Research Article

www.acsami.org

Functionality-Oriented Derivatization of Naphthalene Diimide: A

Molecular Gel Strategy-Based Fluorescent Film for Aniline Vapor
Detection
Jiayun Fan, Xingmao Chang, Meixia He, Congdi Shang, Gang Wang, Shiwei Yin, Haonan Peng,*
and Yu Fang*
Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering,
Shaanxi Normal University, Xi’an 710062, People’s Republic of China
*
S Supporting Information
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ABSTRACT: Modification of naphthalene diimide (NDI)

resulted in a photochemically stable, fluorescent 3,4,5-tris-
(dodecyloxy)benzamide derivative of NDI (TDBNDI), and
introduction of the long alkyl chains endowed the compound
with good compatibility with commonly found organic
solvents and in particular superior self-assembly in the solution
state. Further studies revealed that TDBNDI forms gels with
nine of the 18 solvents tested at a concentration of 2.0% (w/
v), and the critical gelation concentrations of five of the eight
gels are lower than 1.0% (w/v), indicating the high efficiency
of the compound as a low-molecular mass gelator (LMMG).
Transmission electron microscopy, scanning electron micros-
copy, and confocal laser scanning microscopy studies revealed the networked fibrillar structure of the TDBNDI/
methylcyclohexane (MCH) gel. On the basis of these findings, a fluorescent film was developed via simple spin-coating of
the TDBNDI/MCH gel on a glass substrate surface. Fluorescence behavior and sensing performance studies demonstrated that
this film is photochemically stable, and sensitive and selective to the presence of aniline vapor. Notably, the response is
instantaneous, and the sensing process is fully and quickly reversible. This case study demonstrates that derivatization of
photochemically stable fluorophores into LMMGs is a good strategy for developing high-performance fluorescent sensing films.
KEYWORDS: naphthalene diimide, aniline, molecular gels, fluorescent film, sensor

1. INTRODUCTION response speed and sensing reversibility.18−21 This explains

Today, functionality-oriented design and synthesis of low-
molecular mass compound-based molecular gels stimulate
scientific activities of chemistry and physics laboratories
worldwide.1−4 Within molecular gels, the low-molecular mass
gelators (LMMGs) self-assemble into three-dimensional (3D)
networked structures with different morphologies through
noncovalent intermolecular interactions such as hydrogen
bonding, π−π stacking, van der Waals, electrostatic, coordina-
tion, charge-transfer, and additional interactions.5,6 These
special morphologies and interactions make molecular gels
applicable in a wide range of areas.7−13 For instance, gels with
cross-linked nanoring structures exhibit breaking-repair ability
as new kinds of self-healing materials.14 Furthermore, porous
materials, such as xerogels and aerogels, could be produced via
utilization of molecular gels and their relevant gel emulsions.15
These materials show fascinating absorbing properties when
they absorb to a variety of organic liquids or vapors.16,17
Undoubtedly, functionalization of the porous materials would
be a good strategy for developing promising sensing materials
because the skeletons could provide rich molecular channels
and more contact sites for target molecules, facilitating
why molecular gels have been employed for the development of
fluorescent films used for the sensing of humidity, explosives,
organic amines, etc.22−26
Among the gaseous pollutants, organic amines are by-
products of cell growth and decomposition products generated
by biological corruption.27 Meanwhile, as a kind of important
chemical raw material, organic amines have also been widely
used in various areas such as the chemical industry, cosmetic
products, food additives, etc.28−32 This means that organic
amines could diffuse into air from garbage incineration,
wastewater, construction materials, automobile exhaust, factory
emissions, etc.33−35 The excess of organic amines in air would
seriously damage the ecological environment and pose severe
threats to human health.36 In fact, some of the organic amines
are usually considered as air quality indicators and also used as
biomarkers for certain types of diseases such as uremia,
hepatopathy, and lung cancer.37−40 Therefore, developing
Received: April 25, 2016
Accepted: June 27, 2016
Published: June 27, 2016

