Recent progress in the development of fluorescent probes for hydrazine
Received: 29 January 2018
Revised: 8 April 2018
Accepted: 26 April 2018
R E V I E W
Recent progress in the development of fluorescent probes for
hydrazine
Khac Hong Nguyen1 Yuanqiang Hao2 Wansong Chen1 Yintang Zhang2 Maotian Xu2
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Minghui Yang1 You‐Nian Liu1
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1College of Chemistry and Chemical
Abstract
Engineering, Central South University,
Changsha, Hunan Province, P. R. China
Hydrazine (N2H4) is an important and commonly used chemical reagent for the prep-
aration of textile dyes, pharmaceuticals, pesticides and so on. Despite its widespread
industrial applications, hydrazine is highly toxic and exposure to this chemical can
cause many symptoms and severe damage to the liver, kidneys, and central nervous
system. As a consequence, many efforts have been devoted to the development of
fluorescent probes for the selective sensing and/or imaging of N2H4. Although great
efforts have been devoted in this area, the large number of important recent studies
have not yet been systematically discussed in a review format so far. In this review,
we have summarized the recently reported fluorescent N2H4 probes, which are clas-
sified into several categories on the basis of the recognition moieties. Moreover, the
sensing mechanism and probes designing strategy are also comprehensively discussed
on aspects of the unique chemical characteristics of N2H4 and the structures and
spectral properties of fluorophores.
2 Henan Key Laboratory of Biomolecular
Recognition and Sensing, College of Chemistry
and Chemical Engineering, Shangqiu Normal
University, Shangqiu, Henan Province, P. R.
China
Correspondence
Yuanqiang Hao, Henan Key Laboratory of
Biomolecular Recognition and Sensing,
College of Chemistry and Chemical
Engineering, Shangqiu Normal University,
Shangqiu, Henan Province, 476000, P. R.
China.
Email: hao0736@163.com
You‐Nian Liu, College of Chemistry and
Chemical Engineering, Central South
University, Changsha, Hunan Province,
410083, P. R. China.
Email: liuyounian@csu.edu.cn
KEYWORDS
Funding information
fluorescent probes, hydrazine, review
National Natural Science Foundation of China,
Grant/Award Numbers: 21476266,
21475084, 21505091, U1404215 and
B061201; Innovation Scientists and Techni-
cians Troop Construction Projects of Henan
Province, Grant/Award Number: 41
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1
INTRODUCTION
in rocket fuel due to its high heat of combustion and since large vol-
umes of hot gas are generated during its decomposition.
Hydrazine, coined by Emil Fischer in 1875, is an inorganic compound
[1]
Ascribed to its other unique properties, including nucleophility,
reductibility and double nucleophilic character, hydrazine also can be
utilized as an important reactant for many chemical products, including
textile dyes, pharmaceuticals and pesticides.[2–5] Despite its wide-
spread industrial applications, hydrazine is highly toxic. Exposure to
hydrazine may cause symptoms of irritation of the eyes, nose, and
throat, dizziness, headache, nausea, pulmonary edema, seizures, coma
in humans, as well as damage to the liver, kidneys and the central ner-
vous system.[6,7] The US Environmental Protection Agency (EPA) iden-
tified hydrazine as a potential carcinogen with a threshold limit of
10 ppb.[8] Thus, it is highly desirable to develop selective and sensitive
assays for the detection of trace hydrazine. Several traditional analyt-
with the chemical formula N2H4. Hydrazine can also be written as
H2NNH2, called diamidogen, therefore it has basic (alkali) chemical
properties (Kb = 1.3 × 10−6) like ammonia. At ambient conditions,
hydrazine is a colourless fuming liquid with a faint ammonia‐like
odour. Since the by‐products are typically nitrogen gas and water,
hydrazine often acts as a convenient reductant such as antioxidant,
oxygen scavenger and corrosion inhibitor. Additionally, hydrazine is
also used as a propellant in space vehicles or used as a component
Abbreviations used: AIE, aggregation‐induced emission; DMSO, dimethyl
sulfoxide; LOD, limit of detection; N2H4, hydrazine; NIR, near‐infrared; PBS,
phosphate‐buffered saline; TICT, twisted‐intramolecular charge transfer; TPE,
tetraphenylethylene.
ical
techniques,
including
titrimetry,[9]
voltammetry,[10–12]
Luminescence. 2018;1–21.
Copyright © 2018 John Wiley & Sons, Ltd.
1
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NGUYEN ET AL.
chromatography,[13,14] and chemiluminescence[15] have been widely
used for hydrazine detection. However, most of these approaches
have major disadvantages associated with the need for sophisticated
instrumentation and time‐consuming manipulations, and the inability
to be miniaturized for in situ and in vivo studies.
and selectivity. The topics of this review are classified into several cat-
egories based on the different sensing mechanisms and recognizing
moieties of these probes for hydrazine, including probes based on ace-
tyl, 4‐bromobutyryl, vinyl malononitrile, phthalimide, β‐diketone,
levulinate and other moieties.
Alternatively, analytical techniques based on fluorescence sensor
systems are very popular because fluorescence measurements are
usually easy to perform, inexpensive, very sensitive (parts per billion/
trillion) with detection limits as low as sub‐parts‐per million, and able
to be employed for in situ and in vivo monitoring.[16–22] Hydrazine
can act as a good nucleophile for a variety of transformations in syn-
thetic chemistry, such as hydrazone formation, Wolff–Kishner reduc-
tion, heterocyclic chemistry, deprotection of phthalimides and so on.
Recently, these characters of hydrazine have provide a starting point
for the development of a large number of efficient fluorescent hydra-
zine probes (Figure 1). Although great efforts have been devoted in
this area, a large number of important recent studies have not yet
been systematically discussed in a review format to the best of our
knowledge. Herein, we make such an effort to summarize the rapid
progress in the development of fluorescent hydrazine probes and
highlight a variety of inventive strategies to achieve good reactivity
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2
PROBES BASED ON ACETYL MOIETY
Phenol acetate can be readily hydrazinolyzed by hydrazine to generate
its phenolic analogue (Figure 2). Based on this reaction, several probes
containing phenol acetate moieties have been developed for sensing
of hydrazine. Chang and co‐workers developed two phenylacetate‐
based fluorescent probes (1 and 2) for hydrazine detection by incorpo-
rating acetate group onto dichlorofluorescein and resorufin
fluorophore scaffolds, respectively (Figure 3).[23] In a mixture of
dimethyl sulfoxide (DMSO) and Tris buffer solution (pH 8.0, 10 mM,
1:1, v/v), probe 1 is colourless and non‐fluorescent. Treating the probe
solution with 100 equivalents of hydrazine creates a strong absorption
band at 512 nm with a corresponding colour change from colourless
to greenish yellow and a prominent green emission at 534 nm, which
FIGURE 1 Fluorescent hydrazine (N2H4)
probes based on different reaction
mechanisms
FIGURE 2 Proposed sensing mechanism of
probe for hydrazine (N2H4) based on
hydrazinolysis of phenol acetate
NGUYEN ET AL.
