Electrochemical study of structural effects in complexation of nano-baskets: Calix[4]-1,2-crown-3,-crown-4,-crown-5,-crown-6

Article abstract of DOI:10.1080/15533174.2012.680131

Eight nano-baskets of calix[4]arene-1,2-crown-3,-crown-4,-crown-5,-crown-6 were synthesized and their binding abilities towards alkali and alkaline earth metals as well as some lanthanides were studied using differential pulse voltammetry. The novelty of this study was investigation of those macrocyclic complexes by voltammetric behaviors of two acidic moieties in each scaffold during complexation of crown ether ring. The results revealed that by increasing the binding ability of macrocycle and cation, the anodic oxidation peak of carboxylic acids was decreased. Moreover, the voltammetric traces of low energy complexes did not affected by encapsulated cations in the coordination space of crown ether.

Full text of DOI:10.1080/15533174.2012.680131

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Electrochemical Study of Structural Effects in
Complexation of Nano-baskets: Calix[4]-1,2-crown-3, -
crown-4, -crown-5, -crown-6
Bahram Mokhtari a & Kobra Pourabdollah a
a Razi Chemistry Research Center (RCRC), Shahreza Branch , Islamic Azad University ,
Shahreza , I. R. Iran
Accepted author version posted online: 21 Jun 2012.Published online: 28 Aug 2012.
To cite this article: Bahram Mokhtari & Kobra Pourabdollah (2012) Electrochemical Study of Structural Effects in
Complexation of Nano-baskets: Calix[4]-1,2-crown-3, -crown-4, -crown-5, -crown-6, Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry, 42:8, 1091-1097, DOI: 10.1080/15533174.2012.680131
To link to this article: http://dx.doi.org/10.1080/15533174.2012.680131
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:1091–1097, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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DOI: 10.1080/15533174.2012.680131
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Electrochemical Study of Structural Effects in Complexation
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of Nano-baskets: Calix[4]-1,2-crown-3, -crown-4, -crown-5,
-crown-6
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Bahram Mokhtari and Kobra Pourabdollah
Razi Chemistry Research Center (RCRC), Shahreza Branch, Islamic Azad University, Shahreza, I. R. Iran
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calix[4]crowns lag far behind. Combining crown ethers with
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calix[4]arenes increases the cation binding ability of the parent
calixarenes, and control of the selectivity is obtained through
Eight nano-baskets of calix[4]arene-1,2-crown-3, -crown-4,
-crown-5, -crown-6 were synthesized and their binding abilities to-
wards alkali and alkaline earth metals as well as some lanthanides
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modulation of the crown ether size. Attachment of proton-
were studied using differential pulse voltammetry. The novelty of
ionizable groups to calixcrowns can further improve their
this study was investigation of those macrocyclic complexes by
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extraction properties because the ionized group not only par-
voltammetric behaviors of two acidic moieties in each scaffold dur-
ing complexation of crown ether ring. The results revealed that by
increasing the binding ability of macrocycle and cation, the anodic
oxidation peak of carboxylic acids was decreased. Moreover, the
voltammetric traces of low energy complexes did not affected by
encapsulated cations in the coordination space of crown ether.
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E
ans
T
fer
R
aqu
A
eous
C
ph
T
ase
ticipates in metal ion cooErdination, but also eliminates the need
TED
ani
D
ons in
R
to t
E
he o
T
rga
R
nic
A
pha
C
se.
