Anion recognition based on phenolic hydroxyl group in competitive media

Article abstract of DOI:10.1007/s10847-011-0041-4

Two novel artificial receptors, one containing phenolic hydroxyl group and diamide (1), the other only containing diamide (2), were designed and synthesized. The binding ability evaluated by UV-vis and fluorescence titration experiments in dry DMSO reveal

Full text of DOI:10.1007/s10847-011-0041-4

J Incl Phenom Macrocycl Chem (2012) 73:185–192
DOI 10.1007/s10847-011-0041-4
ORIGINAL ARTICLE
Anion recognition based on phenolic hydroxyl group
in competitive media
•
Xin-Juan Li Xue-Fang Shang Lei-Lei Liu
•
•
•
Nan-kai Xi Jin-Lian Zhang Xiu-Fang Xu
•
Received: 28 May 2011 / Accepted: 6 September 2011 / Published online: 26 October 2011
Ó Springer Science+Business Media B.V. 2011
Abstract Two novel artificial receptors, one containing
phenolic hydroxyl group and diamide (1), the other only
containing diamide (2), were designed and synthesized.
The binding ability evaluated by UV–vis and fluorescence
titration experiments in dry DMSO revealed that com-
pound 1 could selectively recognize AcO-. In particular,
the binding ability can also be detected in the DMSO/H2O
solution by UV–vis. The interference experiment result
showed that the binding ability was not influenced by the
existence of other anions. In contrast, there were no
detectable interaction between receptor 2 and anions. The
further insights to the nature of interaction between
due to the important roles of anions in biomedicinal and
chemical processes [1–10]. Artficial anion receptor has
shown prospects of unique application in the synthesis of
anion sensors [11, 12], membrane transmit carriers [13, 14]
and mimic enzyme catalysts, etc. The structural design of
receptors is important in anion recognition. With regard to
the binding sites, the functional groups such as amide [15],
urea [9, 16] and hydroxyl groups [17–20] are numerously
used owing to their ability to perform as hydrogen donors.
However, the interaction mechanism based on the binding
sites of hydroxyl group and amide has been less studied in
anion recognition [21–23].
1
receptor 1 and AcO- were investigated by H NMR titra-
Among various biologically important anions, acetate
anion has attracted growing attention for its established
role in the enzymes and antibodies. Acetate is also the
significant component of numerous metabolic processes.
The sensing of acetate anion has aroused great interest and
several types of synthetic chemosensors have been devel-
oped to date [24, 25]. However, the recognition of acetate
anion in aqueous solution is still a challenge work owing to
the competitive protic solvent which interacts with the host
by H-binding prior to the anion [26–28].
tion experiments and theoretical investigation, which
demonstrated receptor 1 complexed AcO- through the
synergistic hydrogen bonding interaction of OH and NH.
Keywords Anion recognition ꢀ Acetate anion ꢀ
Phenolic hydroxyl group ꢀ Diamide
Introduction
According to this, we synthesized two novel receptors
(Scheme 1), one containing phenolic hydroxyl group and
diamide (1), the other containing only diamide (2), to
examine the difference of anion binding ability based on the
hydroxyl group and diamide recognition sites and explore the
interaction mechanism. Results indicated receptor 1 showed
high selectivity to acetate anion in DMSO and the mixture
solution DMSO/H2O. And the UV–vis spectral interference
experiment in DMSO/H2O (95:5, v/v) showed the binding
ability of AcO- with(and) receptor 1 was not influenced by
the existence of other anions. In addition, the 1H NMR, UV–
vis and theoretical investigation proved that the hydroxyl
group played an indispensable role in anion recognition.
