A new near-infrared ratiometric fluorescent probe for hydrazine

Article abstract of DOI:10.1039/c7ra04270a

It is important to develop fluorescent probes for rapid, selective, and sensitive detection of highly toxic hydrazine in both environmental and biological science. In this text, under mild conditions, a novel near-infrared (NIR) ratiometric and on-off fluorescent probe 1 was synthesized based on hemicyanine and coumarin derivatives, which can detect hydrazine with high selectivity and anti-interference over other amines, biological species, anions and metal ions. The limit of quantification (LOQ) value was 0-400 μM and the detection limit could be as low as 560 nM.

Full text of DOI:10.1039/c7ra04270a

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PAPER
A new near-infrared ratiometric fluorescent probe
for hydrazine†
Cite this: RSC Adv., 2017, 7, 25634
b
Yangyang He,ab Zhanxian Li,b Bingjie Shi,b Zhen An,b Mingming Yu,
Liuhe Weib
a
*
and Zhonghai Ni
It is important to develop fluorescent probes for rapid, selective, and sensitive detection of highly toxic
hydrazine in both environmental and biological science. In this text, under mild conditions, a novel near-
infrared (NIR) ratiometric and on–off fluorescent probe 1 was synthesized based on hemicyanine and
coumarin derivatives, which can detect hydrazine with high selectivity and anti-interference over other
amines, biological species, anions and metal ions. The limit of quantification (LOQ) value was 0–400 mM
and the detection limit could be as low as 560 nM.
Received 15th April 2017
Accepted 8th May 2017
DOI: 10.1039/c7ra04270a
rsc.li/rsc-advances
biomolecules due to its simplicity, high sensitivity, and
instantaneous response.19–32 However, available uorescent
Introduction
probes for hydrazine are still very limited and most of them are
turn-on types.33–41
As an important biochemical reagent and highly reactive base,
hydrazine is extensively used in the chemical, pharmaceutical
and agricultural industries.1–3 Due to its ammable and deto-
nable characteristics, hydrazine is oen applied in rocket-
propulsion systems and missile systems.4 However, hydrazine
is a class of highly toxic and pollutant compound, which can
potentially lead to serious environmental contamination during
its manufacture, use, transport and disposal. In addition,
hydrazine is highly toxic and may affect the liver, lungs, kidneys
and human central nervous system.5–8 As a result, the World
Health Organization has classied hydrazine as possible
cancer-causing environmental contaminants, and Occupational
Safety and Health Administration (OSHA) has recommended
the threshold limit value of hydrazine must be lower than
1 ppm.9 Therefore, the development of sensitive, selective and
reliable methods for trace hydrazine has gained increasing
attention.
To date, several conventional analytical techniques,
including chromatography-mass spectrometry,10–12 spectropho-
tometry13 and electrochemical methods14–18 have been exploited
to measure hydrazine. But most of the methods mentioned
previously are costly, complicated and time consuming for real-
time and on-site analysis. Thus, simple, selective and sensitive
methods for qualitative and quantitative detection of hydrazine
are in great need. In recent years, uorescence analysis system
has been widely used to detect metal ions, anions and
It is obvious that many factors inuence the emission
intensity, such as the illumination intensity and optical path
length, which are prone to disturbance in quantitative detec-
tion. A ratiometric approach can eliminate the effects of these
factors and realize more effective quantitative detection
through measuring the ratio of uorescence intensities at two
different wavelengths.42 In addition, when uorescent intensity
based probes are used in complicated biosystems, the detection
are inuenced by the probe concentration, autouorescence,
and instrumental factors.43,44 Ratiometric sensing is highly
recommended because this property makes it feasible to eval-
uate the analytes more accurately with minimization of the
background signal. By comparison, based on absorption prop-
erties of the ground state, color changes are more suitable for
direct observation with the naked eye.45 Therefore it is of great
interest to design ratiometric uorescent and colorimetric
probes for hydrazine.46–52
On the other hand, the spectral absorption range of bio-
logical tissues and blood samples mainly centered from 200 to
650 nm, and the extinction coefficients of these organisms are
relatively large, which will cause considerable interference on
the optical imaging in the visible light range. Therefore,
uorescent imaging in the NIR light range (650 to 900 nm) will
be ideal for vivo imaging. NIR uorescence can not only
reduce the ratio of signal to noise, but also can achieve the
optimal imaging with the deep penetration ability into the
tissue.
