A highly selective colorimetric and "off-On" fluorescent chemosensor for fluoride ions and its application as a molecular-scale logic device

Article abstract of DOI:10.1039/c5nj00918a

A new sensor 2,2′-((1E,1′E)-((3,3′-dimethyl-[1,1′-biphenyl]-4,4′-diyl)bis(azanylylidene))bis(methanylylidene))diphenol (YT) based on the combination of phenolic hydroxy and imine groups was used as an efficient colorimetric and "turn on" fluorescent senso

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PAPER
A highly selective colorimetric and “Off-On” fluorescent chemosensor
for fluoride ion and its application as a molecular-scale logic devices
GuoTao Yan, Hui Li, Yuan Rong Zhu, BingBing Shi, Wenjuan Qu, Qi Lin, Hong Yao, YouMing Zhang,
TaiBao Wei*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
A new sensor 2, 2'ꢀ((1E, 1'E)ꢀ((3, 3'ꢀdimethylꢀ[1, 1'ꢀbiphenyl]ꢀ4, 4'ꢀdiyl) bis (azanylylidene)) bis (methanylylidene)) diphenol (YT) based
on the combination of phenolic hydroxy and imine group was used as an efficient colorimetric and “turn on” fluorescent sensor for
fluoride anions. The receptor exhibits high selectivity and sensitivity for sensing F−. Furthermore, the enhanced fluorescence caused by
10 fluoride could be recovered upon the addition of calcium ion to this complex solution. The fluorescent changes of YT upon the addition
of F− and Ca2+ can be utilized as an INHIBIT logic gate at molecular level, using F− and Ca2+ as chemical inputs and the fluorescence
intensity signal as outputs.
Till now,
thiourea[19], amide[20], indole[21], have been reported. Among
The design and development of selective optical sensors and 35 the various fluoride anion sensors, although a hydroxyl group can
a
variety of chemosensors for F− based on
1. Introduction
15 receptors for anions has gained considerable attentions, as anions
play important roles in many areas such as medicinal biological,
environmental chemistry and catalysis [1ꢀ5]. In recent years,
considerable efforts has been devoted to developing fluorescent
also be an excellent hydrogenꢀbonding donor and its proton even
exhibits more acidity compared to the proton of NH unit, far less
attention has been paid to the OH based anions receptors and
sensors. With these considerations in mind, we developed a
anion sensors, due to their simplicity, high degree of specificity 40 structurally simple chemosensor, with a hydroxynaphthalene
20 and low detection limit, however, only few of them are “turn on”
fluorescent sensors [6ꢀ11]. In terms of sensitivity concerns, the
recognition process ‘‘turn on’’ fluorescence is advantageous than
that of ‘‘turn off’’ event in terms of the detection limit, because
group as chromogenic signaling subunit and hydroxy as binding
sites, which enable dual channel (absorption and fluorescence)
detection of F− in DMSO solution. The high selectivity for F−
recognition and detection based on noncovalent or covalent
fluorescence “turn off” sensors may report false results caused by 45 interactions between the sensor YT and F−, employing hydrogen
25 other quenchers in practical samples [12ꢀ13].
bonding and deprotonation between the hydroxyl group of the
receptor and the fluoride. According to these, we reported YT
based fluorescent and choromogenic chemosensor, with
characteristics of an “OFFꢀONꢀOFF” fluorescence switch.
Fluoride ion (F−), as the most electronegative atom, being the
smallest anion with high charge density plays important roles in
environmental, medical and chemical processes [14–17].
However, an excessive fluoride ion intake may injure animal and 50 Interestingly, the fluoride induced chromogenic process can be
30 human bodies, result in fluorosis and kidney disorders or even
urolithiasis [18]. Therefore, developing new, simple, and highly
sensitive F− sensors would be highly demanded.
totally reversed with addition of Ca2+. Based on these, using F−
and Ca2+ as inputs IFNOT logic operations can be achieved,
which allows the design of a molecularꢀscale sequential memory
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Scheme 1.Synthetic procedure of YT.
unit displaying “WritingꢀReadingꢀErasingꢀReading” behavior and
“Multiꢀwrite” functions.
2.3. General procedure for UV-VISIBLE Absorption and
Fluorescence experiment
2. Experimental section
40 All the UVꢀvis experiments and fluorescence spectroscopy
were carried out in DMSO solution on a Shimadzu UVꢀ2550
spectrometer and Shimadzu RFꢀ5301 spectrometer, respectively.