Anion recognition by artificial receptors has attracted
considerable attention in the field of host–guest chemistry
X.-J. Li (&)
Henan Normal University, Xinxiang, Henan 453003, China
e-mail: xinjuan2009@yahoo.cn
X.-J. Li ꢀ X.-F. Shang (&) ꢀ L.-L. Liu ꢀ N. Xi ꢀ J.-L. Zhang
Xinxiang Medical University, Xinxiang, Henan 453003, China
e-mail: xuefangshang@126.com
X.-F. Xu
Nankai University, Tianjin 300071, China
123

186
J Incl Phenom Macrocycl Chem (2012) 73:185–192
Experimental
Chemicals
Fuming HNO3 (1.1 mL) was added dropwise with stirring
at 273 K. After that, the mixture was stirred for 2 h and
then poured into ca. 200 mL ice-water. The solution was
filtered and washed with distilled water, then the solid was
recrystallized from methanol and dried in vacuum to give a
yellow solid. Yield: 85%. 1H NMR (DMSO-d6, 298 K)
d = 10.96 (s, 1H), 10.74 (s, 1H), 8.04, 7.3(3H), 3.3 (s, 2H),
Elemental analysis: Calc. for C9H7N3O4: C, 48.88; H, 3.19;
N, 19.00; Found: C, 48.76; H, 3.58; N, 18.61.
All reagents obtained commercially for synthesis were
used without further purification. In the titration experi-
ments, all the anions added in the form of tetrabutylam-
monium (TBA) salts were purchased from Sigma–Aldrich
Chemical and dried fully. DMSO was dried with CaH2 and
then distilled under reduced pressure.
(40-Aminobenzo)[10,20-d]-1,4-diazacycloheptane[2,3-d]-
5,7-dione (5)
Apparatus
1H NMR spectra were obtained on a Varian UNITY Plus-
400 MHz spectrometer. ESI–MS was performed with a
MARINER apparatus. C, H, N elemental analyses were
made on an Elementar Vario EL. UV–vis spectra were
recorded on a Shimadzu UV2450 spectrophotometer with
quartz cuvette (path length = 1 cm) and fluorescent spectra
were recorded on a Shimadzu RF-5301 PC spectrophotom-
eter at 298.2 0.1 K and the width of the slits used is 5 nm.
A slurry of compound (40-nitrobenzo)[10,20-d]-1,4-diaza-
cycloheptane [2,3-d]-5,7-dione (221 mg) and Pd/C (10%,
70 mg) in dry ethanol (200 mL) was maintained under
hydrogen with stirring for 12 h. The mixture was filtered
through a bed of Celite and then washed twice with ethanol
(2 9 20 mL). The solvents were removed under reduced
pressure and the yellowish solid was dried in vacuum.
Yield: 92%. 1HNMR (DMSO-d6, 298 K) d = 10.15 (s,
1H), 9.91(s, 1H), 6.76 (d, 1H), 6.38 (m, 1H), 6.27 (d, 2H),
5.16 (s, 2H) 3.08 (s, 2H). Elemental analysis: Calc. for
C9H9N3O2: C, 56.54; H, 4.74; N, 21.98; Found: C, 56.41;
H, 4.96; N, 21.87.
Synthesis
Receptor 1, 2 were prepared according to the route shown
in Scheme 2.
N-(20-Hydroxyl-30-bromophenyl-methylene-yl)-40-imino-
benzo[10,20-d]-1,4-diazacycloheptane[2,3-d]-5,7-dione
(receptor 1)
Benzo-1,4-diazacycloheptane[2,3-d]-5,7-dione (3)
1,2-Phenylenediamine (10.8 g, 0.1 mol), diethyl malonate
(16 mL, 0.1 mol) and pyridine (200 mL) were put in a
250 mL three-neck flask. The mixture was refluxing under
N2 for 72 h. After cooling, the mixture was filtrated and the
white solid was obtained. The solid was washed with eth-
anol and ether sequentially, and dried in vacuum. Yield:
72%. 1H NMR(DMSO-d6, 298 K) d = 10.38 (s, 2H),
7.11–7.18 (m, 4H), 3.17(s, 2H). Elemental analysis: Calc.
for C9H8N2O2: C, 61.36; H, 4.58; N, 15.90; Found: C,
61.69; H, 4.59; N, 15.96. FAB-MS (m/z): 177 (M ? H)?.
(40-Aminobenzo)[10,20-d]-1,4-diazacycloheptane[2,3-d]-5, 7-
dione (1 mmol, 191 mg) and 3,5-dibromo-salicylaldehyde
(1 mmol, 278 mg) were suspended in dry ethanol (100 mL).
