Aggregation-induced emission nanofiber as a dual sensor for aromatic amine and acid vapor

Article abstract of DOI:10.1039/c7tc03192k

Two cyano-substituted vinylacridine derivatives linked with N-dodecyl-l-phenylalaninamide through succinyl (PC2VA) and glutaryl (PC3VA) groups were synthesized and were found to exhibit aggregation-induced emission properties. These two compounds could fo

Full text of DOI:10.1039/c7tc03192k

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ISSN 2050-7526
PAPER
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Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
the Hofmeister effects
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Aggregation-induced emission nanofiber as dual sensor for
aromatic amine and acid vapor
Pengchong Xue,*,a,b Jipeng Ding,b Yanbing Shen,b Hongqiang Gao,b Jinyu zhao,b Jingbo Sun,b Ran
Lub
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Two cyano-substituted vinylacridine derivatives linked with N-dodecyl-L-phenylalaninamide through succinyl (PC2VA) and
glutaryl (PC3VA) groups were synthesized and were found to exhibit aggregation-induced emission properties. These two
compounds could form gels in some solvents at low concentrations and exhibit fluorescence enhancement during gelation.
The gelation abilities and microstructure intermolecular interactions of these compounds were different, although their
molecular structures varied with only one methylene group. Moreover, a uniform fibrous film that could be used as an
effective dual sensor on glass plates was prepared by PC2VA wet gels to quantitatively detect aromatic amine and volatile
acid vapors caused by low HOMO energy level of the fluorophore and the existence of acridine moiety as an acid binding
site. The response times and detection limits (DL) for vapors are short and low, respectively. The DL of aniline reaches 1.3
µg/m3 because amplifying fluorescence quenching exists within long nanofibers induced by efficient exciton diffusion
along with π–π stacking direction. Moreover, the DL for trifluoroacetic acid is low and determined to be 2.3 mg/m3.
www.rsc.org/
cells.17 However, the AIE molecules in the block solid state are
rarely used as sensing materials to detect analytes because of
their small surface area.18
Introduction
Small
organic
molecules
with
fluorescence
and
The gelation of lowꢀmass weight gelators (LMWGs) in solvents
is a convenient and fast method to prepare a threeꢀdimensional
porous network composed of thin and long nanofibers.19ꢀ22
Such microstructures in gel phases could be damaged by
external stimuli because these nanofibers were constructed by
weak intermolecular interactions.23ꢀ24 Therefore, many smart
emissive πꢀgels have been used as sensing materials to
selectively respond to cations,25ꢀ26 anions,27ꢀ28 neutral
molecules,29ꢀ30 light,31ꢀ32 pH,33ꢀ34 and redox.35 However, the
gelation of these gelators usually follows luminescent
quenching because intermolecular interaction in aggregates
promotes the excited states to decay or relax back to the ground
state via nonꢀradiative channels.36 Moreover, some functional
phosphorescence have been used as multifunctional materials
in organic light-emitting diodes,1-2 biological imaging,3-4
biomolecular sensing,5 and various chemical sensing.6-8
Generally, luminophores emit strong light in dilute solution.
However, emission quenching always emerges after they
aggregate together because of strong π‒π interaction, called
aggregation-caused quenching (ACQ).9 The applied range of
molecules with ACQ will be limited based on the viewpoint of
real-world applications. Another kind of luminophores, which
are nonꢀ or weakꢀ emissive in unassociated state and become
luminophores with enhanced emission in their aggregate states,
was rapidly developed by the Tang group in 2001 10
This
.
phenomenon is called by aggregation-induced emission (AIE).
Taking advantage of the AIE effect, a large amount of AIE
molecules have been explored and developed into smart
materials that are responsive to external stimuli, such as
mechanical force,11-12 temperature change,13 pH variation,14-15
and photonic irradiation.16 These molecules have been widely
applied in biological and chemical sensing in solutions or
groups,
such
as
tetraphenylethene,37ꢀ38
2,3,4,5ꢀ
tetraphenylsilole,39 salicylideneaniline,40ꢀ42 1,3,4ꢀoxadiazole,43
and carbazole,44 have been introduced into gelators to realize
AIE gels. If a gelator contains an AIE luminophore with a
property responsive to gases, then the obtained xerogels will be
better sensing materials to desirable gases.
