Dyes and Pigments 205 (2022) 110561

Contents lists available at ScienceDirect

Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Fabricating a hydroxynaphthalene benzophenone Schiff base into a

wearable fluorescent sensor for point-of-care sensing of volatile
organic compounds
Mengyao Zhang, Li Gao, Xinyi Zhao, Yuai Duan, Yi Liao, Tianyu Han *
Department of Chemistry, Capital Normal University, Beijing, 100048, China

A R T I C L E I N F O A B S T R A C T

Keywords: We herein present a donor-acceptor (D-A) luminogen, (E)-(3- (((2-hydroxynaphthalen-1-yl)methylene)amino)

Donor-acceptor phenyl)(phenyl)methanone (HNPMO), with both intramolecular charge transfer and aggregation-induced
Aggregation-induced emission emission (ICT + AIE) properties. It was developed into a film sensor by drop-casting, exhibiting sharp in­
Wearable sensor
crease in emission when exposing to various volatile organic compounds (VOCs), such as benzene series (e.g.,
Volatile organic compounds
toluene), common organic solvents (e.g., ethyl acetate) and alcohols (e.g., methanol), etc. Spectral analysis and
quantum chemical calculations confirmed that the turn-on response can be ascribed to the transition from the
disordered molecular arrangement to the optimized conformation driven by VOCs in the gas phase, with some
major influence factors including volatility, molecular size, structural compatibility and steric hindrance. In
addition, the fluorescent response is quantified by well-established image technology, using RGB and Lab color
space. In the sensitivity test, Lab color shift (ΔELab) was used to estimate the limit of detection (LOD) of the
HNPMO film sensor, which gives a linear relation with VOC concentration. The resulting LOD value is as low as
7.04 mg/m3 (1.8 ppm), suggesting high sensitivity intrinsic to such turn-on type sensor. We further fabricate a
wearable sensor device based on HNPMO film, employing a reference substance which is inert to VOCs. Thus the
presence of VOCs can be confirmed by the Lab color shift between HNPMO and the inert reference. By cutting
and shaping, the film sensor applies to gloves, labor suits and even nails. It is capable of point-of-care detection of
VOCs, providing an early warning of air contamination in various scenarios.

1. Introduction environments can be regarded as indicators for food quality [8,9],

pathological changes of tissues [10,11], and even insect infestation [12].
The term “volatile organic compounds” (VOCs) typically refers to As listed in Table S1, a great number of VOC sensors and related tech­
organic compounds with boiling points below 250 ◦ C at atmospheric niques have emerged in recent years, which function based on different
pressure (101.325 kPa) [1]. According to the U.S. Environmental Pro­ working mechanisms, respectively. Some gravimetric sensors and elec­
tection Agency, VOCs are defined as “any compound of carbon other trochemical sensors, by virtue of the high sensitivity intrinsic to their
than carbon dioxide, carbon monoxide, metallic carbides, carbonic acid, output signal, could enable much lower limit of detection (LOD) down to
carbonates or ammonium carbonate” with boiling points ranged from ppb level [13,14]. In particular, based on specific host-gest interactions
50 ◦ C to 260 ◦ C (atmospheric pressure, 101.325 kPa) [2]. The most or chemical reactions, some VOC sensors have succeeded in
common VOCs include alkanes, ketones, esters, alcohols, and benzene single-selectivity or species-selectivity, showing a significant advantage
series [3,4]. They are pervasive in both natural and human environ­ in identification and differentiation [15,16].
ments. Most of the VOCs are toxic in some degree, posing health risks to In addition to the effort in improving the sensitivity and selectivity,
every living thing including human beings [5]. It is thus necessary to scientists in this domain have been recently focusing on wearable
sense and monitor VOC level in some cases, such as air quality moni­ application, and this is because of the increasingly high demand for
toring, exhaled breath test and industrial production process, etc. [6,7]. portable test and scenario-based measurements with real-time feedbacks
In addition, the presence of some specific VOCs in particular [17,18]. In this case, sensors have to be built in miniaturized devices,

* Corresponding author.
E-mail address: hanty@cnu.edu.cn (T. Han).

https://doi.org/10.1016/j.dyepig.2022.110561
Received 18 March 2022; Received in revised form 29 June 2022; Accepted 4 July 2022
Available online 9 July 2022
0143-7208/© 2022 Elsevier Ltd. All rights reserved.
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

Scheme 1. Synthetic route to HNPMO.

