A pyrene-cored conjugated microporous polycarbazole for sensitive and selective detection of hazardous explosives

Article abstract of DOI:10.1016/j.inoche.2019.107453

In this article, we report the synthesis and characterization of a highly luminescent conjugated microporous polycarbazole (CK-CMP) by FeCl₃-induced oxidative polymerization of 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene (L). The CK-CMP with small pore sizes exhibits good thermal stability and high luminescence when suspended in polar solvents upon irradiation by UV light, which can be applied to detect 2,4,6-trinitrophenol (PA) with good sensitivity and selectivity by fluorescence quenching.

Full text of DOI:10.1016/j.inoche.2019.107453

Accepted Manuscript
A pyrene-cored conjugated microporous polycarbazole for
sensitive and selective detection of hazardous explosives
Xiao-Li Yang, Dai-Yu Hu, Qiang Chen, Liang Li, Pei-Xian Li,
Shi-Bin Ren, Marcus Bertuzzo, Kai Chen, De-Man Han, Xin-Hui
Zhou, Xing-Hua Xia
PII:
S1387-7003(19)30314-4
https://doi.org/10.1016/j.inoche.2019.107453
107453
DOI:
Article Number:
Reference:
INOCHE 107453
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
1 April 2019
21 June 2019
23 June 2019
Please cite this article as: X.-L. Yang, D.-Y. Hu, Q. Chen, et al., A pyrene-cored conjugated
microporous polycarbazole for sensitive and selective detection of hazardous explosives,
Inorganic Chemistry Communications, https://doi.org/10.1016/j.inoche.2019.107453
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ACCEPTED MANUSCRIPT
A Pyrene-cored Conjugated Microporous
Polycarbazole for Sensitive and Selective Detection
of Hazardous Explosives
a
a
c
c
b
b
Xiao-Li Yang , Dai-Yu Hu , Qiang Chen , Liang Li , Pei-Xian Li , Shi-Bin Ren* , Marcus
d
b
b
c
Bertuzzo , Kai Chen , De-Man Han , Xin-Hui Zhou* and Xing-Hua Xia
a Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine
Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education,
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan
4
53007, China.
b School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 317000,
China.
c Key Laboratory for Organic Electronics & Information Displays (KLOEID) and Institute of
Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, Nanjing
2
10023, China.
1

ACCEPTED MANUSCRIPT
d State Key Laboratory of Analytical Chemistry for Life Science and Collaborative Innovation
Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing
University, Nanjing 210093, China
e School of Physical Sciences, Ingram Building, University of Kent, Canterbury CT2 7NH,
United Kingdom. renshibin@126.com and iamxhzhou@njupt.edu.cn
KEYWORDS: CK-CMP, Polycarbazole; Conjugated microporous polymer; Detection of
Hazardous Explosives
In this article, we report the synthesis and characterization of a highly luminescent conjugated
microporous polycarbazole (CK-CMP) by FeCl -induced oxidative polymerization of 1,3,6,8-
3
tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene (L). The CK-CMP with small pore sizes exhibits
good thermal stability and high luminescence when suspended in polar solvents upon irradiation
by UV light. and , which can be applied to detect 2,4,6-trinitrophenol (PA) with good sensitivity
and selectivity by fluorescence quenching.
Introduction
The detection of nitro explosives has become so important field because as it is closely related
with national security, civilian safety and environmental protection. Nitro explosives, the highly
explosive and dangerous energy sources, can be used as common ingredients of explosive
1
devices as well as Since it is often applied in TNP fireworks, leather and dye industries, which
resulting in serious health and environmental problems due to their being deposited into the soil
and aquatic system. Among these high energy complexes, chemical sensing of 2,4,6-
2

