, Jinzhou, Liaoning 121013, China
A new (8-hydroxyquinolin-2-yl)methylene picolinohydrazide derivative (L) has been successfully synthesized
＋
and characterized. The probe L displays high selectivity to Co2 in CH3CN/HEPES (1∶1, Ｖ/Ｖ, 10 mmol•L1,
＋
pH＝7.4) with a fluorescence “ON-OFF” response. The Co2 ion recognition event possesses some distinct fea-
tures including rapid response, high selectivity and sensitivity, good anti-interference ability and being applicable
within a wide pH range. Based on job’s plot and ESI-MS studies, the 1∶1 binding mode was proposed. The bind-
＋
ing constant of L and Co2 is 1.63×108 L•mol1 and the detection limit is 1.15 μmol•L1. Natural water samples
＋
experiments revealed that probe L can be potentially applied to the detection of Co2 in real environment.
＋
Keywords fluorescent probe, Co2 recognition, aqueous media, environmental
Introduction
cent probes have a better recognition effect, for example,
receptor was processed into organic nanoparticles
Cobalt is an important trace element and exists in
cyanocobalamine of all multicellular organisms, which
plays a significant role in the synthesis of hemoglobin
and metabolism of iron.[1] Exposure to excess cobalt
may cause toxicological effects, such as vasodilatation,
flushing, and cardiomyopathy in human, whereas its
deficiency may cause cardiovascular disease and ane-
mia.[2,3] Thus, the determination of trace amounts of
cobalt is very vital in various biological and environ-
mental applications.[4]
(ONPs), which can be used for fluorescent and colori-
＋
metric detection for Co2 in water with nanomolar de-
tection limit.[20] The imine-linked receptor coated ZnO
was prepared as a ratiometric fluorescence sensor for
＋
detection of Co2 in DMSO/H2O (8∶2; Ｖ/Ｖ).[21]
A
simple naked eye colorimetric method with high sensi-
＋
tivity and selectivity was developed for Co2 recogni-
tion in aqueous solutions on the basis of inducing the
aggregation of carboxyl-functionalized CdS quantum
dots.[22] A ratiometric fluorescent cobalt probe has been
synthesized and achieved the imaging and detection of
cobalt in cells.[23] But in these probes, certain short-
comings including the complexity in synthesis, poor
solubility in water and pure organic solvents, etc. still
exist, hence it is of great significance to design and
synthesize some simple fluorescent probes to recognize
specifically cobalt ion without interference.
Although many methods including atomic absorp-
tion spectroscopy and electrochemistry methods for
＋
Co2 detection have been established,[5-7] they have
their own limitations due to their complex operating
procedures and high costs. Therefore, it is a challenge to
＋
develop a simple, fast detection method for Co2 ions.
So far spectrofluorimetric analysis methods for de-
＋
tection of Co2 ions have been widely used because of
In this work, a novel fluorescent probe that can rec-
＋
ognize Co2 in an aqueous medium was prepared by
their simplicity, sensitivity and low cost.[8] Recently,
more literatures mainly focus on the multiple cations
recognition including cobalt ions,[9-16] in which there is
some interference between cations. However, only a
small number of literatures are specifically designed to
recognize cobalt ions,[17-19] among which some fluores-
using a simple mild Schiff base reaction (Scheme 1).
Combination of 8-hydroxyquinoline (8-HQ) and the
2-pyridinecarboxylic acid hydrazide unit can provide
more binding sites. The diglycol monomethyl ether in-
troduced to quinoline can act as a hydrophilic group to
*
E-mail: lijr6491@163.com, ljtang@bhu.edu.cn; Tel.: 0086-0416-3400302; Fax: 0086-0416-3400158
Received August 31, 2016; accepted November 15, 2016; published online December 20, 2016.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201600555 or from the author.
Chin. J. Chem. 2016, 34, 1329—1334
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Zhong et al.
