A Highly Selective and Sensitive Colorimetric Chemosensor for the Detection of Hydrogen Sulfide: A Real-time Application in Multiple platforms

Article abstract of DOI:10.1111/php.13506

Calorimetric chemosensors are found to be advantageous sensing systems due to their simplicity and favorable responsive properties. Although some colorimetric probes have been reported to detect hydrogen sulfide (H₂S), the creation of rapid, highly selective and sensitive probes for the detection of H₂S remains a challenging target. In this work, we established dinitrosulphonamide decorated phenanthridine and 2,4-dinitro-N-(4-(7,8,13,14-tetrahydrodibenzo[a, i]phenanthridin-5-yl)phenyl)benzenesulfonamide (PHSH), for the calorimetric detection of H₂S. H₂S-triggered thiolysis of PHSH resulted in a marked absorption enhancement alongside a visual color change from colorless to dark yellow. The result indicated that the chemosensor showed high sensitivity and selectivity with a fast response of less than 10?s with a detection limit as low as 6.5?nM. The chemosensor reaction mechanism with H₂S was studied by UV-vis, ¹H NMR, mass and HPLC analysis. In addition, the chemosensor has been used for the determination of H₂S in many real-time samples.

Full text of DOI:10.1111/php.13506

Photochemistry and Photobiology, 20**, **: *–*
Research Article
A Highly Selective and Sensitive Colorimetric Chemosensor for the
Detection of Hydrogen Sulfide: A Real-ftime Application in Multiple
platforms
1
2
1
Dhanapal Jothi , Sathishkumar Munusamy and Sathiyanarayanan Kulathu Iyer *
1
Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, India
2
Institute of Chemical Biology and Nanomedicine, State Key Laboratory of Chemo/Bio-sensing and Chemometrics, College
of Chemistry and Chemical Engineering, Hunan University, Changsha, China
Received 2 May 2021, accepted 10 August 2021, DOI: 10.1111/php.13506
ABSTRACT
monoxide (CO). Though H S contributes to many biological pro-
2
cesses, abysmal metabolism of H S can be associated with an
2
array of diseases such as Alzheimer’s disease (6), Down’s syn-
drome (7), diabetes (8) and liver cirrhosis (9), which necessitates
Calorimetric chemosensors are found to be advantageous
sensing systems due to their simplicity and favorable respon-
sive properties. Although some colorimetric probes have been
the in vivo detection of H
an environmental pollutant and in biological processes, early
detection could ameliorate the dreadful impact of H S.
In recent years, with the ongoing efforts of research groups,
various methods have been developed to detect H S. For exam-
2 2
S. Given the inevitable role of H S as
reported to detect hydrogen sulfide (H
rapid, highly selective and sensitive probes for the detection
of H S remains a challenging target. In this work, we estab-
lished dinitrosulphonamide decorated phenanthridine and
,4-dinitro-N-(4-(7,8,13,14-tetrahydrodibenzo[a, i]phenanth-
ridin-5-yl)phenyl)benzenesulfonamide (PHSH), for the calori-
metric detection of H S. H S-triggered thiolysis of PHSH
2
S), the creation of
2
2
2
2
ple, electrochemical assays (10–14), chromatography (15–17),
metal-induced sulfide precipitation (18) and optical probes are
the main techniques to detect H S. Among these methods, opti-
2
cal detection has received significant attention in recent years
owing to its simplicity, high sensitivity and selectivity, and good
repeatability (19–38). Chemodosimeter is the most common opti-
cal approach in which the chemical probe is incorporated with
2
2
resulted in a marked absorption enhancement alongside a
visual color change from colorless to dark yellow. The result
indicated that the chemosensor showed high sensitivity and
selectivity with a fast response of less than 10 s with a detec-
tion limit as low as 6.5 nM. The chemosensor reaction mech-
an H S selective irreversible responsive unit and optical response
1
2
anism with H
2
S was studied by UV-vis, H NMR, mass and
modulator. Functional groups such as nitro (39–41), azide (42–
HPLC analysis. In addition, the chemosensor has been used
for the determination of H S in many real-time samples.