Aromatic amine, such as aniline, and volatile acid vapors,
including inorganic and organic acids, are important gaseous
pollutants because they seriously damage the ecological
environment and induce severe threats to human health.45ꢀ46
Recently, the fluorescent xerogel films of some functional πꢀ
gelators have been exploited as sensors to quantitatively detect
aromatic amine or acid vapors.47ꢀ51 However, the simultaneous
response of an AIE gelator to gaseous organic amine and
volatile acids still remains as a challenging issue.52 In this study,
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two molecules with cyano group and acridine moiety (Scheme Aggregation-induced emission in solution. The UVꢀvis
1, PC2VA and PC3VA) were designed. These molecules were absorption and fluorescence spectra in THF were measured. Fig.
anticipated to be gelator that exhibit AIE during gelation and S1 shows that the two compounds have almost the same
possess dual sensing for gaseous organic amines and volatile absorption spectra owing to their similar fluorophores. The
acids. Two compounds could form gels in some solvents and maximal absorption peak in the long wavelength region located
AIE phenomenon emerged during gelation. The fluorescence of at 364 nm is accompanied by two shoulder peaks at 348 and
wet gels of the two compounds could be quenched by acid and 387 nm. The color of the THF solution is yellowish because the
aromatic amines. The nanofiber film obtained from PC2VA absorbance above 400 nm is not zero. However, the THF
gels may act as sensing materials to quantitatively detect both solutions of the two compounds have no visible fluorescence
aromatic amine and acid vapors with rapid response times and under 365 nm light (Fig. 1). The two compounds begin to
low detection limits. Thus, the smart molecular design may aggregate when the fraction of water increased above 60%, and
help gelators to not only have AIE characteristics but also the fluorescence intensity rapidly increased, showing that the
achieve excellent multiꢀresponsive properties to gaseous two compounds are typical AIE molecules.61 Thus, the gels of
analytes.
these compounds are expected to exhibit AIE behaviors. A
geometry optimization with DFT calculation was performed to
understand the AIE behavior of these molecules. The dihedral
angle between vinyl and acridine, and vinyl and phenyl groups
are 58.6º and 21.8º, respectively (Fig. S2). Such large dihedral
angles result in a twisted conformation, suppressed radiative
process, and weak emission in solution. After aggregating, the
free rotation of single bonds was suppressed. As a result,
fluorescence enhancement was observed in the mixtures with
more than 60% water.
Scheme 1. Molecular structures of PC2VA and PC3VA with hydrogen bonding units,
proton binding site and steric hindrance group.
Results and discussion
Molecular design and synthesis.
A large amount of
investigations about AIE molecules suggest that free rotation
of single bond in monomer state is mainly responsible for
weak emission and the suppression of intramolecular rotation
in aggregation state may lead to emission enhancement
through suppressing non-radiative decay of excited states.54
Among numerous AIE luminophores, some 9,10-
bis(arylvinyl)anthracene or 9-arylvinylanthracene derivatives
have been found to be AIE activity.55-56 If a gelator contains
these functional groups, it will exhibit enhanced emission
during gelation. Moreover, the highest occupied molecular
orbital (HOMO) energy levels of luminophores have to be
enough low to allow gaseous organic amines to quench their
fluorescence based on photo-induced energy transfer
mechanism. In addition, the gelator fluorophore must consist
of a proton-binding site in order to respond to gaseous acids57
and the cyano group with strong electron-withdrawing
property is an excellent building block to suppress
aggregation-caused quenching and give a molecule with a low
HOMO energy level.58-60 Therefore, cyano and acridine
moieties was introduced in order to achieve a fluorophore
with low HOMO energy level in response to gaseous organic
amines and acids. Moreover, the fluorophore was linked with
N-dodecyl-L-phenylalaninamide through succinyl and glutaryl
groups to enable molecule to self-assemble into nanofibers in
their gel phases.
Fig. 1 Fluorescence spectra of PC2VA (a) and PC3VA (b) and corresponding images
(PC2VA, c, and PC3VA, d) under 365 nm in the mixture of THF and water. λex = 385 nm.
Self-assemblies in gel phases. The gelation abilities of the two
compounds were investigated. Table S1 shows the results in
the investigation. The two compounds are soluble in DMF and
dissoluble in cyclohexane. Gel phases were observed after the
hot solutions of the two compounds were cooled to room
temperature in aromatic hydrocarbon solutions, such as o-
dichlorobenzene, chlorobenzene (CB), and xylene. Moreover,
PC2VA could form gels in many alcohol solvents. PC3VA,
except methanol, precipitated from these solvents. The result
suggests that N-dodecyl-L-phenylalaninamide indeed help
molecules form gels, and the subtle difference in molecular
structure results in distinct gelation abilities.
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and thin fibers to provide large surface areas and favor analyte
adsorption, in which rapid response time and low detection
limit are expected.
Fig. 2 UV-vis absorption and fluorescence spectral changes of PC2VA (a and c) and
PC3VA (b and d) during gelation from 120 ºC to room temperature. Time interval is 1
min. λex = 370 nm. Insets in Fig. a and c are images of gels under natural light. Insets in
Fig. b and d are the images of sols and gels under 365 nm light.
Fig. 3 SEM (a and c) and TEM (b and d) images of PC2VA and PC3VA from CB gels.