3
increase with the concentration of hydrazine in the range
10–80 μM. And the LOD of 3 for hydrazine was determined to
be 2.5 × 10−8 M. Moreover, the probe was successfully utilized
for imaging hydrazine in living MCF‐7 cell line and visualizing
hydrazine in mice (Figure 4B).
Pang and co‐workers designed a ESIPT (excited state intramo-
lecular proton transfer) probe 4 by masking the phenol group of
flavonoid with the ethyl ester (Figure 5).[25] Hydrazine can selec-
tively remove the ester protection group, leading to the recovery
of flavonoid ESIPT. Addition of 20 equivalents of hydrazine to the
probe solution causes a large fluorescence enhancement, giving
intense green fluorescence, which increases by about eight‐fold.
Under optimized conditions, the fluorescence intensity of the probe
solution was nearly proportional to the hydrazine concentration
range from 0 to 50 μM with a calculated LOD of 1.0 × 10−5 M.
The probe was also successfully used for monitoring hydrazine in
live cells and zebrafish.
FIGURE
hydrazine
3
Structures and reactions of probes 1 and 2 with
are the characteristic spectral features of free dichlorofluorescein.
Hydrazinolysis of probe 2 also causes evident chromogenic and fluo-
rescent turn‐on type signals. Both 1 and 2 exhibit excellent selectiv-
ities for hydrazine with limits of detection (LODs) of 9.0 × 10−8
and 8.2 × 10−8 M, respectively, which is sensitive enough for industrial
M
chemical detection.
Sun et al. developed a ratiometric fluorescent hydrazine probe 5
(Figure 6)[26] by incorporating an acetate moiety onto naphthalimide,
a widely used scaffold for the construction of fluorescent probes.[27,28]
Probe 5 displayed a fluorescence maximum at 432 nm. Upon addition
Peng and co‐workers reported
a NIR (near‐infared region)
ratiometric fluorescent probe (3) for hydrazine based on
a
heptamethine cyanine dye derivative (Figure 4).[24] In the presence
of hydrazine in a mixture of acetate buffer (pH 4.5, 10 mM) and
DMSO (1:9, v/v), 3 undergoes a hydrazinolysis process to release
enol form, which further transforms it into its corresponding ketone
form, leading to large hypsochromic shifts in both absorption
and emission maxima. Specifically, the colour of the solution
changes from cyan (784 nm) to pink (520 nm), and the emission
band shifts from 810 nm to 582 nm. The fluorescence intensity
ratio at 582 and 810 nm (I582/I810
)
was found to linearly
FIGURE 5 Structure and reaction of probe 4 with hydrazine
FIGURE 4 (A) Structure and reaction of probe 3 with hydrazine. (B) In vivo images of a mouse given a skin‐popping injection of probe 3 and a
subsequent skin‐popping injection of hydrazine with the effect over different time intervals. The top images were taken with an excitation laser of
740 nm and an emission filter of 820 20 nm, and the bottom ones were taken with an excitation laser of 480 nm and an emission filter of
600 20 nm. (Reprinted from ref. 24)
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NGUYEN ET AL.
FIGURE 6 (A) Structure and reaction of probe 5 with hydrazine. (B) Fluorescence images of 7860 cells, (a–c) cells incubated with 5; (d–f) cells
treated with 5 and hydrazine. (a, d) Bright‐field images, (b, e) blue channel, (c, f) green channel. (Reprinted from ref. 26)
of hydrazine, the emission intensity at 432 nm decreased gradually
with the simultaneous appearance of a new red‐shifted emission band
centred at 543 nm, affording the ratiometric detection. The emission
intensity ratio (I543/I432) showed a good linearity against the hydrazine
concentration in the range 0–10 μM, with a LOD of 2.1 × 10−8 M.
Probe 5 has also been applied to image hydrazine in living cells
(Figure 6B).
highly fluorescent moiety. The fluorescence increase at 680 nm is
directly proportional to the hydrazine concentration from to
40 μM with a LOD of 5.7 × 10−7 M. Obviously, the response time of
7 toward hydrazine is about 1 min, and the probe is also capable
of visualizing hydrazine in MCF‐7 cells by two‐photon microscopy
(TPM) imaging (Figure 8B).
0
Yin and co‐workers recently reported a ratiometric fluorescent
hydrazine probe 8 by incorporating an acetate moiety to a coumarin
derivative (Figure 9).[33] Noticeably, this probe displayed a different rec-
ognition mechanism for hydrazine, in which the carbanyl group of the
probe reacts with hydrazine affording a Schiff‐base intermediate and
further forming a stable heterocyclic structure. The probe exhibited a
high sensitivity for hydrazine with a linear response range 0–10 μM.
Cell imaging experiments also demonstrated the capacity of probe 8
for monitoring hydrazine in live samples.
Compound 6 was reported as a NIR and turn‐on fluorescent
probe for hydrazine detection (Figure 7).[29] Reaction of the probe
with hydrazine removes the acetate moiety, producing the highly
fluorescent NIR hemicyanine fluorophore. In vitro experiments
showed that a linear correlation existed between the fluorescence
response and the concentration of the hydrazine in the range
0–50 μM, with a LOD of 1.9 × 10−7 M. Furthermore, the probe is
capable of imaging hydrazine not only in living cells but also in living
mice due to its efficient NIR emission, a critical feature for application
in bioimaging.[30,31]
Incorporation of the acetate moiety onto a variety of other
fluorophore scaffolds has afforded probes in a range of colour.
Reports of hydrazine based on coumarin and its derivatives
(9–11),[34–36] fluorescein (12),[37] 1,4‐dihydroxyanthraquinone (13),[38]
Peng and co‐workers developed a two‐photon NIR fluorescent
probe 7 for the detection of hydrazine (Figure 8).[32] The probe has
an acetate moiety as the reaction site for hydrazine and a 2‐(2‐(4‐
hydroxystyryl)‐4H‐chromen‐4‐ylidene) malononitrile complex as the
fluorescent reporter unit. The non‐fluorescent 7 reacts with hydrazine
leading to the removal of an acetate group and the release of the
1,8‐naphthalimide
(14),[39]
benzthiazole
(15),[40]
the
dicyanomethylenedihydrofuran scaffold (16)[41,42] and rhodamine
derivative (17)[43] have been described. The structures of these fluo-
rescent hydrazine probes are summarized in Figure 10. However, it
FIGURE 7 Structure and reaction of probe 6
with hydrazine
NGUYEN ET AL.
