Materials Today Chemistry 12 (2019) 178e186

Contents lists available at ScienceDirect

Materials Today Chemistry

journal homepage: www.journals.elsevier.com/materials-today-chemistry/

A novel star-shaped triazine-triphenylamineebased fluorescent

chemosensor for the selective detection of picric acid
G. Sathiyan a, b, *, B. Balasubramaniam a, S. Ranjan a, S. Chatterjee b, P. Sen b, A. Garg c, **,
R.K. Gupta a, d, ***, A. Singh b, ****
a
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
b
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
c
Department of Material Sciences and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
d
Center for Environmental Science and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

a r t i c l e i n f o a b s t r a c t

Article history: This work reports development of a new donor-acceptoretype star-shaped 4,40 ,400 -(1,3,5-triazine-2,4,6-
Received 20 December 2018 triyl)tris(N,N-diphenylaniline) (TRZDPA) molecule towards detection of an ultratrace amount of picric
Received in revised form acid (PA). TRZDPA showed solvent-dependent fluorescence spectra in an excited state owing to its strong
10 January 2019
intramolecular charge-transfer properties. As a fluorescent probe, TRZDPA shows remarkable sensitivity
Accepted 13 January 2019
towards the PA in a highly selective manner compared with other nitroaromatic compounds. Furthermore,
efficiency of the quenching process was evaluated by the SterneVolmer equation. The fluorescence
quenching mechanism of the probe during PA detection was evaluated from the photophysical and other
Keywords:
Donor-Acceptor type
spectral characterizations. The detection limit of PA was 0.37 nM, confirming the detection of PA in aqueous
Fluorescence quenching media at a trace level. To facilitate easy detection of PA, TRZDPA-modified fluorescent thin-layer chro-
Sensor matography (TLC) strips were developed as ‘turn-off’ sensors which can be visualized by the naked eye.
Nitroaromatics © 2019 Elsevier Ltd. All rights reserved.

1. Introduction diseases [3e6]. The high solubility of PA in water renders it very

dangerous in case of accidental spills and/or misuse. Hence, the
Compounds with explosive properties occupy a unique place in sensing and effective monitoring of low concentrations of PA in the
history. While they are indispensable for many lawful activities vapour and solution phase with the help of efficient real-time
such as the construction of civil infrastructure, they are also often sensors is crucial for health and environmental security [7,8].
misused, leading to the development of many methods to detect Various sensing techniques, such as electrochemical methods
such compounds. Commonly used explosive materials such as [9,10], Gas chromatographyemass spectrometry (GC-MS), high-
trinitrotoluene (TNT) and picric acid (PA) contain one or more nitro performance liquid chromatography (HPLC), metal detector, and
functional groups [1]. Until the 1940s, TNT was used as a most ion mobility spectroscopy [11], are currently available to detect the
common explosive, but subsequently, it was replaced by PA, owing nitroaromatics. Most of the available methods are expensive and
to its higher explosive power [2]. PA is widely used in the paint, dye, overly sophisticated for wide applications. Hence, recent research
and pharmaceutical industries, in addition, being an important efforts are focussed on developing cost-effective and novel sensing
component of rocket fuel manufacturing. Exposure to PA can lead to materials such as nanoparticles [12e14], nanofibers [15e17], gels
liver malfunction, eye and skin irritation and other potentially fatal [18,19], polymers [20,21], macromolecules [22], small molecules
sensors [15,23], metaleorganic frameworks (MOFs) [24,25], fluo-
rescence and so on. Among all the methods, fluorescence-based
* Corresponding author. Department of Chemical Engineering, Indian Institute of sensing methods have tremendous potential owing to their
Technology Kanpur, Kanpur 208016, India. Fax: þ91 5122590104.
simplicity, high sensitivity, cost-effectiveness, simple sample
** Corresponding author. Fax: þ91 5122590104.
*** Corresponding author. Department of Chemical Engineering, Indian Institute preparation, and portability [23,26e30]. Electron-rich conjugated
of Technology Kanpur, Kanpur 208016, India. Fax: þ91 5122590104. molecules are widely used for the detection of PA by fluorescence
**** Corresponding author. Fax: þ91 5122590104. quenching mechanism, which is based on p-p interaction (inter-
E-mail addresses: [email protected] (G. Sathiyan), [email protected] action restricts intramolecular charge-transfer [ICT], proton
(A. Garg), [email protected] (R.K. Gupta), [email protected] (A. Singh).

https://doi.org/10.1016/j.mtchem.2019.01.002
2468-5194/© 2019 Elsevier Ltd. All rights reserved.
 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186 179

Scheme 1. Synthesis of TRZDPA.