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improve water solubility. The structure of L was con-
solution. 2.5 mL of the above solution was moved into a
250-mL volumetric flask, and added CH3CN/H2O (1∶1,
Ｖ/Ｖ, HEPES 10 mmol•L1, pH＝7.4) buffer solution
to the scale line of the volumetric flask. The obtained
solution was considered a 10 μmol/L solution of fluo-
rescent probe L.
1
firmed by H nuclear magnetic resonance (NMR), 13C
NMR, and high-resolution mass spectrometry (HRMS)
(Figures S1－S3). To our knowledge, these are rarely
reported fluorescent probes that can recognize cobalt
ions rapidly, highly selectively and sensitively, and with
good anti-interference ability and a wide working pH
range in an aqueous solution.
Preparation of various metal cations solution In
this paper, we tested 19 kinds of metal cations including
＋
＋
＋
＋
＋
＋
＋
Ni2 , Hg2 , Ba2 , Mg2 , Ag＋, Fe2 , K＋, Al3 , Pb2 ,
Na＋, Mn2 , Sr2 , Cu2 , Co2 , Zn2 , Cd2 , Cr3 , Fe3 ,
＋
＋
＋
＋
＋
＋
＋
＋
Scheme 1 Synthesis route of fluorescence probe L
＋
＋
and Ca2 (as chloride or nitrate salts), and chose Cu2
as an example of preparation process. Cu(NO3)2•3H2O
(0.0121 g, 0.05 mmol) was accurately weighed and
added in a 10-mL volumetric flask, then CH3CN/H2O
solution (1∶1, Ｖ/Ｖ, HEPES 10 mmol•L1, pH＝7.4)
was added to the scale line of the volumetric flask. The
obtained solution was shaken up and considered a 5
mmol/L solution, which was diluted to the required low
Experimental
concentration of metal cations. Preparation methods of
＋
other metal cations were the same as that of Cu2 ion.
Materials and apparatus
Treatment of real water samples The water from
tap, lake and river was used to prepare the required
samples. Before use, lake and river water was filtered to
remove the insoluble substances, and heated to boiling
for 0.5 h together with tap water in order to remove the
chlorine content. The 10 μmol•L1 fluorescent probe L
aqueous solution (CH3CN/H2O＝1∶1, Ｖ/Ｖ) was
prepared using these water samples and acetonitrile. The
L aqueous solution was spiked with different concentra-
tions of CoCl2 (0－20 μmol•L1), then fluorescence
measurements were performed after equilibration.
Unless otherwise stated, all reagents were purchased
from Aladdin Industrial Corporation (Shanghai, China)
and used without further purification. Solvents were
purified by standard methods prior to use, and twice-
distilled water was used throughout all experiments.
NMR spectra were recorded on an Agilent 400-MR
spectrometer (Agilent, USA), HRMS was measured on
an Agilent 1200 Series Binary SL HPLC/Bruker mi-
crOTOF mass spectrometer (Bruker, Germany). Fluo-
rescence measurements were performed on a Sanco
970-CRT spectrofluorometer (Shanghai, China) and the
excitation and emission slit widths were 2 and 5 nm,
respectively. The column chromatography was con-
ducted by using silica gel (200－300 mesh).
Synthesis of pyridine-2-carbohydrazide (1) Pyr-
idine-2-carboxylic acid ethyl ester (1.21 g, 8 mmol),
hydrazine hydrate (1.2 g, 24 mmol, 1.2 mL), and etha-
nol (20 mL) were added into a round bottomed flask,
then the mixture was stirred for 12 h at r.t. After the end
of reaction, the crude product was poured into water
(200 mL), the precipitates were collected by filtration,
washed with cold water and dried to afford compound 1
Experimental methods and synthesis
All titration experiments were carried out at r.t. Flu-
orescence spectra were measured with a 10 mmol•L1
solution of L in CH3CN/H2O solution (1∶1, Ｖ/Ｖ,
HEPES 10 mmol•L1, pH＝7.4) by excitation at 340 nm.