© 2016 American Chemical Society 18584 DOI: 10.1021/acsami.6b04915

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Scheme 1. Synthesis of TDBNDI and Its Intermediates a−f
effective methods for the detection of organic amines is
significantly important.41,42 Recently, Zang and co-workers
reported that well-defined nanofibers based on a perylene
bisimide derivative showed high sensitivity to organic amines.43
Liu and co-workers presented a perylene−cyclodextrin
conjugate that exhibited a pronounced improvement in both
selectivity and reversibility for detecting aniline.44 Recently, Lu
et al. developed an L-phenylalanine derivative (C12PhBPCP)
containing a cyano group and a strong emission fluorophore of
benzoxazole and realized quantitative detection of volatile acid
and organic amine in the vapor phase with a fast response and a
low detection limit.45 With the exception of fluorescence
techniques, other techniques were also used for the detection of
aromatic amines. As an example, recently, Shiratori and co-
workers developed a kind of carbon nanocage-embedded
nanofibrous film, which shows enormous adsorption to aniline
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and other aromatic amines.40 Utilizing a quartz crystal
microbalance, even parts per million (ppm) levels of aniline
could be repetitively detected. However, considering the
photochemical stability, reversibility, selectivity, sensitivity,
and other measures of performance of the methods reported
until now, developing more pronounced methods for the
detection of the volatile organic amines remains a challenge.
To develop a superior and photochemically stable fluorescent
sensing film of organic amines, naphthalene diimide (NDI) was
chosen as a core structure because of its better solubility, ease
of modification, and ideal photochemical stability.46−49 For this
purpose, the HOMO and LUMO energy levels of the structure
must be adjusted to adapt the sensing requirement of organic
amines, such as aniline. In addition, the aforementioned
molecular gel strategy would be a preferential method for
fabricating the film as it could provide greater porosity, which is
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Figure 1. (a) UV−vis absorption spectra of TDBNDI in different solvents at a concentration of 5.0 × 10−6 mol/L at room temperature. (b)
Fluorescence emission spectra of TDBNDI recorded in different solvents at a concentration of 1 × 10−6 mol/L at room temperature (λex = 348 nm).
The inset shows the normalized fluorescence emission spectra.
favorable for sensing. Accordingly, the degree of conjugation of
NDI was intentionally extended via introduction of two
phenylacetylene structures at its two bay positions. Moreover,
two iso-octyl structures and two tris(dodecyloxy)-benzamide
residues were also chemically linked at the proper positions of
the extended conjugate because of their good compatibility
with common organic solvents.50 In this way, a new NDI
derivative, TDBNDI, was designed and synthesized (cf. Scheme
1). It is believed that the compound as designed would be a
good candidate for sensing fluorophores of organic amines and
may possess the ability to form a variety of molecular gels,
laying the foundation for fabricating porous fluorescent films
with superior sensing properties. This paper reports the details.
2. EXPERIMENTAL SECTION
2.1. Materials and Reagents. 1,4,5,8-Naphthalenetetracarboxylic
dianhydride (Ourchem, 98%), dibromoiso-cyanuric acid (Energy
Chemical, 97%), methyl gallate (J&K, 99%), bromodecane (Aladdin,
98%), 2-ethylhexylamine (TCI, 98%), N-(3-dimethylaminopropyl)-N-
ethylcarbodiimide hydrochloride (J&K, 99%), Pd(PPh3)4 (Alfa Aesar,
99%), and CuI (Alfa Aesar, 98%) were used as received. Diisopropyl-
amine and dimethylformamide were distilled from calcium hydride
under argon prior to use. Toluene was distilled from sodium
benzophenone ketyl under argon prior to use. All other reagents
were of analytical grade and used without further purification. Water