Ung
aro
et al.[9] reported the first di-proton-ionizable calix[4]crown-5 in
1984 and it showed quite high efficiency in extraction of diva-
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lent cations from water into dichloromethane. Combining crown
ethers with calix[4]arenes increases the cation binding ability
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Keywords nano-basket, calixcrown, differential pulse voltammetry
of the parent calixarenes.[10–12] Some voltammetric techniques
using calixarenes are shown in Table 1. Other applications of
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Nano-baskets can be found in literatures.[34-57]
INTRODUCTION
Nano-baskets of calixarenes and calixcrowns are a versa-
tile class of macrocycles, which have been subject to exten-
In this work, eight diacid proton-ionizable calixcrowns
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were synthesized including cone p-tert-butyl-25,26-di(carbox-
ymethoxy) calix[4]arene1,2-crown-3 (10), cone p-tert-butyl-25,
sive research in development of many extractants, transporters,
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26-di(carboxymethoxy) calix[4]arene1,2-crown-4 (11), cone p-
and stationary phases (using gas chromatograph, Teif Gostar
tert-butyl-25,26-di(carboxymethoxy) calix[4]arene1,2-crown-5
Faraz Co., Iran) over the past four decades.[1–5] Functional-
ization of calix[4]arenes at both the upper rim and the lower
rim has been extensively studied. Attaching donor atoms to the
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(12), cone p-tert-butyl-25,26-di(carboxymethoxy) calix[4]
arene1,2-crown-6 (13), cone 25,26-di(carboxymethoxy) calix
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[4]arene1,2-crown-3 (23), cone 25,26-di(carboxymethoxy)
lower rim of a calix[4]arene can improve the binding strength
calix[4]arene1,2-crown-4 (24), cone 25,26-di(carboxymethoxy)
of the parent calixarene dramatically. The two main groups of
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calix[4]arene1,2-crown-5 (25), and cone 25,26-di(carboxy-
lower rim functionalized calix[4]arenes are calix[4]arene po-
RETRACTED RETRACTED RhmaevtiEhoorxy) calix[4]arene1,2-crown-6 (26). The voltammetric be-
TED
T
of t
R
he s
A
ynth
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esiz
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ed
E
scaffolds
D
R
wa
E
s d
T
eter
R
min
A
ed u
C
sin
g some
dands and calixarene-crown ethers.[6,7] Distal hydroxyl groups
can be connected to give 1,3-bridged calix[4]crowns, while con-
nection between proximal hydroxyl groups leads to 1,2-bridged
calix[4]crowns.
alkali, alkaline earth, transition metals, and lanthanides. Figure 1
depicts the chemical structure of eight calixcrown scaffolds as
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extractant agents.
It is found that the 1,3-bridged calix[4]crowns exhibit
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high binding affinity and selectivity toward alkali and alka-
line earth metal cations,[8] while the researches on 1,2-bridged
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THE SYNTHESIS PROCEDURE
Reagents were obtained from commercial suppliers and
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used directly, unless otherwise noted. Acetonitrile (MeCN)
was dried over CaH2 and distilled immediately before use.
Received 21 August 2011; accepted 27 December 2011.
This work was supported by Islamic Azad University (Shahreza
branch) and Iran Nanotechnology Initiative Council.
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Tetrahydrofuran (THF) was dried over sodium with benzophe-
none as an indicator and distilled just before use. Cs2CO3 was
Address correspondence to Kobra Pourabdollah, Razi Chemistry
activated by heating at 150◦C overnight under high vacuum and
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Research Center (RCRC), Shahreza Branch, Islamic Azad University,
Shahreza, I. R. Iran. E-mail: pourabdollah@iaush.ac.ir
stored in a desiccator. Melting points were determined with a
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1091
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TABLE 1
List of some calixarenes used in the voltammetric techniques.
