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A novel biomass-based reusable AIE material:

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AIE properties and potential applications in amine/

Cite this: J. Mater. Chem. C, 2019,
7, 8404 ammonia vapor sensing and information storage†
Ensheng Zhang, ab Xiufang Hou,b Ze Zhang,b Yuqi Zhang, *b Jijiang Wang, b

Hua Yang,b Jinmao Youa and Ping Ju *a

A novel biomass-based aggregation-induced emission (AIE) material, 4-chloro-2-(2-hydroxy-5-(methoxy-

Received 31st March 2019,
Accepted 12th June 2019
DOI: 10.1039/c9tc01725a
rsc.li/materials-c
carbonyl)phenylamino)benzoic acid (CHMPBA), was constructed by using ( )-methyl-3-dehydroshikimiate
(3-MDHS) and 2-amino-4-chlorobenzoic acid via the tandem cross-coupling and aromatization reaction. AIE
properties of CHMPBA were studied in ethanol, dimethyl sulfoxide, dimethyl formamide and tetrahydrofuran
with gradually increasing water fractions and characteristic AIE phenomena were observed. Portable sensors
for the detection of amine vapors were prepared by depositing CHMPBA on filter paper. Good selectivity, high
sensitivity and real-time fluorescence quenching were observed when this portable sensor was exposed to
ammonia vapor. The detection limit for ammonia vapor is up to 20 ppm in air. A plausible mechanism for the
fluorescence ‘‘ON–OFF–ON’’ phenomenon in the detection of ammonia vapor was proposed based on the
DFT calculations, 1H NMR tests and reusability studies. In addition, further practical application studies proved
that CHMPBA might be commercially used as information storage material in the future.

1. Introduction or analytical methods for real-time detection of ammonia/

Amines including ammonia are typical nitrogen-containing com-
pounds that are widely used as raw materials or intermediates in
agrochemical, pharmaceutical and food industries.1–7 However,
some of the low molecular weight amines such as triethylamine
(TEA), diethylamine (DEA), hydrazine and ammonia are highly
volatile compounds that would be gaseous pollutants due to
their serious damage to the ecological environment and human
health.5,6 Thus, the development of a detection method for
ammonia/amine vapor monitoring is critical in several areas
such as environmental and food safety. Fortunately, a variety of
analytical methods including titrimetry,8 gas chromatography-
mass spectrometry,9 UV-visible absorption spectrometry10 and
electrochemical devices11–14 have been exploited for the detection
of ammonia/amines. Although most of these methods performed
successfully for the detection of ammonia/amines in solution,
some of them suffer from drawbacks such as high cost, not
real-time monitoring and being unsuitable for detection of
ammonia/amines in the vapor phase. Therefore, new materials
a
College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu,
Shandong, 273165, China. E-mail: xiangjianhuan110@163.com
b
Laboratory of New Energy & New Functional Materials, College of Chemistry and
Chemical Engineering, Yan’an University, Yan’an, Shaanxi, 716000, China.
E-mail: yqzhang@iccas.ac.cn; Fax: +86-911-2332317; Tel: +86-911-2332037
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9tc01725a
amine vapors with high sensitivity and selectivity are especially
desirable.
Aggregation-induced emission (AIE) phenomena were first
reported by Tang and co-workers in 2001.15 AIE luminescent
materials are strongly emissive in the solid or aggregated states
but very weakly emissive in dilute solution. This is exactly
opposite to the traditional aggregation-caused quenching
(ACQ) luminescent materials. A large number of AIE materials
have been synthesized for various applications such as sensors
for metal ions,16–20 explosives21–25 and bioactive molecules,26,27
as well as indicators for tissue28–32 and fingerprint imaging.33,34
In recent years, AIE luminescent sensors for gas detection have
been paid continuous attention due to their high sensitivity
and multi-responses.35–40 Meanwhile, with the rapid decrease
of fossil oil reserves, sustainable development has become the
consensus of human society and the diverse utilization of
renewable biomass has attracted considerable interest.41–46
Based on our continuous works on transformations of the
renewable bio-feedstock shikimic acid to fine chemicals and
functional materials,47–50 herein, we revealed a biomass-based
reusable AIE probe, 4-chloro-2-(2-hydroxy-5-(methoxycarbonyl)-
phenylamino)-benzoic acid (CHMPBA), for the selective and
sensitive detection of ammonia/amine vapors.
