A novel approach for the design of a highly selective sulfate-ion-selective

electrodew
Amarchand Sathyapalan,
a
Anhong Zhou,*
a
Tapas Kar,
b
Feng Zhou
c
and Haibin Su
c
Received (in Cambridge, UK) 13th October 2008, Accepted 31st October 2008
First published as an Advance Article on the web 20th November 2008
DOI: 10.1039/b817957c
A hydroxyl Schi base molecule was synthesized from tetra-
ethylenetetramine and 4-nitrosalicylaldehyde and explored as an
ionophore with ionic liquid, cation excluder in PVC membranes
showing remarkable sulfate selectivity; the optimal recognition
site was predicted by density function theory (DFT) simulation.
Electrochemical sensors have played an important role in the
development of sensors for selective determination of chemical
species at low concentrations.
1,2
Ion-selective electrodes (ISEs)
are one of the most exciting developments in the eld of
electro-analytical chemistry. The interest in ISEs have grown
over recent years as they are portable, easy, and can provide
accurate rapid measurements with reasonable sensitivity and
selectivity.
3,4
Though there have been numerous reports of
cation-selective electrodes and few anion-selective electrodes,
the primary study was mainly restricted to cation ISEs and
there are still investigations that use anion-selective electrodes
for selectivity, detection limit, and selective determination of
particular anion of interest.
49
Anion-selective membrane
electrodes using selective ionophores to respond to anions
following the Hofmeister selectivity tend to diminish response
for decreasing lipophilicity.
10
Sulfate and phosphate are highly
hydrophilic anions, and electrodes based on such anions func-
tion very poorly in aqueous solutions as compared to lipophilic
anions in the early Hofmeister series members. It is still highly
challenging to achieve useful selectivity for sulfate over hydro-
phobic anions by receptor-based chemical sensors such as
selective electrodes. This is due to the high hydrophilicity of
such anions (sulfate and phosphate), which leads to the diculty
of compensating for large dierences in Gibbs free energies of
transfer between sulfate and interfering anions by selective
complexation. The eect of solvating environment at the inter-
face inherently suitable for the recognition of hydrophilic sub-
strates and the reverse eect to bulk two-phase distribution
systems and the notochord of complete dehydration of hydro-
phobic anions for interfacial binding event to selectively bind to
hydrophilic anions over hydrophobic anions.
The sulfate ion has a signicant role in biological, medical
and environmental elds, such as elimination of pollution in
water. Commonly, sulfate is present in water in association
with calcium, iron, magnesium and sodium ions as salts and
hence, the determination of sulfate by sensitive, rapid, precise,
and accurate methods is important in assessing the salinity and
quality of water.
11,12
For a better ion-selective electrode, a
strong interaction between the ionophore and the anion is
essential in order to complex anions selectively, and the
potential response is believed to be based on this characteristic
of the membrane. Recent trends showed an increasing demand
for developing novel ionophores.
13
A variety of approaches
for designing and bringing possible combinations of
membrane compositions for sulfate-ion-selective electrodes
as evidenced in the literature.
1417
For the design of a suitable
ionophore for anions, the hostguest interaction via hydrogen
bonding and solvating environment are crucial factors.
18
The
Schi bases (SB) are known to form stable complexes with
transition metal ions, and they act as ion carriers in the
polymeric membrane. Almost all of metals form 1 : 1 metal
complexes with SBs. The feature of SBs gives geometric and
cavity control of hostguest complexation and modulation of
its lipophilicity, and produce remarkable selectivity, sensitivity
and stability for a specic ion. The resulting complexes have
attracted increasing attention in the domain of ionic binding
due to their unique properties and reactivity. Schi bases with
N and O as donor atoms are well known to form strong
complexes with transition metal ions and recently were used
as ionophores in ion-selective electrodes for determining
cations.
8,1922
Coll
14
et al. for the rst time introduced ionic
liquids to increase the dielectric constant of PVC-based mem-
branes for sulfate determination followed by Pletnev et al.
23
and Peng et al.
24
In this work, we introduce a novel hydroxyl
Schi molecule in combination with an ionic liquid and
cation excluder for the selective determination of sulfate.
The principle for designing our ionophore was based on
hydrogen bonding, solvating environment and dielectric
property. DFT simulation of hostguest chemistry has been
gained recent attention to study the interaction between
sulfate and guest molecules.
18,25,26
A theoretical simulation
approach has been developed in this study to optimize the
geometry of the ionophore.
The imine molecule 2,2
0
-((1E,11E)-2,5,8,11-tetraazadodeca-
1,11-diene-1,12-diyl)bis(4-nitrophenol) was synthesized by fol-
lowing the Schi base synthesis procedure of condensation
between an aldehyde (I) and amine (II), see Scheme 1.
Simply, the ionophore (III) was obtained by reuxing the
salicylaldehyde (0.01 M) with tetraethylenetetramine (0.01 M)
in methanol with stirring. The mixture was reuxed for 36 h,
a
Department of Biological and Irrigation Engineering, Utah State
University, Logan, Utah, 84322-4105, USA.
E-mail: Anhong.Zhou@usu.edu; a.sathyapalan@usu.edu;
Fax: +1 (435)797-2863; Tel: +1 (435)797-2863
b
Department of Chemistry, Utah State University, Logan, Utah,
84322-0300, USA. E-mail: Tapas.Kar@usu.edu; Tel: (435)797-7230
c
Division of Materials Science, Nanyang Technological University, 50
Nanyang Avenue, 639798, Singapore. E-mail: hbsu@ntu.edu.sg;
Tel: +65 6790-4346
w Electronic supplementary information (ESI) available: Fig. S1: the
regression plot of the calibration curve for sulfate ions using sulfate-
ion-selective electrode at the range of log[SO
4
2
] from 1 to 4. See
DOI: 10.1039/b817957c
This journal is c The Royal Society of Chemistry 2009 Chem. Commun., 2009, 325327 | 325
COMMUNICATION www.rsc.org/chemcomm | ChemComm
cooled and concentrated under reduced pressure. The residue
was extracted and recrystallized in methanol and dried in
vacuum to obtain a pale yellow solid; yield 76%, mp 182 1C.
MS
27
445.
1
H NMR (DMSO): d 7.017.06 (m, 5H, Ar-H), 2.62
(m, 1HNH), 3.4, 0.831.32 (m, 6H, CH
2
), 2.60 (s, 3H).
IR
27
(KBr) 33733406 cm
1
(n
NH
), 29142968 cm
1
(n
OH
),
1637 cm
1
(n
CN
) and 1532 cm
1
, 1315 cm
1
(n
NO
).
The electrode was fabricated as described.
28
Typical
calibration curve for sulfate-selective electrode
29
in solutions
of sulfate are given in Fig. 1. The slope 28.7 mV per decade
(R = 0.993) was close to the theoretical Nernstian value of
30 mv per decade. In Fig. 1, the regression plot with rst four
concentrations was also obtained (see ESIw for the plot with
10
1
10
4
M). The working pH range of the electrode was
assessed by taking a series of solutions of sulfate with 10
2
M
concentrations by adjusting the pH from 212. The pH was
varied by the addition of acid or alkali using standard buers
for maintaining the pH. The potential of each solution was
measured and plotted against the respective pH values. The
range in which the electrode potential remains constant is the
required working range of the electrode. The electrode showed
a broad working pH range of pH 39 (Fig. 1). Below pH 3,
sulfate is partially converted into hydrosulfate predominating
in the SO
4
2
/HSO
4