4
8), hydroxylamine (49) (H
ethers (50–60), disulfide bonds (61), nitrobenzoxadiazole ether
62, 63) and nitrobenzofurazan (64–68) (NBD) (H S induced
2
S induced reduction), dinitrophenyl
2
(
2
INTRODUCTION
hydrolysis) are the functional groups dexterously employed for
the detection of H S. As H S has a strong binding affinity
toward metal ions, its metal displacement or coordination has
also been copiously used to detect H S (69, 70). Though most of
the optical techniques to detect H S are based on fluorescence
changes, visible color change of the probes in the presence of
2
2
Since the industrial revolution, there has been an uninterrupted
pile up of toxic and dangerous gaseous pollutants in the environ-
ment. Among them, hydrogen sulfide (H S) has been broadly
2
studied for its known environmental hazard. Industrial production
of natural gas, biogas and mining are the primary contributors to
2 2
the ecological release of H S. In particular, H S in biogas can
range up to 10–2000 ppm, a nuisance with no energy value and
an impediment that acts like poison for catalyst and as corrosive
2
agent. As a water-soluble gas, H S, in industrial wastewater,
exudes not only a foul smell resembling “rotten eggs” (1) but
2
2
H
2
S is also often reported.
Sensors based on the colorimetric approach are gaining sub-
stantial interest as they offer instantaneous detection of analyte
and visually detectable color change. With these valuable traits,
colorimetric systems can monitor the H S emission levels in the
2
target industrial platforms and can be employed in geological
monitoring. Nevertheless, the research on the development of
selective and sensitive chromogenic probes to detect H S is inad-
2
equate. As part of our ongoing interest in developing optical sen-
sors for important analytes (71–75), in this work, we developed
a simple phenanthridine-based colorimetric probe to detect H S.
2
also instills a severe threat to human health when humans con-
sume H S-contaminated water and food (2). Besides, H S is an
2 2
unwelcoming component of wine, as it negatively contributes to
the quality of wine, which incurs significant economic losses (3–
5
). Again, from the physiological point of view, H
2
S is a vital
gasotransmitter next only to nitric oxide (NO) and carbon
In the design of this probe, phenanthridine was incorporated with
the 2,4-dinitrobenzene sulfonyl (DNBS) group, a widely used
*
Corresponding author email: sathiya_kuna@hotmail.com (Sathiyanarayanan
Kulathu Iyer)
2021 American Society for Photobiology.
selective signaling unit for H S. On the other hand, phenan-
2
©
thridine is a simple chromogenic molecule with outstanding
1

2
Dhanapal Jothi et al.
advantages of straightforward synthesis, intriguing optical prop-
erty and easy functionalization. To our surprise, the colorimet-
added to the real-time samples. Finally, the results were tested by the
absorbance measurements. The data were calculated as the average of
three separate measurements.
ric
H
2
S
sensor derived from DNBS was conspicuously
S in mul-
uncommon. Moreover, sensor PHSH could detect H
2
tiple real-time geological and industrial samples such as
wastewater and wine.
RESULTS AND DISCUSSION
Design and synthesis of PHSH
MATERIALS AND METHODS
The above-mentioned concerns inspired us to build a colorimet-
ric probe for monitoring H S with ultra-sensitivity. We opted for
2
phenanthridine core as they exhibit excellent optical property,
structural stability and easy maneuvers for switching signals. The
All the chemical reagents and organic solvents were purchased as AR
and LR grade from commercial sources and used without further
purification. The compound purifications were done by13 column
1
chromatography using 100-200 mesh silica gel. H NMR and C NMR
key to developing the optical probe for H S is to judiciously
2
spectra were recorded on a Bruker 400 MHz NMR spectrometer using
tetramethylsilane (TMS) as an internal standard. HRMS results were
acquired from Joel GC Mate II GC-Mass spectrometer. Electronic
absorption spectra were recorded with
spectrophotometer.