CHMPBA was constructed by using ( )-methyl-3-dehydro-
shikimiate (3-MDHS) and 2-amino-4-chlorobenzoic acid via the
tandem cross-coupling and aromatization reactions we have

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developed.50 Typical AIE phenomena were observed in ethanol 6.93 (d, J = 2.0 Hz, 1H), 6.79 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H), 3.79
(EtOH), dimethyl sulfoxide (DMSO), dimethyl formamide (DMF) (s, 3H); MS (EI): m/z = 321 [M]+, 271, 244; FT-IR (Fig. S5 (ESI†), KBr)
and tetrahydrofuran (THF) with gradually increasing water fractions. vmax/cm 1 3345, 3224, 1699, 1594, 1577, 1433, 1289, 1241, 759.
Portable sensors for ammonia/amine vapors were fabricated by
depositing CHMPBA on filter paper. Real-time fluorescence
quenching was observed when the as-prepared portable sensors 3. Results and discussion
were exposed to ammonia/amine vapors. Good selectivity to 3.1 Optical properties of CHMPBA
ammonia over other volatile amines was observed. It is worth
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The optical spectra of CHMPBA in the solid state and in ethanol

mentioning that this portable sensor can be easily recovered and
solution were recorded and are displayed in Fig. 1. CHMPBA
reused several times. Further practical application studies
exhibits an absorption band in the region of 325–350 nm in
proved that CHMPBA might be commercially used as a fluor-
ethanol solution (Fig. 1, 50 mM, the black line) and a strong
escent invisible ink and anti-false trademark material.
fluorescence emission band centered at 480 nm in the solid
state (Fig. 1, the red line). Interestingly, the absorption intensity of
2. Experimental section CHMPBA solution sharply decreased with increasing water fraction
from 0% (Fig. 1, the black line) to 90% (Fig. 1, the green line).
2.1 Instruments and reagents
However, the fluorescence intensity remarkably enhanced during
1
H NMR measurements were performed on Bruker AVII-400 MHz the process of increasing water fraction (Fig. 1, the blue line
(1H NMR, 400 MHz) and OXFORD AS-500 (1H NMR, 500 MHz) compared with the yellow line), revealing the typical AIE property
spectrometers using DMSO-d6 as the solvent at 298 K. Chemical of CHMPBA and the formation of aggregates. The concentration of
shifts were reported in parts per million (ppm). MS spectra were CHMPBA decreased with the above process, which could be
recorded using a GCMS-QP5050A in EI mode. FT-IR spectra were responsible for the decrease of absorption intensity.
measured using a Shimadzu IR Affinity-1S FT-IR spectro-
photometer using a KBr pellet. Fluorescence spectra were 3.2 AIE characteristics of CHMPBA
recorded using an Agilent Cary Eclipse fluorescence spectro-
In order to reveal the AIE properties of CHMPBA, various
photometer (lex = 340 nm, lem = 480 nm). Absorption spectra were
influencing factors such as solvent, concentration and water
recorded using a Shimadzu UV-2550 spectrophotometer. Particle
volume fraction (fw) were studied. Fluorescence spectra and
size study was performed using a dynamic light Scattering
particle size of the CHMPBA solutions (50 mM) were recorded
instrument (DelsaNano S).
with gradually increasing fw.
The intermediate ( )-methyl 3-dehydroshikimate (3-MDHS)
Initially, the fluorescence spectra of CHMPBA (50 mM) in
was prepared according to our reported method49 and purified
EtOH, THF, DMF and DMSO were recorded respectively with
by recrystallization from EtOAc-PE. Unless specifically noted, all
gradually increasing fw. As shown in Fig. 2a, CHMPBA exhibits
other reagents were obtained commercially and used without
very weak fluorescence emission at 480 nm in pure EtOH, DMF,
further purification. The amine solutions of p-phenylenediamine
DMSO and THF (fw = 0%), and no remarkable fluorescence
(PPDA), 2-nitroaniline (2-NA), 3-nitroaniline (3-NA), Et3N, diethyl-
emission was observed when fw was below 60%. The AIE
amine (DEA), NH2NH2 (N2H4), and ethyldiamine (EDA) were pre-
fluorescence emission firstly appeared with 70% fw in DMSO
pared in ethanol at a concentration of 20 wt%. Ammonia (NH3)
and EtOH; however, similar AIE phenomena were observed in
solution was prepared at a concentration of 20 wt% in water.
THF and DMF in the presence of 80% and 90% water, respec-
2.2 Synthesis of CHMPBA tively. As expected, the fluorescence emission intensities of
CHMPBA enhanced rapidly after aggregation occurred and
The purified 3-MDHS (5.0 mmol), 2-amino-4-chlorobenzoic
acid (5.0 mmol) and p-TsOH (0.25 mmol) were dissolved in
dry ethanol (20 mL) and refluxed for 10 h (Scheme 1). The
precipitated crude product was filtered and recrystallized from
EtOH to afford pure CHMPBA as yellow crystals in 83% yield.