The mixture was refluxed for 8 h and the orange-yellow
precipitate was separated by filtration. The solid was washed
with diethyl ether and dried under vacuum. Yield: 88%. 1H
NMR (400 MHz, DMSO-d6, 298 K) d = 12.79 (s, 1H),
10.46 (s, 2H), 8.96 (s, 1H), 7.88(d, 1H), 7.51 (m, 1H), 7.26
(m, 1H), 7.21 (m, 1H), 7.12(s, 1H), 6.95 (m, 1H), 3.23 (s,
2H). Elemental analysis: Calc. for C16H12BrN3O3: C, 51.36;
H, 3.23; N, 11.23; Found: C, 51.32; H, 3.24; N, 11.28. ESI–
MS(m/z):374.92 [(M ? H)-, Calcd. 375.00].
(40-Nitrobenzo)[10,20-d]-1,4-diazacycloheptane[2,3-d]-5,7-
dione (4)
Benzo-1, 4-diazacycloheptane[2, 3-d]-5, 7-dione(10 mmol,
1.7 g) was dissolved in concentrated H2SO4 (43 mL).
N-(20-Hydroxyl-40-chlorobenzene-methylene-yl)-40-imino-
benzo[10,20-d]-1,4-diazacycloheptane[2,3-d]-5,7-dione
(receptor 2)
OH
H
N
H
N
O
O
O
O
H
H
(40-Aminobenzo)[10,20-d]-1,4-diazacycloheptane[2,3-d]-5, 7-
dione (1 mmol, 191 mg) and 4-chlorobenzene-salicylalde-
hyde (1 mmol, 278 mg) were suspended in dry ethanol
(100 mL). The mixture was refluxed for 8 h and the orange-
yellow precipitate was separated by filtration. The solid was
washed with diethyl ether and dried under vacuum. Yield:
Br
C
C
N
N
Cl
N
H
N
H
1
2
Scheme 1 Chemical structure of receptor 1 and 2
123

J Incl Phenom Macrocycl Chem (2012) 73:185–192
187
H
N
O
O
H
N
O
O
H
N
O
O
NH2
CH2(COOC2H5)2
O2N
H2N
fuming HNO3
Pd/C H2
pyridine,reflux
NH2
N
H
N
H
N
H
3
4
5
OH
Br
CHO
1 or 2
Cl
or
CHO
Scheme 2 Synthesis route for 1 and 2
88%. 1H NMR (400 MHz, DMSO-d6, 298 K) d = 10.43 (s,
2H), 8.64 (s, 1H), 7.94(d, 2H), 7.60 (m, 2H), 7.16 (m, 2H),
7.04 (s, 1H), 3.23 (s, 2H). Elemental analysis: Calc. for
C16H12ClN3O2: C, 61.25; H, 3.86; N, 13.39; Found: C,
61.27; H, 3.84; N, 13.40. ESI–MS(m/z):314.12 [(M ? H)-,
Calcd. 313.06].
correlation coefficients obtained by noninear least-square
calculation method according to UV–vis data were listed in
Table 1 [31, 32]. The order of selectivity: AcO- [ F- [
H2PO4- [ Cl-, Br-, I-. Receptor 1 showed the highest
binding ability with acetate anion which could be selec-
tively recognized from other anions based on its associa-
tion constant. It was likely that 1 could interact with AcO-
through multiple hydrogen bonding [23]. To investigate the
effect of hydroxyl groups in receptor 1 on anion recogni-
tion, compound 2 was synthesized as a reference com-
pound. Interestingly, there was no change in the absorption
spectra of compound 2 (Fig. 3), even though F- and AcO-
were added, which showed that there was almost no or very
weak binding ability between compoud 2 and anions. The
above facts fully proved that the receptor 1 interacted with
anions through hydrogen bonding. That is to say, the effect
of the hydroxyl group on receptor 1 was indispensable for
anion recognition.
Results and discussion
UV–vis titration studies
The anion binding ability of the compounds was firstly
investigated through UV–vis titration spectra by adding a
standard tetrabutylammonium salt solution of anions to the
dry DMSO solution of compounds at 298.2 0.1 K.
