A self-assembled supramolecular gel constructed by phenazine derivative and its application in ultrasensitive detection of cyanide

Article abstract of DOI:10.1016/j.dyepig.2019.108066

In this work, we constructed a supramolecular gel (PN-G) by phenazine derivative, which can ultrasensitive detect cyanide (detection limit equals to 4.18 × 10^?10 M). The decrease of fluorescent intensity displayed a linear relationship in the range of 0–0.4 equivalents of cyanide. And no significant fluorescence quenching was observed for all used interfering ions. The cyanide recognition mechanism of PN-G was verified by XRD, NMR, MS and SEM. With addition of cyanide to the supramolecular gel (PN-G), cyanide broken π-π stacking of PN-G, and then PN-G undergoes a nucleophilic addition reaction with CN^?, resulting in fluorescence quenched.

Full text of DOI:10.1016/j.dyepig.2019.108066

Journal Pre-proof
A self-assembled supramolecular gel constructed by phenazine derivative and its
application in ultrasensitive detection of cyanide
Hu Fang, Wen-Juan Qu, Hao-Hang Yang, Jun-Xia He, Hong Yao, Qi Lin, Tai-Bao
Wei, You-Ming Zhang
PII:
S0143-7208(19)32438-6
DOI:
https://doi.org/10.1016/j.dyepig.2019.108066
DYPI 108066
Reference:
To appear in: Dyes and Pigments
Received Date: 17 October 2019
Revised Date: 18 November 2019
Accepted Date: 21 November 2019
Please cite this article as: Fang H, Qu W-J, Yang H-H, He J-X, Yao H, Lin Q, Wei T-B, Zhang Y-
M, A self-assembled supramolecular gel constructed by phenazine derivative and its application
in ultrasensitive detection of cyanide, Dyes and Pigments (2019), doi: https://doi.org/10.1016/
j.dyepig.2019.108066.
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Graphical Abstract:
A supramolecular gel (PN-G) was constructed, which could ultrasensitively
detect cyanide.

A Self-Assembled Supramolecular Gel Constructed by
Phenazine Derivative and Its Application in Ultrasensitive
Detection of Cyanide
a
*
a
a
a
a
a
Hu Fang, Wen-Juan Qu , Hao-Hang Yang, Jun-Xia He, Hong Yao, Qi Lin,
a
* a, b
Tai-Bao Wei, You-Ming Zhang ,
a
Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China;
Key Laboratory of Polymer Materials of Gansu Province; College of Chemistry and Chemical
Engineering, Northwest Normal University, Lanzhou, Gansu, 730070. P. R. China
b
College of chemistry and Chemical Engineering, Lanzhou City University, Lanzhou, Gansu,
730070, P. R. China
Abstract:
In this work, we constructed a supramolecular gel (PN-G) by phenazine derivative,
-10
which can ultrasensitive detect cyanide (detection limit equals to 4.18×10 M). The
decrease of fluorescent intensity displayed a linear relationship in the range of 0-0.4
equivalents of cyanide. And no significant fluorescence quenching was observed for
all used interfering ions. The cyanide recognition mechanism of PN-G was verified
by XRD, NMR, MS and SEM. With addition of cyanide to the supramolecular gel
(PN-G), cyanide broken π-π stacking of PN-G, and then PN-G undergoes a
−
nucleophilic addition reaction with CN , resulting in fluorescence quenched.
Keywords: supramolecular gel, phenazine derivative, cyanide, assemble, nucleophilic
addition
*
Corresponding author
E-mail address: quwenjuanlz@163.com (Wen-Juan Qu)
*
Corresponding author
E-mail address: zhangnwnu@126.com (You-Ming Zhang)

1
. Introduction
Noncovalent interactions(NCI), such as hydrogen bonds [1-2], hydrophobic
interaction [3], π-π stacking [4-5], C-H-π [6-7], exo-wall π-π interactions [8], cation-π
9-10] and anion-π [11-12] interactions et al, arise from the balance between attractive
[
and repulsive effects and are usually classified into multipole-multipole interactions
are ubiquitous in nature [13-14]. They play significant roles in broad areas, for
instance: supramolecular chemistry, structural biology, and material science [15-16].
As we all know, the DNA/RNA double-helix is a life-matter example in which
stabilization arises from both π-stacking and hydrogen-bonds between the base pairs
[
17-18].
In recent years, benefiting from the dynamic and reversible nature of noncovalent
interactions (NCI), supramolecular gels have attracted increasing attention in diverse
fields including, sensors, biomedicine, environmental monitoring, and materials
synthesis [19-22]. In particular, reversible nature in the supramolecular gels and the
physical properties of these gels in response to a specific signal input are thus pivotal
for the creation of smart materials [23-25]. The integration of selective molecular
recognition units into the gelator molecules is advantageous to create specific
responses or develop multistimuli-responsive gels. The recognition process of these
units inevitably affects the structure of the supramolecular gels, resulting in changes
in macroscopic properties. In particular, anions and metal ions also play a crucial
structural and regulatory role in supramolecular gels [26-28].
−
Cyanide (CN ) is known for their high toxic effects [29-31]. Therefore, the

