Rationally introduce AIE into chemosensor: A novel and efficient way to achieving ultrasensitive multi-guest sensing

Article abstract of DOI:10.1016/j.saa.2019.04.014

Recently, ultrasensitive detection and multi-guest sensing have received extensive attention due to their high sensitivity and efficiency. Herein, we report a novel approach to achieve ultrasensitive detection of multi-analyte. This approach is concluded as “rationally introduce Aggregation-Induced Emission (AIE) into chemosensor”. According to this approach, by rationally introducing self-assembly moiety, the obtained chemosensor DNS could serve as a novel AIEgen and show strong AIE in DMSO/H₂O (water fraction 80%) binary solution. Interestingly, a simple fluorescent sensor array based on the DNS has been developed. This sensor array could selectively sense Fe³⁺, Al³⁺, H₂PO₄ ^? and L-Arg in water solution. More importantly, this sensor array shows ultrasensitive detection for Fe³⁺, Al³⁺ and L-Arg. The LODs of the sensor array for Fe³⁺, Al³⁺ and L-Arg are in the range of 3.54 × 10^?9 M to 9.42 × 10^?9 M. Moreover, H₂PO₄ ^? could realize the reversible detection of Fe³⁺ in the DMSO/H₂O (water fraction 80%) solution. Meanwhile, DNS-based test papers and thin films were prepared, which could serve as test kits for convenient detection Fe³⁺, Al³⁺, and L-Arg in water. In addition, they could also act as efficient erasable fluorescent display materials.

Full text of DOI:10.1016/j.saa.2019.04.014

Accepted Manuscript
Rationally introduce AIE into chemosensor: A novel and efficient
way to achieving ultrasensitive multi-guest sensing
Yan-Yan Chen, Qi Lin, You-Ming Zhang, Hong Yao, Tai-Bao
Wei, Yan-Qing Fan, Xiao-Wen Guan, Guan-Fei Gong, Qi Zhou
PII:
DOI:
Reference:
S1386-1425(19)30389-0
https://doi.org/10.1016/j.saa.2019.04.014
SAA 17022
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
To appear in:
Received date: 27 January 2019
Revised date:
Accepted
date:
4 April 2019
9 April 2019
Please cite this article as: Y.-Y. Chen, Q. Lin, Y.-M. Zhang, et al., Rationally introduce
AIE into chemosensor: A novel and efficient way to achieving ultrasensitive multi-
guest sensing, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,
https://doi.org/10.1016/j.saa.2019.04.014
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ACCEPTED MANUSCRIPT
Rationally introduce AIE into chemosensor: a novel and efficient
way to achieving ultrasensitive multi-guest sensing
Yan-Yan Chen a, Qi Lin a,*, You-Ming Zhang a, b,*, Hong Yao a, Tai-Bao Wei a, Yan-Qing Fan a,
Xiao-Wen Guan a, Guan-Fei Gong a, Qi Zhou a
a. Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China;
Research Center of Gansu Military and Civilian Integration Advanced Structural Materials;
College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu,
730070, China.
b. College of Chemistry and Chemical Engineering, Lanzhou City University, Lanzhou, Gansu,
730070, China.
Key words: ultrasensitive detection; AIE-based chemosensor; multi-analyte; aggregation induced
emission enhancement (AIE); aroyl hydrazone
Corresponding authors: Pro. Dr. Qi Lin - linqi2004@126.com; Pro. Dr. You-Ming Zhang -
zhangnwnu@126.com.

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Abstract:
Recently, ultrasensitive detection and multi-guest sensing have received extensive attention due
to their high sensitivity and efficiency. Herein, we report a novel approach to achieve
ultrasensitive detection of multi-analyte. This approach is concluded as “rationally introduce
Aggregation-Induced Emission (AIE) into chemosensor”. According to this approach, by
rationally introducing self-assembly moiety, the obtained chemosensor DNS could serve as a
novel AIEgen and show strong AIE in DMSO/H2O (water fraction 80%) binary solution.
Interestingly, a simple fluorescent sensor array based on the DNS has been developed. This sensor
-
array could selectively sense Fe3+, Al3+, H2PO4 and L-Arg in water solution. More importantly,
this sensor array shows ultrasensitive detection for Fe3+, Al3+ and L-Arg. The LODs of the sensor
array for Fe3+, Al3+ and L-Arg are in the range of 3.54 × 10-9 M to 9.42 × 10-9 M. Moreover,
-
H2PO4 could realize the reversible detection of Fe3+ in the DMSO/H2O (water fraction 80%)
solution. Meanwhile, DNS-based test papers and thin films were prepared, which could serve as
test kits for convenient detection Fe3+, Al3+, and L-Arg in water. In addition, they could also act as
efficient erasable fluorescent display materials.