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FIGURE 8 (A) Structure and reaction of probe 7 with hydrazine. (B) Confocal microscope images of MCF‐7 cells. (a–c) cells treated with 7; (d–i)
cells treated with hydrazine and subsequent treatment of the cells with 7; (d–f) OPM image of cells upon excitation at 560 nm, emission window
650–750 nm; (g–i), TPM image of cells upon excitation at 820 nm, emission window 575–630 nm. (Reprinted from ref. 32)
FIGURE 9 Structure and reaction of probe 8
with hydrazine
should be pointed out that, the acetyl group located on the aromatic
anions. Thus, fluorescent probes with excellent selectivity for
hydrazine would be afforded by taking advantage of this special reac-
tivity. For exploiting the double nucleophilic ability of hydrazine, a
4‐bromo butyrate group has been employed as the reaction moiety
for the design of hydrazine probes. This type of fluorescent probe is
normally prepared via the incorporation of 4‐bromo butyrate onto a
phenolic‐containing fluorophore. The sensing process involves
two steps (Figure 11), hydrazine first nucleophilically substitutes
bromine atom and then performs a nucleophilic attack on the ester
carbonyl, followed by intramolecular cyclization to release the
fluorophore.
−
phenol is also a reaction site for BO3 anion, and several fluorescent
−
probes have been develop for BO3 ions based on the acetyl
recognition moiety,[44–47] indicating that BO3 may interfere with
−
the hydrazine detection by using this type of probe.
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PROBES BASED ON 4‐BROMOBUTYRYL
MOIETY
Hydrazine, also written as H2NNH2, can actually be regarded as a
simple molecule consisted of two amino groups, which implies that it
can perform two consecutive nucleophilic reactions. This double
nucleophilic character is unique to hydrazine over other amines and
Goswami et al. firstly developed a fluorescent hydrazine probe (18)
employing 4‐bromo butyrate as the reaction moiety (Figure 12).[48]
The probe is designed in such a way that ESIPT of the HBT
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NGUYEN ET AL.
FIGURE 10 Structures of fluorescent hydrazine probes 9–17 with an acetate moiety
FIGURE 11 Proposed sensing mechanism of 4‐bromobutyryl‐based probes for hydrazine
(2‐(2'‐hydroxyphenyl)benzothiazole) moiety gets blocked by the
substituted 4‐bromo butyrate group. The presence of hydrazine can
result in the release of the HBT moiety as well as the recovery of the
ESIPT of fluorophore through subsequent substitution, cyclization
and elimination processes. Moreover, live‐cell imaging experiments
establish the utility of this probe for tracking hydrazine in live cells.
Incorporation of a 4‐bromo butyrate moiety onto a resorufin
fluorophore afforded a turn‐on fluorescent probe (19) for N2H4
(Figure 13).[49] Reaction of the probe with hydrazine in a HEPES buffer
(10 mM, pH 7.4, containing 10% acetonitrile (CH3CN)) leads to the
release of fluorescent resorufin. The fluorescence increase is directly
proportional to the hydrazine concentration in the range 10–200 μM
with a LOD of about 2 × 10−6 M. The dramatic colour change of
the probe solution from colourless to red upon the treatment with
hydrazine demonstrated that 19 can serve as a ‘naked‐eye’ probe for
hydrazine. Probe 19 also has been applied to image hydrazine in living
cells (Figure 13B).
Recently, our group reported a ratiometric fluorescent hydrazine
probe (20) based on the 1,8‐naphthalimide fluorophore (Figure 14).
[50]
The probe operates by hydrazine‐mediated removal of the
4‐bromo butyrate moiety via a substitution‐cyclization‐elimination
process to liberate the 1,8‐naphthalimide moiety. Upon the treatment
with hydrazine, the probe solution displayed a bathochromic shift in
emission from 420 to 550 nm. The emission intensity ratio (I550/I420
)
is found to be proportional to the concentration of hydrazine in the
range 1.0–30.0 μM with a LOD of 2.7 × 10−7 M. Moreover, the probe
has been utilized for practical detection of gaseous hydrazine, as well
as imaging hydrazine in live cells.
Lu and co‐workers developed a NIR ratiometric fluorescent probe (21)
(Figure 15) for hydrazine detection.[51] Addition of hydrazine to a
solution of 21 in DMSO–H2O (1:4, v/v, phosphate‐buffered saline
(PBS) 20 mM, pH 7.4) induced a significant hypsochromic shift of
the emission maximum from 810 to 627 nm. The probe displayed high
sensitivity (LOD = 1.2 × 10−8 M) and excellent selectivity over other
interfering analytes. Furthermore, the probe is capable of imaging
exogenous hydrazine not only in living cells but also in living mice
(Figure 15B).
Installation of
a 4‐bromo butyrate moiety onto different
fluorophores has afforded a series of fluorescent hydrazine probes in
a variety of colours (Figure 16). Based‐on fluorescein, Goswami et al.
reported
a
‘turn on’ fluorescent probe (22).[52] By utilizing
FIGURE 12 Structure and reaction of probe 18 with hydrazine
NGUYEN ET AL.
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FIGURE 13 (A) Structure and reaction of probe 19 with hydrazine. (B) Confocal fluorescence images of Chinese hamster ovary (CHO) cells: cells
incubated with 19 (a–c); image of cells after treatment with 19 and subsequent treatment of the cells with hydrazine for (e–g). (a and e) Bright‐field
images; (b and f) red channel; (c and g) merged images. (Reprinted from ref. 49)
FIGURE 14 Structure and reaction of probe
20 with hydrazine
FIGURE 15 (A) Structure and reaction of probe 21 with hydrazine. (B) Representative fluorescence images of the mice that were pre‐treated
with 21 and subsequently incubated with hydrazine. Images were taken after incubation of hydrazine for 0, 3, 6, and 10 min. (Reprinted from
ref. 51)
dicyanomethylenedihydrofuran scaffold, Li and co‐workers prepared a
far‐red fluorescent hydrazine probe (23).[53] Zhu and co‐workers
developed two flavonoid‐based fluorescent hydrazine sensors (24
and 25),[54,55] and both of them have been applied to the detection
of hydrazine in living cells. Chen et al. reported a highly sensitive fluo-
rescent turn‐on probe (26) for hydrazine based on a coumarin
fluorophore.[56] Using the similar strategy, a new ESIPT hydrazine
probe (27) was also developed. It displayed good water solubility and
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NGUYEN ET AL.