sensitive and selective detection of this extremely toxic anion is highly necessary. In
recent years, various analytical and spectroscopic methods have been developed to
detect metal ions and anions in various chemical and biological systems, but problems
associated with high cost and low sensitivity limit their use [32-45]. Recently, our
group has devoted to comprehensive investigations of the phenazine derivative
assembly mechanism and supramolecular gel, in which the close π-π stacking of
phenazine derivatives is the driving factor of the final structures [46-48]. In this work,
2
-(hexadecylthio)oxazolo[4,5-b]phenazine (PN) was successfully synthesized
(Scheme 1). PN was capable of forming supramolecular gel in DMSO solution by van
der waals interaction and π-π stacking. We surveyed the response of PN gel (PN-G)
to various anions in water. The result displayed that when added cyanide anion at
room temperature, the fluorescent of PN-G didn’t show any change. Nevertheless,
after heating from the gel to the sol and gelling again, the fluorescence was
dramatically quenched from bright yellow.
2
. Experimental section
2
.1. Materials and Characterizations
All reagents were commercially available and used as supplied without further
purification. The fluorescence spectra were recorded on a Shimadzu RF-5301PC
1
13
fluorescence spectrophotometer. H NMR (400 MHz and 600 MHz) and C NMR
spectra (151 MHz) were carried out with a Mercury-600 BB spectrometer.
High-resolution mass spectra were recorded with a Bruker Esquire 3000 Plus
spectrometer. Melting points were measured on an X-4 digital melting-point

apparatus. The X-ray diffraction (XRD) pattern was generated using a Rigaku
RINT2000 diffract meter equipped (copper target; λ = 0.154073 nm). Scanning
electron microscopy (SEM) images of the xerogels were investigated using
JSM-6701F instrument.
2
.2. Synthesis of receptor molecule PN Compound
A mixture of oxazolo[4,5-b]phenazine-2-thiol (0.253 g, 1 mmol), K CO (0,138 g,
2
3
1
mmol), KI (1.992 g, 1.2 mmol), 1-bromohexadecane (0.365 g, 1.2 mmol) and
acetonitrile (50 mL) were add to a 100 mL round-bottom flask under nitrogen
atmosphere. The reaction mixture was stirred at 80℃ for 72h. The crude product was
purified by silica gel column chromatography using petroleum ether/ethyl acetate (v/v
=
20:1) as the eluent, compound PN as yellow solid (0.393 g, yield 80%) was isolated,
1
(
Fig. S1, Fig. S2 and Fig. S3). m.p. >300℃, H NMR (600 MHz, CDCl ) δ 8.33 (s,
3
1
1
H), 8.24 (d, J = 2.8 Hz, 2H), 8.13 (s, 1H), 7.83 (dd, J = 3.5, 1.3 Hz, 2H), 3.43 (s, 2H),
.90 (s, 2H), 1.52 – 1.51 (m, 2H), 1.37 (d, J = 7.8 Hz, 4H), 1.24 (s, 22H), 0.87 (s, 3H).
1
3
C NMR (151 MHz, CDCl ) δ 172.45, 153.76, 146.53, 142.66, 142.58, 141.62,
3
1
2
41.27, 130.19, 130.15, 129.29, 129.11, 114.92, 105.76, 32.64, 31.89, 29.67, 29.66,
9.64, 29.62, 29.60, 29.53, 29.42, 29.33, 29.04, 29.03, 28.65, 22.66, 14.09. ESI-MS
+
m/z: Calcd for C H N O [PN + H] : 478.2892; Found 478.2881.
2
2
13
4
2
2
.3. General Experimental Procedures
2
.3.1. General procedure for fluorescence spectra experiments.
All the fluorescence spectroscopy was carried out in DMSO solution on a
Shimadzu RF-5301 spectrometer. Any changes in the fluorescence spectra of

