Talanta 219 (2020) 121237

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Talanta
journal homepage: www.elsevier.com/locate/talanta

A smart low molecular weight gelator for the triple detection of copper (II), T
mercury (II), and cyanide ions in water resources
Fatemeh Mandegania, Hassan Zali-Boeinia,∗, Zohreh Khayatb, Rosario Scopellitic
a
Department of Chemistry, University of Isfahan, 81746-73441, Isfahan, Iran
b
Department of Chemistry, Jundi Shapur University of Technology, 64615-334, Dezful, Iran
c
Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland

ARTICLE INFO ABSTRACT

Keywords: Novel supramolecular gelators based on quinoline-indolin-2-one structure were synthesized. These gelators
Stimuli-responsive gel formed stable organogels in a mixture of DMSO/H2O (1:1). The scanning electron microscopy (SEM), IR and
Chemosensor NMR spectroscopies, and rheological measurements were used to study the properties of the gels. Among the
Heavy metal ion synthesized compounds, G2 was chosen as the best gelator and utilized as a naked eye chemosensor for the
Detection limit
selective detection of Cu2+ and Hg2+ ions alongside and CN‾ ion as toxic and hazardous materials. The gelator
Cyanide
Molecular logic gate
G2 was selectively transformed into a sol state in the presence of Cu2+ ion alongside with a vivid change of color
from orange to cherry red. Hg2+ ion showed a notable change in color from orange to brick red, but the gel state
remained intact. The detection limit for the gelator G2 toward Cu2+and Hg2+ were 7.25 × 10−6 mol. L−1 and
4.80 × 10−6 mol. L−1 respectively. All the tested anions had no distinct effect on the gel state and/or the color
of G2, while, in the presence of CN‾, although the gel state was again unchanged a drastic color change from
orange to dark purple was observed. The detection limit for G2 toward CN− was 1.36 × 10−4 mol. L−1. The
gelator G2 also operated simultaneously the roles of INH and OR gates in which water, Hg2+, Cu2+ ions are
inputs, and the gel state and absorbance around 600 nm (color change) are outputs.

1. Introduction
Small molecules that are capable of making self-assembled supra-
molecular architectures and entangling and immobilizing solvent mo-
lecules, may produce supramolecular gels, which are defined generally
as Low Molecular Weight Gelators (LMWGs). In these systems, the
driving forces responsible for the gel formation are generally non-
covalent interactions such as hydrogen bonding, van der Waals forces of
long alkyl chains, π-π stacking, and dipole-dipole interactions [1,2].
These intermolecular physical forces are weak and can be easily af-
fected by an external environmental stimulus such as heat [3], ions [4],
pH [5], light [6,7], ultrasound [8,9], electric or magnetic fields [10],
and oxidative/reductive reactions [11]. Nowadays, considerable efforts
have been devoted to the development of smart supramolecular gels
due to their applications in diverse fields, including tissue engineering
and drug delivery [12,13], optoelectronic devices [14], pollutant re-
moval [15], reaction vessels and catalysts [16] and so on [17–21].
Moreover, the reversible nature of the self-assembling process marks
the supramolecular gels as excellent candidates for sensing applications
[22–25].
Due to the biological importance and problematic issues of the ex-
istence of toxic and heavy transition metal ions in biological systems
and the environment [26–28], design, synthesis, and application of
efficient receptors for the selective recognition of these ions are still
matter of concerns in supramolecular chemistry [29,30]. Copper, at
definite levels, plays an important function in numerous physiological
processes in the human body [31]. By contrast, excess of copper ion can
cause adverse effects on human health and lead to various diseases such
as increased blood pressure and neurodegenerative diseases [32]. Fur-
thermore, copper is a significant environmental pollutant as it is used in
various industries worldwide [33]. The maximum allowed copper in
drinking water has been set to be 1.3 ppm (2.0 × 10−5 mol. L−1) by
the U.S. Environmental Protection Agency (EPA) [34,35]. Mercury is
also one of the most toxic heavy metals, which may enter into water
resources or food chain, therefore causing many serious health pro-
blems in the brain, kidney, and central nervous system (CNS) even at
low concentrations [36,37]. The U.S. EPA directive for the acceptable
concentration of mercury in drinking water is 2 ppb (9.97 × 10−9 mol.
L−1) [38]. Similarly, the crucial role of anions in various fields, in-
cluding biology, medicine, industrial raw materials, and the