Any changes in the UVꢀvis spectra of the synthesized compound
were recorded on addition of tetrabutylammonium salts while
2.1. Materials and physical methods
5
All reagents and solvents were commercially available at
1
analytical grade and were used without further purification. H
NMR and 13C NMR spectra were recorded on a Bruker AvanceIII
400 MHz spectrometer at 400 MHz and 100 MHz, respectively.
Chemical shifts are reported in parts per milliom (ppm) 45 keeping the ligand concentration constant (2.0 × 10ꢀ5 M) in all
10 downfield from tetramethylsilane (TMS, dscale with solvent
experiments. Tetrabutylammonium salt of anions (F−, Cl−, Br−, I−,
−
−
−
resonances as internal standards). UVꢀvis spectra were recorded
AcO−, H2PO4 , HSO4 , ClO4 , CN− and SCN−) were used for the
on
a Shimadzu UVꢀ2550 spectrometer. Photoluminescence
UVꢀvis experiments and fluorescence experiments.
2.4. General procedure for 1H NMR experiments
spectra were performed on a Shimadzu RFꢀ5301 fluorescence
1
spectrophotometer. Mass spectra was recorded on an esquire 50 For H NMR titrations, sensor YT was prepared in DMSOꢀd6,
15 6000 MS instrument equipped with an electrospray (ESI) ion
source and version 3.4 of Bruker Daltonics Data Analysis as the
data collection system. Melting points were measured on an Xꢀ4
digital meltingꢀpoint apparatus (uncorrected).
(Bu4N)F was prepared in DMSOꢀd6. one of them containing host
only and the second one containing an appropriate concentration
of guest. Aliquots of the two solutions were mixed directly in
NMR tubes.
2.2. Synthesis of the sensor YT
55 3. Results and Discussion
20 Sensor YT could be easily synthesized by condensation of
salicylaldehyde (0.5124 g, 4mmol) and 3,3'ꢀdimethylbenzidine
(0.45 g, 2.0mmol) in refluxing absolute ethanol (30 mL) (Scheme
1). The reaction mixture was stirred under reflux for 8 h. After
The selectivity of YT toward different anions was monitored
−
by treating YT with excessive F−, Cl−, Br−, I−, AcO−, H2PO4 ,
−
−
HSO4 , ClO4 , CN− and SCN− in DMSO, respectively. Figure 1
shows the changes in the UVꢀvis spectra of YT (2.0 × 10ꢀ5 M) in
completion of the reaction, the obtained yellow precipitate was 60 DMSO after adding 50 equiv. of various anions. when sensor YT
25 filtered, washed four times with hot absolute ethanol, then
was treated with the fluoride anions, the absorbance at 375 nm
declined sharply from 1.05 to 0.52, while the one at 454 increased
significantly, which induced the color of the solution changes
from colorless to yellow, which could be detected by the ‘naked
recrystallized with EtOH to give a luminous yellow powder
1
product YT (0.72 g) in 85.1% yield (m.p. 220ꢀ222 ). H NMR
(DMSOꢀd6, 400 MHz): δ 13.42 (d 2H, OH), δ 8.99 (d 2H,
ꢀCH=N), δ 7.65ꢀ7.76 (m 6H, ArH), δ 7.42ꢀ7.54 (m 4H, ArH), δ 65 eye’. In contrast, for the other anions no obvious changes in color
30 6.95ꢀ7.47 (m 4H, ArH), δ 2.43 (s 6H, ꢀCH3); 13C NMR
(DMSOꢀd6, 100 MHz): δ/ppm 162.44, 160.31, 145.94, 137.70,
133.04, 132.36, 132.22, 128.39, 124.95, 119.33, 118.90, 118.31,
116.41, 17.71. ESIꢀMS m/z: (M+H)+ Calcd for C28H24N2O2
421.18; Found 421.17; Anal. Calcd for C28H24N2O2: C, 79.98; H,
35 5.75; N, 6.66; O, 7.61Found C 79.87; H, 5.68; N, 6.57; O, 7.60.
were observed (inset of Fig. 1).
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30 receptor YT ((2.0 × 10ꢀ5 M). Fig. 3 shows absorption spectral
changes of receptor YT in the course of titration. Upon
successive addition of tetrabutylammonium fluoride (TBAF), the
absorption peak initially at 375nm gradually decreased while the
absorption intensities at 453 nm increased together with a marked
Fig. 1 Absorption spectra change of YT (20 µM) upon addition of
selected competing anions (50 equiv). Inset: the corresponding color
changes.