compound were recorded on addition of sodium salt, while gelation concentration of
−
−
−
−
the sensor was 5% in all experiments. Sodium salt (1 M) of anions (F , Cl , Br , I ,
−
3−
2−
4
2−
2−
3
2−
−
2−
3
−
−
AcO , PO , SO , CO , NO , S , HS , ATP, SO , SCN and CN ) were used
4
3
for the fluorescence experiments.
. Result and Discuss
Due to the excellent self-assemble properties of phenazine [49-52], and the
3
introduced of alkyl group in PN, we explored whether this receptor can formed as gel
in various solvents. Firstly, we configured PN in 10 different solvents into the
proportion of 5% and heated it completely. As shown in Table S1, when cooled to
room temperature, we found that PN could form as gel only in DMSO and DMF. The
lowest critical gelation concentration (CGC) was 2% (w/v, 10 mg/mL = 1%), while
the gel-sol transition temperature (T ) was 25-97℃. As shown in Fig. 1, PN-G didn’t
gel
have any fluorescence in DMSO (T＞T ). After the temperature cooling down to the
gel
T (T＜T ) gradually, the emission dramatically enhanced at 523 nm and reached a
gel
gel
steady state within 1 min. At the same time, PN-G showed a bright yellow
fluorescence, which indicated that PN assembled as supramolecular gel in DMSO
(Fig. S6). To further confirm the stability of PN-G, fluorescence decay experiments
were conducted. The decay curve of PN-G was fitted, which showed the fluorescence
lifetimes of τ = 0.3670 ns, τ = 2.3650 ns and τ = 7.3668 ns (Fig. S7). And
1
2
3
time-dependent experiments showed that the fluorescence intensity of PN-G
remained unchanged (Fig. S8). Moreover, it was interesting to find that PN-G showed
reversible transition (gel−sol) in response to temperature and performed many times

with small fluorescence efficiency loss (Fig. S9).
As is well-known, selectivity and sensitivity are important properties for sensors.
Therefore, we carefully investigated the specific selectivity of PN-G toward various
−
−
−
−
−
3−
2−
4
2−
−
anions. Firstly, a serious of anions (F , Cl , Br , I , AcO , PO , SO , S , HS , ATP,
4
2−
−
2−
2−
−
SO , SCN , CO , NO
3
and CN , 1 equivalent) were diffused into PN-G in
3
3
DMSO (T＞T ). After the temperature cooling down to the Tgel (T＜T ) gradually,
gel
gel
−
−
3−
2−
−
2−
3
2−
−
the results showed that basic ions (F , AcO , PO , CO , CN , SO , S , HS )
4
3
caused a small amount of red shift in the fluorescence spectrum of PN-G, but only
−
CN could lead to complete fluorescence quenching. However, other miscellaneous
−
−
−
2−
2−
−
anions including (Cl , Br , I , SO , NO , ATP, SCN ) did not lead to any
4
3
significant change in the PN-G sensing process as shown in Fig. 2. And make bar
graph to comparison them with error bar. As shown in Fig. S10, No significant
fluorescence quenching was observed for all used interfering ions.
To further explore the optimized condition about the sensing behavior of PN-G
−
toward CN , The sensitivity and lowest fluorescence detection concentrations of
−
PN-G for CN was determined by fluorescent titrations (Fig. 3). The incremental
addition of cyanide (0−0.55 equivalents) to PN-G (5%) at room temperature reveals a
gradual decrease of the strong fluorescence emission at 523 nm with a significant red
shift. At the same time, a visible fluorescence quenched from yellow could be
observed by naked eyes (Fig. 3). This should be attributed to destruction of phenazine
π-π stacking. However, no further change was observed in the fluorescence spectra
−
beyond the addition of 0.55 equivalents of CN (Fig. S11). On the basis of the 3δ/S

−
-10
method, the LODs of PN-G for CN was 4.18×10 M (Fig. S12). The most
−
noteworthy was that the lowest detection limit of supramolecular gel PN-G for CN
−
was much better than most reported fluorescent gel sensors for CN (Table 1) [29, 39,
5
3-55]. This result indicates that PN-G could be used as good fluorescence material
−
for detecting CN in water.
What we predicted that the self-assembly behavior of PN-G could be demonstrated
by XRD through monitoring the molecular spacing (Scheme 2). The XRD patterns of
xerogel PN-G suggested that there was a distances of 3.46 Å at 2θ = 25.74° which
confirmed the π-π stacking consisted of phenazine groups in PN-G (Fig. S13). The
result proved that the orderly arrangement characteristics of PN molecules induce
their assembly into stable supramolecular gel of PN-G. There results were further
1
confirmed by H NMR spectra. As shown in Fig. S14 and Fig. S15, as the PN
concentration increases, all proton peaks on the phenazine aromatic ring shifted
upfield, which suggested that the self-assembled system was formed by π-π stacking
in the solution. Interestingly, Partial peak shift to downfield on the PN alkyl chain,
which shows that Van der Waals interactions also participated in the PN self-assembly
process.
−
The possible mechanism of PN-G interacted with CN was further investigated by
1
H NMR, MS and SEM (Scheme 2). Because PN had poor solubility in DMSO
1
solution, PNM, a compound with similar structure to PN was synthesized for H
−
NMR titration experiments (Fig. S4, Fig. S5 and Fig. 4,).Upon addition of CN in
a
b
c
PNM solution, the signals of protons H , H and H on PNM aromatic hydrocarbon

