A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine

Article abstract of DOI:10.1016/j.tet.2020.130921

Hydrazine (N₂H₄) has been classified as an environmental contaminant and human carcinogen owing to its high toxicity. Exposed to high concentration of hydrazine can cause irreversible damage to human bodies. Hence, it is significant to explore an effective analytical method to selectively recognize and detect it. In this work, an intramolecular charge transfer (ICT) based probe 1 was designed and synthesized by condensation of V-shaped bis-coumarin and 4-bromobutyric acid. The V-shaped bis-coumarin with π-expanded system endowed the probe 1 larger stokes shift and superior tolerance to photobleaching. This “turn-on” probe exhibited a high selectivity towards hydrazine over other common ions and amine-containing species with a distinct fluorescent enhancement at 555 nm. It could rapidly detect hydrazine over a wide pH range and the detection limit was as low as 4.2 ppb. The large shift of absorption spectrum enabled it to detect hydrazine in real water samples and gas-state hydrazine by “naked-eyes".

Full text of DOI:10.1016/j.tet.2020.130921

Tetrahedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
A “turn-on” fluorescent probe based on V-shaped bis-coumarin for
detection of hydrazine
Xingzong Jiang a, Mingqin Shangguan a, Zhen Lu a, Sili Yi b, Xiaoyang Zeng a,
,
*
Yongle Zhang a, Linxi Hou a
a College of Chemical Engineering, Fuzhou University, Fuzhou, 350108, PR China
b Institute of Food Safety and Environment Monitoring of Photocatalysis on Energy and Environment College of Chemistry, Fuzhou University, Fuzhou,
350116, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Hydrazine (N2H4) has been classified as an environmental contaminant and human carcinogen owing to
its high toxicity. Exposed to high concentration of hydrazine can cause irreversible damage to human
bodies. Hence, it is significant to explore an effective analytical method to selectively recognize and
detect it. In this work, an intramolecular charge transfer (ICT) based probe 1 was designed and syn-
thesized by condensation of V-shaped bis-coumarin and 4-bromobutyric acid. The V-shaped bis-
Received 30 October 2019
Received in revised form
19 December 2019
Accepted 3 January 2020
Available online xxx
coumarin with
p-expanded system endowed the probe 1 larger stokes shift and superior tolerance to
photobleaching. This “turn-on” probe exhibited a high selectivity towards hydrazine over other common
ions and amine-containing species with a distinct fluorescent enhancement at 555 nm. It could rapidly
detect hydrazine over a wide pH range and the detection limit was as low as 4.2 ppb. The large shift of
absorption spectrum enabled it to detect hydrazine in real water samples and gas-state hydrazine by
“naked-eyes".
Keywords:
Fluorescent probe
Bis-coumarin derivative
Hydrazine detection
Gaseous detection
© 2020 Published by Elsevier Ltd.
1. Introduction
To date, various methods have been developed to determine
hydrazine. Traditional analytical techniques including surface-
Hydrazine (N2H4), known as a crucial weak base and a typical
reducing agent, has been widely used in various fields, such as the
pharmacy, chemistry, catalysis and agriculture [1e3]. Additionally,
due to its high enthalpy of combustion, hydrazine is often
employed as high-energy fuel in rocket-propulsion and missile
systems [4,5]. Although hydrazine plays an important and positive
role in production and manufacturing process, the toxicity and
carcinogenicity of it shouldn’t be ignored. As a volatile and water-
soluble compound, it can cause irreversible damage to the lungs,
liver, kidneys, respiratory system and central nervous system of
living bodies through easily absorbed by dermal, breathing or oral
routes [6e8]. In fact, hydrazine has been denoted as a possible
human carcinogen by the U.S. Environmental Protection Agency
(EPA) with the threshold limit value (TLV) of 10 ppb [9]. Therefore,
the convenient and high-efficiency detection methods for trace
hydrazine have gained increasing attention.
enhanced Raman spectroscopy [10], chromatography [11e13]
electrochemistry [14,15] and titration [16,17] are inferior for
detecting hydrazine due to the apparent limitations such as time-
consuming, requirement of expensive instruments and pro-
fessionals, as well as complicated pre-treatments. In comparison,
fluorescent probes are flourishing as promising technique in virtue
of unique advantages such as real-time visual monitoring, in-situ
analysis and ease to operation [18,19]. A number of fluorescent
probes for detecting molecules and ions in vivo or vitro have been
reported. However, the fluorescent probes for hydrazine have been
reported less [20]. Until now, most of the probes for hydrazine are
designed via anchoring a fluorophore with reaction sites including
4-bromobutanoate [21,22], acetyl [23e25], aldehyde [26,27],
malononitrile [28,29], phthalimide [30], and trifluoroacetyl aceto-
nate [31]. However, many of them suffer from several ineradicable
defects such as narrow pH range, complicated synthesis proced-
ures, long response time or poor selectivity.