In the absence of anions, compound 1 (4.0 9 10-5 M in
DMSO) displayed obvious absorption peak at 365 nm. As
shown in Fig. 1, the addition of F-, AcO- and H2PO4 to
It is well known that the added protic solvents such as
water or methanol will form hydrogen-bonding with the
-
DMSO solution of 1 led to obvious changes in the
absorption spectrum [29, 30]. The absorption peak at
365 nm decreased obviously and a new absorption peak at
about 449 nm developed. The red-shift phenomenon has
also been observed with the addition of anions. In contrast,
the addition of other anions (Cl-, Br-, I-) did not trigger
noticeable spectral change of compound 1 (Fig. 1), indi-
cating very weak or no interaction between these anions
and compound 1. Noticeably, colorless DMSO solution of
compound 1 turned yellow after interaction with F-, AcO-
and H2PO4-, which contributed to significant development
of absorption peak at 449 nm.
Figure 2 showed the significant UV–vis spectral chan-
ges of receptor 1 when the acetate concentration changed
from 0 to 200 9 10-5 M. The main absorption decreased at
365 nm and increased at 449 nm, and two distinct isos-
bestic points appeared at 316 nm and 392 nm. The job-plot
analysis based on this concentration indicated that the
spectral change could be ascribed to the formation of 1:1
host–guest complexation. The association constants and
Fig. 1 UV–vis spectra of 1(4 9 10-5 M) in DMSO in the presence
of 50 equiv. of AcO-, F-, H2PO4 and miscellaneous anions
-
including Cl-, Br- and I-
123

188
J Incl Phenom Macrocycl Chem (2012) 73:185–192
Fig. 2 Evolution of UV–vis
spectrum of receptor 1
(4 9 10-5 M) on addition of
[AcO-] = 0–200 9 10-5 M in
DMSO. The inset showed the
changes of absorbance at
448 nm against the added AcO-
Table 1 Association constants (Kass, M-1) of the receptor 1 with anions in DMSO and DMSO/H2O (95/5, v/v) at 298.2 0.1 K
-
Anionsa
AcO-
F-
H2PO4
Cl-
Br-
I-
Kassb
Kassd
Kasse
a
8.62 0.37 9 104
7.86 0.85 9 104
1.81 0.26 9 104
1.60 0.19 9 103
2.47 0.48 9 103
1.56 0.19 9 103
329 76
281 41
ND
NDc
ND
ND
ND
ND
ND
ND
ND
ND
The anions were added as their tetrabutylammonium salts
b
c
d
e
Association constant was determined in DMSO by fluorescence in dry DMSO
Association constant could not be determined due to very weak complexation
Association constant was determined by UV–vis in dry DMSO
Association constant was determined by UV–vis in DMSO/H2O (95/5, v/v)
binding site of receptor, which influences the interaction of
response of receptor 1 upon the addition of the mixed
anions was almost the same as the addition of only acetate
anion, which showed the binding ability of AcO- with
receptor 1 was not influenced by the existence of other
anions even though 5% water was added.
receptor-anion. In view of the high selectivity of receptor 1
in the dry DMSO, we also design experiments in DMSO/
H2O (95:5, v/v) solution to further investigate their per-
formance. In DMSO/H2O solution, receptor 1 revealed a
different spectrum which showed two bands at 320 nm and
366 nm due to 5% protic water. With the addition of
AcO-, the bands centered at 428 nm were gradually
Fluorescent titrations
enhanced and
a
well-defined isosbestic at 395 nm
The binding behavior of receptor 1 and anions was inves-
tigated by fluorescent titrations in dry DMSO solution.
Obviously, compound 1 exhibited weak fluorescent emis-
sion peaks at 456 nm (see Fig. 6), upon excitation wave-
length at 407 nm. Significant spectral changes were
appeared. Receptor 1 still had recognition ability for AcO-
in DMSO/H2O (95:5, v/v) as shown in Fig. 4. The binding
ability of receptor 1 with AcO- was the strongest among
the anions studied according to association constant (see
Table 1).
-
observed upon the addition of F-, AcO- and H2PO4 to
To make clear whether the binding ability of receptor 1
with AcO- changed under the condition that all anions
studied existed simultaneously, we conducted the UV–vis
spectral interference experiment [33] in DMSO/H2O (95:5,
v/v) (Fig. 5). Results indicated that the intensity of spectral
DMSO solution of compound 1. Interestingly, the addition
of AcO- to DMSO solution of receptor 1 made the emis-
sion peak shift to the long-wave direction, concomitant
with an obvious increase in its emission intensity (Fig. 6).