∗
Corresponding author.
E-mail address: h.zali@chem.ui.ac.ir (H. Zali-Boeini).

https://doi.org/10.1016/j.talanta.2020.121237
Received 22 April 2020; Received in revised form 5 June 2020; Accepted 6 June 2020
Available online 03 July 2020
0039-9140/ © 2020 Elsevier B.V. All rights reserved.
F. Mandegani, et al.
corresponding environmental concerns, urges the development of
highly sensitive anion sensors [39–41]. Among various anions, the
detection of cyanide ion, as an extremely poisonous but indispensable
chemical in industry, is an attractive issue [42–44]. Even minimal
amounts of cyanide might consequence in deeply damage to numerous
biological functions and leading to convulsion, vomiting, un-
consciousness, and eventual death [45–47]. The maximum allowed
concentration of cyanide in drinking water is only 1.9 × 10−6 mol. L−1
by the World Health Organization (WHO) [48]. Up to the present, there
have been numerous reports on supramolecular chemosensors for the
detection of metal cations and anions [49–55]. However, supramole-
cular gel-based sensors for the detection of these ion species are still
rare [56–61]. Accordingly, due to easy naked-eye detection via sol-gel
transition, the ion responsive supramolecular gels are favorable to de-
velop. Following of our previous research on the LMWG's [62,63], in
this work, new supramolecular organogelators (aqueous/organogela-
tors) composed of indolin-2-one and quinoline moieties bearing a long
chain N- alkyl substituted amide group were designed and synthesized.
Two of the synthesized compounds (G2 and G3) were able to form
stable gels, but compound G2 was superior to G3. Hence, compound G2
was further investigated as a highly selective and sensitive sensor for
the detection of Cu2+, Hg2+, and CN‾ in aqueous media at room
temperature.
2. Results and discussion
2.1. Synthetic pathway
Compounds G1-G3 were prepared in three steps using isatin
(Scheme 1). 1H NMR, 13C NMR, and FT-IR analyses were used to
characterize the final products.
The structure of compound B2 (the precursor of G2, R = n-C12H25)
was further established by single-crystal X-ray analysis (Fig. 1,
CCDC1993195).
2.2. Gelation study
The gelation ability of compounds G1-G3 was inspected in different
types of organic solvents by the vial inversion technique. In a 2 mL vial,
the proper amount of gelator compound was dissolved upon heating in
the desired organic solvent (1 ml) to form a homogeneous solution.
Then, the solution was slowly allowed to cool to room temperature,
shaken, and left aside. After 30 min, the vial inversion test was per-
formed. We found that the compounds G1-G3 could not form any gels
in all tested single-solvent methods. Using water-miscible organic sol-
vents, the solution was cooled, and the same volume of water was
added. Thereafter, the tube inversion test was executed after 20 min.
Among these solvents, G2 and G3 formed stable and durable gels in
DMSO/H2O (1:1). Most likely, the addition of water enhances the sol-
vophobic interactions and causes the hydrophilic–lipophilic balance of
solvent, which acts as a driving force for the gel formation in DMSO/
H2O (1:1) mixture. In order to study the thermal stability of the gels,
Scheme 1. Synthetic pathway for the compounds G1-G3.
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Talanta 219 (2020) 121237
Tgel value of each gelator G2 and G3 in DMSO/H2O (1:1) were mea-
sured. Tgel values of G2 and G3 at different concentrations were also
recorded. As shown in Fig. 2, while the gelator concentration increases
from 1 to 5% w/v, Tgel values grow from 51 °C to 74 °C for G2 and
54 °C–78 °C for G3. The increase in Tgel values is most likely indorsed to
the superior supramolecular interactions between gelator molecules at
greater concentrations such as π–π stacking, hydrogen bonding, the
solvophobic interaction, and van der Waals interactions of lengthy alkyl
chain.
As shown in Fig. 2, the minimum gelation concentration (MGC) of
G2 and G3 was 1% w/v, and therefore, they are called supergelators.
The above results indicate that G2 and G3 could form robust gels,
comprising stable supramolecular frameworks with high thermal sta-
bility in DMSO/H2O. Among the three synthesized compounds, even
though both compounds G2 and G3 were strong gelators and exhibited