The solutions of metal salts were prepared in distilled
water. These solutions were used for all spectroscopic
studies after appropriate dilution. The fluorescence
spectra were measured 30 min after addition of metal
ion. Titration experiments were carried out in 10 mm
quartz cuvettes at 25 ℃. Metal ions (as chloride or ni-
trate salts, 5 mmol•L1) solutions were added to the host
solution and used for the titration experiment.
Preparation of HEPES buffer solution HEPES
(1.192 g) was added in deionized water (~500 mL), then
stirred it to dissolve and adjusted pH to 7.4 with 10%
(w/w) sodium hydroxide. The obtained solution is
known as HEPES buffer solution.
1
as white needles (943 mg, 86%). H NMR (400 MHz,
CDCl3) δ: 9.00 (s, 1H), 8.52－8.56 (m, 1H), 8.14－8.16
(m, 1H), 7.85 (td, J＝7.6, 1.8 Hz, 1H), 7.44 (dd, J＝7.6,
1.8 Hz, 1H), 4.09 (s, 2H); 13C NMR (100 MHz, CDCl3)
δ: 164.7, 149.0, 148.4, 137.3, 126.5, 122.2.
Synthesis of compound 2 Compound 2 was syn-
thesized according to our previously published litera-
ture.[24]
Synthesis of compound L A mixture of com-
pounds 1 (343 mg, 2.5 mmol) and 2 (630 mg, 2.5 mmol)
in dry ethanol (20 mL) was refluxed for 3 h. After cool-
ing to room temperature, the solvent was removed in a
rotary evaporator. The obtained brown crude product
was further purified by silica gel chromatography using
hexane/ethyl acetate (1∶1, Ｖ/Ｖ) as eluent to afford
1
810 mg light yellow solid (82%). H NMR (400 MHz,
Preparation of probe L solution L (19.8 mg) was
added into a 50-mL volumetric flask, then DMSO was
poured to the scale line of the volumetric flask and
shaken up to obtain a 1 mmol/L fluorescent probe L
DMSO-d6) δ: 12.69 (s, 1H), 8.85 (s, 1H), 8.77 (d, J＝
4.5 Hz, 1H), 8.39 (d, J＝8.8 Hz, 1H), 8.18 (dd, J＝7.7,
8.8 Hz, 2H), 8.10 (t, J＝7.7 Hz, 1H), 7.70－7.73 (m,
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Chin. J. Chem. 2016, 34, 1329—1334

＋
A Highly Selective and Sensitive Fluorescent Probe Recognition for Co2 in Aqueous Media
1H), 7.55 (d, J＝4.5 Hz, 2H), 7.28 (t, J＝4.5 Hz, 1H),
4.35 (t, J＝4.4 Hz, 2H), 3.92 (t, J＝4.4 Hz, 2H), 3.71 (t,
J＝4.8 Hz, 2H), 3.52 (t, J＝4.8 Hz, 2H), 3.27 (s, 3H);
13C NMR (100 MHz, CDCl3) δ: 160.34, 154.51, 152.22,
149.15, 148.79, 148.20, 139.64, 137.61, 136.43, 129.74,
127.65, 126.94, 123.02, 119.93, 119.13, 109.53, 71.87,
70.72, 69.51, 68.15, 59.11. HRMS (ESI＋) m/z, calcd
for C21H22N4O4 [M＋H]＋ 395.1641, found 395.1718.
Figure 2 Fluorescence color change of L (10 μmol•L1) upon
addition of 1.5 equiv. of various metal ions under a portable UV
lamp at 365 nm.