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Concept of study
Type of calixarene
Analyte
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Differential pulse anodic stripping
voltammetry[13]
p-isopropylcalix[6]arene
Silver
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Stripping voltammetry[14]
Langmuir–Blodgett film of a calix[4]arene
derivative
Silver
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Stripping voltammetry[15]
Langmuir–Blodgett film of allylcalix[4]arene
Langmuir–Blodgett film of
p-allylcalix[4]arene
Langmuir–Blodgett film of
p-allylcalix[4]arene
4-tert-butyl-1-
Cadmium
Cadmium
Anodic stripping voltammetry[16]
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Anodic stripping voltammetry[17]
Mercury
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Anodic stripping voltammetry[18]
Mercury
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(ethoxycarbonylmethoxy)thiacalix[4]arene
Differential pulse anodic stripping
Langmuir–Blodgett film of allylcalix[4]arene
Copper
[19]
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voltammetry
Adsorptive square wave voltammetry[20]
Cyclic voltammetry[21]
tetrabenzyl ether calix[4]arene
calix[4]arene derivative
p-tert-butyl-calix[6]arene
calix[4]arene crown-4 ether
calix[4]arene crown-4 ether
Adduct formation of 2-furaldehyde
Dopamine
Folic acid
Norepinephrine
Dopamine
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Adsorptive stripping voltammetry[22]
Voltammetric methods[23]
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Cyclic voltammetry[24]
Cyclic and differential pulse
p-tetra-butyl calix[6]arene-L-Histidine
Epinephrine and serotonin
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voltammetry[25]
Voltammetric methods[26]
calixcrownchips
c-methylcalix[4]resorcenarene and
calix[8]arene
c-benzylresorcinolcalixarene
calix[4]arene crown-4 ether film
Antigens and antibodies
Nicotinamide
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Voltammetric methods[27]
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Conductometric chemosensor[28]
Electrochemical impedance
Amines and amino acids
Norepinephrine
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spectroscopy[29]
Conductivity gas sensor[30]
—
—
Methanol, ethanol, and propanol
Amino acids
Carbofuran
[31]
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Capacitive sensing sensor
Electrochemical flow injection
resorcin[4]arene
[32]
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analysis
Faradic electrochemical impedance
carboxylic-calixarene, benzyl-calixarene, and
long chain sulphonated-calixarene
Arginine and lysine
[33]
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spectroscopy
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AL CTED RETRACTED
R
M
E
el-T
T
em
R
p m
A
eltin
C
g p
T
oin
E
t ap
D
parat
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us.
E
Inf
T
rare
R
d (I
A
R) s
C
pec
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we
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E
R
XP
Voltammetric measurements were utilized by a Model
660 electrochemical workstation (CH Instruments, Austin,
E
ERI
T
ME
R
NT
A
recorded with a Perkin-Elmer Model 1600 FT-IR spectrometer
¨
(Uberlingen, Germany) as deposits from CH2Cl2 solution on
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NaCl plates. The H and 13C NMR spectra were recorded
1
Texas, USA) with a three-electrode cell including a Pt wire
counter electrode, a glassy carbon working electrode and an
with a Varian Unity INOVA 500 MHz FT-NMR (1H 500 MHz
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and 13C 126 MHz) spectrometer (Welnut Creek, CA, USA)
in CDCl3 with Me4Si as internal standard unless mentioned
Ag/Ag+(0.1 M) reference electrode, separated from the solution
by a plug. The surface of the glassy carbon electrode was pol-
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otherwise. Chemical shifts (δ) are given in ppm downfield
from TMS and coupling constants (J) values are in Hz. The
ished using 0.3 µm alumina (Buehler, Lake Bluff, Minnesota,
USA) and residual alumina particles were thoroughly removed
by placing the working electrode in an ultrasonic cleaner for
20 min and was dried and washed with pure acetonitrile. 0.1 mM
calixcrowns and stock solution of metal perchlorate salts with
various concentrations were prepared using acetonitrile. 0.1 M
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synthesis scheme for preparation of cone p-tert-butyl-25,26-
di(carboxymethoxy)calix[4]arene-1,2-crown-3,4,5,6 (10–13)
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and cone 25,26-di(carboxymethoxy)calix[4]arene-1,2-crown-
3,4,5,6 (23–26) are presented in Figure 2.
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STUDY OF BINDING NANO-BASKETS BY VOLTAMMETRY
1093
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FIG. 1. The chemical structure of eight calixcrown scaffolds were synthesized and studied.
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FIG. 2. Synthesis of cone p-tert-butyl-25,26-di(carboxymethoxy)calix[4]arene-1,2-crown-3,4,5,6 (10–13) and cone 25,26-di(carboxymethoxy)calix[4]arene-
1,2-crown-3,4,5,6 (23–26).
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tetra-n-butylammonium hexa-fluorohphosphate (TBAPF6) was
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used as supporting electrolyte.