Similar fluorescence enhancement phenomena were also
123

J Incl Phenom Macrocycl Chem (2012) 73:185–192
189
Fig. 5 UV–vis spectrum of receptor 1 (4 9 10-5) on addition of
anion in DMSO:H2O (95:5 v/v) solution (the concentration of anion is
50 equiv.)
Fig. 3 UV–vis spectra of 2 (2 9 10-5 M) in DMSO in the presence
of 50 equiv. of AcO-, F-, H2PO4 and miscellaneous anions
-
including Cl-, Br- and I-
Fig. 6 Fluorensecence spectra of 1 (2 9 10-5 M) in DMSO in the
-
presence of 50 equiv. of AcO-, F-, H2PO4 and miscellaneous
Fig. 4 UV–vis spectrum of receptor 1 (4 9 10-5) on addition of
[AcO-] = 0–200 9 10-5 M in DMSO: H2O (95:5 v/v) solution.
Arrows indicate the direction of increasing anion concentration
anions including Cl-, Br- and I-
Scheme 3 The proposed host–
guest binding mode in solution
OHa
CH3
O
O
AcO-
H
Hb
N
O
H
Hd
H
Hc
C
H
N
O
O
O
Br
H
N
Br
C
N
DMSO DMSO/H2O(95/5)
N
Hb' O
N
H
found after the addition of other anion (F- and H2PO4-),
but the increasing intensity was not obvious [23]. Other-
wise, the addition of excess equiv. Cl-, Br-, I- ions had a
slight effect on fluorescence intensity. As demonstrated in
Scheme 3, the conformational restriction of receptor 1 was
induced upon interaction with acetate ion through
hydrogen-bonding. Therefore, there existed astonishingly
strong enhancement of the fluorescence intensity observed
in Fig. 7, which could be derived from the increase of the
rigidity in receptor molecules [23].
The association constants were also calculated accord-
ing to fluorescence results. As expected, the analytical
123

190
J Incl Phenom Macrocycl Chem (2012) 73:185–192
results of the fluorescence titration were very consistent
with those results of the UV–vis titration, which can be
seen from Table 1 [34].
1H NMR titrations
To shed a light on the nature of the interaction between the
anions tested and receptor 1, 1H NMR titrations were
carried out in DMSO-d6. Figure 8 showed 1H spectral
changes of receptor 1 (2 9 10-3 M) in DMSO-d6 in the
absence and presence of different equivalent of acetate
ions. Obviously, after addition of 0.5 equiv. of AcO-, the
proton signal of the –OH group (Ha) at 12.79 ppm disap-
peared, which showed the proton of the hydroxyl group
formed the hydrogen bonding with acetate ion. The double
peak signal at 10.46 ppm (Hb) of amides broadened by
addition of the AcO- from 0 to 1 equiv.. With the further
addition of AcO- (5 equiv.), the resonance signal of the –
NH also broadened obviously and exhibited a little
downfield shift due to the hydrogen bond formation
between the acetate and the diamide in receptor 1. No
obvious change was observed in the proton signal of the
–CH group at 8.96 ppm (Hc) when the addition of the
AcO- changed from 0 to 1 equiv.. When the concentration
of AcO- was up to 5 equiv., the chemical shift of the –CH
shifted to the upfield. With the addition of acetate ions, the
phenyl protons especially for the protons Hd (at 7.51 ppm)
shifted to upfield significantly, which indicated the increase
of the electron density on the phenyl ring owing to the
through-bond effects. The phenyl ring proton away from
OH at 7.26, 7.12 and 6.95 ppm all moved upfield due to the
shielding effect which resulted from the electron density
increase of the phenyl rings through the bond spreading.
These changes clearly indicated that the host–guest inter-
action indeed involved the formation of hydrogen-bond by
hydroxyl group and diamide (Scheme 3).