transfer, or acidebase interactions) and photoinduced electron Avra. Nitrobenzene, 2,4-dinitrotoluene and 4-nitrobenzoic acid
transfer (PET), which depends on the energy gap between lowest were obtained from TCI Chemicals. Trifluoromethanesulfonic acid
unoccupied molecular orbital (LUMO) levels of the quencher and was bought from Alfa Aesar. tris(dibenzylideneacetone)dipalla-
fluorophore molecules [20,21,31,32]. Several MOFs, oligo(p-phe- dium/tri-tert-butyl phosphonium tetrafluoroborate mixture (mole
nylenevinylene)ebased gelators, and molecular imprinted poly- ratio: 1/1.2) was obtained from Sigma-Aldrich. Column chroma-
mers already exist to detect the presence of electron-deficient tography was performed using silica gel (60e120 mesh) from SD
nitroaromatics [33]. Another set of fluorophores sensitive to Fine Chemical Company. Other solvents were purchased
nitroaromatic compounds (NACs) are polycyclic aromatic hydro- commercially at AR-grade quality and used without any further
carbons such as anthracene and pyrene [34]. In comparison to purification.
conjugated polymers, small conjugated molecules are more inter-
esting owing to their well-defined structures, better reproduc- 2.2. Measurements
ibility, simple synthesis, purification, and broader detection range
for explosive compounds [35,36]. 1
H and 13C NMR spectra were recorded using a Bruker Avance
Recently, triphenylamine was explored as an excellent hole 500 (500 MHz) in CDCl3 using solvent and tetramethylsilane as an
transport material and a very useful candidate for organic elec- internal standard. The UV-visible absorption spectra were recorded
tronic materials owing to its strong affinity to locate the cationic using Cary 7000 spectrophotometer, Agilent technologies. The
charge [37,38]. This scaffold has also been used for the selective fluorescence spectra studies were performed using Horiba Jobin
detection of PA with a detection limit of ~400 ppb which was re- Yvon Fluorolog-3 spectrofluorometer. Fluorescence lifetime was
ported by Pati and Zade [26]. Chowdhury and Mukherjee [27] have measured at the magic-angle condition with a picosecond time-
developed electron-rich fluorescent esters containing a triphenyl- correlated single-photon counting setup (LifeSpeceII, Edinburgh
amine backbone and their analogous carboxylic acids. Murugavel Instruments, UK). Scanning electron microscope (SEM) images
et al. [39e41] have reported a series of triphenylbenzene-based were obtained on field emission scanning electron microscope
chemosensors for the detection of PA by fluorescence quenching. (Quanta 200, Zeiss). Fourier transform infrared spectra were
Sathiyan and Sakthivel [22] reported a triazine-linked carbazole- recorded using KBr pellet method (FTIR, PerkinElmer, USA). Raman
based fluorescent probe for the selective detection of PA in spectra were carried out using Raman spectrometer (WiTec, Ger-
aqueous media. Herein, we report a new star-shaped triazine-tri- many, 532 nm). Cyclic voltammetry (CV) was measured in three-
phenylamineebased organic fluorophore (TRZDPA) which exhibi- electrode system such as platinum and platinum wire used as a
ted donor-acceptor (D-A) properties while maintaining electron- working electrode and counter electrode and Ag/AgCl used as a
rich character. We studied the photophysical properties of this reference electrode in tetrahydrofuran (THF) solutions with 0.1 M
new molecule (TRZDPA) in detail and established that it is a very tetrabutylammonium hexafluorophosphate [nBu4N]þ[PF6]
selective and sensitive sensor for PA. electrolyte.

2. Experimental procedure 2.3. Synthesis

2.1. Materials and methods 2.3.1. 2,4,6-tris(4-bromophenyl)-1,3,5-triazine

4-Bromobenzonitrile (35.7 g, 0.196 mol) was dissolved in CHCl3

Diphenylamine, 4-bromobenzonitrile, sodium tert-butoxide, (80 mL) and the solution was cooled to 0 C under N2 atm. Tri-
1,3-dinitrobenzene, 4-nitrotoluene, 2,4-dinitrophenol (DNP), 4- fluoromethanesulfonic acid (20 mL) was added dropwise, and the
nitrophenol (NP) and 4-nitrobenzaldehyde were purchased from reaction was warmed slowly to room temperature and stirred

Fig. 1. (a) Normalized UV-visible absorption and (b) emission spectra of TRZDPA in different solvents (Inset photographs of TRZDPA in different solvents).
ACN, acetonitrile.
180 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186

Table 1
Photophysical properties of TRZDPA.

Solvents Absorbance Emission Dss (cm1)a (FF)b t (ns)c krd (107S1) knre (107S1)
Maximum Maximum
lmax (nm) lmax (nm)
Hexane 390 434 2599 0.13 1.76 0.73 4.93
Toluene 395 478 4395 0.31 3.30 0.93 2.09
EA 390 496 5479 0.42 3.74 1.13 1.56
CHCl3 396 495 5050 0.59 3.20 1.84 1.28
THF 394 504 5539 0.61 3.80 1.60 1.02
DMF 394 525 6333 0.44 4.08 1.07 1.37
Acetonitrile 389 529 6803 0.40 3.23 1.23 1.85
a
Dss (Stokes shift) ¼ Absorbance maximum-Emission maximum
b
Quantum yield was calculated using riboflavin (0.3) as the reference standard [44,45].
c
Lifetime experiment was carried out using time-correlated single-photonecounting technique exciting at 375 nm.
d
Kr was calculated using FF/t.
e
Knr was calculated by using Kr[(1/FF)-1].

