A nitroolefin functionalized DPP fluorescent probe for the selective detection of hydrogen sulfide

Article abstract of DOI:10.1039/c6nj03432b

In this paper, a nitroolefin functionalized probe DPP-NO₂ was designed and synthesized as a selective fluorescent probe for detection of hydrogen sulfide (H₂S). The specific reduction reaction between the nitro group and H₂

Full text of DOI:10.1039/c6nj03432b

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The role of atropisomers on the photo-reactivity and fatigue of
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A nitroolefin functionalized DPP fluorescent probe for selective detection of
hydrogen sulfide
Lingyun Wang *, Xianggen Chen, Derong Cao
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of
Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China,
510641
*Corresponding author: Tel. +86 20 87110245; fax: +86 20 87110245. Eꢀmail:
lingyun@scut.edu.cn
Abstract
In this paper, a nitroolefin functionalized probe DPP-NO2 was designed and
synthesized as a selective fluorescent probe for detection of hydrogen sulfide (H2S).
The specific reduction reaction between nitro group and H2S gave 800ꢀfold
fluorescence turnꢀon at 550 nm in the fluorescence emission spectrum, along with a
21 nm blueꢀshift from 506 nm to 485 nm in the absorption spectrum as well as the
color change from pink to light yellow. In addition, high selectivity, fast response (3
minutes) and low detection limit of 5.2 nM of the probe DPP-NO2 for H2S detection
was observed. What is more, through the fluorescence turnꢀon signal toward H2S in
Hela cells, probe DPPꢀNO2 was successfully applied to monitor H2S in living Hela
cells.
Keywords: Diketopyrrolopyrrole; Nitroolefin; Hydrogen sulfide; Fluorescent probe

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Introduction
Hydrogen sulfide (H2S), historically known for its characteristic rotten egg smell
and as a poison for centuries,1 is the third most common gaseous signaling molecule
in biology apart from gasotransmitters.2 On one hand, accumulating evidence has
confirmed that H2S is involved in a vast number of physiological and pathological
processes such as vasodilatation, neuromodulation, apoptosis, and regulation of
inflammation.3 On the other hand, abnormal H2S levels have also been associated
with various diseases, including Alzheimer’s disease,4 Down’s syndrome,5 diabetes,6
and liver cirrhosis.7 Therefore, it is of considerable significance to develop efficient
methods for detection of H2S in order to get better understanding of its functions in
physiology and pathology.
In the past few years, fluorescent probes have been widely applied in detection of
anions, cations, and biological molecules on account of their high selectivity and high
sensitivity as well as realꢀtime imaging. After several pioneering fluorescent probes
have been reported for detection of H2S,8 a large number of new fluorescent probes
for H2S have been developed.9ꢀ14 The probes classified according to their reaction type
with H2S are as follow: (1) the reduction of RNO2 or RN3 to the parent amine
moieties,15 (2) two steps nucleophilic reactions,16 (3) sulfideꢀselective chemosignal
with Cu2+ complex,17 (4) sulfideꢀselective cleavage benzenesulfonate or
benzenesulfonamide.18 However, most of these probes showed a delayed response
time (almost > 20 min) and small change of the fluorescence emission intensity,
which might be inefficient to capture H2S in biological systems due to the transient

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nature of H2S. In fact, it is still difficult to develop fluorescent probe for detection of
H2S with high selectivity and fast response time.
It is reported that the nitro group could be converted to amino group in the presence
of hydrogen sulfide,19ꢀ22 we sought to exploit this chemistry for H2S sensing.
Diketopyrrolopyrrole (DPP) as brilliant red and strong fluorescent high performance
pigments was chosen as the fluorophore due to its ease of synthetic modification,
prominent lightꢀresistant, weatherꢀresistant, and solventꢀresistant performances. It is
expected nitroolefinꢀbased DPP fluorescent probe DPP-NO2 (Scheme 1) could serve
as a reactive colorimetric and fluorescent probe for the selective detection of H2S. The
probe DPP-NO2 in CH3CN shows no fluorescence as a result of strong
electronꢀwithdrawing effect of nitro group. Nevertheless, mild reduction between
probe DPP-NO2 and H2S regenerates the parent amine and results in fluorescence
turnꢀon at 550 nm. Moreover, DPP-NO2 displayed a high selectivity and a fast
response time for detection of H2S without interference from other reactive sulfur,
oxygen, nitrogen species (RSONs) and anions.
2. Experimental
2.1 Chemicals and instruments
Nitromethane was purchased from the Macklin, Nꢀmethylꢀ2ꢀpyrrolidone,
tetrahydrofuran and acetonitrile were redistilled prior to use. Compound 5 was
synthesized according to our published literature.23 1H NMR (400 MHz) and 13C
NMR (100 MHz) were recorded on Bruker Avance III 400 MHz and chemical shifts