d
shifted downfield. Meanwhile, the signals of protons H on PNM alkyl group shifted
upfield. These results confirmed that the ubiquitous intermolecular interaction would
−
−
occur between CN and phenazine rings of PNM. Firstly, CN destroyed the π-π
assembly in PNM. To further verify rationality of sensing mechanism, we tested the
−
reaction mixture of PN and CN by mass spectrometer. To our delight, Fig. S16
manifests an increased molecular weight of 27, which was equal to the molecular
−
weight of HCN. CN destroys the π-π stacking of PN, and then PN undergoes a
−
nucleophilic addition reaction with CN , resulting in fluorescence quenched.
−
Finally, the morphologies of PN, PN-G and PN-G with CN were investigated by
scanning electron microscope (SEM). As shown in Fig. 5, PN powder showed
fragment structure (Fig. 5a), and PN-G showed regular large pieces of layered
structure (Fig. 5b), the images demonstrated the idea that PN could self-assemble into
supramolecular gel by π-π stacking interactions and van der waals interaction.
−
However, after adding CN in PN-G, the xerogel showed thin strips are inlaid in
blocks structure (Fig. 5c). The above experiments further support the correctness of
our proposed sensing mechanism.
4
. Conclusion
In summary, we efficiently synthesized a simple organic molecule with 16 alkyl
group 2-(hexadecylthio)oxazolo[4,5-b]phenazine (PN) and investigated its
1
self-assembly behavior by H NMR and XRD. The aggregation formation was found
to be dependent on the π-π stacking interactions and van der waals interaction
between PN molecules. We surveyed the response of PN gel (PN-G) to various

−
anions in water, whereas with the addition of CN and heated from gel to sol, after
−
gelation again, the ability to selected recognize CN unfolding. The yellow
fluorescence quenching of PN-G could be observed by naked eyes. The detection
−
-10
−
limit of PN-G to CN was as low as 4.18×10 M. Detailed analyses reveal that CN
destroyed the π-π assembly in PN-G, and PN-G undergoes a nucleophilic addition
−
reaction with CN .
Acknowledgements
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 (NO: IRT1177).
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Scheme 1 Structure and synthesis of the sensor PN.
Fig. 1 Fluorescence spectra and photograph of supramolecular gel PN-G and sol.

−
-
Fig. 2 Fluorescent spectra of target supramolecular gel PN-G in the presence of CN
ion and other anions (1 equiv.). Inset: photograph showing the change in color of the
−
supramolecular gel of PN-G after addition of CN ion and other anions using
UV-lamp (365 nm) at room temperature.

`
Fig. 3 Fluorescence titration spectra of PN-G (5%) in DMSO solution upon added
−
different concentrations of CN anions; Inset: fluorescent photograph of PN-G and
−
after added CN anions in it. (λ = 390 nm).
ex
−
Table 1 Comparison of the Analytical Performance of the Sensor Molecules for CN .
Ref.
State
solution
solution
solution
solution
polymer
gel
Mechanism
nucleophilic addition
deprotonation
nucleophilic addition
Complexation approach
Complexation approach
nucleophilic addition
LOD−
7
5
5
5
2
3
3
4
5
9
9
4.97 × 10 M
−7
1.48 × 10 M
−7
1.60 × 10 M
−7
5.77 ×10 M
\
-10
This work
4.18 × 10
M

−
Scheme 2 Chemical structures and cartoon representations of PN and CN and the
reaction mechanism in this system.

1
Fig. 4 Partial H NMR spectra of PNM (DMSO–d ) and in the presence of varying
6
−
amounts of CN (1M, D O).
2
Fig. 5 SEM images of (a) PN powder, (b) the large pieces of layered self-assembled
−
from PN-G, (c) the thin strips are inlaid in blocks structure after adding CN in
PN-G.

Highlights
1
2
3
. Constructed a supramolecular gel by self-assembly.
. A novel supramolecular gel for highly selective and sensitive detection of cyanide.
. Taking advantage of a simple mechanism of nucleophilic addition reaction.

Author Statement
Hu Fang: Investigation, Software, Writing- Original draft preparation.
Wen-Juan Qu: Data curation, Writing- Reviewing and Editing, Project administration.
Hao-Hang Yang: Visualization, Investigation.
Jun-Xia He: Supervision.
Hong Yao: Validation, Resources.
Qi Lin: Formal analysis, Funding acquisition.
Tai-Bao Wei: Methodology, Funding acquisition.
You-Ming Zhang: Conceptualization, Funding acquisition.

Declaration of interests
☒
The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐
The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: