Fast and ratiometric naked eye detection of hydrazine for both solid and vapour phase sensing

Article abstract of DOI:10.1039/c4nj02220c

A new naked-eye ratiometric colorimetric and fluorometric chemodosimeter (PBF) was constructed to enable trace vapor detection of hydrazine. This probe utilizes an irreversible and fast hydrazine-promoted cleavage of the ester linkage in PBF. This probe was shown to be highly selective for hydrazine, and showed real time response as well as a positive linear relationship to hydrazine concentration. The probe also shows an excellent performance in the dip stick method.

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ARTICLE TYPE
Fast and ratiometric “ Naked eye” detection of hydrazine both solid and
vapour phase sensing
Shyamaprosad Goswami*, Sima Paul and Abhishek Manna
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
However, that complication can be removed by the use of
simple chemodosimeter fluorescence probes for hydrazine
50 because those probes are highly sensitive, easyꢀtoꢀoperate and
of low cost. However, up to now, only a limited number of
fluorescence probes for hydrazine have been reported in the
literature.11 Chemodosimeters appended with specific
protection groups for selective detections via target specific
55 deprotection for various analytes have often been utilized
effectively.12 Ratiometric and reaction specific fluorescent
chemodosimeters are exceptionally useful due to their
specificity and they allow the measurement of emission
intensities at two different wavelengths which permit the
60 correction for environmental effects. Thus, we have designed
a ratiometric “naked eye” as well as fluorescent probe for the
detection of hydrazine.
A
new ‘‘naked-eye’’ ratiometric colorimetric and
fluorescence chemodosimeter (PBF) was constructed to
enable trace vapor detection of hydrazine. This probe utilizes
an irreversible and fast hydrazine -promoted cleavage of ester
10 linkage in PBF. This probe was shown to be highly selective
for hydrazine, and showed real time response as well as a
positive linear relationship to hydrazine concentration. The
probe also shows an excellent performance in the ‘‘dip stick’’
method.
15 Introduction :
In the past decade, efficient and reaction specific synthetic
probes with better sensitivity for the detection of small
20 molecule has been a subject of intense research interest,
because they play important roles in biological systems and
also constitute some pollutants in our environment.1 As a
significant industrial chemical, hydrazine exhibits various
applications in chemical, pharmaceutical, and agricultural
25 industries involving catalysts, corrosion inhibitors, and
pesticides.2 Hydrazine is a wellꢀknown highꢀenergy fuel in
rocket propulsion and missile systems due to its improved
detonable properties.3
Our hydrazine sensor discussed herein, is synthetically simple
65 and based on the photoinduced electron transfer (PET)
principles where a fluorophore is connected to a receptor by a
short spacer. Initially the probe becomes non fluorescent due
to the PET effect. In this type of chemodosimeter, the
fluorescence intensity can be enhanced by breaking the
70 linkage of the electron withdrawing and electron donating
groups through a chemical reaction promoted by special
analytes. In our chemodosimeter, two hydroxyl groups in
fluorescein were protected by para bromo benzoic acid. The
fluorescence of the probe was partly suppressed due to
75 photoinduced electron transfer (PET) from electronꢀdonating
fluorescein moiety to electron deficient bromo benzoic
moiety. Now, hydrazine could readily break the ester linkage
of the fluorochrome to yield a deprotected analogue and
regenerate the phenolic moiety of fluorochromes of
80 fluorescein. In the later case the yield of the receptor is also
higher than the former. The target compound para
bromobenzoic acid protected fluorescein probe (PBF) was
synthesized through the following reaction detailed in Scheme
1. The structure of the receptor was confirmed using 1H NMR,
85 13C NMR and HR MS spectra (ESI†).
30 But due to its toxicity to human beings, hydrazine has been
classified as a probable human carcinogen by the U.S.
Environmental Protection Agency (EPA) with a low threshold
limit value (TLV) of 10 ppb.4 Hydrazine is a neurotoxin and
has severe mutagenic effects causing serious damage to the
35 liver, lungs, kidneys, and the human central nervous system.5
Therefore, reliable analytical approaches for
detection with satisfactory sensitivity and selectivity are of
great interest and importance.
hydrazine
40 To date,
chromatographyꢀ
a
variety of analytical techniques, including
mass
spectrometric,6 titrimetric,7
O
O
O
4-Bromobenzoicacid
spectrophotometry8 and electrochemical methods9 have been
exploited for the purpose of hydrazine analysis. But those
methods are complicated and time consuming for realꢀtime
45 and onꢀsite analysis.10 So, simple but reliable detection
methods for the rapid and sensitive detection of hydrazine
both qualitatively and quantitatively are in great need.
O
DCC, DMAP, DCM
O
O
r.t, 12hr
O
O
O
HO
OH
O
Br
Br
90 Scheme 1: Synthetic route of the receptor (PBF).
[journal], [year], [vol], 00–00 | 1
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where,
Experimental section
General :
X
& S indicate the unknown and standard solution
respectively, φ = quantum yield,
F = area under the emission curve, A = absorbance at the
60 excitation wave length,
n = index of refraction of the solvent. Here φ measurements
were performed using anthracene in ethanol as standard [φ =
0.27] (error ~ 10%).
The quantum yield of PBF itself is 0.003 which is remarkably
65 changed into 0.28, an enhancement around 93 fold is
observed.
The chemicals and solvents were purchased from Sigmaꢀ
Aldrich Chemicals Private Limited and were used without
further purification. Melting points were determined on a hotꢀ
plate melting point apparatus in an openꢀmouth capillary and
were uncorrected. 1HꢀNMR and 13CꢀNMR spectra were
recorded on Brucker 400 MHz instruments respectively. For
5
10 NMR spectra, d6ꢀDMSO was used as solvent with TMS as an
internal standard. Chemical shifts are expressed in δ units
and 1H–1H coupling constants in Hz. UVꢀvis titration
experiments were performed on JASCO UVꢀV530
General method of UV-vis and fluorescence
titrations:
a
spectrophotometer and fluorescence experiment was done
15 using PTI fluorescence spectrophotometer with a fluorescence
cell of 10 mm path. IR spectra were recorded on a JASCO
FT/IRꢀ460 plus spectrometer, using KBr discs.
70
By UV-vis and fluoescence method:
For UVꢀvis and fluorescence titrations, stock solution of the
sensor was prepared (c = 2 x 10ꢀ5 MLꢀ1) in CH3CN: H2O (6:4,
75 v/v). The solution of the guest cations and anions were
prepared (2 x 10ꢀ4 MLꢀ1) in CH3CN: H2O (6:4, v/v) at pH 7.4
by using 10 mM HEPES buffer. The original volume of the
receptor solution is 2 ml. Solutions of the sensor of various
concentrations and increasing concentrations of cations,
80 anions and amine containing compounds were prepared
separately. The spectra of these solutions were recorded by
means of UVꢀvis and fluorescence methods.
Methods for the preparation of receptor :
20
Synthesis of receptor (PBF): Fluorescein (700 mg, 2.1
mmol) and DMAP (100 mg, 0.82 mmol), were added to 4ꢀ
bromobenzoic acid (1 gm, 4.9 mmol). The mixture was
dissolved in dry dicholoromethane (20 mL) and chilled at 0°C
25 followed by the addition of a solution of DCC (900 mg, 4.36
mmol) in dry dichloromethane. The reaction mixture was
stirred under nitrogen atmosphere at 0°C for 15 minutes and at
room temperature for 12 hrs. The precipitate of urea was
removed by filtration and the filtrate was concentrated in high
30 vacuum to give an oily residue. This residue was purified by
column chromatography using silica gel (100ꢀ200 mesh size)
and 10% ethyl acetate in pet ether as eluent to give a colorless
gummy liquid, which solidifies on cooling (1.5 gm, 88%).
85 Results and discussion
UV-vis and Fluorescence study :
The colorimetric sensing abilities of PBF was primarily
90 investigated in a CH3CN–H2O solution (6 : 4, v/v, 10 mM
HEPES, pH 7.4) with various metal ions and anions (Ag+,
35 1H NMR (CDCl3, 400 MHz) δ (ppm): 8.02 (m, 4H), 7.65 (m,
6H), 7.16 (m, 3H), 6.88 (m, 3H), 6.66 (m, 1H), 6.57 (m, 1H).
13C NMR (CDCl3, 100 MHz): δ (ppm): 84.9, 107.3, 113.4,
116.9, 121.0, 121.3, 123.3, 124.8,125.2, 127.2, 127.8, 129.0,
129.4, 134.8, 134.9, 151.4, 159.5, 164.9, 171.5.
Cd2+, Co2+, Cu2+, Fe3+, Mn2+, Pd2+, Clꢀ, Brꢀ, Iꢀ, SO42ꢀ, SO3 ,
ꢀ
ꢀ
ꢀ
ClO4 , HPO4 ). The probe PBF without hydrazine exhibited a
moderate UVꢀvis absorption band at 438 nm which was
95 attributed to the photoinduced electron transfer (PET)
transition in the molecule. Addition of hydrazine to a solution
of PBF led to an obvious absorption enhancement at 508 nm,
along with a color change from colorless to yellow which
allows the detection of hydrazine with the naked eye (Figure
100 1). Upon increasing the concentration of hydrazine, the
absorbance of PBF is also increased and it reaches saturation
when 2 equiv. hydrazine is added. Thus, this hydrazinolysis
reaction by hydrazine generated fluorescein, which exhibited
its characteristic chromogenic behavior. In contrast, the
105 addition of other metal ions and anions resulted in a negligible
response (Figure 2). This indicates that under signaling
conditions, the possible interference of ester hydrolysis
assisted by common metal ions or anions is not a practical
problem in hydrazine sensing by PBF. The absorbance at 508
110 nm changed almost 64ꢀfold (from 0.031 to 1.974) in the
presence of hydrazine (Figure 1b). To our pleasure, the
detection limit of PBF for hydrazine was found to be 0.41ꢁM
40 MS (ESI MS): (m/z, %): 698.0076 [(M+, 100 %]
Synthesis of hydrazine product of PBF: PBF is mixed with
two equivalents of hydrazine in acetonitrile at room temperature
to give a yellow solution. On removing the solvent, a solid
1
45 product was obtained which was used for HꢀNMR and MASS
spectroscopy.
1H NMR (CDCl3, 400 MHz) δ (ppm): 9.99 ( s, 1H ), 9.80 (s,
1H), 8.30(s, 1H), 7.96 (d, 2H, J=7.5 Hz), 7.84 (m, 2H), 7.65
(m, 2H), 7.46 (t, 1H, J=7.5 Hz), 7.35 (d, 1H, J= 7.5 Hz), 7.19
50 (d, 1 H, J= 7.5 Hz), 7.09 (m, 1H)
MS (ESI MS): (m/z, %): 331.1101 [(M+, 100 %]
Determination of fluorescence quantum yield:
Here, the quantum yield φ was measured by using the
following equation,
2
2
55 φx = φs ( Fx / Fs)( As / Ax)(nx / ns )
2
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(Figure 1b), which lies below the safe hydrazine level (10
ppb), indicating that the probe PBF may further be developed 60 phenomenon implied that PBF was potentially useful for the
of 0.56–28.0 ꢁM, with the coefficient R2 = 0.99. This
for the detection of hydrazine in practical applications.
quantitative determination of hydrazine concentration.
5
(a)
2.0
2.0
65
1.5
1.0
0.5
0.0
1.5
10
1.0
70
0.5
0.0
15
75
300
400
500
600
Wavelength (nm)
20 (b)
Figure 2: The variation of absorbance for probe PBF in a
CH3CN–H2O solution (6 : 4, v/v, 10 mM HEPES, pH 7.4) in
80 presence of various metal ions and anions.
2.0
1.5
1.0
0.5
0.0
Y = 0.552X - 0.0453
R2 = 0.99
3.5x106
25
2.8x106
85
2.1x106
30
1.4x106
90
5
10
15
20
25
7.0x105
[N2H4] in micromolar
35
Figure 1: (a) UV absorption spectra of sensor PBF in the
presence of an increased concentration of hydrazine (0–200
ꢁM) in CH3CN–H2O solution (6 : 4, v/v, 10 mM HEPES, pH
40 7.4); the inset shows the color change detectable by the naked
eye of sensor PBF with the addition of hydrazine (b)
95
0.0
350
400
450
500
550
Wavelength (nm)
Figure 3: (a) Fluorescence emission spectra of PBF (2.0 X 10ꢀ
5
Absorbance change at 508 nm of PBF upon gradual addition 100 M) with hydrazine (2.0 X 10ꢀ4 M) at pH 7.4 in CH3CN–H2O
of hydrazine.
(6: 4, v/v), λex = 380 nm. The inset shows the naked eye
fluorescence change of PBF with addition of hydrazine.
45 The fluorescence detection of hydrazine by PBF was also
pronounced. As shown in Figure 3, PBF exhibited an
extremely weak blue fluorescence under the fluorescence
excitation at 380 nm (Q = 0.003). Upon addition of hydrazine,
the fluorescence intensity at 418 nm diminished and the band
50 at 530 nm (Q = 0.28) increased due to the ringꢀopened
fluorescein structure. Concomitantly, the fluorescence color of
the solution changed from blue to green under UV
illumination (inset of Figure 3). These changes in the
fluorescence spectra stopped when the amount of added
55 hydrazine reached 2 equiv. The probe induced a nearly 43ꢀ
fold variation in the fluorescence ratio (F530/F418) (Figure S2).
From this figure, we also concluded that (F530/F418) varies
almost linearly vs. the concentration of hydrazine in the range
The receptor is inert towards all cations and anions except
105 hydrazine (Figure 4a). Next, ion interference experiments
were carried out both in buffered aqueous solution for
evaluation of the sensing ability of the PBF chemosensor (1
mM) towards hydrazine and in the presence of 10 equiv. of a
series of background metal ions and anions by means of
110 fluorescence spectra (Figure 4b). Clearly, the presence of
background metal ions and anions did not cause any
significant fluorescence change of PBF. This showed that the
PBF probe could selectively detect hydrazine in the presence
of other metal ions and anions. The chemosensor PBF was
115 also treated with some amine containing compounds. It was
found that these compounds had no obvious interference to
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probe PBF in the aqueous CH3CN solution (Figure S1).
Y=0.067X- 0.061
R=0.99
In the time dependent fluorescence spectra, it is seen that the
reaction is completed within 1 min, with a rate constant of
15.43 × 10−2 s−1, which strongly supports the high reactivity
of the probe (Figure 5).
0.5
0.4
0.3
0.2
0.1
0.0
2
60
5
10
15
(a)
35
65
30
25
20
15
10
5
0
10 20 30 40 50 60
70
Time(sec.)
Figure 5: The time vs. fluorescence spectra of (a) PBF (c =
2.0 x 10–5 M) in presence of 2 equiv. hydrazine (c = 2.0 x 10–4
M) at pH 7.4 in CH3CN:H2O (6:4, V/V) at different time [ (b)
75 5 (c) 10 (d) 20 (e) 30 (f) 40 (g) 50 (h) 60 sec] (left) and the
time vs. fluorescence at fixed wavelength (530 nm) plot using
first order rate equation (right). λex = 380 nm.
0
20 (b)
35
28
21
14
7
80 1HNMR and HR MS study of receptor and adduct
:
25
1
Furthermore, we investigated the HꢀNMR spectra of PBF in
the presence of hydrazine and compared with that of the
85 sensor itself. The protons of benzene ring in PBF dramatically
shifted upfield upon hydrazine addition, indicating that
hydrazine functions as a nucleophile. Most interestingly, a
new peak is generated at 9.994 ppm which is due to
generation of hydroxyl group, breakage of ester linkage in
90 receptor PBF when hydrazine is added to it. In high resolution
HR MS specta, there is a peak at m/z 698.0076 corresponding
to PBF. Hydrazine adduct give a peak at m/z 331.1101 which
indicates regeneration of fluorescein moiety. All of these
results are consistent with our proposed mechanism
95 (supporting information)
30
0
35
Figure 4: (a) The variation of fluorescence intensity ratio
(F530/F418) for probe PBF in a CH3CN–H2O solution (6: 4, v/v,
10 mM HEPES, pH 7.4) in presence of various metal ions and
40 anions (b) Fluorescence intensity ratio (F530/F418) of PBF (2.0
X 10ꢀ5 M) to hydrazine (2 equiv.) containing 10 equiv. of
various metal ions and anions (λex = 380 nm).
Sensing Mechanism of receptor towards
hydrazine:
O
100
O
(h)
6
O
O
1.25x10
(g)
(f)
45
50
55
O
O
O
Br
Br
6
NH2-NH2
NH2-NH2
1.00x10
105
110
115
(e)
(d)
(c)
Colorless and light blue fluorescence
5
7.50x10
5
5.00x10
O
5
2.50x10
O-
Br
2
C NH
O
NH2
(b)
(a)
0.00
350
HO
O
O
400
450
500
550
600
Yellow Colored and Strong green fluorescence
Wavelength(nm)
4
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Scheme 2: Signaling of hydrazine by chemodosimeter (PBF)
60
Figure 7: Color changes on test paper (a) PBF (b) PBF in
Based on these experimental observations we outlined the
plausible signalling mechanism. Deprotection of the hydroxyl
group of probe PBF proceeds first at the carbonyl position by
presence of hydrazine.
5
The fluorescence response of PBF solutions before and after
the nucleophilic addition of hydrazine. The subsequent 65 exposure to saturated hydrazine vapor for various time
nucleophile attacked on the carbonyl group to generate
fluorescein and 4ꢀ bromobenzohydrazine, which possessed a
10 unique colorimetric and ratiometric response (Scheme 2).
intervals is illustrated in Figure 8. PBF solutions were kept
being stirred during the overall absorbing process. Emission
intensity at 530 nm of the solutions was enhanced after
exposing to hydrazine vapor for 60 s. Further work on
70 determination of hydrazine in practical vapor samples is still
in progress.
Applications with Water and TLC plates:
15
20
25
75
80
85
Figure 8: Change in the TLC plate (coated with PBF) in the
presence of hydrazine vapour
30 Figure 6: Fluorescence detection of hydrazine in distilled
water and tap water by PBF. [PBF] = 2.0 X 10ꢀ6 M,
[hydrazine] = from 0 to 2.0 X 10ꢀ5 M at pH 7.4 in
CH3CN:H2O (6:4, V/V). λex = 380 nm.
Conclusions
90
We have developed a smart fluorescence turnꢀon sensor that
easily detect trace amount of hydrazine vapor. The sensor
mechanism is based on hydrazine mediated cleavage of ester
linkage in PBF moiety which turns to be strongly fluorescent
95 upon conversion into the fluorescein state. The recognition
events of the sensor toward hydrazine are demonstrated nicely
by absorbance and fluorescence spectroscopy and explained
by other spectroscopic data with NMR and mass. This
fluorescence turn on reaction is extremely selective towards
100 hydrazine. In addition, the probe could serve as a practical
colorimetric sensor for ‘‘inꢀtheꢀfield’’ measurement, which
does not require any additional equipment, just using a ‘‘dipꢀ
stick’’ approach.
35 We also explored opportunities for PBF in practical
applications because hydrazine is a suspected carcinogen and
is widely used in various industrial processes and thus
hydrazine detection in aqueous samples is of interest. We
analyzed hydrazine in and distilled water and tap water. An
40 aliquot of hydrazine was added in both types of water and and
the pH was adjusted to 7.4. Then the results of the recovery of
hydrazine by PBF from these two water samples were
compared (Figure 6). The analysis of hydrazine in both
solutions agreed well at hydrazine concentrations up to 2.0 X
45 10ꢀ5 M. We also prepared the TLC plates were prepared to
detect hydrazine both in its liquid (Figure 7) and in its vapour
phase (Figure 8)
105 Acknowledgements
(i)
(ii)
Authors thank the DST and CSIR (Govt. of India) for
financial supports. S.P. and A.M. acknowledge the UGC and
CSIR respectively for providing fellowships.
50
110 Notes and references
Bengal Engineering And Science University, Shibpur, Howrah 711103,
India. Fax: +91-3326682916; E-mail: spgoswamical@yahoo.com
† Electronic Supplementary Information (ESI) available: [details of
55
charectarisation
and
spectral
data
are
avialable].
See
115 DOI: 10.1039/b000000x/
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