FIGURE 16 Structures of fluorescent hydrazine probes 22–28 with a 4‐bromo butyrate moiety
can be performed in a PBS buffer (pH 7.4) solution with 1% etha-
nol.[57] Lu et al. reported a NIR fluorescent probe (28) for hydrazine
by using a hemicyanine dye.[58]
hydrazone. The probe displays a dynamic range of 5.0 to 20.0 μM
for hydrazine with a LOD of 1.2 × 10−8 M. Moreover, the probe has
an excellent biocompatibility, and has been successfully applied to
visualize hydrazine in live cells and zabrafish.
Kumar et al. reported a N,N‐dimethylaminocinnamaldehyde‐based
ICT fluorescent probe (31) (Figure 20) for the ratiometirc detection of
hydrazine.[62] Due to the efficient ICT from electron‐donating
dimethylamino group to the electron‐withdrawing cyano groups,
probe 31 exhibits an emission in the red region. The addition of hydra-
zine to the solution of 31 in HEPES buffer–CH3CN (10 mM, pH 7.2,
99.5/0.5, v/v), the emission band at 582 nm shifts to 480 nm due to
the conversion of cyano groups to hydrazone and the consequent
inhibition of the ICT process within the probe molecule. The probe
displays an ultralow LOD of 8.87 × 10−9 M. Furthermore, the
probe has been applied for intracellular imaging of hydrazine and
the preparation of fluorescent test strips to detecting trace level of
hydrazine in water.
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PROBES BASED ON VINYL
MALONONITRILE
Previous studies have demonstrated that arylidene malononitrile can
selectively react with hydrazine to yield a product of hydrazone
(Figure 17).[59] This specific reactivity of hydrazine combined with
the synthetic ease of incorporating malononitrile onto fluorophores
possessing a vinyl aldehyde or benzaldehyde moiety has led to rapid
progress in the development of fluorescent hydrazine probes. The first
fluorescent probe (29) based on this approach was developed by Peng
and co‐workers (Figure 18).[60] Probe 29 displays a strong emission
with a maximum in the red region around 640 nm due to the intramo-
lecular charge transfer (ICT) process from the 7‐N,N‐diethyl group to
the electron‐withdrawing vinyl malononitrile through a π‐conjugated
system. Upon reacting with hydrazine, the vinyl malononitrile can be
converted to hydrazone, which inhibits the ICT process within the
probe and thus leads to ratiometric responses both in absorption
and fluorescence signals. In addition, this ICT‐based ratiometric probe
is exploited to image hydrazine in living cells (Figure 18B).
Incorporating dicyanovinyl group to derivated tetraphenylethylene
(TPE) moieties, Liu and co‐workers devised a series of aggregation‐
induced emission (AIE) probes (32–34)[63] (Figure 21) for both fluores-
cence and colourimetric detection of hydrazine in solution as well as in
solid state based on the probe‐stained paper strips. These probes were
designed on the basis of the different electron‐donating abilities of the
substituent groups. Introducing the electron‐donating groups, such as
methoxyl and N,N‐dimethylamino, into the TPE structure, the yielded
probes (33 and 34) feature a more red‐shifted absorption and emission
in the visible region due to the enhanced ICT system. Thus, probe 34
gives the best response to hydrazine, and 34‐stained paper strip can
achieve sensing low‐level hydrazine vapour.
The malononitrile trigger has been incorporated onto a phenothi-
azine dye by Yang and co‐workers to give a fluorescent hydrazine
probe (30) (Figure 19).[61] Upon reaction with hydrazine in DMF–Tris
buffer (10 mM, pH 7.4, 7:3, v/v), the probe exhibits a distinct turn‐
on fluorescence response at 490 nm, which can be ascribed to the
change in electronic structure of the probe due to the formation of
The vinyl malononitrile as the recognition moiety has also expanded
to develop family fluorescent hydrazine probes by using various
fluorophore scaffolds or their derivatives, including benzothiazole (35),[64]
carbazole (36),[65] acenaphthequinone (37),[66] anthraldehyde (38),[67]
pydazoline (39),[68] naphthaoxazole (40),[69] formylated benzothiazole
(41)[70] and dicyanomethylene‐4H‐chromene (42)[71] (Figure 22).
Besides vinyl malononitrile, some other electron‐deficient alkene
structures also can react with hydrazine to form the hydrazone via a
similar mechanism. Based on this type of reaction, several new
FIGURE 17 Proposed sensing mechanism of vinyl malononitrile‐
based probe for hydrazine
NGUYEN ET AL.
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FIGURE 18 (A) Structure and reaction of probe 29 with hydrazine. (B) Confocal fluorescence images of HeLa cells. Cells incubated with 29 (top);
image of cells after treatment with 29 and subsequent treatment of the cells with hydrazine. (a, d) Bright‐field images; (b, e) green emission
(540 20 nm); and (c, f) red emission (640 20 nm). (Reprinted from ref. 60)
fluorescent hydrazine probes have been reported recently (Figure 23).
Two probes (43 and 44)[72,73] based on a recognition unit of 2‐cyano-
acrylate have been designed by using two different signalling
moieties, pyridomethene and phenanthroimidazole. Compound
(45)[74] was synthesized as a colorimetric and fluorogenic probe for
hydrazine detection based on the degradation of π‐conjugated
system of the probe triggered by hydrazine. By utilizing
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5
PROBES BASED ON PHTHALIMIDE
MOIETY
Gabriel synthesis, named after the German chemist Siegmund Gabriel,
is a classical approach for the preparation of primary amines, specifi-
cally transforming alkyl halides into primary amines. Traditionally, this
reaction involves the N‐alkylation of phthalimide by a target primary
alkyl halide, followed by hydrazine‐mediated cleavage of the phthaloyl
group to liberate the primary amines. This strategies involved in
Gabriel synthesis has been successfully adapted for the development
of fluorescent hydrazine probes, typically by incorporating phthalimide
into amine‐containing fluorophores (Figure 24). The first two
phthalimide‐based fluorescent hydrazine probes (49 and 50) were
reported simultaneously by Lin, Cui and their co‐workers by using
4‐aminonaphthalimide as the fluorescent reporters (Figure 25).[78,79]
In a mixture of PBS buffer (10 mM, pH = 7.2) and ethanol (1:9, v/v),
probe 49 exhibits a UV–vis absorption band and a fluorescence
emission band at 344 and 467 nm, respectively. Upon reaction
with hydrazine, the phthalimide group was cleaved, the released
4‐aminonaphthalimide displays a yellow colour (λabs = 467) and emits
yellowish‐green fluorescence (λem = 528). The probe demonstrates
an ultralow LOD of 4.2 × 10−9 M, and is capable of imaging intracellu-
lar hydrazine. Probe 50 exhibits similar highly specific ratiometric
response for hydrazine over other primary amines.