equilibrium, and the hydroxide inuence

aects the working pH above 9. The selectivity coecients to
eight ions are given in Table 1.
Atomistic simulation, using density function theory (DFT)
at B3LYP
30,31
method with double-z quality basis functions
6-31+G* (augmented with polarized and diuse sp func-
tions for all non-hydrogen atoms), was used to optimize the
geometry of the ionophore. Geometry was fully relaxed and no
symmetry constraints were imposed during optimization using
Gaussian 03 code.
32
Harmonic vibrational analyses showed no
imaginary frequency, indicating a structure with two intra-
molecular OH N hydrogen bonds (shown in Fig. 2) is a
local minimum.
Theoretical IR spectrum exhibits bands at 33733406 cm
1
(n
NH
), 29142968 cm
1
(n
OH
), 1637 cm
1
(n
CN
) and
1532 cm
1
, 1315 cm
1
(n
NO
), which are in accordance with
experimental results. The large HOMOLUMO gap (closely
related to band gap) of 3.56 eV and high ionization potential
of 6.50 eV indicates favorable stability of the ionophore and
implies that it may be a better electron acceptor than electron
donor. This suggests that the two secondary NH groups, as
shown by arrows in Fig. 2, are open for attachment of SO
4
2
units via intermolecular NH O bonds, where the ionophore
acts as a proton donor. It is well known that proton donors
usually accept electrons.
33
It is interesting to note that both the
highest occupied molecular orbital (HOMO) and the
HOMO 1 orbital are mainly composed of nitrogen and
oxygen 2p
z
, 2
s
and p orbitals from carbons in the benzene rings
(p orbitals) (Fig. 3). We would like to highlight that the
substantial spatial overlapping of these two orbitals is critical
for the high value of dielectric constant. The dielectric
constant 2.30 obtained strongly supports the ionophores
excellent capacity as a potentiometric sensor.
The presence of possible hydrogen bonding in ionophore
with high dielectric value is able to selectively recognize
hydrophilic anions over hydrophobic anions, eventually
increases selectivity of the ISE. Thus, the solvating environ-
ment at the interface suitable for hydrogen-bonding iono-
phores facilitated the sulfate ion transfer. The impact of
dielectric constant of the membrane on the value of anion-
salvation energy for highly hydrophilic anions such as sulfate,
Scheme 1 Synthesis of hydroxyl Schi base ionophore (III).
Fig. 1 Calibration curve for sulfate ions using a sulfate-ion-
selective electrode. Inset: eect of pH on sulfate ISE responses at
[SO
4
2
] = 0.01 M.
Table 1 Selectivity coecients of sulfate electrode
Interfering ion Selectivity coecient
NO
3