capable of generating transient output signals in response to VOCs [19]. performed by Hanon MP-420 digital melting point apparatus. UV–vis
Gravimetry sensing and electricity-based detection, however, would absorption spectra were measured by SHIMADZU-UV-2550 spectro­
possibly pale in wearable application due to the dependence of artificial photometer. Emission spectra were measured by HITACHI F-7000
power source as well as the necessity of signal translation module [20, fluorescence spectrophotometer (solid support was equipped in the
21]. In contrast, fluorescent probes with visualized output signals, offer event of film samples). QY were calculated by a calibrated integrating
the potential to be fabricated into wireless, battery-free built-in sensors, sphere. The average thickness of the HNPMO film was measured by a
which paves the way for device-miniaturization and point-of-care Smart-Sensor Coating thickness gauge. The morphology of the film was
detection in wearable applications [22,23]. observed by a Hitachi-SU-8010 scanning electron microscope (SEM).
In general, a fluorescent VOC sensor contains two major units, an Photographs in the color-quantification experiments and wearable ap­
active luminogen and a solid substrate, the former is intentionally plications were taken by a Nikon-D90 digital single lens reflex (DSLR)
functionalized to interact with the VOCs, generating fluorescent changes camera. Electronic density distributions of HOMO and LUMO were
as the output signal; while the latter optimizes the aggregation structure calculated by DFT in Guassian-09 Program, using B3LYP/6-31+G* basis
of the luminogen and facilitates the physical contact between the set.
luminogen and the VOCs [24,25]. From the perspective of emission ef­
ficiency in solid state, luminogens with aggregation-induced emission 2.2. Synthesis and structural analysis
(AIE) property would be suitable candidates, as their twisted molecular
configuration would avoid π-π stacking to allow high quantum efficiency The synthesis of the present compound HNPMO is shown in Scheme
when aggregating [26,27]. Furthermore, the aggregation state of the 1, with detailed procedures as follows. To a round-bottom flask was
AIE luminogens could be sensitive to VOCs, as the VOCs would diffuse added 3-aminobenzophenone (5.07 mmol, 1.00 g) and 5 mL DMF. The
into the molecular packing to influence the intramolecular motion, mixture was stirred until fully dissolved, followed by addition of 2-hy­
thereby leading to notable changes in emission [27]. In addition, droxy-1-naphthaldehyde (5.07 mmol, 0.8730 g) which was dissolved
attaching electron-donating\withdrawing groups into AIE cores would in 90 ml anhydrous ethanol. After dropwise addition of 20 μL acetic acid,
red-shift the emission wavelength by virtue of the transition from the mixture was heated to 60 ◦ C, under magnetic stirring. After 6 h, the
locally-excited (LE) state to intramolecular charge transfer (ICT) state mixture was cooled down to room temperature and stirred overnight,
[28,29]. And the resulting luminogens tend to be susceptible to chemical accompanied by the formation of yellow-brown precipitates. After
environment on account of the conformation-sensitivity intrinsic to ICT vacuum filtration, the resulting product was rinsed by ethanol and then
state [30,31]. Specifically, when the luminogen is surrounded by VOCs, dried in a blast air oven. Yield: 59% (1.05 g). Melting point of HNPMO:
the molecular conformation is readily optimized by the polarity effect, 139.8–141.7 ◦ C (at standard atmospheric pressure). The chemical
leading to a lower energy level in the photo-excited state [32,33]. structure was confirmed by 1H NMR (Figs. S1–S2), 13C NMR
Therefore, the ICT emission would be tuned into a different state (e.g., (Figs. S3–S4), HRMS (Fig. S5) and IR spectroscopy (Fig. S6). 1H NMR
on/off switching and color-shifting). Our previous works have (600 MHz, DMSO‑d6), δ (ppm): 9.72 (d, 1H, J = 4.2 Hz), 8.50 (d, 1H, J =
confirmed that the fusion of AIE and ICT allows the creation of active 8.4 Hz), 7.94 (d, 1H, J = 9.6 Hz), 7.92 (d, 1H, J = 7.8 Hz), 7.90 (s, 1H),
luminogens with multi-stimuli-responsive behaviors even including 7.82–7.79 (m, 3H), 7.70 (t, 1H, J1 = 7.8 Hz, J2 = 15.0 Hz), 7.66 (t, 1H,
vapochromism [34–36]. In this work, we adopt such design philosophy, J1 = 7.8 Hz, J2 = 15.6 Hz), 7.60–7.57 (m, 3H), 7.53 (t, 1H, J1 = 8.4 Hz,
and synthesized a donor-acceptor (D-A) AIE compound, J2 = 15.6 Hz), 7.35 (t, 1H, J1 = 7.8 Hz, J2 = 15.0 Hz), 7.03 (d, 1H, J =
(E)-(3-(((2-hydroxynaphthalen-1-yl)methylene)amino)phenyl)(phenyl) 9.0 Hz). 13C NMR (151 MHz, DMSO‑d6), δ (ppm): 195.74, 169.89,
methanone (HNPMO), which exhibits turn-on emission in response to 157.63, 145.28, 139.05, 137.37, 137.16, 133.49, 133.41, 130.23,
VOCs. Based on its high sensitivity, fast response as well as the 130.19, 129.42, 129.09, 128.53, 127.85, 127.25, 124.98, 124.03,
compatibility with miniaturized solid substrates, it was further devel­ 122.10, 121.89, 121.00, 109.25. HRMS of HMPMO: m/z 352.1484 [(M
oped into a wearable VOC sensor adapted to point-of-care detection in + H)+], calcd 352.1338.
various scenarios.
2.3. Film preparation
2. Experimental section
A stock solution was prepared by dissolving HNPMO into THF (10
2.1. Materials and instruments mM). The film sensor was prepared by either soaking or capillary drop-
casting, using a cellulose paper substrate. Film thickness: 11.9 μm,
3-Aminobenzophenone and 2-hydroxy-1-naphthaldehyde were pro­ density: 12.7 nM/cm2. The film was dried by air oven prior to use. For
vided by J&K Scientific, LTD. Other involved chemicals were provided miniaturized film sensor, firstly, a cellulose paper was cut into small
by Aladdin Reagent Co., LTD. 1H and 13C NMR measurements were pieces to serve as the substrate; then HNPMO was impregnated on the
performed by a 600 MHz Varian-VNMRS NMR spectrometer. High res­ substrate by drop-casting using a capillary. After drying, the film sensor
olution mass spectrum (HRMS) was performed on Waters Xevo-G2-XS was ready for VOC fumigation in in-situ measurements or wearable
QTof mass spectrometer using positive ionization mode. Infrared spec­ applications.
trum was measured by Shimadzu IR-Prestige-21 Fourier transform
infrared spectrometer (FTIR). Melting point measurement was

