Quantitative analysis of holmium ion by a Ho3+ ion-selective sensor based on a symmetric thio-Schiff's base

Article abstract of DOI:10.1002/cjoc.201180274

A poly(vinyl chloride) (PVC) membrane sensor for holmium ions was fabricated based on N-[(Z)-1-(2-thienyl)- methylidene]-N-[4-(4-{[(Z)-1-(2- thienyl)methylidene]amino} phenoxy)phenyl] amine (TPA) as a new ion carrier, acetophenon (AP) as plasticizing solv

Full text of DOI:10.1002/cjoc.201180274

FULL PAPER
＋
Quantitative Analysis of Holmium Ion by a Ho3 Ion-Selective
Sensor Based on a Symmetric Thio-Schiff's Base
Hassan, Ali Zamani*,a
Fatemeh, Rahimia
Mohammad, Reza Ganjalic
Masoud, Salavati-Niasarid
Fatemeh, Naghavi-Reyabbib
Ali, Arvinfara
Alihossien, Imania
Farnoush, Faridbodc
a Department of Applied Chemistry, Quchan Branch, Islamic Azad University, Quchan, Iran
b Resident of General Surgery, Endoscopic & Minimaly Invasive Surgery Research Center, Ghaem Hospital,
Faculty of Medicine, Mashhad University of Medical Sciences, Mashhad, Iran
c Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran
d Department of Chemistry, Faculty of Science, University of Kashan, Kashan, Iran
A poly(vinyl chloride) (PVC) membrane sensor for holmium ions was fabricated based on N-[(Z)-1-(2-thienyl)-
methylidene]-N-[4-(4-{[(Z)-1-(2-thienyl)methylidene]amino} phenoxy)phenyl] amine (TPA) as a new ion carrier,
acetophenon (AP) as plasticizing solvent mediator ＋and sodium tetraphenyl borate (NaTPB) as an anion excluder.
The electrode shows a good selectivity towards Ho3 ions respect to other inorganic cations, including alkali, alka-
line earth, transition and heavy metal ions. The constructed sensor displays a Nernstian behavior (19.5±0.3
－6
－2
－1
mV/decade) over the concentration range of 1.0×10 to 1.0×10 mol•L with the detection limit of the elec-
－
－7
trode being 4.6×10 mol•L 1 and very short response time (ca. 5 s). It has a useful working pH range of 3.2—9.8
for at least 8 weeks. The electrode was successfully applied as an indicator electrode for the potentiometric titration
＋
of a Ho3 solution with EDTA ＋and holmium determination in some alloys. The proposed sensor accuracy was stud-
ied by the determination of Ho3 in mixtures of three different ions.
Keywords holmium ion, PVC membrane, sensor, potentiometry, Schiff's base, ion-selective electrode
Introduction
nide ions is using ionophores with semi-cavity, heteroa-
toms (N, O and S as donating atoms), and high flexibil-
ity. Such an ionophore can easily form a template with
reference to the size of cation.5-7
Nowadays, applications of rare earth elements in ag-
ricultural, metallurgical, optical and glass industries,
ceramics, and biological areas have increased. Thus,
having a convenient, fast, selective and sensitive analy-
sis method for monitoring rare earth elements are re-
quired.