4-Chloro-2-(2-hydroxy-5-(methoxycarbonyl)phenylamino)-
benzoic acid (CHMPBA), m.p. 271–273 1C, 1H NMR (Fig. S1 and S2
(ESI†), DMSO-d6, 400 MHz) ppm: 13.25 (s, 1H, COOH), 10.80
(s, 1H), 9.62 (s, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.85 (d, J = 2.0 Hz,
1H), 7.63 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H),

Fig. 1 UV-vis absorption spectra of CHMPBA in ethanol solution in the

absence of water (black line) and in the presence of 90% water (green line);
fluorescence spectra of CHMPBA in the solid state (red line), in ethanol
Scheme 1 The synthetic route of CHMPBA. (yellow line) and in the mixture of ethanol and water (blue line, 1 : 9, v/v).

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Fig. 2 (a) Fluorescence intensities of 50 mM CHMPBA in mixed solvent
with gradually increasing water fractions (lex = 340 nm, lem = 480 nm,
slits: 5 nm/5 nm); (b) fluorescence spectra of 50 mM probe solution in EtOH
(fw = 90%), THF (fw = 92%), DMF (fw = 97%) and DMSO (fw = 95%); (c) CIE
chromaticity diagram of CHMPBA in solid form and in different mixed
solvents; (d) particle size analysis of CHMPBA in the mixed solvent of
EtOH–H2O (fw = 90%).
reached the maximum intensity at different fw (Fig. 2b, 90% for
EtOH, 92% for THF, 97% for DMF and 95% for DMSO). Further-
more, the chromaticity coordinates51 of CHMPBA calculated from
the spectra in Fig. 1 and 2b were found to be (0.18, 0.36) in the solid
state, (0.17, 0.30) in DMF–H2O and CH3OH–H2O, (0.18, 0.33) in
DMSO–H2O and (0.16, 0.22) in THF–H2O (Fig. 2c).
The aggregation-induced emission of CHMPBA was further
confirmed by DLS studies with 50 mM CHMPBA in different
solvents. As depicted in Fig. 2(d) and Fig. S6 (ESI†), the particle
size of CHMPBA was measured in the presence of water in
EtOH, DMF, THF and DMSO, respectively. As shown in Fig. 2d,
the average particle size of the aggregate is about 51 519 nm
when fw increased to 90% in EtOH. Meanwhile, the fluorescence
intensity increased 28-fold (Fig. 2a and b, the fluorescence
intensity changed from 3.8 to 107.9). In addition, a similar
changing trend was observed in DMF and THF (Fig. S6a and b,
ESI†). Interestingly, the fluorescence intensity of CHMPBA in
DMSO changed quickly with the increase of fw, while the average
particle size of the aggregates only increased to about 1120 nm
during the above process (Fig. S6c, ESI†).
8406 | J. Mater. Chem. C, 2019, 7, 8404--8411
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Fig. 3 Fluorescence intensities of CHMPBA at different concentrations in
co-solvents DMF–H2O (a), DMSO–H2O (b), and THF–H2O (c) with gradu-
ally increasing water fraction (lex = 340 nm, lem = 480 nm, and slits: 5 nm/
5 nm); photographs of CHMPBA in co-solvents DMF–H2O (d), DMSO–
H2O (e), and THF–H2O (f) with gradually increasing fw under a 365 nm
luminescent lamp.
The aggregation-induced emission properties were further
studied in DMF, DMSO and THF by changing the concentration
of CHMPBA (50 mM, 100 mM, 200 mM, and 500 mM) and fw. The
fluorescence intensities of CHMPBA with gradually increasing
fw were recorded and are displayed in Fig. 3.
As is apparent from Fig. 3, typical AIE phenomena of CHMPBA
were observed in DMF, DMSO and THF with gradually increasing
fw. For example, the fluorescence intensity of 50 mM CHMPBA in
mixed-solvent DMF–H2O was very weak and showed no obvious
change when fw was below 90%, revealing no aggregation. However,
the fluorescence emission intensity (lem = 480 nm) increased
rapidly and reached the maximum intensity when fw increased to
92%. After that, the fluorescence intensity decreased and precipi-
tates that were visible to the naked eye formed. Interestingly, after
increasing the concentration of CHMPBA from 50 mM to 200 mM
and even 500 mM, the aggregation phenomena appeared with lower
fw (Fig. 3a and d). Similar changes were observed in mixed-solvents
including DMSO–H2O (Fig. 3b and e) and THF–H2O (Fig. 3c and f).
3.3 Amine/ammonia vapor sensing properties
Preparation of paper-based sensor. Portable sensors were
prepared by immersing filter paper into the DMSO solution of
CHMPBA (10 mM) for 30 seconds and drying in air. CHMPBA-
coated filter paper was cut into small pieces and used as
portable sensors in the following detection experiments.