aSchool of Chemical Engineering and Technology, China University of Mining and
Technology, Xuzhou 221116, Jiangsu Province, China. E-mail: nizhonghai@cumt.
edu.cn
In this paper, a highly sensitive, colorimetric and NIR
ratiometric uorescent probe 1 was synthesized, which can
quantitatively detect hydrazine. The detection limit on uores-
cence response of the probe can be as low as 560 nM.
bCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou
450001, China
† Electronic supplementary information (ESI) available: Synthesis procedure and
spectral data. See DOI: 10.1039/c7ra04270a
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Results and discussions
Hydrazine recognizing properties of probe 1
To study the recognizing properties of 1 toward hydrazine, UV-vis
and uorescence titration experiments (Fig. 1 and 2) were con-
ducted with 0.1 M hydrazine water solution in aqueous solution of
1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5, pH 7.40). Upon addition of
hydrazine, the peak at 584 nm in the UV-vis spectrum decreased
gradually while a new band developed at 418 nm, and then, the
band reached the maxima at 100 equiv. of hydrazine (Fig. 1a). As
demonstrated in Fig. 1b, in the concentration range of 350 mM
and 1 mM, the absorbance ratio of A418 to A584 (A418/A584) is in good
linear relationship with hydrazine concentration. From the linear
calibration graph with the absorbance titration experiment, the
detection limit of probe 1 for hydrazine was found to be about 3.2
mM based on signal-to-noise ratio (S/N) ¼ 3.53,54 Fig. S1 in ESI†
indicate the relationship of the absorbance ratio of A418/A584 with
the concentration of hydrazine. The solution color of 1 changed by
degrees from blue to pale yellow in the presence of different
concentrations of hydrazine (Fig. 1c), implying that compound 1
can be served as a highly sensitive ‘naked-eye’ probe for hydrazine
in aqueous solution.
Fig. 2 Emission spectra of compound 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO
¼
5/5, pH 7.40) upon titration of hydrazine water solution (0–100.0
equiv. to 1) with excitation at 450 nm (a) and 580 nm (b). The linearity
of emission intensity ratio of I510/I660 (c) and the emission intensity at
660 nm (I660) (d) with hydrazine concentration increasing respectively.
(e) Photographs of compound 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5, pH
As shown in Fig. 2, upon excitation at 450 nm, there were two
emission peaks centered at 510 nm and 660 nm in the emission
spectrum of compound 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5, pH
7.40). Upon gradual addition of hydrazine, the emission at
660 nm decreased while the emission at 510 nm increased with 7.40) upon addition of hydrazine at various concentrations (0 M, 5 ꢀ
a clear isosbestic point at 633 nm observed (Fig. 2a). Upon
10ꢁ5 M, 10 ꢀ 10ꢁ5 M, 20 ꢀ 10ꢁ5 M, 30 ꢀ 10ꢁ5 M, 40 ꢀ 10ꢁ5 M, 50 ꢀ
10ꢁ5 M, 60 ꢀ 10ꢁ5 M, 70 ꢀ 10ꢁ5 M, from left to right) in water under
excitation at 580 nm, its emission spectrum displayed the
characteristic emission band of cyanine centered at 660 nm,
a UV lamp (365 nm). The reaction time was 24 hours.
which underwent a decrease of about 10 times with the
concentration of hydrazine increasing from 0 to 100 equiv.