Various organic fluorophores such as benzothiazole [32,33],
coumarins [34e39], rhodamine [40], 1,-8 naphthalimide [23,41]
and heptamethine cyanine [24] have been utilized to design
* Corresponding author.
E-mail address: lxhou@fzu.edu.cn (L. Hou).
https://doi.org/10.1016/j.tet.2020.130921
0040-4020/© 2020 Published by Elsevier Ltd.
Please cite this article as: X. Jiang et al., A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine, Tetrahedron,
https://doi.org/10.1016/j.tet.2020.130921

2
X. Jiang et al. / Tetrahedron xxx (xxxx) xxx
fluorescent probes recent years. Among these fluorophores,
coumarin and its derivatives, especially coumarin-fused heterocy-
cles, attract more attention for their large stokes shift, superior
tolerance to photobleaching and great fluorescent quantum yield
[42]. In addition, due to the extension of the conjugated system and
the plentifulness of electrons in coumarin-fused heterocycles,
finished, the solvent was removed under reduced pressure. The
residue was purified by silica gel column chromatography (CH2Cl2/
CH3OH ¼ 10/1, v/v) to afford pure probe 1 as white solid (1.31 g, 62%
yield). 1H NMR (600 MHz, DMSO)
d 8.57 e8.41 (m, 2H), 7.87 (dd,
J ¼ 8.5, 7.3, 1.4 Hz, 1H), 7.50 (ddd, J ¼ 79.4, 11.3, 8.6, 1.7 Hz, 4H), 3.67
(t, J ¼ 6.6 Hz, 2H), 2.84 (t, J ¼ 7.3 Hz, 2H), 2.23 (p, J ¼ 6.8 Hz, 2H)
coumarins with
p-expanded system show several distinguished
(Fig. S3). 13C NMR (101 MHz, DMSO)
d 174.03 (s), 170.86 (s), 157.21
properties, such as larger stokes shift, red shift in the excitation and
emission wavelengths, and colorimetric properties compared with
the traditional coumarins whose absorption and emission wave-
length generally locate on short-wave band [43]. Taking significant
(s), 155.66 (s), 155.36 (s), 154.75 (s), 152.30 (s), 135.50 (s), 131.12 (s),
129.66 (s), 125.47 (s), 119.43 (s), 117.99 (s), 115.57 (s), 113.55 (s),
111.39 (s), 106.88 (s), 34.64 (s), 32.51 (s), 28.20 (s) (Fig. S6). HRMS:
m/z calcd for C20H13BrO6 [MþH]þ: 428.9968, found: 428.9975
(Fig. S8).
advantages stated above into consideration,
p-expanded couma-
rins can be applied in environmental detection and even
biosensors.
2.3. General procedures for analysis
In this work, the V-shaped bis-coumarin was selected as fluo-
rophore combined with 4-bromobutanoate to afford a “turn-on”
fluorescent probe 1. This V-shaped bis-coumarin possessed a
electron-donating group (hydroxyl) and a electron-withdrawing
group (carbonyl) at the site corresponding to position 7 and 2 of
the coumarin moiety respectively, which formed the push-pull
electron structure and emitted fluorescent according to ICT
(intramolecular charge transfer) theory [44]. In addition, it was
reported that bromo-ester derivatives could react with hydrazine
through nucleophilic substitution to the bromine group and
nucleophilic addition to the ester carbonyl with subsequent intra-
molecular cyclization to release the fluorophore [45]. So we
assumed that the electron-withdrawing 4-bromobutanoate could
prohibit the ICT process and quench the fluorescent emission of the
fluorophore by esterification. When reacted with hydrazine, the
fluorophore could be released and the ICT process was recovered,
which resulted fluorescent enhancement simultaneously. As ex-
pected, upon addition of hydrazine, the emission intensity
distinctly increased at 555 nm in DMSO: PBS buffer solution (3:1, v/
v, pH ¼ 7.4), simultaneously, the UVeVIS absorption spectrum
showed a red shift with the color changing from colorless to yellow.
The color change provided a visual method of detecting hydrazine
by “naked-eye”. The limit of detection value (LOD) was found to be
4.2 ppb, which was lower than the TLV (10 ppb) according to the
EPA. The probe exhibited excellent selectivity and rapid response
towards hydrazine. Moreover, the probe could be used for practical
detection of hydrazine in real water samples and gas-state
hydrazine.