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RESULTS AND DISCUSSION
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The complexation of 0.1 mM compounds 10–13 and 23–26
toward various cations (including alkali, alkaline earth, transi-
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tion metals, and lanthanides) were investigated by cyclic voltam-
metry (CV) and differential pulse voltammetry (DPV) at glassy
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carbon electrode in 0.1 M TBAPF6/acetonitrile solution. Ac-
cording to Figure 3, CVs of host macrocycles show almost
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same voltammetric behavior, which is no reduction peak and
two anodic peaks at 0.8 and 1.4 V in scaffolds 23–26, and 0.9
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and 1.3 V in scaffold 10–13, respectively.
FIG. 3. Cyclic voltammograms of 0.1 mM 10–13 and 23–26 at glassy carbon
working electrode.
This phenomenon is related to the redox behavior of car-
boxylic acids and intramolecular H-bonding (between two of
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carboxylic acid groups) in 10–13 and 23–26. Although the
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1094
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FIG. 4. Differential pulse voltammograms of 0.1 mM 10–13 in the presence of 0.1 mM alkali, alkaline earth, transition metals and lanthanides in CH3CN.
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oxidation of carboxylic acid exhibits one oxidation peak with
two electron and proton transfer in organic solution, the for- to get a better resolution of waves in the same condition. The
In the rest of the experiments, DPV was used instead of CV
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mation of intramolecular H-bonding between two carboxylic voltammetric behaviors of carboxylic acids in each host scaf-
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acids in 10–13 and 23–26 causes one proton transfer easier and folds were compared with different cations in DPV to investigate
the other more difficult, leading to oxidation peaks at a more the binding properties of 10–13 and 23–26. A constant volume
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positive potential and a less positive potential, respectively. Ox- of 10 µL per injection of the cation in 0.1 M TBAPF6 was added
idation behavior of two carboxylic acid groups in 10–13 and into the cell to make 0.1–3.0 equivalent of cation in the solution.
RETRACTED RETRACTED DRPVEs wTereRreAcordCed aTfteEr adDdingRstoEichiTomRetricAeqCuivaTlenEt ofD
23–26 implies that H-bonding to carboxylic acid moiety is in-
fluenced by binding to cations because the carboxylic acids are cations successively to the respective electrochemical solution.
RETRACTED RETRACTED DRPVEs oTf 1R0–1A3 aCnd 2T3–E26 DdepicRt alEmoTst sRameAvoCltamTmeEtricD
located around the crown ether moiety.
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STUDY OF BINDING NANO-BASKETS BY VOLTAMMETRY
1095
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TABLE 2
The changes of current ratio in the first anodic peak for complexation of 0.1 mM scaffolds 10–13 and 23–26 with the 0.1 mM
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solutions of different metal perchlorate salts in CH3CN.
+
+
+
+
2+
2+
2+
2+
2+
2+
2+
2+
3+
3+
3+
3+
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Macrocycle Cs
Rb
K
Na
Ba
Sr
Ca
Mg
Pb
Co
Zn
Nd
Eu
Tb
Dy
10 0.89 0.92 0.94 0.43 0.88 0.96 0.95 0.99 0.90 0.96 0.99 0.94 0.98 0.98 0.99 0.99
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11
12
13
23
24
25
26
0.88 0.90 0.88 0.56 0.47 0.94 0.96 0.99 0.96 0.98 0.99 0.98 0.99 0.98 0.99 0.99
0.92 0.92 0.41 0.48 0.92 0.89 0.90 0.96 0.37 0.88 0.86 0.92 0.94 0.95 0.98 0.98
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0.92 0.92 0.89 0.96 0.95 0.89 0.90 0.96 0.44 0.88 0.86
0.94 0.95 0.98 0.98
0.90 0.91 0.95 0.51 0.91 0.94 0.96 0.97 0.97 0.98 0.98 0.97 0.96 0.99 0.99 0.98
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0.90 0.94 0.91 0.89 0.44 0.92 0.93 0.97 0.94 0.98 0.97
0.98 0.98 0.98 0.99
0.89 0.93 0.42 0.91 0.39 0.88 0.89 0.98 0.88 0.89 0.94 0.96 0.97 0.99 0.99 0.98
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0.89 0.88 0.93 0.89 0.91 0.90 0.58 0.97 0.49 0.89 0.95 0.95 0.96 0.99 0.98 0.99
Bold values show high complexation ability.