tert-butoxide (0.53 g, 6.26 mol) was dissolved in anhydrous

toluene. Nitrogen was purged through the mixture for 10 min
followed by the addition of tris(dibenzylideneacetone)
dipalladium/tri-tert-butyl phosphonium tetrafluoroborate
mixture (mole ratio: 1/1.2) (0.08 g) and the reaction mixture was
heated to reflux for 30 h. The reaction mixture was filtered
through celite, and the organic layer was extracted using ethyl
acetate and dried over anhydrous magnesium sulphate. The crude
product was purified through column chromatography using
hexane: ethyl acetate as eluent to give TRZDPA as a light green
solid (yield: 85%). 1H NMR (CDCl3, 400 MHz) d: 8.52 (d, J ¼ 8.7 Hz,
6H), 7.33e7.29 (t, 12H), 7.17 (d, J ¼ 7.4 Hz, 12H), 7.14e7.07 (m, 12H).
13
C NMR (CDCl3, 100 MHz) d: 170.66, 151.65, 147.16, 130.11, 129.60,
125.64, 124.12, 121.39, 117.94. HRMS, calculated: 811.3505; found:
811.3631.

3. Results and discussion

Fig. 2. Lifetime decay curve of TRZDPA in different solvents. The synthetic procedure for the triazineetriphenylamine fluo-
ACN, acetonitrile.
rophore TRZDPA is outlined in Scheme 1. TRZ-Br was synthesized
by an acid-catalysed cycloisomerization reaction and confirmed by
1
overnight. The reaction mixture was poured into ice-cold water and H NMR and FTIR. Furthermore, the target compound TRZDPA was
neutralized with aqueous ammonia solution. The precipitate ob- synthesized via the BuchwaldeHartwig coupling reaction, and its
tained was collected by filtration and washed with ethanol, structure was confirmed by the spectroscopic techniques such as
hexane and chloroform to give the product as a white powder NMR, FTIR and HRMS. The synthesized molecule is freely soluble in
(yield: 75%). 1H NMR (CDCl3, 400 MHz) d: 8.58 (d, J ¼ 8.8 Hz, 1H), common organic solvents and completely insoluble in water at
7.69 (d, J ¼ 8.8 Hz, 1H). room temperature.

3.1. Photophysical properties

2.3.2. 4,40 ,400 -(1,3,5-triazine-2,4,6-triyl)tris(N,N-diphenylaniline)
A mixture of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TRZ-Br) The UV-visible absorption and emission spectra of TRZDPA in
(1.00 g, 2.09 mol), diphenylamine (0.65 g, 4.38 mol) and sodium CHCl3 are depicted in Fig. S1. TRZDPA shows two absorption bands

Fig. 3. (a) UV-vis absorption spectra of TRZDPA with different NACs and (b) UV-vis absorption titration of TRZDPA with increasing concentration of PA (0e10 eq.).
NACs, nitroaromatic compounds; PA, picric acid; DNP, 2,4-dinitrophenol.
 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186 181

Fig. 4. (a) Fluorescence emission spectra of TRZDPA with 3 equivalent addition of different NACs and (b) their quenching percentage of TRZDPA with different NACs.
NACs, nitroaromatic compounds; NT, 4-nitrotoluene; NB, nitrobenzene; NBAO, 4-nitrobenzoic acid; NBA, 4-nitrobenzaldehyde; DNB, 1,3-dinitrobenzene; DNT, 2,4-dinitrotoluene;
NP, 4-nitrophenol; DNP, 2,4-dinitrophenol; PA, picric acid.

Fig. 5. (a) Fluorescence titration of TRZDPA with increasing concentration of PA (Inset photographs show the presence and absence of PA in TRZDPA) and (b) lifetime decay curve of
TRZDPA in THF solvent in the presence and absence of the PA analyte.
PA, picric acid.

with absorption maxima at 294 and 396 nm. The first weak ab-
sorption band at 270e330 nm was assigned to p-p* transitions
[27], and the second strong absorption band at 333e460 nm was
attributed to the ICT transitions between the donor and acceptor
[22,42,43]. TRZDPA exhibited a strong emission band at
430e660 nm, on being excited at 396 nm. To ascertain the like-
lihood of ICT transitions, we recorded the absorption and fluo-
rescence spectra of TRZDPA in solvents of different polarity, as
shown in Fig. 1a, and the corresponding data are summarized in
Table 1. The absorption spectra of TRZDPA show slight red ab-
sorption because of weak interactions in the ground state. In
contrast, emission spectra show significant changes which can be
attributed to solvent polarity. A comparison between the data
obtained in hexane and acetonitrile solvents reveals that TRZDPA
shows strong bathochromic shift (~95 nm), which indicates more
interaction in the excited state as the polarity of the medium
increases.
The inset photograph in Fig. 1b provides a visual assessment of
the solvatochromism properties of TRZDPA. Furthermore, Stokes
shift values of TRZDPA steadily increased with the solvent polarity
(2599 cm1 for hexane and 6803 cm1 for acetonitrile [ACN]).
This trend in Stokes shift values is indicative of the ICT properties
of this molecule. In addition, TRZDPA showed an increase in
quantum yields (Ffl) as the solvent polarity was increased, where,
Ffl ¼ 0.13, 0.31, 0.42, 0.59, 0.61, 0.44 and 0.40 for hexane, ethyl
acetate (EA), toluene, CHCl3, THF, N,N-dimethylformamide (DMF)
Fig. 6. The SterneVolmer plot of different NAC (0e10 equivalent) addition on the
and ACN, respectively. The lifetime of TRZDPA was measured in emission of TRZDPA.
different organic solvents, and obtained spectra were shown in NAC, nitroaromatic compound. PA, picric acid; NT, 4-nitrotoluene; NB, nitrobenzene;
Fig. 2. The spectra were fitted with biexponential fit, and it was DNP, 2,4-dinitrophenol; NP, 4-nitrophenol; DNB, 1,3-dinitrobenzene; NBA, 4-
found that the lifetime was increased with increasing solvent nitrobenzaldehyde; DNT, 2,4-dinitrotoluene; DNBO, 4-nitrobenzoic acid.
182 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186