The stock solution of probe 1 (1 mM) was prepared in DMSO,
and then diluted with DMSO: PBS buffer solution (3:1, v/v,
pH ¼ 7.4). Stock solutions of hydrazine and other common analytes
(cations: Naþ, Kþ, Ca2þ, Mg2þ, Liþ, Fe2þ, Zn2þ, Fe3þ, Mn2þ, Co2þ
,
Al3þ; anions: Clꢀ, HPO42ꢀ, CO23ꢀ, SO24ꢀ, Fꢀ, NO3ꢀ, Iꢀ, AcOꢀ, SO32ꢀ; and
amine-containing species: Triethylamine, Diethylamine, 2-
Aminoethanol, Sulfamic acid, Aniline, NH3$H2O, L-Cys, Ala, Glu,
Hcy, GSH) were prepared in distilled water. The stock solutions
were used freshly and were diluted to appropriate concentrations
as needed.
All spectral analysis experiments were carried out in DMSO: PBS
buffer solution (3:1, v/v, pH ¼ 7.4) with probe 1 (900
mL, 200/9 mM)
and hydrazine (100 L, appropriate concentration). When con-
m
ducted the fluorescent experiment, the stock solution of probe 1
was added into a quartz cuvette (1 cm ꢁ 1 cm), followed by addition
of 100 mL of the hydrazine stock solutions with different concen-
trations. The fluorescent spectra were recorded after 15 min. The
process of selectivity and competition studies were same as above,
except interfering substances (1 mM, 50
mL) were added in front of
hydrazine (100 L, 500 M). The excitation wavelength was
m
m
460 nm, and the PMT voltage was 550 V. The excitation and
emission slit width were 5 nm and 5 nm, respectively.
2.4. Water samples test
Tap water in laboratory and Minjiang River water were selected
for the practical sample analysis. The stock solution of probe 1
(900
followed by addition of 50
After that, 100 L of different concentrations of standard hydrazine
solution (100 M, 300 M, 500 M) were added to the solution. The
m
L, 200/9
m
M) was added into a quartz cuvette (1 cm ꢁ 1 cm),
m
L of the water samples respectively.
2. Experimental section
m
m
m
m
2.1. Materials and instruments
fluorescent spectra of these samples were recorded after 15 min.
All chemical reagents and solvents were purchased from com-
mercial suppliers, further purification was not required. Absorption
spectra were detected on Lambda 750 UVevis spectrophotometer.
Fluorescent spectra were measured on the Hitachi F-4600 spectro-
fluorometer. 1H NMR spectra were recorded on a Bruker Avance III
600 MHz spectrometer and referenced to the solvent signals. The
mass spectra were performed on Agilent HPLC-MS.
2.5. Detection of gaseous hydrazine
Filter papers were immersed in DMSO solution of probe 1
(2 mM) for 5 min and then dried at room temperature. Different
concentrations of hydrazine solution (0, 0.5%, 1%, 5%, 10%, 20%, 30%)
were prepared in test tubes. The above filter paper strips were hung
in respective test tubes at room temperature for 10 min. Observing
the color and fluorescent changing under the natural light and UV
light (commercial hand-held 365 nm UV lamp) respectively.
2.2. Synthesis of probe 1
The detailed synthesis route was given in the Electronic sup-
plementary information (Scheme. S1) [46]. Compound 1 (1.40 g,
5 mmol) and 4-bromobutyric acid (1.17 g, 7 mmol) were mixed in
3. Results and discussion
3.1. UVevis and fluorescent spectra
the
dichloromethane
(20
mL)
with
stirring.
4-
dimethylaminopyridine (DMAP, 0.23 g, 2 mmol) and N, N0-dicy-
clohexylcarbodiimide (DCC, 0.40 g, 2 mmol) were added into the
solution and stirred at room temperature for 6 h. After the reaction
The optical property of probe 1 was investigated first. The time-
dependent absorption spectra of the probe 1 (20
mM) were exam-
ined at room temperature after addition of hydrazine (100
mM) to
Please cite this article as: X. Jiang et al., A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine, Tetrahedron,
https://doi.org/10.1016/j.tet.2020.130921

X. Jiang et al. / Tetrahedron xxx (xxxx) xxx
3
Fig. 1. (a) The time-dependent UVevis absorption spectral of probe 1 (20
gradually increasing concentration of hydrazine (0e100
m
M) in the presence of hydrazine (100
m
M). (b) Fluorescent emission spectra of probe 1 (20
m
M) with the
m
M) in DMSO: PBS buffer solution (3:1, v/v, pH ¼ 7.4). lex ¼ 460 nm lem ¼ 555 nm. (c) Fluorescent photographs of probe 1 in
the presence of increasing concentrations of hydrazine. (d) The fluorescent intensities (lem ¼ 555 nm) of probe 1 were linearly related to the concentrations of hydrazine (0e50
mM).
lex ¼ 460 nm, dex ¼ 5 nm, dem ¼ 5 nm.