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behaviors with two anodic peaks, as indicated in CV. Figure 4 observed in the peak current and the peak potentials except for
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shows the differential pulse voltammograms of 0.1 mM 10–13 in Pb2+
.
the presence of 0.1 mM alkali, alkaline earth, transition metals,
and lanthanides in CH3CN.
Regarding to the role of binding site in the complex, the
crown ether groups of 10–13 (and 23–26) act mainly as landing
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As depicted in the first column of Figure 4, the macrocycle 10 sites for cations, while the carboxylic acid groups constitute the
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in the presence of Na+ shows significant voltammetric changes redox active centers as well as the supporting landing sites for
of DPV in the peak current and the potential. This is due to binding. The inclusion of divalent metal ions by the crown loop
RETRACTED RETRACTED RETRACTED RETRACTED
the electrostatic interaction between 10 and the cations, lead- (and hydroxyl groups of carboxylic acids) may cause deproto-
ing to electrostatic perturbation of intramolecular H-bonding by nation of carboxylic acids, which makes it difficult to oxidize
RETRACTED RETRACTED RETRACTED RETRACTED
encapsulation of Na+ into crown ether and two carboxylic acid carboxylic ion to carboxy radical in the oxidation process. The
groups. According to the second column of Figure 4, by addition reason is contributed to the repulsion between the carboxy rad-
RETRACTED RETRACTED RETRACTED RETRACTED
of one equivalent of alkali, alkaline earth, transition metals, and ical and the positive cations in scaffolds 10–13 and 23–26. The
lanthanides to a solution containing macrocycle 11, no changes peak height changes of the first oxidation potential of one equiv-
+
RETRACTED RETRACTED RETRACTED RETRACTED
were observed in the peak current or potentials except for Na
alent of 10–13 and 23–26 in the presence of one equivalent of
and Ba2+. Based on the thir+d column of Figure 4, the addition different cations are tabulated in Table 2. The current dec+reas-
+
2+
RETRACTED RETRACTED RETRACTED RETRACTED
of one equivalent of K , Na , Pb to 12 caused large decrease ing orders of 10–13 and 23–26 of the first+peak+are Na2+ for
R
isneEcaonnodic peak currents or even disappearance of the original
TR
d an
od
A
ic pe
C
ak.
T
Th
E
is b
D
ehavi
R
or i
E
s re
T
late
R
d to
A
the
C
ele
T
ctro
E
statDic scaffold 10, Na < Ba
R
scaf
E
fold
T
12R, P +
A
b2+
C
forT2s+caEffofroscaffold 11, Na < K < Pb
D
ld 13
R
, N
E
a+
T
for
R
sca
A
ffold
C
23T, B for
E
a2+
D
perturbation of intramolecular H-bonding by binding of cations for scaffold 24, K+ < Ba2+ for scaffold 25, and Ca2+ < Pb2+
into crown ether and two carboxylic acid groups. As presented for scaffold 26 that are in accordance with the order of po-
RETRACTED RETRACTED RETRACTED RETRACTED
in the fourth column of Figure 4, by addition of one equiv- tential shifts (ꢀEp2 = Ep2∗ – Ep2), which are tabulated in
alent of selected cations to macrocycle 13, no changes were Table 3.
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
TABLE 3
Differences of peak potentials (mV) between free and complexed macrocycles 10–13 and 23–26, which were determined by
differential pulse voltammetry
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Macrocycle Cs+ Rb+ K+ Na+ Ba2+ Sr2+ Ca2+ Mg2+ Pb2+ Co2+ Zn2+ Ni2+ Nd3+ Eu3+ Tb3+ Dy3+
RETRACTED RETRACTED RETRACTED RETRACTED
10
11
12
13
23
24
25
26
15
12
5
5
13
14
11
14
13
16
9
9
8
12
10 201
11
6
5
18
18
7
7
8
12
12
12
6
10
10
161
2
2
6
6
4
0
8
0
12
16
234
179
5
9
12
5
6
14
14
6
7
1
3
15
15
2
4
11
4
9
9
9
3
10
8
2
0
3
3
6
1
4
5
5
3
1
1
4
2
2
4
3
2
0
0
4
3
2
2
2
2
4
4
3
2
3
2
7
188 204
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191 165
3
7
6
11
188
222
9
RETRACTED RETRACTED RETRACTED RETRACTED
6
7
158
6
RETRACTED RETRACTED RETRACTED RETRACTED
5
12
198
6
6
3
14
6
8
5
10
11
12
178
RETRACTED RETRACTED RETRACTED RETRACTED
Bold values show high complexation ability.