used in this work was acquired from a Milli-Q reference system except
where specified otherwise.
2.2. Measurements and Characterization. 1H nuclear magnetic
resonance (NMR) spectra were acquired on a Bruker AV 600 NMR
spectrometer at room temperature. Pressed KBr disks for the powder
samples were used for the transmission infrared spectroscopy
measurements, and the measurements were conducted on a Bruker
VERTEX 70v spectrometer. The MS spectra were recorded on a
Bruker maxis UHR-TOF mass spectrometer in ESI positive mode.
Elemental analysis of C, H, and N was performed after combustion at
950−1200 °C using IR detection and gravimetric analysis by means of
a Vario EL III device. Melting point measurements were taken on an
X-5 microscopic melting point meter (Beijing Tech Instrument).
Scanning electron microscopy (SEM) images of the films were
acquired on a Quanta 200 scanning electron microscope (Philips-FEI).
Transmission electron microscopy (TEM) images were obtained using
a JEOL JEM-2100 transmission electron microscope at an acceleration
voltage of 200 kV. Optical and fluorescence microscopic observations
were made on a Nikon ECLIPSE Ti-U instrument. Fluorescence
measurements were performed at room temperature on a time-
correlated single-photon counting Edinburgh Instruments FLS 920
fluorescence spectrometer.
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2.3. Synthesis of TDBNDI. The synthesis of TDBNDI is shown in
Scheme 1. The details of the synthesis and the data from the
characterizations are provided in the Supporting Information.
3. RESULTS AND DISCUSSION
3.1. Solution Behavior of TDBNDI. 3.1.1. UV−Vis
Absorptions of TDBNDI in Different Solvents. UV−vis
absorption is a simple but powerful technique for interrogating
the solution behavior of a fluorophore in the solution state.
Accordingly, the solution behavior of the as-prepared
compound, TDBNDI, in different solvents with varying
polarities was systematically studied at a concentration of 5.0
× 10−6 mol/L, and the results are shown in Figure 1a.
Examining the figure reveals that the five solvents tested can be
divided into two groups, of which the first includes toluene,
chloroform, and tetrahydrofuran (THF) and the second n-
hexane and methylcyclohexane (MCH). Clearly, in the first
group of the solvents, the compound shows two sets of sharper
absorption bands, which are located around 340 and 528 nm. In
contrast, in the second systems, the two sets of absorptions
appear to be the same, but the intensities decreased, which were
accompanied by broadening of the absorptions, in particular the
one appearing at longer wavelengths. Theoretical calculations
revealed that the absorptions located around 528 and 340 nm
originate from the transition from S0 to S1 and that from to S0
to S6, respectively [cf. energy level structure of TDBNDI
(Figure S1)]. The weakening and broadening of the
absorptions in the second group of the solvents might be a
result of aggregation of TDBNDI possibly due to intermo-
lecular π−π stacking and hydrogen bond formation. Compared
with n-hexane and MCH, toluene is an aromatic solvent, and
THF and chloroform are polar solvents, which are both
unfavorable for the aggregation of the molecules of the
compound due to screening of the π−π stacking or hydrogen
bond formation, resulting in the greater solubility of
TDBNDI.51 With further interrogation of the absorption
band appearing at longer wavelengths, it can also be observed
that the absorptions of the compound in the two “poor”
solvents are not only broadened, but also red-shifted, which is
further confirmed by temperature-dependent absorption spec-
troscopy studies of the MCH solution of TDBNDI (cf. Figure
2), suggesting J-aggregation of the compound.52,53
3.1.2. Fluorescence of TDBNDI in Different Solvents. Via
inspection of the structure of TDBNDI (Scheme 1), we
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Figure 2. UV−vis absorption spectra of TDBNDI in MCH at a