DMSO: PBS buffer solution (3:1, v/v, pH ¼ 7.4) (Fig. 1a). It can be
observed that the free probe 1 showed a maximum absorption peak
at 357 nm. After addition of hydrazine, the absorption peak at
357 nm was decreased gradually. Inversely, the absorption peak at
460 nm was increased dramatically. A well-defined isobestic point
appeared at 390 nm. Such a large red shift of 103 nm in absorption
spectrum transformed the solution from colorless and transparent
to orange, suggesting hydrazine could be detected with the “naked-
eyes".
SO23ꢀ) were performed in the DMSO: PBS buffer solution (3:1, v/v,
pH ¼ 7.4) to prove the selectivity of probe 1 to hydrazine. Upon
addition 50 L of different analytes (1 mM) respectively, only hy-
m
drazine triggered a prominent fluorescent emission enhancement
at 555 nm while other species appeared negligible variation
(Fig. 2a). Moreover, competitive assays indicated that the co-
existence of cations and anions had no interference on the detec-
tion of hydrazine (Fig. 2b). Subsequently, the response of the probe
1 toward amine-containing species (Triethylamine, Diethylamine,
2-Aminoethanol, Sulfamic acid, Aniline, NH3$H2O, L-Cys, Ala, Glu,
Hcy, GSH) was performed in the same condition (Fig. S9). The re-
sults demonstrated the probe 1 had the same excellent selectivity
and anti-interference ability to these amine-containing species.
Such a high selectivity and anti-interference ability of the probe 1
indicated it could be used as a sensing platform for hydrazine
detection in complex environment.
Subsequently, the fluorescent titration experiment of the probe
1 was carried out in the DMSO: PBS buffer solution (3:1, v/v,
pH ¼ 7.4) (Fig. 1b). Originally, the free probe 1 solution (20
mM)
exhibited a very weak emission peak at 555 nm under the excita-
tion of 460 nm. After addition of hydrazine with increasing con-
centration (0 e100
intensity at 555 nm was observed and reached to a plateau at the
concentration of 60 M. The fluorescent color changed from
mM), a significant increase of the fluorescent
m
colorless to yellow gradually (Fig. 1c). Such a large Stokes shift of
95 nm in emission spectrum made it have a higher signal-noise
ratio than other probes (Table S1). Meanwhile, the fluorescent in-
tensity at 555 nm exhibited an excellent linear relationship
(y ¼ 2.79 þ 52.79x, R2 ¼ 0.9960) with the concentrations of hy-
3.3. Effect of pH and reaction time
In view of the importance of pH value adaptation in practical
applications, the pH effects on fluorescent response of probe 1 in
the absence and presence of hydrazine were investigated (Fig. 3a).
The probe 1 was inert to pH in the range of 2.0e11.0 in the absence
drazine in the range of 0 e50
m
M (Fig. 1d). The detection limit was
calculated to be 0.0099 M (4.2 ppb) based on 3
m
s
/k, which was
of hydrazine. Upon treatment with hydrazine (50 mM), the maximal
lower than TLV of 10 ppb. These results indicated that the probe 1
was competent for detecting hydrazine qualitatively and
quantitatively.
fluorescent signal was observed in the pH range of 4.0e11.0. These
results indicated that the probe 1 could exist steadily and detect
hydrazine with excellent sensitivity over a wide pH range.
For kinetic studies, time-dependent fluorescent intensity mea-
3.2. Selectivity and competition studies
surement was performed on probe 1 (20
(50
Upon introduction of hydrazine to the probe solution, a significant
enhancement of the fluorescent intensity at 555 nm arose and
reached the plateau within 15 min. These results implied the probe
1 had a fast response to hydrazine.
mM) with hydrazine
M) in DMSO: PBS buffer solution (3:1, v/v, pH ¼ 7.4) (Fig. 3b).
m
The selectivity of fluorescent probe was an important parameter
in performance evaluation. The response of the probe 1 toward
common cations (Naþ, Kþ, Ca2þ, Mg2þ, Liþ, Fe2þ, Zn2þ, Fe3þ, Mn2þ
,
Co2þ, Al3þ) and anion (Clꢀ, HPO24ꢀ, CO23ꢀ, SO42ꢀ, Fꢀ, NO3ꢀ, Iꢀ, AcOꢀ,
Please cite this article as: X. Jiang et al., A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine, Tetrahedron,
https://doi.org/10.1016/j.tet.2020.130921

4
X. Jiang et al. / Tetrahedron xxx (xxxx) xxx
Fig. 2. Fluorescent emission of probe 1 (20
mM), upon the addition of different ions (50
mM) and N2H4 (50
m
M), in DMSO: PBS buffer solution (3:1, v/v, pH ¼ 7.4). (a) Represents the
addition of hydrazine or various other ions to the solution of probe 1. (b) Represents the addition of hydrazine to the above ions-containing solutions (bars show: 0. Blank, 1. Naþ, 2.