Potentiometric ion selective electrode is one of the
selective methods for monitoring and determination of
rare earth elements. Although instrumental techniques
such as inductively coupled plasma atomic emission
spectroscopy and neutron activation analysis provide an
accurate measurement in trace amount of elements, they
destroyed the samples. In comparison, potentiometric
ion selective sensors offer advantages of low cost, port-
ability, selectivity, and simple operatory. They also pro-
vide an analysis method without destruction of sam-
ple.1-3
Schiff's base compounds refer to the branch of su-
pramolecules that have above properties.1,2 A Schiff's
base (or azomethine or imine), named after Hugo Schiff
(German Chemist, 1834—1915), is a functional group
with general formula of R1R2C＝N—R3. A Schiff's base
mainly binds metal ions via their donor atoms. The
electronic effect around the metal core can be finely
tuned by an appropriate selection of electron withdraw-
ing or electron donating substituent, incorporated into
the Schiff's bases.1,2,8
Holmium compounds have been used in ceramic,
glass, and phosphor lamps. It is also used in nuclear
reactors to keep the atomic chain reactions from running
out of control.9-11 Holmium is applied for some biologi-
cal aspects too.12
There are some reports on the literature for selective
determination of holmium ion by potentiometric elec-
trodes.13-18 In this work, selectivity of N-[(Z)-1-(2-
thienyl)methylidene]-N-[4-(4-{[(Z)-1-(2-thienyl)methyli-
dene]amino}phenoxy)phenyl]amine (TPA) (Figure 1),
Different radii of lanthanide ions causes their differ-
ent properties, such as charge densities and hydration
＋
＋
energy (from Ce3 to Lu3 their hydration energy
ranges from 3370 to 3760 kJ/mol).4 Hence, the only
way to design an ion-selective electrode for the lantha-
*
E-mail: haszamani@yahoo.com; Tel.: 0098-581-2224180; Fax: 0098-581-2226093
Received June 1, 2010; revised February 24, 2011; accepted March 18, 2011.
Chin. J. Chem. 2011, 29, 1523— 1528
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1523

Hassan et al.
FULL PAPER
which is a thio-Schiff's base was conductometrically
studied in acetonitrile. Since TPA showed a selective
behavior toward holmium ion, it was applied in con-
struction of a Ho(III) selective PVC membrane sensor.
about 10 s, so that a transparent membrane of about 0.3
mm in thickness was formed.19-25 Afterwards, the tube
was removed from the solution kept at room tempera-
tur－e for 12 h and filled with an internal solution (1.0×
3
－1
10 mol•L HoCl3). The electrode was finally condi-
－
－3
tioned for 36 h by soaking in a 1.0×10 mol•L 1 solu-
tion of HoCl3. A silver/silver chloride coated wire was
used as an internal reference electrode.
Electromotive force (emf) measurements
Figure 1 Chemical structure of TPA.
All emf measurements were carried out with the fol-
lowing assembly:
Experimental
Ag-AgCl|1.0 10－3 mol L－1 HoCl3|PVC membrane:
×
•
Reagents
test solution|Hg-Hg2Cl2, KCl (satd).
Merck Chemical and Aldrich Co. were the suppliers
for the nitrate and chloride salts of all cations and the
reagent grades of dibutyl phthalate (DBP), nitrobenzene
(NB), benzyl acetate (BA), acetophenone (AP), sodium
tetraphenyl borate (NaTPB), tetrahydrofuran (THF) and
high relative molecular weight PVC. All reagents were
used without any modification. As far as nitrate and
chloride salts of all employed cations are concerned,
they were of the highest available purity and were
P2O5-vacuum dried. During the experiments, distilled
deionized water was used.
A corning ion analyser 250 pH/mV meter was used
for the potential measurements at 25.0 ℃. The activi-
ties were calculated according to Debye-Hückel proce-
dure.26
Results and discussion
Potential response of TPA-PVC membrane sensor
In order to check selectivity of TPA toward lantha-
nide cations, its interaction with lanthanide ions was
investigated conductometrically in an acetonitrile solu-
tion by previously describe method.27-31 The complex
formation constant, Kf,＋shows the selectivity of the used
ionophore toward Ho3 ions (Kf 5.7×106) among the
all other cations tested.