Selectivity study. In order to investigate the selectivity of the
as-prepared paper-based sensor, various amine/ammonia stock
solutions were prepared in ethanol with a concentration of 20 wt%.
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Fig. 4 Fluorescence intensity changes of CHMPBA-coated paper sensors
when exposed to various amine/ammonia, water and ethanol vapors (a);
photograph of CHMPBA-coated paper-based sensors after exposure to
various amine/ammonia, water or ethanol vapors for 30 seconds under
portable 365 nm UV-light (b).
2 mL of a stock solution of 2-NA, 3-NA, PPDA, N2H4, DEA, Et3N,
EDA, and NH3 and contrast samples (EtOH and water) were
added into glass bottles, respectively. The bottles were covered
by the as-prepared paper sensors. The fluorescence intensities
of the paper before and after fuming were recorded at room
temperature. The changes of fluorescence intensity are dis-
played in Fig. 4a. Herein, F0 represents the fluorescence inten-
sity of the paper-based sensor before fuming and F represents
the fluorescence intensity of the paper sensor after fuming for
30 seconds.
It is obvious that the fluorescence quenching efficiency of
the paper-based sensors greatly depended on the features of the
amine/ammonia at room temperature. For example, ammonia
vapor led to significant fluorescence quenching after fuming
for 30 seconds and the fluorescence intensity decreased by
more than 5-fold. Et3N and EDA resulted in moderate to low
fluorescence quenching under the same conditions. However,
N2H4 and DEA gave rise to slight fluorescence intensity
changes. In addition, no fluorescence quenching was observed
for the portable sensors after treatment with other non-volatile
amines such as 2-NA, 3-NA and PPDA. The same phenomenon
was also observed when the sensors were exposed to neutral
reagents such as ethanol and water. It is worth mentioning that
these paper-based fluorescent sensors could be used as naked-
eye indicators for volatile amine/ammonia vapors under a
portable UV lamp (Fig. 4b)
Sensitivity study. In order to further study the sensing
properties, fluorescence spectra of the portable sensor when
exposed to different concentrations of ammonia vapor were
recorded at room temperature and are displayed in Fig. 5.
As shown in Fig. 5a, a strong emission band centered at
480 nm was observed in the fluorescence spectra of CHMPBA.
Interestingly, fluorescence quenching occurred when this
sensor was exposed to 20 ppm ammonia vapor and reached a
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Fig. 5 (a) Fluorescence spectra of the paper-based sensor when exposed
to different concentrations of ammonia vapor for 30 seconds; (b) enlarged
view of the fluorescence spectra in the presence of 0–100 ppm ammonia
vapor; (c) nonlinear fitting analysis for the fluorescence intensity versus the
concentration of ammonia vapor (insets: photographs of this portable
sensor before and after exposure to ammonia vapor).
remarkable extent when the ammonia vapor concentration was
100 ppm (Fig. 5b). The above encouraging results revealed the
high sensitivity of this portable sensor. Further increasing the
ammonia vapor concentration would lead to a decrease of
fluorescence intensity accordingly (Fig. 5a). It is worth men-
tioning that the fluorescence quenching efficiency calculated
from the equation (1 F/F0)  100%52 (F0 represents the
fluorescence intensity in the absence of ammonia vapor, and
F represents the fluorescence intensity of the sensor in the
presence of ammonia vapor) reached 91.4% upon exposure to
1000 ppm ammonia vapor in air (Fig. 5a).
The fluorescence emission intensities at 480 nm were
recorded with gradually increasing the concentration of ammo-
nia vapor and are shown in Fig. 5c. Nonlinear fitting analysis
for the fluorescence intensity versus the concentration of
ammonia vapor was obtained. As depicted in Fig. 5(c), the
experimental data fitted well with the following non-linear
equation53 y = 3.67 + 597.69/(1 + (x/421.68)2.74) (R2 = 0.9995,
y represents the fluorescence emission intensity, and x repre-
sents the concentration of ammonia vapor), revealing that this
portable sensor might be used in the quantitative detection of
ammonia vapor. In addition, an obvious color change was
observed before and after exposure to ammonia vapor under
365 nm UV-light, suggesting that this portable sensor could
serve as a naked-eye sensor for ammonia vapor (Fig. 5c, insets).