Afterward, UV-vis absorption and IR spectra were utilized to
study intermolecular interactions in gels and the driving forces
of gelation. Fig. 2a shows that the maximal peak of PC2VA
located at 367 nm in the hot CB solution arises and then
gradually decreases on account of aggregate while cooling the
sample. The absorbance at 367 decreased from 1.8 to 1.5 after
16 min and the absorption band became wide. However, the
absorption peaks did not shift (Fig. S3). This result indicates
that the π–π interaction between chromophores is weak. In
other words, the distance between chromophores is large
because the non-planar conformation of aromatic moiety and
large cyano unit prevent chromophores from close packing.62
Similar spectral change appears during the gelation of PC3VA
(Fig.s 2c and S3b). Subsequently, the IR spectra of xerogels
were measured to explore the interaction among amide
groups. The stretching vibration peaks of N–H and C=O of
aliphatic amide groups for both gels appeared at 3290 and
1638 cm−1, respectively, suggesting that intermolecular
hydrogen bonds among aliphatic amides exist and are the
same in gels contained by PC2VA and PC3VA. The C=O in
aromatic amide moiety in PC2VA gel has a vibration peak at
1669 cm-1, but two vibration peaks at 1669 and 1655 cm-1 for
PC3VA gel exists, showing that two kinds of hydrogen bonds
between aromatic amide groups in PC2VA gel exist.63
Arrows in Fig. d show wide ribbons.
The XRD patterns of xerogels were obtained to further
understand the intermolecular packing in gel phases. Three
diffraction peaks at 1.80°, 3.60°, and 5.5°, corresponding to
5.45, 2.72, and 1.81 nm in PC2VA gel were observed,
respectively, suggesting a layer stacking with a long period of
5.45 nm.64 A significant diffraction peaks at 3.33° emerged in
PC3VA gel, indicating that a layer stacking with a short period
of 2.65 nm exists. Molecular modeling calculations were
performed to obtain a stable aggregate to elucidate the self-
assembling behavior of molecules in gels. Fig. S6a shows the
optimal 1D stacking of PC2VA in MMFF4 force field,65 in which
one molecule attends six hydrogen bonds with two other
molecules by three amide groups, and the distance of two
adjacent acridine units is ca. 4.0 Å. Large distance suggests
weak π–π interaction, which is in agreement with the result
obtained by UV-vis absorption spectra. Considering a 3.45 nm
width of 1D packing and a large long period of 5.45 nm
obtained by XRD pattern, PC2VA molecules should adopt an
interpenetrating bimolecular stacking (Fig. S6c). The modeling
calculation shows that PC3VA has a similar 1D stacking. A titled
monomolecular layer stacking is possible for PC3VA based on
longer 1D packing width and a short XRD period of 2.65 nm
(Fig. S6d).
The morphologies of self-assemblies in the CB gels of the two
compounds were investigated using scanning electron
microscopes (SEM) and transmission electron microscopes
(TEM). Many long nanoribbons with diameters ranging from 50
nm to 100 nm were found in the SEM and TEM images of
PC2VA gel (Fig.s 3a and 3b). PC3VA also self-assembled into
one-dimensional (1D) nanoribbon with a diameter ranging
from 20 nm to 50 nm. These nanoribbons intertwined one
another to construct wide fibers. Another kind of
microstructure called wide ribbons exist (arrows in Fig. 3d) in
PC3VA gel. Two kinds of self-assemblies should be responsible
for the two kinds of hydrogen bonds among amide groups. The
results suggest that two gelators may self-assemble into long
The hot solutions of the molecules in CB emit weak
fluorescence under 365 nm light. The fluorescence intensity
gradually increased and the gels obtained strong fluorescence
as the temperature decreased (insets in Fig. 2b and 2d). This
result shows the AIE enhancement during gelation.
Fluorescence spectra were used to monitor this process. Fig.
2b shows that the CB solution of PC2VA at 120 °C has a weak
emission band with a maximum at 506 nm, which gradually
arose with decreasing temperature. After 20 min, the gel
formed and the fluorescence intensity increased by 12.4-fold.
Similarly, the gelation process of PC3VA also induced
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fluorescence enhancement (Fig. 2d). These results significantly 3.4 Response of xerogel film to gaseous acids. As shown in 3.3,
imply that both designed gelators possess emission the fluorescence of wet gel could be completely quenched by a
enhancement characteristics not only in THF/water mixture small amount of TFA. Thus, the xerogel film was anticipated as
but also in gels.