Kþ, 3. Ca2þ, 4. Mg2þ, 5. Liþ, 6. Fe2þ, 7. Zn2þ, 8. Fe3þ, 9. Mn2þ, 10. Co2þ, 11. Al3þ, 12. Clꢀ, 13. HPO42ꢀ, 14. CO23ꢀ, 15. SO42ꢀ, 16. Fꢀ, 17. NO3ꢀ, 18. Iꢀ,19. AcOꢀ, 20. SO23ꢀ).
Fig. 3. (a) The fluorescent intensity of probe 1 (20
1 (20 M) with hydrazine (50 M).
mM) in the absence (black line) or presence (red line) of hydrazine (50 mM) at various pH values. (b) Reaction time profiles of probe
m
m
Then we extended the reaction time to determined the photo-
stability of probe 1 (Fig. S10). Under the irradiation of 460 nm UV-
light, there was no change in the fluorescence intensity of probe 1
ICT process and quench the fluorescent. After reaction with hy-
drazine, the fluorophore was released and the ICT process was
recovered, which resulted in fluorescent enhancement (Scheme 1).,
In order to determine the reaction, UV eVis absorption spectra
were analyzed (Fig. S11), the free probe 1 exhibited a broad ab-
sorption band at 300 e400 nm, but there was a negligible ab-
sorption at 460 nm. When reacted with hydrazine, the peak at
350 nm decreased gradually, whereas the peak at 460 nm which
in the absence of hydrazine within 1 h. When hydrazine (50 mM)
was added, as expect, the fluorescence intensity increased imme-
diately and reached the maximum within 15 min. Additionally, the
fluorescence intensity was nearly unchanged over time, which
indicated the photostability of probe 1.
regarded as characteristic absorption peak of compound
1
increased sharply. Additionally, it was similar to the absorption
spectra of compound 1 which confirmed our hypothesis. 1H NMR
was further taken to verify the mechanism, and the results were
performed in Fig. 4. After the addition of hydrazine into probe 1 in
DMSO-d6, the protons of probe 1 at 8.52 ppm (a), 8.45 ppm (b),
7.87 ppm (c), 7.57 ppm (d), 7.54 ppm (e), 7.50 ppm (f), 7.36 ppm (g)
remarkably shifted to 8.39 ppm (a), 8.31 ppm (b), 7.83 ppm (c),
6.84 ppm (d), 6.98 ppm (e), 7.52 ppm (f), 7.50 ppm (g). As expected,
3.4. Proposed detection mechanism
To our knowledge, bromo-ester derivatives could react with
hydrazine through nucleophilic substitution to the bromo group
and nucleophilic addition to the ester carbonyl with subsequent
intramolecular cyclization to release the fluorophore [45]. So the
electron-withdrawing group bromo-ester derivatives was intro-
duced into the V-shaped bis-coumarin fluorophore to prohibit its
Scheme 1. The proposed mechanism of probe 1 reacting with hydrazine.
Please cite this article as: X. Jiang et al., A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine, Tetrahedron,
https://doi.org/10.1016/j.tet.2020.130921

X. Jiang et al. / Tetrahedron xxx (xxxx) xxx
5
Fig. 4. The changes of 1H NMR spectra of probe 1 after reacted with hydrazine.
it was similar to the 1H NMR spectra of compound 1 (Fig. S4). All the
above results confirmed that probe 1 could react with hydrazine to
release the fluorophore.
light and UV light respectively (Fig. 5). The fluorescent color from
colorless to yellow were observed with the increase of hydrazine
vapor concentration, meanwhile, the color clearly changed from
colorless to yellow by “naked-eyes”. Furthermore, this analytic
method could identify hydrazine vapor even at a concentration as
low as 0.5%. Hence, it had great application value for the rough
detection of gaseous hydrazine.
3.5. Water samples test
Hydrazine had been widely used in various industrial processes,
the detection and quantification of it in real aqueous samples was
significant. The probe 1 was applied to detect hydrazine in tap
water and Minjiang River in Fuzhou city, respectively. The water
4. Conclusion
samples (50
there was no significant fluorescent enhancement observed. Then,
an aliquot of hydrazine solution (10 M, 30 M, 50 M) was added
mL) were added into the probe 1 solution (20 mM), and
In summary, a new type of V-shaped bis-coumarin “turn-on”
fluorescent probe for hydrazine detection had been reported. It
exhibited distinct changes in the intensity of both absorption and
emission spectra upon addition of hydrazine. The remarkable color
change can be observed visually. The sensing mechanism was
elucidated by spectroscopy and 1H NMR analysis. The probe ex-
hibits prominent selectivity and sensitivity with a low detection
limit. It was a candidate for “naked-eyes” and fluorescent detection
of hydrazine in real water samples and gas-state hydrazine.
m
m
m
to the above real samples and recorded the fluorescent spectra. As
shown in Table 1, the resultant hydrazine recoveries were in the
range of 101e105%, indicating the possibility of probe 1 for hy-
drazine detection in practical water samples.