respectively. As demonstrated in Fig. 2c and d, in the concen-
(Fig. 2b). Fig. S2 and S3 in ESI† indicate the relationship of the
tration range of 0–400 mM and 50–300 mM, I510/I660 and I660 were
emission intensity ratio of I510 to I660 (I510/I660) and the emission
in good linear relationship with hydrazine concentration
intensity at 660 nm (I660) with the concentration of hydrazine
respectively, implying that hydrazine can be quantitatively
detected in a wider concentration range in dual-uorescence
mode. From the linear calibration graphs with the uorescence
titration experiments (Fig. 2c and d), the detection limit of probe
1 for hydrazine was found to be about 560 nM based on signal-to-
noise ratio (S/N) ¼ 3, which was sufficiently low for the detection
of hydrazine. Further experiments indicated that the uores-
cence color of probe 1 aqueous solution changed from purple to
green under excitation of 365 nm light (Fig. 2e). These results led
us to conclude that 1 could be an effective ratiometric and on–off
uorescent probe for hydrazine. In the previous reported work,55
an organic molecular probe was reported, which had the same
2ꢁ
chemical structure and could detect SO3 and HSO3ꢁ. The
different recognition results may be ascribed to the different
solution. In addition, the group of professor Feng in Central
China Normal University has reported some hemicyanine deriv-
Fig. 1 Absorption spectra of 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5, pH
7.40) upon titration of hydrazine water solution (0–100 equiv. to 1) (a).
The relationship of absorbance ratio of A418/A584 with the concen-
atives, which have similar chemiꢁcal structures as that herein and
tration of hydrazine (b). Photographs of compound 1 (1.0 ꢀ 10ꢁ5 M,
can detect both SO32ꢁ and HSO3 56–58 Such strange results make
.
V
HEPES/VDMSO ¼ 5/5, pH 7.40) upon addition of hydrazine at various
concentrations (0 M, 5 ꢀ 10ꢁ5 M, 10 ꢀ 10ꢁ5 M, 15 ꢀ 10ꢁ5 M, 20 ꢀ
10ꢁ5 M, 25 ꢀ 10ꢁ5 M, 30 ꢀ 10ꢁ5 M, 35 ꢀ 10ꢁ5 M, 40 ꢀ 10ꢁ5 M, 45 ꢀ
10ꢁ5 M, 50 ꢀ 10ꢁ5 M, 55 ꢀ 10ꢁ5 M, 60 ꢀ 10ꢁ5 M, 65 ꢀ 10ꢁ5 M, 70 ꢀ
10ꢁ5 M, 75 ꢀ 10ꢁ5 M, 80 ꢀ 10ꢁ5 M, 90 ꢀ 10ꢁ5 M, 100 ꢀ 10ꢁ5 M from
left to right) in water in daylight (c). The reaction time was 24 hours.
us have interest to work hard to clarify the difference in proper-
ties of similar organic dyes.
The recognition mechanism was studied by mass spec-
trometry. For probe 1, a characteristic peak at m/z ¼ 451.2385
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was found which corresponds to the species [M ꢁ I] (Fig. S4 in N3ꢁ, Clꢁ, Brꢁ, Iꢁ, ClO3ꢁ, ClO4ꢁ, NO3ꢁ, SO42ꢁ) were tested. As
ESI†), whilst aer reaction with hydrazine, the peak at 451.2385 shown in Fig. 4, green bars of Fig. 5, 6, and 7, only the intro-
disappeared and two new peaks appeared at m/z ¼ 224.1440 and duction of hydrazine to the probe 1 solution induced a signi-
261.1413, which are corresponding to compounds 2 [M ꢁ I] and cant uorescence change. In the same condition, other tested
1-NHNH2 [M + H] (Fig. S5 in ESI†). Such mass spectral data species mentioned above did not induce any obvious uores-
indicating the decomposition of probe 1 and the formation of cence change to the probe 1 solution (Fig. 4, green bars of Fig. 5,
new compounds 2 and 1-NHNH2 (Scheme 1).
pH range in application of probe 1 toward hydrazine
The pH is an important factor affecting the reaction of probe 1
with hydrazine. To investigate the pH effect, the uorescence of
10.0 mM probe 1 in the absence and presence of 1 mM hydrazine
were examined at pH range from 4.0 to 10.0. From Fig. 3, we nd
that uorescence ratio of probe 1 showed no apparent change
with the pH changing from 6.0 to 10.0. However, the uores-
cence ratio of 1-NHNH2 exhibited obvious change when the pH
increased to 10.0. Such result implies that probe 1 is able to
detect hydrazine in a relatively wide pH range.
Fig. 4 Emission spectra of 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5, pH
7.40) upon addition of 100 equiv. of various species (hydrazine, thio-
urea, triethylamine, N,N-diisopropylethylamine, ammonia water,
carbamide, aniline) with excitation at 450 nm (a) and 580 nm (b).