3.3 Responses to acids in solution and gel phases. The TFA. The xerogel films were conveniently prepared by casting
response of the two compounds to acid in solutions was the hot solution on glass plate followed by solvent
a sensitive sensing material to quantitatively detect gaseous
a
investigated. The PC2VA solution in CHCl3 is yellowish, and the evaporation. It was found that a homogeneous wet gel formed
addition of trifluoroacetic acid (TFA) deepened the color (inset when the hot solution of PC2VA was cooled, and then a
in Fig. 4a). Fig. 4a shows the absorption spectral change of uniform xerogel film of PC2VA with strong green fluorescence
PC2VA upon the addition of TFA. The absorption peak at 390 could be obtained. However, while the hot solution of PC3VA
nm continuously decreased upon the addition of TFA and a on the surface of glass plate, an obvious phase separation was
new peak appeared at 413 nm. The isosbestic point was observed and then the xerogel film of PC3VA was
observed at 304 nm. This result implies that PC2VA can bind a inhomogeneous after solvent was removed (Fig. S9). Therefore,
proton to form a cation (PC2VAH+).66 A continuous quenching only the xerogel film of PC2VA was selected as sensing
in fluorescence could be observed upon the addition of TFA, material. When the xerogel film was exposed to saturated TFA
suggesting that PC2VAH+ is a luminophore with weak emissive vapor, its green fluorescence rapidly disappeared (response
performance. The PC2VA gel in CB can also respond to TFA. time = 1.1 s). From yellow, the film became orange and
The absorption band at approximately 390 nm became weak, emitted extremely weak red fluorescence (Fig. 5a). The
and an absorption band at approximately 420 nm appeared maximal absorption peak of the film was exposed to TFA
after increasing the concentration of TFA by 1.0 equiv. located at 440 nm (Fig. S10), suggesting that the green
Thereafter, an orange gel emerged (Fig. 4c), suggesting that fluorescence quenching in xerogel film is also ascribed to the
only partial PC2VA molecules bound proton. Interestingly, 0.3 protonation of acridine moieties. In addition, although the
equiv. TFA could completely quench the gel fluorescence at sensing film was exposed to air, the quenched fluorescence did
508 nm and resulted in the appearance of new weak peak at not recover because a stable PC3VAH+ formed. However, it
600 nm, which should be ascribed to the emission of PC2VAH+ was found that quenched film might recover its fluorescence
in CB because acridine unit became a stronger electron- through exposing film to NH3 vapor for 10 s. Moreover,
withdraw group after it bound a proton. The amplified fluorescence recovered film could be quenched by TFA vapour
fluorescence quenching involved in exciton diffusion should be again.
responsible for sensitive fluorescence response of wet gel to
TFA because the gel fibers and a large amount of PC2VA
molecules without bound protons still exist after adding 0.3
equiv. TFA (Fig. S7).67 Similar spectral changes upon the
addition of TFA were observed in PC3VA gel, indicating that
PC3VA also acts as a sensor to respond to TFA in solution and
gel phase.
Fig. 4 UV-vis absorption (a and c) and fluorescence (b and d) spectral changes for
PC2VA CHCl3 solution (a and b, 10‒5 M) and the PC2VA CB system (c and d, 1.0 mg/mL)
upon addition of TFA. λex = 380 nm. Insets are absorbance (420 nm) of PC2VA upon the
addition of TFA and photos under natural and 365 nm light.
Fig. 5 (a) Time-course of fluorescence quenching of the PC2VA xerogel film upon
exposure to saturated TFA vapor. Inset: photos of xerogel film before and after
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exposing to TFA. (b) Changes in the spectral emission of the xerogel film exposed to
different concentrations of TFA vapors for 10 s. Inset: Concentration-dependent
fluorescence quenching efficiency (QE) of the xerogel film. The intensity was monitored
at 508 nm.
PC2VA gel will be expected to selectively respond to aromatic
amines. When the sensing film was exposed to saturated
aniline vapor (480 ppm), its fluorescence was rapidly quenched.
Fig. 6a shows the change of fluorescence intensity at 508 nm
after the sensing film was exposed to saturated aniline vapor.
The response time to aniline was determined as 0.53 s based
on the quenching curve. Moreover, the quenching efficiency of
aniline vapor is strongly dependent on aniline concentration.
Fig. 6b shows that QE increases rapidly with increasing aniline
concentration (< 0.3 ppm). A low concentration of aniline (0.33
ppm) induces a large QE of 69%. This result illustrates that the
response of the sensing film to gaseous aniline is sensitive. The
The fluorescence intensity at 508 nm was dependent on the
concentration of gaseous TFA. Fig. 5b shows that the film
emission decreased significantly with increased TFA vapor
concentration (Fig. 5b). The concentration-dependent
fluorescence quenching efficiency (QE, 1-I/I0) was plotted to
account for the sensitivity of the xerogel film to sensing
gaseous TFA. The QE increases nonlinearly with increasing TFA
concentration, and increases slowly when the concentration is
above 400 ppm. Moreover, a linear relationship between QE
and TFA concentrations was confirmed when the TFA
concentrations are below 200 ppm. A significant fluorescence
decrease of 14.4% for sensing film was observed upon the
exposure to TFA at a concentration of 48 ppm. Considering
that a well-calibrated photo detector can detect intensity
changes as low as 0.1%, the detection limit for TFA vapor was
calculated to be as low as 0.5 ppm, corresponding to 2.3
mg/m3.68 Similarly, the quenched fluorescence could be not
restored by exposing the film to air, suggesting an irreversible
sensing property. When the sensing film was exposed to TFA
at a concentration of 1120 ppm, only a small number of
gelators bound proton to convert into PC2VAH+ because the
absorbance at 450 nm had a slight increase (Fig. S10b).