3.6. Detection of gaseous hydrazine
To explore the practical applications of the probe, the detection
of gaseous hydrazine was also performed. Primarily, the tailored
filter paper strips were immersed in the probe 1 solution (2 mM)
for 5 min. Then took them out and dried at room temperature.
Different concentrations of hydrazine solution (0, 0.5%, 1%, 5%, 10%,
20%, 30%) were prepared in test tubes, the above filter paper strips
were hung in respective test tubes at room temperature for 10 min.
The color and fluorescent changing was observed under the natural
Table 1
Detection of hydrazine in environmental samples.
Spiked (
mM)
Detected (
m
M)
Recovery (%)
RSD (%)
Tap water
0
Not detected
10.17
20.83
31.51
Not detected
10.19
e
e
10
20
30
0
10
20
30
101.7
104.2
105.0
e
0.41
0.28
0.30
e
Minjiang River
Fig. 5. Photographs for probe 1 coated filter papers upon exposure to gaseous hy-
drazine with different concentrations. Upper: under natural light; Lower: under a
hand-hold UV lamp with an excitation at 365 nm in dark.
101.91
103.8
104.0
0.18
0.23
0.28
20.77
31.20
Please cite this article as: X. Jiang et al., A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine, Tetrahedron,
https://doi.org/10.1016/j.tet.2020.130921

6
X. Jiang et al. / Tetrahedron xxx (xxxx) xxx
Chem. Soc. 139 (1) (2017) 285e292.
Declaration of competing interest
[20] Y. Qian, J. Lin, L. Han, L. Lin, H. Zhu, A resorufin-based colorimetric and fluo-
rescent probe for live-cell monitoring of hydrazine, Biosens. Bioelectron. 58
(2014) 282e286.
There are no conflicts to declare.
[21] S. Chen, P. Hou, J. Wang, L. Liu, Q. Zhang, A highly selective fluorescent probe
based on coumarin for the imaging of N2H4 in living cells, Spectrochim. Acta,
Part A 173 (2017) 170e174.
Acknowledgements
[22] Z. Lu, W. Fan, X. Shi, Y. Lu, C. Fan, Two distinctly separated emission colori-
metric NIR fluorescent probe for fast hydrazine detection in living cells and
mice upon independent excitations, Anal. Chem. 89 (18) (2017) 9918e9925.
[23] X. Xia, F. Zeng, P. Zhang, J. Lyu, Y. Huang, S. Wu, An ICT-based ratiometric
fluorescent probe for hydrazine detection and its application in living cells
and in vivo, Sens. Actuators, B 227 (2016) 411e418.
[24] C. Hu, W. Sun, J. Cao, P. Gao, J. Wang, J. Fan, et al., A ratiometric near-infrared
fluorescent probe for hydrazine and its in vivo applications, Org. Lett. 15 (15)
(2013) 4022e4025.
This work was supported by the National Natural Science
Foundation of China (No: 21676057), United Fujian Provincial
Health and Education Project for Tackling the Key Research P.R.
China (WKJ2016-2-04) and Scientific Research Topics of Traditional
Chinese Medicine in Fujian Provincial Department of Health
(WZZY201317).
[25] X.R. Shi, F.J. Hou, J.B. Chao, Y.B. Zhang, C.X. Yin, An isophorone-based NIR
probe for hydrazine in real water samples and hermetic space, New J. Chem.
43 (2019) 10025e10029.
Appendix A. Supplementary data
[26] L. Xiao, J. Tu, S. Sun, Z. Pei, Y. Pei, Y. Pang, et al., A fluorescent probe for hy-
drazine and its in vivo applications, RSC Adv. 4 (79) (2014) 41807e41811.
[27] X. Chen, Y. Xiang, Z. Li, A. Tong, Sensitive and selective fluorescence deter-
mination of trace hydrazine in aqueous solution utilizing 5-
chlorosalicylaldehyde, Anal. Chim. Acta 625 (1) (2008) 41e46.
[28] X. Yang, Y. Liu, Y. Wu, X. Ren, D. Zhang, Y. Ye, A NIR ratiometric probe for
hydrazine "naked eye" detection and its imaging in living cell, Sens. Actuators,
B 253 (2017) 488e494.
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2020.130921.
References
[1] U. Ragnarsson, Synthetic methodology for alkyl substituted hydrazines, Chem.
Soc. Rev. 30 (4) (2001) 205e213.