2‐benzothiazoleacetonitrile as
a new recognition site, Lin and
co‐workers reported a turn‐on two‐photon fluorescent hydrazine
probe (46).[75] By conjugating hemicyanine to a coumarin fluorophore,
Ni and co‐workers developed
a NIR‐emissive (λex = 580 nm,
λem = 660 nm) hydrazine selective probe (47).[76] Reaction of 47 with
hydrazine gives a coumarin hydrazone derivative and a corresponding
blue‐shift emission, and thus a ratiometric fluorescence response is
achieved. Based on a similar hemicyanine linked electron‐deficient
alkene structure, Ban et al. synthesized a mitochondria‐targeted
ratiometric fluorescent hydrazine probe (48).[77]
FIGURE 19 Structure and reaction of probe 30 with hydrazine
FIGURE 20 Structure and reaction of probe
31 with hydrazine
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NGUYEN ET AL.
DMSO (1/9, v/v), the probe only shows extremely weak fluorescence
at 475 nm (ɸ = 0.093), and addition of hydrazine leads to a ‘switched
on’ emission (ɸ = 0.4983) with a bathochromic shift to 512 nm.
The probe has also successfully exploited to detect gaseous and intra-
cellular hydrazine.
Notably, Cui et al. reported a multi‐responsive optical probe (52)
for the specific detection of hydrazine (Figure 27).[81] On the basis
of a Gabriel‐type reaction, hydrazinolysis of 52 can produce 7‐
amino‐4‐methylcoumarin as a chromogenic and fluorogenic reporter,
and luminol as a chemiluminescence probe. The ratiometric fluores-
cence response of the probe 52 toward hydrazine is highly selective
over other interfering substances, with a linear dynamic range of 0.1
to 1.0 μM and a LOD of 1 × 10−7 M. The probe is also used to detect
hydrazine in vapour state. Furthermore, the probe has also been
applied for the detection of hydrazine in HeLa cells (Figure 27B).
FIGURE 21 Structures and reactions of probes 32–34 with
hydrazine
By installing phthalimide onto the dansyl fluorophore, Zhao and
co‐workers synthesized a turn‐on fluorescent hydrazine probe (51)
(Figure 26).[80] In a solution of HEPES buffer (pH 7.0, 20 mM) and
FIGURE 22 Structures of fluorescent hydrazine probes 35–42 with a malononitrile moiety
FIGURE 23 Structures of fluorescent hydrazine probes 43–48 possessing electron‐deficient alkene structure
FIGURE 24 Proposed sensing mechanism of
phthalimide‐based probe for hydrazine
NGUYEN ET AL.
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6
PROBES BASED ON Β‐DIKETONE
MOIETY
The reaction of amine with carbonyl compound is a well precedent
synthetic route to prepare the corresponding Schiff base. As expected,
hydrazine, which possesses two amine groups, can react with the
β‐diketone derivatives leading to the formation of five‐membered het-
erocyclic species (Figure 30). It is worth noting that the adjacent
attachment of a strong electron acceptor, such as CF3, to the ketone
group would result in an increase of the reaction kinetics. On the basis
of the earlier reaction, Kim, Sessler and co‐workers first reported a
trifluoroacetyl acetonate‐based fluorescent hydrazine probe (60) by
using naphthalimide as the fluorophore (Figure 31).[88] In CH3CN solu-
tion, probe 60 can selectively react with hydrazine to give a five‐mem-
bered ring, and thus resulting in a turn‐on fluorescence response with
a maximum intensity at 532 nm. The LOD of 60 for hydrazine was
found to be 9.9 × 10−8 M. Moreover, by loading on a silica gel thin‐
layer chromatography (TLC) plate, 60 can act as both fluorimetric
and colorimetric probe for detecting hydrazine vapour (Figure 31B).
Goswami et al. designed a coumarin‐based ratiometric fluorescent
probe 61 for hydrazine (Figure 32).[89] The addition of hydrazine to a
solution of 61 in CH3CN can promote selective hydrazinolysis at
the carbonyl group of trifluoroacetyl acetonate moiety of the probe
followed by cyclization to give a new species. The absorption band
of the probe changes from 485 to 445 nm, and the emission band
shifts from 545 to 500 nm. These spectral changes upon the addition
of hydrazine can be easily observed by the naked eye. Two similar
coumarin‐based fluorescent probes were also reported for the detec-
tion of hydrazine.[90,91]
FIGURE 25 Structures and reactions of probes 49 and 50 with
hydrazine
FIGURE 26 Structure and reaction of probe 51 with hydrazine
Das and co‐workers reported a fluorescent hydrazine probe (53)
based on phenanthroimidazole fluorophore (Figure 28).[82] The probe
exhibits high selectivity toward hydrazine in the presence of several
other competing amine derivatives, and has been applied for real time
detection of in situ generated hydrazine during the metabolism of
isoniazid (a crucial tuberculosis drug) in living cells. Moreover, based
on 53, an in vitro assay for aminoacylase‐1 has also been developed.
Based on the recognition moiety of phthalimide and the sensing
mechanism adapted from Gabriel reaction, several other fluorescent
hydrazine probes have been designed by using several other
fluorophore scaffolds (Figure 29) including pyrazoline (54),[83]
benzothiadiazole (55),[84] BODIPY (56, 57),[85] 4‐hydrazine‐
naphthalimides (58),[86] and fluorescein (59).[87]
Goswami et al. prepared a fluorescent hydrazine probe (62) by the
condensation of 2‐hydroxy‐1‐naphthaldehyde dye and acetyl acetone
(Figure 33).[92] The fluorescence of the probe was quenched due to
FIGURE 27 (A) Structure and reaction of probe 52 with hydrazine. (B) Fluorescence images of HeLa cells in the presence of 52 before (a–c) and
after (d–f) loading with hydrazine. (Reprinted from ref. 81)
12
NGUYEN ET AL.
FIGURE 28 Structure and reaction of probe
53 with hydrazine
FIGURE 29 Structures of fluorescent
hydrazine probes 54–59 with a phthalimide
moiety
FIGURE 30 Proposed sensing mechanisms of β‐diketone‐based probes for hydrazine
FIGURE 31 (A) Structure and reaction of probe 60 with hydrazine. (B) Confocal microscopic images of HeLa cells treated with 60. Cells were
incubated with 60 and separately incubated with media containing hydrazine (0, 0.1, 0.5 and 1.0 mM). Fluorescence images were obtained
using a two‐photon excitation wavelength of 740 nm and emission wavelengths of 400 to 600 nm. (Reprinted from ref. 88)
masked –OH group in the hemiketal form and the resulted inhibition
of the ICT process. The reaction of 62 with hydrazine leads to the
opening of the chromenyl derivative and the consequent formation
of a hydroxyl group and a pyrazole moiety. Thus, an ICT process from
the electron‐donating hydroxyl group to the electron‐withdrawing
pyrazole moiety group occurs in the resulting compound, leading to
the appearance of a strong blue emission. The probe shows very fast
(<30 s) and highly sensitive (LOD = 6.8 × 10−9 M) fluorescence
responses towards hydrazine, and also has been used for the detec-
tion of hydrazine in human lung cancer cells.
