Three-input-three-output logic operations based on absorption and fluorescence dual-mode from a thiourea compound

Article abstract of DOI:10.1039/c2dt31808c

A simple organic molecule of 2-naphthol-1-aldehyde-conjugated thiourea (denoted as receptor 1) is designed and prepared. Absorption and fluorescence spectra response profiles of receptor 1 with different ionic inputs vary significantly in a DMSO-H₂O solution (V/V = 9 : 1) through modulating intramolecular charge transfer (ICT) processes. In particular, the changes of the dual-modal spectra when anions, such as F^-, AcO^- or H₂PO₄^-, are introduced in such an aqueous solution indicate that receptor 1 could be tolerant to H₂O at least to some extent in recognizing anions. On the basis of the above results, binary logic operations (OR, NOR and INHIBIT) and their multiply-logic functions with different combinations have been achieved at the molecular level by changing different chemical inputs. The output signals can be encoded as absorption and fluorescence dual-mode, depending on the choice of 2-naphthol as the chromophore and fluorophore core.

Full text of DOI:10.1039/c2dt31808c

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Binary logic operations and combinational logic circuits from a thiourea compound have been achieved at
molecular level.

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Cite this: DOI: 10.1039/c0xx00000x
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ARTICLE TYPE
Threeꢀinputꢀthreeꢀoutput logic operations based on absorption and
fluorescence dualꢀmode from a thiourea compound
Lianlian Wang,a,b Bin Li,*a Liming Zhanga and Yongshi Luoa
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/c0xx00000x
A simple organic molecule of 2ꢀnaphtholꢀ1ꢀaldehydeꢀconjugated thiourea (denoted as receptor 1) is designed and prepared.
Absorption and fluorescence spectra response profiles of receptor 1 with different ionic inputs vary significantly in DMSO/H2O
solution (V/V = 9:1) through modulating intramolecular charge transfer (ICT) processes. In particular, the changes of the dualꢀ
ꢀ
modal spectra when anions, such as Fꢀ, AcOꢀ or H2PO4 , are introduced in such an aqueous solution indicate that receptor 1 could
10 be tolerant to H2O at least to some extent in recognizing anions. On the basis of the above results, binary logic operations (OR,
NOR and INHIBIT) and their multiplyꢀlogic functions with different combinations have been achieved at the molecular level by
changing different chemical inputs. The output signals can be encoded as absorption and fluorescence dualꢀmode, depending on
the choice of 2ꢀnaphthol as the chromophore and fluorophore core.
Introduction
Logic gates, as a class of important and basic logic operations,
are switches whose output state (0 or 1) depends on input
50 conditions (0 or 1).3e Generally, one output mode shows one logic
function by a combination of certain two chemical inputs. More
recently, construction of molecules, whose multiꢀoutput logic
functions can be modulated by multiꢀinput combination, has
induced great interests.5 It would be possible to extend the
55 information processing and computing to molecular level if only
molecular logic gates are available, which could perform binary
arithmetic and logical operations. Besides, receptor molecules
obtained through simple synthetic protocols but capable of
performing multiple logic operations are the first choice for any
60 supramolecular chemist towards the construction of molecular
devices and machines.