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are expressed in ppm using TMS as an internal standard. The UVꢀVis absorption
spectra were recorded using a Helios Alpha UVꢀVis scanning spectrophotometer.
Fluorescence spectra were obtained with a Hitachi Fꢀ4500 FL spectrophotometer.
Melting points were measured on an Xꢀ4B digital microꢀmelting point apparatus.
2.2 Synthesis of probe DPP-NO2
113.6 mg (0.2 mmol) compound 5, 15 mL nitromethane and 77.4 mg ammonium
acetate (1 mmol) were added to a 25 mL round bottomed flask, stirred at 80 0C for 2 h
under the monitoring of TLC, then 50 ml water were added, and the mixture was
extracted with ethyl acetate (50 ml, 3 times). The organic layer was separated and
dried over Na2SO4. After concentration under reduced pressure, the crude product was
purified by chromatography on a silica gel column with a mixture of petroleum ether
and CH2Cl2 (1:6, v:v) to afford the reddish black solid product DPP-NO2 45.8 mg in
35% yield. m.p. 206ꢀ207 . 1H NMR (CDCl3, 400 MHz, δ, ppm): 8.02 (d, J=13.6Hz,
2H), 7.91 (d, J=8.4Hz, 4H), 7.69 (d, J=8.0Hz, 4H), 7.63 (d, J=13.6Hz, 2H), 3.75 (t,
J=7.2Hz, 4H), 1.57 (t, J=7.2Hz, 4H), 1.21 (m, 20H), 0.83 (t, J=6.8Hz, 6H). 13C NMR
(CDCl3, 100 MHz, δ, ppm): 162.56, 147.61, 138.59, 137.66, 132.84, 131.38, 129.69,
111.19, 42.32, 31.89, 29.65, 29.25, 26.88, 22.77, 14.25. HRMSꢀESI: m/z calcd (%) for
C38H46N4O6: 654.3417 [M+H]+; Found: 655.3490.
2.3 Experimental procedure for hydrogen sulfide detection
NaHS was used as hydrogen sulfide donor, and the NaHS solution was freshly
prepared each time before use. Deionized water was used to prepare solution (10 mM)
of NaHCO3, Na2HPO4, NaH2PO4, NaNO2, NaHSO3, Na2SO3, Na2SO4, NaSCN,

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Na2S2O3, Na2S2O5, H2O2, NaHS, cysteine, homocysteine, glutathione, ONOOꢀ,
NaOCl, Vitamin C, Vitamin B1, 2ꢀMercapto acetic acid (TGA), 2ꢀMercaptoethanol
and 3ꢀMercaptopropionic acid (3ꢀMPA). Probe DPP-NO2 was dissolved in
acetonitrile (CH3CN) to afford the stock solution (1 mM). Test solutions were
prepared by placing 1 mL of probe DPP-NO2 stock solution into a 100 mL volumetric
flask, adding an appropriate aliquot of each anion stock, and diluting the solution to
100 mL with dry acetonitrile (CH3CN). The resulting solution (10 ꢁM) was shaken
well for absorption and fluorescence spectral analysis.
2.4 Cellular imaging
2.4.1 Cell culture
HeLa cells were cultured in highꢀglucose Dulbecco’s Modified Eagle’s Medium
(HꢀDMEM) containing 10% fetal bovine serum (FBS) and 1% penicillin streptomycin
at 37 0C in a humidified environment containing 5% CO2. Before the experiment, the
cells were precultured until confluence was reached.
2.4.2 Cell imaging
The HeLa cells were seeded in the 12ꢀwell plate and cultured in HꢀDMEM with
0
10% FBS at 37 C in a humidified environment containing 5% CO2. After 80%
confluence, the medium was removed and the adherent cells were rinsed twice with 1
× PBS. Cells were supplemented with 200 ꢁM NaHS in the growth media for 30 min
at 37 °C and subsequently stained with DPP-NO2 (10 ꢁM) in DMSO/PBS (2/98, v/v)
for another 30 min at 37 °C The cell monolayer was then washed twice with 1 × PBS