Results and Discussion
UV-Vis absorption and fluorescent properties of L
In order to examine the metal ion selectivity of L,
the corresponding UV-Vis absorption and fluorescence
spectra of L solution (CH3CN/H2O＝1∶1, Ｖ/Ｖ,
HEPES 10 mmol•L1, pH＝7.4) have been measured in
the absence and presence of various metal ions. L ex-
hibits dual absorption with the maximum absorption
wavelengths at 295 and 330 nm (Figure S4). Upon indi-
+
We speculated that the Co2 -induced fluorescence
quenching of L was attributed to the heavy atom effect
of cobalt ions, namely, ligand-to-metal charge transfer
(LMCT) effect.[25-28]
Fluorescence titration studies of L
＋
vidual addition of 1.5 equiv. of various metal ions, Co2 ,
The fluorescence titration experiments were per-
＋
formed to check the sensitivity of L toward Co2 . As
＋
＋
＋
Ni2 , Ca2 , and Zn2 elicited a new absorption band at
ca. 380 nm, while other metal ions only induced absorp-
tion intensity decrease with different extent. These re-
sults infer that L cannot effectively recognize a certain
metal ion via UV-vis method. Figure 1 shows the fluo-
rescence changes of the probe upon the addition of var-
ious metal ions. The free L displays a strong emission at
500 nm (Φf＝0.13), but a remarkable fluorescence
quenching (95.4%, Φf＝0.028) was observed upon ad-
shown in Figure 3, the fluorescence intensity steadily
＋
decreased with the increasing of Co2 concentration
＋
until reaching 1.5 equiv. Further increasing Co2 con-
centration did not induce significant fluorescence inten-
＋
sity changes, indicating that L may bind Co2 through a
1∶1 stoichiometry. In order to verify our inference, a
Job plot experiment was achieved as shown in Figure 4.
The tested solution exhibited inflexion of fluorescence
＋
intensity when the molar fraction of Co2 was 50%,
＋
dition of 1.5 equiv. of Co2 . The fluorescence changes
which indicated the 1∶1 binding stoichiometry of L
＋
[29-31]
and Co2
.
In addition, the HRMS spectrometry
were faint upon addition of other metal ions such as
＋
＋
＋
＋
＋
＋
＋
＋
Na＋, Sr2 , Cu2 , Zn2 , Cd2 , Cr3 , Fe3 , Ca2 , Ni2 ,
analyses further supported the 1∶1 interaction of L and
＋
＋
＋
＋
＋
＋
＋
Hg2 , Ba2 , Mg2 , Ag＋, Fe2 , K＋, Al3 , Mn2 , and Pb2 .
＋
Co2 , in which the most prominent peak appearing at
m/z 452.0880 was assignable to [L＋Co2 -H＋]＋ (calcd
＋
This result clearly indicates that L exhibits a high selec-
＋
tivity to Co2 over other cations. Furthermore, the flu-
452.0973) (Figure S5). The above results showed the
＋
binding stoichiometry of L and Co2 was 1∶1.
orescence color is changed from green to quenching
＋
＋
upon addition of Co2 , which indicates Co2 can also
be qualitatively detected by the naked eye (Figure 2).
DFT calculations
To gain better insight into the binding mode of L
700
700
L+other ions
560
0
Cd2+
560
Co2+
420
420
1.5 equiv.
280
280
140
0
140
Co2+
0
400
450
500
550
600
650
Wavelength/nm
400
450
500
550
600
650
Wavelength/nm
Figure 1 Fluorescence spectra of L (10 μmol•L1) upon addi-
＋
＋
＋
tion of 1.5 equiv. of metal ions, including Na＋, Sr2 , Cu2 , Co2
,
,
Figure 3 Fluorescence emission spectra of L (10 μmol•L1)
＋
＋
＋
＋
＋
＋
＋
＋
＋
＋
Zn2 , Cd2 , Cr3 , Fe3 , Ca2 , Ni2 , Hg2 , Ba2 , Mg2 , Ag＋, Fe2
＋
upon addition of different amounts of Co2 (0－1.5 equiv.) in
K＋, Al3 , Mn2 , and Pb2 in CH3CN/H2O (1∶1, Ｖ/Ｖ, HEPES
＋
＋
＋
CH3CN/H2O (1∶1, Ｖ/Ｖ, HEPES 10 mmol•L1, pH＝7.4) (λex
＝340 nm).