The construction of logic gates at molecular level can be
carried out by using chemical and/or optical inputs and optical
outputs.6 Typically, in these systems, addition of acid/base, metal
65 ions, or/and anions leads to changes in the absorption spectrum
(i.e., color changes) or alterations of fluorescence properties (i.e.,
change of intensity or band shifts) of the molecule which can be
detected and influenced by a quite small but extremely versatile
toolbox of excited state processes, such as photoinduced electron
70 transfer (PET),7 intramolecular charge transfer (ICT),8 and
fluorescence resonance energy transfer (FRET).9
15
The signal communication at molecular level is important and
necessary in the development of innovative materials for data
storage and processing. In 1988, Aviram suggested the use of
“molecules for memory, logic and amplification” in the context
of molecular electronics.1 Ever since the pioneer work about
20 molecular AND logic gate in 1993 by de Silva and coworkers,2
the design and construction of molecular systems capable of
performing binary arithmetic and logical operations has been
explored extensively.3 The molecular approach to logic devices is
usually associated with the mimicry of functions performed by
25 siliconꢀbased microprocessors, by moving beyond siliconꢀbased
technology simultaneously. The elementary logic operations,4
such as logic gates, encoders/decoders, molecular digital
demultiplexers, and keypad locks, central to the functioning of
electronic circuitry, can be performed by cleverly designing
30 organic molecules, and can access those areas inaccessible by
even the smallest electronics.
a State Key Laboratory of Luminescence and Applications, Changchun
Institute of Optics, Fine Mechanics and Physics, Chinese Academy of
Sciences, 3888 Eastern South Lake Road, Changchun 130033, P. R.
35 China
Tel./Fax: +86 431 86176935
Eꢀmail address: lib020@yahoo.cn (B. Li)
Keep these considerations in mind, we have designed a single
molecule, 2ꢀnaphtholꢀ1ꢀaldehydeꢀconjugated thiourea ligand 1
(denoted as receptor 1), and studied the logic responses of
75 receptor 1 by using appropriate combinations of anions and
cations as inputs based on absorption and fluorescence dualꢀmode
in DMSO/H2O solution (V:V=9:1). The thioamide moiety, linked
with 2ꢀnaphthol by a CH=N group, has often been used as a
binding group for anions and cations chemosensors10 because the
80 thiourea group offers an ideal binding and signal transduction
b Graduate School of the Chinese Academy of Sciences, Chinese Academy
of Sciences, Beijing, 100039, P. R. China
40 †Electronic Supplementary Information (ESI) available: The job’s plots
for determining the stoichiometry of receptor 1 with various ions, spectra
responses of receptor 1 in the presence of various interference ions,
spectra responses of receptor 2 in the presence of anions, reversibility of
receptor 1 with various ions, 1H NMR spectra of thiocarbohydride,
45 receptor 1 and 2.
See DOI: 10.1039/c0xx00000x
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

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unit. However, it has been considerably less used as a logic
device.6f
Results and discussion
A. Absorption and fluorescence spectra
5
A.1 Absorption and fluorescence spectra of pure 1.
Receptor 1 was synthesized with a very simple protocol shown in
Scheme 1. The 2ꢀnaphthol moiety in receptor 1 serves as the
chromophore and fluorophore core. The amine and hydroxyl
groups in receptor 1 serve as chelating sites for anions and
10 cations. Due to the electronꢀdonating property of 2ꢀnaphthol and
the electronꢀwithdrawing property of the thioketone group,
receptor 1 gives a “pushꢀpull” based excited state.
R
R
S
C
N
N
C
H
N
N
C
H
H
H
1: R=OH
2: R=H
Fig. 2 Absorption (a) and normalized fluorescence spectra (b, λex =342
nm) of receptor 1 (50 ꢁM) in the presence of anions of increasing
concentration from 0 to 20 equiv in DMSO/H2O solution (V:V = 9:1).
Scheme 1 Molecular structure of receptor 1 and 2.
15
The absorption spectrum of receptor 1 shown in Fig. 1 is
recorded in DMSO/H2O solution (V:V = 9:1), which displays an
ICT band at 381 nm and a shoulder band of 367 nm, mainly due
to the ArꢀCH=NꢀNH conjugation.10a Receptor 1 in DMSO/H2O
solution exhibits an emission centered at 437 nm upon excitation
40 Contemporarily, a wellꢀdefined isosbestic point emerges at 408
nm during absorption spectral titration, which indicates the
formation of a stable complex with a certain stoichiometric ratio
between receptor 1 and Fꢀ through hydrogen bond interaction.