5.79 10
4
Cl

5.42 10
4
H
2
PO
4

5.97 10
4
SCN

6.27 10
4
CH
3
COO

6.17 10
4
Br

5.93 10
4
ClO
4

4.94 10
4
HCO
3

2.18 10
3
Fig. 2 DFT optimized structure of the ionophore. Color scheme:
Carbon (grey), nitrogen (blue), oxygen (red) and hydrogen (white).
Arrows indicate possible attachment sites of SO
4
2
to the molecule via
O HNQhydrogen bonds.
326 | Chem. Commun., 2009, 325327 This journal is c The Royal Society of Chemistry 2009
has been established.
14
Thus, by using an ionophore with high
dielectric value and also in combination with an ionic liquid,
such as 1-butyl-3-methylimidazolinium hexauorophosphate,
one can increase the dielectric property of the ion-selective
membrane. For such a membrane, even a relatively low
increase in dielectric constant could cause substantial gain in
solvation energy and favorable selectivity.
14
The interaction of
sulfate over the ionophore used here is expected to be strong
enough to antagonize the established Hofmeister lipophilicity
selectivity for anions. More studies with this electrode are in
progress.
In summary, we have synthesized a high dielectric con-
stant molecule, hydroxy Schi base 2,2
0
-((1E,11E)-2,5,8,11-
tetraazadodeca-1,11-diene-1,12-diyl)bis(4-nitrophenol), and
explored it for making a highly selective sulfate sensor. The
detection limit of the electrode was down to 10
7
M.
We would like to thank the support from Utah Water
Research Laboratory, Logan, Utah, for generous funding this
research at Utah State University (A.Z.). We would also like
to acknowledge Dr Chad C. Nelson, from the Mass Spectro-
metry and Proteomics Core Facility, University of Utah, for
the MS analysis. Work at NTU was supported in part by
MOEAcRF-Tier-1 grant (No. M52070060).
Notes and references
1 D. M. Pranitis and M. E. Meyerho, Anal. Chim. Acta, 1989, 217,
123133.
2 M. E. Meyerho and W. N. Opdycke, Adv. Clin. Chem., 1986, 25,
147.
3 P. Bu hlmann, E. Pretsch and E. Bakker, Chem. Rev., 1998, 98,
1593.
4 S. Amarchand, S. K. Menon and Y. K. Agrawal, Electroanalysis,
2000, 12, 522526.
5 S. K. Menon, A. Sathyapalan and Y. K. Agrawal, Rev. Anal.
Chem., 1997, XVI, 333.
6 S. K. Srivastava and C. K. Jain, Water Res., 1985, 19,
5356.
7 S. Makarychev-Mikhailov, A. Shvarev and E. Bakker,
Electrochem. Sens., Biosens. Biomed. Appl., 2008, 71114.
8 S. Sadeghi, F. Fathi, A. A. Esmaeili and H. Naeimi, Sens.
Actuators B: Chem., 2006, 114, 928935.
9 T. Cserfalvi and G. G. Guilbault, Anal. Chim. Acta, 1976, 84,
259270.
10 F. Hofmeister, Arch. Exp. Patol. Pharmakol., 1888, 24, 247.
11 Y. S. Fung, C. C. W. Wong, J. T. S. Choy and K. L. Sze, Sens.
Actuators B: Chem., 2008, 130, 551560.
12 E. Kirowa-Eisner, D. Tzur, M. Brand and C. Yarnitzky,
Microchem. J., 1999, 61, 4052.
13 T. Br za, Z. Kej k, I. C sar ova , J. Kra lova , P. Marta sek and
V. Kra l, Chem. Commun., 2008, 19011903.
14 C. Coll, R. H. Labrador, R. M. Man ez, J. Soto, F.
Sanceno n, M.-J. Segu and E. Sanchez, Chem. Commun., 2005,
30333035.
15 H. Zhang, X. Li, C. Sunl, J. Mei, S. Li and M. Zhao, J. Alloys
Compd., 1994, 210, 171175.
16 X. W. J. Liu, Z. Zhang, S. Wakida and K. Higashi, Sens. Actuators
B: Chem., 2000, 66, 216218.
17 M. Morigi, E. Scavetta, M. Berrettoni, M. Giorgetti and
D. Tonelli, Anal. Chim. Acta, 2001, 439, 265272.
18 P. D. Beer and P. A. Gale, Angew. Chem., Int. Ed., 2001, 40,
486516.
19 A. K. Singh, V. K. Gupta and B. Gupta, Anal. Chim. Acta, 2007,