nearly instant gelation, G2 has higher stability compared to G3. Our
research revealed that G2 gel was firm in a secured tube for at least six
months at 25 °C, while G3 gel was stable only up to five weeks. Then G2
was selected for additional studies as a chemosensor.
2.3. Morphological and rheological studies
The aggregation morphology of DMSO/H2O (1:1) xerogels of G2
was investigated by scanning electron microscopy (SEM). As shown in
Fig. 3, the closely spaced plate-like matrix is responsible for the gel
formation.
Rheological studies were utilized to investigate the viscoelastic be-
havior of the gel. Fig. 4 shows the stress and frequency response of 1%
DMSO/H2O (1:1) gel of G2. Variation of stress amplitudes (graph A),
frequencies (graph B), and shear stress (graph C) for the gel showed
that the dynamic storage modulus G′ was constantly higher than the
corresponding loss modulus G″ over the studied range. The stress sweep
test at a costant frequency (ω = 1 rad/s) provided an almost linear
response of both G′ and G″ at about 0.1–1% strain. In frequency sweep
experiment under constant strain value of 0.5%, both G′ and G″ were
frequency independent over the entire experiment range, and displayed
more than five times higher magnitude of G′ than those of G″ at any
frequency. Moreover, the shear stress sweep trial showed the yield
stress point at 44.8 Pa. The abovementioned results, especially the G′
dominance and frequency-independence supported the viscoelastic
nature of the gel.
2.4. Investigation of the gelation mechanism
To investigate the H-bonding role of quinolone-OH in the self-as-
sembling process, the 1H NMR spectra of G2 in DMSO‑d6 and upon the
addition of D2O in DMSO‑d6 was recorded. As shown in Fig. 5, the
quinoline hydroxyl proton peak was experienced an upfield shift from
10.54 ppm to a broad peak at 9.26 ppm upon the addition of D2O. These
results demonstrate the strong participation of the OH functional group
in hydrogen bonding interaction and the self-assembling process of G2
with the aid of D2O.
F. Mandegani, et al.
Fig. 1. ORTEP view of B2. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as small spheres of arbitrary radii.
Fig. 2. Plots of Tgel values of G2 and G3 against the gelator concentration in DMSO/H2O (1:1).
Fig. 3. SEM images of G2 xerogel obtained from 1% gel in DMSO/H2O (1: 1, v/
v).
To further investigate the H-bonding role of quinoline-OH in the
self-assembling process, FT-IR spectra of G2 in powder, xerogel, and
DMSO/H2O gel forms were also recorded, and compared (Fig. 6).
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Talanta 219 (2020) 121237
As displayed in Fig. 6, in the powder and xerogel state, the O–H
stretching band of hydroxyl group appears at 3277 cm−1. In contrast,
the corresponding band was shifted to a higher wavenumber alongside
with a broadening in the gel state with the value of 3413 cm−1 re-
ceptively. These findings suggest that more likely intermolecular hy-
drogen bonding exist and predominate in the gel states.
According to the abovementioned studies, the self-assembling pro-
cess for the compound G2 can be attributed to the π-π stacking of the
aromatic ring of the quinoline and the indoline moieties, hydrogen
bonding of hydroxyl group, and the hydrophobic interactions of long
alkyl chain in organic-aqueous media (Fig. 7).
2.5. Investigation of cation-responsive behavior
The cation responsive nature of the G2 in DMSO/H2O (1:1) was
investigated by adding nitrate salt solutions of several metal ions (Al3+,
Pb2+, Cu2+, Hg2+, Cd2+, Mg2+, Zn2+) at room temperature. That way,
DMSO solutions of G2 were prepared in 2 mL vials, and equal volumes
of the solutions of different cations were added and mixed (the molar
concentration of G2 and metal ions were 4.2 × 10−2 mol. L−1, 2% w/
v). Afterward, the vials were set aside for 30 min, and the vial inversion
examination was performed. Among seven cations were examined, an
aqueous solution of Cu2+ was the only metal ion that prevented gel
formation along with a color change from orange to cherry red.
Additionally, in the presence of Hg2+ ions, the gel color was altered
from orange to brick red, but the gel sate remained unchanged. Fig. 8
F. Mandegani, et al. Talanta 219 (2020) 121237