2
incorporate an appropriate H S signaling unit into the probe. Ide-
ally, such a functional group should react only with H S but not
2
with other sulfur species and anions. In this study, we opted for
the 2,4-dinitrobenzene sulfonyl (DNBS) group as the H S signal-
2
a Hitachi-2910 UV-Vis
Synthesis of 4-(7,8,13,14-tetrahydrodibenzo[a,i]phenanthridine-5-yl)
aniline (PHN). 4-(7,8,13,14-tetrahydrodibenzo[a,i]phenanthridine-5-yl)
aniline (PHN) was prepared based on a previous literature procedure
ing group. Thiolysis of DNBS has many advantages, such as the
ability of DNBS to be attached to the central core by single-step
reaction, diminishment of optical property due to the presence of
[
92]. Yield: 70%, HRMS (ESI) m/z: Calcd for C27
H
22
N
2
374.1783;
Found: 374.1769. H NMR(400MHz, DMSO-d6) : d 2.702-2.717 (t,
H, J = 6 Hz), 2.896-2.902 (d, 4H, J = 2.4 Hz), 3.033-3.050 (t, 2H,
1
TM
2
the nitro group and its high selectivity toward H S than other
2
competitive thiols, for example, glutathione and cysteine (Cys).
Following these rationales, we herein designed and synthesized
the PHSH (see Scheme 1) as a new probe for the selective col-
orimetric detection of hydrogen sulfide. We started our work by
synthesizing 4-(7,8,13,14-tetrahydrodibenzo[a, i]phenanthridin-5-
yl)aniline (PHN) from 2-tetralone and 4-amino benzaldehyde
using the previously reported procedure by our group (76). Then,
the synthesis of PHSH was realized by reaction between (PHN)
and DNBS. Notably, both reactions proceeded efficiently under
simple reaction conditions with good yields. The molecular struc-
J = 6.8 Hz), 6.702-6.723 (d, 2H, J = 8.4 Hz), 6.850-6.868 (m, 2H,
J = 7.2 Hz), 7.124-7.126 (m, 3H, J = 0.8 Hz), 7.291-7.297 (m, 3H,
J = 2.4 Hz), 7.383-7.388 (m, 1H, J = 2 Hz), 7.578-7.595 (t, 1H,
13
J = 6.8 Hz) and 9.658 (s, 2H, NH
2
). C NMR (DMSO-d6, 100 MHz):
d 29.07, 29.17, 29.21, 33.07, 115.37, 125.83, 126.67, 126.79, 127.35,
1
1
27.56, 128.13, 128.27, 128.35, 129.08, 129.18, 131.38, 132.82, 132.92,
33.34, 139.11, 139.47, 145.97, 153.70, 157.55 and 157.80.
Synthesis
of
2,4-dinitro-N-(4-(7,8,13,14-tetrahydrodibenzo[a,i]
phenanthridine-5-yl)phenyl)benzenesulfonamide (PHSH). Compound 4-
(
(
Et
7,8,13,14-tetrahydrodibenzo[a,i]phenanthridine-5-yl) aniline (PHSH)
1 g, 0.00267 mmol) was clearly dissolved in 10 mL of CH Cl2, and
(0.577 mL, 0.004 mmol) was added dropwise. Finally, 2,4-
2
3
N
1
ture of the probe PHSH was thoroughly confirmed by H and
Dinitrosulfonyl chloride (0.852 mg, 0.0032 mmol) was charged into the
reaction mixture solution. The resulting crude mixture was stirred at
room temperature for 9 h, and the completion of the reaction was
monitored by TLC. The crude residue was purified by column
chromatography (eluent n-hexane/ethyl acetate ratio 8:2) to give the
13
C NMR and HRMS analyses (see the Supporting Information
for full details).