[2] J. Sanabria-Chinchilla, K. Asazawa, T. Sakamoto, K. Yamada, H. Tanaka,
P. Strasser, Noble metal-free hydrazine fuel cell catalysts: EPOC effect in
competing chemical and electrochemical reaction pathways, J. Am. Chem. Soc.
133 (14) (2011) 5425e5431.
[3] L.L. Xiao, J. Tu, S.G. Sun, Z.C. Pei, Y.X. Pei, Y. Pang, et al., A fluorescent probe for
hydrazine and its in vivo applications, RSC Adv. 4 (79) (2014) 41807e41811.
[4] J. Waser, B. Gaspar, H. Nambu, E.M. Carreira, Hydrazines and azides via the
metal-catalyzed hydrohydrazination and hydroazidation of olefins, J. Am.
Chem. Soc. 128 (35) (2006) 11693e11712.
[5] K. Yamada, K. Yasuda, N. Fujiwara, Z. Siroma, H. Tanaka, Y. Miyazaki, et al.,
Potential application of anion-exchange membrane for hydrazine fuel cell
electrolyte, Electrochem. Commun. 5 (10) (2003) 892e896.
[6] S. Garrod, M.E. Bollard, A.W. Nichollst, S.C. Connor, J. Connelly, J.K. Nicholson,
et al., Integrated metabonomic analysis of the multiorgan effects of hydrazine
toxicity in the rat, Chem. Res. Toxicol. 18 (2) (2005) 115e122.
[7] C.A. Reilly, S.D. Aust, Peroxidase substrates stimulate the oxidation of hy-
dralazine to metabolites which cause single-strand breaks in DNA, Chem. Res.
Toxicol. 10 (3) (1997) 328e334.
[8] S.D. Zelnick, D.R. Mattie, P.C. Stepaniak, Occupational exposure to hydrazines:
treatment of acute central nervous system toxicity, Aviat. Space Environ. Med.
74 (12) (2003) 1285e1291.
[9] O. o R a D a U S Environmental Protection Agency (EPA, Integrated Risk In-
formation System (IRIS) on Hydrazine/hydrazine Sulfate, National Center for
Environmental Assessment, DC, 1999.
[10] X. Gu, J.P. Camden, Surface-enhanced Raman spectroscopy-based approach
for ultrasensitive and selective detection of hydrazine, Anal. Chem. 87 (13)
(2015) 6460e6464.
[29] B. Chen, X. Sun, X. Li, H. Agren, Y. Xie, TICT based fluorescence "turn-on"
hydrazine probes, Sens. Actuators, B 199 (2014) 93e100.
[30] M.V.R. Raju, E.C. Prakash, H.-C. Chang, H.-C. Lin, A facile ratiometric fluores-
cent chemodosimeter for hydrazine based on Ing-Manske hydrazinolysis and
its applications in living cells, Dyes Pigments 103 (2014) 9e20.
[31] S. Goswami, S. Das, K. Aich, D. Sarkar, T.K. Mondal, A coumarin based che-
modosimetric probe for ratiometric detection of hydrazine, Tetrahedron Lett.
55 (16) (2014) 2695e2699.
[32] Y. Wang, H. Xiang, R. Zhao, C. Huang, A renewable test strip combined with
solid-state ratiometric fluorescence emission spectra for the highly selective
and fast determination of hydrazine gas, Analyst 143 (16) (2018) 3900e3906.
[33] J. Zhou, R. Shi, J. Liu, R. Wang, Y. Xu, X. Qian, An ESIPT-based fluorescent probe
for sensitive detection of hydrazine in aqueous solution, Org. Biomol. Chem.
13 (19) (2015) 5344e5348.
[34] Y.-H. Xiao, G. Xi, X.-X. Zhao, S. Zhou, Z.-Q. Zhou, B.-X. Zhao, A novel coumarin-
based fluorescent probe for the detection of hydrazine both in aqueous so-
lution and vapor state, J. Fluoresc. 25 (4) (2015) 1023e1029.
[35] H. Tse, Q. Li, S. Chan, Q. You, A.W.M. Lee, W. Chan, A ratiometric fluorescent
and colorimetric probe for selective detection of hydrazine, RSC Adv. 6 (18)
(2016) 14678e14681.
[36] X.R. Shi, F.J. Hou, J.B. Chao, C.X. Yin, A ratiometric fluorescent probe for hy-
drazine based on novel cyclization mechanism and its application in living
cells, Sens. Actuators, B 260 (2018) 609e616.
[37] X.R. Shi, C.X. Yin, Y. Wen, Y.B. Zhang, F.J. Hou, A probe with double acetoxyl
moieties for hydrazine and its application in living cells, Spectrochim. Acta,
Part A 203 (2018) 106e111.