However, the fluorescence of sensing film was almost
quenched, suggesting that amplified fluorescence quenching
also exist in sensing film (Fig. S7). Furthermore, the
fluorescence of sensing film can be quenched upon exposure
to other volatile acid vapors, such as HCl and acetic acid. Fig.
S11 shows that the fluorescence intensity of the film gradually
decreases with increased acid concentration. The detection
limits of sensing film to HCl and acetic acid were determined to
be 1.26 and 0.12 ppm, respectively, based on the same
method. Therefore, the xerogel film can be used as sensing
material to quantitatively detect volatile strong acid vapors.
Furthermore, we measured and compared the absorption
spectra of xerogel film when it was exposed to acetic acid, and
found that there was not new absorption peak (Fig. S12). This
result suggests that acetic acid did not protonate PC2VA to
form PC2VA+H and hydrogen bond between HOAc and
acridine group should be responsible for fluorescence
quenching.
detection limit can be derived as 0.33 ppb (1.26
µ
g/m3).
Moreover, the green fluorescence could be restored after the
quenched film was exposed to air for 20 min. This process
could be repeated (Fig. 6c), suggesting that the response of
3.5 Response of xerogel film to gaseous amines. If the
fluorescence response mechanism of a gelator for organic
amines is based on the photo-induced electron transfer from
organic amine HOMO to luminophore HOMO, then the HOMO
energy level of the gelator has to be lower than the energy
level of organic amines. Cyclic voltammetry was measured to
gain the HOMO energy level of PC2VA. Table S2 shows the
result. The HOMO energy level was determined to be −5.73 eV.
Quantum chemical calculation also provides a similar HOMO
energy level (5.68 eV). This energy level is higher than the
energy level of common aliphatic amines and lower than rich
aromatic amines, such as aniline, N-methylaniline, and N,N-
dimethylaniline (Table S3). Therefore, the sensing film of
Fig. 6 (a) Time-course of fluorescence quenching of the PC2VA xerogel film upon
exposure to saturated aniline vapor (480 ppm). Inset: photos of xerogel film before and
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after exposing to aniline. (b) Changes in the spectral emission of the PC2VA xerogel film
exposed to different concentrations of aniline vapors for 10 s. Inset: concentration-
dependent fluorescence quenching efficiency (QE) of the xerogel film. The intensity
was monitored at 508 nm. (c) Cycles of the fluorescence quenching and recovery by
exposing the PC2VA film to aniline (100 ppm) and the air (20 min).
with succinyl group might form uniform xerogel film, which
can be used as a dual sensor to selectively and quantitatively
detect gaseous volatile acids and aromatic amines. The
detection limits for acid and amines are low. The detection limit
for TFA vapor is 0.5 ppm, corresponding to 2.3 mg/m3,
sensing film to aniline is reversible. Thus, the film could be whereas the detection limit for aniline is 1.3µ
g/m3. This work
reused, and the mechanism of sensing film to aniline is based provides enlightenment that proper structure design may not
on the physical absorption and followed photo-induced only offer AIE property to avoid aggregationꢀcaused
electron transfer.69
quenching, but also enables formed gels to perform multiple
The sensing film of PC2VA also exhibits excellent response to stimuli responses.
other aromatic amines, such N-methylaniline and N,N-
dimethylaniline. Large QEs were observed after exposing the
film to both aromatic amine vapors (Fig. S13). For instance, N-
methylaniline at a 0.3 ppm concentration results in a QE of
69%. The detection limits of sensing film to N-methylaniline
and N,N-dimethylaniline are as low as 0.48 and 1.38 ppb,
respectively. The fluorescence of the sensing film only
exhibited poor sensitivities to gaseous aliphatic amines (Fig.
7a). For example, only 2% decrease in fluorescence intensity
was observed when the film was exposed to triethylamine
(100 ppm). The poor response to aliphatic amines should be
responsible for the suppression of photo-induced electron
transfer from HOMO of aliphatic amines at ground state to
HOMO of luminophore at excited state because aliphatic
amines possess low HOMO energy levels (Table S3). To further
understand response mechanism, phenylhydrazine with a
higher HOMO energy level (-4.36 eV) was selected an analyte.
It was found that a gradual quenching was observed while the
concentration of pheylhydrazine increased.
A
low
concentration of 1 ppm results in a 26.6 % fluorescence
quenching. This result indicates that the response of xerogel
film is indeed based on the photo-induced electron transfer.
