Triphenylamine based lab-on-a-molecule for the highly selective and sensitive detection of Zn2+ and CN- in aqueous solution

Article abstract of DOI:10.1039/c6ra17354c

Simple dual sensing of Zn²⁺ and CN^- was reported for the first time using the triphenylamine based lab-on-a-molecule TATP in both UV-Vis and fluorescence channels over other tested ions. Meanwhile, the sensing mechanism for both title ions was further studied using NMR titration and DFT calculations.

Full text of DOI:10.1039/c6ra17354c

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Triphenylamine based lab-on-a-molecule for the highly selective
2
+
-
and sensitive detection of Zn and CN in aqueous solution
Received 00th January 20xx,
Accepted 00th January 20xx
a
a,*
a
a
a
b,*
c,*
Shichao Sun , Qinghai Shu , Pengchao Lin , Yanyue Li , Shaohua Jin , Xin Chen , Dequan Wang
DOI: 10.1039/x0xx00000x
www.rsc.org/
2
+
-
54
A simple dual sensing of Zn and CN was reported for the isomerization of C=N could be used to detect metal ions via
4
2-44
first time by triphenylamine based lab-on-a-molecule TATP in CHEF effect
. Thus we designed a new probe TATP with
both UV-Vis and fluorescence channels over other tested ions. well structured triphenylamine linked with C=N as recognition
Meanwhile, the sensing mechanism of both title ions was further receptor, and cooperated with phenolic hydroxyl group to form
studied by NMR titration and DFT calculations.
another recognition site for metal ions. As a result, TATP-
2+
performed excellent sensing behaviour towards Zn and CN
among a series of cations and anions, respectively comparing
with recently reported probes. (Table 1)
The selective and sensitive detection of ions has emerged as
an area of great interest in biological, chemical and
environmental processes. However, most of the reported ion
sensors are effective only in selective recognition of one
particular analyte due to the specific structural properties.
1-11
Therefore, the development of lab-on-a-molecule
which
1
2-15
has multiple recognition capability
still a challenging task.
Among metal ions, Zn
in competitive fashion is
2+
is the second most abundant
1
6
essential trace element in human body . It plays an important
mediation role in lots of physiological processes including
regulation of gene expression, apoptosis,1 co-factors in
Figure 1 The synthetic route of probe TATP.
7
metalloenzyme catalysis and neurotransmission .
On the other hand, cyanide is one of the most concerned
18-20
anions due to its high toxicity
and reactivity. It is
extensively produced in large quantities and applied in gold
mining, plastics production and other industrial activities.
2+
-
Therefore, the detection of Zn and CN are particularly
concerned in many areas. Although some of the probes have
2
+ 21-31,49-51
- 32-
been reported for the detection of either Zn
or CN
41,52,53
,
to the best of our knowledge, a simple sensor that can
2+
-
detect both Zn and CN competitively has rarely been reported.
As the cyanide shows a high activity of nucleophilic addition
to double bonds, the easily constructed reaction site C=N was
herein ultilized for the recognition of cyanide. Further, the
Figure 2 View of the crystal structure of TATP. Color code: C, gray;
H, white; N, blue; O, red. The deposit CCDC number: 1476312.
a.
School of Materials Science & Engineering, Beijing Institute of Technology,
Beijing, China. Email: qhshu121@bit.edu.cn
State key Laboratory of Oncology in South China, Collaborative Innovation
Center of Cancer Medicine, Sun Yat-Sen University Cancer Center, Guangzhou,
China. Tel: +86-20-87343193;Email: chenxin@sysucc.org.cn.
Institute of Theoretical Chemistry, Jilin University, Changchun, China. Email:
b.
As shown in Fig. 1, TATP could be readily prepared by
reduction of tris(4-nitrophenyl)amine, followed by aldimine
condensation with salicylide. The structure of TATP was
confirmed by NMR, mass spectroscopy and elementary
analysis. Crystal of TATP (Fig. 2), suitable for single-crystal
X-ray diffraction, was obtained by slow evaporation from
c.
dequan_wang@jlu.edu.cn..
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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J. Name., 2013, 00, 1-3 | 1
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mixture solution (ethyl acetate/ dichloromethane = 4:1, v/v) at bond turned to intermolecular hydrogen bond dueViteow AtrhtieclemOneltinael
room temperature, displaying as monoclinic crystal system complex’s formation.