10 mmol•L1, pH＝7.4) (λex＝340 nm).
Chin. J. Chem. 2016, 34, 1329—1334
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Zhong et al.
FULL PAPER
1/(Ks×CL)[1＋x/CL＋1/(Ks×CL)]24×(x/CL)}0.5), in
which Y0 is the fluorescence intensity value of L, Ylim is
1000
800
600
400
200
0
the fluorescence intensity of L solution upon additon of
＋
excess Co2 ion, CL is the concentration of the experi-
mental test probe, Ks is the binding constant.[33] The
＋
association constant (Ka) of L and Co2 was calculated
to be 1.63×108 L•mol1 by nonlinear least-squares fit-
ting (R2＝0.99392) and showed that the chelates of L
＋
and Co2 were very stable (Figure 6). In addition,
＋
time-course study revealed that the Co2 -induced fluo-
0.0
0.2
0.4
0.6
0.8
1.0
[Co2+] /([Co2+]+[L])
rescence quenching can complete within 6 min (Figure
＋
S6), indicating the rapid response of L to Co2 .
Figure 4 Job’s plot for determining the stoichiometry of L and
700
560
420
280
140
0
＋
Co2
.
with Co2＋, the structure optimizations of complexes
were performed with the Gaussian 09 program. DFT
calculations were carried out using Becke’s three pa-
rameter functional and the correlation function of
B3LYP with LanL2DZ for cobalt and with 6-31G(d)
basis set for other atoms. The applications of the B3LYP
＋
method to metal Co2 -ligand systems suggest that the
B3LYP relative energies for systems are in good agree-
ment with those determined by highly correlated elec-
tronic structure methods.[32] After structure optimization,
harmonic vibrational frequencies were calculated to
confirm that the structures were indeed local minima.
0.0
0.6
1.2
1.8
mol/L)
2.4
3.0
[Co2+]/(

Figure 6 Nonlinear fitting of fluorescence intensity against
＋
Co2 concentration (λem ＝500 nm). The association constant (Ka)
The optimized configuration is shown in Figure 5,
＋
of L and Co2 was calculated to be 1.63×108 L•mol1
.
＋
which shows that the Co2 was five coordinated by
four N atoms and one O atom from 8-hydroxyquinolin-
2-carbaldehyde-2-pyridyl formylhydrazone skeleton.
The Co－O bond length is 2.36 Å and Co－N bond
lengths are 2.01 Å (Co－Nquinolin), 1.94 Å (Co－Nimine),
1.99 Å (Co－Namide) and 2.08 Å (Co－Npyridine), respec-
tively, and the whole molecular system forms a
non-planar structure. It is noteworthy that the hydrogen
atom on the nitrogen of amide does not exist, which is
consistent with the HRMS spectrometry data. These
data indicate that L could provide a suitable space to
better accommodate cobalt ion.
The detection limit evaluation of L
To evaluate the practical applicability of probe L, the
＋
fluorescence detection limit of L for Co2 was studied.
Based on the fluorescence titration data, plotting of
＋
(Imax−I)/(Imax−Imin) versus log[Co2 ] afforded a nice lin-
ear relationship (R＝0.99), the point at which this line
crossed the ordinate axis was regarded as the detection
limit[34] and was calculated to be 1.15×10−6 L•mol1
(Figure 7), which was below or in the same range com-
＋
pared with some recently reported Co2 probes. The
probe to reach the micromolar orders of magnitude de-
tectable concentration can be potentially applied to the
＋
detection of Co2 in environmental systems.
0.20
0.15
0.10
0.05
0.00
＋
.