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1 Introduction
In recent years, ultrasensitive response has gained extensive attentions due to their vital
applications [1-6]. So far, many methods have developed to achieving ultrasensitive response for
various guests. For instance, Jiang et al. [7] prepared two fluorescent probes for ultra-high
sensitive detection hypochlorite acid (HOCl). Govindaraju et al. [8] proposed a novel
optoelectronic approach based on nanoarchitectonics of small-molecule templated DNA system
for ultrasensitive response of mercury. Therefore, it’s still an intriguing issue to develop novel and
efficient way for ultrasensitive sensing important analytes.
In addition, because ions and amino acids play significant roles in chemical, biological and
environmental fields [9-12], ultrasensitive detection special ions and amino acids is needed. For
example, Fe3+ is an essential transition metal ion in the human body, the deficiency or nimiety of
Fe3+ in human body could result in pathological diseases [13, 14]. In addition, the excessive Al3+
in the body might restrain the uptake of other essential trace element, which would cause
multifarious health problems, including Alzheimer's disease and Parkinson's disease [15-17].
Moreover, as the most alkaline amino acid, arginine plays vital role in biological functions and it
is related to the pathogenesis of many cardiovascular disorders such as atheroma, hypertension
and diabetes [18-22]. Therefore, it’s very meaningful to develop methods for ultrasensitive and
selective recognition of these important ions and amino acids in environmental or living cells.
In the past decades, since Tang et al. proposed the concepts of “Aggregation-Induced Emission”
(AIE), the applications on AIE have gained increasing attentions [23, 24]. The AIE is a
phenomenon that some compounds showed no/weak fluorescence emission in good solvent but
highly emissive in the aggregated state [25]. Based on this pioneering research and other numerous
fundamental studies, AIE has shown extensive applications in fluorescent sensors [26-28], organic
light-emitting diodes (OLED) [29], light harvesting, bio-imaging and so on [30-32]. In addition,
fluorogens with aggregation induced emission characteristics (AIEgens) have been served as a
diverse and strong tool for sensing and imaging of versatile analytes including pH [33], ions [34],
gas [35], biomolecules [36] and different processes, such as self-assembly [37-41]. Therefore, the
rapid development of the AIE supplied good opportunity for design novel method to achieving
ultrasensitive multi-guest detection. However, rationally introducing AIE into small molecule

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chemosensors and using them for ultrasensitive detection of multi-analyte is rarely reported.
In view of these, and based on our research interests in ions and molecules recognition [42-49],
herein, we report a novel approach to achieving ultrasensitive detection of multi-guest. This
approach is concluded as “rationally introduce AIE into chemosensor”. Our strategies are as
follows: firstly, in order to achieve the aggregation of the chemosensor, we rationally introduced
multiple self-assemble driving forces, such as strong van der Waals force (through the long alkyl
chain), π-π stacking (through the aromatic groups) and multiple hydrogen bondings (through the
acyl hydrazone group). Secondly, naphthalene was employed as an efficient fluorogen for the
purpose of producing AIE. Moreover, the acylhydrazone group was introduced as multi-guest
recognition site. Benefited from this rational design, as shown in Scheme 1-2, the obtained
chemosensor DNS could act as a novel AIEgen and show strong AIE in DMSO/H2O (water
fraction 80%) binary solution. Interestingly, the simple DNS-based fluorescent sensor array was
-
constructed, which could selectively sense Fe3+, Al3+, H2PO4 and L-Arg in water solution. More
importantly, the chemosensor DNS shows ultrasensitive response properties for sensing Fe3+, Al3+
and L-Arg in different aqueous systems. The LODs of the sensor for Fe3+, Al3+ and L-Arg range
-
from 3.54 × 10-9 M to 9.42 × 10-9 M. Moreover, H2PO4 could realize the reversible detection of
Fe3+ in the DMSO/H2O (water fraction 80%) solution. Furthermore, DNS-based test papers and
thin films were prepared, which could serve as test kits for convenient detection Fe3+, Al3+, and
L-Arg in water. In addition, the DNS could also act as efficient erasable fluorescent display
materials.
2 Experimental sections
2.1 Materials
All initial reagents and solvents were commercially available at analytical grade and were used
without further purification. All metal ions were used from their perchlorate salts. All anions were
used from their tetrabutylammonium salts, which were purchased from Alfa Aesar and used as
received. All amino acids were purchased from Aladdin. Fresh double distilled water was used
throughout the experiment.
2.2 Instruments
Melting points were measured on an X-4 digital melting-point apparatus (uncorrected). NMR

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spectra were recorded on Varian Mercury-400 (400 MHz) and Varian Inova 600 instruments (600
MHz). 1H chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, TM scale
with the solvent resonances as internal standards). Mass spectra were performed on a Bruker
Esquire 3000 plus mass spectrometer (Bruker-FranzenAnalytik GmbH Bremen, Germany)
equipped with ESI interface and ion trap analyzer. The IR spectra were performed on a Digilab
FTS-3000 Fourier transform-infrared spectrophotometer. Fluorescence spectra were recorded on a
Shimadzu RF-5301PC spectrofluorophotometer. Ultraviolet-visible (UV-vis) spectra were
recorded on a Shimadzu UV-2550 spectrometer.
2.3 Synthesis of AIEgen DNS
2.3.1 Synthesis of DN
Compound D was synthesized according to previous literature [50]. A solution of compound D
(1.72 g, 5 mmol), methylparaben (0.91 g, 6 mmol), K2CO3 (2.76 g, 20 mmol) and KI (0.33 g, 2
mmol) in 30 mL acetone was heated and stirred at 60 °C for 84 h. After the reaction was
completed, the solid was filtered off and the solvent was collected, the filtrate was concentrated
and recrystallized in acetone and pour water. Yield: 1.84 g, 89%; m. p. 117 ~ 120 °C; 1H NMR
(600 MHz, DCCl3, room temperature) δ (ppm): 7.97 (d, J = 8.92 Hz, 2H), 6.89 (d, J = 8.91 Hz,
2H), 6.82 (m, 4H), 3.91 (s, 3H), 3.79 (s, 3H), 1.80 (m, 5H), 1.48 (m, 5H), 1.36 (m, 6H); ESI-MS
m/z: [DN + Na]+ Calcd [C25H34O5Na]+ 437.23, found 437.27.
2.3.2 Synthesis of DNH
Hydrazine hydrate (0.3182 g, 6 mmol, 85%) was added into a solution of the DN (2.07 g, 5
mmol) in ethanol (150 mL). The mixture was heated in a round-bottomed flask at 85 °C for 12 h.
The solvent was removed and the residue was recrystallized in ethanol. The product was collected
by filtration, and dried under vacuum. Yield: 1.93 g, 93%; m. p. 147~151 °C; 1H NMR (400 MHz,
DCCl3, room temperature) δ (ppm): 7.69 (d, J = 8.86 Hz, 2H), 7.22 (s, 1H), 6.90 (d, J = 8.86 Hz,
4H), 6.82 (s, 4H), 4.07 (s, 2H), 3.99 (t, J = 6.55 Hz, 2H), 3.90 (t, J = 6.57 Hz, 2H), 3.76 (s, 3H),
1.77 (m, 4H), 1.44 (m, 4H), 1.33 (m, 8H); ESI-MS m/z: [DNH + Na]+ Calcd [C24H34N2O4Na]+
437.24, found 437.26.
2.3.3 Synthesis of DNS
2-hydroxy-1-naphthaldehyde (0.34 g, 2 mmol) was added into a solution of the DNH (0.41 g, 1
mmol) in ethanol (50 mL), 2 mL acetic acid was added as catalyst. The mixture was heated in a

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round-bottomed flask at 80 °C for 14 h. The solvent was removed and the residue was
recrystallized in ethanol. The product was collected by filtration, and dried under vacuum. Yield:
1
0.41 g, 71%; m. p. 143~145 °C; H NMR (400 MHz, DMSO-d6, room temperature) δ (ppm):
12.86 (s, 1H), 12.09 (s, 1H), 9.48 (s, 1H), 8.20 (d, J = 8.81 Hz, 1H), 7.96 (d, J = 9.02 Hz, 2H),
7.91 (d, J = 8.00 Hz, 2H), 7.62 (t, J = 8.00 Hz, 1H), 7.42 (t, J = 8.89 Hz, 1H), 7.24 (d, J = 8.89 Hz,
1H), 7.11 (d, J = 8.48 Hz, 1H), 6.83 (s, 4H), 4.07 (t, J = 6.42 Hz, 2H), 3.87 (t, J = 6.47 Hz, 2H),
3.68 (s, 3H), 1.70 (m, 4H), 1.41 (m, 4H), 1.31 (m, 8H); ESI-MS m/z: [DNS + H]+ Calcd
[C35H41N2O5]+ 569.30, found 569.38.
Scheme 1.
3 Results and discussion
To observe the Aggregation-Induced Emission (AIE) properties of DNS, the fluorescence
emission behaviors of the DNS were studied in the mixture of DMSO/H2O binary solution with
different volume fractions of water. Because the DMSO is a good solvent for DNS while water is
a poor solvent for DNS, as shown in Scheme 2b and Fig. 1, the low concentration DNS (DMSO, 1
× 10-4 M) solution showed faint fluorescence emission, upon the addition of water into the DMSO
solution of DNS, with the increase of the water volume fractions, the fluorescent emission
intensity at 480 nm showed a gradual increase and reached the strongest state when the water
volume fraction was at 80%. However, when the water contents reach to 90%, the fluorescence
intensity of DNS was decreased, which could be attributed to the formation of precipitate when
more water was added in the DNS (water fractions 80%) solution. Moreover, as shown in Scheme
2c, when DNS was dissolved in DMSO (1 × 10-4 M), there is no Tyndall effect. However, with the
gradual addition of water into the DNS solution, a distinct Tyndall effect could be observed. These
phenomena indicated that DNS could aggregate in DMSO/H2O binary solution and the DNS
showed AIE in DMSO/H2O (water fraction 80%) binary solution [23]. Meanwhile, fluorescence
quantum yield of the DNS in DMSO/H2O (water fraction 80%) solution is calculated to be 0.36
(Fig. S7) according to the corresponding formula [51].
Scheme 2.

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Fig. 1.
1
Moreover, the self-assembly mechanism of the DNS was studied by concentration H NMR
spectra and SEM. Interestingly, as shown in Fig. 2, with the increasing of DNS concentration, the
signals of H1 (at 12.87 ppm, Ar-OH), H2 (at 12.09 ppm, NH) and H3 (at 9.48 ppm, N=CH)
showed distinct downfield shifts, which could be attributed to the formation of intramolecular
hydrogen bond C=N…H-O-Ar and intermolecular hydrogen bonds C=O…H-N and N=C-H…O-Ar
(Scheme 2). These intermolecular hydrogen bonds induced the DNS self-assemble into
one-dimensional supramolecular polymer. Meanwhile, the signals of H10 (at 7.11 ppm, Ar-H),
H11 (at 6.83 ppm, Ar-H), H12 (at 4.07 ppm, Ar-O-CH2), H13 (at 3.87 ppm, Ar-O-CH2), H15 (at
1.71 ppm, -CH2), and H16 (at 1.42 ppm, -CH2) showed upfield shifts, which indicated that there
are π-π interactions [52] and van der Waals force existing in the aromatic rings and long alkyl
chains on adjacent DNS. Therefore, the DNS could self-assemble into supramolecular system and
form aggregation through intermolecular hydrogen bonds, van der Waals force and π-π stacking
effects. This proposed self-assembly mechanism also supported by SEM. As shown in Scheme 2d
and 2e, the powder of DNS showed amorphous structure, however, the DNS solid obtained from
the DMSO/H2O (80% water fraction) binary solution showed neat strips structure. This result also
indicated that the DNS could aggregate in DMSO/H2O binary solution.
Fig. 2.
According to the above experiments, we speculate the self-assembly and AIE mechanism of the
DNS. Before the molecule DNS aggregation, the long alkyl chain and acyl hydrazine group made
the molecule conformationally flexible and underwent active intramolecular rotations, which
could serve as a nonradiative transition channel for electrons from the excited states to the ground
states [24]. While, after aggregation, the aggregated process limited the innate rotation of DNS by
multiple noncovalent interactions (H-bond, π-π stacking, and van der Waals force) and the
radiationless pathway is blocked, meanwhile, the radiative channel is opened and emitted strong
AIE fluorescence at 480 nm simultaneously [23, 24].
Fig. 3.
Then, the response abilities of DNS for different guests were studied in different water contents
systems. Firstly, the cations response property of the DNS in DMSO/H2O (water fraction 80%)

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solution was carefully investigated. For convenience, the DMSO/H2O (water fraction 80%)
solution of DNS was named as D80 in the after. Via adding and diffusing 10 equiv. various cations,
including Mg2+, Ca2+, Cr3+, Fe3+, Co2+, Ni2+, Al3+, Cu2+, Zn2+, Ba2+, Ag+, Cd2+, Hg2+, and Pb2+
(water solution, 0.1 M), into the D80 solution, interestingly, only the addition of Fe3+ induced the
fluorescence of the D80 “turned off”, and other cations did not show a similar response (Fig. 3 and
4a), which indicated that the D80 could selectively fluorescence detect Fe3+. Then, the Fe3+
specific selectivity of D80 over other competitive cations was investigated by competitive
experiment (Fig. S8). The results showed that the competitive cations did not lead to any
significant influence in Fe3+ sensing process. Furthermore, according to the fluorescent titration
experiments (Fig. S10) and calculation based on the 3σ/m method [53], the limit of detection
(LOD) of the D80 for Fe3+ is 9.42 × 10-9 M, which indicated that the sensor D80 could
ultrasensitively detect Fe3+ (Fig. S9 and S11).
Fig. 4.
Due to the Fe3+ quenching the AIE fluorescence of D80, the successive anions sensing
properties of DNS-Fe3+ complex (named as D80Fe) was carried out in DMSO/H2O (water fraction
-
-
-
80%) solution. Upon the addition of various anions (including F-, Cl-, Br-, I-, HSO4 , H2PO4 , N3 ,
-
2-
CN-, ClO4 , SCN-, AcO-, S2 , 0.1 M, in water) into the D80Fe solution, as shown in Fig. 3, 4b and
-
S12, only the addition of H2PO4 could induce the fluorescence of D80Fe “turn-on”. This result
-
-
indicated that the D80Fe could selectively detect H2PO4 . And the LOD of the D80Fe for H2PO4
-
is 2.41 × 10-7 M (Fig. S9, S13 and S14), which indicated a highly sensitive detection for H2PO4 .
Furthermore, the reversibility of the chemosensor function was tested by alternate adding Fe3+ and
-
H2PO4 into the D80 solution. As shown in Fig. S15, the fluorescent emission of D80 solution
showed alternating quenching and enhancing processes in a sequence, and the reversible process
could be repeated at least three times with little fluorescent efficiency loss. Hence, the sensor D80
could be considered as an “OFF-ON-OFF” fluorescent switch.
In addition, because the fluorescence emission of DNS solution under the 20% (including 20%)
water volume fraction is very weak, so, a series of host-guest recognition property of DNS in the
DMSO/H2O (water fraction 20%) solution was carried out and the system was named as D20 in
the after. At first, we investigated the recognition property of the D20 toward various cations

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through similar methods. After adding and diffusing 10 equiv. of various cations into the solution
of D20, as shown in Fig. 5a, only the addition of Al3+ could enhance the fluorescence of D20.
Meanwhile, other cations did not induce a similar response (Fig. 3). Therefore, the D20 could
selectively sense Al3+ through fluorescence enhancement way. As shown in Fig. S16, the LOD of
the D20 for Al3+ was obtained by fluorescent titration and calculated to be 3.54 × 10-9 M (Fig. S9
and S17), this result indicated that the detection of D20 for Al3+ reached to ultrasensitive level.
Fig. 5.
Moreover, the successive response property of the complex DNS-Al3+ toward various metal
ions was studied in the DMSO/H2O (water fraction 20%) solution of the DNS-Al3+ (the system
was named as D20Al) via similar method. As shown in Fig. 3, 5b and S18, only the addition of
Fe3+ could make the fluorescence D20Al “turn off” and the other metal ions have no similar
response, which indicated the D20Al could selectively detect Fe3+. And the LOD of the D20Al for
Fe3+ was calculated to be 4.75 × 10-8 M (Fig. S9, S19 and S20).
Fig. 6
Furthermore, it is well known that amino acids are the most basic substances which have close
relationship with biological activities. So, we investigated the recognition property of D20 toward
various amino acids, including L-Phe, L-Gln, L-Ile, L-Thr, L-Glu, L-Ala, L-Ser, L-Met, L-Val,
L-Tyr, L-Arg, L-Asp, L-Pro, L-His, L-Leu, L-Gly, L-Trp, L-Asn, and L-Cys (water solution, 0.1
M), by similar methods. As shown in Fig. 3 and 6, the D20 could selectively dual-channel detect
L-Arg by fluorescence increase and color change. Meanwhile, the competitive experiments also
demonstrated that other amino acids couldn’t induce any significant influence for the recognition
process of L-Arg (Fig. S21 and S22). In addition, the fluorescence and UV-vis LODs of the D20
for L-Arg were measured by fluorescence and UV-vis titrations (Fig. S23 and S25) and calculated
to be 8.97 × 10-9 M and 8.25 × 10-9 M, respectively (Fig. S9, S24 and S26), which indicated
ultrasensitive sensing for L-Arg.
According to the above results, as shown in Fig. 3, a novel sensor array based on DNS was
successfully constructed. The sensor array could sense different guests: firstly, the D80 could
-
ultra-sensitively detect Fe3+, meanwhile, the D80Fe could act as a new sensor to detect H2PO4 .

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Secondly, the D20 could ultrasensitively sense Al3+ and L-Arg by the fluorescence enhanced. In
addition, D20 also showed colorimetric sensing property for L-Arg. Furthermore, the D20Al could
be employed as a new sensor to sense Fe3+ with high selectivity and sensitivity. Based on these
results, a novel four units sensor array was constructed, which could selectively and sensitively
-
detect Fe3+, H2PO4 , Al3+ and L-Arg in aqueous solutions.
Then, the recognition mechanisms of the DNS for different guests were investigated by FT-IR,
1H NMR, ESI-MS and SEM experiments. At first, the recognition mechanism of D80 for Fe3+ and
-
H2PO4 were investigated. In the IR spectra (Fig. S27), the stretching vibrational peaks appeared at
3435, 3221, 1647 and 1547 cm-1 are assigned to the vibrational absorption peaks of NH, OH, C=O,
and C=N groups of DNS, respectively. However, in the mixture of D80 and Fe3+, the OH vibration
band disappeared, the C=O, and C=N vibration absorption peaks shifted to 1634 cm-1 and 1537
cm-1, which indicated that upon the addition of Fe3+, the DNS chelated with Fe3+ through the
oxygen atom of C=O, the nitrogen atom of the C=N group and the oxygen of Ar-O. Meanwhile,
the coordination process destroyed the self-assembly and aggregation of DNS and a significant
emission quenching was observed after complexing with Fe3+ (Scheme 3). In the ESI-MS (Fig.
S31), a peak at m/z 1190.51 for [2DNS - 2H + Fe]+ was observed, which revealed a 2:1
stoichiometry for the complexation between DNS and Fe3+. Furthermore, in the SEM image, after
adding Fe3+, the morphological feature of D80 changed from neat strips to amorphous powder, this
-
result also support the proposed Fe3+ coordination mechanism. Moreover, after adding H2PO4 (1.0
M, H2O) into the D80Fe, in the FT-IR (Fig. S27), the OH vibration recovered, the C=O and C=N
vibration absorption peaks shifted to 1650 cm-1 and 1545 cm-1. Meanwhile, the corresponding
SEM images changed from amorphous powder to layer (Fig. S30b and c). These results indicated
-
that H2PO4 competitively coordinated with Fe3+ in the D80 and destroyed the complex of
DNS-Fe3+, meanwhile, the DNS self-assembled into an aggregation state and the AIE recovered
again. (Scheme 3).
In addition, the response mechanisms of D20 for Al3+ and D20Al for Fe3+ were also
investigated. Firstly, in the 1H NMR titration spectra (Fig. S28), after the addition of 1.0 equiv. of
Al3+, the single of naphthol OH peak at 12.87 ppm disappeared due to the deprotonation of sensor
DNS. What’s more, after adding more equivalents of Al3+, new proton peaks appeared around
H3-8 and H10, and all the new peaks showed downshifts. These new proton peaks could be

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attributed to the Al3+ coordination inducing downshifts of the H3-8 and H10 and forming new
peaks. Moreover, as shown in Fig. S32, in the ESI-MS, a peak at m/z 297.13 for [DNS - H + Al]2+
was observed, which revealed a 1 : 1 stoichiometry for the complexation between DNS and Al3+.
To sum up, upon the addition of Al3+, the DNS coordinate with Al3+ through the oxygen atom of
C=O, the nitrogen atom of the C=N group and the oxygen of Ar-O (Scheme 3), which induced a
significant emission enhancement. However, as shown in Fig. S30d, after adding Fe3+ to D20Al,
the morphological feature of D20Al changed to amorphous powder. Based on the above study, as
shown in Scheme 3, the proposed sensing of D20Al toward Fe3+ is a competitive coordination
process between Fe3+ and Al3+. Due to the stronger coordination property of Fe3+, after adding
Fe3+ to the solution of D20Al, Fe3+ could replace Al3+ from D20Al and form more stable complex
DNS-Fe.
1
1
Finally, the L-Arg response mechanism was studied by H NMR experiment. In the H NMR
spectra (Fig. S29), after the addition of L-Arg (0.1 M, water solution), the singles of naphthol OH
and imide NH peak at 12.87 ppm and 12.09 ppm disappeared, meanwhile, the other peaks show
upshifts. This result indicated that the naphthol OH and imide NH moiety of DNS underwent a
deprotonation process, which induced the fluorescent enhancement of the DNS through ICT
mechanism. (Scheme 3).
Scheme 3.
Furthermore, the DNS-based test papers were prepared by immersing the filter paper into the
DNS (DMSO/H2O, 1 × 10-3 M) solution and then drying in air. Interestingly, the test papers could
serve as an efficient test kits for convenient detection of Fe3+, Al3+ and L-Arg in water. As shown
in Fig. 7a, these test papers exhibit weak fluorescence emission; upon dipping the test papers into
the different concentration (from 1 × 10-1 M to 1 × 10-9 M) of Fe3+, Al3+ and L-Arg solution,
respectively, the test papers showed distinct fluorescence changes. The lowest response
concentration of these test papers for Fe3+, Al3+ and L-Arg are 1 × 10-9 M, 1 × 10-8 M and 1 × 10-8
M, respectively.
In addition, the DNS-based thin films were obtained by immersing the silica plate into the DNS
(DMSO/H2O, 1 × 10-3 M) solution and then drying in air. As shown in Fig. 7b, the thin films
showed weak fluorescence under the UV lamp (365 nm), when writing on the film with a capillary

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tube inhaling Fe3+ water solution, a dark fluorescent writing image appeared and the dark
-
fluorescent writing image could be erased by brushing H2PO4 on the film again. Meanwhile, the
same experiment was tested by Al3+ and L-Arg, when writing on the film with Al3+ (0.1 M, water
solution), a brilliant blue fluorescent writing image appeared, and the fluorescence enhanced after
writing with the L-Arg (0.1 M) water solution. Therefore, the DNS-based thin films could act as
efficient erasable fluorescent display materials.
Fig. 7.
Furthermore, as shown in Table 1, after comparison with other reported Fe3+, Al3+ and L-Arg
selective sensors [15, 54-63], the sensor DNS is synthesized in simple, low cost and high yield.
More importantly, many reported chemosensors only could sense single guest, while the sensor
DNS showed selective and ultrasensitive response for multi-guest in different water content
systems.
Table 1.
4 Conclusion
In summary, based on the “rationally introduce AIE into chemosensor” strategy, a novel
AIE-based chemosensor DNS was synthesized. Interestingly, the obtained chemosensor DNS
could aggregate and show strong AIE in the DMSO/H2O (water fraction 80%) binary solution. In
addition, the DNS could act as a novel fluorometric and colorimetric chemosensor to selectively
-
detect Fe3+, Al3+, H2PO4 and L-Arg in different aqueous systems. Moreover, DNS-based sensor
array was constructed, which could conveniently and selectively sense multi-guest in water
solution. More importantly, the sensor could ultrasensitively detect Fe3+, Al3+ and L-Arg, the
LODs of the sensor for Fe3+, Al3+ and L-Arg could reach to 10-9 M. Furthermore, DNS-based test
papers and thin films were prepared, the test papers could serve as test kits for convenient
detection Fe3+, Al3+ and L-Arg in water, meanwhile, the thin films could act as erasable
fluorescent display materials. Overall, the concept “rationally introduce AIE into chemosensor” is
a novel and efficient approach for design fluorescent chemosensors and materials to achieving
ultrasensitive detection and multi-guest response.