DOI: 10.1039/C6RA17354C
with space group P21/c.
Consistent with the change of fluorescence spectrum, the
solution of TATP resulted in an immediate color change from
2
+
colorless to yellow with Zn , indicating that TATP can
Results and discussion
2+
serve as a ‘naked-eye’ Zn indicator.
From the fluorescence titration profiles (Fig. 3a), the
association constant for TATP-Zn in 0.1 M Tris-ClO buffer
2
+
Selective cation sensing of Zn by TATP
2+
4
The UV-Vis and fluorescence of TATP were investigated in
.1 M Tris-ClO buffer solution (pH = 7.24, DMF: buffer = 1 / 2, v /
4
v) by the presence of various mental ions (as perchlorate salts):
solution (pH = 7.24, DMF: buffer = 1 / 2, v / v) was determined as
1
9
-2
0
1.68 × 10
M
by the Hill equation. A Job plot indicated 1:3
2
+
stoichiometric complexation of TATP with Zn (Fig. S5).
The detection limit of TATP for the analysis of Zn2+ ion
was determined as 14 nM. Compare to the well-known Zn
sensor, TATP has shown a highly selective and sensitive
response to Zn over other various cations with a nanomolar
detection limit.
Further, the selectivity toward Zn was ascertained by the
+
2+
2+
2+
2+
2+
2+
2+
2+
2+
Ag , Ba , Ca , Cd , Co , Cu , Hg , Ni , Pb and Zn .
Fig. S4a showed no significant variations in the absorption
spectrum of TATP among most of the added cations except for
2+
2+
2
+
Zn which exhibited a red shift from 412 nm to 425 nm.
6
5
5
5
5
5
5
5
Host+Zn2+
Host+Zn2++ Xn+
6
5
5
5
5
(
a)
1x10
9x10
1
8
6
4
2
.0x10
.0x10
.0x10
.0x10
.0x10
2
(b)
R
=0.996
2+
8
x10
x10
7
6
6
6
6
6
6
6
5
4.0x10
6x10
2
R
=0.997
5
x10
x10
4
3.5x10
3.0x10
competition experiments. As shown in Fig. 3b, TATP was
3x10 0.0 0.5 1.0 1.5 2.0 2.5 3.0
2+
2+
[
Zn ]/[Host]
treated with 50 eqv. of Zn in the presence of other metal
2
.5x10
.0x10
2
ions of the same concentration, no significant changes in the
fluorescence intensities or emission wavelength was found in
1.5x10
.0x10
5.0x10
.0
1
0
.0
2+
the presence of other metal ions, indicated that TATP–Zn
0
450
500
550
600
650
700
750
1
2
3
4
5
6
7
8
9
10
system was hardly affected by these coexistent metal ions.
Wavelength / nm
Cations
Thus, TATP can be used as selective and sensitive fluorescent
sensor for Zn determination.
Figure 3 Fluorescence spectra (λex = 350 nm) of TATP (10 μM)
2+
2
+
2+
upon addition of (a) increasing concentrations of Zn and (b) Zn in
the presence of other competitive metal ions in 0.1 M Tris-ClO4
buffer solution (pH = 7.24, DMF: buffer = 1 / 2, v / v). Inset: The
(
a)
6
6
6
6
6
5
5
5
1
.8x10
-
Host+CN
Host+CN-+other ions
1.6x10
1.4x10
1.2x10
1.0x10
(b)
6
6
5
5
0eq
R =0.994
2
1
.6x10
2
+
emission intensity of TATP at 565 nm as a function of Zn
8.0x10
n+
+
2+
2+
2+
2+
1.2x10
8.0x10
6.0x10
4.0x10
1.0x10
5.0x10
5
4
concentration. [X = Ag (1), Ba (2), Ca (3), Cd (4), Co (5),
0
10
20-
30
40
50
[
CN ]/[Host]
2
+
2+
2+
2+
2+
Cu (6), Hg (7), Ni (8), Pb (9), Zn (10)]
50eq
4.0x10
From the emission of TATP (Fig. S4b), it exhibited a
0
.0
prominent fluorescence enhancement at 565 nm upon addition
450
500
550
600
650
700
750
0.0
1
2
3
4
5
6
7
2+
Wavelength / nm
Anions
of Zn , which could be attributed to the formation of a rigid
2+
system after binding with Zn , causing the chelation-
Figure 4 Fluorescence spectra (λ = 350 nm) of TATP (10μM)
in the presence of (a) increasing concentrations of CN and (b)
CN in the presence of other competitive anions in 0.1 M Tris-ClO4
ex
4
2-44
-
enhanced fluorescence (CHEF) effect
that inhibits the C=N
-
isomerisation. This also can be verified by a small red shift of
1
1
3 nm in the UV-Vis spectra (Fig. S4a) and H NMR titration buffer solution (pH = 7.24, DMF: buffer = 1 / 2, v / v). Inset: The
-
experiment (Fig. S12), in which the sharp peak of –OH fluorescence intensity of TATP at 565 nm as a function of [CN ]
becomes gentle, suggesting that the intramolecular hydrogen [X = F (1), AcO (2), Cl (3), Br (4), I (5), H PO (6), PF (7)]
.