ACCEPTED MANUSCRIPT
trinitrophenol (PA) and 2,4,6-trinitrotoluene (TNT) is especially necessary as they are still highly
2
explosive and toxic in extremely low concentrations. However, conventional detecting
techniques such as Surface-enhanced Raman spectroscopy, Cyclic Voltammetry, Capillary
Electrophoresis and Gas Chromatography-Mass Spectrometry, are expensive and difficult to
operate. Therefore, there is a compelling need to develop new porous materials that can be used
to rapidly to detect nitro explosives. Since sensing based on by fluorescence quenching is a much
2
,3
simpler and highly sensitive technique, it has now been widely applied in fluorescent MOFs.
Chemical sensing using MOFs has attracted considerable attention, but weak coordination bonds
within MOFs can result in low stability and high water affinity. In sharp contrast, conjugated
microporous polymers (CMPs) have emerged as a new kind of porous materials due to their
applications in heterogeneous catalysis, gas separation and storage energy, electronic devices and
4
chemical sensing. CMPs are a purely organic frameworks, which exhibit high thermo stability,
5
large surface areas, well-tuned pore structures, and can be readily functionalized. In addition to
this, commercial nitro explosives, such as PA or TNT all possess an electron deficient –NO2
group, could interact with electron donating CMPs. resulting efficient excitation migration
within the porous structures of CMPs to raise quenching sensitivity. Thus, these features of
CMPs can make Porous Organic Frameworks (POFs) suitable for the detection of the hazardous
5
explosives.
As a class of CMPs, polycarbazoles possess the rigid conjugated framework, which is favorable
for the formation of microporous polymer structures with permanent porosity, high surface areas,
6
and excellent stability. Due to oxidative sites of carbazoles, carbazole-functionalized monomers
are readily polymerized into CMPs via FeCl oxidative coupling. To date, pyrene-based porous
3
materials have also been widely applied in photo-catalysis, photoelectric devices and chemical
3

ACCEPTED MANUSCRIPT
7
sensing due to their excellent rigidity and photophysical properties. Motivated by all the above,
we designed and synthesized selected 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene (L), a
carbazole-functionalized monomer, as the building unit to construct a pyrene-cored Conjugated
Microporous Polycarbazole (CK-CMP) by oxidative polymerization. Additionally, And the
photophysical properties of the polymers were studied, followed by investigation of their
application in and sensitive detection of hazardous explosives.
*
*
N
N
N
N
*
*
FeCl in CH NO
2
3
3
*
*
N
N
N
N
*
*
L
CK-CMP
Scheme 1 The synthesis of CK-CMP
Experimental Section
1
,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene (L) was synthesized according to the
8
reported method. (4-(9H-carbazol-9-yl)phenyl)boronic acid were purchased from Energy
Chemical Technology (Shanghai) Co. Ltd. Tetrakis(triphenylphosphine)palladium(0) and
1
,3,6,8-tetrabromopyrene was prepared by in our own lab. All other reagents were of analytical
grade and used without further purification.
Caution! Nitro-explosives are highly explosive and should be used carefully and in a small scale
amounts. The explosives were handled as dilute solutions and with safety measures to avoid
explosion
4

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Preparation of 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene (L)
In a 250 mL three-necked round-bottomed flask, 1,3,6,8-Ttetrabromo-Ppyrene (1.0356 g, 2
mmol) and 4-(9H-Ccarbozol-9yl)phenylboronic acid (2.8712 g, 10 mmol) was were dissolved in
dioxane (100 mL) and then an aqueous solution of potassium carbonate (3.15 g, 23 mmol) in
water (10 mL) and Pd(PPh ) catalyst (0.6 g, 0.50 mmol) was were added to the reaction mixture
3
4
and it was stirred under N at 100℃ for 3 days. After cooling to room temperature, the yellow
2
reaction mixture was transferred to dilute hydrochloric acid solution (100 mL). The precipitate
was collected by filtration and then washed with water (3×40 mL). The solid was transferred to a
Soxhlet and continuously extracted with CHCl for 48 h. The CHCl extracts were was
3
3
evaporated under reduced pressure. The crude product L was further purified by silica-gel
column chromatography using CHCl as mobile phase to afford a bright yellow solid (0.5 g,
2
2
7
1
2%). 1H NMR (400 MHz, CDCl ): δ(ppm) 8.51(4H), 8.32(2H), 8.22(8H), 8.03(8H), 7.84 (8H),
3
.61(8H), 7.51(8H), 7.35(8H). FT-IR (ATR4000–400 cm-1) 3418, 3047, 2910, 1600, 1514, 1493,
451, 1359, 1338, 1312, 1223, 1164, 1004, 839, 746, 717, 628, 561, 533. MS(ESI): m/z for
+
C H N cacld 1166, M , 1166.02.
88
54
4
The Synthesis of CK-CMP
The monomer L (300 mg, 0.52 mmol) was dispersed in anhydrous chloroform (30 mL), and then
transferred dropwise to a suspension of FeCl (415 mg, 2.5 mmol) in anhydrous chloroform (15
3
o
mL). The mixture was stirred for 24 hours under N at 60 C, and then 100 mL of methanol was
2
added to the reaction mixture. The resulting mixture was kept stirring for another hour and the
precipitate was collected by filtration. After being washed with methanol, the obtained solid was
stirred vigorously in hydrochloric acid solution for 1 h. The suspension was then filtered and
5