Similar phenomena are also observed with the isosbestic point at
45 411 nm for AcOꢀ and 408 nm for H2PO4 , respectively. Job’s
ꢀ
20 of 342 nm (Fig. 1). Compared with the control receptor 2, the
redꢀshifted absorption and fluorescence of receptor 1 is mainly
due to the electronꢀdonating ability of hydroxyl substituent.
Furthermore, the fluorescent intensity of receptor 1 is also
enhanced by the electronꢀdonating nature of hydroxyl substituent.
plots indicate the formation of a 1:2 complex between receptor 1
and anions (Fig. S1a†). The association constants (Ks) of receptor
1 for Fꢀ, AcOꢀ, and H2PO4 are calculated from equation (1) and
ꢀ
their results are summarized in Table 1. On the other hand, the
50 addition of other anions into receptor 1 solution gives no spectral
change (Fig. S2a†).
For a better understanding of the binding mode, fluorescence
variations of receptor 1 in DMSO/H2O solution (V/V = 9:1) in
the presence of all above anions are studied. It is evident from Fig.
55 2b that the emission of receptor 1 displays red shifts towards Fꢀ,
ꢀ
AcOꢀ and H2PO4 , which should be attributed to the enhanced
ICT efficiency caused by the hydrogenꢀbonding interaction
between receptor 1 and above anions (Scheme 2a). The addition
of other anions into receptor 1 causes insignificant changes in its
60 fluorescence spectra (Fig. S2b†).
As well known, only aprotic solvents are usually permitted
for the hydrogenꢀbondingꢀbased anions chemosensors. In
protic solvents such as H2O or MeOH, the hydrogenꢀbinding
of the sensor with anions would be completely quenched
65 because anions give priority to the interaction with protic
solvent molecules.11 However, the thioamide group could be
tolerant to H2O to some extent due to the high acidity of NH
protons,10a and hydroxyl group could further enhance such
ability. So detection for anions is expected to be carried out in
70 solution of DMSO/H2O (V/V=9:1). To further prove the
tolerant ability of receptor 1 towards water, receptor 2 which
has a similar molecular structure with that of receptor 1 is
synthesized and investigated. With receptor 2 (50 ꢁM), no
hydroxyl substituent compared to receptor 1, addition of
25
Fig. 1 The absorption and normalized emission spectral overlay of
receptor 1 (■) and 2 (●) in DMSO/H2O solution (V:V = 9:1).
A.2 Absorption and fluorescence spectra of receptor 1 in
the presence of anions. The binding behavior of receptor 1 with
30 various anions (such as Fꢀ, Clꢀ, Brꢀ, Iꢀ, AcOꢀ, H2PO4 , ClO4 ) are
firstly monitored by visual observation in DMSO/H2O solution
(V/V = 9:1) (Fig. 2a and 3a). As shown in Fig. 2a, the intensity
of ICT band at 381 nm decreases gradually and a new
ꢀ
ꢀ
absorption
band
appears
with
a
maximum
35 absorption at 439 nm upon increasing the concentration of Fꢀ.
2
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Table 1. Binding constants (Ks) of anions and cations with receptor 1 in
DMSO/H2O solution (V/V = 9:1).
Ions
Fꢀ
λabs (nm)
439
441
439
439
Ks (Mꢀ2)
(2.13 ± 0.11) × 108
(1.18 ± 0.01) × 108
(1.53 ± 0.05) × 107
(5.83 ± 0.20) × 107
(9.94 ± 0.33) × 109
(3.20 ± 0.07) × 108
(7.43 ± 0.09) × 108
AcOꢀ
H2PO4
Zn2+
Cu2+
Ni2+
ꢀ
442
450
Co2+
456
Scheme 2. Proposed structures of the hydrogen bonding [N21] complex
(a) and the doubly deprotonated [M21] complex (b) (N = anion; M =
metal ion).