Synthesis of TPA
Thio Schiff-base: N-[(Z)-1-(2-thienyl)methylidene]-
N-[4-(4-{[(Z)-1-(2-thienyl)methylidene]amino}phenoxy)-
phenyl]amine was synthesized in the usual manner by
reaction of thiophene-2-carbaldehyde with diamine in a
2∶1 molar ratio in methanol as follows. Thiophene-2-
carbaldehyde (0.01 mol, 1.12 g) and 4,4'-diaminodi-
phenylether (0.005 mol, 1.00 g) were placed in 100 mL
round-bottom flask equipped with a condenser and a
magnetic bar. Methanol (50 mL) was then added to the
mixture and the mixture was refluxed far 3 h while
stirring, and then cooled to room temperature. The solid
product was filtered, and the product was re-crystallized
In the next experiment, TPA was used as a neutral
carrier to prepare the PVC membrane ion-selective
electrodes for a wide variety of cations, including alkali,
alkaline earth, transition and h＋eavy metal ions. Among
different metal ions tested, Ho3 with the most sensitive
response seems to be suitably determined with the
membrane sensor based on TPA. This ob＋servation is
most probably due to the proper size of Ho3 ion to the
semi cavity of flexible TPA, and the rapid exchange
1
from chloroform. Yield 82%, m.p. 157 ℃; H NMR
＋
kinetics of the resulting TPA-Ho3 complex.
(CDCl3, 400 MHz) δ: 8.61 (s, 2H, CH＝N), 7.48—7.52
(ddd, 4H, aminophenyl), 7.24 — 7.27 (ddd, 4H,
aminophenyl), 7.14—7.16 (m, 2H, C4H3S), 7.04—7.06
Membrane composition
－1
Some important features of the PVC membranes,
such as properties of plasticizer, plasticizer/PVC ratio,
nature and amount of ionophore and, especially, the na-
ture and the amount of the used additives, are reported
to significantly influence ISEs sensitivity and selectiv-
ity.32-36 Thus, the influence of the membrane composi-
tion, nature and amount of plasticizer along with
NaTPB amount (as a suitable lipophilic addit＋ive) was
investigated on the potential response of Ho3 sensor.
The corresponding results are provided in Table 1.
Clearly, among the three plasticizers tested, AP offers
the best sensitivity. This phenomenon can be due to the
dielectric constant of the plasticizer on membrane
phase.
(m, 4H, C4H3S); IR (KBr) ν: 1610 (C＝N) cm . Anal.
calcd for C22H16N2OS2: C 68.02, H 4.15, N 7.21; found
C 67.88, H 4.01, N 7.33.
Electrode preparation
The required amounts of the membrane ingredients
(30 mg powdered PVC and 64 mg AP as plasticizer)
were mixed and dissolved in 5 mL of THF. To this mix-
ture, 2 mg NaTPB and 4 mg ionophore TPA were added
and the solution was mixed well. The resulting mixture
was transferred into a glass dish of 2 cm in diameter.
The THF content of the mixture was evaporated slowly,
until an oily concentrated mixture was obtained. A Py-
rex tube (3—5 mm i.d.) was dipped into the mixture for
1524
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1523— 1528

＋
Quantitative Analysis of Holmium Ion by a Ho3 Ion-Selective Sensor
Table 1 Optimization of the membrane ingredients
Composition/wt%
－1
－1
No.
Linear range/(mol•L
)
Slope/(mV•decade )
PVC
30
30
30
30
30
30
30
30
30
Plasticizer
TPA
4
NaTPB
－6
－2
1
2
3
4
5
6
7
8
9
NB, 64
AP, 64
BA, 64
DBP, 64
AP, 68
AP, 65
AP, 66
AP, 65
AP, 63
2
2
2
2
2
2
0
1
2
1.0×10 —1.0×10
18.7±0.2
19.5±0.3
15.9±0.3
17.3±0.5
9.8±0.4
－6
－2
－2
－2
－2
－2
－2
－2
－2
4
1.0×10 —1.0×10
－6
4
5.0×10 —1.0×10
－5
4
1.0×10 —1.0×10
－5
0
5.0×10 —1.0×10
－6
3
1.0×10 —1.0×10
16.5±0.6
14.7±0.3
17.2±0.5
16.3±0.4
－6
4
1.0×10 —1.0×10
－6
4
1.0×10 —1.0×10
－6
5
1.0×10 —1.0×10
－1
It should be noted that the presence of lipophilic
anions in the cation-selective membrane electrodes not
only diminishes the ohmic resistance, but also enhances
their response behavior and selectivity.37-40 Table 1 dis-
plays that the optimum response characteristics were
obtained with a membrane composition of 30% PVC,
64% AP, 4% TPA and 2% NaTPB (No. 2).
L ) on the potential response of the membrane sensor
(membrane No. 2) was tested in pH range of 2.0—12.0.
These results are depicted in Figure 3. Obviously, po-
tential remains constant over a pH range of 3.2—9.8,
beyond which the potential changes considerably. The
observed drift at higher pH values could be d＋ue to the
formation of some hydroxyl complexes of Ho3 ions in
solution. The observed potential increase at low pH
values indicates that th＋e protonated ionophore possesses
a poor response to Ho3 ions and strong response to the
H3O＋ in solution.
Calibration curve
＋
Emf vs. pHo3 plot (Figure 2) for optimal mem-
brane ingredients indicates that it has a Nernst＋ian be-
havior over a broad concentration range of Ho3 ions.
The slope and the linear range of the resulting calibra-
－6
tion graph were 19.5±0.3 mV/decade and 1.0×10 —
－2
－1
1.0×10 mol•L , respectively. The limit of detection
＋
defined as Ho3
ion concentration obtained by
extrapolating two segments of the ion-selective calibra-
tion curve (as shown in Figure 2), was calculated to be
－7
－1
4.6×10 mol•L . The standard deviation of 8 repli-
cate potential measurements for the proposed electrode
was ±0.3 mV at most. This certain electrode was
satisfactorily stable and it could be used for at least 8
weeks (use of 1 h daily) without observing any change
in its response characteristics.
pH effect
－3
－1
－3
Figure 3 pH effect of the test solution (1.0×10 mol•L of
pH influence of the test solution (1.0×10 mol•
＋
＋
Ho3 ) on the potential response of Ho3 ion-selective electrode.
Dynamic response time
Dynamic response time is an important factor, for
the evaluation any sensor. In this study, the practical
response time was recorded by changing solutions with
different holmium concentrations. The measurement
－6
－1
sequence was from the lower (1.0×10 mol•L ) to
－2
－1
higher (1.0×10 mol•L ) concentration. The actual
potential versus time traces is shown in Figure 4. As it is
seen, the electrode reaches its equilibrium response in a
short time of about 5 s.
Selectivity of the sensor
Selectivity coefficient, which reflects the relative
response of the membrane sensor towards the primary
Figure 2 Calibration curves of TPA-based holmium electrode.
Chin. J. Chem. 2011, 29, 1523— 1528
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1525

Hassan et al.
FULL PAPER
electrodes reported in the literature by other research-
ers.14-18 From the data given in Table 3, the proposed
sensor in terms of not only response time, but also se-
＋
lectivity is superior to the previously reported Ho3
ion-selective membrane electrode.
Reproducibility of the sensor
Reproducibility of the sensor was tested by con-
struction of two electrodes in a same condition (mem-
bran＋e composition of No. 3). Then, parallel analysis－of
5
Ho3 －ions in three same－concentrations (1×10
,
－
1×10 4 and 1×10 3 mol•L ) was carried out. RSD of
the tests were calculated to be 2.34%, 3.11%, and 2.67%
respectivly.
1
Figure 4 Dynamic response time of holmium electrode for step
Analytical application ＋
＋
－6
－1
changes in the Ho3 concentration: (A) 1.0×10 mol•L ; (B)
The suggested Ho3 PVC-membrane sensor was
found to work well under the laboratory conditions. The
selective holmium membrane sensor was used as an
－5
－1
－4
－1
－3
1.0×10 mol•L ; (C) 1.0×10 mol•L ; (D) 1.0×10
－1
－1
－
mol•L ; (E) 1.0×10 2 mol•L
.
－4
indicator electrode in the titration of a 1.0×10 mol•
ion over the other ions present in the solution, is perhaps
the most important characteristic of an ion-selective
electrode. In this research, the potential responses of the
－1
L
holmium ion solution－(pH＝4;－sodium acetae buffer)
2
1
with a standard 1.0×10 mol•L EDTA (pH＝10).
The resulting titration curve is shown in Figure 5. Ac-
cording to this figure, the sensor is capable of monitor-
ing the amount of holmium ions.
＋
recommended Ho3 membrane sensor to a wide variety
of cations were investigated by matched potential
method (MPM).41-45 The resulting selectivity coefficient
values are summarized in Table 2. In line with the in-
formation of this Table, the selectivity coefficients for
the monovalent tested cations (Na＋, K＋) are smaller
than 3.7×10−3. Additionally, the selectiv＋ity coe＋fficien＋ts
＋
for the divalent tri＋ed cations (Mg2 , Cd2 , Hg2 , Ca2 ,
＋
＋
Co2 , Ni2 , Pb2 ) are also small in the range of
2.2×10−4—7.7×10−3 . In th＋e case＋of trivalent cations
＋
＋
＋
＋
＋
＋
＋
(Er3＋ , Pr3 , Nd3 , Tm3 , Yb3 , Gd3 , Tb3 , Eu3 , Sm3 ,
＋
Lu3 , Fe3 ), the selectivity coefficients are relatively
small (from 1.0×10−3 to 6.7×10−3). Eventually, it can
be stated that because of the good selectivity coeffi-
cients values, the disturbance produced by these cations
in the function of the developed membrane sensor is
negligible.
－4
Figure 5 Potential titration curve of 25.0 mL from a 1.0×10
Table 3 also compares the selectivity coefficients,
response times, detection limits and dynamic ranges of
＋
－
－1
－2
mol•L Ho3 solution with 1.0×10 mol•L 1 of EDTA.
＋
＋
the Ho3 sensor with those of the best previous Ho3
Because of high selectivity and low detection limit
＋
of the developed Ho3 sensor (membrane No. 2), it was
Table 2 Selectivity coefficients of various interfering ions (B)
＋
also applied for the determination of Ho3 ions concen-
MPM
MPM
Interfering ions (B)
K
Interfering＋ions (B)
K
Ho3＋ ,B
Ho3＋ ,B
tration in mixtures of three different ions. pH of the so-
lutions were adjusted to 4 by using sodium acetate
Na＋
K＋
2.4×10
3.7×10
4.5×10
4.8×10
8.5×10
2.2×10
7.2×10
7.7×10
6.8×10
6.6×10
Er3＋
5.6×10
6.2×10
6.7×10
1.0×10
2.1×10
2.6×10
3.3×10
3.9×10
4.6×10
1.0×10
－3
－3
－3
－3
－4
－4
－4
－3
－3
－3
－3
－3
－3
－3
－3
－3
－3
－3
－3
－3
Pr3
Nd3
buffer. The corresponding results in Table 4 reveal that
＋
the recovery of Ho3 io＋ns in all mixtures is acceptable.
＋
＋
Ca2
The proposed Ho3 sensor was also applied to
＋
＋
Mg2＋
Yb3
＋
determination of Ho3 contents in some holmium
＋
Co2＋
Tm3＋
alloys samples. 0.1 g of holmium alloys (Ho2Co14Fe3
and HoFe11.4Ta0.6) powder (from Sigma-Aldrich) was
weighed carefully and transferred to a 50 mL beaker and
10 mL of H2SO4 (10%) was added. The solution was
stirred and heated (50 ℃). Then, the pH was adjusted to
4 with ammoniac and the solution was filtered.
The resulted solution was transferred to a 250 mL
Ni2
Cd2
Gd3＋
＋
Tb3
Eu3
＋
Pb2
＋
＋
Hg2＋
Sm3＋
Fe3
Lu3
1526
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1523— 1528

＋
Quantitative Analysis of Holmium Ion by a Ho3 Ion-Selective Sensor
＋
＋
Table 3 Comparison of selectivity coefficients of proposed Ho3 sensor with the previous reported Ho3 ion-selective electrodes
Parameter
LR/(mol•L
Ref. 13
Ref. 14
Ref. 15
Ref. 16
Ref. 17
Ref. 18
This work
－6
－6
－5
－5
－6
－5
－6
1.0×10
—
1.0×10
—
1.0×10
—
1.0×10
—
1.0×10
—
2.0×10
—
1.0×10
—
－1
)
－1
－2
－2
－2
－2
－2
－2
－7
1.0×10
1.0×10
1.0×10
1.0×10
1.0×10
1.0×10
1.0×10
－1
－7
－7
－6
－6
－6
－6
DL/(mol•L
)
7.5×10
6.3×10
7.0×10
8.0×10
8.5×10
5.0×10
4.6×10
Response time/s
pH range
15
10
＜15
5
＜15
＜10
5
3.8—8.0
4.5—9.0
4.0—9.5
3.0—11.5
2.7—9.8
2.5—10.5
19.5±0.3
3.2—9.8
－1
Slope/(mV•decade
)
19.9±0.3
19.9±0.3
19.7±0.2
19.6±0.2
19.7±0.3
19.5±0.3
Na, Mg, Sm, Dy, Sm, Er,
lg Ksel＞－2
—
Lu, La, Yb
Dy, Tb, Pb
Sm, Dy, Cu
—
Pb, Dy, Gd
Na, Pb
Table 4 Determination of Ho3+ ions in mixtures of different ions
Serial No.
Comp－osition
Observed content/(mol•L-1)
0.000098
－
－
－
－
－
－
－
－
－1
1
2
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Tm(NO3)3＋0.001 mol•L 1 Yb(NO3)3
－
－1
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Er(NO3)3＋0.001 mol•L 1 Pr(NO3)3
0.000101
－
－1
3
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Lu(NO3)3＋0.001 mol•L 1 Sm(NO3)3
0.000102
－
－1
4
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Eu(NO3)3＋0.001 mol•L 1 Gd(NO3)3
0.000097
－
－1
5
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 La(NO3)3＋0.001 mol•L 1 Nd(NO3)3
0.000105
－
－1
6
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Fe(NO3)3＋0.001 mol•L 1 Cr(NO3)3
0.000104
－
－1
7
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Ca(NO3)2＋0.001 mol•L 1 Ni(NO3)2
0.000107
－
－1
8
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Pb(NO3)2＋0.001 mol•L 1 KNO3
0.000098
－
－
－
－
－1
9
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Co(NO3)2＋0.001 mol•L 1 Zn(NO3)2
0.000103
－
－1
10
11
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Cd(NO3)2＋0.001 mol•L 1 Mg(NO3)2
0.000104
－
－1
0.00010 mol•L Ho(NO3)3＋0.001 mol•L 1 Cu(NO3)2＋0.001 mol•L 1 NaNO3
0.000102
volumetric flask. Then, 25 mL of acetate buffer was
added and the solution was made up to volume by dis-
tilled water. Then, holmium content of 10 mL of this
solution was measured using the proposed sensor by
calibration method. The results were compared with
inductively coupled plasma atomic emission spectros-
copy (ICP-AES) and presented in Table 5. As it can be
seen from Table 5, there is a satisfactory agreement be-
tween the results obtained from the proposed sensor and
ICP method.
very low interference from common alkali, alkaline
earth, transition and heavy metal ions. The practical
utility of the sensor was demonstrated by using it as an
indicator electrode in the potentiometric titration of
＋
Ho3 ions with EDTA and some holmium alloy sam-
ples.
Acknowledgements
The authors acknowledge the kind financial support
provided by the Research Council of Quchan Islamic
Azad University for the preparation of this study.
Table 5 Analysis of holmium alloys
Sample
The proposed methoda
104.6±1.5 mg/L
77.2±1.2 mg/L
ICP-AES
References
Ho2Co14Fe3
HoFe11.4Ta0.6
102.4±0.3 mg/L
1
Faridbod, F.; Ganjali, M. R.; Dinarvand, R.; Norouzi, P.
Comb. Chem. High Throughput Screening 2007, 10, 527.
Zamani, H. A.; Hamed-Mosavian, M. T.; Aminzadeh, E.;
Ganjali, M. R.; Ghaemy, M.; Behmadi, H.; Faridbod, F.
Desalination 2010, 250, 56.
73.5±0.3 mg/L
a The results are based on 5 replicates measurements.
2
Conclusion
3
4
5
6
7
Zamani, H. A.; Ganjali, M. R.; Norouzi, P.; Adib, M.;
Aceedy, M. Anal. Sci. 2006, 22, 943.
Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements,
Pergamon, New York, 1984.
Ganjali, M. R.; Memari, Z.; Faridbod, F.; Dinarvand, R.;
Norouzi, P. Electroanalysis 2008, 20, 2663.
Ganjali, M. R.; Faridbod, F.; Norouzi, P.; Adib, M. Sens.
Actuators B 2006, 120, 119.
Using N-[(Z)-1-(2-thienyl)methylidene]-N-[4-(4-{[(Z)-
1-(2-thienyl)methylidene]amino}phenoxy)phenyl]amine
(TPA) in poly(vinyl chloride) membrane sensor as a
selective ionophore with AP as plasticizer creates a
＋
Ho3 -PVC membrane electrode. The sensor showed a
Nernstian response (slope of 19.5±0.3 mV/decade),
－7
－1
low limit of detection (4.6×10 mol•L ), applicable
pH range of 3.2—9.8, fast response time (about 5 s) and
－6
－2
－1
Ganjali, M. R.; Norouzi, P.; Atrian, A.; Faridbod, F.; Megh-
wide linear range (1.0×10 —1.0×10 mol•L ) and
Chin. J. Chem. 2011, 29, 1523— 1528
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Hassan et al.
FULL PAPER
dadi, S.; Giahi, M. Mater. Sci. Eng. C 2009, 29, 205.
25 Zamani, H. A.; Masrournia, M.; Rostame-Faroge, M.;
Ganjali, M. R.; Behmadi, H. Sensor. Lett. 2008, 6, 759.
26 Arrhenius, G. J. Chem. Educ. 1954, 31, 501.
27 Pourghobadi, Z.; Seyyed-Majidi, F.; Daghighi-Asli, M.;
Parsa, F.; Moghimi, A.; Ganjali, M. R.; Aghabozorg, H.;
Shamsipur, M. Pol. J. Chem. 2000, 74, 837.
8
Ganjali, M. R.; Tavakoli, M.; Faridbod, F.; Riahi, S.; No-
rouzi, P.; Salavati-Niassari, M. Int. J. Electrochem. Sci.
2008, 3, 1559.
Kabalin, J.; Gilling, P.; Fraundorfer, M. J. Clin. Laser Med.
Surg. 1998, 16, 21.
9
10 Sastri, V. S.; Bunzli, J. C. G.; Rao, V. R.; Rayudu, G. V. S.;
Perumareddi, J. R. Modern Aspects of Rare Earths and
Their Complexes, Elsevier Publication, Amsterdam, 2003.
11 Kirk, O. R.; Othmer, F. D. Encyclopedia of Chemical Tech-
nology, Vol. 19, Wiley, New York, 1982.
12 Harvey, L. J.; Majsak-Newman, G.; Dainty, J. R.; Wharf, S.
G.; Reid, M. D.; Beatte, J. H.; Fairweather-Tait, S. J. Clinic.
Sci. 2002, 102, 233.
13 Zamani, H. A.; Arvinfar, A.; Rahimi, F.; Imani, A.; Ganjali,
M. R.; Meghdadi, S. Mater. Sci. Eng. C 2011, 31, 307.
14 Masrournia, M.; Zamani, H. A.; Mirrashid, H. A.; Ganjali,
M. R.; Faridbod, F. Mater. Sci. Eng. C 2011, 31, 574.
15 Zamani, H. A.; Imani, A.; Arvinfar, A.; Rahimi, F.; Ganjali,
M. R.; Faridbod, F.; Meghdadi, S. Mater. Sci. Eng. C 2011,
31, 588.
28 Ganjali, M. R.; Rouhollahi, A.; Mardan, A. R.; Shamsipur,
M. J. Chem. Soc., Faraday Trans. 1998, 94, 1959.
29 Pooyamanesh, M. J.; Zamani, H. A.; Rajabzadeh, G.;
Ganjali, M. R.; Norouzi, P. Anal. Lett. 2007, 40, 1596.