Fig. 4. (A) Rheological studies of 1 wt % of G2 gel in DMSO/H2O (v/v, 1:1); (B) Strain sweep under constant frequency of 1 rad/s; (C) Frequency sweep under
constant 0.5% strain.

shows that other metal cations make no notable changes on the formed
gels. Since, the gel to sol switch and the color transformation in the gel-
gel state was selective; it was used for the oculus detection of Cu2+ and
Hg2+ in water.
The UV absorption spectra of gelator G2 (10−4 mol. L−1) in the
presence of 1 equivalent of various metal cations (Al3+, Pb2+, Cu2+,
Hg2+, Cd2+, Mg2+, Zn2+) in DMSO were recorded. From Fig. 9, it can
be seen that the absorption peak around 290 nm was dramatically rose
upon the addition of Cu2+ or Hg2+ ions into a G2 solution. No sig-
nificant spectral change was observed in the presence of other metal
cations, implying that there is no bonding or feeble interactions be-
tween the gelator G2 and the other metal cations.
To measure the sensitivity of G2 toward Cu2+ and Hg2+ ions, dif-
ferent concentrations of Cu2+ and Hg2+ were added to DMSO solutions
of G2 (10−5 mol. L−1), and their spectra were recorded. As shown in
Fig. 10(A) and (B), upon a progressive increase in the concentration of
Cu2+ and Hg2+, the absorbance peaks at 290 nm and 269 nm, were
gradually increased. A good linear relationship was observed between
the absorbance intensity at 290 nm and the concentration of Cu2+ (0–1
equiv.) (Fig. 10C) and absorbance intensity at 269 nm and concentra-
tion of Hg2+ (0–1 equiv.) (Fig. 10D). Thus, the detection limit of G2 for
Cu2+ and Hg2+ was found to be about 7.25 × 10−6 mol. L−1 and
4.80 × 10−6 mol. L−1 respectively, under the examination conditions.
Although the detection limit of G2 for Hg2+ was very far from the EPA

Fig. 5. 1H NMR spectra of G2 in DMSO‑d6 and upon D2O addition.

Fig. 6. FTIR spectra of powder, xerogel and DMSO/H2O gel of G2.

4
F. Mandegani, et al. Talanta 219 (2020) 121237

Fig. 7. A proposed self-assembling mechanism for the gel formation of G2 in DMSO/H2O.

Fig. 8. Photograph of gel-to-sol transformation and color change of G2 in DMSO solution (4.2 × 10−2 mol. L−1) upon addition of (1 equiv.) of aqueous cations. (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

acceptable concentration of mercury, the detection limit for the Cu2+
was quite bellow the EPA allowed amount of copper ion in drinking
water. These results indicate that G2 can be employed for quantitati-
veand rather fast detection of Cu2+ and Hg2+ over a wide range with
good sensitivity.
Additionally, to determine the binding stoichiometry of G2 with
Cu2+ and Hg2+ ions, the Job's plot analysis was carried out. As seen in
Fig. 11(A) and (B), the Job's plot analysis showed a 1:1 stoichiometry
for both G2: Hg2+ and G2: Cu2+.
To study the interaction behavior between G2 and Hg2+, 1H NMR
spectrum of G2 in the presence of Hg2+ was recorded, and then the
spectra were compared. It is evident from Fig. 12 that in the presence of

Fig. 9. The UV–Vis spectra of G2 (10−4 mol. L−1) in the presence of different metal cations (1 equiv.) in DMSO.