The selectivity study of probe 1 for hydrazine
To evaluate the selectivity of probe 1 for hydrazine, various
species including various amines (thiourea, triethylamine, N,N-
diisopropylethylamine, ammonia water, carbamide, aniline),
some nucleophilic species (Tyr, Ala, H2O2, Pro, Cys, Met, Lys,
Phe, Thr, Ile, Trp, Ser, Val), various metal ions (Na+, Mg2+, K+,
Ca2+, Cd2+, Mn2+) and anions (C2O42ꢁ, H2PO4ꢁ, SO32ꢁ, HSO3
,
ꢁ
Fig. 5 Fluorescence responses of 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/
5, pH 7.40) upon addition of different species (100 equiv. of species
relative to 1) (green bars) with excitation at 450 nm (a) and 580 nm (b),
and fluorescence changes of the mixture of 1 and hydrazine (1.0 ꢀ
10ꢁ3 M in water) after addition of an excess of the indicated species
(100 equiv. relative to 1) (red bars) with excitation at 450 nm (a) and
580 nm (b). I510 and I660 represent the emission intensity at 510 nm and
660 nm. I660 means the emission intensity at 660 nm. The species
used were Tyr, Ala, H2O2, Pro, Cys, Met, Lys, Phe, Thr, Ile, Trp, Ser, Val.
The reaction time was 24 hours.
Scheme 1 Synthetic route of probe 1 and the proposed mechanism of
the response of 1 to hydrazine.
Fig. 6 Fluorescence responses of 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/
5, pH 7.40) upon addition of different species (100 equiv. of species
relative to 1) (green bars) with excitation at 450 nm (a) and 580 nm (b),
and fluorescence changes of the mixture of 1 and hydrazine (1.0 ꢀ
10ꢁ3 M in water) after addition of an excess of the indicated species (50
equiv. relative to 1) (red bars) with excitation at 450 nm (a) and 580 nm
Fig. 3 Fluorescence change of 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5) (b). I510 and I660 represent the emission intensity at 510 nm and
before (black line) and after (red line) addition of hydrazine (1 mM) with 660 nm. Intensity means the emission intensity at 660 nm. The species
different pH with excitation at 450 nm (a) and 580 nm (b). The reaction used were Na+, Mg2+, K+, Ca2+, Cd2+, and Mn2+. The reaction time was
time was 24 hours.
24 hours.
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Synthesis of compound 4
4-Diethylaminosalicylaldehyde (0.48 g, 2.5 mmol), dieth-
ylmalonate (750 mL, 5 mmol) and piperidine (250 mL) were
combined in absolute ethanol (15 mL) and stirred for 6 hours
under reux conditions. Ethanol was evaporated under reduced
pressure, and then concentrated HCl (10 mL) and glacial acetic
acid (10 mL) were added to hydrolyze the reaction with stirring
for another 10 hours. The solution was cooled to room
temperature and poured into 15 mL ice water. NaOH solution
(40%) was added dropwise to modulate pH of the solution to
ꢃ5, and a pale precipitate was formed immediately. Aer stir-
ring for 30 minutes, the mixture was ltered, washed with water,
dried and recrystallized with toluene. And then the nal
product 4 was puried with the yield of 48% by silica gel column
chromatography using dichloromethane as eluent. Character-
ization of 4: 1H NMR (400 MHz, CDCl3-d6, TMS) (Fig. S8 in ESI†):
dH 7.54 (d, 1H), 7.27 (t, 1H), 6.50 (m, 1H), 6.50 (d, 1H), 6.03 (d,
1H), 3.42 (m, 4H), 1.24 (t, 6H). 13C NMR (100 MHz, CDCl3-d6)
(Fig. S9† in ESI†): dC 12.44, 44.82, 97.53, 108.29, 108.67, 109.19,
128.77, 143.70, 150.66, 156.74, 162.28.