2
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

Fig. 1. (A) Emission spectra of HNPMO in DMF-water mixtures with step-increased fw. Excitation wavelength: 370 nm. Concentration: 0.1 mM. Insets: chemical
structure of HNPMO; growth rate (I/I0-1) as a function of fw; photos of HNPMO solution and aggregates taken under UV lamp. (B) Absorption and (C) normalized
emission spectra of HNPMO in different organic solvents, measured at the concentration of 0.1 mM. Excitation wavelength: 370 nm. (D) Optimized conformation of
HNPMO for DFT calculation. (E) Molecular orbital distribution of HOMO/LUMO and (F) electrostatic potential map calculated using B3LYP/6–31 + G* set.

2.4. Preparation of the VOC environment 3. Results and discussion

To an airtight container was added excess amount of volatile organic 3.1. Photophysical characteristics
solvents such as ethyl acetate, toluene, dichloromethane, etc. After the
equilibrium state, where the concentration reading from the commercial The present compound HNPMO contains multiple single-bonds, i.e.,
VOC detector stabilized, the film sensor was ready to install. C–C and C–N bonds, which facilitate the intramolecular rotation to
suppress the emission in the solution state and simultaneously avoid π-π
2.5. Cytotoxicity test stacking by conformation-twisting to the advantage of the AIE property
(Scheme 1). On the other hand, D-A pairs, namely naphthol and
The cytotoxicity of the film sensor was performed by MTT assay benzophenone units, respectively, are incorporated in the molecular
using the L-929 cell (standard: ISO 10993–5 2009 and 10993–12 2012). structure, which would polarize the molecule to activate the ICT pro­
The L-929 cells were cultured in a cell incubator with 5% CO2 for 24 h cess. As indicated in Fig. 1A, a typical AIE experiment was performed, in
(temperature: 37 ◦ C, RH: >90%) before being seeded in a 96-well plate. which HNPMO was firstly dissolved in N,N-dimethylformamide (DMF)
Then the cells were treated with aqueous solution extracted from the and then gradually aggregated by adding water. As the water fraction
film. After incubating for 24 h, the viability was evaluated by measuring (fw) increases from 10% to 60%, the emission shows negligible change.
the absorbance of the cells in the 96-well plate using a microplate However, higher fw (>70%) leads to remarkable enhancement in
reader. emission intensity. The highest emission appears at 80% fw, while 90%
fw causes some decrease in emission. It was caused by the bulky pre­
cipitates visible to the naked eyes formed in such high fw, and the
mixture in the spectrophotometer cuvette is no longer a homogeneous
system as seen in the inset of Fig. 1A. The formation of the aggregates
can be evidenced by the absorption spectra in DMF-water mixed solvent

3
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

Fig. 2. (A) Schematic illustration showing the fabrication of the HNPMO film and the fumigation experiment. Time-dependent emission spectra of the HNPMO film
with in-situ fumigation in (B) methanol and (C) toluene. Photographs showing the emission turn-on process are shown in the insets. Excitation wavelength: 370 nm.
(D) Plot of the growth rate (I/I0-1) versus fumigation time using different VOCs. Structures and physical parameters of the VOCs involved in this experiment are listed
in Table S2.