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED

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RETRACTED RETRACTED RETRACTED RETRACTED
1096
RETRACTED RETRBA. MOCKHTTAREI ADND K.RPOUERATBDORLLAAH CTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
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RETRACTED RETRACTED RETRACTED RETRACTED
FIG. 5. Differential pulse voltammograms of 0.1 mM 10 (left) and 23 (right) with Na+ in CH3CN.
RETRACTED RETRACTED RETRACTED RETRACTED
Complexion behavior of 10–13 and 23–26 scaffolds with 10. Mokhtari, B.; Pourabdollah, K. J. Coord. Chem. 2011, 64, 4029.
RETRACTED RETRACTED 1R1. MEokThtariR, B.;APourCabdoTllahE, K.DJ. CooRrd. CEhemT. 20R11, 6A4, 31C89. TED
increasing amounts of corresponded cations was continued.
12. Mokhtari, B.; Pourabdollah, K. J. Coord. Chem. 2011, 64, 3081.
Figure 5 depicted the effect of concentration of corresponded
13. Zheng, H.; Yan, Z.; Dong, H.; Ye, B. Sens. Actuators B 2007, 120, 603.
RETRACTED RETRACTED RETRACTED RETRACTED
cations to scaffolds 10 and 23. With increasing the amounts of
14. Dong, H.; Zheng, H.; Lin, L.; Ye, B. Sens. Actuators B 2006, 115, 303.
15. Raoof, J.B.; Ojani, R.; Alinezhad, A.; Rezaie, S. Z. Monatshefte Chem.
cations, the anodic peaks at 0.8 V and 1.4 V decreased. The
RETRACTED RETRACTED RETRACTED RETRACTED
peak current at 0.8 V decreased quantitatively by increasing the
2010, 141, 279.
concentration of Na+, and gradually reached to the minimum
16. Wang, L.; Zhao, B.T.; Ye, B.X. Electroanalysis 2007, 19, 923.
17. Dong, H.; Lin, L.; Zheng, H.; Zhao, G.; Ye, B. Electroanalysis 2006, 18,
RETRACTED RETRACTED RETRACTED RETRACTED
value at around one equivalent.
1202.
18. Wang, F.; Liu, J.; Wu, Y.J.; Gao, Y.M.; Huang, X.F. J. Chin. Chem. Soc.
RETRACTED RETRACTED RETRACTED RETRACTED
2009, 56, 778.
CONCLUSIONS
19. Canpolat, E.C.; Sar, E.; Coskun, N.Y.; Cankurtaran, H. Electroanalysis
The voltammetric behavior of calix[4]crowns 10–13 and
2007, 19, 1109.
RETRACTED RETRACTED RETRACTED RETRACTED
23–26 and their binding abilities toward alkali, alkaline earth,
20. Shamsipur, M.; Miranbeigi, A.A.; Teymouri, M.; Rasoolipour, S.; Asfari,
transition metals, and lanthanides were examined by differential
Z. Anal. Chem. 2009, 81, 6789.
RETRACTED RETRACTED 2R1. SEnejdTarkRova, AM.; PCoturnTayoEva, AD.; RybRar, PE.; LhTotakR, P.;AHim,CM.;TFlidrEovaD,
pulse voltammetry. Comp+ounds 12 and 25 showed their voltam-
+
K.; Hianik, T. Bioelectrochem. 2010, 80, 55.