585, 171178.
20 A. K. Singh and S. Mehtab, Talanta, 2008, 74, 806814.
21 S. A. V. K. Gupta, A. Jakob and H. Lang, Sens. Actuators B:
Chem., 2006, 114, 812818.
22 D. W. Kim, K. W. Park, M.-H. Yang, T. H. Kim, R. K. Mahajan
and J. S. Kim, Talanta, 2007, 74, 223228.
23 N. V. Shvedene, M. G. Khrenova, D. V. Chernyshov,
A. A. Formanovsky, V. E. Baulin and I. V. Pletnev, Electroanalysis,
2006, 18, 14161421.
24 B. Peng, J. Zhu, X. Liu and Y. Qin, Sens. Actuators B: Chem.,
2008, 133, 308314.
25 Q. Ma, G. S. Ellis, A. Amrani, T. Zhang and Y. Tang, Geochim.
Cosmochim. Acta, 2008, 72, 45654576.
26 A. Ferna ndez-Mart nez, G. Roma n-Ross, G. J. Cuello,
X. Turrillas, L. Charlet, M. R. Johnson and F. Bardelli, Physica
B: Condens. Matter, 2006, 385386, 935937.
27 Thermo Scientic Nicolet iN10 FT-IR microscope, powered by
new OMNIC Picta software was used for FTIR measurements.
The MS analysis was done using a Quattro-II triple-quad mass
spectrometer (Micromass, Inc.). Analyses were performed using
positive-ion electrospray ionization (ESI) in MS-only mode, 2.8 kV
spray voltage, and 30 eV cone energy. Samples were electrosprayed
in a solution of MeOH and H
2
O (3 : 1), and 1% formic acid was
added to the solvent for the nitrobenzaldehyde samples. The
instrument was scanned from 100 to 1500 m/z.
28 The electrode membrane was casted with cetyltrimethylammonium
bromide (CTAB), dioctylphthalate (DOP), and 1-butyl-3-methyl-
imidazolinium hexauorophosphate (IL). 200 mg of ionophore
was weighed accurately and dispersed over 10 ml THF. 100 mg of
PVC were then added into the mixture with constant stirring.
Meanwhile 50 g of CTAB and 5 ml ionic liquid were added with
2 ml DOP. The glass plate was previously xed with PVC in THF
as adhesive. The solution was kept covered and allowed
to evaporate slowly to form an homogeneous membrane. The
membrane of 5 mm diameter was cut and mounted onto an
electrode body (Fluka). Solutions of dierent concentrations were
diluted from the stock standard 0.1 M sulfate solution. A series of
seven solutions 10
7
, 10
6
, 10
5
, 10
4
, 10
3
, 10
2
and 10
1
M were
prepared and 5 ml of 0.001 M KCl was added to each solution.
The electrode potential of sulfate ISE was measured (n = 9)
against the calomel electrode (Fluka).
29 The potential measurements were carried out at 25 0.1 1C using
an Expandable Orion Ion Analyzer 940A, (Orion, USA). pH
measurements were made with an Orion glass electrode and Orion
Ion Analyzer in pH mode. 0.01 M sulfate solution was used as
internal reference solution diluted from standard 0.1 M sulfate
solution (Hanna Instruments, USA) and all standard test solutions
(1.0 10
7
to 1.0 10
1
M) were prepared by successive dilution.
The electrode performance was evaluated from low concentration
to high concentration and vice versa. The solution was stirred with
a magnetic stirrer at equal intervals of time in order to obtain
consistency.
30 A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
31 W. Y. C. Lee and R. G. Parr, Phys. Rev. B, 1988, 37, 785.
32 Gaussian03 package, Gaussian, Inc., Wallingford, CT,
2004.
33 S. Scheiner, T. Kar and J. Pattanayak, J. Am. Chem. Soc., 2002,
124, 13257.
Fig. 3 The MOs energy levels LUMO + 1, LUMO, HOMO and
HOMO 1 of ionophore together with plot of orbital.
This journal is c The Royal Society of Chemistry 2009 Chem. Commun., 2009, 325327 | 327