Fig. 7 Fluorescence responses of 1 (1.0 ꢀ 10ꢁ5 M, VHEPES/VDMSO ¼ 5/5,
pH 7.40) upon addition of different species (100 equiv. of species
relative to 1) (green bars) with excitation at 450 nm (up) and 580 nm
(down), and fluorescence changes of the mixture of 1 and hydrazine
(1.0 ꢀ 10ꢁ3 M in water) after addition of an excess of the indicated
species (50 equiv. relative to 1) (red bars) with excitation at 450 nm (up)
and 580 nm (down). I510 and I660 represent the emission intensity at
510 nm and 660 nm. Intensity means the emission intensity at 660 nm.
The species used were C2O42ꢁ, H2PO4ꢁ, SO32ꢁ, HSO3ꢁ, N3ꢁ, Clꢁ, Brꢁ,
Iꢁ, ClO3ꢁ, ClO4ꢁ, NO3ꢁ, and SO42ꢁ. The reaction time was 24 hours.
6, 7, S6 and S7 in ESI†). Such results approved the remarkably
high selectivity of 1 towards hydrazine over other competitive
species at physiological pH 7.40.
Synthesis of compound 3
Fresh distilled DMF (1 mL) was added dropwise to POCl3 (1 mL)
at 20–50 C with N2 atmosphere and stirred for 30 minutes to
The anti-disturbance effect study of 1 for hydrazine detection
ꢂ
To further assess its utility as a hydrazine-selective uorescent
probe, its uorescence spectral response to hydrazine in the
presence of other species mentioned above was also tested (red
bars of Fig. 5, 6, 7, S6 and S7 in ESI†). The results demonstrated
that all of the selected species have no interference in the
detection of hydrazine. This result strongly indicates that
compound 1 could be an excellent uorescent probe towards
hydrazine with strong anti-interference ability.
yield a red solution. This solution was combined with a portion
of 4 (0.2543 g, 1.2 mmol, dissolved in 2 mL DMF) to yield
a scarlet suspension. The mixture was stirred at 60 ꢂC for 12
hours and then poured into 15 mL ice water. NaOH solution
(20%) was added to adjust the pH of the mixture to yield large
amount of precipitate. The crude product was ltered, thor-
oughly washed with water, dried and recrystallized in absolute
ethanol to give 3 (1.20 g, 4.89 mmol). The nal product 3 was
puried (57.5% yield) by silica gel column using chromatog-
raphy using ethanol/dichloromethane (1/3 v/v) as eluent. 1H
NMR (400 MHz, CDCl3-d6, TMS) (Fig. S10 in ESI†): dH 10.13 (s,
1H), 8.26 (s, 1H), 7.43 (d, 1H), 6.67 (m, 1H), 6.51 (d, 1H), 3.50 (m,
4H), 1.27 (t, 6H). 13C NMR (100 MHz, CDCl3-d6) (Fig. S11 in
ESI†): dC 12.46, 29.70, 45.29, 97.15, 108.23, 110.20, 132.52,
145.37, 153.47, 158.93, 161.89, 187.92.
Experimental section
Materials and methods
4-Diethylaminosalicylaldehyde, diethylmalonate, piperidine,
HCl, glacial acetic acid, POCl3, 1,1,2-trimethylbenzo[e]indole-
nine, CH3I, NaCl, MgCl2, KCl, CaCl2, MnCl2, Cd(NO3)2, Na2SO4,
Na2SO3, KNO3, Na2N3, NaI, NaHSO3, NaH2PO4, NaClO4, NaClO3,
NaCl, Na2C2O4, NaBr, thiourea, triethylamine, N,N-diisopropy-
lethylamine, ammonia water, carbamide, aniline, Tyr, Ala,
H2O2, Pro, Cys, Met, Lys, Phe, Thr, Ile, Trp, Ser, and Val. All
commercial grade chemicals and solvents were purchased and
were used without further purication. Mass spectra were ob-
tained on high resolution mass spectrometer (IonSpec4.7 Tesla
FTMS-MALDI/DHB). 1H and 13C NMR spectra were recorded on
a Bruker 400 NMR spectrometer. Chemical shis were reported
in parts per million using tetramethylsilane (TMS) as the
internal standard.
Synthesis of compound 2
1,1,2-Trimethylbenzo[e]indolenine (313.51 mg, 1.5 mmol) and
CH3I (2.5 mL, 7.5 mmol) were dissolved in 10 mL acetonitrile.