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buffer and imaged using inverted phase contrast fluorescence microscope (Nikon
Eclipsc TiꢀU) with imaging software (Nikon NIS Elements).
3. Results and discussions
3.1 Design and synthesis of probe DPP-NO2
Since nitro group could be converted to amino in the presence of hydrogen sulfide,
some nitroꢀbased fluorescent probes have been used for detection of H2S.24,25 Herein,
the nitroolefin functionalized DPP (DPP-NO2) was very useful to create a fluorescent
probe by following the changes in the spectral properties.
A convenient synthetic route to probe DPP-NO2 was developed as shown in
Scheme 1. Compound 5 was prepared from pꢀcyanobenzaldehyde as a starting
material in four steps. Probe DPP-NO2 was achieved from compound 5 and
nitromethane with ammonium acetate as a catalyst in 35% yield as a reddish black
solid, which was characterized by 1H NMR, 13C NMR and HRMS spectra.
H
N
O
O
O
O
CHO
CN
O
O
O
CH2OH
CH2OH
O
O
O
O
O
t-C5H11OH
t-C5H11ONa
N
H
NH2SO3H
CN
3
2
C8H17
N
C8H17
N
O
O
O
O
CHO
O
O
C8H17Br
t-C4H9OK
HCl/H2O
THF
OHC
O
O
N
N
C8H17
C8H17
4
5
C8H17
N
NO2
CH3NO2
NH4OAc
O
O2N
O
N
C8H17
DPP-NO2
Scheme 1. Synthesis of probe DPP-NO2.

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3.2 Spectroscopic responses of probe DPP-NO2 to Hydrogen sulfide (H2S)
We firstly evaluated the capability of DPP-NO2 to detect H2S in CH3CN. The
titration of NaHS (a standard source for hydrogen sulfide) to the probe DPP-NO2 was
performed. DPP-NO2 in CH3CN showed two major absorption peaks at 334 nm and
506 nm. It is interesting that upon addition of NaHS solution, both the two absorption
peaks showed considerable changes: the absorption peak at 506 nm shifted to 485 nm
with a 21 nm blueꢀshift, meanwhile the absorption peak at 334 decreased gradually
(Figure 1). And two isosbestic points at 387 nm and 485 nm were observed during the
titration process. Consistent with the changes observed in the absorption spectra, an
important change was observed in the fluorescence emission spectra. The free
DPP-NO2 was essentially nonꢀfluorescent and its spectrum was almost a flat line
parallel to the abscissa due to the quenching effect of nitro groups. However,
introduction of NaHS elicited a significant fluorescence turnꢀon response (800ꢀfold
fluorescence enhancement) at 550 nm (Figure 2). These changes may all be attributed
to the reduction process that electronꢀwithdrawing nitro group was reduced to amino
group.

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0.5
0.4
0.3
0.2
0.1
0.0
334 nm
0 eq
21 nm
506 nm
485 nm
387 nm
NaHS
20 eq
485 nm
500
300
400
600
700
Wavelength (nm)
Figure 1. The absorption spectra of DPP-NO2 (10 ꢁM) in CH3CN upon addition of
increasing equivalents of NaHS solution (10 mM).
4000
3000
20 eq
550 nm
2000
1000
0
NaHS
0 eq
650
500
550
600
Wavelength (nm)
Figure 2. The fluorescent emission spectra of DPP-NO2 (10 ꢁM) in CH3CN upon
addition of increasing equivalents of NaHS solution.
The response time is an important factor of the fluorescent probe which can reflect
whether the probe is sensitive enough or not. Therefore, the timeꢀdependent
fluorescence emission spectra were investigated for DPP-NO2. As shown in Figure 3,

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treatment of a 10 ꢁM solution of DPP-NO2 in CH3CN with 10 equiv NaHS resulted
in the emission enhancement after a couple of minutes. The emission intensity was
enhanced swiftly within 3 min (800ꢀfold turn on at 550 nm), and the fluorescence
intensity at 550 nm could reach saturation after 10 min. Since the catabolism of H2S is
very fast in vivo but it was reported that most of the H2S probes display slow response
time (more than 20 min) in vitro,26 it is worthy to note that such a huge change of
signal is highly desirable for fluorescent probes as the sensitivity. The shorter response
time suggests that DPP-NO2 is more suitable for real time detection of H2S. To enable
the nitro group to be completely reduced to an amino group, a time scale of 5 min was
used after addition of H2S in our experiments.
3000
3000
2500
2000
2500
1500
2000
1000
500
1500
0
0
2
4
6
8
10
550 nm
1000
500
0
500
550
600
650
Wavelength (nm)
Figure 3. The timeꢀdependent fluorescence emission intensity at 550 nm of probe
DPP-NO2 (10 ꢁM) in CH3CN from 0 min to 10 min with 10 equivalents of NaHS
solution (10 mM).

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It is known to us all that the selectivity of fluorescent probe is another important
factor. Encouraged by the distinct fluorescence emission changes of DPP-NO2 upon
treatment with H2S, we further evaluated the specific nature of this probe by
coꢀincubation with various reactive sulfur, oxygen, nitrogen species (RSONs) and
anions. The fluorescence emission spectra (Figure 4a) of probe DPP-NO2 upon
addition of 20 equivalents of other species, including NaHCO3, Na2HPO4, NaH2PO4,
NaNO2, NaHSO3, Na2SO3, Na2SO4, NaSCN, Na2S2O3, Na2S2O5, H2O2, cysteine,
homocysteine, glutathione, ONOOꢀ, NaOCl, Vitamin C, Vitamin B1, 2ꢀMercapto
acetic acid, 2ꢀMercaptoethanol, 3ꢀMercaptopropionic acid did not cause any
fluorescence emission changes and only H2S could lead to pronounced fluorescence
emission enhancement. In addition, the absorption spectra (Figure 4b) showed a
similar result for the selectivity of probe DPP-NO2 to H2S over other species. What is
more, with respect to the spectra changes, obvious color and emission changes from
were observed in presence of H2S alone, as shown in Figure 5. The excellent
selectivity for H2S over other reactive analytes shows that the DPP-NO2 is promising
for the detection of H2S.

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5000
4000
3000
2000
1000
0
Probe with NaHS
(a)
Probe with others
500
550
600
650
Wavelength (nm)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
Probe with others
Probe with NaHS
300
400
500
600
700
800
Wavelength (nm)
Figure 4. The (a) fluorescent emission and (b) UVꢀvis spectra of DPP-NO2 (10 ꢁM)
in CH3CN upon addition of 20 equivalents of various species and NaHS solution.
In addition, to test whether probe DPP-NO2 can detect H2S selectively even in the
presence of other species, competitive anion and biothiols titrations were carried out.
As shown in Figure 6, the results indicated miscellaneous competitive species did not

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lead to any significant spectral change and H2S still resulted in the similar
fluorescence enhancement in the presence of competitive anions. All these findings
suggested that DPP-NO2 allowed selective and sensitive H2S detection by both
colorimetric and fluorometric analyses.
Figure 5. The (a) color and (b) emission changes of DPP-NO2 (10 ꢁM) in CH3CN
upon addition of 20 equivalents of various species solution. (1) blank; (2) NaH2PO4;
(3) Na2HPO4; (4) NaHCO3; (5) Na2SO3; (6) NaHSO3; (7) Na2SO4; (8) Na2S2O3; (9)
Na2S2O5; (10) NaSCN; (11)NaNO2; (12) H2O2; (13) NaHS; (14) glutathione; (15)
homocysteine; (16) cysteine; (17) ONOOꢀ; (18) NaOCl; (19) Vitamin C; (20) Vitamin
B1; (21) 2ꢀMercapto acetic acid; (22) 2ꢀMercaptoethanol; (23) 3ꢀMercaptopropionic
acid.