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Acknowledgments
This work was supported by the National Natural Science Foundation of China (NSFC) (No.
21574104; 21662031; 21661028) and the Program for Changjiang Scholars and Innovative
Research Team in University of Ministry of Education of China (IRT 15R56).
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List of Schemes, Figures and Table:
Scheme 1. The synthesis of DNS.
Scheme 2. (a) The proposed AIE-induced self-assemble mechanism of the chemosensor DNS; (b)
Fluorescence photographs of the DNS (1 × 10-4 M) in DMSO and DMSO/H2O (water fraction
80%) solution. (c) Photos showing the Tyndall effect of DNS in DMSO and DMSO/ H2O (water
fraction 80%) binary solution. (d) and (e) The SEM images of the powder DNS and DNS in the
DMSO/H2O (water fraction 80%) solution.
Fig. 1. The fluorescence intensity of the DNS (1 × 10-4 M, λex = 365 nm, λem = 480 nm, Slit =
1.5/20 nm) in DMSO/H2O binary solution with different volumetric fractions of water (vol %).
1
Fig. 2. Partial H NMR spectra (400 MHz, 298 K) of DNS in DMSO-d6 with various
concentration: (a) 10.0 (b) 40.0 (c) 80.0 and (d) 120.0 mg/mL.
Fig. 3. Multi-analyte response properties of DNS-based sensor array in different water aqueous for
different ions and amino acids.
Fig. 4. (a) Fluorescence spectra of D80 (1 × 10-5 M) in the presence of an excess (10 equivalents)
of various cations in mixed aqueous medium. (b) Fluorescence spectra of D80Fe (1 × 10-5 M) in
the presence of an excess (10 equivalents) of various cations in mixed aqueous medium (λex = 365
nm, Slit = 1.5/20 nm).
Fig. 5. (a) Fluorescence spectra of D20 (1 × 10-4 M) in the presence of an excess (10 equivalents)
of various metal ions in mixed aqueous medium. (b) Fluorescence spectra of D20Al (1 × 10-4 M)
in the presence of an excess (10 equivalents) of various metal ions in mixed aqueous medium (λex
= 365 nm, Slit = 3/1.5 nm).
Fig. 6. (a) Fluorescence spectra of D20 (1 × 10-4 M) in the presence of an excess (10 equivalents)
of various amino acids in mixed aqueous medium (λex = 365 nm, Slit = 5/5 nm). (b) UV-vis
absorption spectra of D20 (1 × 10-4 M) in the presence of an excess (10 equivalents) of various

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amino acids in mixed aqueous medium.
Scheme 3. The proposed aggregation process of the chemosensor DNS and the recognition
-
mechanisms to Fe3+, Al3+, L-Arg and H2PO4 .
Fig. 7. (a) Fluorescence changes of DNS-based test papers after addition different concentration
(from 1 × 10-1 M to 1 × 10-9 M) of Fe3+, Al3+ and L-Arg. (b) Writing and erasing of a natural light
invisible image on DNS thin films. The photographs were taken at room temperature under 365
nm ultraviolet light (UV).
Table 1. Comparison of the LODs of different chemosensors for analytes.

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Table 1. Comparison of the LODs of different chemosensors for analytes.
Analytes
Fe3+
Refs
Solvents
Water
LOD (nM)
1.40 × 106
9.00 × 102
3.00 × 102
1.72 × 102
9.42
54
55
Aqueous Solution
56
Aqueous Solution
15
THF/H2O (water fraction 30%)
DMSO/H2O (water fraction 80%)
DMSO/H2O (water fraction 20%)
Water
This work
This work
47.5
54
1.50 × 104
4.32 × 103
2.90 × 103
5.50 × 102
3.54
4.00 × 103
1.94 × 103
28.50
57
CH3OH/H2O (water fraction 10%)
DMSO/H2O (water fraction 50%)
CH3CN
Al3+
58
59
This work
60
DMSO/H2O (water fraction 20%)
Aqueous Solution
61
Aqueous Solution
62
Aqueous Solution
L-Arg
63
Aqueous Solution
13.80
This work
This work
DMSO/H2O (water fraction 20%)
DMSO/H2O (water fraction 20%)
8.97
8.25

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Rationally introduce AIE into chemosensor: a novel and efficient
way to achieving ultrasensitive multi-guest sensing
Yan-Yan Chen a, Qi Lin a,*, You-Ming Zhang a, b,*, Hong Yao a, Tai-Bao Wei a,
Yan-Qing Fan a, Xiao-Wen Guan a, Guan-Fei Gong a, Qi Zhou a
Highlights
1. A novel approach to realizing ultrasensitive detection multi-analyte.
2. Rationally induce AIE into the small molecular chemosensor.
-
3. A simple sensor array for Fe3+, Al3+, H2PO4 and L-Arg was created.
4. Ultrasensitive detection for Fe3+, Al3+ and L-Arg in aqueous solutions.
5. LODs of the sensor array for Fe3+, Al3+ and L-Arg reached 10-9 M.
6. Fe3+, Al3+, L-Arg test papers and fluorescent display materials were prepared.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7