The fluorescence intensity changes of film after exposing to
common organic solvent were also measured. When the
concentrations of the films were maintained at 100 ppm, less
than 3% changes for all solvents were found. These results
imply that the obtained xerogel film can act as an efficient
sensor to selectively detect aromatic amine vapors. Moreover,
the time-dependent fluorescence spectra of the xerogel film
exposed to air were measured to evaluate its stability. Fig. 7b
shows that only a small change in fluorescence intensity was
observed after the film was exposed to air for 6 h, implying
that our sensing film is stable enough for practical applications.
4. CONCLUSION
Fig. 7 (a) QEs of the PC2VA xerogel film in response to the vapors of different reagents:
1) aniline, 2) N-methylaniline, 3) N,N-dimethylaniline, 4) phenylhydrazine, 5) acetone, 6)
ethanol, 7) ethyl acetate, 8) CH2Cl2, 9) THF, 10) toluene, 11) triethylamine, 12) n-
butylamine, 13) cyclohexylamine, 14) NH3, 15) tributylamine. Concentrations of aniline,
N-methylaniline and N,N-dimethylaniline are 1.0 ppm, those of other analytes are 100
ppm. (b) Time-dependent fluorescence spectra of the PC2VA xerogel film exposed to
air. Inset: fluorescence intensity changes with times.
Two cyanoꢀsubstituted vinylacridine derivatives linked with Nꢀ
dodecylꢀLꢀphenylalaninamide through succinyl and glutaryl
groups were synthesized to obtain two gelators, which will be
anticipated to exhibit AIE, gelation, and dual response to
gaseous volatile acids and aromatic amines. As expected, two
compounds emitted weak fluorescence in the solution and have
enhanced emission after aggregation, implying their AIE
characteristics. Moreover, both compounds could form stable
gels in some solvents. Thin nanoribbons in their gels also
assembled. Moreover, according to the gelation abilities of the
compounds, microstructure intermolecular interactions were
different although the molecular structures of the compounds
varied with only one methylene group. Furthermore, the gelator
Experimental Section
Measurements and Characterization. IR spectra were
measured using a Nicolet-360 FTIR spectrophotometer by
incorporating the samples in KBr disks. The UV− vis spectra
were obtained on a Mapada UV-1800pc spectrophotometer. C,
H, and N elemental analyses were performed on a PerkinElmer
240C elemental analyzer. Mass spectra were obtained with
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DOI: 10.1039/C7TC03192K
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AXIMA CFR MALDI-TOF (Compact) mass spectrometer. tetrabutylammonium hydroxide (TBAOH, Energy Chemical, 50%
Fluorescence spectra were taken on Cary Eclipse in water), Hydrazinium hydroxide (NH2NH2 H2O), Energy
a
∙
Luminescence Spectrophotometer. NMR spectra were carried Chemical, 80%), anhydrous zinc chloride (Energy Chemical,
out on a Mercury plus 400 MHz instrument. Transmission 97%) were used as received. THF was distilled from sodium
electron microscopy (TEM) images were observed with a benzophenone ketyl under N2 prior to use. All other solvents
Hitachi H-8100 apparatus by wiping the samples onto a 200- were
used
without
further
purification.
2-(4-
mesh carbon coated copper grid followed by naturally nitrophenyl)acetonitrile, 5a and 5b were synthesized by
evaporating the solvent. Scanning electron microscopy (SEM) reported procedures.53 The synthesis routes of PC2VA and
was performed on HITACHI SU8020 (operating at 3.0 kV). The PC3VA shown in Scheme 2.
samples were prepared by casting the wet gels onto a clean
silicon wafer followed by drying in air. Before observation, the
samples were coated by a gold film. Cyclic voltammetry was
employed using a three-electrode cell and an electrochemistry
workstation (CHI604). The working electrode was a glass
carbon disc, the auxiliary electrode was a Pt wire, and Ag/AgCl
was used as reference electrode. Tetrabutylammonium
tetrafluoroborate (TBABF4, 0.1 M) was used as the supporting
+
electrolyte in dry DMF. The ferrocenium/ferrocene (Fc/Fc )
redox couple was used as an internal potential reference. Xꢀ
ray diffraction (XRD) patterns were obtained on a PANayltical
Empyrean powder Xꢀray diffractometer, by employing a
scanning rate of 0.05 º/s (from 1.1 to 30º). Geometrical
optimizations were performed by density functional theory
(DFT) calculations at B3LYP/6-31G level with the Gaussian 09W
program package. Molecular stacking stimulation was
Scheme 2. Synthesis routes of PC2VA and PC3VA.
performed with a MMFF94 force field in Chem3D.