5
F. Mandegani, et al. Talanta 219 (2020) 121237

Fig. 10. (A) Absorbance spectra of G2 (10−5 mol. L−1) upon the addition of Cu2+ (0–1 equiv.) and (B) Hg2+ (0–1 equiv.) in DMSO/H2O (95/5, v/v); (C) linear
relationship between the absorbance intensity at 290 nm and the concentration of Cu2+ (0–1 equiv.) and (D) the absorbance intensity at 268 nm and the con-
centration of Hg2+ (0–1 equiv.). The error bars were based on three duplicate experiments.

Hg2+ ion, the hydroxyl proton peak has wholly vanished. This ob-
servation suggests that there is a strong interaction between the OH
group and N atoms of quinoline moiety and Hg2+ ion.
Scheme 2 is shown the suggested modes of interaction for the G2-
Cu2+ and G2-Hg2+. Accordingly, when compound G2 interact with
Cu2+, the mechanism of sensing can be accredited to the chelation of
G2 and Cu2+ thus forming a complex adduct, and destroying the co-
planarity of the π-conjugated systems, leading to the observed color
change. Moreover, the G2-Cu2+ interaction avoids intermolecular hy-
drogen bonding and weakens the π–π stacking interactions of the aro-
matic rings of G2 and prevents the gel formation process. According to
the observed results, after the addition of Hg2+ to a DMSO solution of
G2, it is more likely a sandwich-like organometallic Hg2+-metallogel
produces in which a color change observes but the gel state remains
unchanged.

Fig. 11. (A) Job's plot for the interaction of G2 with Hg2+ in aqueous DMSO (B) Job's plot for the interaction of G2 with Cu2+ in aqueous DMSO. The total
concentration of ligand and metal ions was 10−5 mol. L−1.

6
F. Mandegani, et al. Talanta 219 (2020) 121237

Fig. 12. 1H NMR spectra of G2 in the presence of 1.0 equiv. of Hg (NO3)2 in DMSO‑d6

Scheme 2. Proposed sensing mechanisms of G2 for Cu2+ and Hg2+ ions.

2.6. Investigation of anion responsive behaviour
To evaluate the G2 response toward anions, an aqueous solution of
various anions as their sodium salt was added to DMSO solutions of G2
under the same conditions as in metal ions. As can be seen in Fig. 13,
the gel formation occurred in all vials, but surprisingly in the presence
of cyanide anion, an extreme color change from orange to dark purple
was observed. These observations remark that the gelator G2 can act as
a visual sensor to detect CN‾ ions selectively in the aqueous media.
Besides, to determine the selectivity of G2 towards the other anions,
the UV absorption spectra of G2 (10−4 mol. L−1) in the presence of 1
equivalent of various common anions including AcO‾, CN‾, F‾, Br‾, I‾,
and HS‾ were added to DMSO solution of G2, and their spectral changes
were recorded. As shown in Fig. 14, significant changes in the ab-
sorption spectra were only observed upon the addition of CN‾ ion. In
contrast, the addition of the other anions to the G2 solution showed
negligible differences.
Based on UV–Vis spectrophotometric titrations, the sensing prop-
erties of the G2 (10−5 mol. L−1) were examined by adding a standard
solution of CN‾ to the DMSO solution of G2 (Fig. 15 A). After addition
of CN‾ ion (0–1 equiv.), the absorption intensity around 600 nm was
increased slowly, which is characteristic of the observed dark purple
color. As realized in Fig. 15 B, there is a good linear relationship be-
tween the absorbance intensity at 600 nm and the concentration of CN‾
with a detection limit of 1.36 × 10−4 mol. L−1.
Finally, to study the nature of the interaction between the gelator
G2 and cyanide ion, 1H NMR experiments were conducted. Fig. 16A
shows the 1H NMR spectra of G2 in the absence and the presence of 1.0
equivalent of CN‾ ion in DMSO‑d6. It was found that the addition of 1.0
equiv. of CN‾ results in significant chemical shift and demonstrates the
intense interaction between G2 and CN‾ ion. Presumably, the observed
selectivity for the cyanide ion among the other tested anions can be
attributed to the contribution of an entirely different interaction me-
chanism. We assumed that G2 at first undergoes a pseudo-Michael at-
tack by CN‾ ion and consequently, after ring closure alongside the
proton shift, transforms to the shown fully conjugated anion (Fig. 16B)
responsible for the dark purple color. All the above mentioned results
indicate that G2 can be used as an extremely selective and fast

Fig. 13. Photograph of gel formation and color change of G2 in DMSO solution (4.2 × 10−2 mol. L−1) upon addition of aqueous solution of anions (1 equiv.). (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

7
F. Mandegani, et al. Talanta 219 (2020) 121237

Fig. 14. UV spectra of G2 (10−4 mol. L−1) in DMSO solution upon the addition of various anions (1equiv.).

chemosensor for the detection of CN‾ ion in the environmental water logic gate system (the INH and OR logic gate) based on gelator G2 are
resources. depicted in Fig. 17.

2.7. Gel function as molecular logic gate 3. Conclusions

It is well known that molecular switches transform input stimuli
into output signals. The role of compound G2 as the molecular opera-
tion of logic gate was also considered and established that G2 imple-
ments simultaneously the functions of Inhibit (INH) and OR gates.
Inputs for this combinational logic gate were water, Cu2+, and Hg2+
ions and the outputs were formation of gel and color change (absor-
bance at 600 nm). The truth table and the corresponding scheme for the
Novel low-molecular weight and stimuli-responsive supramolecular
gelators based on indolin-2-one structure have been synthesized via
three simple steps starting from isatin, and their gelation character-
istics, spectral data, and applications as chemosensor were studied.
Excellent gelation ability was observed for the gelators G2 and G3 in
some water-miscible solvents, but the best results were found for G2 in
DMSO. Compound G2 was utilized as an effective colorimetric sensor to

Fig. 15. (A) UV titration of G2 (10−5 mol. L−1) with CN‾ (0–1 equiv.) in DMSO/H2O (95/5, v/v); (B) linear relationship between the absorbance intensity at 290 nm
and concentration of CN‾. The error bars were based on three duplicate experiments.