3.4 Sensing mechanism
1
H NMR analysis. In order to reveal the sensing mechanism,
1
H NMR analysis of NH3
H2O, CHMPBA and CHMPBA + NH3
was carried out using DMSO-d6 as the solvent. The sample
CHMPBA + NH3 was prepared by bubbling ammonia vapor into
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Fig. 6 1H NMR tests of CHMPBA, CHMPBA + NH3 and NH3
H2O in
DMSO-d6.
the CHMPBA solution in DMSO-d6. As displayed in Fig. 6, the
chemical shift of Hg in CHMPBA greatly shifted to the low-field
(d = 9.62 ppm) due to the strong intramolecular hydrogen bond
formed between carboxyl oxygen and Hg. In the spectrum of
CHMPBA + NH3, the peak near 4.14 ppm was assigned to the
signal of Hg. Obviously, a big upfield shift (Dd = 5.52 ppm) was
observed for Hg after treatment with ammonia vapor, demon-
strating that the hydrogen bond between carboxyl oxygen and
Hg might have been greatly weakened or destroyed. Interestingly,
the signal of Hi (d = 13.29 ppm), which could be assigned to the
carboxyl hydrogen in CHMPBA disappeared and a new peak near
1.22 ppm (Hk) appeared after interaction with ammonia. The
spectral changes proved that ammonium salt might be obtained
from the reaction of carboxyl (Hi) and ammonia. At the same
time, no obvious chemical change was observed for Hh after
treatment with ammonia vapor, which suggested there is no
obvious interaction between the hydroxyl group and ammonia.
DFT calculations. To further reveal the causes for the
fluorescence quenching phenomenon, detailed structural analysis
was performed with the Gaussian 09 suite of programs.54 The
geometry of the molecular structure was optimized without
symmetry constraints at the B3LYP level of theory. The 6-311+g*
basis set was used and frequency analysis was undertaken at the
same theoretical level. Optimized geometries and molecular orbital
plots of HOMO–LUMO of CHMPBA and CHMPBA + 4NH3 are
displayed in Fig. 7.
By comparing the optimized structures and molecular orbital
plots (HOMO and LUMO) of CHMPBA (Fig. 7a) and CHMPBA +
4NH3 (Fig. 7b), we found the following changes: A N–Hg


O
bond length extended from 1.902 Å to 2.025 Å; B the dihedral
angle DNHCO between N–Hg and COOH changed from 8.171 to
13.671; C the band gap between the HOMO and LUMO increased
from 4.00 eV to 4.23 eV. The above-mentioned changes indicated
that the hydrogen bond between N–Hg and carboxyl oxygen was
weakened with the addition of ammonia. Furthermore, the
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Fig. 7 DFT optimized structure and molecular orbital plots of the HOMO
and LUMO of CHMPBA (a) and CHMPBA + 4NH3 (b).
weakening of the coplanarity was not conducive to electron
transmission, resulting in a broader band gap. This might lead
to fluorescence quenching. In addition, the bond length of O–Hi
in the carboxyl group enlarged from 0.969 Å to 1.023 Å when
CHMPBA was exposed to four ammonia molecules. A further
increase in ammonia number will result in the complete break-
ing of the O–Hi bond and Hi will transfer to ammonia, which is
consistent with the experimental results.
Reusability study. Based on the DFT calculations and
1
H NMR analysis results, we envisioned that the quenched
fluorescence emmission might be recovered after treatment
with acidic gas and the as-prepared paper sensors might be
reused again. Therefore, a recycling study for this portable
fluorescent sensor was carried out by alternately exposing it
to ammonia and hydrogen chloride vapors. The normalized
fluorescence intensities are displayed in Fig. 8. To our delight,
no obvious fluorescence intensity change was observed after
four cycles of continuous ammonia vapor sensing, revealing the
good reusability of the paper-based portable sensor.
Plausible mechanism. According to the above DFT calculations,
1
H NMR analysis, and reusability study, we believe that the restricted
intramolecular rotation (RIR) mechanism could be responsible
for the ‘‘Fluorescence ON–OFF–ON’’ phenomenon of CHMPBA.55
Fig. 8 Fluorescence intensity changes of the paper-based sensor after
fuming with ammonia vapor and hydrogen chloride in sequence.
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Fig. 9 Plausible reaction mechanism for the ‘‘Fluorescence ON’’ and
‘‘Fluorescence OFF’’ phenomena.
The intramolecular hydrogen bond between carboxyl oxygen and Hg
(N–H) restricts the intramolecular rotation (RIR) of the C–N bond,
leading to a relatively rigid intramolecular co-planarization configu-
ration (Fig. 9 ring A and ring B). Upon restriction of intramolecular
rotation (RIR) of CHMPBA, the radiative decay channel is activated,
which leads to the high fluorescence emission.56–58 However, after
treatment with NH3, the intramolecular hydrogen bond between
carboxyl oxygen and Hg (N–H) was destroyed and the rotation of
the C–N single bond was activated, which would result in the
nonradiative decay of CHMPBA, thus the fluorescence was
‘‘TURNED OFF’’.56–58 While, after fuming with hydrogen chloride,
the ammonia molecules were taken away from CHMPBA and the
intramolecular hydrogen bond was reconstructed, thus the fluores-
cence was ‘‘TURNED ON’’ (Fig. 9). In addition, the RIR mechanism
for CHMPBA was further confirmed by recording the fluorescence
intensities of CHMPBA with increasing/decreasing temperatures and
solvent viscosity (mechanism study in ESI†).
3.5 Practical applications
Fluorescent invisible ink, fingerprint storage material and
anti-false trademark material. In order to reveal the potential
applications, a stock solution of CHMPBA was prepared in THF
(10 mM). The as-prepared solution was injected into a marker
pen and used as fluorescent invisible ink. As shown in
Fig. 10(a), the word ‘‘AIE’’ was invisible under daylight, while
the bright blue letters could be clearly observed under 365 nm
UV light (Fig. 10b). To further explore the potential application
Fig. 10 Practical applications of CHMPBA as fluorescent invisible ink,
information storage material and anti-false trademark material.
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of CHMPBA in the field of information storage, a fingerprint
was produced by dipping an index finger into the stock solution
of CHMPBA and gently stamping the fingertip on microscopic
TLC glasses. As displayed in Fig. 10(c), the fingerprint is
ambiguous at first, but after drying with a dryer, the bright
blue fingerprint emerged immediately (Fig. 10d). Intrigu-
ingly, the bright blue fingerprint became blurred when
exposed to ammonia vapor (Fig. 10e) and recovered after
fuming with hydrogen chloride (Fig. 10f). The results demon-
strate that CHMPBA might be used for personal information
storage.
Due to the strong fluorescence emission in the aggregation
state and the quick ‘‘TURN OFF’’/‘‘TURN ON’’ phenomena
when exposed to amine/ammonia vapors and acidic gases,
CHMPBA might be commercially used in anti-false trademarks.
As displayed in Fig. 10g, the pattern ‘‘TM’’ (trademark) is
invisible under daylight and legible under 365 nm UV light
(Fig. 10h). However, after exposure to ammonia vapor, the
pattern ‘‘TM’’ became blurred (Fig. 10i). In order to reveal the
potential application of CHMPBA in daily life, white vinegar,
which is extensively used as a seasoning in the kitchen, was
used in our experiments. As shown in Fig. 10j, the bright
emission could be recovered by fuming with white vinegar.
The above experiments revealed that CHMPBA has good appli-
cation potential for commercial use as an anti-false trademark
material in the future.
4. Conclusions
A novel biomass-based AIE material, CHMPBA, has been constructed
from ( )-methyl-3-dehydroshikimiate (3-MDHS) and 2-amino-4-
chlorobenzoic acid by using the tandem cross-coupling and
aromatization reactions. The AIE properties of CHMPBA were
investigated in mixed solvents and typical AIE phenomena were
observed. Portable sensors were prepared by depositing
CHMPBA on filter paper and used in the highly sensitive detec-
tion of ammonia vapor in air. A plausible mechanism for the
fluorescence ‘‘TURN OFF’’/‘‘TURN ON’’ phenomena in the detec-
tion of ammonia vapor was proposed based on 1H NMR tests,
DFT calculations and a reusability study. Further application
studies revealed that CHMPBA might be commercially used as
an information storage material, such as fluorescent invisible
ink and anti-false trademark ink, in the future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the Natural Science Foundation of
China (21663032), the Natural Science Foundation and Inno-
vative Talents Promotion Plan of Shaanxi Province (2019KJXX-
075, 2018JQ2079, 2018JQ2040, and 2018JM2055), and Startup
Foundation for Doctors of Qufu Normal University.
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Notes and references
1 M. Höhne and U. T. Bornscheuer, ChemCatChem, 2009, 1(1),
42–51.
2 Q. L. Shen and J. F. Hartwig, J. Am. Chem. Soc., 2006, 128(31),
10028–10029.
3 C. Gunanathan and D. Milstein, Angew. Chem., Int. Ed.,
2008, 47(45), 8661–8664.
Published on 13 June 2019. Downloaded by National Chiao Tung University on 4/27/2021 5:27:21 AM.
4 L. J. Xu, Q. Yao, Y. Zhang and Y. Fu, ACS Sustainable Chem.
Eng., 2017, 5(4), 2960–2969.
5 S. A. Lawrence, Amines: Synthesis, Properties and Applications,
Cambridge University Press, Cambridge, 2004.
6 T. Gao, E. S. Tillman and N. S. Lewis, Chem. Mater., 2005,
17(11), 2904–2911.
7 M. Gao, S. W. Li, Y. H. Lin, Y. Geng, X. Ling, L. C. Wang,
A. J. Qin and B. Z. Tang, ACS Sens., 2016, 1(2), 179–184.
8 Y. Takagai, Y. Nojiri, T. Takase, W. L. Hinze, M. Butsugan
and S. Igarashi, Analyst, 2010, 135(6), 1417–1425.