2.2 Gelation Ability and Gel-to-sol Transition Temperature
9-Methylacridine
mmol), glacial acetic acid (11.0 ml), and anhydrous zinc
chloride (40.0 g, 215.6 mmol) was stirred and heated to 180
for 1.5 h. Then excess glacial acetic acid was removed by
distillation and the residue was further heated at 220 C for
(1). A mixture of diphenylamine (10.0 g, 59.2
Investigation. The solution containing 5.0 mg gelator in
selected organic solvent (1.0 mL) was heated in a sealed bottle
with 1 cm diameter by a heating panel until the solid was
dissolved. After the solution was cooled to room temperature
and placed for 6 h, the gel state was evaluated by the “stable
to inversion of a test tube” method. Gel-to-sol phase transition
temperatures were measured in oil bath. The bottle with a gel
firstly was put at room temperature for 6 h, and then was
inverted and immersed in an oil bath. The oil bath was heated
at rate of 0.5 °C/min. Corresponding temperature was set as
Tgel when the gel started to flow.
ºC
º
additional 6 h. The reaction mixture was digested with hot 10%
aqueous sulphuric acid and then alkalified with concentrated
aqueous ammonia to dissolve the zinc chloride. The resulted
yellow precipitates were generated. The residue was extracted
by toluene and organic layer was washed with aqueous
NaHCO3 and dried over anhydrous Na2SO4. The organic solvent
was then removed under reduced pressure to give crude
product, which was further purified by column
chromatography (petroleum ether/ethyl acetate = 5/1, v/v).
Preparation and measurement of sensing film. PC2VA or
PC3VA (1.0 mg) was dissolved in chlorobenzene (CB) (2.0 mL)
under heating to form clear solution, and then hot solution of
7.0 μl was casted on the glass slide (1.3×2.5 cm). The sample
was aged at room temperature until a gel film was formed.
After 2 h, the solvent was removed in a vacuum oven. The
glass slide was placed in a cell (optical path = 1 cm) and the cell
was sealed by sealing film. The gaseous amines or acids at
different concentrations were obtained by a simply method of
dilution. In detail, saturated vapor with certain volume (such
as 1.0 μl) was injected into a quartz cuvette (volume = 3.4 mL),
and then a gaseous concentration could be determined by an
Yield: 73%. Melting point (m.p.): 117−118 ºC. Elemental anal.
calcd. for C14H11N: C, 87.01; H, 5.74; N, 7.25; found: C, 87.07; H,
5.70; N, 7.28. 1H NMR (400 MHz, CDCl3) δ 8.24 (dd, J = 8.3, 4.6
Hz, 4H), 7.77 (dd, J = 8.2, 7.1 Hz, 2H), 7.55 (dd, J = 8.3, 7.0 Hz,
2H), 3.11 (s, 3H).
9-Acridinaldehyde (2). The mixture of selenium dioxide (1.0 g,
8.8 mmol) and 9-methylacridine (1.6 g 8.7 mmol) in 1,4-
dioxane (20 mL) was refluxed for 2.5 h. Then, the solid was
filtered and the solvent was removed under reduced pressure.
The crude product was purified by column chromatography
(silica gel, petroleum ether/ethyl acetate =3/2). Yield: 68%.
equation: C (ppm) = (106
×VS×Ps)/(VC×P), where Vs and Vc are
amines or acids vapor volume and cuvette volume, respectively,
and Ps and P are saturated vapour pressure of amines or acids
and atmospheric pressure. Then, the fluorescence of xerogel
film was measured after 5 min.
Melting point (m.p.): 146-147 ºC. Elemental anal. calcd. for
C14H9NO: C, 81.14; H, 4.38; N, 6.76; found: C, 81.19; H, 4.34; N,
6.73. 1H NMR (400 MHz, DMSO-d6) δ 11.51 (s, 1H), 8.85 (d, J =
8.9 Hz, 2H), 8.28 (d, J = 8.7 Hz, 2H), 7.95 (ddd, J = 8.7, 6.6, 1.3
Hz, 2H), 7.81 (ddd, J = 8.8, 6.6, 1.3 Hz, 2H).
Synthesis and Characteristics. Diphenylamine (Meryer, 98%),
EDC∙HCl (Energy Chemical, 99%), Pd/C (Energy Chemical, 10%),
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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DOI: 10.1039/C7TC03192K
ARTICLE
Journal Name
(Z)-3-(acridin-9-yl)-2-(4-nitrophenyl)acrylonitrile
nitrophenyl)acetonitrile (0.47 g, 2.9 mmol) and 9- yellow solid was obtained by suction filtration and washed
acridinaldehyde (0.6 g, 2.9 mmol) were dissolved in ethanol with CH2Cl2 and THF. Yield: 82 %. Melting point (m.p.): 230 C.