22. Vaze, V.D.; Srivastava, A.K. Electrochim. Acta 2007, 53, 1713.
23. Zhang, H.L.; Liu, Y.; Lai, G.S.; Yu, A.M.; Huang, Y.M.; Jin, C.M. Analyst
R
an
E
d 2
T
5 to
R
wa
metric behavAior toward K , 10–12 and 23 towards Na ; 11, 24,
rd B
C
a+;
T
26
E
tow
D
ard
R
Ca2+
E
;
T
and
R
12
A
, 13
C
, an
T
d 2
E
6 t
D
o- RETRACTED RETRACTED
ward Pb2+ in CH3CN. This was mainly related to the presence
of crown ether group between two proximal carboxylic acid
2009, 134, 2141.
24. Lai, G.S.; Zhang, H.L.; Jin, C.M. Electroanalysis 2007, 19, 496.
25. Liu, H.; Zhao, G.; Wen, L.; Ye, B. J. Anal. Chem. 2006, 61, 1104.
26. Amiri, A.; Choi, E.Y.; Kim, H.J. J. Incl. Phenom. Macrocycl. Chem. 2010,
RETRACTED RETRACTED RETRACTED RETRACTED
moieties in the complex frameworks. Comparing of scaffolds
10–13 (tert-butyl as upper rim) with 23–26 (without upper rim)
RETRACTED RETRACTED RETRACTED RETRACTED
66, 185.
revealed that such complexes are formed in the lower rim, and
27. Kotkar, R.M.; Srivastava, A.K. J. Incl. Phenom. Macrocycl. Chem. 2008,
the upper rim moieties have no remarkable effect on the lower
60, 271.
RETRACTED RETRACTED RETRACTED RETRACTED
rim complexation with cations.
28. Sosovska, O.; Korpan, Y.; Vocanson, F.; Jaffrezic-Renault, N. Sens. Lett.
2009, 7, 989.
RETRACTED RETRACTED 2R9. ZEhanTg, HR.L.; ALiu, YC.; LTai, GE.S.;DYu, A.RM.; EHuanTg, YR.M.;AJin,CC.MT. AnEalystD
REFERENCES
2009, 134, 2141.
30. Filenko, D.; Gotszalk, T.; Kazantseva, Z.; Rabinovych, O.; Koshets, I.; Shir-
1. Mokhtari, B.; Pourabdollah, K.; Dalali, N. J. Incl. Phenom. Macrocycl.
RETRACTED RETRACTED RETRACTED RETRACTED
Chem. 2011, 69, 1.
shov, Y.; Kalchenko, V.; Rangelow, I.W. Sens. Actuators B 2005, 111–112,
264.
31. Ijeri, V.; Vocanson, F.; Martelet, C.; Jaffrezic-Renault, N. Electroanalysis
2007, 19, 510.
32. Nikolelis, D.P.; Raftopoulou, G.; Psaroudakis, N.; Nikoleli, G.P. Electro-
2. Mokhtari, B.; Pourabdollah, K.; Dalali, N. J. Coord. Chem. 2011, 64,
RETRACTED RETRACTED RETRACTED RETRACTED
743.
3. Mokhtari, B.; Pourabdollah, K.; Dalali, N. J. Radioanal. Nucl. Chem. 2011,
287, 921.
RETRACTED RETRACTED RETRACTED RETRACTED
4. Mokhtari, B.; Pourabdollah, K.; Dalali, N. Chromatographia 2011, 73,
analysis 2008, 20, 1574.
33. Hassen, W.M.; Martelet, C.; Davis, F.; Higson, S.P.J.; Abdelghani, A.;
829.
R
5.
E
Mo
T
khta
R
ri, B
A
.; Po
C
urab
T
dolla
E
h, K
D
. Asia
R
n J. C
E
hem
T
. 20
RAC
717.TED RHEelaTli, S.R; JafAfrezicC-RenTaultE, N.DSens. ARctuaEtorsTB 2R007,A124,C38. TED
11,
23, 4
6. Salorinne, K.; Nissinen, M. J. Incl. Phenom. Macrocycl. Chem. 2008, 61,
34. Mokhtari, B.; Pourabdollah, K. J. Coord. Chem. 2011, 64, 4079.
35. Mokhtari, B.; Pourabdollah, K. Supramol. Chem. 2012, 24, 255.
36. Mokhtari, B.; Pourabdollah, K. Bull. Korean Chem. Soc. 2011, 32, 3855.
37. Mokhtari, B.; Pourabdollah, K. Bull. Korean Chem. Soc. 2011, 32, 3979.
11.