n-
-
-
-
-
-
-
4
-
2
6
Figure 5 The proposed sensing mechanism of TATP.
2
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Table 1. Comparison between our work and other reported probes in recent years
Probe for Zinc ions
Probe for Cyanide
Compounds
TATP in our work
Compounds
LOD
Ref.
-
LOD
Ref.
-
TATP in our work
14 nM
0.37 μM
-
11
−7
6
.3×10
M
22
2.8× 10
M
33
−
7
7
.25 × 10
M
24
24
25
1.5 μM
34
35
35
−
7
3
.08 × 10
M
0.478 μM
1.66 μM
0
.01 μM
−7
3
.2 μM
49
3.2× 10
M
38
4
.6 μM
.4 μM
50
51
1.6 μM
52
53
5
37 nM
－
Selective anion sensing of CN by TATP
The UV-Vis and fluorescence spectra (Fig. S6a) of TATP
were investigated in 0.1 M Tris-ClO4 buffer solution (pH =
7
.24, DMF: buffer = 1 / 2, v / v) by the presence of various
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anions (as n-tetrabutylammonium salts): F , AcO , Cl , Br ,
Journal Name
-
-
-
-
View Article Online
DOI: 10.1039/C6RA17354C
-
-
-
-
I , H PO , PF and CN . The selective response in absorbance of
2
4
6
TATP at 414 nm decreased and a new band at 512 nm emerged
-
only in the presence of CN , along with the solution color change
from colorless to brown (Fig. S6b inset),
intramolecular charge transfer (ICT) mechanism
indicating
by the
-
4
5-47
clear isosbestic point at 461 nm between TATP and CN
upon addition of excessive cyanide (Fig. S7). Meanwhile, the
strong emission quenching effect at 565 nm was only
-
observed upon addition of CN (Fig. S6b).
-
The recognition properties of TATP with CN were further
studied by absorption titration (Fig. S7) and fluorescence
titration (Fig. 4a) experiments. As shown in Fig. 4a, the
continuous emission quenching at 379 nm was observed after
-
addition of CN . The Job plot for the binding between TATP
-
and CN exhibited a 1:3 stoichiometry (Fig. S9) as depicted in
Figure
6
HOMO and LUMO diagrams of (a) TATP (b)
Fig. 5. From the fluorescence titration data, the apparent
-
2+
-
TATP+3CN (c) TATP+3Zn in the gas phase.
association constant for TATP and CN was determined as
3
1
.7 × 10 using the nonlinear-fitting analysis of the change in
Finally, the cellular imaming of TATP in the presence of
target ions were also carried out (Fig. 7). It could be found that
TATP was aggregated in quasi-water matrix instead of taken in cells,
which weakened its reaction with ions. Nevertheless, a slight
emission enhancement could be seen in the presence of zinc and
cyanide ions. Comparing with the results observed in solution, the
ion recognition performance of probe TATP was not so obvious
because its water solubility is not good enough to perform a
biological experiment.
2
48
the absorbance at 565 nm ( R = 0.994 ), and the detection
limit of TATP for the analysis of CN could be realized as 5
-
μM based on the fluorescence titration experiments, and 0.37
μM the UV-vis absorb, which lower than the WHO drinking
3
4,38
water standard 1.9μM
.
-
The selectivity toward CN was further ascertained by the
competition experiment. As shown in Fig. 4b, TATP was
-
treated with 50 equivalents of CN in the presence of other
anions of the same concentration. Relatively low interference
-
was observed for the detection of CN in the presence of
other anions. Thus TATP can be used as a selective fluorescent
-
sensor toward CN in the presence of most competing anions.