[38] Y.K. Yue, F.J. Hou, P. Ning, Y.B. Zhang, J.B. Chao, X.M. Meng, C.X. Yin, Dual-site
fluorescent probe for visualizing the metabolism of cys in living cells, J. Am.
Chem. Soc. 139 (2017) 3181e3185.
[39] M.X. Fang, A. Rashmi, J.H. Bi, M. Wafa, D. Nethaniah, H.Y. Liu, et al., Fluorescent
probes for sensitive and selective detection of pH changes in live cells in
visible and near-infrared channels, J. Mater. Chem. B 5 (2017) 9579e9590.
[40] K. Tiensomjitr, R. Noorat, K. Wechakorn, S. Prabpai, K. Suksen,
P. Kanjanasirirat, et al., A rhodol-based fluorescent chemosensor for hydrazine
and its application in live cell bioimaging, Spectrochim. Acta, Part A 185
(2017) 228e233.
[11] G.E. Collins, Gas-phase chemical sensing using electrochemiluminescence,
Sens. Actuators, B 35 (1e3) (1996) 202e206.
[12] O. Gyllenhaal, L. Gronberg, J. Vessman, Determination of hydrazine in hy-
dralazine by capillary gas-chromatography with nitrogen-selective detection
after benzaldehyde derivatization, J. Chromatogr. 511 (1990) 303e315.
[13] M. Sun, L. Bai, D.Q. Liu, A generic approach for the determination of trace
hydrazine in drug substances using in situ derivatization-headspace GC-MS,
J. Pharm. Biomed. Anal. 49 (2) (2009) 529e533.
[41] X.R. Shi, C.X. Yin, Y.B. Zhang, Y. Wen, F.J. Hou, A novel ratiometric and
colorimetric fluorescent probe for hydrazine based on ring-opening reaction
and its applications, Sens. Actuators, B 285 (2019) 368e374.
[14] S.E.F. Kleijn, B. Serrano-Bou, A.I. Yanson, M.T.M. Koper, Influence of hydrazine-
induced aggregation on the electrochemical detection of platinum nano-
particles, Langmuir 29 (6) (2013) 2054e2064.
[42] R.M. Christie, K.M. Morgan, M.S. Islam, Molecular design and synthesis of N-
arylsulfonated coumarin fluorescent dyes and their application to textiles,
Dyes Pigments 76 (3) (2008) 741e747.
[15] A. Umar, M.M. Rahman, S.H. Kim, Y.-B. Hahn, Zinc oxide nanonail based
chemical sensor for hydrazine detection, Chem. Commun. (2) (2008)
166e168.
[43] Y. Liu, D. Ren, J. Zhang, H. Li, X.-F. Yang, A fluorescent probe for hydrazine
based on a newly developed 1-indanone-fused coumarin scaffold, Dyes Pig-
ments 162 (2019) 112e119.
[44] M. Tasior, Y.M. Poronik, O. Vakuliuk, B. Sadowski, M. Karczewski, D.T. Gryko,
V-shaped bis-coumarins: synthesis and optical properties, J. Org. Chem. 79
(18) (2014) 8723e8732.
[16] H.E. Malone, Determination of mixtures of hydrazine and 1,1-
dimethylhydrazine, Anal. Chem. 33 (1961) 575e577.
[17] Z.K. He, B. Fuhrmann, U. Spohn, Coulometric microflow titrations with
chemiluminescent and amperometric equivalence point detection - bromi-
metric titration of low concentrations of hydrazine and ammonium, Anal.
Chim. Acta 409 (1e2) (2000) 83e91.
[45] X.D. Jin, C.Z. Liu, X.M. Wang, H. Huang, X.Q. Zhang, H.J. Zhu, A flavone-based
ESIPT fluorescent sensor for detection of N2H4 in aqueous solution and gas
state and its imaging in living cells, Sens. Actuators, B 216 (2015) 141e149.
[46] B. Yu, C. Chen, J. Ru, W. Luo, W. Liu, A multifunctional two-photon fluorescent
probe for detecting H2S in wastewater and GSH in vivo, Talanta 188 (2018)
370e377.
[18] Q. Zhai, W. Feng, G. Feng, Rapid detection of hydrazine in almost wholly water
solution and in living cells with a new colorimetric and fluorescent turn-on
probe, Anal. Methods. 8 (29) (2016) 5832e5837.
[19] D. Cheng, Y. Pan, L. Wang, Z. Zeng, L. Yuan, X. Zhang, et al., Selective visual-
ization of the endogenous peroxynitrite in an inflamed mouse model by a
mitochondria-targetable two-photon ratiometric fluorescent probe, J. Am.
Please cite this article as: X. Jiang et al., A “turn-on” fluorescent probe based on V-shaped bis-coumarin for detection of hydrazine, Tetrahedron,
https://doi.org/10.1016/j.tet.2020.130921