polarity, and the maximum lifetime was observed in DMF peak at 504 nm of TRZDPA was quenched on addition of PA, without
(4.08 ns). any changes in the emission peak position. In the case of NP and
DNP, slight quenching was observed but other NACs did not cause
3.2. Detection of explosives any changes in the emission spectrum. Fluorescence quenching
efficiency was calculated using the equation h ¼ Io-I/Io X 100%,
The D-A architecture, p-electronerich feature and highly fluo- where, Io and I denote before and after addition of quencher into
rescent nature of TRZDPA encouraged us to explore its potential TRZDPA. The bar diagram shows that only nitroaromatics bearing a
application for the detection of NACs. Because NACs are highly phenolic moiety interact with the fluorophore (TRZDPA) (Fig. 4b).
electron-deficient, they can easily interact with electron-rich fluo- Among the nitroaromatics that resulted in the quenching of
rescent probes, causing restriction of ICT or p-p interaction, thereby TRZDPA fluorescence, it was observed that higher number of nitro
resulting in a change in photophysical properties, which can be groups in the molecule resulted in more effective quenching
measured. The UV-vis absorption spectra of TRZDPA were per- (PA > DNP > NP). These compounds showed higher fluorescence
formed in THF with different NACs dissolved in aqueous media quenching for 3 eq. addition, while the same concentration of all
(Fig. 3a). The absorbance peak of TRZDPA at 394 nm increases on the other analytes only slightly quenches the original fluorescence
addition of PA. But, the addition of other NACs to TRZDPA does not of the TRZDPA (less than 9%), which is confirmation of the selective
cause a significant change in the absorption intensity. Furthermore, detection of PA.
we performed a titration of TRZDPA against PA which showed Fig. 5a showed excellent fluorescent turn-off behaviour towards
increasing absorbance intensity as PA was being added, as shown in the PA at 8 eq. concentration of the analyte wherein complete
Fig. 3b. The absorbance intensity increased in a linear fashion with quenching was observed. At lower concentrations of PA in TRZDPA,
increasing concentration of PA. It was observed that the absorbance the SterneVolmer plot is linear due to static quenching mechanism,
band at 394 nm becomes broad with a slight blue shift to 378 nm, whereas higher concentration of PA results in the plot becoming
demonstrating the formation of a charge-transfer complex in the upwards due to the superamplified quenching effect (Fig. S2)
ground state between electron-rich TRZDPA and electron-deficient [48,49]. The quenching constant (Ksv) value for PA was calculated
PA [29,46,47]. to be 3.53  105 M1 according to the slope of the SterneVolmer
Similarly, the fluorescence spectra of TRZDPA were recorded plot, which is higher than the previous values reported in the
with different NACs and are shown in Fig. 4a. The intense emission literature. The quenching constant for PA is two orders of

Fig. 7. SEM images of (a) TRZDPA, (b) magnified view of TR ZDPA, (c) TRZDPA þ PA and (d) magnified view of TR ZDPA þ PA.
PA, picric acid.
 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186 183

Fig. 8. (a) Cyclic voltammogram of the TRZDPA in THF solvent in the absence and presence of PA analyte and (b) energy level comparison of TR ZDPA and PA analyte.
PA, picric acid.