Visual observation
light-yellow color solid, m.p 218°C HRMS (ESI) m/z: Calcd for
1
C
33
)
H
24
:
N
d
4
O
6
S 604.1417; Found: 604.1279. H NMR (400 MHz, DMSO-
TM
As a preliminary confirmation, the colorimetric sensitivity of
d
6
2.721-2.735 (d, 2H, J = 5.6 Hz), 2.906-2.915 (d, 4H,
-5
J = 6 Hz), 3.057-3.073 (t, 2H, J = 6.4 Hz), 6.682-6.702 (d, 1H, J = 8),
PHSH (2 x 10 M) toward various anions was studied. Various
anionic solutions were added separately (2 equiv.) to the sensor
solution, and the color change was observed visually. As shown
6
7
.941-6.959 (t, 1H, J = 7.2 Hz), 7.143-7.163 (d, 3H, J = 8 Hz), 7.298-
.316(m, 3H, J = 7.2 Hz), 7.402-7.422 (d, 3H, J = 8 Hz), 7.594-7.606
(
d, 1H, J = 4.8 Hz), 8.279-8.301 (d, 1H, J = 8.8 Hz, 8.642-8.664 (d, 1H,
13
in Fig. 1a, upon the addition of H S to the solution of PHSH, a
2
J = 8.8 Hz and 9.142 (s, NH). C NMR (DMSO-d
6
, 100MHz): d 28.90,
sudden color change from transparent to dark yellow was
observed. However, the solution PHSH remained transparent
over the addition of other competitive anions. In addition, the
color change of PHSH from translucent to dark yellow was
gradual with increasing concentration of H S (Fig. 1b). Hence,
2
without the need for customary complex instrumentation, initial
2
1
1
1
9.04, 29.10, 121.59, 122.28, 126.03, 126.69, 127.69, 127.73, 127.78,
27.82, 128.32, 128.42, 129.00, 129.21, 129.42, 131.06, 132.18, 132.48,
32.55, 134.21, 139.36, 139.57, 142.27, 146.23, 148.39, 148.65, 151.89,
51.95 and 158.07.
Stock solution preparation. A stock solution of PHSH (2 9 10⁻⁵ M)
was prepared in acetonitrile: water (7:3, v/v) solvent medium. All the
solutions of anions and ligands (0.2 M) were prepared in PBS buffer
solution (pH = 7.4). The change in absorbance was monitored at
H S analysis can be made using PHSH by simple visualization.
2
435 nm.
Preparation of test paper strip. To investigate real-time analyses of
cellulose-based test paper (Whatman, Grade 1, US), a probe of 20 lM
solution was prepared in acetonitrile solvent. Test papers were immersed
in probe solution followed by air drying at room temperature. PHSH-
coated test paper strips were dipped into various anion solutions to detect
the anions. Color changes were captured with a digital camera.
Absorption spectral studies of PHSH with H2S
High photostability is an essential attribute of a chemosensor for
sustainable utilization in chemical and biological experiments.
Hence, time-dependent absorption studies were carried out by
irradiating the solution of PHSH with UV light (254 nm). The
absorption spectra of PHSH remained almost unaffected upon
the UV irradiation for about 60 min (Figure S4), which indicates
that PHSH is highly photostable.
2
H S detection in real water samples. The water samples, including
the tap water, well water and lake water collected from in and around
Vellore Institute of Technology, Vellore, were filtered through a 0.20-lm
pore size membrane filter to remove suspended particulate matters. Red
wine and beer samples were acquired from commercial sources and used
as such. The collected samples were mixed with the PHSH stock
solution, and the final ratio was acetonitrile/sample (v/v = 70:30) for the
The UV-vis studies of PHSH were carried out with 2 X
À6
1
0
M sensor solution prepared in acetonitrile: water (7:3)
2
test of real water samples. After that, different amounts of H S were

Photochemistry and Photobiology
3
Scheme 1. Schematic representation of the synthesis of sensor PHBS.
-
5
Figure 1. (a) Colorimetric response of PHBS (2 9 10 M) in acetonitrile solution upon addition of 2 equivalents of various anions. (b) Visible color
change of PHBS upon addition of increasing concentration of H S.