9 W. G. Stillwell, M. S. Bryant and J. S. Wishnok, Biomed.
Environ. Mass Spectrom., 1987, 14, 221–227.
10 B. Mailhot, S. Morlat-Thérias, M. Ouahioune and
J. L. Gardette, Macromol. Chem. Phys., 2005, 206(5), 575–584.
11 Y. B. Zhang, C. Peng, X. J. Ma, Y. K. Che and J. C. Zhao,
Chem. Commun., 2015, 51, 15004–15007.
12 S. Pandey and K. K. Nanda, ACS Sens., 2016, 1, 55–62.
13 D. J. Michael and R. M. Wightman, J. Pharm. Biomed. Anal.,
1999, 19(1–2), 33–46.
14 S. Tombelli and M. Mascini, Anal. Chim. Acta, 1998, 358(3),
277–284.
15 J. D. Luo, Z. L. Xie, J. W. Y. Lam, L. Cheng, H. Y. Chen,
C. F. Qiu, H. S. Kwok, X. W. Zhan, Y. Q. Liu, D. B. Zhu and
B. Z. Tang, Chem. Commun., 2001, 1740–1741.
16 S. Samanta, S. Goswami, M. N. Hoque, A. Ramesh and
G. Das, Chem. Commun., 2014, 50(80), 11833–11836.
17 S. Samanta, U. Manna, T. Ray and G. Das, Dalton Trans.,
2015, 44(43), 18902–18910.
18 W. Y. Fang, G. B. Zhang, J. Chen, L. Kong, L. M. Yang, H. Bi
and J. X. Yang, Sens. Actuators, B, 2016, 229, 338–346.
19 D. D. La, S. V. Bhosale, L. A. Jones and S. V. Bhosale, ACS
Appl. Mater. Interfaces, 2017, 10(15), 12189–12216.
20 J. C. Qin, B. D. Wang, Z. Y. Yang and K. C. Yu, Sens.
Actuators, B, 2016, 224, 892–898.
21 D. D. Li, J. Z. Liu, R. T. Kwok, Z. Q. Liang, B. Z. Tang and
J. H. Yu, Chem. Commun., 2012, 48(57), 7167–7169.
22 X. G. Hou, Y. Wu, H. T. Cao, H. Z. Sun, H. B. Li, G. G. Shan
and Z. M. Su, Chem. Commun., 2014, 50(45), 6031–6034.
23 Y. W. Wu, A. J. Qin and B. Z. Tang, Chin. J. Polym. Sci., 2017,
35(2), 141–154.
24 Q. Y. Li, Z. Ma, W. Q. Zhang, J. L. Xu, W. Wei, H. Lu, X. S. Zhao
and X. J. Wang, Chem. Commun., 2016, 52(75), 11284–11287.
25 L. Shao, J. Sun, B. Hua and F. Huang, Chem. Commun., 2018,
54(38), 4866–4869.
26 Y. S. Dong, B. Liu and Y. Y. Yuan, J. Controlled Release, 2018,
290, 129–137.
27 Y. F. Wang, Y. X. Zhang, J. J. Wang and X. J. Liang, Adv. Drug
Delivery Rev., 2018, DOI: 10.1016/j.addr.2018.12.004.
8410 | J. Mater. Chem. C, 2019, 7, 8404--8411
View Article Online
Paper
28 W. H. Zhuang, B. X. Ma, G. Y. Liu, G. C. Li and Y. B. Wang,
J. Appl. Polym. Sci., 2018, 135(1), 45651.
29 Y. X. Qian, Y. H. Wang, F. Jia, Z. H. Wang, C. Y. Yue,
W. K. Zhang, Z. Y. Hu and W. Z. Wang, Biomaterials, 2019,
188, 96–106.
30 D. Tian, F. Li, Z. C. Zhu, L. B. Zhang and J. T. Zhu, Chem.
Commun., 2018, 54(64), 8921–8924.
31 Y. L. Wang, C. Fan, B. Xin, J. P. Zhang, T. Luo, Z. Q.
Chen, Q. Y. Zhou, X. N. Li, Z. L. Huang, C. Li, M. Q.
Zhu and B. Z. Tang, Mater. Chem. Front., 2018, 2(8),
1554–1562.
32 T. Gao, X. Z. Cao, A. Y. Bi, J. Dong, S. Huang, X. Y. Huang,
S. J. Wen and W. B. Zeng, Sens. Actuators, B, 2018, 273,
1139–1145.
33 R. Suresh, S. K. Thiyagarajan and P. Ramamurthy, Sens.
Actuators, B, 2018, 258, 184–192.