magnitude higher than that for other nitroaromatics (~103 M1), lifetime in the excited state due to collisional energy transfer from
which indicates that TRZDPA shows better sensitivity and selec- the excited fluorophore to the quencher [29,46,50]. Therefore, we
tivity towards PA. The limit of detection is also an important factor measured the lifetime of TRZDPA with and without the PA analyte,
for practical applications, and it was calculated to be 0.37 nM. and the results are shown in Fig. 5b. The lifetime of TRZDPA without
Furthermore, to identify specific recognition of PA, the study of any PA was determined to be 3.80 ns, and on addition of PA, it was
interference with other NACs is necessary owing to the identical decreased marginally to 3.60 ns. These results suggest that static
electron-deficient nature of all other NACs. The quenching per- fluorescence quenching due to the ground state complexation be-
centage of TRZDPA was calculated by the equimolar mixture of PA tween electron-rich fluorophore (TRZDPA) and electron-deficient PA
in the presence of other NACs (Fig. S5). These results clearly show is the primary pathway. The rate of fluorescence quenching of
significant selectivity of TRZDPA towards PA even in the presence of TRZDPA by other NACs was also investigated using the SterneVolmer
other interfering NACs. relationship. The 3D SterneVolmer plot of different NACs was shown
The fluorescence lifetime of TRZDPA was measured in the pres- in Fig. 6, which clearly demonstrates the effectiveness of PA
ence and absence of PA to gain insights into the mechanism of compared with other NACs.
fluorescence-quenching response. The non-linear SterneVolmer Furthermore, we investigated the morphology of TRZDPA using
plot also suggests that more than one quenching process is operative an SEM. Fig. 7 shows the images of TRZDPA and TRZDPA þ PA. The
in this detection process. Fluorescence lifetimes can indicate SEM image of TRZDPA shows the congested and clogged cluster
whether the quenching process is static or dynamic as the former morphology. It was noticed from the magnified images that the
does not impact lifetimes because the complexation between the addition of PA stabilised the TRZDPA matrix. Hence a neat and
non-fluorescent fluorophore and quencher occurs in the ground compact morphology was observed in TRZDPA þ PA compared with
state [29]. However, dynamic quenching will affect the fluorescence TRZDPA.

Fig. 9. 1H NMR spectra of before and after addition of PA to TRZDPA in CDCl3 solvent.
PA, picric acid.
184 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186

Fig. 10. Schematic representation of the sensing mechanism of TRZDPA towards PA.
PA, picric acid. ICT, intramolecular charge transfer.

To gauge the possibility of an electrostatic interaction or with and without addition of PA. In the pristine state, TRZDPA
electron transfer between electron-rich TRZDPA and electron- shows Raman peaks at 1000, 1058, 1148, 1173, 1276, 1376, 1419, 1511
deficient PA, CV was carried out. Fig. 8 depicts the CV curve of and 1609 cm1. After interaction with PA, TRZDPA shows slight shift
TRZDPA in THF solvent in the presence and absence of the PA to lower values of Raman signals at 1607, 1509, 1417, 1368, 1246,
analyte. The HOMO and LUMO levels of TRZDPA were calculated 1212, 1162, 1053 and 986 cm1. 1609 cm1 peak corresponds to C]
using the equations highest occupied molecular orbital C vibration, and 1511 cm1 peak corresponds to C]N vibration [51].
þ
(HOMO) ¼ eeV (Eonset ox eE1/2 Fc /Fc þ 4.8) and LUMO ¼ eeV These results and pervious reports indicate the restrictions of ICT or
onset þ
(Ered eE1/2 Fc /Fc þ 4.8). In the presence of PA, the reduction formation of the charge-transfer (CT) complex between TRZDPA
potential was increased, which is clearly visible. From the CV, the and PA [52].
TRZDPA LUMO level was calculated to be 3.32 eV, which is close As per the experimental results, a reasonable picture can be
to the LUMO level of PA (3.93 eV). These values indicate that constructed that explains the mechanism of PA sensing by TRZDPA
there is a possibility of electron transfer from the TRZDPA LUMO and it is shown in Fig. 10. TRZDPA's fluorescence can be attributed
level to the PA LUMO level. Furthermore, the fluorescence to ICT which is restricted after the addition of PA due to the for-
quenching titration also supports these data, providing possibility mation of a charge-transfer complex. For on-site application, visual
of PET process [32]. detection can be an important tool for the detection of NACs. We
To further investigate the ground state interaction between prepared TLC test trips of TRZDPA in THF and TRZDPA þ PA (Fig. 11).
electron-rich TRZDPA and PA, 1H NMR studies were conducted with The pure TRZDPA showed bright colour illumination and after the
and without the addition of PA as shown in Fig. 9. The triphenyl- PA over the TRZDPA showed fluorescence quenching.
amine proton peak at 8.55 ppm shifted slightly upfield to 8.52 ppm
on addition of PA. The remaining peaks are unaffected by the 4. Conclusions
addition of PA, which indicates that there is no interaction bond
between TRZDPA and PA. The PA peak was observed in the position In conclusion, a D-Aetype star-shaped fluorescent molecule
of 9.18 ppm. The results of NMR and CV studies clearly reveal that (TRZDPA) was synthesized with a good yield. Photophysical char-
fluorescence quenching is mainly due to the restriction of ICT of acterization of TRZDPA revealed interesting solvatochromism
TRZDPA on addition of PA. FTIR spectra of TRZDPA were performed properties in an excited state with a good quantum yield in polar
in the presence and absence of PA and obtained spectra are shown solvent. TRZDPA exhibited selective sensing response towards PA
in Fig. S6. After interaction with PA, TRZDPA shows significant compared with other NACs. The detailed optical and electro-
spectral changes. Appearance of new absorbance peaks at 1561, chemical studies revealed that restriction of ICT is responsible for
1635 and 3088 cm1 support the intramolecular interactions. the fluorescence quenching. The sensing ability of the TRZDPA to-
Additionally, intensity of the C]N stretching absorbance band at wards PA was demonstrated on a TLC plate to show the practical
1420 cm1 was decreased owing to the presence of partially pro- utility as an on-site detection tool that can be visualized by the
tonated nitrogen groups. Fig. S7 shows Raman spectra of TRZDPA naked eye. The reported material can be accessed in a low-cost
manner, owing to the simple synthetic protocol. TRZDPA's simple
synthesis coupled with its highly selective detection of PA could
render it as a valuable fluorescence-based tool for environmental
and security applications.