concentration of 5.0 × 10−6 mol/L at various temperatures. Figure 3. Fluorescence emission spectra of TDBNDI in MCH at
various concentrations at room temperature.

anticipate that the compound could be a solvatochromic concentration. Moreover, the emission is increasing with a
fluorophore as it consists of both a donor unit(s), the two further increase in the concentration of the compound, and
aromatic amido-benzylethenyl structures, and an acceptor unit, ultimately, it dominates the whole emission as shown in the
the NDI residue. In other words, the fluorescence emission of inset of the figure, suggesting full aggregation of the compound.
the compound should be sensitive to solvent polarity. As for the systems with very low TDBNDI concentrations, their
Accordingly, the fluorescence emissions of the TDBNDI emissions are composed of the first two emissions appearing at
solutions employed for UV−vis absorption measurements shorter wavelengths, of which one belongs to the LE state and
were also measured at a concentration of 1.0 × 10−6 mol/L the other to the ICT state as discussed earlier, a typical
at room temperature with 348 nm as the excitation wavelength, behavior of solvatochromic probes. The diversity of the
and the results are shown in Figure 1b. As expected, both the fluorescence emission of the compound observed in MCH at
emission positions and the emission profiles of the compound different concentrations may explain why the fluorescence
are highly dependent on the nature of the solvent. With the emission of TDBNDI varies from one solvent to another at the
exception of n-hexane, the positions of the main emissions of concentration studied.
the compound in other solvents shift to longer wavelengths 3.1.3. Photophysical Parameters of TDBNDI. To under-
along with an increase in solvent polarity (cf. inset of Figure stand the optical properties of the as-prepared compound more
1b), specifically in the following order: MCH < toluene < thoroughly, the absorption wavelength, the molar absorption
chloroform < THF. As for the solvent n-hexane, it is coefficient, the maximal emission wavelength, and the
exceptional possibly because of the poor dissolving ability of fluorescence quantum yield were measured, and the results
the compound in it, which must promote aggregation of are presented in Table 1. The high molar absorption
TDBNDI. It is the aggregate as formed that produces the broad coefficients in the tested solvents demonstrate the large
and strong long wavelength emission around 665 nm, in absorption cross section of the compound as prepared. While
support of the conjecture of J-aggregate formation as the fluorescence quantum yield of TDBNDI varies from solvent
mentioned above. to solvent, and specifically from <10% to nearly 40%, this
Further inspection of the emissions shown in the figure indicates that the compound is not an overly poor fluorophore,
reveals that the most typical one is from the system with MCH
as the solvent as it is more complicated and contains three Table 1. Photophysical Parameters of TDBNDI Measured in
parts, appearing around 530, 590, and 670 nm. Considering the Different Solventsa
possible solvatochromic and aggregation properties of the
compound, it is reasonable to deduce that the first two of the λabsb (nm) εc (×104 M−1 cm−1) λemd (nm) ΦF (%)e
three emissions should originate from two different excited n-hexane 320, 342, 548 6.74, 6.58, 2.09 665 6
states of TDBNDI, which are the S1 or the local excited (LE) MCH 341, 527 7.03, 2.27 541 38
state and the solvent-relaxed state or the intramolecular charge- toluene 340, 496, 528 9.28, 4.11, 5.53 561 28
transfer (ICT) state of the compound. The third, however, THF 340, 525 8.49, 4.29 610 10
should be from the as-mentioned J-aggregate. For other chloroform 331, 527 8.44, 4.47 588 11
solvents, the observations are similar except for the absence
of one or two of the emissions.
a
Photophysical parameters recorded at a concentration of 1.0 × 10−5
To further confirm the understanding described above, mol/L with the exception of fluorescence quantum yield. bWave-
lengths of maximal absorbance of the relevant absorbance bands.
concentration-dependent fluorescence measurements were c
Molar extinction coefficient. dMaximum emission wavelength.
further conducted with MCH as the solvent, and the results e
Fluorescence quantum yields measured at a concentration of 1.0 ×
are shown in Figure 3. As expected, the profile of the emission 10−6 mol/L. It should be noted that the fluorescence quantum yields
is highly dependent on concentration. The compound starts to reported here were obtained by conducting the determination on an
aggregate at concentrations lower than 5.0 × 10−7 mol/L as the Edinburgh Instruments FLS-920 time-resolved fluorescence spectrom-
aggregate’s emission (∼650 nm) is becoming obvious at this eter through the use of the integrating sphere.