5
various anions does not induce any discernible spectral
changes in the same solution (Fig. S3†). However, a problem
worthy to point out is that receptor 2 would also be tolerant to
10 H2O to some extent when its concentration is high.
Considering that the addition of Fꢀ ion into the solution of
receptor 1 can lead to representative spectral change, it is thus
chosen as the input for studying logic operations of receptor 1 in
subsequent experiments.
Fig. 3 Absorption (a) and normalized fluorescence spectra (b, λex =342
nm) of receptor 1 (50 ꢁM) in the presence of cations of increasing
45 concentration from 0 to 20 equiv in DMSO/H2O solution (V:V = 9:1).
the ions.12 What deserves to be mentioned is that the capture of
Cu2+ by receptor 1 produces new band at 375 nm and the
fluorescence increases sharply, while Co2+ and Ni2+ only have
little fluorescence increase below 400 nm without appearance of a
50 new band. For most receptors, the communication between them
and transition metal ions is too strong compared with the other
interactions, which is believed to be the main reason for the
quenching of fluorescence. In our work, receptor 1 forms a proper
cavity and has a strongest binding with Cu2+ among the test metal
55 cations. According to literature report, the Cu2+ꢀfluorophore
interaction might be suppressed with the increasing concentration
of Cu2+ꢀreceptor. As a result, fluorescence of receptor 1 is
maintained.13 It should be emphasized that other metal ions, such
as Na+, K+, Cd2+, Mg2+, Al3+, Pb2+ and Ca2+ were also tested, but
60 no obvious influence on absorption and fluorescence spectra of
receptor 1 is detected (Fig. S2†).
15
A.2 Absorption and fluorescence spectra of receptor 1 in
the presence of cations. The interaction of receptor 1 with metal
ions Zn2+, Cu2+, Co2+ and Ni2+ is demonstrated by its absorption
and fluorescence responses of receptor 1 (50 ꢁM) in DMSO/H2O
solution (V/V = 9:1) (Fig. 3).
As for UVꢀVis spectra, the ICT band of receptor 1 at 381 nm is
gradually reduced upon addition of the above metal ions, a series
of new bands appear at 439 nm, 442 nm, 450 nm and 456 nm,
respectively (Fig. 3a). The appearance of the isosbestic points in
titration traces suggests the formation of wellꢀdefined binding
20
25 complexes between receptor 1 and the above tested metal ions,
which thereby allows their binding constants (Ks) to be fitted by a
nonlinear fitting procedure for 1:2 binding complexes (Table 1,
Scheme 2b).10e
As two representative metal ions, Zn2+ and Cu2+ are chosen as
two of the signal inputs for studying the logic operations of
receptor 1 in the subsequent experiment.
The changes of fluorescence spectra of receptor 1 along with
30 concentration increase of Zn2+, Cu2+, Co2+, Ni2+ are shown in Fig.
3b. Upon titration of Zn2+, a gradual decrease in fluorescence
intensity at 437 nm and simultaneous appearance of a new redꢀ
shifted emission band at 486 nm are observed with an
isoemission point at 467nm. The distinctive redꢀshift on the
35 maximum absorption peak is caused by the enhanced ICT process
due to the chelation of receptor 1 with Zn2+, as an electronꢀ
deficient group, different from that between 1 and anions. On the
contrary, the coordination of Cu2+, Co2+ or Ni2+ with receptor 1
blocks the ICT process and causes significant blueꢀshift on the
40 fluorescent peak because they can lead to an energy transfer from
the excited naphthalene unit to the lowꢀlying empty d orbital of
65 A.3 Reversibility of receptor 1 binding to various ions. In the
recognition of specific analytes, the reversibility of chemical
responding system is a very important factor. In this work, the
reversibility of receptor 1 after immersion in Fꢀ, Zn2+, or Cu2+ is
examined, respectively. The interactions between receptor 1 and
70 these ions are chemically reversible, which can be verified by the
introduction of Ca2+ into the system for Fꢀ and EDTA (sodium
salt) for Zn2+/Cu2+, respectively (Fig.S4ꢀS6†).14 The
corresponding absorption and fluorescent spectra of receptor 1
binding to Fꢀ, Zn2+ and Cu2+ could all immediately be restored.
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Fig. 4 (a) Absorption and (b) fluorescence (λex = 342 nm) spectra about
different situations of receptor 1 with Zn2+ (IN1, 5 equiv) and Fꢀ (IN2, 5
equiv).
10
Fig. 6 (a) Absorption about different situations of receptor 1 with Zn2+
(IN1, 5 equiv), Fꢀ (IN2, 5 equiv) and Cu2+ (IN3, 5 equiv). (b) and (c) The
changes of absorbance at 381 nm and 439 nm, respectively (□ represents
inputs that are 0, ■ represents inputs that are 1).
15 These processes could all be repeated for at least three times.
These regenerations indicate that receptor 1 could be reused with
proper treatment.
5
B. Logic gating behavior of receptor 1 with anions and
cations as inputs
Fig. 5 (a) The changes of absorbance at 381 nm and 439 nm and
fluorescence intensity at 520 nm for receptor 1 with Zn2+ (IN1, 5 equiv)
and Fꢀ (IN2, 5 equiv).(□ represents inputs that are 0, ■ represents inputs
that are 1). (b) The logic circuit for the NOR/OR logic gates.
20
On the basis of aboveꢀmentioned results, different spectral
outputs of receptor 1, encoded as absorption and fluorescence
4
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30 (a)
Input
Output
IN1
IN2
Fꢀ
0
0
1
1
0
0
1
IN3
OUT1
A381nm
OUT2
A439nm
OUT3
F520nm
Zn2+
0
Cu2+
0
1
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
0
1
1
1
0
0
0
0
1
0
1
0
1
0
1
0
0
0
1
1
1
1
1
(b)
Fig. 8 A threeꢀinput, threeꢀoutput molecular switch: (a) truth table for a
threeꢀinput situation. (b) Combinatorial logic scheme.
35 520 nm would be quenched by the introduction of Cu2+ (IN3) no
matter with or without Zn2+ (IN1) or/and Fꢀ (IN2), which is read
as “0”. The spectra changes in response to the three inputs are in
accordance with an INHIBIT logic gate, which is integrated with
an OR gate and a NOT gate. According to the two histograms
40 (Fig. 6b, Fig. 6c and Fig. 7b), the truth table (Fig. 8a) can be
achieved. It can be seen that this chemical system responds to an
input string of three binary digits (IN1, IN2, IN3) with an output
string of three binary digits (OUT1, OUT2, OUT3). Consequently,
this chemical system can be integrated to a combinational logic
45 circuit at monomolecular level with a NOR gate, an OR gate and
an INHIBIT gate (Fig. 8b). It is worthy noting that all these logic
types can be observed simultaneously if required.
Fig. 7 (a) Fluorescence spectra (λex = 342 nm) about different situations
of receptor 1 with Zn2+ (IN1, 5 equiv), Fꢀ (IN2, 5 equiv) and Cu2+ (IN3, 5
equiv). (b) The changes of fluorescence intensity at 520 nm (□ represents
inputs that are 0, ■ represents inputs that are 1).
5
dualꢀmode, can provide an entry for developing multiple logic
operations at molecular level using various ions as inputs. These
inputs and outputs can be encoded with binary digits applying
positive logic conventions (off = 0, on = 1).10b
Conclusions
In this work, a thiocarbazone derivative bearing 2ꢀnaphthol as
50 the chromophore and fluorophore core, denoted as receptor 1, has
been synthesized and characterized. The absorption and
fluorescence spectra response profiles of receptor 1, which are
sensitive towards anions and metal cations have been investigated
in DMSO/H2O solution (V/V = 9:1). We find that receptor 1 can
55 proceed upon logic operations with multiplyꢀconfigurable dual
outputs by selecting different ionic inputs through modulating
ICT processes. As a result, binary logic operations (OR, NOR
and INHIBIT) and combinational logic circuits have been
achieved at molecular level. Since all logic operations mentioned
60 above can be operated with two/three inputs by a single molecule,
the system of receptor 1 reported here shows a high versatility.