Conflict of interest

The authors declare no competing financial interest.

Acknowledgements
Fig. 11. Photographs of TLC plate with TRZDPA (left side) and drop of PA spotted over
TRZDPA (Right side) under 365 nm UV light. The authors acknowledge the financial support from DST-RCUK
PA, picric acid. Grant no SR/RC-UK/APEX Phase II/2015, UKRI Global Challenge
 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186 185

Research Fund project, SUNRISE (EP/P032591/1) and DST Grant No. [21] W. Huang, E. Smarsly, J. Han, M. Bender, K. Seehafer, I. Wacker, et al., Truxene-
based hyperbranched conjugated polymers: fluorescent micelles detect ex-
DST/TMD/CERI/C140(G) under Clean Energy Research Initiative.
plosives in water, ACS Appl. Mater. Interfaces 9 (2017) 3068e3074.
R.K.G. acknowledges financial assistance from Department of Sci- [22] G. Sathiyan, P. Sakthivel, A multibranched carbazole linked triazine based
ence and Technology (DST), India, through the INSPIRE Faculty fluorescent molecule for the selective detection of picric acid, RSC Adv. 6
Award (Project No. IFA-13 ENG-57) and Grant No. DST/TM/WTI/ (2016) 106705e106715.
[23] D.D. La, S.V. Bhosale, L.A. Jones, S.V. Bhosale, Tetraphenylethylene-based AIE-
2K16/23(G). GS acknowledges the Science and Engineering active probes for sensing applications, ACS Appl. Mater. Interfaces 10 (2018)
Research Board (SERB), Department of Science and Technology 12189e12216.
(DST), for the financial support through NPDF reference no. PDF/ [24] B. Gole, A.K. Bar, P.S. Mukherjee, Modification of extended open frameworks
with fluorescent tags for sensing explosives: competition between size
2017/001079. selectivity and electron deficiency, Chem. Eur J. 20 (2014) 2276e2291.
[25] B. Gole, A.K. Bar, P.S. Mukherjee, Fluorescent metal-organic framework for
selective sensing of nitroaromatic explosives, Chem. Commun. 47 (2011)
Appendix A. Supplementary data 12137e12139.
[26] P.B. Pati, S.S. Zade, Highly emissive triphenylamine based fluorophores for
Supplementary data to this article can be found online at detection of picric acid, Tetrahedron Lett. 55 (2014) 5290e5293.
[27] A. Chowdhury, P.S. Mukherjee, Electron-rich triphenylamine-based sensors
https://doi.org/10.1016/j.mtchem.2019.01.002. for picric acid detection, J. Org. Chem. 80 (2015) 4064e4075.
[28] J.-F. Xiong, J.-X. Li, G.-Z. Mo, J.-P. Huo, J.-Y. Liu, X.-Y. Chen, et al., Benzimidazole
derivatives: selective fluorescent chemosensors for the picogram detection of
References picric acid, J. Org. Chem. 79 (2014) 11619e11630.
[29] M. Shyamal, S. Maity, P. Mazumdar, G.P. Sahoo, R. Maity, A. Misra, Synthesis of
[1] X. Sun, Y. Wang, Y. Lei, Fluorescence based explosive detection: from mech- an efficient pyrene based AIE active functional material for selective sensing
anisms to sensory materials, Chem. Soc. Rev. 44 (2015) 8019e8061. of 2,4,6-trinitrophenol, J. Photochem. Photobiol., A 342 (2017) 1e14.
[2] G.V. Perez, A.L. Perez, Organic acids without a carboxylic acid functional [30] V. Mahendran, K. Pasumpon, S. Thimmarayaperumal, P. Thilagar,
group, J. Chem. Educ. 77 (2000) 910. S. Shanmugam, Tetraphenylethenee2-pyrone conjugate: aggregation-
[3] T.D. James, K.R.A. Samankumara Sandanayake, S. Shinkai, Chiral discrimina- induced emission study and explosives sensor, J. Org. Chem. 81 (2016)
tion of monosaccharides using a fluorescent molecular sensor, Nature 374 3597e3602.
(1995) 345. [31] M. Li, H. Liu, X. Ren, Ratiometric fluorescence and mesoporous structured
[4] Y. Ferrand, M.P. Crump, A.P. Davis, A synthetic lectin analog for biomimetic imprinting nanoparticles for rapid and sensitive detection 2,4,6-
disaccharide recognition, Science 318 (2007) 619e622. trinitrophenol, Biosens. Bioelectron. 89 (2017) 899e905.
[5] B. Lachance, P.Y. Robidoux, J. Hawari, G. Ampleman, S. Thiboutot, [32] K. Bauri, B. Saha, J. Mahanti, P. De, A nonconjugated macromolecular lumi-
G.I. Sunahara, Cytotoxic and genotoxic effects of energetic compounds on nogen for speedy, selective and sensitive detection of picric acid in water,
bacterial and mammalian cells in vitro, Mutat. Res. Genet. Toxicol. 444 (1999) Polym. Chem. 8 (2017) 7180e7187.
25e39. [33] V. Vajpayee, H. Kim, A. Mishra, P.S. Mukherjee, P.J. Stang, M.H. Lee, et al., Self-
[6] M. Wang, H. Zhang, L. Guo, D. Cao, Fluorescent polymer nanotubes as assembled molecular squares containing metal-based donor: synthesis and
bifunctional materials for selective sensing and fast removal of picric acid, application in the sensing of nitro-aromatics, Dalton Trans. 40 (2011)
Sensor. Actuator. B Chem. 274 (2018) 102e109. 3112e3115.
[7] J.F. Wyman, M.P. Serve, D.W. Hobson, L.H. Lee, D.E. Uddin, Acute toxicity, [34] Y. Peng, A.-J. Zhang, M. Dong, Y.-W. Wang, A colorimetric and fluorescent
distribution, and metabolism of 2,4,6-trinitrophenol (picric acid) in Fischer chemosensor for the detection of an explosive-2,4,6-trinitrophenol (TNP),
344 rats, J. Toxicol. Environ. Health 37 (1992) 313e327. Chem. Commun. 47 (2011) 4505e4507.
[8] G.P. Anderson, J.D. Lamar, P.T. Charles, Development of a luminex based [35] G. Sathiyan, E.K.T. Sivakumar, R. Ganesamoorthy, R. Thangamuthu,