18587 DOI: 10.1021/acsami.6b04915

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Figure 4. Concentration-dependent 1H NMR spectra of TDBNDI in toluene-d8.
in particular when the fact that it emits brightly in the
aggregated state is considered. As for why the fluorophore
displays different fluorescence quantum yields in different
solvents, this may be a result of aggregation of the compound
and specific interaction of it with the solvents. As it is known,
aggregation of a fluorophore in solution could result in an inner
filtering effect due to the heterogeneous distribution of the
compound, which must diminish the fluorescence quantum
yield of the fluorophore in the system.54 For example, toluene is
an aromatic solvent, and it could screen the aggregation of the
compound via weakening the π−π interaction among the
molecules of the compound, resulting in a fluorescence
quantum yield significantly higher than that in n-hexane (cf.
Table 1).
3.2. Gelation Behavior of TDBNDI. 3.2.1. Gelation Test.
To employ the as-mentioned molecular gel strategy for the
fabrication of fluorescent films, the gelation behavior of
TDBNDI must be investigated in advance. To this end, a
known weight (10 mg) of the as-synthesized TDBNDI and a
measured volume (500 μL) of a given liquid were put in a
sealed vial. The vial was heated until the solid was dissolved
completely and then cooled slowly to room temperature. If a
gel is formed, the system is denoted as “G”, and if only part of
the solution forms a gel, it is denoted as “PG”. The systems of
solutions and those with insoluble solids are labeled “S” and
“IS”, respectively. The results from the tests along with relevant
critical gelation concentrations (CGCs) are listed in Table S1.
The data in the table demonstrate that TDBNDI exhibits
significant gelation behavior in nine of the 18 solvents tested;
the solvents vary from alkanes to aromatics as well as ethyl
acetate. The CGCs of five of the gels as obtained are <1.0% (w/
v), indicating efficient gelation ability of the compound. For
three other gel systems, the CGCs are all around 1.5% (w/v).
Considering the poor solubility of NDI, it is safe to say that
modification of the extended NDI conjugate with multiple alkyl
chains does enhance the solubility, in particular the gelation
ability of the compound, which lays the foundation for further
film fabrication.
3.2.2. Morphology Studies. As is well-known, molecular
functionality relies strongly on the microstructures of the
molecule’s aggregates. Therefore, it would be important to
explore the network structures of the molecular gels before they
are used for sensing film fabrication. Accordingly, SEM images
of the gels from different solvents and different concentrations
were recorded. As an example, Figure S2 shows the SEM
images of the xerogels from the TDBNDI/MCH system with
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the gelator concentration varying from 1.0 to 1.5%, and then
increasing to 2.0% (w/v). It is seen that the microstructures of
the gel networks change from short wormlike aggregates at
1.0% (w/v) to less organized assemblies at 1.5% (w/v) to well-
organized assemblies at 2.0% (w/v). It is the loosely packed
structure that must be beneficial for vapor sensing because of
the large surface area and molecular diffusion channels. In
contrast, the xerogels from the TDBNDI/toluene system are
characterized as densely packed ribbons and platelike structures
at gelator concentrations of 0.1 and 2.0% (w/v), respectively
(cf. Figure S3), which are not good for sensing.
To further examine the aggregation structure of TDBNDI
from the gels of MCH, TEM measurements were also
conducted, and the results are shown in Figure S4. We are
lucky to find that the morphologies of the TDBNDI aggregates
in the MCH gels are characterized by networked ultrathin fibers
with diameters of tens of nanometers. Furthermore, the
diameters of the fibers increase with an increase in the gelator
concentration, which provides an additional route for
controlling the networked structures of the gels.
3.2.3. 1H NMR and X-ray Diffraction (XRD) Measurements.
As anticipated from the structure of TDBNDI, the main driving
forces for the assembly of the compound should be hydrogen
bonding between the amide groups, the π−π stacking of the
extended NDI conjugate, and the van der Waals interaction of
the long alkyl chains. To verify what we have found,
concentration-dependent 1H NMR studies were conducted,
and some of the 1H NMR traces are presented in Figure 4. It
can be seen from the traces that the signal of the as-denoted
NDI proton appearing at 8.83 ppm shifted to a higher field with
an increase in the gelator concentration from 0.1 to 1.5% (w/
v), suggesting the presence of π−π stacking in the system. The
signal of the N−H proton shifted from 7.76 to 8.19 nm with
the increase in the gelator concentration, revealing the existence
of the anticipated hydrogen bond. These results confirm that
the aggregation of TDBNDI in the systems being studied is
driven by the expected intermolecular π−π stacking and
hydrogen bonding. This packing is further verified by XRD
analysis. As shown in Figure S5, the XRD trace of the xerogel
from the TDBNDI/MCH wet gel [2.0% (w/v)] is charac-
terized by three well-resolved reflection peaks, corresponding to
spacings (d) of 2.99, 1.54, and 1.17 nm. The ratios of the d
values are 1:1/2:1/3, suggesting a layered structure of the
aggregate with an interlayer distance of ∼3.0 nm, which is
appropriately half of the length of a molecule of TDBNDI.