(Fig. S7). The absorption spectra show a level-off tails in the long- distribution as a theoretical support for both electronic push-pull effect
wavelength region (>500 nm) with high fw values (≥70%), which can and molecular polarization.
be ascribed to the light reflex/scattering effect of the aggregates. Similar From the density functional theory (DFT) calculations in Fig. 1D, it is
results have been observed in the transmittance spectra (Fig. S8). When obvious that the molecular conformation is highly twisted, with two
fw has reached 70%, there is significant reduction in transmittance in the dihedral angles up to 24.7o and 38.9o, respectively. The twisting would
long-wavelength region (>500 nm). The spectral analyses also imply avoid π-π interactions to achieve the desired AIE nature. On the other
that the optical density of the excitation light would be disturbed when hand, the resulting poor planarity may lead to loose packing in the ag­
HNPMO forms aggregates. It is therefore inaccurate to evaluate the AIE gregation state to facilitate the adsorption of guest molecules. Fig. 1E
property simply by emission spectra. Considering this situation, it is demonstrates that the electronic cloud distribution of the highest
necessary to measure the fluorescence quantum yield (QY) for an ac­ occupied molecular orbital (HOMO) mainly locates at the naphthalene
curate description of the AIE phenomenon. From QY measurements, it and the central benzophenone unit, which confirms their electron-
was found that the QY of HNPMO is much lower in solution (QY = 2.6%) donating nature. The lowest unoccupied molecular orbital (LUMO),
but increased to 7.2% when forming aggregates (fw = 90%), and even to however, has partially shifted to the benzophenone moiety, which im­
8.6% as solid powder. These results suggest a typical AIE phenomenon of plies its electron-withdrawing nature. The electrostatic potential map
HNPMO. suggests that the hydrogen atoms generally exhibit electropositivity
The ICT nature of HNPMO was confirmed by polarity-dependent because of losing electron upon bonding, while the aromatic nucleuses
spectroscopic analysis. The absorption spectra in Fig. 1B suggests that show electronegativity due to the delocalization of π-electron (Fig. 1F).
there are two major bands locating at ca. 318 nm and ca. 377 nm, In contrast, there is high electronegativity with both hydroxyl and
respectively, which denote the localized π-π* transition. They are carbonyl groups, which can be ascribed to the lone pair electrons on the
insensitive to solvent polarity. In contrast, the absorption band in the oxygen atoms. DFT calculations not only provide the evidence of D-A
long-wavelength region (>440 nm), which represents the ICT transition, effects required for the ICT process, but also confirm the polarization of
undergoes a remarkable growth from an inconspicuous shoulder peak in the molecule as a result of imbalanced electrostatic potential energy.
nonpolar solvent (e.g., hexane) to a major band in polar solvents (e.g., Therefore, it is speculated that HNPMO offers the potential to combine
DMF and DMSO). The changes indicate the strengthening of the ICT with guest molecules via dipolar interactions, leading to changes in local
transition in polar solvents, wherein the charge separation between chemical environment whereby the emission could be variable.
donor and acceptor would be intensified by polarity to facilitate a nar­
rowed energy gap [37]. The polarity-dependent emission spectra were
measured as well (Fig. 1C). The maximum emission wavelength of 3.2. Fluorescent response to VOCs
HNPMO locates at ca. 490 nm in hexane, and shows a bathochromic
effect as solvent polarity increases. Notwithstanding the clear signal On the basis of the above results and discussions, we try to develop a
from spectroscopic analysis implying the ICT process, quantum chemical VOC sensor using HNPMO. As indicated in Fig. 2B, the in-situ real-time
calculations are still necessary, as they would provide a clear charge photoluminescence measurements were performed, wherein the film
sensor was fixed in a sealed quartz cell before VOC fumigation in the

4
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

Fig. 3. SEM images of the cellulose substrate (A), the as-prepared HNPMO film (B) and the film after ethyl acetate fumigation (C).

sample cell of the fluorescence spectrophotometer. Taking methanol between the probe and the guest molecule that enhances the physical
vapor for example, the as-prepared film glows weak emission at ca. 523 interactions at the solid-gas interface. The final growth rate of the sensor
nm, but undergoes a gradual growth when exposed to methanol. After in methanol and toluene has reached as high as ca. 540% and 416%,
400 s, the film reaches the equilibrium state, exhibiting bright green respectively, indicating high off-to-on ratio featured by the turn-on
emission (Fig. 2B). The weak emission of the film in the initial state can working mechanism. Expectedly, the intense green emission after
be ascribed to the highly disordered molecular arrangement on the fumigation can be readily detected by naked eyes as shown in the inset
cellulose substrate wherein the intermolecular voids would exist of Fig. 2B and C. In addition to the growth of emission intensity, the
extensively to allow intramolecular motion to some extent. And this spectra exhibit a gradually narrowed peak pattern, which implies the
would cause inactivation of the AIE effect according to restriction of transition from the disordered molecular arrangement to the optimized
intramolecular motion (RIM) mechanism, manifesting as the weak conformation driven by the VOCs in the gas phase. Besides methanol and
emission [27]. When exposing to toluene vapor, the emission of the film toluene, a variety of VOCs were used to perform the in-situ
sensor exhibits a faster growth (Fig. 2C). It takes only 200 s to reach the time-dependent measurements (Fig. S9), including esters, alcohols,
equilibrium state. The faster change is owing to the structural similarity benzene series, etc. The resulting growth rate (I/I0-1) was summarized in

Fig. 4. (A) Schematic illustration that describes the color-picking using Photoshop CS3 software, the data processing via RGB/Lab color space, as well as the ex­
pressions of the color shift equations (ΔELab and ΔERGB). (B) RGB and (C) Lab values in three-dimensional coordinate system showing the color change of the film after
exposing to saturated ethyl acetate vapor. Fumigation time: 5 min. DSLR parameters: aperture f/1.8, shutter speed 0.05 s, iso 200, focal length 50 mm. (D) change of
ΔELab as a function of Cvoc. Error bars denote standard deviation of mean (n = 4).

5
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

Fig. 5. Schematic illustration showing the drop-casting of the film using HNPMO and the inert reference MMA.