We believe that the present system will provide useful
information to the range of optical devices that can operate at
molecular level.
10 Monitoring changes of absorption and fluorescence as outputs
this molecule can operate simultaneously as NOR and OR logic
gates when Zn2+ (IN1) and Fꢀ (IN2) are used as inputs, as shown
in Fig. 4 and 5. The absorption value at 381 nm can only be
monitored when there is no chemical input, which leads to a NOR
15 logic gate. Without the two inputs of IN1 and IN2, the absorption
value at 439 nm or the fluorescence intensity at 520 nm of
receptor 1 is relatively low, so the output is read as “0”. Whereas
the two values are both obviously enhanced in the presence of
individual or both of the two inputs, giving the output of “1”, and
20 this behavior is can be described as two OR logic gates. Since
there are two OR gates with different responses to the inputs, the
order can be exchanged when needed.
With the introduction of Cu2+ as the third input (IN3), the
molecular device can achieve a more complicated logic function.
25 With the similar behaviors on the absorption of receptor 1 upon
addition of Cu2+ compared with Zn2+ and Fꢀ, as we mentioned
above, the NOR and OR gates are both retained when Cu2+ (IN3)
acts on the combination of Zn2+ (IN1) and Fꢀ (IN2) (Fig. 6). On
the other hand, as shown in Fig. 7, the fluorescence intensity at
65 Experimental
General Considerations
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Analytical grade solvents and compounds were used for all
Acknowledgments
preparations. Anions and metal ions were used as the
tetrabutylammonium salt and nitrate, respectively. The water
used in our present work was deionized. UV/Visible (UV/Vis)
absorption spectra were obtained on a ShiꢀmadzuꢀUVꢀ3101
scanning spectrophotometer. Fluorescence spectra were measured
with a Hitachi Fꢀ4500 fluorescence spectrophotometer. The
excitation and emission wavelength bandpasses were both set at 5
nm. All spectral titrations were carried out by keeping the
The authors gratefully thank the financial supports of the NSFC
(Grant Nos. 51172224 and 51103145) and the Science and
55 Technology Developing Project of Jilin Province (Grant No.
20100533).
5
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6 (a) D. Margulies, G. Melman, A. Shanzer, J. Am. Chem. Soc. 2006,
128, 4865ꢀ4871; (b) S. D. Straight, P. A. Liddell, Y. Terazono, T. A.
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Synthesis of receptor 1 and 2
80
25 The compounds of 1 and 2 were synthesized according to the
procedure described in the literature10a
:
Thiocarbohydride: CS2 (13 mL) was added dropwise to a
solution of excess hydrazine hydrate (80%, 60 mL) in water (70
mL). After the addition, the mixture was refluxed with stirring for
30 4h and then cooled 30 min in iceꢀwater bath. The product was
filtrated and washed with ethanol and ether. A white solid of
thiocarbohydride was obtained by recrystallization in dilute
hydrochloric acid. Yield: 71%; 1H NMR (300 MHz, DMSOꢀd6), δ
(ppm): 4.50 (4H, NH2, s), 8.71 (2H, NH, s).
85
90
95
35 2ꢀnaphtholꢀ1ꢀaldehydeꢀconjugated thiourea (1): A solution of
2ꢀnaphtholꢀ1ꢀaldehyde (0.43 g, 2.5 mmol) or 1ꢀnaphthaldehyde
(0.39 g, 2.5 mmol) in ethanol (20 mL) was added slowly to a
solution of thiocarbohydride (0.1062g, 1 mmol) in water (10 mL).