competitive immunoassay for 2,4,6-trinitrotoluene (TNT), Environ. Sci. Tech- P. Sakthivel, Review of carbazole based conjugated molecules for highly
nol. 41 (2007) 2888e2893. efficient organic solar cell application, Tetrahedron Lett. 57 (2016)
[9] J. Huang, L. Wang, C. Shi, Y. Dai, C. Gu, J. Liu, Selective detection of picric acid 243e252.
using functionalized reduced graphene oxide sensor device, Sensor. Actuator. [36] R. Kumar, S. Sandhu, P. Singh, G. Hundal, M.S. Hundal, S. Kumar, Tripodal
B Chem. 196 (2014) 567e573. fluorescent sensor for encapsulation-based detection of picric acid in water,
[10] J.R.C. Junqueira, W.R. de Araujo, M.O. Salles, T.R.L.C. Paix~ ao, Flow injection Asian J. Org. Chem. 3 (2014) 805e813.
analysis of picric acid explosive using a copper electrode as electrochemical [37] P. Agarwala, D. Kabra, A review on triphenylamine (TPA) based organic hole
detector, Talanta 104 (2013) 162e168. transport materials (HTMs) for dye sensitized solar cells (DSSCs) and perov-
[11] R.G. Ewing, D.A. Atkinson, G.A. Eiceman, G.J. Ewing, A critical review of ion skite solar cells (PSCs): evolution and molecular engineering, J. Mater. Chem.
mobility spectrometry for the detection of explosives and explosive related A 5 (2017) 1348e1373.
compounds, Talanta 54 (2001) 515e529. [38] G. Sathiyan, J. Prakash, R. Ranjan, A. Singh, A. Garg, R.K. Gupta, Chapter 9 e
[12] Y. Jiang, H. Zhao, N. Zhu, Y. Lin, P. Yu, L. Mao, A simple assay for direct recent progress on hole-transporting materials for perovskite-sensitized solar
colorimetric visualization of trinitrotoluene at picomolar levels using gold cells, in: B.A. Bhanvase, V.B. Pawade, S.J. Dhoble, S.H. Sonawane,
nanoparticles, Angew. Chem. 120 (2008) 8729e8732. M. Ashokkumar (Eds.), Nanomaterials for Green Energy, Elsevier, 2018,
[13] S.S.R. Dasary, A.K. Singh, D. Senapati, H. Yu, P.C. Ray, Gold nanoparticle based pp. 279e324.
label-free SERS probe for ultrasensitive and selective detection of trinitro- [39] S. Nagendran, P. Vishnoi, R. Murugavel, Triphenylbenzene sensor for selective
toluene, J. Am. Chem. Soc. 131 (2009) 13806e13812. detection of picric acid, J. Fluoresc. 27 (2017) 1299e1305.
[14] A. Muhulet, F. Miculescu, S.I. Voicu, F. Schütt, V.K. Thakur, Y.K. Mishra, Fun- [40] P. Vishnoi, M.G. Walawalkar, S. Sen, A. Datta, G.N. Patwari, R. Murugavel,
damentals and scopes of doped carbon nanotubes towards energy and bio- Selective fluorescence sensing of polynitroaromatic explosives using tri-
sensing applications, Mater Today Energy 9 (2018) 154e186. aminophenylbenzene scaffolds, Phys. Chem. Chem. Phys. 16 (2014)
[15] T. Naddo, Y. Che, W. Zhang, K. Balakrishnan, X. Yang, M. Yen, et al., Detection 10651e10658.
of explosives with a fluorescent nanofibril film, J. Am. Chem. Soc. 129 (2007) [41] D. Kaleeswaran, R. Murugavel, Picric acid sensing and CO2 capture by a ste-
6978e6979. rically encumbered azo-linked fluorescent triphenylbenzene based covalent
[16] N. Singh, J. Prakash, M. Misra, A. Sharma, R.K. Gupta, Dual functional Ta-doped organic polymer, J. Chem. Sci. 130 (2018) 1.
electrospun TiO2 nanofibers with enhanced photocatalysis and SERS detec- [42] J.B. Arockiam, S. Ayyanar, Benzothiazole, pyridine functionalized triphenyl-
tion for organic compounds, ACS Appl. Mater. Interfaces 9 (2017) amine based fluorophore for solid state fluorescence switching, Fe3þ and
28495e28507. picric acid sensing, Sensor. Actuator. B Chem. 242 (2017) 535e544.
[17] S. Lotfian, C. Giraudmaillet, A. Yoosefinejad, V.K. Thakur, H.Y. Nezhad, Elec- [43] G. Sathiyan, P. Sakthivel, Synthesis and characterization of triazine linked
trospun piezoelectric polymer nanofiber layers for enabling in situ measure- carbazole derivatives green-light-emitting molecules, Dyes Pigments 143
ment in high-performance composite laminates, ACS Omega 3 (2018) (2017) 444e454.
8891e8902. [44] M. Sikorski, E. Sikorska, A. Koziolowa, R. Gonzalez Moreno, J.L. Bourdelande,
[18] N. Dey, S.K. Samanta, S. Bhattacharya, Selective and efficient detection of R.P. Steer, et al., Photophysical properties of lumichromes in water,
nitro-aromatic explosives in multiple media including water, micelles, orga- J. Photochem. Photobiol. B Biol. 60 (2001) 114e119.
nogel, and solid support, ACS Appl. Mater. Interfaces 5 (2013) 8394e8400. [45] F. Wilkinson, W.P. Helman, A.B. Ross, Quantum yields for the photosensitized
[19] V. Bhalla, A. Gupta, M. Kumar, D.S.S. Rao, S.K. Prasad, Self-assembled penta- formation of the lowest electronically excited singlet state of molecular ox-
cenequinone derivative for trace detection of picric acid, ACS Appl. Mater. ygen in solution, J. Phys. Chem. Ref. Data 22 (1993) 113e262.
Interfaces 5 (2013) 672e679. [46] P. Mazumdar, S. Maity, M. Shyamal, D. Das, G.P. Sahoo, A. Misra, Proton
[20] B. Xu, X. Wu, H. Li, H. Tong, L. Wang, Selective detection of TNT and picric acid triggered emission and selective sensing of picric acid by the fluorescent
by conjugated polymer film sensors with donoreacceptor architecture, aggregates of 6,7-dimethyl-2,3-bis-(2-pyridyl)-quinoxaline, Phys. Chem.
Macromolecules 44 (2011) 5089e5092. Chem. Phys. 18 (2016) 7055e7067.
186 G. Sathiyan et al. / Materials Today Chemistry 12 (2019) 178e186