In order to further explore sensing ability of the receptor YT,
fluorescence measurements were carried out. As shown in Fig. 2,
5
YT alone exhibited a very weak fluorescence emission upon 35 red shift. This should be attributed to the strong intramolecular
excitation at 462nm. Treatment with F−, resulted in a drastic
enhancement of the fluorescence intensity at 552 nm, the
fluorescent enhancement observed upon addition of fluoride to
hydrogenꢀbonding interaction in sensor and the deprotonation of
the hydroxyl group coordinated to fluoride anion. As a result,
leading to a color change from yellow to red, which could be
detected by the ‘naked eye’. The binding affinity of sensor YT
10 the sensor YT might be attributed to the intramolecular charge
transfer (ICT) transition from the phenolate[22ꢀ23]. The 40 with F− anion was estimated by performing emission titration
increasingly negative charge density of the phenol oxygen atom
promoted the intramolecular charge transfer (ICT) from hydroxyl
anion to the aromatic rings. In comparison, the addition of
experiments when excited at 462 nm. As shown in Fig. 4 free
probe YT showed weak fluorescence at 552 nm due to the
structure of intramolecular hydrogen bond. On further increasing
the concentration of F− (4ꢀ13.6 equiv.), the original fluorescent
−
−
−
15 various anions such as Cl−, Br−, I−, AcO−, H2PO4 , HSO4 , ClO4 ,
CN− and SCN− to the solution of YT exhibited no or small 45 emission peak at 552 nm increased progressively with a 15.3 nm
changes at 552 nm. Moreover, when being excited by 365 nm UV
lamp it emits yellow lights, which acts as a typical of “OFF–ON”
based optical response as shown in the photograph inset of Fig. 2.
20 These results clearly indicated that the selectivity of YT toward
redꢀshift of the emission maximum. The detection limitation of
sensors towards F− was obtained according to fluorescence
titration on the basis of 3SB/S [24] was 2.5 × 10ꢀ7 M, as shown in
(Fig. S1). This value is far below the guideline (211 ꢁM) of the
F− over other competitive anions in DMSO was remarkably high. 50 U.S Environment Protection Agency.
Fig. 2 Change in emission spectra of YT (20 µM) upon the addition of
25 different anions (50 equiv) in DMSO. Inset shows the change in color
under UV.
Fig. 3 UVꢀvis titration spectra of YT (20 µM) upon the addition of F−
anions (0ꢀ118 equiv.) in DMSO solution. Inset: Absorbance at 453 nm
versus the number of equiv of F− added.
55
The interaction between YT and F− was further investigated
through spectrophotometric titration methods by adding
a
standard solution of corresponding anions to a solution of the
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Fig. 4 Fluorescence titration of YT (20 µM) with F− (as the TBAF salt
from 0 to 13.6 equiv) in DMSO excited at 462 nm.
The mechanism of the interaction between sensor YT and F−
was further studied by 1H NMR titration experiments. Fig. 5
shows partial 1H NMR spectrum of interaction of receptor and F−.
In the absence of fluoride anion, sensor YT showed a single peak
at 13.42 ppm in DMSOꢀd6, which was confirmed to the proton of
OH. In this case, there is a twoꢀstepwise mechanism involving the
30
Fig. 5 1H NMR spectra of YT (1 mg) with the addition of TBAF
(DMSOꢀd6 solution). (a) YT only; (b) YT + F− (0.5 equiv.); (c) YT + F−
(4.5 equiv.); (d) YT + F− (6.0 equiv.); (e) YT + F− (8.0 equiv.).
5
10 formation of hydrogen bond between OH and F− first and then
deprotonation of the OH by excessive F−. With the increasing of
the fluoride concentration, the singlet of Ha was downshifted
gradually from 13.42 ppm to13.66 ppm by hydrogen bonding
with fluoride. After the addition of 6 equiv of fluoride, the singlet
Scheme 2 Proposed sensing mechanism of YT for fluoride
15 peak of Ha was broadened, and then completely disappeared by 35 Due to the reversibility is an important aspect for a chemical
the deprotonation. Furthermore, a new signal appears at 16.12
ppm when 8 equiv. of fluoride was introduced, this peak is indeed
sensor to be widely employed in the detection of specific analyses,
so the reversibility in the response of YT has been further
verified during its seven cycles of titrations by alternating
addition of F− and Ca2+ to YT solution. The fluorescence
−
suggestive of the formation of bifluoride, HF2 ion and thus
supports the deprotonation of hydroxyl groups [25ꢀ26]. The
20 protons of the aromatic rings were shifted to upfield which 40 emission of the tested solution performed alternate enhancing and
suggests that the negative charges generated from the
deprotonation of YT by fluoride were delocalized over the
receptor molecular. These results corresponded with the
spectrophotometric titration results and further suggested that the
reviving processes in a sequence as shown in Fig. 6. In addition,
the F− exhibits a remarkable fluorescence change by showing ON
behavior through complex formation. Upon addition of excess
amount of Ca(ClO4)2 to the mixture of YT and F− results in
25 mechanism of the F− sensing process was a combination of an 45 quenching the fluorescence intensity and hence acts as OFF
intramolecular hydrogen bond, deprotonation, and Pꢀπ
conjugation effect. We propose the sensing mechanism of YT to
fluoride as shown in Scheme 2.
switch. This “OFFꢀONꢀOFF” switching process could be
repeated at several times with little fluorescent efficiency loss.