ACCEPTED MANUSCRIPT
washed with water and methanol, and then extracted using a Soxhlet extractor with THF for 24 h.
o
The resulting product was dried at 120 C on vacuum for 24 h to obtain a yellow powder (yield:
7
8%).
Preparation of CK-CMP Suspension
Finely ground samples of CK-CMP were was dispersed in ethanol solution to form a suspension
solution with concentration of 1 mg/mL, which were was ultrasonically agitated for 15 min
before testing.
Preparation of CK-CMP Ffilm
Finely ground samples of CK-CMP (3 mg) was dispersed in 0.5 mL ethanol solution to form a
suspension solution, which were was ultrasonically agitated for 15 min. Then, the suspension
was uniformly added dropwise onto a clean quartz plate and dried at 50 ℃ at vacuum for 3 hours
to obtain the CK-CMP film.
Detection of PA Vapor
The 300 mg of PA was placed in a vacuum glass vial (150 mL) for 1 week to obtain saturated
vapour of PA, and the CK-CMP film on quartz plate was placed into a vacuum cuvette (4 mL).
They were connected by the rubber tube with valve. When the valve is opened, the PA saturated
vapor will pass into the quartz cuvette. In repeatability test, the CK-CMP film was vacuumed at
2
5 ℃ for 1 hour to remove the absorbed PA.
Physical characterization of CK-CMP
6

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Fourier transform infrared (FT-IR) spectra of the samples was recorded using a Bruker Vector 22
1
3
spectrophotometer. Solid-state CP/MAS NMR spectra was performed on a Bruker Advance II
WB 400MHz NMR spectrometer. The Thermogravimetric Analysis (TGA) was performed in a
nitrogen atmosphere using Seiko Extar 6000 TG/DTA equipment at the heating rate of
1
0 °C/min. Powder X-ray diffraction (PXRD) was carried out on a Bruker D8 ADVANCE X-ray
diffractometer with Cu-Kα radiation. The morphology and microstructure were observed on a
field emission scanning electron microscope (FE-SEM, Hitachi S-4800). Gas adsorption-
desorption isotherms were tested on a ASAP 2020 HD88 instrument after the samples were
degassesed under dynamic vacuum at 423 K for 12 hours. The specific surface area was
calculated using the Brunauer-Emmett-Teller (BET) method and pore size distribution (PSD)
was evaluated by non-local density functional theory (NLDFT). Photoluminescence spectra was
were measured using a PerkinElmer LS55 Fluorescence Spectrometer. Fluorescence decay
curves were measured with Edinburgh FLS920P spectrophotometer with double xenon lamp
houses, one was with 450 W for steady state measurement and another was 60 W microsecond
flash lamp for dynamic spectrum recording). Electrochemical behaviour was investigated by
cyclic voltammetry (CV) with a standard three-electrode electrochemical cell in a 0.1 M tetra-n-
butylammonium hexafluorophosphate (Bu NPF ) in nonaqueous acetonitrile at room temperature
4
6
under nitrogen with a scanning rate of 50 mV/s. A platinum working electrode, a glassy carbon
electrode, and an Ag/AgNO (0.1 M) reference electrode was were used. The CV curves were
3
calibrated using ferrocene/ferrocenium (Fc/Fc+) redox couple (4.8 eV below the vacuum level)
as the internal standard. The formal potential of Fc/Fc+ was measured as 0.04 V against Ag/Ag+.
Thus, the lowest unoccupied molecular orbital (LUMO) energy levels could be calculated
according to: ELUMO = -e(E + 4.76 V).
red
7