1
-
To make certain the sensing mechanism of TATP to CN ,
H NMR titration experiment was performed as shown in
1
Fig. S13. The peak of –OH at 13.20 ppm disappeared rapidly
after cyanide addition due to the deprotonation effect.
Meanwhile, the peak of –N=CH
－ at 9.00 ppm weakened and a
new peak at around 10.20 ppm raised which was
considered to be –C-NH-, further proved the cyanide addition
mechanism and thus destroyed the conjugation structure to
cause the fluorescence quenching.
To get the insight into the electronic structures of TATP, TATP-
-
2+
Figure 7 Cellular imaging of TATP.
CN and TATP-Zn , DFT calculations were performed using the
B3LYP/6- 31G (d, p) basis set to understand the intermolecular
interactions between probe TATP and ions (Fig. 6). The highest
occupied molecular orbital (HOMO) and lowest unoccupied
Experimental
-
Synthesis
molecular orbital (LUMO) diagrams of TATP, TATP+CN and
2+
TATP+Zn indicated that the internal charge transfer occurred
Synthesis of Tris(4-aminophenyl)amine Pd/C (10 wt.%,
during the anion recognition process.
In case of TATP, the main molecular orbital (MO) contribution of
0
.15 g) was added to a solution of Tris(4-nitrophenyl)amine
(1.05g, 2.76mmol) in EtOH (40mL), followed by
the first lowest excited state was determined for HOMO → LUMO
transition , which was assigned to be ICT band. In contrast, the
cyanide addition and zinc binding of TATP caused the decrease of
HOMO-to-LUMO energy gap, which substantially resulted in the
bathochromic shift, which supported the absorbance at longer
wavelength.
H2NNH2.H2O (5.30 mL). The mixture was heated at reflux
for 20 h. After immediate filtrition through a Celit pad, the
filtrate was cooled to below 0  . Light yellow crystals were
obtained upon recrystallization from the filtrate above (0.73g,
9
7
8
1.2 %). IR (KBr) v: 3405, 3335, 1619, 1503, 1328, 1260, 829,
23, 569, 511cm ; H-NMR (DMSO-d , 400 MHz, ppm) δ:
.48 (d, 6H), 8.47 (d, 6H), 4.73 (s, 6H);
-
1
1
6
1
3
C-NMR (DMSO-
4
| J. Name., 2012, 00, 1-3
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2
+
-
d , 400 MHz, ppm) δ: 115.65, 124.96, 139.65, 144.12. MS m/z: for Zn and CN by TATP was determined as 14 nm and 0.37
6
View Article Online
+
2
91.16 [M
＋1] .
μM, respectively. On the basis of the reDsOulI:ts1,0.1w0e39/bCe6liReAv1e735th4aCt
receptor TATP will offer an important guidance to the development
Synthesis of TATP Tris(4-aminophenyl)amine (500 mg, of single receptor for recognizing both cations and anions in
.72 mmol) in EtOH (50 mL) was added to a solution of aqueous solution.
1
Salicylaldehyde (0.90 mL). The solution was stirred under
reflux conditions for 5 h in the presence of 2–3 drops of
acetic acid. The precipitate was filtrated, washed with cold
Acknowledgements
absolute ethanol three times, then recrystallized with ethyl We acknowledge the financial support from the National Natural
acetate/chloroform (4/1, v/v) to get orange crystal, yielding Science Foundation of China (21507005) and the Excellent Young
0
8
.85 g (81.7 %). IR (KBr) v: 3420, 1615, 1490, 1320, 1182, Scholar Research Found of Beijing Institute of Technology of China
-1
1
29, 756cm ; H-NMR (DMSO-d , 400 MHz, ppm) δ: 13.20 (3090012331542). We also acknowledge the assistance of the
6
(
s, 3H), 9.00 (s, 3H), 7.64 (m, 3H), 7.45 (d, 6H), 7.40 (m, 3H), cell imaging tests from Ms. Shan Sun in Ningbo Institute of
1
3
7
.16 (d, 6H) , 6.99 (m, 3H), 6.96 (m, 3H); C-NMR Industrial Technology, Chinese Academy of Sciences.