NGUYEN ET AL.
13
FIGURE 32 Structure and reaction of probe
61 with hydrazine
and co‐workers first reported a fluorescent probe (65) for hydrazine
by coupling levulinyl chloride with 3‐cyano‐7‐hydroxycoumarin
(Figure 36).[96] The treatment of probe 65 with hydrazine in a mixture
of acetate buffer (pH 4.5, 10 mM) and DMSO (3:7, v/v), lead to a dra-
matic fluorescence enhancement at 458 nm, which was attributed to
the hydrazine‐mediated deprotection of the levulinate group and the
subsequent release of fluorescent coumarin derivative. The probe dis-
plays high selectivity toward hydrazine with a LOD of 2.45 × 10−6 M.
Lin and co‐workers developed a NIR fluorescent hydrazine probe
(66) by incorporating levulinate to a HD NIR dye (Figure 37).[97] In a
solution of HEPES/CH3CN (pH 7.4, 7:3, v/v), the probe is almost
non‐fluorescent when excited at 670 nm, but exhibits significant
fluorescence enhancement at 725 nm upon addition of hydrazine,
FIGURE 33 Structure and reaction of probe 62 with hydrazine
Recently, Bandyopadhyay and co‐workers developed a pair of
pyrene‐ and anthracene‐based turn‐on fluorescent probes (63 and
64) for hydrazine (Figure 34).[93] These two probes can be easily
obtained in a single‐step process by condensing acetylacetone with
1‐pyrenecarboxaldehyde and 9‐anthraldehyde, respectively. Reaction
of each probe with hydrazine can lead to the formation of a five‐mem-
bered cyclic intermediate, which then undergoes a dehydration pro-
cess to generate a fluorescent product. As a result, 83‐ and 173‐fold
increases in emission intensity were observed for 63 and 64, respec-
tively. And this turn‐on fluorescence response was not affected by
pH over a wide range 3.86–10.10. Both of these two probes were
successfully applied to visualize hydrazine in olive fruit fly.
accompanied by
a bathochromic absorption shift from 582 to
679 nm. The probe displays excellent selectivity for hydrazine over
other species, and shows a stable fluorescence response over a
wide pH range 4–9. As both excitation and emission bands of the
probe are located in the NIR region, 66 allows for ready imaging of
hydrazine in living cellular systems (Figure 37B).
Mahapatra et al. synthesized a BODIPY‐pyrene conjugate (67) via
a levulinate linkage, which can serve as a turn‐off fluorescent probe
for hydrazine (Figure 38).[98] Hydrazine‐mediated hydrazinolysis of
67 can lead to the formation of a meso‐phenyl BODIPY and a pyrene
derivative. Both of these two products are non‐emissive due to the
photoinduced electron transfer (PET) processes. In H2O–DMSO (3:7,
v/v) solution (10 mM HEPES buffer, pH 7.4), 67 displays high selectiv-
ity for hydrazine over other species with a LOD of 1.87 × 10−6 M.
Moreover, the probe can be used to detect vapour hydrazine by coat-
ing on TLC silica gels, and visualize hydrazine in living cells.
|
7
PROBES BASED ON LEVULINATE
MOIETY
Levulinoyl ester moiety has often been employed as a protecting
group for phenolic hydroxyl group in organic synthesis, and can be
readily cleaved by certain nucleophilic reagents.[94,95] This
deprotection reaction also exploited the double nucleophilic character
of hydrazine, and thus can be adapted to the design of fluorescent
hydrazine probes with high selectivity. The carbonyl group at the
4‐position of the levulinate group serves as the initial nucleophilic
reaction site. The resulting hydrazone can subsequently perform
intramolecular attack on the ester carbonyl leading to cleavage of
the ester function (Figure 35). On the basis of this strategy, Chang
A ratiometric two‐photon fluorescent probe (68) for hydrazine
was devised by Meng and co‐workers (Figure 39).[99] The hydrazine‐
promoted deprotection of the levulinate moiety can enhance the ICT
process of the probe system, and lead to a red shift in fluorescence
emission from 414 to 460 nm, thus achieving a ratiometric response
for hydrazine. The probe also exhibits an increase in two‐photon
FIGURE 34 Structures and reactions of
probes 63 and 64 with hydrazine
FIGURE 35 Proposed sensing mechanism of
levulinate‐based probe for hydrazine
14
NGUYEN ET AL.
terminal pyridyl nitrogen atoms to C=N groups. Upon the addition
of hydrazine, all nitrogen atoms within the probe molecule can form
hydrogen‐bonds with hydrogen atoms of hydrazine, which can
impede the PET process and result in a significant enhancement in
fluorescence intensity. And the spectral response of 69 for hydrazine
can be achieved within 10 s.
FIGURE 36 Structure and reaction of probe 65 with hydrazine
absorption cross‐section upon the addition of hydrazine (from 250 to
494 GM). Due the large two‐photon absorption cross‐sections, the
probe can be also successfully used for the ratiometric two‐photon
fluorescent imaging of hydrazine in living cells.
Das and co‐workers prepared a rhodamine‐cyanobenzene
conjugate (70) for both colorimetric and fluorimetric detection of
hydrazine (Figure 40).[103] Hydrazine was speculated to form a
hydrogen bonded dimer with 70 affording an electron deficient
C=N bond, which may promote the hydrolysis of the probe 70.
The released rhodamine derivative further undergoes a spirolactam
ring‐opening process, thus achieving a turn‐on fluorescence response
to hydrazine. Probe 70 reveals a high sensitivity with a LOD of
5.8 × 10−8 M and is also used for the detection of intracellular
hydrazine.