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3.3. Fabrication of Fluorescent Films and Their
Sensing Applications. 3.3.1. Fabrication of Fluorescent
Films. Commercially available glass plates were chosen as
substrates (0.9 cm × 2.5 cm) for fluorescent film fabrication.
The substrates were first treated in a chromic acid solution for
more than 3 days and then washed thoroughly with deionized
water. The pretreated substrates were dried at 100 °C in a dust-
free oven for 5 h. Then, a certain volume (15 μL) of the MCH
solution of TDBNDI [0.1% (w/v)] was dropped onto the
substrate surface at ambient temperature under the MCH
atmosphere, which was achieved by placing MCH liquid around
the substrate within a capped container. A fluorescent film was
acquired after evaporation of the solvent.
3.3.2. Microstructures and Fluorescence Properties of the
Films. The microstructures of the films as fabricated with the
MCH solution of TDBNDI [0.1% (w/v)] were examined by
confocal laser scanning microscopy (CLSM), and a typical
example of the image is shown in the inset of Figure 5. The
Figure 5. Excitation and emission spectra of TDBNDI in MCH at a
concentration of 0.1% (w/v) and confocal laser scanning microscope
image of the aggregates of TDBNDI (inset).
image demonstrates the uniform and networked fibrillar
structures of the film. The average diameter of the fibers is
∼0.5 μm. Further inspection of the structures shows that the
fibers are also porous and consist of even fine intertwined
structures, a result that is consistent with that observed in the
Figure 6. Fluorescence response of a TDBNDI-functionalized film to the presence of different organic vapors at a concentration of 3060 mg/m3
(error of ±3%).
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TEM studies of the MCH gel of TDBNDI (cf. Figure S4).
Undoubtedly, the porous and large specific surface area
structures are ideal for sensing applications.
To explore the sensing performances of the films as
fabricated, their fluorescence properties were examined first.
Figure 5 shows the excitation and emission spectra of the films
in a dry state. It is observed that the profile of the excitation
spectrum of the film is almost the same as that of the
absorption spectrum of TDBNDI dissolved in a “poor” solvent
such as MCH (cf. Figure 1a or 2), suggesting that the
compound does exist in an aggregated state as revealed by
CLSM observations. The aggregation of TDBNDI within the
film is further reflected by the emission spectrum of the film,
which is characterized by an obvious, broad, structure-less
emission centered at 670 nm, confirming the π−π stacking of
the extended NDI conjugate of the compound as revealed by
1
H NMR studies. Photochemical stability tests demonstrated
that the film as fabricated is exceptionally stable upon
continuous UV light illumination [348 nm (cf. Figure S6)].
3.3.3. Aniline Sensing of the Films. Theoretical calculation
of the energy level structures of TDBNDI and aniline
demonstrates that the HOMO energy of the latter is reasonably
higher than that of TDBNDI, implying that the hole of
TDBNDI after excitation could be filled by an electron from
the HOMO orbital of aniline, the so-called photoinduced
electron transfer, resulting in fluorescence quenching (cf. Figure
S7). Considering the importance of aniline monitoring for air
quality control, the sensing performance of the film with
respect to aniline vapor was studied.
The test was conducted as follows. First, the film was placed
into a cell, and fluorescence emission was recorded. Then the
cell was put into a chamber with a specific concentration of
aniline vapor, and the fluorescence spectrum was recorded
again. The measurement was repeated at different aniline vapor
concentrations, and the results are shown in Figure S8. It is
found that the emission of the film decreases along with an
increase in aniline vapor concentration. Saturated aniline vapor
could result in an ∼92% reduction in the initial emission of the
film at room temperature (∼20 °C). The calculated detection
limit (DL) of the film to aniline vapor is ∼12.7 mg/m3, which is
below the acceptable minimal concentration of exposure.55
Selectivity is an important factor for a film to realize its
practical applications. Therefore, the properties of the as-
prepared film in other commonly found organic amines,
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including o-toluidine, diethylamine, isopropamide, dimethyl-
amine, methylamine, hydrazine hydrate, diethylenetriamine,
ammonium hydroxide, and triethylamine in the vapor phase,
and commonly found liquids, such as phenol, acetone,
dichloroethane, water, methanol, chloroform, THF, acetic
acid, p-xylene, toluene, and benzene in the vapor phase, were
also examined. The results are shown in Figure 6 as histograms,
in which 1 − I/I0 represented quenching efficiency, and the
data presented were obtained by keeping the concentrations of
the interference at 3060 mg/m3, which is the concentration of
saturated aniline vapor. Clearly, with the exception of aniline, o-
toluidine, another organic amine that is important for air quality
control and disease diagnosis,56 is also an efficient fluorescence
quencher of the film. In contrast, other liquid vapors as
examined have little effect on the fluorescence emission of the
film, implying that the film is quite specific to the presence of
aniline and its analogue, o-toluidine.
The response speed and reversibility are also crucial for real-
time detection. However, it could be affected by many factors