Fig. 2D. In general, the film sensor shows a turn-on fluorescent response expectedly turned-on, showing green fluorescence. The photograph of
with all the involved VOCs, showing no obvious selectivity, and the the sensor array was taken by a DSLR camera using fixed parameter
response time and the final growth rate vary from case to case. In whereby the RGB and Lab information can be collected by color-picking
addition to the aforementioned structural compatibility, there are other tools. Using RGB and Lab color space, the output fluorescence signals
significant influence factors, e.g., volatility and molecular size. The can be processed and further revealed by three-dimensional coordina­
former facilitates a fast diffusion of the VOC at the solid-gas interface; tion. Considering the preference of the human visual system, the colour
while the latter is unfavorable to solid-gas interactions, but would in­ shift of Lab value (ΔELab) would be more reliable, as our naked eye is
fluence the AIE effect after VOC diffuses into the film. In particular, able to detect low ΔELab value down to 1 au [39]. In contrast, the RGB
VOCs with bigger molecular size would pose high steric hindrance on color model is compatible with electronic display systems and therefore
the luminogen to strengthen the RIM mechanism, causing emission adapted to instruments and apparatus.
enhancement. Due to these combined effects, the emission of the film As indicated in Fig. 4B, R, G, B values were respectively collected
sensor shows various degrees of emission-enhancement in response to from multipoint color-picking (n = 20) on the sensor array, which yield
different VOCs, showing non-selectivity in VOCs detection. In some a dot matrix in the coordinate system. After fumigation in VOC (ethyl
excellent solvents e.g., methyl acetate and dichloromethane, the emis­ acetate), the dot matrix appears in another region, where the G value
sion of the film undergoes a gradual decrease followed by stabilization becomes particularly high, suggesting a clear discrimination with the
after reaching the maximum value (Fig. 2D). The reason is that the green channel. The signal change from the RGB color space corresponds
solvent molecules adsorbed on the film would render HNPMO partially with the emission spectra, in which the film changes from “dark” to
dissolved, by which the emission would be quenched to some degree. In bright green. Similarly, the L, a, b values from color-picking were plotted
general, the variation of the emission spectra is caused by the synergistic in the coordinate system as well (Fig. 4C). The as-prepared sensor array
effect related to AIE, ICT and solid-gas interaction. locates around the origin of coordinates, where the L, a, b values all stay
SEM observations were performed to reveal the morphology features at low level because of low luminosity. After exposing to ethyl acetate, L
of the HNPMO film. The blank cellulose paper substrate shows fibrous value is remarkably increased, which is consistent with the turn-on
textures with wrinkles on the surfaces, implying large specific surface single mode. In addition, the a value turns negative while the b value
area which is beneficial to the physical contact between the luminogen becomes positively higher, which indicates the enhancement of the
and the VOCs (Fig. 3A). After drop-casing, the film exhibits no signifi­ green color and the yellow color, respectively. By comparison with the
cant change in morphology except some increase in surface roughness, RGB color space with only monotonic change with G channel, the Lab
indicating uniform coating (Fig. 3B). After fumigation in ethyl acetate color space is more suitable for color-quantification owing to its three-
vapor, there is some decrease in roughness because of the etching effect channel output.
of the vapor (Fig. 3C). In the sensitivity test, ΔELab was used to estimate the LOD. The
experiment was conducted in a closed system wherein the VOC con­
centration (Cvoc) can be manually increased by adding liquid ethyl ac­
3.3. Quantitative analysis via color space
etate and measured in real time by a commercial VOC detector. As Cvoc
rises, the emission of the film sensor exhibits sharp increase. After col­
The above spectral analyses have confirmed the high off-to-on ratio
lecting the L, a, b values from the DSLR photos, the ΔELab was generated
and facile coating technology featured by the HNPMO film, whereby, an
via the color shift equations illustrated in Fig. 4A. The change in ΔELab as
easy-to-use sensor technique with visualized signal output could be
a function of Cvoc was presented after data processing (Fig. 4D). The
realized. The visualized detection has a clear advantage in terms of
ΔELab shows a linear relation with Cvoc ranging from 1.7 mg/m3 to 24.6
qualitative observation, allowing rapid feedback in various scenarios,
mg/m3, where the correlation coefficient (R2) is approximately equal to
but pales in quantitative monitoring. In view of this case, scientists try to
0.98. Thus the LOD can be evaluated according to signal-to-noise ratio,
regulate the optical signal by well-established image technology, with
which is expressed as LOD = 3Sd/k (k denotes the linear slope; Sd in­
the help of RGB (red-green-blue) or CIELAB (i.e., Lab, L = luminosity, a
dicates the standard deviation of the initial state). The resulting LOD
= red/green, b = yellow/blue) color space [38]. We believed that the
value is as low as 7.04 mg/m3, i.e., 1.8 ppm. This experiment demon­
HNPMO film sensor is liable to such quantitative model owing to its
strates that the LOD calculation can be implemented by virtue of ΔELab,
turn-on signal response. As illustrated in Fig. 4A, a sensor array was
and further confirms the high sensitivity of such turn-on type sensor.
prepared by integrating twenty miniaturized HNPMO films (4 × 5).
After exposing to VOCs (i.e., ethyl acetate vapor), the emission was

6
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

Fig. 6. Representative DSLR photographs of the wearable film sensors applicable to (A) glove, (B) labor suit and (C) nail. (D) Representative DSLR photographs of the
film sensor in scenario-based application. DSLR parameters for the fluorescent images: aperture f/1.8, shutter speed 0.05 s, iso 200, focal length 50 mm.