Figure 5 Calculated energy-minimized structure of L-Co2
The binding constants evaluation of L
-6.00
-5.85
-5.70
-5.55
-5.40
-5.25
lg([Co2+]/(mol/L))
In order to confirm the binding constants of L and
＋
Co2 , we achieved the nonlinear fitting utilizing the 1∶
Figure 7 Normalized response of the fluorescence against
log[Co2 ]. The calculated detection limit is 1.15×106 L•mol1
＋
1 binding equation, y＝Y0＋[(YlimY0)/2]×(1＋x/CL＋
.
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＋
A Highly Selective and Sensitive Fluorescent Probe Recognition for Co2 in Aqueous Media
The competition experiment studies of L
700
L+Co2+
The anti-interference capability of probe L is an im-
L
portant indicator, so we completed the competition ex-
560
periment of L by fluorescence spectroscopy. When L
(10 mmol•L1) was mixed with 1.5 equiv. of various
＋
metal ions (Figure 7, black bars), only Co2 can cause
420
＋
＋
significant fluorescence quenching and Cd2 and Pb2
280
140
0
can lead to slight quenching as well. While upon further
＋
addition of the same amount of Co2 (Figure 8, red
＋
bars), even in the presence of other metal ions, Co2
could still combine with L and cause dramatic fluores-
cence quenching. These results reveal that L can detect
＋
Co2 in aqueous solution without interference from
2
4
6
8
pH
10
12
14
other metal ions.
＋
Figure 9 The fluorescence changes of L and L-Co2 solution
L+metal ions
L+metal ions+Co2+
700
560
420
280
140
0
at different pH (λex ＝340 nm).
was prepared through using the treated actual water
＋
samples and acetonitrile. Co2 (0－20 μmol•L1) was
spiked into L aqueous solution and the fluorescence
emission changes were detected after 60 min. As shown
in Figure 10, the fluorescence intensities were propor-
＋
tional to the concentrations of Co2 in the range of 0－9
μmol•L1. The good linear dependence of fluorescence
＋
intensity on Co2 concentration indicates the presented
＋
probe L can be used for quantitative detection of Co2
＋
within 9 μmol•L1 and trace Co2 analyses in these
three complicated environmental systems.
Figure 8 Fluorescence intensities of L (10 μmol•L1) in the
Tap water
River water
Lake water
400
presence of various metal ions (1.5 equiv., black) and additional
＋
Co2 (1.5 equiv., red) in CH3CN/H2O (1∶1, Ｖ/Ｖ, HEPES 10
300
mmol•L1, pH＝7.4). Intensity was recorded at 500 nm, excita-
tion at 340 nm.
200
100
0
Effect of pH
In order to find the suitable pH application range of
＋
L for Co2 recognition, we tested the fluorescence
＋
changes of L with and without Co2 at different pH
values (Figure 9). Acid-base titration results show that
0
1
2
3
4
5
6
7
8
9
10
[ Co2+ ]/(10-6 mol/L)
free L displays strong emission at a wide pH range from
Figure 10 Linear fluorescence intensities of L (10 μmol•L1)
3 to 11 (blue line), as well as the fluorescence intensity
＋
of L-Co2 complex is quenching between pH 7 to 13
＋
upon addition of Co2 (0－9 μmol•L1) in three natural water
(red line). Therefore, combination with the fluorescence
samples.
＋
intensity change of L and L-Co2 , the optimal pH range
＋
of L recognition for Co2 is optimal between 7 to 11.
Conclusions
The above results indicate that probe L has a potential
＋
practical applicability for Co2 detection in both physi-
In summary, the fluorescent probe L was obtained
by the mild and simple Schiff Base reaction using
2-pyridinecarboxylic acid hydrazide with the modified
ological and environmental systems.