Fig. 7 Fluorescent changes of the sensor 1 in DMSO (2 9 10-5 M)
upon addition of AcO-, Arrow indicates the direction of increasing
anion concentration
Fig. 8 1H NMR titration of a 2.0 9 10-3 M solution of 1 in DMSO-
d6 with AcO-
Theoretical investigation on the structure
To understand the geometry of the receptor-acetate com-
plex, the structures of receptor were optimized. The cal-
culations were carried out at the B3LYP level of theory
with 3-21G as the basis set through Gaussian 03 package
[35]. For geometry optimizations, the first guess was fully
optimized by AM1 semi-empirical Hamiltonian. Then the
models were re-optimized at B3LYP/3-21G level of theory.
The B3LYP/3-21G-optimized structures for the complexes
of receptor 1 with acetate [36] are represented in Fig. 9. As
for acetate, two oxygens participated in the formation of
hydrogen bond, one oxygen atom formed hydrogen bond
˚
with the protons of OH (dOꢀꢀꢀH(a) = 1.946 A) and imine
˚
(dOꢀꢀꢀH(c) = 2.025 A), another oxygen atom formed
Fig. 9 B3LYP/3-21G-predicted optimized geometry of complex of 1
with acetate
˚
hydrogen bond with one (dOꢀꢀꢀH(b) = 2.072 A) of two
123

J Incl Phenom Macrocycl Chem (2012) 73:185–192
191
Fig. 10 The selected frontier
orbitals. a HOMO of 1,
b LUMO of 1, c HOMO of 2,
d LUMO of 2
–NH protons and the proton of benzene ring (dOꢀꢀꢀH(d) =
Table 2 The calculation results on the energy gap of ELUMO, EHOMO
of 1 and 2
˚
2.041 A). Finally, the receptor 1 is bound to the acetate
anion by four hydrogen bond contacts yielding a highly
stable 1:1 complex (Scheme 3).
Compound
1
2
ELUMO (a.u.a)
EHOMO (a.u.)
DE (kJ mol-1
a
-0.03186
-0.22168
498.37
-0.03082
-0.22218
502.42
Theoretical investigation on molecular orbital level
using density functional theory at B3LYP/3-21G level with
Gaussion03 program can also explain the hydrogen bond
interaction (Fig. 10). The calculation results on the energy
gap of ELUMO, EHOMO of 1 and 2 were listed in Table 2.
From Table 2, the energy gap DE(ELUMO- EHOMO) of
compound 2 is larger than that of 1, which implies com-
pound 1 has higher reaction activity than compound 2.
Therefore it is easier for compound 1 to interact with
anions than compound 2 and has stronger binding ability.
In addition, selected frontier orbitals for compounds are
shown in Fig. 10. We introduced molecular frontier orbital
in order to explain UV–vis absorption spectra in host–guest
interacted process by electron transition of frontier orbital.
The HOMO density in compound 1 is localized on the
whole molecular while the LUMO density is only localized
on diamide moiety, which illustrates the electron transition
of the LUMO arouses the red shift phenomenon in UV–vis
spectra and the fluorescence enhancement of 1-anion.
In receptor 1, the charge of the oxgyen atom (O) of –OH
group is -0.582572, and the charges of the nitrogen atoms
of –NH are -0.829401 and -0.830528, respectively. The
charges of the nitrogen atoms in receptor 2 are -0.828908
and -0.830347, respectively. The smaller the charge of the
oxgyen atom of phenolic hydroxyl group is, the stronger
the binding ability is. Thus it is easier for AcO- to interact
with hydrogen of OH than that of NH.
)
1 a.u. = 2625.5 kJ mol-1
Conclusion
In summary, a new receptor bearing phenolic hydroxyl
group and diamide (1) showed anion-binding ability
through UV–vis, fluorescent and 1H NMR titrations in
DMSO and DMSO/H2O (95:5 v/v). The results demon-
strated that 1 could bind strongly with anions and selec-
tively distinguish AcO- from other anions according to the
association constants. The experimental results and theo-
retical investigation proved that receptor 1 interacted
AcO- through multiple hydrogen bonding interaction with
the –OH and the –NH. In addition, the binding ability of
AcO- with receptor 1 was not influenced by the existence
of other anions even in DMSO/H2O (95:5 v/v). The
experiments and theoretical investigation may contribute to
the development of more colorimetric and fluorescent
chemosensors.
Acknowledgment This work was supported by the NSF of Henan
Province (2010B150024) and Doctorial Science Fund of Henan
Normal University and Xinxiang Medical University.