2
solvent medium. Free PHSH showed a single absorption peak at
2
H S to PHSH solution in acetonitrile: water (7:3) solvent med-
ium, a gradual absorbance increase at 435 nm was observed. The
absorption increase at 435 nm was about 38-fold and reached
-1
-1
the wavelength of 315 nm (e = 13 000 M cm ), which could
electron transition. Upon adding H
be corroborated to p-p*
2S (2 equiv.),
a new absorption peak emerged at the wavelength of 435 nm
2
saturation over the addition of 2 equiv. of H S. Encouraged by
the absorption results, we moved on to check the photo-
-
1
-1
(
e = 18 500 M cm ) with diminution of absorption at 315 nm.
The formation of a significant red-shifted new absorption peak
for the sensor indicates the newly formed product’s enhanced
internal charge transfer (ICT). The sensing ability of PHSH was
also checked with other competing anions and ligands, such as
luminescence properties of PHSH before and after the addition
of H S. However, PHSH did not exhibit any fluorescent proper-
2
ties. This could be due to the photo-induced electron transfer
(PET) caused quenching. As the reaction between PHSH and
H S leaves the probe with a free amino group, there could be
2
possible PET form from amino group to phenanthridine core.
-
-
-
-
-
-,
-
-
2-
-
F , Cl , Br , I , OAc , OH NO
2
, NO
3
, CO
3
, H
2
O
2
, HSO
4
,
-
-
HPO
4
, PF
6
, arginine, glutathione, cysteine and homocysteine.
As shown in Fig. 2a, the addition of other anions had almost no
influence on the absorption of the sensor PHSH. Evidently, only
Besides, the plot of ΔA against the concentration of H S
showed a linear relationship (Fig. 3b) with R value of 0.9833.
2
2
the presence of H
2
S caused a distinct appearance of absorbance
With the slope obtained from this linear equation and standard
deviation (r) from six blank measurements, we calculated the
limit of detection (LOD) using the formula 3r/K. LOD of
at 435 nm with an instant color change, as discussed above. The
extent of absorption change at 435 nm was also compared with
anions using a bar diagram (Fig. 2b).
2
PHSH for H S was found to be 6.5 nM (Figure S5), which is
Furthermore, to check the suitability of PHSH to detect H
2
S
comparable with the acceptable limit in the ambient environment
quantitatively, systematic UV-vis titration was carried out. As
shown in Fig. 3a, upon the successive incremental addition of
proposed by U.S scientific advisory (<83 ppb) (77). As PHSH
exerts optical change over the reaction between probe and H S,
2

4
Dhanapal Jothi et al.
-
6
Figure 2. (a) UV-vis spectra of probe PHBS (2 9 10 ) in acetonitrile: water (7:3) solvent medium upon addition of different anions and ligands. (b)
Bar diagram which indicates variation of absorption intensity at 450nm over the addition of anions.
Figure 3. (a) Absorbance spectra of PHBS (1 lM) after incremental addition of H
changes at 435 nm with increasing concentration of H S.
2
S up to 2 equiv. in acetonitrile: water (7:3) (v/v). (b) Absorption
2
the reaction rate might affect the quality of the sensing (Fig-
ure S6). Hence, we investigated the influence of the reaction
time on the probing results. From the temporal absorption track-
ing, we figured out that the absorption reached the plateau at
This study revealed that PHSH could detect H S even in the
presence of other potential competing anions. To study the
practical applicability of probe PHSH, the effect pH was per-
2
formed for PHSH and PHSH+ H S at various pH ranges to
2
1
0 s, indicating that the concluding analytical results of H2S
fix a particular pH to investigate real-time samples as they
were found to appear in different pH ranges. It was found
that for free PHSH, the absorption at 435 nm was insignifi-
cant and unperturbed at the pH ranges tested (pH = 2 to 12).
detection can be achieved in a rapid manner.