(3). 2-(4- 24h at room temperature and poured into water (200 ml). The
º
(25 mL). The mixture was heated to reflux for 1 h. After a few Elemental anal. calcd. for C48H55N5O3: C, 76.87; H, 7.39; N, 9.34;
drops of piperidine were added, the mixture was further found: C, 76.89; H, 7.32; N, 9.31. 1H NMR (400 MHz, DMSO-d6)
refluxed 12h. A yellow solid was obtained after filtration and δ 10.21 (s, 1H), 8.90 (s, 1H), 8.26 (d, J = 8.7 Hz, 2H), 8.16 (d, J =
thorough washing with ethanol (3×10 mL). After drying under 8.6 Hz, 2H), 8.10 (d, J = 8.3 Hz, 1H), 7.94 (t, J = 9.6 Hz, 5H), 7.84
vacuum, a yellow product (0.94g) was obtained in a 93 % yield. (d, J = 8.4 Hz, 2H), 7.79 – 7.62 (m, 2H), 7.36 – 7.07 (m, 5H), 4.48
Melting point (m.p.): 294-296 ºC. Elemental anal. calcd. for (q, J = 8.4 Hz, 1H), 3.01 (m, 3H), 2.85 – 2.66 (m, 1H), 2.29 (t, J =
C22H13N3O2: C, 75.20; H, 3.73; N, 11.96; found: C, 75.25; H, 7.0 Hz, 2H), 2.15 (m, 2H), 1.85 – 1.63 (m, 2H), 1.22 (s, 20H),
3.70; N, 11.93. 1H NMR (400 MHz, DMSO-d6) δ 9.31 (s, 1H), 0.82 (d, J = 6.7 Hz, 3H). 13C NMR (151 MHz, DMSO-d6) δ 171.95,
8.47 (d, J = 8.9 Hz, 2H), 8.37 – 8.24 (m, 4H), 8.21 (d, J = 8.6 Hz, 171.82, 171.42, 148.53, 141.68, 139.85, 138.49, 137.05, 131.15,
2H), 7.95 (ddd, J = 8.4, 6.6, 1.0 Hz, 2H), 7.77 – 7.67 (m, 2H).
(Z)-3-(acridin-9-yl)-2-(4-aminophenyl)acrylonitrile ).
mixture of
130.14, 129.58, 128.43, 127.46, 127.29, 127.00, 126.61, 126.18,
123.84, 121.21, 119.72, 116.58, 54.45, 38.95, 38.44, 36.23,
(
4
A
3
(0.8 g, 2.3 mmol), Pd/C (0.07 g) and N2H4•H2O 34.88, 31.76, 29.48, 29.20, 26.76, 22.55, 21.58, 14.41. MS: m/z
(0.92 g, 18.3 mmol) in ethanol (35 mL) was stirred and refluxed calcd: 735.4; found: 737.9 [M+H]+.
under an inert atmosphere for 12 h. A brownish yellow solid
was obtained after filtration and thorough washing with
ethanol (3×10 mL). The crude product was dissolved in
Acknowledgements
dichloromethane (50 mL) and insoluble Pd/C was removed by
filtration. After removing the solvent under reduced pressure,
the residue was recrystallized in the mixture of EtOH and THF
to afford 0.51 g orange-yellow solid (63%). Melting point
This work was financially supported by the National Natural
Science Foundation of China (21103067 and 21374041), the
Youth Science Foundation of Jilin Province (20130522134JH),
the Open Project of the State Key Laboratory of
Supramolecular Structure and Materials (SKLSSM2015014),
and the Open Project of State Laboratory of Theoretical and
Computational Chemistry (K2013-02).
(m.p.): 227-279 ºC. Elemental anal. calcd. for C22H15N3: C, 82.22;
1
H, 4.70; N, 13.08; found: C, 82.26; H, 4.74; N, 13.01. H NMR
(400 MHz, DMSO-d6) δ 8.58 (s, 1H), 8.23 (d, J = 8.7 Hz, 2H),
8.14 (d, J = 8.7 Hz, 2H), 7.99 – 7.84 (m, 2H), 7.74 – 7.60 (m, 4H),
6.74 (d, J = 8.5 Hz, 2H), 5.81 (s, 2H).
(S,Z)-N1-(4-(2-(acridin-9-yl)-2-cyanovinyl)phenyl)-N4-(1-
(dodecylamino)-1-oxo-3-phenylpropan-2-yl)succinamide
Notes and references
(PC2VA).
4 (0.13 g, 0.40 mmol), 5a (0.18 g, 0.41 mmol) and 4-
1
2
3
4
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DMSO-d6) δ 10.32 (s, 1H), 8.91 (s, 1H), 8.26 (d, J = 8.5 Hz, 3H),
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MS: m/z calcd: 735.4; found: 737.9 [M+H]+.
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8 | J. Name., 2012, 00, 1-3
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ARTICLE
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Journal of Materials Chemistry C
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DOI: 10.1039/C7TC03192K
Graphic abstract
An AIE gelator was used as sensor to quantitatively detect both volatile acid and aromatic amine
vapors.