RETRACTED RETRACTED RETRACTED RETRACTED
7. Kim, J.S.; Vicens, J. J. Incl. Phenom. Macrocycl. Chem. 2009, 63, 189.
8. Lamare, V.; Dozol, J.F.; Ugozzoli, F.; Casnati, A.; Ungaro, R. Eur. J. Org.
Chem. 1998, 1559.
RETRACTED RETRACTED 3R8. MEokThtariR, B.;APourCabdoTllahE, K.DBull. KRoreaEn ChTem.RSocA. 201C2, 33T, 15E09. D
9. Mokhtari, B.; Pourabdollah, K. Supramol. Chem. 2011, 23, 696.
RETRACTED RETRACTED 3R9. MEokThtariR, B.;APourCabdoTllahE, K.DBull. KRoreaEn ChTem.RSocA. 201C2, 33T, 23E20. D
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED

RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RETRACTED RETRACTED
STUDY OF BINDING NANO-BASKETS BY VOLTAMMETRY
1097
RETRACTED RETRACTED RETRACTED RETRACTED
40. Mokhtari, B.; Pourabdollah, K. J. Incl. Phenom. Macrocycl. Chem. 2012, 50. Mokhtari, B.; Pourabdollah, K. J. Incl. Phenom. Macrocycl. Chem. 2012,
73, 1. doi:10.1007/s10847-011-0099-z.
RETRACTED RETRACTED RETRACTED RETRACTED
41. Mokhtari, B.; Pourabdollah, K. J. Incl. Phenom. Macrocycl. Chem. 2012, 51. Mokhtari, B.; Pourabdollah, K. J. Incl. Phenom. Macrocycl. Chem. 2012,
73, 269.
doi:10.1007/s10847-012-0212-y.
42. Mokhtari, B.; Pourabdollah, K. Desalination 2012, 292, 1.
43. Mokhtari, B.; Pourabdollah, K. Electroanalysis 2012, 24, 219.
52. Mokhtari, B.; Pourabdollah, K. J. Incl. Phenom. Macrocycl. Chem. 2012,
RETRACTED RETRACTED RETRACTED RETRACTED
doi:10.1007/s10847-012-0210-0.
44. Mokhtari, B.; Pourabdollah, K. J. Electrochem. Soc. 2012, 159, 53. Mokhtari, B.; Pourabdollah, K. J. Sci. Food Agric. 2012, doi:10.1002/
RETRACTED RETRACTED RjEsfa.5T688R. ACTED RETRACTED
K61.
45. Mokhtari, B.; Pourabdollah, K. Electrochim. Acta 2012, 76, 363.
46. Mokhtari, B.; Pourabdollah, K. Can. J. Chem. 2012, 90, 560.
54. Mokhtari, B.; Pourabdollah, K. Synth. React. Inorg. Met. Org. 2012, doi:10.
1080/15533174.2012.654879.
RETRACTED RETRACTED RETRACTED RETRACTED
47. Mokhtari, B.; Pourabdollah, K. J. Chilean Chem. Soc. 2012, 58, 55. Mokhtari, B.; Pourabdollah, K. J. Chinese Chem. Soc. 2012, doi:10.1002/
827. jccs.201100737.
RETRACTED RETRACTED RETRACTED RETRACTED
48. Mokhtari, B.; Pourabdollah, K. Drug Chem. Toxicol. 2012, doi:10.3109/ 56. Mokhtari, B.; Pourabdollah, K. J. Liq. Chromatogr. R. T. 2012, doi:10.
01480545.2011.653490.
1080/10826076.2011.643524.
49. Mokhtari, B.; Pourabdollah, K. J. Therm. Anal. Calorim. 2012, doi:10.1007/
57. Mokhtari, B.; Pourabdollah, K. Korean J. Chem. Eng. 2012, doi:10.1007/
RETRACTED RETRACTED RETRACTED RETRACTED
RETRACTED RETRACTED RsE118T14-0R12-0A085-C1. TED RETRACTED
s10973-011-2014-7
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