|
8
PROBES BASED ON HYDROGEN‐BOND
FORMATION ABILITY AND/OR
REDUCIBILITY CHARACTER OF HYDRAZINE
Hydrogen‐bond formation ability is very important in many chemical
reactions, and has also been extensively exploited for the construc-
tion of various fluorescent probes for the recognition of anions,
including F−, CN−, AcO− and H2PO4−.[100,101] Hydrazine contains
two amino groups, as such hydrazine can readily form extended
arrays of hydrogen bonding (NH···O and/or NH···N) with compound
possessing several electronegative atoms (such as N and O), which
may perturb the electronic properties of the interacted compound
and in turn lead to a change in the spectral profile. On the basis of
this concept, Patra and co‐workers developed a Schiff‐base derivative
(69) as a turn‐on fluorescent probe for hydrazine (Figure 40).[102]
Probe 69 is weakly fluorescent due to the PET process from the
By exploiting the ability of hydrazine to form intermolecular
hydrogen bonds as well as its reducibility character, Sun and co‐
workers developed a turn‐on fluorescence assay for the detection
of hydrazine using
a
naphthalenediimide‐based probe (71)
(Figure 41).[104] In DMSO, probe 71 is weakly fluorescent due to
the twisted‐intramolecular charge transfer (TICT) quenching. The
introduced hydrazine can lead to the generation of hydrazone and
quinone structures within the probe molecule, which restrains the
formation of the TICT state, and thus resulting in a turn‐on fluores-
cent response. In water, compound 71 can gradually self‐assemble
into non‐emissive one‐dimensional nanoribbons. The addition of
hydrazine can decompose the nanoribbons into nanovesicles by
FIGURE 37 (A) Structure and reaction of probe 66 with hydrazine. (B) Fluorescence images of HeLa cells with the probe 66 (b), and cells
incubated with 66 and then addition of hydrazine (d), (a) and (c) are bright‐field images. (Reprinted from ref. 97)
FIGURE 38 Structure and reaction of probe
67 with hydrazine
NGUYEN ET AL.
15
FIGURE 39 Structure and reaction of probe 68 with hydrazine
FIGURE 40 Structures and reactions of probes 69 and 70 with hydrazine
FIGURE 41 Structures and reactions of probes 71 and 72 with hydrazine
synergistic formation of the hydrogen‐bond and the reduction of aro-
matic building blocks. These transformations lead to an extremely
strong green emission located at 500 nm. Based on the reducibility
character of hydrazine, Liu and co‐workers reported a AIE fluorescence
turn‐on probe (72) for hydrazine by using the tetraphenylethylene
fluorophore (Figure 41).[105] Specifically, the probe 72 is non‐fluores-
cent due to the attached N=N group, and the hydrazine‐mediated
reduction of N=N to NH–NH can produce a significant increase in
the fluorescence intensity. It is notable that the probe is recyclable
by oxidizing the intermediate with O2 in the air. Recently, Zhang and
co‐workers developed two coumarin‐based fluorescent probes (73,
74) for detecting both palladium and hydrazine (Figure 42).[106] Lead
ion (Pb2+) can be effectively reduced to Pb0 by hydrazine, which fur-
ther mediate the removal of the masking groups of 73 and 74. Based
on this cascade reaction, 73‐Pd2+ fluorescent assay was successfully
applied for the sensitive detection of hydrazine with a LOD of 37 nM.
FIGURE 42 Structures and reactions of
probes 73 and 74 with hydrazine
16
NGUYEN ET AL.
FIGURE 43 Structures of probes (75–77)
for hydrazine based on ketone or aldehyde
moiety
|
capturing. A fluorescent on–off type probe (76) for hydrazine based
on a spirobenzopyran dye was prepared and successfully applied to
living cells.[108] Commercially available Alizarin red S (77) can also be
used as a colorimetric probe for hydrazine.[109]
9
PROBES BASED ON OTHER
RECOGNITION MOIETIES
|
9.1
Based on ketone or aldehyde recognition
moiety
|
9.2
Based on benzoate or nitrobenzenesulfonyl
The condensation of hydrazine with ketones or aldehydes to form
hydrazones is a well‐established reaction in organic synthesis, which
has also been exploited for the design of fluorescent hydrazine probes
(Figure 43). Xu and co‐workers reported ESIPT probe (75) for hydra-
moiety
As mentioned earlier, hydrazinolysis of phenol acetate to the corre-
sponding phenolic analogue has been extensively exploited to develop
fluorogenic probes for hydrazine. Besides, several recent reports dem-
onstrated that electron‐deficient benzoate also can act as a reaction
site for hydrazine (Figure 44). Goswami et al. developed a turn‐on
fluorescent hydrazine probe (78) by coupling p‐bromobenzoic acid to
zine
based
on
2‐(2′‐hydroxyphenyl)
benzoxazole
(HBO)
fluorophore.[107] The adjacent hydroxyl group can activate the alde-
hyde moiety and promote a condensation reaction to afford the
phenylhydrazone via intramolecular hydrogen bonding and hydrazine
FIGURE 44 (A) Structures and reactions of probes 78–80 with hydrazine. (B) Confocal microscopy images. Probe 80 incubated with HeLa cells
(a–c); image of cells after treatment with 80 and subsequent treatment of the cells with hydrazine (d–f). (Reprinted from ref. 110)
NGUYEN ET AL.
17
FIGURE 45 Structures and reactions of
probes 81 and 82 with hydrazine
FIGURE 46 Structures and reactions of probes 83 and 84 with hydrazine
FIGURE 47 Structures and reactions of
probes 85–87 with hydrazine
fluorescein.[111] Addition of hydrazine to the solution of 78 can induce
the cleavage of the benzoate ester and the subsequent spirolactam
ring‐opening of rhodamine, thus achieving a turn‐on fluorescent
response. By using p‐nitrobenzoate as the recognition moiety, Ye
and co‐workers, reported a similar fluorescent hydrazine probe (79)
based on fluorescein scaffold.[112] Probe 79 also displays high reactiv-
ity toward hydrazine due to the presence of strong electron‐with-
drawing nitro group. The 2,4‐dinitrobenzenesulfonyl group is a well‐
18
NGUYEN ET AL.
known recognition moiety adapted for fluorogenic thiol probes.[113]
Jiang and co‐workers developed a fluorescent hydrazine probe (80)
based on p‐nitrobenzenesulfonyl moiety which have higher electron
density than the dinitro one and is inactive toward thiols.[110] The
probe displays excellent selectivity and high sensitivity for hydrazine
detection with a LOD of 2.2 × 10−8 M and is also successfully
employed for imaging hydrazine in living cells (Figure 44B).
extended π‐conjugation of the probe and the resultant truncated
π‐system exhibits the characteristic spectral feature of coumarin. As
a result, the ratiometric detection of hydrazine was achieved in the
concentration range 1.0–9.0 μM with a LOD of 4.7 × 10−8 M. By
using δ‐ynone as a recognition moiety, Cao and co‐workers reported
a turn‐on fluorescent probe (87) for hydrazine.[121] After nucleophilic
attack of hydrazine on alkynyl, the resulting intermediate also
retains an amino group, which can further react with the carbonyl
to form an aromatic pyrazole ring, thus leading to a strong fluores-
cence enhancement.
|
9.3
Based on 2‐fuoro‐5‐nitro‐benzoic ester moiety
2‐Fluoro‐5‐nitro‐benzoic ester has previously been employed as a
reaction moiety for the construction of H2S2 probes by Xian and
co‐workers.[114] Due to the similar molecular structure and double
nucleophilic character between H2S2 with N2H4. It can be speculated
that this moiety also may react with hydrazine. Zhou and co‐workers
reported a turn‐on fluorescent hydrazine probe (81) by incorporating
2‐fluoro‐5‐nitrobenzoic acid onto the resorufin fluorophore
(Figure 45).[115] Nucleophilic substitution of fluorine by hydrazine
affords an Ar‐NH‐NH2 intermediate, which subsequently undergoes
an intramolecular cyclization to release highly fluorescent resorufin.