7
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

3.4. Wearable and scenario-based applications 4. Conclusion

As illustrated in Fig. 5, the fabrication of the drop-casting film can be This work presents a D-A luminogen HNPMO based on a molecular
performed by either capillary-coating or substrate-soaking. The former design strategy that combines AIE and ICT. Its photophysical behavior
helps to minimize the size of the film to the advantage of applications in was outlined, which mainly manifests as turn-on fluorescence in
narrow space or on subminiature solid supports; while the latter is response to VOCs. The mechanism lies in the transition from the disor­
conducive to shaping, thereby facilitating the encapsulation or imbedi­ dered molecular arrangement to the VOC-assistant conformation-opti­
bility of the film in various devices. In order to achieve higher contrast mization. This process is influenced by some major factors including
ratio, an inert luminogen MMA which is insensitive to VOCs was also volatility, molecular size, structural compatibility and steric hindrance,
used in film fabrication, serving as reference [40]. In the presence of the which render the response rate together with the off-to-on ratio of the
inert reference, the color shift would be easier to be detected through HNPMO film sensor varying toward different VOCs. In addition, the
both cameras and eyes. Considering the inevitable physical contact be­ fluorescent response can be quantified by well-established image tech­
tween the film and the human skin, it is necessary to perform a cyto­ nologies wherein the output signals from detection can be processed by
toxicity test. It was done by MTT assay using the aqueous solution RGB and Lab color space, and further revealed in three-dimensional
extracted from the film. The results in Fig. S10 suggest that the cells coordination. By virtue of ΔELab, the sensor is capable of detecting
merely lost 12% in saturated solution, and maintained as high as 96% VOCs down to ppm level. This work demonstrates an archetype of
viability in the 75% diluent, suggesting a low toxicity. wearable sensor that can be encapsulated into gloves, labor suits and
Fig. 6A demonstrates a representative example wherein the film even nails, etc., providing an early warning of air contamination in
sensor was inserted into a self-prepared protective casing before being various scenarios. The superiorities of the wearable sensor include
fixed on a glove. Through the window, HNPMO-impregnated region is portability, feasibility, fast response as well as low-cost fabricating/
non-emissive under UV lamp while the inert reference, i.e., MMA- operating, establishing an online point-of-care test platform for VOC
impregnated region, emits orange fluorescence. After exposing the glove level in the gas phase. Furthermore, this study may enrich the molecular
to VOC for 2 min, the emission of MMA remains unchanged, while design for new sensors and functional materials by combining AIE and
HNPMO is brightened from dark state by emitting intense green light, ICT, and hopes to offer new insights for advanced wearable devices.
showing sharp contrast from naked-eye observation (Fig. 6A). The
advantage of using the inert reference stems from the fact that it turns Declaration of competing interest
the monotonous signal into the chromatic contrast based on dual-
channel outputs, which is easy to identify. Furthermore, it minimizes The authors declare that they have no known competing financial
the errors and deviations in regard to the light perception that differs interests or personal relationships that could have appeared to influence
from person to person, ensuring the accuracy of the results from quali­ the work reported in this paper.
tative observation. In another wearable applications depicted in Fig. 6B,
HNPMO together with MMA was made into a “clothing label” before Data availability
being pasted on a labor suit, in which the former was tailored into a
plant pattern and the latter was cut into a “flowerpot”. In the initial Data will be made available on request.
state, the “flowerpot” is explicit whereas the “plant” is invisible. After a
volunteer wearing the labor suit stayed in VOC environment for 2 min, Acknowledgments
the “plant” becomes visible by emitting strong green light. Besides
clothes and gloves, the film sensor can be directly attached to human We acknowledge the supports from the Youth Project from National
body, and this requires applicable miniaturization of the film in Natural Science Foundation of China (Grant No. 51703135).
consideration of convenience and wearing comfortableness. Taking the
“nail decoration” for example, the film was significantly minified by Appendix A. Supplementary data
capillary drop-casting, rendering itself easily fit for a thumbnail
(Fig. 6C). After the volunteer stayed in VOC environment for 2 min, Supplementary data to this article can be found online at https://doi.
there is a green spot on the “nail decoration” beside the reference point, org/10.1016/j.dyepig.2022.110561.
indicating the presence of VOC. Comparing with many other wearable
VOC sensors in literature reports [20,21,41–43], HNPMO may fall short References
of selectivity and sensitivity but has some advantages, including
simplicity, miniaturization, low costing and eye identification. [1] He C, Cheng J, Zhang X, Douthwaite M, Pattisson S, Hao ZP. Recent advances in the
catalytic oxidation of volatile organic compounds: a review based on pollutant
In addition to the wearable applications, HNPMO can be also sorts and sources. Chem Rev 2019;119:4471–568.
fabricated into a mobile indicator for environment monitoring. As [2] Yang L, Li YZ, Sun YD, Wang W, Shao ZP. Perovskite oxides in catalytic combustion
demonstrated in a scenario-based experiment in Fig. 6D, we fabricated a of volatile organic compounds: recent advances and future prospects. Energy
Environ. Mater. 2022. https://doi.org/10.1002/eem2.12256.
warning sign using a drop-casting film, in which MMA and HNPMO [3] Lu SC, Liu QL, Han R, Guo M, Shi JQ, Song CF, Ji N, Lu XB, Ma DG. Potential
were coated into a triangle frame and an exclamation mark, respec­ applications of porous organic polymers as adsorbent for the adsorption of volatile
tively. Before fuming in the chemical cabinet (VOC environment), the organic compounds. J Environ Sci 2021;105:184–203.
[4] Jin TN, Zhou JC, Lin HYG, Lin PT. Mid-infrared chalcogenide waveguides for real-
former exhibits orange emission while the latter remains invisible. After
time and nondestructive volatile organic compound detection. Anal Chem 2019;91:
20 min, the exclamation mark turns into bright green, which gives a 817–22.
clear alerting signal of VOCs. Compared with the wearable device, the [5] Li AJ, Pal VK, Kannan K. A review of environmental occurrence, toxicity,
biotransformation and biomonitoring of volatile organic compounds. Environ.
mobile indicator has time lags in response, which can be ascribed to the
Chem. Ecotoxicol. 2021;3:91–116.
nice leakproofness of the reagent bottles as well as a worse volatility of [6] Galstyan V, D’Arco A, Di Fabrizio M, Poli N, Lupi S, Comini E. Detection of volatile
the chemicals relative to the previously used organic solvents. In brief, organic compounds: from chemical gas sensors to terahertz spectroscopy. Rev Anal
the above results have revealed a successful archetype of a VOC sensor Chem 2021;40:33–57.
[7] Li BL, Zhou Q, Peng SD, Liao YM. Recent advances of SnO2-based sensors for
that would be applicable to diverse forms of wearable applications and detecting volatile organic compounds. Front Chem 2020;8:321.
point-of-care monitoring of air quality. [8] Kang WC, Lin H, Jiang H, Adade SYSS, Xue ZL, Chen QS. Advanced applications of
chemo-responsive dyes based odor imaging technology for fast sensing food quality
and safety: a review. Compr. Rev. Food Sci. F. 2021;20:5145–72.
[9] Liu KW, Zhang C. Volatile organic compounds gas sensor based on quartz crystal
microbalance for fruit freshness detection: a review. Food Chem 2021;334:127615.