The repeated behavior of the system by fluorescence change
clearly suggests that YT is reversible and hence is a reusable
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sensor for F−, the possible binding mode between YT toward F−
is proposed in Scheme 3. Here, the actual results from an
experiment are shown in Fig. 7, using F− and Ca2+ act as inputs
while the emission intensity at 552 nm (I 552) band acts as output.
Based on the reversible and reproducible fluorimetric switch, the
sensor YT can switch between different fluorescence emission
states, i.e. “on” (strong fluorescence emission) or “off” (quenched
fluorescence emission), which display “ReadꢀEraseꢀWriteꢀRead”
behavior with the help of reversible logic operations [27]. In this
5
30
Fig. 6 Reversible switching cycles of fluorescence intensity (λex = 462 nm)
by alternate addition of F− ions and Ca2+ in DMSO.
10 concrete system (Fig. 8), the ON state (Output 2 = 1) is defined as
the strong fluorescence at 552 nm, whereas the OFF state (Output
2 = 0) corresponds to the weak fluorescence. The two chemical
inputs of fluoride and calcium ions are designated as (ln F) and
(ln Ca2+) for the Set (S) and Reset (R), respectively. The
15 operation of this memory unit is as follows: whenever the Set
input is high (S = 1), the system writes and memorizes the binary
state 1; on the other hand, when the Reset input is high (R = 1),
the 1 state is erased and the 0 state is written and memorized. As
Fig. 7 Performance of YT in the INHIBIT gate mode. The bars
shown in Fig. 8a, The reversible and reconfigurable sequences of 35 show the fluorescence output of YT at 552 nm in the presence of
20 Set/Reset logic operations in a feedback loop demonstrate the
memory feature with “ReadꢀEraseꢀWriteꢀRead” functions with
the optical output signal. Fig. 8b defines the bistability behavior,
“ONꢀOFF” state, of sensor YT and reveals the nonꢀvolatile nature
of the memory effect. More importantly, the present logic device
25 has a great advantage over early reported relative systems at least
in terms of the reversible and reproducible characteristics.
F− and Ca2+ as inputs.
Fig. 8 (a) The sequential logic circuit of the memory machine and its truth
table. (b) Feedback loop showing reversible logic operations for memory
element with “WritingꢀReadingꢀErasingꢀReading” functions.
Scheme 3 The recyable mechnaism of sensor YT toward F−
after addition of Ca2+.
40
4. Conclusions
In conclusion, we have designed and synthesized a simple
colorimetric and fluorescent chemosensor for highly selective
recognition of the fluoride anion. Upon interaction with F− YT
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7
8
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showed an obvious color change from colorless to yellow;
meanwhile the fluorescence spectra show a 15.3 nm redꢀshift
with enhanced intensity, which makes the receptor YT a dual
channel sensor for fluoride. More interestingly, the F− induced
chromogenic process could be totally reversed by addition of
Ca2+, this “OFFꢀONꢀOFF” switching process could be repeated at
several times with little fluorescence loss. So, the fluorescence
responses can be utilized as output to build an INHIBIT logic
gate by using F− and Ca2+ as inputs. Base on this, we has
40
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A new sensor 2, 2'ꢀ((1E, 1'E)ꢀ((3, 3'ꢀdimethylꢀ[1, 1'ꢀbiphenyl]ꢀ4, 4'ꢀdiyl) bis (azanylylidene)) bis
(methanylylidene)) diphenol (YT) based on the combination of phenolic hydroxy and imine group was
used as an efficient colorimetric and “turn on” fluorescent sensor for fluoride anions. The receptor
exhibits high selectivity and sensitivity for sensing F−. Furthermore, the enhanced fluorescence caused
by fluoride could be recovered upon the addition of calcium ion to this complex solution. The
fluorescent changes of YT upon the addition of F− and Ca2+ can be utilized as an INHIBIT logic gate at
molecular level, using F− and Ca2+ as chemical inputs and the fluorescence intensity signal as outputs.