＋
Detection of Co2 ions in real water samples
8-hydroxyquinoline-2-carbaldehyde. The probe L rec-
＋
ognized for Co2
in CH3CN/H2O (1 ∶ 1, Ｖ / Ｖ ,
The potential utility of L was also verified by ex-
periments.[35,36] Water from the tap, lake and river was
collected from laboratory, the pool of Tinglin lake in
Bohai University, and Xiaoling river (Linghe district,
Jinzhou), respectively. The 10 μmol•L1 fluorescent
probe L aqueous solution (CH3CN/H2O＝1∶1, Ｖ/Ｖ)
HEPES 10 mmol•L1, pH＝7.4) with a fluorescence
“ON-OFF” response, and possessed many advantages
containing rapid response, high selectivity and sensitiv-
ity, good anti-interference ability and a wide working
pH range. We proved that the binding stoichiometry of
Chin. J. Chem. 2016, 34, 1329—1334
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FULL PAPER
＋
probe L and Co2 was 1∶1 through Job’s plot and
Eur. J. Inorg. Chem. 2013, 2013, 6019.
＋
HRMS studies. The binding constant of L and Co2 is
[14] Pathak, R. K.; Dessingou, J.; Rao, C. P. Anal. Chem. 2012, 84, 8294.
[15] Wang, P.; Li, Z.; Lv, G.-C.; Zhou, H.-P.; Hou, C.; Sun, W.-Y.; Tian,
Y.-P. Inorg. Chem. Commun. 2012, 18, 87.
[16] Song, E. J.; Kang, J.; You, G. R.; Park, G. J.; Kim, Y.; Kim, S.-J.;
Kim, C.; Harrison, R. G. Dalton Trans. 2013, 42, 15514.
[17] Liu, Z.; Jia, X.; Bian, P.; Ma, Z. Analyst 2014, 139, 585.
[18] Au-Yeung, H. Y.; New, E. J.; Chang, C. J. Chem. Commun. 2012, 48,
5268.
[19] Luo, H.-Y.; Zhang, X.-B.; He, C.-L.; Shen, G.-L.; Yu, R.-Q. Spec-
trochim. Acta Part A: Mol. Biomol. Spectros. 2008, 70, 337.
[20] Kuwar, A.; Patil, R.; Singh, A.; Bendre, R.; Singh, N. Chem-
PhysChem 2014, 15, 3933.
[21] Sharma, H.; Singh, A.; Kaur, N.; Singh, N. ACS Sustain. Chem. Eng.
2013, 1, 1600.
1.63×108 L•mol1 and the detection limit is 1.15×106
mol•L1. The proof-of-concept experiments with natural
water samples revealed that probe L can be potentially
＋
applied to the detection of Co2 in real environment.
Acknowledgement
This work is supported by the National Natural Sci-
ence Foundation of China (21304009, 21476029,
31471639), the Program for Liaoning Excellent Talents
in University (LJQ2014125, LR2015001), and the
Liaoning Provincial Science & Technology Department
(2015103020).
[22] Gore, A. H.; Gunjal, D. B.; Kokate, M. R.; Sudarsan, V.; Anbhule, P.
V.; Patil, S. R.; Kolekar, G. B. ACS Appl. Mater. Interf. 2012, 4,
5217.
[23] Zhang, S.; Zhao, M.; Zhu, W.; Xu, Y.; Qian, X. Dalton Trans. 2015,
44, 9740.
References
[1] Karovic, O.; Tonazzini, I.; Rebola, N.; Edström, E.; Lövdahl, C.;
Fredholm, B. B.; Daré, E. Biochem. Pharmacol. 2007, 73, 694.
[2] Gharehbaghi, M.; Shemirani, F.; Farahani, M. D. J. Hazard. Mater.
2009, 165, 1049.
[24] Zhong, K.; Zhou, X.; Hou, R.; Zhou, P.; Hou, S.; Bian, Y.; Zhang, G.;
Tang, L.; Shang, X. RSC Adv. 2014, 4, 16612.