Probe 81 displays good selectivity for hydrazine against other species,
and has been used for imaging of exogenous hydrazine in HeLa cells.
Following a similar strategy, another hydrazine probe (82) has been
developed by using 1,8‐naphthalimide as the fluorescent reporter
(Figure 45).[116]
|
10
CONCLUSIONS AND PERSPECTIVES
The development of fluorescence probes for sensing important envi-
ronmental and biological relevant species is growing into a very vibrant
and active field. Owing to the widespread industrial applications and
the diverse toxicological functions of hydrazine, many efforts have
been made to prepare effective optical probes for its detection in
different media, including in solution of aqueous and/or organic
solvent, gaseous state, and biological systems. In this review, we have
systematically summarized the reported fluorescent hydrazine probes,
most of which are synthetic small organic molecules. These probes
were classified on the basis of the sensing mechanism and the type
of recognition moieties for hydrazine. By exploiting the unique reactiv-
ity of hydrazine and elaborately choosing the proper fluorophore,
some of these presented probes displayed good sensing properties,
such as high selectivity and sensitivity, ratiometric response, ability
for in situ and/or real‐time detection, etc. Despite some of these
impressive examples, further refinement of the recognition moiety
and improvement of the biological compatibility of the probes are still
required to achieve high specificity and to realize in vivo sensing.
|
9.4
Others
Jiang et al. constructed a NIR fluorescent hydrazine probe (83) by
coupling cinnamoyl moiety to a Nile Red derivative (Figure 46).[117]
Hydrazine‐mediated direct hydrazinolysis of the probe can lead to
the release of hydroxyl substituted Nile Red in which the fluorescence
is effectively quenched via the PET process from phenoxide to the
excited fluorophore. Probe 83 also owns high selectivity over other
species including Cys and Hcy. The cinnamoyl moiety has also been
adopted to develop another fluorescent probe (84) for hydrazine but
with a different proposed sensing mechanism (Figure 46).[118] Nucleo-
philic 1,4‐addition of hydrazine at the β‐carbon of the cinnamate
moiety gives an unstable intermediate, which further undergoes an
nucleophilic amine attack to carbonyl ester and intramolecular cycliza-
tion to release the fluorescent rhodamine moiety. The probe exhibits
high sensitivity, and has also been applied to detect hydrazine in live
HepGs cells.
i. Hydrazine (N2H4), comprised of two –NH2 groups, is a powerful
nucleophile, and can participate in diverse nucleophilic reactions,
such as nucleophilic addition and substitution, hydrazinolysis of
ester moiety and electron‐deficient alkene, condensation with
C=O structure to form hydrazone and so on. Some of the
reported hydrazine probes feature a single electrophilic site for
nucleophilic attack by hydrazine. But this type of probe may suf-
fer from poor selectivity, slow reaction rate or inferior stability.
However, some probes possess two nucleophilic reaction sites,
which utilized the ability of hydrazine to perform two consecutive
nucleophilic reactions, and thus achieving high selectivity. Future
efforts can continuously exploit the unique double nucleophilic
character of hydrazine to design novel high‐specific recognition
moieties and hence the more efficient probes, which are expected
from the combination of the various nucleophilic properties of
hydrazine to offer diverse possibilities.
Li and co‐workers synthesized a turn‐on fluorescent hydrazine
probe (85) by condensation of 7‐diethylamino coumarin‐3‐aldehyde
and a 1,8‐naphthalimde derivative (Figure 47).[119] In a mixture of
DMSO and HEPES (6:4, v/v, pH 7.4), hydrazine can selectively decom-
pose the probe into a non‐emissive 4‐hydrazine‐1,8‐naphthalimide
and a highly fluorescent coumarin derivative, thus achieving a turn‐
on fluorescent response to hydrazine. Zhao and co‐workers developed
a NIR ratiometric fluorescent hydrazine probe (86) based on a hybrid
fluorophore of coumarin and benzopyrylium (Figure 47).[120] The
probe displays an emission band at 694 nm and an absorption peak
at 645 nm. The addition of hydrazine to the probe solution can lead
to the formation of spirocyclic hydrazide, which interrupts the
ii. To further explore toxicological functions of hydrazine in organ-
isms, fluorescent probes are required to be capable of sensing
and/or imaging hydrazine in biological systems, and thus some
performances are favoured, including good stability, proper solu-
bility, and especially low interference from substances in biologi-
cal environments. NIR and two‐photon probes possess the
NGUYEN ET AL.
19
[20] K. Wechakorn, S. Prabpai, K. Suksen, P. Kanjanasirirat, Y. Pewkliang,
virtues of good tissue penetration and low autofluorescence. AIE
S. Borwornpinyo, P. Kongsaeree, Luminescence 2018, 33, 64.
probes are also practicable in biological systems as they permit
the use of dye solutions with any concentration for bioassays
and enable the achievement of turn‐on fluorescent responses
by taking the advantage of luminogenic aggregation. The phos-
phorescent probes can eliminate interference from the normal
background fluorescence by using time‐resolved technology;
nevertheless this kind of probe for hydrazine has not yet
been reported. Ratiometric probes, which rely upon emission or
excitation at two different wavelengths, are also favourable due
to the ability to correct for differences in probe concentration,
photo‐bleaching, and other variants that may complicate the
detection results.
[21] P. Hou, S. Chen, X. Song, Luminescence 2014, 29, 423.
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Zhang, Anal. Chem. 2015, 87, 9101.
[30] K. Aita, T. Temma, Y. Kuge, H. Saji, Luminescence 2007, 22, 455.
This work was financially supported by the National Natural Science
Foundation of China (Grant Numbers B061201, U1404215,
21505091, 21475084, and 21476266) and Innovation Scientists and
Technicians Troop Construction Projects of Henan Province (No: 41).
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[34] K. Li, H.‐R. Xu, K.‐K. Yu, J.‐T. Hou, X.‐Q. Yu, Anal. Methods 2013, 5,
There are no conflicts to declare.
2653.
[35] Y.‐Z. Ran, H.‐R. Xu, K. Li, K.‐K. Yu, J. Yang, X.‐Q. Yu, RSC Adv. 2016,
6, 111016.
ORCID
[36] H. Tse, Q. Li, S. Chan, Q. You, A. W. M. Lee, W. Chan, RSC Adv. 2016,
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