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Results and discussion
Oxidative coupling of the carbazole-functionalized monomers with FeCl resulted in the
3
formation of the bulk polymer as a yellow fine powder in high yields. The method has various
advantages in building microporous polycarbazoles, such as using low-priced catalysts, under the
mild reaction conditions and with high yields. In addition to this, the rigid fused rings of
carbazoles also facilitates the formation of polymers with high porosity and good stability. It is
well-known that pyrene itself is electrically neutral and so the electric properties of this
polycarbazole depends on those of the carbazole based monomers through p-conjugation. The
carbazoles is an electron-donating group, but and the pyrene moiety is considered as an acceptor.
Therefore, electron-donating CMP containing carbazole units could attract the electronegative –
NO groups by means of coulombic interactions. In this work, we choose designed and
2
synthesized 1,3,6,8-tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene to obtain this highly luminescent
CK-CMP by FeCl -induced oxidative polymerization due to its high lifetime and quantum yield
3
of the pyrene core. (Scheme 1). CK-CMP is chemically stable, even in dilute solutions of acid
and or base. Scheme 1 shows the chemical structure of the polycarbazole (CK-CMP).
Thermal analysis indicates that its thermal decomposition temperature is stable up to 500 °C
under N atmosphere due to its cross-linking structures (Figure S1). Scanning electron
2
microscopy images showed the similar amorphous aggregated morphologies of that CK-CMP
(Figure S2) Powder X-ray diffraction (PXRD) pattern of CK-CMP did not show any diffraction
signals, which further confirms the formation of a porous amorphous structure (Figure S3).
Nitrogen adsorption measurement at 77 K over this activated sample shows a typical type I
behavior, suggesting the presence of microporous structures in CK–CMP (Figure S4). The
8

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1
3
structure of CK-CMP was further confirmed at the molecular level by C CP/MAS NMR
1
3
spectrum. The C NMR spectrum for the obtained polymer with assignment of the resonances is
shown in Figure 1. The high-intensity peak at 123 ppm is ascribed to the signal peak of
substituted phenyl carbons. Signal peak at 137 ppm corresponds to the substituted phenyl
carbons binding with nitrogen atom. The signal peak for unsubstituted phenyl carbons is located
at 123 and 107 ppm, respectively. In addition, CK-CMP exhibited a rather broad absorption band
in the range of 200 to 500 nm, indicating the formation of the highly conjugated polymer (Figure
[
9]
S4). The main peaks of CK-CMP are similar to those of the previously reported results , which
also confirms the formation of this polycarbazole.
1
3
Figure 1 Solid-state C CP/MAS NMR spectrum of CK-CMP.
Fluorescence Properties
The photoluminescence spectra of solid monomer and CK-CMP are shown in Figure 1. Upon
excitation at 380 nm, CK-CMP exhibited an emission band with the emission maximum at 513
9

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nm, which was red-shifted by 6 nm from that of monomer. The CK-CMP suspension exhibited
an emission band with the emission maximum at 535 nm, which was red-shifted by 22 nm from
that of solid CK-CMP (Figure S6).
Since CK-CMP exhibited porous structure and intense fluorescence, we are very interested in its
fluorescent chemosensing behaviour for nitro compounds. The luminescent responses of CK-
CMP suspension to 0.2 mM nitro compounds such as 2,3-dimethyl-2,3-dinitrobutane (DMNB),
1
,3-dinitrobenzene (1,3-DNB), 2,4-dinitrotoluene (2,4-DNT), 4-nitrotoluene (4-NT), 3,4-
dinitrotoluene (3,4-DNT), 2-nitrotoluene (2-NT) and picric acid (PA) were measured (Figure2).
Interestingly, PA exhibited drastic quenching effect on the fluorescence of CK-CMP suspension
with the quenching percentage (QP = (I –I)/I × 100%, I and I are luminescence intensities of
0
0
0
CK-CMP suspension before and after exposure to the nitro compounds, respectively) of 89.3 %
by monitoring emission peak at 535 nm. However, other nitro compounds had almost no effect
on the emission. It shows that CK-CMP possesses the extremely high selectivity towards PA
among the nitro compounds.
1
0

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Figure 2 The fluorescence spectra of CK-CMP suspension without and with different nitro
compounds (0.2 mM).
Figure 3 Change in fluorescence intensities at 535 nm of CK-CMP suspension with different
nitro compounds (0.2 mM).
To investigate the quenching behaviour of PA for CK-CMP suspension, the concentration-
dependent luminescence measurement for PA was carried out in the concentration range of 0.01
to 0.4 mM (Figure 4 and 5). It was found that the luminescent intensities of the CK-CMP
suspension rapidly decreased with the addition of PA. Moreover, the Stern–Volmer (SV)
equation, I /I= K [Q]+1 (K is the quenching constant, and [Q] is the concentration of the
0
sv
sv
quencher) was used for the analysis of concentration-dependent luminescence data. As shown in
4
2
Figure 5, the I /I exhibited a good linear dependence relation (I /I = 0.121 + 9.9×10 ´ [PA], R =
0
0
0
9
.974) with the concentrations of PA in the range of 0 ~ 0.1 mM, with slope K of SV curve of
sv
4
-1
.9×10 M . As far as we know, this K is among the highest values for the detection of PA
sv
9
(Table 1).
1
1

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Table 1. Comparison of sensing performances of materials towards PA
-
1
Material
Quenching constant (M )
Ref.
4
CK-CMP
9.9×10
This work
4
[
Gd L (NMP) ]n
4.48  10
9a
9b
9c
9d
9e
2
1.5
2
4
[
Zn (ad) (BPDC) O2Me NH ]
4.6  10
8
4
6
2
2
4
{
[Tb(L ) (H O)]·3H O}
n
7.47  10
1
1.5
2
2
4
UiO-68@NH2
NH (CH ) ][Zn O(bpt) (bdc-
5.8  10
4
[
6.19  10
2
3 2
4
2
NH ) ]·5DMF
2
0.5
4
[
Zn (NH BDC) (dpNDI)]
n
7.3  10
9f
2
2
2
Figure 4 Concentration-dependent luminescence quenching of CK-CMP suspension after adding
different concentrations of PA.
1
2

ACCEPTED MANUSCRIPT
Figure 5 Stern-Volmer plot for fluorescence quenching of CK-CMP suspension by PA.
The quenching behaviour of PA for CK-CMP suspension was further studied by fluorescence
lifetime (Figure S7). As illustrated in Table S1, CK-CMP suspension had a lifetime value of 1.89
ns, and the lifetimes showed little decrease (1.88 to 1.78 ns) with addition of PA (0.01 to 0.1
mM). The linear Stern–Volmer relationship and minimal change in lifetimes indicate that a static
quenching process is dominant.
The high sensitivity of CK-CMP suspension towards PA prompted us to investigate its ability for
sensing PA vapour, which were was conducted by exposing CK-CMP film on the quartz plate to
saturated PA vapour at room temperature. The photoluminescence spectra showed that after
exposure to saturated PA vapour, the fluorescence of CK-CMP film was significantly quenched
with quenching percentage of 55% (Figure 6). When there is air in the saturated PA vapour, the
result is the same.
1
3

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The repeatability of detection of CK-CMP film for saturated PA vapour was also studied. As
shown in Figure 7, CK-CMP film exhibited the same degree of fluorescence quenching
percentages after each cycle, and the fluorescence intensity recovered to a similar level when the
PA vapour was removed. Therefore, CK-CMP film maintained high sensitivity to saturated PA
vapour after repeated cycles.
Figure 6 The fluorescence spectra of CK-CMP film in the absence and presence of PA vapor.
7
b,9
According to previous reports , the fluorescent quenching of CK-CMP on addition of PA may
be attributed to the following factors: (a) resonance energy transfer and/or (b) photo-induced
electron transfer between CK-CMP and PA. Firstly, we checked the possibility of resonance
energy transfer. As shown in Figure 8, it is evident that partial overlap exists between the
absorption spectrum of PA and the emission spectrum of CK-CMP. Thus, resonance energy
transfer may contribute to fluorescence quenching. Secondly, the possibility of photo-induced
electron transfer was also checked by comparison of molecular orbital energy levels of CK-CMP
and PA. The LUMO energy level of CK-CMP was evaluated by the cyclic voltammogram curve
1
4