Interference and the effect of pH
2
For PHSH+ H S, under neutral and basic conditions, the
To establish uninterrupted detection of H
dual anion cross tainting test was carried out, as shown in
Fig. 4a. The competition experiments indicated the changes in
2
S by PHSH, the
absorbance had very little change. On the contrary, at acidic
pH conditions (≤5), absorbance tended to decrease steadily
with decreasing pH. These results demonstrated that PHSH
the absorbance before and after adding H
2
S into the PHSH
2
could be used to detect H S under physiological and basic
solution with other anions (10 equiv.). PHSH was treated
pH conditions. In addition, PHSH+ H S was found to exhibit
2
with two equiv. of H S in the presence of different anions,
and it did not induce any substantial absorbance changes.
emission at a lower pH value. This could be due to the inhi-
bition of photo-induced electron transfer (PET) from the free
2

Photochemistry and Photobiology
5
-6
Figure 4. (a) Absorption response at 435 nm of free PHBS (2 9 10 M) and PHBS+ H
2
S on addition of other anions (10 equiv.) (b) Effect of pH of
free probe PHBS and PHBS+ H S.
2
amino group to phenanthridine due to the protonation of the
free amino group, which resulted from the reaction between
2
was dipped in the solution of different concentrations of H S,
the color of PHSH-coated filter paper gradually changed from
PHSH and H S.
colorless to yellow. These dip strips are quite helpful as an
2
2
instant and low-cost tool for the qualitative detection of H S.
Sensing mechanism
Practical application
To further confirm that the colorimetric response was due to
the H
2
S-triggered thiolysis reaction of PHSH and the release of
The potential applicability of PHSH for the facile detection of
S was further extended to analyze real-time samples, such as
water and food samples (Red wine, beer). The excessive pres-
ence of H S in wine and beer causes severe damage to the qual-
yellow free amino-containing compound (PHN) (Fig. 5), we
recorded and compared H NMR (in DMSO‑d6 solvent) of free
H
2
1
PHSH in the presence of various levels of H
protons responsible for the aryl portion of 2,4- dinitrophenyl
H ) started to vanish (d = 9.18, 8.51, 8.49) steadily, and the
2
S. The aromatic
2
ity. Chosen and collected samples were spiked with the known
(
concentration of H S and added to the solution of PHSH. The
a
2
new peaks (H ) began to appear at (d = 8.91, 8.58, 8.57),
increase in the absorbance at 435 nm was investigated for the
b
which was due to the release of 2,4-dinitrobenzenethiol by
2
data analysis. As can be seen in Table 1, the spiked H S concen-
product. A new peak at d 9.52 ppm started to form, indicating
tration was determined with satisfactory recovery in the range of
87.0 À 95%. These results indicated that this phenanthridine-
based colorimetric probe could be a promising candidate for
the formation of the free –NH group. In addition, the thiolysis
2
product was purified and subjected to HRMS analysis. The
mass peak at m/z = 374.1769 confirmed the structure of PHN
determining H
2
S content in various real-time matrices and for
(
Figure S7). High-performance liquid chromatography (HPLC)-
based reaction monitoring was carried out for the reaction
between PHSH and H S. Under the HPLC method used,
PHSH had a retention time of 5.49 minutes with very high
purity. When various levels of H S were allowed to react with
quality control.
2
CONCLUSION
2
In summary, we have reported a new phenanthridine-based sen-
sor PHSH with 2,4-dinitrobenzene sulfonyl group for the selec-
tive and sensitive detection of H S. When added with H S,
PHSH, a new peak at 8.32 minutes started to appear due to
the formation of PHN (Figure S8). Thus, the mechanism of
2
2
probe PHSH for sensing H S is based on the thiolysis of the
dinitrophenyl ether group.
PHSH showed rapid (within 10s) and remarkable absorption
enhancement at 435 nm and responded to concentration at a
level as low as LOD = 6.5 nM. Besides, the PHSH solution
2
became dark yellow from colorless over the addition of H S.