30 Zamani, H. A.; Ganjali, M. R.; Norouzi, P.; Adib, M. Sensor
Lett. 2007, 5, 522.
31 Zamani, H. A.; Ganjali, M. R.; Norouzi, P.; Tajarodi, A.;
Hanifehpour, Y. J. Chil. Chem. Soc. 2007, 52, 1332.
32 Gupta, V. K.; Jain, A. K.; Maheshwari, G. Int. J. Electro-
chem. Sci. 2007, 2, 102.
33 Zamani, H. A. Anal. Lett. 2008, 41, 1850.
34 Abedi, M. R.; Zamani, H. A.; Ganjali, M. R.; Norouzi, P.
Sensor Lett. 2007, 5, 516.
35 Zamani, H. A.; Ganjali, M. R.; Adib, M. Sensor Lett. 2006,
4, 345.
16 Zamani, H. A.; Rohani, M.; Zangeneh-Asadabadi, A.;
Zabihi, M. S.; Ganjali, M. R.; Salavati-Niasari, M. Mater.
Sci. Eng. C 2010, 30, 917.
17 Zamani, H. A.; Abedini-Torghabeh, J.; Ganjali, M. R. Bull.
Korean Chem. Soc. 2006, 27, 835.
18 Abedi, M. R.; Zamani, H. A. Anal. Lett. 2008, 41, 2251.
19 Zamani, H. A.; Ganjali, M. R.; Adib, M. Sens. Actuators B
2007, 120, 545.
36 Zamani, H. A.; Rajabzadeh, G.; Ganjali, M. R. Sensor Lett.
2009, 7, 114.
37 Bakker, E.; Bühlmann, P.; Pretsch, E. Chem. Rev. 1997, 97,
3083.
38 Zamani, H. A.; Ganjali, M. R.; Seifi, N. Collect. Czech.
Chem. Commun. 2007, 72, 1189.
39 Gehrig, P. M.; Morf, W. E.; Welti, M.; Pretsch, E.; Simon, W.
Helv. Chim. Acta 1990, 73, 203.
20 Zamani, H. A.; Mohammadhossieni, M.; Nekoei, M.;
Ganjali, M. R. Sensor Lett. 2010, 8, 303.
21 Abedi, M. R.; Zamani, H. A.; Ganjali, M. R.; Norouzi, P.
Intern. J. Environ. Anal. Chem. 2008, 88, 353.
22 Zamani, H. A.; Hamed-Mosavian, M. T.; Hamidfar, E.;
Ganjali, M. R.; Norouzi, P. Mater. Sci. Eng. C 2008, 28,
1551.
40 Zamani, H. A.; Ganjali, M. R.; Norouzi, P.; Tadjarodi, A.;
Shahsavani, E. Mater. Sci. Eng. C 2008, 28, 1489.
41 Buck, P. R.; Lindneri, E. Pure Appl. Chem. 1994, 66, 2527.
42 Umezawa, Y.; Umezawa, K.; Sato, H. Pure Appl. Chem.
1995, 67, 507.
43 Zamani, H. A.; Ganjali, M. R.; Norouzi, P.; Adib, M. Mater.
Sci. Eng. C 2008, 28, 157.
23 Zamani, H. A.; Rajabzadeh, G.; Masrornia, M.; Dejbord, A.;
Ganjali, M. R.; Seifi, N. Desalination 2009, 249, 560.
24 Zamani, H. A.; Masrournia, M.; Rostame-Faroge, M.;
Ganjali, M. R.; Behmadi, H. Sensor Lett. 2008, 6, 759.
44 Zamani, H. A.; Rajabzadeh, G.; Firouz, A.; Ganjali, M. R. J.
Anal. Chem. 2007, 62, 1080.
45 Faridbod, F.; Ganjali, M. R.; Dinarvand, R.; Norouzi, P.;
Riahi, S. Sensors 2008, 8, 1645.
(E1006012 Sun, H.)
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Chin. J. Chem. 2011, 29, 1523— 1528