In previous text, the anion binding ability of compound
2 only containing –NH was very weak and could not be
used for anion recognition. However, compound 1 con-
taining –OH and –NH showed strong anion binding ability
which may be relevant to multiple hydrogen bond [23].
These results proved that the hydroxyl group played an
important role in anion recognition.
References
1. Sjevcjuk, S.V., Lynch, V.M., Sessler, J.L.: A new terpyrrolic
analogue of dipyrrolylquinoxalines: an efficient optical-based
sensor for anions in organic media. Tetrahedron 60, 11283–11291
(2004)
123

192
J Incl Phenom Macrocycl Chem (2012) 73:185–192
2. Gale, P.A.: Anion coordination and anion-directed assembly:
highlights from 1997 and 1998. Coord. Chem. Rev. 199, 181–233
(2000)
3. Beer, P.D., Gale, P.A.: Anion recognition and sensing: the state
of the art and future perspectives. Angew. Chem. Int. Ed. 40,
486–516 (2001)
4. Gale, P.A.: Anion receptor chemistry: highlights from 1999.
Coord. Chem. Rev. 213, 79–128 (2001)
5. Sessler, J.L., Davis, J.M.: Sapphyrins: versatile anion binding
agents. Acc. Chem. Rev. 34, 989–997 (2001)
6. Sancenon, F., Martinez-Manez, R., Miranda, M.A., Segui, M.J.,
Soto, J.J.: Towards the development of colorimetric probes to
discriminate between isomeric dicarboxylates. Angew. Chem.
Int. Ed. 42, 647–650 (2003)
7. Bondy, C.R., Loeb, S.J.: Amide based receptors for anions.
Coord. Chem. Rev. 240, 77–99 (2003)
8. Gale, P.A.: Anion and ion-pair receptor chemistry: highlights
from 2000 and 2001. Coord.Coord. Chem. Rev. 240, 191–221
(2003)
9. Valeria, A., Luigi, F., Lorenzo, M.: Anion recognition by
hydrogen bonding: urea-based receptors. Chem. Soc. Rev. 39,
3889–3915 (2010)
21. Zhang, X., Guo, L., Wu, F.Y., Jiang, Y.B.: Development of
fluorescent sensing of anions under excited-state intermolecular
proton transfer signaling mechanism. Org. Lett. 5, 2667–2670
(2003)
22. Bao, X.P., Zhou, Y.H.: Synthesis and recognition properties of a
class of simple colorimetric anion chemosensors containing OH
and CONH groups. Sensors and Actuators B 147, 434–441 (2010)
23. Bao, X.P., Yu, J.H., Zhou, Y.H.: Selective colorimetric sensing
for F- by a cleft-shaped anion receptor containing amide and
hydroxyl as recognition units. Sensors and Actuators B 140,
467–472 (2009)
24. Gunnlaugsson, T., Davis, A.P., O’Brien, J.E., Glynn, M.: Fluo-
rescent sensing of pyrophosphate and bis-carboxylates with
charge neutral PET chemosensors. Org. Lett. 4, 2449–2452
(2002)
25. Shao, J., Lin, H., Lin, H.K.: Rational design of a colorimetric and
ratiometric fluorescent chemosensor based on intramolecular
charge transfer (ICT). Talanta. 77, 273–277 (2008)
26. Li, Y.P., Li, J.W., Lin, H., Shao, J., Cai, Z.S., Lin, H.K.: A novel
colorimetric receptor responding AcO- anions based on an azo
derivative in DMSO and DMSO/water solution. Journal of
Luminescence 130, 466–472 (2010)
10. Gabriella, C., Pierangelo, M., Tullio, P., Giuseppe, R., Maurizio,
S., Giancarlo, T.: Halogen bonding: a general route in anion
recognition and coordination. Chem. Soc. Rev. 39, 3772–3783
(2010)
27. Zhang, Y.H., Yin, Z.M., He, J.Q., Cheng, J.P.: Effective receptors
for fluoride and acetate ions: synthesis and binding study of
pyrrole- and cystine-based cyclopeptido-mimetics. Tetrahedron
Lett. 48, 6039–6043 (2007)
11. Buhlmann, P., Pretsch, E., Bakker, E.: Carrier-based ion-selective
electrodes and bulk optodes. 2. Ionophores for potentiometric and
optical sensors. Chem. Rev. 98, 1593–1688 (1998)
12. Hassan, S.S.M., Attawiya, A.M.Y.: A novel uranyl membrane
sensor with potentiometric anionic response. Talanta. 70, 883–
889 (2006)
13. Kral, V., Sessler, J.L.: Molecular recognition via base-pairing and
phosphate chelation. Ditopic and tritopic sapphyrin-based
receptors for the recognition and transport of nucleotide mono-
phosphates. Tetrahedron 51, 539–554 (1995)
28. Maeda, H., Ito, Y.: BF2 complex of fluorinated dipyrrolyldike-
tone: a new class of efficient receptor for acetate anions. Inorg.