8
M. Zhang et al. Dyes and Pigments 205 (2022) 110561

[10] Bannaga AS, Kvasnik F, Persaud KC, Arasaradnam R. Differentiating cancer types [28] Liu M, Xiao RS, Feng B, Fan DY, Huang S, Bi AY, Zhong SB, Feng XP, Liu S,
using a urine test for volatile organic compounds. J Breath Res 2021;15:017102. Zeng WB. Elegant cooperation of AIE, ESIPT and ICT effects into
[11] Lubes G, Goodarzi M. GC-MS based metabolomics used for the identification of tetraarylimidazole-based fluorophore and its tuning for ratiometric detection of
cancer volatile organic compounds as biomarkers. J. Pharmaceut. Biomed. 2018; carbon monoxide. Sens Actuators, B 2021;342:130038.
147:313–22. [29] Li MR, Fang WW, Wang BW, Du YC, Hou YQ, Chen LG, Cui SQ, Li Y, Yan XL.
[12] Liu KW, Zhang C, Xu JY, Liu QQ. Research advance in gas detection of volatile A novel dual-site ICT/AIE fluorescent probe for detecting hypochlorite and polarity
organic compounds released in rice quality deterioration process. Compr. Rev. in living cells. New J Chem 2021;45:21406–14.
Food Sci. F. 2021;20:5802–28. [30] Cheng YH, Wang JG, Qiu ZJ, Zheng XY, Leung NLC, Lam JWY, Tang BZ. Multiscale
[13] Qin YX, Wang XY, Zang JS. Ultrasensitive ethanol sensor based on nano-Ag&ZIF-8 humidity visualization by environmentally sensitive fluorescent molecular rotors.
co-modified SiNWs with enhanced moisture resistance. Sens Actuators, B 2021; Adv Mater 2017;29:1703900.
340:129959. [31] Hou Y, Li Y, Zhang MY, Zhang XX, Xu ZZ, Li YP, Duan YA, Han TY. A dihedral-
[14] Shim DY, Chang SM, Kim JM. Development of fast resettable gravimetric aromatic angle-controlled mechanochromic luminescent material: application for pressure
gas sensors using quartz crystal microbalance. Sens Actuators, B 2021;329:129143. sensing. Dyes Pigments 2020;180:108505.
[15] Thangamani JG, Pasha SKK. Hydrothermal synthesis of copper (II) oxide- [32] Fang W, Liu K, Wang G, Liang YZ, Huang RR, Liu TH, Ding LP, Peng JX, Peng HN,
nanoparticles with highly enhanced BTEX gas sensing performance using Fang Y. Dual-phase emission AlEgen with ICT properties for VOC chromic sensing.
chemiresistive sensor. Chemosphere 2021;277:130237. Anal Chem 2021;93:8501–7.
[16] Song SR, Chen D, Wang HF, Guo QQ, Wang W, Wu MZ, Yu WH. Film bulk acoustic [33] Sasaki S, Drummen GPC, Konishi G. Recent advances in twisted intramolecular
formaldehyde sensor with polyethyleneimine-modified single-wall carbon charge transfer (TICT) fluorescence and related phenomena in materials chemistry.
nanotubes as sensitive layer. Sens Actuators, B 2018;266:204–12. J Mater Chem C 2016;4:2731–43.
[17] Xu H, Xiang JX, Lu YF, Zhang MK, Li JJ, Gao BB, Zhao YJ, Gu ZZ. Multifunctional [34] Hu JT, Wu MM, Zhao XY, Duan YA, Yuan J, Han TY. A donor-acceptor luminogen
wearable sensing devices based on functionalized graphene films for simultaneous serving as a haptic film sensor for identity recognition. Dyes Pigments 2022;198:
monitoring of physiological signals and volatile organic compound biomarkers. Acs 110034.
Appl. Mater. Inter. 2018;10:11785–93. [35] Hu JT, Liu Y, Zhang XX, Han HL, Li ZF, Han TY. Fabricating a mechanochromic AIE
[18] Zhang QK, An CH, Fan SQ, Shi SG, Zhang RJ, Zhang J, Li QN, Zhang DH, Hu XD, luminogen into a wearable sensor for volatile organic compound (VOC) detection.