(
DMSO-d , 400 MHz, ppm) δ: 116.54, 119.11, 119.41, 122.81,
6
1
6
9
24.54, 132.40, 133.00, 142.94, 145.76, 160.21, 162.00. MS m/z: Notes and References
+
03.2 [M
＋1] . Anal, calcd for C H O N : C, 77.72; H, 5.02; N,
39 30 3 4
†
These authors contributed equally.
.30. Found: C, 77.49; H, 5.11; N, 9.18.
1.
K. Chen, Q. Shu and M. Schmittel, Chem. Soc. Rev. 44(2015) 136-
Theoretical studies
160.
The structural optimization and theoretical UV-Vis spectral 2. M. Schmittel and Q. Shu, Chem. Commun., 48(2012) 2707-2709.
2+
-
of probe TATP,
TATP+Zn and TATP+CN were performed 3. K. Chen and M. Schmittel, Analyst 138(2013) 6742-6745.
using the computer program Gaussian 09W by applying the 4. K. Chen and M. Schmittel, Chem. Comm. 50(2014) 5756-5759.
density functional theory (DFT) and time dependent DFT 5. D. C. Magri, G. J. Brown, G. D. Mcclean and A. Prasanna de Silva, J.
(
TD-DFT) methods with a hybrid functional B3LYP using the
Am. Chem. Soc. 128(2006) 4950.
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1
011.
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2865.
Q. Shu, B. Lars and S. Michael, Aqueous Solution, Inorg. Chem.
Cellular imaging
1
The potential for cellular imaging of TATP was tested by the use
8.
of MCF-7 cancer cells. 2.0 mL of MCF-7 cells in DMEM medium at
an initial density of 4×10 cell per mL were seeded in each dish and
5
1(2012) 13123-13127.
4
9.
B. Shan Y. Liu, R. Shi, S. Jin, L. Li, S. Chen, Q. Shu, RSC Adv.
cultured at 37 ℃ for 24 h under a humidified atmosphere containing
5
(2015) 96665-96669.
10. L. Wan, Q. Shu, J. Zhu, S. Jin, N. Li, X. Chen and S. Chen, Talanta.
52(2016) 39-44.
5
% CO . The dispersion of TATP was prepared in DMEM medium
2
(with 1% DMF) with a concentration of 10 μg/mL (first dissolved in
1
DMF 1 mg/mL and then diluted with DMEM medium to target
concentration). Cells were cultured with the dispersion TATP for 6h
and then washed three times with PBS to remove the free materials,
and then cultured with the solution of Zn (15 μg/mL) or CN (100
μg/mL) for 30 min and then washed three times with PBS to remove
the free materials. Finally, the samples were observed with confocal
laser fluorescence microscopy (TCS SP5II, Leica, Germany).
1
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In summary, we have successfully designed and synthesized a
simple lab-on-a-molecule TATP, capable of sensing both
cations and anions in aqueous solution. TATP exhibited an
L. Zhang,
8. B. Vennesland, E. E. Comm, C. J. Knownles, J. Westly and F.
Wissing, Academic Press, London, 1981.
2+
-
excellent selectivity and sensitivity towards Zn and CN by
inducing instantaneous solution color change by naked-eye and
dramatic emissive responses, even in the presence of other
ions. The binding model between host and guests was
demonstrated by Job’s Plot, NMR titration and DFT
9. J. Y. Noh, I. H. Hwang, H. Kim, E. J. Song, K. B. Kim and C. Kim,
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2
+
calculations, suggesting that the sensing of TATP towards Zn
-
and CN was achieved through metal-ligand coordination and
nucleophilic attack mechanism, respectively. The detection limit
2. A. A. A. Aziz, S. H. Seda and S. F. Mohammed, Sens. Actuat. B,
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RSC Advances
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DOI: 10.1039/C6RA17354C
Triphenylamine based Lab-on-a-molecule for the highly selective and
2
+
-
sensitive detection of Zn and CN in aqueous solution
a
a,*
a
a
a
b,*
c,*
Shichao Sun , Qinghai Shu , Pengchao Lin , Yanyue Li , Shaohua Jin , Xin Chen , Dequan Wang
A
triphenylamine based lab-on-a-molecule TATP was designed and systhesized as
bifunctional sensor for the detection of zinc and cyanide ions through fluorescence
and UV-Vis absorption channels with detection limit 14 nM and 0.37 µM,
respectively.