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of the monomer, because the CK-CMP is insoluble in common organic solvents (Figure S8). The
result shows that the LUMO energy level of the monomer to be -3.74 eV, which is much higher
7
b
than HOMO energy level of PA (-4.88 eV) , indicating the possible electron transfer from the
HOMO of CK-CMP to the LUMO of PA upon photoexcitation. Thus, the fluorescent quenching
of CK-CMP by PA is the result of two synergistic mechanisms.
Figure 7 Cycling test of CK-CMP film upon exposure to PA vapor.
1
5

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Figure 8 Absorption spectrum of PA and emission spectrum of CK-CMP in EtOH.
Conclusions
We have successfully synthesised a pyrene-cored conjugated microporous polycarbazole CK-
CMP via FeCl -induced oxidative self-condensation of 1,3,6,8-tetrakis(4-(9H-carbazol-9-
3
yl)phenyl)pyrene (L). Particularly, owing to the introduction of pyrene into this three-
dimensional structure, CK-CMP exhibits high luminescence in various polar solvents upon
irradiation with UV light. In addition to this, CK-CMP has high thermal stabilities and also
features selective and sensitive detection of PA over other nitro-explosives. Thus, explosives
detection experiments of CK-CMP exhibits that pyrene based polycarbazoles are a candidate for
the detection of nitroaromatic explosives.
ASSOCIATED CONTENT
Supporting Information. The Supporting Information is available free of charge on the
ACS Publications website at DOI: xxxxxxxxxx.
FT-IR, TGA, PXRD, SEM of CK-CMP, the fluorescence spectra and The fluorescence decay
curves.
AUTHOR INFORMATION
Corresponding Author
*
Tel.: +86-576-83137082. * Fax.: +86-576-83137082. Email: renshibin@126.com and
iamxhzhou@njupt.edu.cn
1
6

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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful for financial support from Zhejiang Provincial Natural Science Foundation of
China (LY19E030001 and LGF19B050002), the National Natural Science Foundation of China
(
21471110 and 21575097), the State Key Laboratory of Analytical Chemistry for Life Sciences
SKLACLS1206) and the Foundation and Advanced Technology Research Program of Henan
(
Province (152300410084).
ABBREVIATIONS
CMPs, conjugated microporous polymers; MOFs, metal-organic frameworks; L, 1,3,6,8-
tetrakis(4-(9H-carbazol-9-yl)phenyl)pyrene; CK-CMP, Pyrene-cored Conjugated Microporous
Polycarbazole
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SYNOPSIS (Word Style “SN_Synopsis_TOC”). If you are submitting your paper to a journal
that requires a synopsis, see the journal’s Instructions for Authors for details.
Graphical Abstract and image
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Xiao-Li Yang , Dai-Yu Hu , Qiang Chen , Liang Li , Pei-Xian Li , Shi-Bin Ren* , Marcus
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Bertuzzo , Kai Chen , and Xin-Hui Zhou*
A Pyrene-cored Conjugated Microporous Polycarbazole for Sensitive and Selective Detection of
Hazardous Explosives
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Graphical Abstract and image
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Xiao–Li Yang , Dai–Yu Hu , Qiang Chen , Liang Li , Pei–Xian Li , Shi–Bin Ren* ,
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Marcus Bertuzzo , Kai Chen , De–Man Han , Xin–Hui Zhou* , and Xing–Hua Xia
A Pyrene–cored Conjugated Microporous Polycarbazole for Sensitive and Selective Detection
of Hazardous Explosives
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Highlights
. A highly luminescent conjugated microporous polycarbazole (CK-CMP) was by FeCl3-
induced oxidative polymerization
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. CK-CMP with small pore sizes exhibits good thermal stability and high luminescence .
. CK-CMP can detect 2,4,6-trinitrophenol (PA) with good sensitivity and selectivity by
fluorescence quenching.
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