Liu J. Flexible gas sensor based on graphene/ethyl cellulose nanocomposite with Dyes Pigments 2021;192:109393.
ultra-low strain response for volatile organic compounds rapid detection. [36] Zhao RX, Zhang MY, Liu Y, Zhang XX, Duan Y, Han TY. Fabricating D-A type AIE
Nanotechnology 2018;29:285501. luminogen into film sensor for turn-on detection of methanol vapour. Sens
[19] Zhou C, Shi NQ, Jiang X, Chen MR, Jiang JL, Zheng YB, Wu WW, Cui DX, Haick H, Actuators, B 2020;319:128323.
Tang N. Techniques for wearable gas sensors fabrication. Sens Actuators, B 2022; [37] Grabowski ZR, Rotkiewicz K, Rettig W. Structural changes accompanying
353:131133. intramolecular electron transfer: focus on twisted intramolecular charge-transfer
[20] McGinn CK, Lamport ZA, Kymissis I. Review of gravimetric sensing of volatile states and structures. Chem Rev 2003;103:3899–4031.
organic compounds. ACS Sens 2020;5:1514–34. [38] Zhao XY, Wei W, Zhang MY, Zhang XX, Han TY. Fabricating a photochromic
[21] Dai J, Ogbeide O, Macadam N, Sun Q, Yu WB, Li Y, Su BL, Hasan T, Huang X, material into a cellulose film for UV sensing and photo-patterning. Mater Lett
Huang W. Printed gas sensors. Chem Soc Rev 2020;49:1756–89. 2022;314:131865.
[22] Yang B, Kong JL, Fang XE. Bandage-like wearable flexible microfluidic [39] Butterfield JL, Keyser SP, Dikshit KV, Kwon H, Koster MI, Bruns CJ. Solar freckles:
recombinase polymerase amplification sensor for the rapid visual detection of long-term photochromic tattoos for intradermal ultraviolet radiometry. ACS Nano
nucleic acids. Talanta 2019;204:685–92. 2020;14:13619–28.
[23] Kassal P, Steinberg MD, Horak E, Steinberg IM. Wireless fluorimeter for mobile and [40] Zhang MY, Li YP, Gao K, Li ZF, Liu Y, Liao Y, Duan Y, Han TY. A turn-on
low cost chemical sensing: a paper based chloride assay. Sens Actuators, B 2018; mechanochromic luminescent material serving as pressure sensor and rewritable
275:230–6. optical data storage. Dyes Pigments 2020;173:107928.
[24] You L, Zha DJ, Anslyn EV. Recent advances in supramolecular analytical chemistry [41] Jiang Y, Ma JL, Lv J, Ma HT, Xia HB, Wang J, Yang C, Xue MQ, Li GY, Zhu N. Facile
using optical sensing. Chem Rev 2015;115:7840–92. wearable vapor/liquid amphibious methanol sensor. ACS Sens 2019;4:152–60.
[25] Jiang XY, Gao HF, Zhang XQ, Pang JH, Li YQ, Li K, Wu YC, Li SZ, Zhu J, Wei Y, [42] Liu HB, Zheng HX, Xiang HC, Wang W, Wu HW, Li ZJ, Zhuang J, Zhou HW. Paper-
Jiang L. Highly-sensitive optical organic vapor sensor through polymeric swelling based wearable sensors for humidity and VOC detection. ACS Sustainable Chem
induced variation of fluorescent intensity. Nat Commun 2018;9:3799. Eng 2021;9:16937–45.
[26] Cao SP, Shao JX, Abdelmohsen LKEA, van Hest JCM. Amphiphilic AIEgen-polymer [43] Rajapakse MY, Borras E, Fung AG, Yeap D, McCartney MM, Fabia FM, Kenyon NJ,
aggregates: design, self-assembly and biomedical applications. Aggregate 2021: Davis CE. An environmental air sampler to evaluate personal exposure to volatile
e128. organic compounds. Analyst 2021;146:636–45.
[27] Mei J, Leung NLC, Kwok RTK, Lam JWY, Tang BZ. Aggregation-induced emission:
together we shine, united we soar. Chem Rev 2015;115:11718–940.