such as the morphology of the film, the temperature, and even
the operation of the instruments, in particular when the
response is fast. Therefore, we conduct the test on the platform
of a homemade device, which could record fluorescence
emission intensity at specific excitation and emission wave-
lengths in real time and in an online manner.57 To conduct the
test, the film was first placed in the sample chamber of the
device, and its fluorescence emission was continuously
monitored. Then, an aniline vapor-contaminated plastic lid
was put to the sampling nozzle of the system (∼1 cm away),
and <1 s later the lid was removed. This process was repeated
many times, and as examples, Figure 7 shows only eight
Figure 7. Instantaneous response of the TDBNDI-functionalized
fluorescent film to the presence of aniline. Note that the traces were
recorded from a continuous measurement with a homemade sensing
device as a test platform.
continuous results. It is clearly seen that the response is
instantaneous, and recovery of the test is also very fast. Actually,
it needs only a few seconds to complete a cycle of the test,
which is a result significantly superior to that previously
reported from similar solid-state fluorescence measure-
ments.58,59 However, via careful examination of the results
shown in the figure, it can also be seen that the response degree
for each test is not the same even though the same sample was
used. This variation may be understood by considering the fact
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that the distance between the lid and the nuzzle and the
sampling time for each test may not be strictly the same. To
further verify the reversibility, the test was again conducted on a
commercial machine, and the relevant results are shown in
Figure S9. Clearly, in this case, 10 tests resulted in little change
in the initial fluorescence intensity and the response degree of
the film, confirming the reliability of the results obtained from
our homemade device.
It is reported in the literature that aniline and o-toluidine are
closely related to certain diseases such as methemoglobinemia
(Met-Hb).60−62 In particular, O’Neil and colleagues identified
28 VOCs as causers of lung cancer; aniline and o-toluidine are
typical.63,64 Moreover, with industrialization of the world, the
use of petrochemicals has been increasing, and this increases
the risk of release of anilines and o-toluidine into the air;
therefore, monitoring aniline and o-toluidine online and in real
time is greatly important. Considering the superior sensing
performance of the as-created fluorescent film, there is no
doubt that developing the film into a sensory device is of
practical value. The relevant work is under progress.
4. CONCLUSIONS
In conclusion, a 3,4,5-tris(dodecyloxy)benzamide derivative of
naphthalene diimide (TDBNDI) was designed and synthesized.
The compound as prepared possesses superior optical and rich
gelling properties. Fluorescence studies revealed that the
compound could emit from two excited states in “good”
solvents, and an additional one in “poor” solvents due to
aggregate formation. For the later emission, the Stokes shift
could be as large as 320 nm. The gelation test demonstrated
that the compound is an ideal LMMG and forms gels with nine
of the 18 liquids tested, of which the CGCs of five of them are
<1.0% (w/v). In particular, the networked structures of some of
the gels are loosely packed nanofibers, which can be further
tuned by varying the gelator concentration, the nature of the
solvent, etc. 1H NMR and optical studies revealed that the
driving forces behind the aggregation of the compound are π−π
stacking, hydrogen bonding, van der Waals, and other
interactions. On the basis of our studies, a fluorescent film
was fabricated via utilization of a molecular gel strategy, of
which the MCH solution of TDBNDI was chosen as the
fabricating system. The film as fabricated shows a strong, broad,
and structure-less emission around 670 nm, which is a typical
emission from TDBNDI aggregates. Sensing performance
studies revealed that (1) the emission of the film is sensitive
to the presence of aniline or o-toluidine, with a calculated DL
for the former of <13 mg/m3, (2) the sensing is fast with a
response time of <1 s, (3) the response is fully reversible and
the recovery instantaneous, and (4) interference from other
commonly found amines and liquids is negligible. Because of
these findings, we firmly believe that films as created possess
great potential to be developed into applicable sensors.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b04915.
Detail experimental methods, determination limit, and
supplementary figures and schemes (PDF)
DOI: 10.1021/acsami.6b04915
ACS Appl. Mater. Interfaces 2016, 8, 18584−18592
ACS Applied Materials & Interfaces
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: yfang@snnu.edu.cn. Telephone: +86 29 81530786.
*E-mail: phn@snnu.edu.cn. Telephone: +86 29 81530717.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21273141 and 21527802), the 111
project (B14041), and the Program for Changjiang Scholars
and Innovative Research Team in University (IRT-14R33).
The authors acknowledge Dr. Kaiqiang Liu, Dr. Rong Miao,
and Ms. Weina Wang for their help in the performance of the
TEM and CLSM measurements, as well as in the conduct of
the theoretical calculations.
■
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18592 DOI: 10.1021/acsami.6b04915

ACS Appl. Mater. Interfaces 2016, 8, 18584−18592