8
F. Mandegani, et al.
Fig. 16. (A) Partial 1H NMR spectra of G2 and G2 + 1 equiv. CN‾ in DMSO‑d6; (B) A proposed mechanism for the interaction of CN‾ with G2.
sense Cu2+, Hg2+, and CN‾ ions between numerous metal ions and
anions in aqueous media. While Cu2+ ion prohibited the formation of
gel together with a color change from orange to cherry-red, the gel state
in the presence of Hg2+ remained intact, and only a color change to
brick red was detected. The calculated detection limit for Cu2+ was
found to be 7.25 × 10−6 mol. L−1, which is about three times lower
than the EPA maximum allowed concentration for Cu2+. More inter-
estingly, G2 was able to detect CN‾ ion selectively among various en-
vironmentally important anions. We found that the gel color was se-
lectively changed from orange to a dark purple color in the presence of
CN‾ ion with high sensitivity. The gelator G2, also as a molecular logic
gate, operates synchronously the functions of Inhibit (INH) and OR
gates in which water, Hg2+, and Cu2+ ions stands for inputs and the gel
formation and absorbance are outputs. Consequently, G2 was proved to
be a successful and efficient chemosensor for fast instrument-free de-
tection of toxic metal ions such as Cu2+ and Hg2+ besides CN‾ as a
toxic anion in water resources, which are huge environmental issues.
4. Experimental
4.1. Procedure for the synthesis of compounds G1-G3
Compounds G1-G3 were synthesized in three steps from isatin
(Scheme 1):
The synthetic procedures for the preparation of N-alkyl isatin deri-
vatives are reported in supporting information. N-alkyl isatin (5 mmol)
and 2-Methyl-8-quinolinol (5 mmol) were added to dried acetic anhy-
dride (5 ml). Then the reaction mixture was stirred and refluxed for 3 h
9
Talanta 219 (2020) 121237
at 138 °C. Completion of the reaction was monitored by thin-layer
chromatography (TLC). After cooling down to room temperature, the
resulting mixture was treated with 30 ml of ice-cooled water, extracted
with ethyl acetate (3 × 30 ml), and the collected organic layers were
dried over anhydrous magnesium sulfate. Removing the solvent after
filtration afforded the crude products as their acetate esters. These were
further purified by silica gel column chromatography with hexane:
ethyl acetate (10:1) as the eluent to yield pure compounds B1–B3.
Compounds B1–B3 (5 mmol) were added to a solution of
NaOMe–MeOH (1 mol. L−1, 8 ml) and the reaction mixtures were
stirred at 65 °C for 1 h. After completion of the reaction, the reaction
mixtures were cooled to room temperature. The reaction mixture was
neutralized by adding a solution of NH4Cl, and the organic layer was
extracted with ethyl acetate (3 × 15 ml). The collected organic layer
was dried over anhydrous magnesium sulfate and concentrated under
reduced pressure. The crude product was purified by silica gel column
chromatography using hexane: ethyl acetate (12:1) as the eluent to
yield pure G1-G3 as deep orange powders.
4.2. Procedure for Tgel measurement: To measure gel to the sol
transition temperature, gel samples of G2 and G3 in DMSO/H2O (1:1)
at different concentrations (1–5%) were prepared. Using the ‘inverse
flow’ method, the gelation temperature (Tgel) for the gels of G2 and G3
were determined. After the gelation, the inverted vial was placed in a
temperature-regulated silicone oil bath. The temperature of the oil bath
was progressively increased, and the temperature at which the gel fell
from the bottom of the vial was taken as Tgel for that sample.
4.3. Investigation of the sensing ability of G2: To evaluate the
sensing ability of G2, aqueous solutions of metal ions or anions were
F. Mandegani, et al.
Fig. 17. Molecular implementation and truth table of INH and OR logic gates
for compound G2.
added to a DMSO solution (final concentration of ligand and ions were
4 × 10−2 mol. L−1), slightly shaken, and set aside. After 30 min, the
vial inversion test was done, and the color changes and/or gel to sol
transitions were recorded.
Aqueous solutions (10−5 mol. L−1) of the metal ions of Cd2+, Hg2+,
Mg2+, Al3+, Cu2+, Pb2+ and Zn2+ as nitrate salts and F‾, Br‾, I‾, AcO‾
and CN‾ as sodium salts were prepared in water. UV–Vis measurements
were performed using 10−5 mol. L−1of G2 in the DMSO solution at
25 °C.
4.4. Preparation of single crystals of B2: For preparing the high-
quality single crystals of B2 (acetate ester and precursor of G2) for the
single-crystal X-ray analysis, compound B2 (4 mg) was dissolved in 1-
Propanol (1 ml) and heated to dissolve. After cooling down to ambient
temperature, distilled water (3 drops) was added, slightly shaken up the
vial, set aside, and after 2 h beautiful single crystals of compound B2
were formed.
CRediT authorship contribution statement
Fatemeh Mandegani: Investigation, Methodology, Writing - original
draft. Hassan Zali-Boeini: Conceptualization, Supervision, Writing - re-
view & editing, Data curation. Zohreh Khayat: Visualization, Validation.
Rosario Scopelliti: Resources, Formal analysis.
Declaration of competing interest
Authors confirm that there is no competing interests to declare.
Acknowledgements
We are grateful to the University of Isfahan research council for
financial support of this work.
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Talanta 219 (2020) 121237
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.talanta.2020.121237.
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