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5000
Probe
Probe With NaHS
Probe with other species
Probe with oother species and NaHS
4000
400
300
200
100
0
Figure 6. Competing responses of probe DPP-NO2 (10 ꢁM) in CH3CN toward
various anions and NaHS.
3.3 Limits of detection (LOD) experiment
Having demonstrated the selectivity of DPP-NO2 for the detection of H2S, we next
investigated its ability to quantify the H2S concentration. The fluorescence intensity at
550 nm was measured and the calibration graph of fluorescence emission response
versus different NaHS concentration is presented in Figure 7, and the linear
correlation follows the equation: FI (fluorescence intensity) =3.19+6.39×106×CNaHS
(M) with a correlation coefficient of 0.993. The limits of detection (LOD) were
determined from the equation LOD =3σ/K, where σ is the standard deviation of the
blank solution and K is the slope of the calibration curve. The limits of detection of

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probe DPP-NO2 was determined to be 5.2 nM for hydrogen sulfide detection, which
is at a much lower level than most probes.27ꢀ32
200
150
100
Equation
Weight
y = a + b*x
No Weighting
50
0
Residual Sum
of Squares
169.22572
0.99294
Adj. R-Square
Standard Erro
Value
r
B
B
Intercept
Slope
3.19471
3.96407
6.39277E6 219886.8039
5.0x10-6 1.0x10-5 1.5x10-5 2.0x10-5 2.5x10-5 3.0x10-5
NaHS (M)
0.0
Figure 7. The linear dynamic fluorescence response at 550 nm for the titration of
probe DPP-NO2 with NaHS solution to determine the limits of detection (LOD).
3.4 The proposed mechanism of probe DPP-NO2 towards H2S
Since nitro group could be converted to amino in the presence of hydrogen sulfide,
it is expected that reductive product (DPP-NH2) from reaction of DPP-NO2 with H2S
can be obtained. This hypothesis can be verified by HRMS, in which
[DPP-NH2+H2O+H]+ peaked at 613.3336 (m/z calcd. for [DPP-NH2]+ C38H50N4O2:
594.3934), as shown in Figure 8. We also compare fluorescence emission spectra and
absorption spectra between DPP-NH2 and DPP-NO2 + H2S, as shown in Figs. S4ꢀS5.
It can be seen that they are almost identical. Proposed mechanism of probe DPP-NO2
to H2S was shown in Scheme 2.

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Figure 8. HRMS spectrum of DPP-NO2 with NaHS solution.
C8H17
C8H17
N
NO2
NH2
N
O
O
H2S
O2N
H2N
O
O
N
N
C8H17
C8H17
DPP-NH2 Strongly fluorescent
DPP-NO2
non-fluorescent
Exact Mass: 594.3934
Exact Mass: 654.3417
Scheme 2. Proposed mechanism of probe DPP-NO2 to H2S.
3.5 Cellular imaging
The application of DPP-NO2 in cellular imaging was investigated by fluorescence
images. In these experiments, HeLa cells were individually incubated in culture
medium with DPP-NO2 (10 ꢁM) for 30 min, and then imaged, as shown in Figure 9.
The confocal microscopic image showed a negligible fluorescence signal. When the
cells were supplemented with 200 ꢁM NaHS in the growth medium for 30 min at

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37 °C and then loaded with DPP-NO2 under the same conditions, the bright green
fluorescence image was then observed in cells. These results suggest that DPP-NO2
can be explored for monitoring NaHS within living cells.
(a)
(b)
(c)
(d)
Figure 9. Fluorescence images of HeLa cells. (a) brightfield image: cells stained by
DPP-NO2 (10 ꢁM) for 30 min; (b) the fluorescent image of “a”; (c) brightfield image:
cells supplemented with 200 ꢁM NaHS in the growth media for 30 min at 37 °C and
stained with DPP-NO2 (10 ꢁM) for 30 min at 37 °C; (d) The fluorescent image of “c”.
4. Conclusions
In summary, we presented a nitroolefin functionalized fluorescent probe DPP-NO2
for selective detection of hydrogen sulfide based on the reduction reaction of nitro
group to amino group. This probe has an excellent selectivity to H2S over other
reactive sulfur, oxygen, nitrogen species and anions. The high selectivity, fast
response and the turnꢀon fluorescence signal may offer a valuable fluorescent probe

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for detection of H2S in physiological and pathological processes. What is more,
through the fluorescence turnꢀon signal toward H2S in HeLa cells, probe DPP-NO2
was successfully employed in cells imaging.
Acknowledgements
The supports by National Natural Science Foundation of China (No. 21274045),
the Fundamental Research Funds for the Central Universities (2015ZZ037) and the
Natural Science Foundation of Guangdong Province (2015A030313209,
2016A030311034) are gratefully acknowledged.

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A novel reduction-based fluorescent probe for the sensitive detection of hydrogen
sulfide has been reasonably designed and developed.