Sensor PHSH exhibits high selectivity for H S over other rele-
2
2
Naked eye detection of H
To simplify the detection process of H
test strips were prepared by soaking filter papers in acetonitrile
solution of PHSH (2 x 10 M), and the filter papers were air-
dried before further analysis. As can be seen in Fig. 6a, test
paper strips exhibited no color. After treating with various
2
S by test strips
2
S, PHSH impregnated
vant thiols and anions in a semi aqueous solution. H S-triggered
2
1
thiolysis of PHSH was confirmed by H NMR and HRMS
-5
study. The potential real-time application of PHSH has been suc-
cessfully demonstrated in various platforms, such as paper-based
testing, analysis in different real-time matrixes. With the numer-
ous advantages such as high sensitivity and selectivity, fast
response time, ease of preparation and stability at a broad pH
range, PHSH could stand as the ideal colorimetric chemosensor
anions (those chosen in the optical study), only H S caused an
2
obvious color change to yellow. Hence, PHSH-coated filter
papers can be used as a qualitative testing tool for rapid onsite
detection of H S. As shown in Fig. 6b, when the test paper
for H S.
2
2

6
Dhanapal Jothi et al.
1
1
Figure 5. H NMR titration spectra [400 MHz] of PHBS in DMSO-d6 at 25°C over the incremental addition of H
2
S; Expansion of H NMR region at
9–10 ppm; Reaction scheme indicating thiolysis of PHBS.
-
5 M
Figure 6. (a) Photograph showing naked eye visible color change of PHBS (2 9 10
)-coated test paper strips after treating with various anions. (b)
-
5 M
Photographs of PHBS (2 9 10
)-coated test paper strips dipped into H S solutions (0, 10, 20, 30, 40 and 50 lM) under daylight.
2

Photochemistry and Photobiology
7
Table 1. Determination of H
ples
2
S Concentrations in various real-time sam-
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chloride mouse model of alzheimer’s disease. ACS Chem. Neurosci.
Spiked level
Found level
(M)
Recovery
(%)
(n = 3)
(%)
Matrix
(M)
À6
À6
Tap
1 9 10
0.92 9 10
92
89
90
0.17
0.31
0.27
1
0, 3500–3509.
water*
Lake
water*
Well
7
. Kamoun, P., M.-C. Belardinelli, A. Chabli, K. Lallouchi and B.
Chadefaux-Vekemans (2003) Endogenous hydrogen sulfide overpro-
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À6
À6
À6
1 9 10
1 9 10
0.89 9 10
À6
0.90 9 10
3
11.
water*
Red wine
Beer
8
. Qian, L.-L., X.-Y. Liu, Q. Chai and R.-X. Wang (2018) Hydrogen
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À6
À6
À6
1 9 10
1 9 10
0.88 9 10
88
87
1.03
0.14
À6
0.87 9 10
9
*
Water samples were collected from in and around VIT campus, Vellore.
†
Relative standard deviation.
1
0. Sui, L., T. Yu, D. Zhao, X. Cheng, X. Zhang, P. Wang, Y. Xu, S.
Gao, H. Zhao, Y. Gao and L. Huo (2020) In situ deposited hierarchi-
cal CuO/NiO nanowall arrays film sensor with enhanced gas sensing
Acknowledgements—Dhanapal
J thanks VIT for providing financial
support through research associateship. S M gratefully acknowledges the
Youth 1000 Talent Program of China and Interdisciplinary Research
Program of Hunan University. The DST-FIST NMR facility at VIT
University is duly acknowledged. The authors thank Dr. R. Srinivasan,
SSL-VIT, for language editing.
2
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13
Figure S1. H and C NMR spectra of (PHN).
1
13
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Figure S2. H and C NMR spectra of PHSH.
Figure S3. HRMS spectra of PHSN.
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Figure S4. Time-dependent stability analysis spectra of
À6
PHSH. Sensor probe PHSH 2 X 10 M solution prepared in
acetonitrile: water (7:3) solvent medium
Figure S5. LOD determination of PHSH with H
culated LOD of probe PHSH is 6.5 nM.
Figure S6. Effect of response time-dependent absorption spec-
2
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