34 P. Singh, H. Singh, R. Sharma, G. Bhargava and S. Kumar,
J. Mater. Chem. C, 2016, 4(47), 11180–11189.
35 L. Y. Hu, J. Y. Sun, J. Q. Han, Y. A. Duan and T. Y. Han, Sens.
Actuators, B, 2017, 239, 467–473.
36 Z. J. Ning, Z. Chen, Q. Zhang, Y. L. Yan, S. X. Qian, Y. Cao
and H. Tian, Adv. Funct. Mater., 2007, 17(18), 3799–3807.
37 D. D. Li, Y. P. Zhang, Z. Y. Fan and J. H. Yu, Chem. Commun.,
2015, 51(72), 13830–13833.
38 Y. Ma, M. Cametti, Z. Džolić and S. Jiang, J. Mater. Chem. C,
2018, 6(34), 9232–9237.
39 M. Jang, S. Kang and M. S. Han, Dyes Pigm., 2019, 162,
978–983.
40 X. Zhang, H. F. Mu, H. M. Li, Y. Zhang, M. An, X. H. Zhang,
J. Yoon and H. T. Yu, Sens. Actuators, B, 2018, 255,
2764–2778.
41 Y. C. Feng, M. Z. Li, Z. B. Gao, X. Zhang, X. H. Zeng, Y. Sun,
X. Tang, T. Z. Lei and L. Lin, ChemSusChem, 2019, 12(2),
495–502.
42 R. Q. Fang, P. L. Tian, X. F. Yang, R. Luque and Y. W. Li,
Chem. Sci., 2018, 9(7), 1854–1859.
43 B. Wozniak, A. Spannenberg, Y. Li, S. Hinze and J. G. de
Vries, ChemSusChem, 2018, 11(2), 356–359.
44 R. Lu, F. Lu, J. Z. Chen, W. Q. Yu, Q. Q. Huang, J. J. Zhang
and J. Xu, Angew. Chem., Int. Ed., 2016, 55(1), 249–253.
45 J. N. Chheda, G. W. Huber and J. A. Dumesic, Angew. Chem.,
Int. Ed., 2007, 46(38), 7164–7183.
46 C. G. Lima, J. L. Monteiro, T. de Melo Lima, M. Weber
Paixão and A. G. Corrêa, ChemSusChem, 2018, 11(1), 25–47.
47 E. S. Zhang, T. L. Xu, W. Wei, T. K. Huang, M. Yuan, W. Zeng
and Y. Zou, Synthesis, 2014, 1167–1176.
48 E. S. Zhang, T. L. Xu, D. J. Wang, T. K. Huang, M. Yuan, J. Li
and Y. Zou, RSC Adv., 2014, 10022–10027.
49 E. S. Zhang, X. J. Zhang, W. Wei, D. J. Wang, Y. C. Cai,
T. L. Xu, M. Yan and Y. Zou, RSC Adv., 2015, 5(7), 5288–5294.
50 W. Wu, Y. Zou, Y. Chen, J. Li, Z. L. Lv, W. Wei, T. K. Huang
and X. K. Liu, Green Chem., 2012, 14(2), 363–370.
51 C. Gayen, S. Basu, U. N. Pan and A. Paul, ACS Omega, 2018,
3(12), 17220–17226.
52 Y. Rachuri, B. Parmar, K. K. Bisht and E. Suresh, Cryst.
Growth Des., 2017, 17(3), 1363–1372.
This journal is © The Royal Society of Chemistry 2019

Paper
53 B. Chowdhury, S. Khatua, R. Dutta, S. Chakraborty and
P. Ghosh, Inorg. Chem., 2014, 53(15), 8061–8070.
54 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone,
B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng,
J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
Published on 13 June 2019. Downloaded by National Chiao Tung University on 4/27/2021 5:27:21 AM.
H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta,
F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin,
V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand,
K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar,
J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene,
J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin,
This journal is © The Royal Society of Chemistry 2019
View Article Online
Journal of Materials Chemistry C
R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin,
K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador,
J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas,
J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox,
Gaussian 09, Revision E.01, Gaussian, Inc., Wallingford CT,
2013.
55 J. Liang, B. Z. Tang and B. Liu, Chem. Soc. Rev., 2015, 44(10),
2798–2811.
56 S. F. Gan, W. W. Luo, B. R. He, L. Chen, H. Nie, R. R. Hu,
A. J. Qin, Z. J. Zhao and B. Z. Tang, J. Mater. Chem. C, 2016,
4(17), 3705–3708.
57 W. Tang, Y. Xiang and A. J. Tong, J. Org. Chem., 2009, 74(5),
2163–2166.
58 B. K. An, S. K. Kwon, S. D. Jung and S. Y. Park, J. Am. Chem.
Soc., 2002, 124(48), 14410–14415.
J. Mater. Chem. C, 2019, 7, 8404--8411 | 8411