[25] Li, C.-Y.; Zhang, X.-B.; Jin, Z.; Han, R.; Shen, G.-L.; Yu, R.-Q. Anal.
Chim. Acta 2006, 580, 143.
[3] Khorrami, A. R.; Hashempur, T.; Mahmoudi, A.; Karimi, A. R. Mi-
crochem. J. 2006, 84, 75.
[4] Tian, J.; Cheng, N.; Liu, Q.; Xing, W.; Sun, X. Angew. Chem., Int.
Ed. 2015, 54, 5493.
[26] Lu, W.; Qin, X.; Liu, S.; Chang, G.; Zhang, Y.; Luo, Y.; Asiri, A. M.;
Al-Youbi, A. O.; Sun, X. Anal. Chem. 2012, 84, 5351.
[27] Zhang, S.; Zhao, M.; Zhu, W.; Xu, Y.; Qian, X. Dalton Trans. 2015,
44, 9740.
[5] Au-Yeung, H. Y.; New, E. J.; Chang, C. J. Chem. Commun. 2012, 48,
5268.
[28] Zhong, K.; Zhou, X.; Hou, R.; Zhou, P.; Hou, S.; Bian, Y.; Zhang, G.;
Tang, L.; Shang, X. RSC Adv. 2014, 4, 16612.
[6] Zhen, S. J.; Guo, F. L.; Chen, L. Q.; Li, Y. F.; Zhang, Q.; Huang, C.
Z. Chem. Commun. 2011, 47, 2562.
[7] Lin, W.; Yuan, L.; Long, L.; Guo, C.; Feng, J. Adv. Funct. Mater.
2008, 18, 2366.
[29] Kim, H. N.; Nam, S.-W.; Swamy, K. M. K.; Jin, Y.; Chen, X.; Kim,
Y.; Kim, S.-J.; Park, S.; Yoon, J. Analyst 2011, 136, 1339.
[30] Han, X.; Lü, X.; Chen, Z.; Yu, G.; Yin, J.; Liu, S. Chin. J. Chem.
2015, 33, 1064.
[8] Monteil-Rivera, F.; Dumonceau, J. Anal. Bioanal. Chem. 2002, 374,
1105.
[9] Guo, C.; Li, P.; Pei, M.; Zhang, G. Sens. Actuators B: Chem. 2015,
221, 1223.
[10] Çimen, O.; Dinçalp, H.; Varlıklı, C. Sens. Actuators B: Chem. 2015,
209, 853.
[11] Cao, Y.; Ding, L.; Hu, W.; Peng, J.; Fang, Y. J. Mater. Chem. A 2014,
2, 18488.
[31] Zhang, F.; Cao, X.; Tian, D.; Li, H. Chin. J. Chem. 2015, 33, 368.
[32] Rimola, A.; Rodriguez-Santiago, L.; Ugliengo, P.; Sodupe, M. J.
Phys. Chem. B 2007, 111, 5740.
[33] Shiraishi, Y.; Sumiya, S.; Kohno, Y.; Hirai, T. J. Org. Chem. 2008,
73, 8571.
[34] Kim, M. H.; Jang, H. H.; Yi, S.; Chang, S.-K.; Han, M. S. Chem.
Commun. 2009, 4838.
[35] Zhu, H.; Fan, J.; Lu, J.; Hu, M.; Cao, J.; Wang, J.; Li, H.; Liu, X.;
Peng, X. Talanta 2012, 93, 55.
[12] Ghosh, K.; Sarkar, T.; Majumdar, A. Tetrahedron Lett. 2013, 54,
6464.
[13] Kumar, C. K.; Trivedi, R.; Kumar, K. R.; Giribabu, L.; Sridhar, B.
[36] Li, H.; Fan, J.; Song, F.; Zhu, H.; Du, J.; Sun, S.; Peng, X.
Chem.–Eur. J. 2010, 16, 12349.
(Pan, B.)
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