[47] V. Bhalla, A. Gupta, M. Kumar, Fluorescent nanoaggregates of pentacenequi- [50] A. Maity, P. Mazumdar, S. Samanta, D. Das, M. Shyamal, G.P. Sahoo, et al.,
none derivative for selective sensing of picric acid in aqueous media, Org. Lett. Morphology directing synthesis of 1-aminopyrene microstructures and its
14 (2012) 3112e3115. super quenching effect towards nitro aromatics, J. Mol. Liq. 221 (2016)
[48] D. Zhao, T.M. Swager, Sensory responses in solution vs solid State: a fluo- 358e367.
rescence quenching study of poly(iptycenebutadiynylene)s, Macromolecules [51] S. Gunasekaran, E. Sailatha, S. Seshadri, S. Kumaresan, FTIR, FT Raman Spectra
38 (2005) 9377e9384. and Molecular Structural Confirmation of Isoniazid, 2009.
[49] J. Liu, Y. Zhong, P. Lu, Y. Hong, J.W.Y. Lam, M. Faisal, et al., A superamplification [52] A. Gupta, Y.-A. Kang, M.-S. Choi, J.S. Park, Characteristic response of
effect in the detection of explosives by a fluorescent hyperbranched poly(- tetra(methylbenzyloxy)-substituted zinc-phthalocyanine toward picric acid,
silylenephenylene) with aggregation-enhanced emission characteristics, Sensor. Actuator. B Chem. 209 (2015) 225e229.
Polym. Chem. 1 (2010) 426e429.