Chem. 45, 8205–8210 (2006)
29. Wu, F.Y., Li, Z., Wen, Z.C., Zhou, N., Zhao, Y.F., Jiang, Y.B.: A
novel thiourea-based dual fluorescent anion receptor with a rigid
hydrazine spacer. Organic letter 4, 3203–3205 (2002)
30. Han, F., Bao, Y.H., Yang, Z.G., Fyles, T.M.: Simple bis-
thiocarbonohydrazones as sensitive, selective, colorimetric, and
switch-on fluorescent chemosensors for fluoride anions. Chem.
Eur. J. 13, 2880–2892 (2007)
´
´
14. Jesus Seguı, M., Lizondo-Sabater, J., Benito, A.: A new ion-
selective electrode for anionic surfactants. Talanta 71, 333–338
(2007)
31. Liu, Y., Han, B.H., Zhang, H.Y.: Spectroscopic studies on
molecular recognition of modified cyclodextrins. Curr. Org.
Chem. 8, 35–46 (2004)
15. Hossain, M.A., Liljeren, J.A., Powell, D., Jame, K.B.: Anion
binding with a tripodal amine. Inorg. Chem. 43, 3751–3755
(2004)
16. Shao, J., Lin, H., Shang, X.F., Chen, H.M., Lin, H.K.: A novel
neutral receptor for selective recognition of H2PO4-. J. Inclusion
Phenom. Macrocyclic Chem 59, 371–375 (2007)
17. Shin-ichi, K.: Effect of hydroxyl groups in receptors bearing
disulfonamide on anion recognition in acetonitrile-d3. Tetrahe-
dron Lett. 43, 7059–7061 (2002)
18. Shang, X.F., Lin, H., Cai, Z.S., Lin, H.K.: Effects of the receptors
bearing phenol group and copper(II) on the anion recognition and
their analytical application. Talanta. 73, 296–303 (2007)
19. Jose, D.A., Kar, P., Koley, D., Ganguly, B.: Phenol- and catechol-
based ruthenium(II) polypyridyl complexes as colorimetric sen-
sors for fluoride ions. Inorg.Chem. 46, 5576–5584 (2007)
20. Davis, A.P., Perry, J.J., Wareham, R.S.: Anion recognition by
alkyl cholates: neutral anionophores closely related to a natural
product. Tetrahedron Lett. 39, 4569–4572 (1998)
32. Liu, Y., You, C.C., Zhang, H.Y.: Supramolecular Chemistry.
Nankai University Publication, Tian Jin (2001)
33. Korendovych, I.V., Cho, M., Butler, P.L., Staples, R.J., Rybak-
Akimova, E.V.: Anion binding to monotopic and ditopic mac-
rocyclic amides. Org Lett 8, 3171–3174 (2006)
34. Lee, D.H., Im, J.H., Lee, J.H., Honga, J.I.: A new fluorescent
fluoride chemosensor based on conformational restriction of a
biaryl fluorophore. Tetrahedron Lett. 43, 9637–9640 (2002)
35. Frisch, M.J., Trucks, W., Schlegel, H.B., Scuseria, G.E.: Gaussian
03, Revision A. 1. Gaussian, Inc., Pittsburgh, PA (2003)
36. Shang, X.F., Xu, X.F., Lin, H., Shao, J., Lin, H.K.: Efficient
fluoride-selective receptor: experiment and theory. J. Incl. Phe-
nom. Macrocycl. Chem. 58, 275–281 (2007)
123