The heterogonous mixture was refluxed with stirring for 5 h.
40 Then the mixture was cooled to room temperature and filtered.
The precipitate was washed with ethanol and dried under vacuo
100
105
110
115
7 D. C. Magri, A. P. de Silva, New J. Chem. 2010, 34, 476ꢀ481.
8 A. P. de Silva, N. D. McClenaghan, Chem. Eur. J. 2002, 8, 4935ꢀ4945.
9 M. J. Yuan, W. D. Zhou, X. F. Liu, M. Zhu, J. B. Li, X. D. Yin, H. Y.
Zheng, Z. C. Zuo, C. B. Ouyang, H. B. Liu, Y. L. Li, D. B. Zhu, J.
Org. Chem. 2008, 73, 5008ꢀ5014.
1
to afford receptor 1 in quantitative yield. Yield: 65%; H NMR
(300 MHz, DMSOꢀd6), δ (ppm): 12.89 (2H, NH, br s), 12.09 (2H,
OH, s), 9.17ꢀ9.63 (2H, CH=N, d), 8.20ꢀ8.54 (2H, ArH, d), 7.88ꢀ
45 7.96 (4H, ArH, q), 7.60ꢀ7.65 (2H, ArH, t), 7.39ꢀ7.44 (2H, ArH,
t), 7.23ꢀ7.26(2H, ArH, d).
10 (a) F. Han, Y. H. Bao, Z. G. Yang, T. M. Fyles, J. Z. Zhao, X. J. Peng,
J. L. Fan, Y. K. Wu, S. G. Sun, Chem. Eur. J. 2007, 13, 2880ꢀ2892;
(b) F. Otón, A. Espinosa, A. Tárraga, I. Ratera, K. Wurst, J. Veciana,
P. Molina, Inorg. Chem. 2009, 48, 1566ꢀ1576; (c) M. M. M. Raposo,
B. GarcíaꢀAcosta, T. Ábalos, P. Calero, R. MartínezꢀMáñez, J. V. Rosꢀ
Lis, J. Soto, J. Org. Chem. 2010, 75, 2922–2933; (d) P. Bose, P.
Ghosh, Chem. Commun. 2010, 46, 2962ꢀ2964; (e) D. Maity, T.
Govindaraju, Chem. Eur. J. 2011, 17, 1410ꢀ1414; (f) J. L. Wu, Y. B.
He, Z. Y. Zeng, L. H. Wei, L. Z. Meng, T. X. Yang, Tetrahedron 2004,
60, 4309–4314; (g) S. Y. Liu, L. Fang, Y. B. He, W. H. Chan, K. T.
Yeung, Y. K. Cheng, R. H. Yang, Orgnic. Lett. 2005, 7, 5825ꢀ2828; (h)
A. F. Li, J. H. Wang, F. Wang, Y. B. Jiang, Chem. Soc. Rev. 2010, 39,
3729ꢀ3745; (i) F. Wang, W. B. He, J. H. Wang, X. S. Yan, Y.Zhan, Y.
1ꢀaldehydeꢀconjugated thiourea (2): the synthesis procedure of
receptor 2 is same with that of receptor 1. Yield: 73%; H NMR
(300 MHz, DMSOꢀd6), δ (ppm): 11.83ꢀ12.03 (2, NH, d), 9.16
50 (2H, CH=N, br s), 8.31ꢀ8.45 (2H, ArH, d), 8.02ꢀ8.08 (6H, ArH,
t), 7.59ꢀ7.72 (6H, ArH, m).
1
6
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5
11 Y. Sun, Y. L. Liu, M. L. Chen, W. Guo, Talanta 2009, 80, 996ꢀ1000.
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14 (a) D. Maity, A. K. Manna, D. Karthigeyan, T. K. Kundu, S. K. PaTi,
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