The mixture was reuxed for 12 hours and then allowed to cool to
room temperature. By ltration of the above mixture, the solid
was obtained as product 2 (393 mg, 1.17 mmol) in 78% yield. 1H
NMR (400 MHz, DMSO-d6, TMS) (Fig. S12 in ESI†): dH 8.39 (d,
1H), 8.29 (d, 1H), 8.21 (d, 1H), 8.10 (d, 1H), 7.75 (m, 2H), 4.11 (s,
3H), 2.88 (s, 3H), 1.76 (s, 6H). 13C NMR (100 MHz, DMSO-d6)
(Fig. S13 in ESI†): dC 14.50, 21.75, 35.60, 55.73, 113.63, 123.89,
127.80, 128.85, 130.22, 130.99, 133.50, 136.98, 139.95, 196.39.
All spectral characterizations were carried out in HPLC-grade
solvents at 20 ꢂC within a 10 mm quartz cell. UV-vis absorption
spectra were measured with a TU-1901 double-beam UV-vis
spectrophotometer. Fluorescence spectroscopy was deter-
mined on a Hitachi F-4600 spectrometer.
Synthesis of probe 1
Compound 2 (0.1755 g, 0.5 mmol), and compound 3 (0.121 g,
Probe 1 was synthesized according to Scheme 1.
0.5 mmol) were dissolved in 10 mL ethanol. The mixture was
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ꢂ
reuxed for 3 hours at 80 C and cooled to room temperature. 10 E. Gionfriddo, A. Naccarato, G. Sindona and A. Tagarelli,
The nal product 1 was obtained by ltration and being washed Anal. Chim. Acta, 2014, 835, 37–45.
with ethanol for three times (0.1404 g, 0.25 mmol, 50%). 11 J.-A. Oh, J.-H. Park and H.-S. Shin, Anal. Chim. Acta, 2013,
Characterization of 1: HRMS (EI) m/z: calcd for C30H31N2O2I [M 769, 79–83.
ꢁ I], 451.2380; found, 451.2385. H NMR (400 MHz, DMSO-d6, 12 L. Cui, K. Jiang, D. Q. Liu and K. L. Facchine, J. Chromatogr.
TMS) (Fig. S14 in ESI†): dH 8.87 (s, 1H), 8.43 (d, 1H), 8.37 (d, 1H), A, 2016, 1462, 73–79.
8.27 (d, 1H), 8.21 (d, 1H), 8.09 (d, 1H), 7.87 (s, 1H), 8.27 (d, 1H), 13 D. S. Kosyakov, A. S. Amosov, N. V. Ul'yanovskii,
1
7.80 (t, 1H), 7.70 (t, 1H), 7.62 (d, 1H), 6.94 (m, 1H), 6.73 (d, 1H),
4.12 (s, 3H), 3.57 (m, 4H), 2.00 (s, 6H), 1.19 (t, 6H). 13C NMR (100
A. V. Ladesov, Y. G. Khabarov and O. A. Shpigun, J. Anal.
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53.49, 97.04, 109.82, 110.32, 111.71, 112.77, 113.54, 123.54, Biosens. Bioelectron., 2017, 92, 372–377.
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Conclusions
In summary, we here developed a novel multi-mode uorescent
probe for determination of hydrazine in aqueous solution. The
probe 1 could detect hydrazine based on the nucleophilicity of
hydrazine. And this probe displayed high selectivity and sensi-
tivity toward hydrazine, with a color change from blue to pale
yellow by the naked eye. Probe 1 exhibited a good linear rela-
tionship between hydrazine concentration and the ratiometric
uorescence enhancement in concentration range of 0–400 mM
and the LOD could be as low as 560 nM.
Acknowledgements
23 R. Zhang, J. Zhao, G. Han, Z. Liu, C. Liu, C. Zhang, B. Liu,
C. Jiang, R. Liu, T. Zhao, M.-Y. Han and Z. Zhang, J. Am.
Chem. Soc., 2016, 138, 3769–3778.
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M. Xian, Angew. Chem., Int. Ed., 2016, 55, 9993–9996.
25 W. Zhou, Y. Cao, D. Sui and C. Lu, Angew. Chem., Int. Ed.,
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This work was supported by “the Fundamental Research Funds
for the Central Universities (2015XKZD08)”.
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