1035

Review

Potentiometric Anion Selective Sensors

Martijn M.G. Antonisse,+ and David N. Reinhoudt*
Department of Supramolecular Chemistry and Technology, MESA Research Institute, University of Twente, PO Box 217, 7500 AE Enschede,
The Netherlands
‡
Present address: DSM-Resins, Zwolle, The Netherlands

Received: January 15, 1999

Final version: April 26, 1999
Abstract
In comparison with selective receptors (and sensors) for cationic species, work on the selective complexation and detection of anions is of
more recent date. There are three important components for a sensor, a transducer element, a membrane material that separates the
transducer element and the aqueous solution, and the receptor molecule that introduces the selectivity. This review deals with potentiometric
transduction elements that convert membrane potentials into a signal. The structure and properties of membrane materials is discussed. The
nature of the anion receptor ultimately determines the selectivity. Both coordination chemistry and hydrogen bonding have been used to
design anion receptor molecules. The integration of all three elements by covalent linkage of all elements in durable sensorsystem concludes
the review.
Keywords: Potentiometric sensors, Chemical sensors, Selector, Transduction element, Anion complexation, Anion receptors, Ion-selective electrode, Coated
wire electrode, Ion-selective membranes, Plasticizer, MEMFET, CHEMFET, Hofmeister series, Ion-exchange membranes, Heparin sensor, Uranyl salophenes,
Porphyrins, Phthalocyanines, Polyacrylate membranes, Polysiloxanes

1. Introduction
The determination of the concentrations of ionic species in
aqeous samples is important in many areas of applied analytical
chemistry, e.g., in process control, and in the analysis of clinical,
horticultural, or environmental samples. For sensing of charged
species potentiometric sensors offer several advantages. The
sensors have generally a large dynamic range because the signal
is proportional to the logarithm of the ion activity. Short response
times in the order of seconds make the devices very suitable for
process control and allow a high sample through-put in, for
example, ¯ow injection analysis. Moreover, the potentiometric
sensors can have very small dimensions, and consequently only
small sample volumes are required.
Chemical sensors have two elements: the selector and the
transduction element (Fig. 1). In the selector element the chem-
ical information is converted into a domain which is measurable
by the transduction element. As the transduction element is
nonselective the selector element must also introduce the selec-
tivity. In potentiometric sensors, chemical interactions of the
selector element with charged species in the solution are trans-
formed into an electrochemical potential of an indicator electrode
relative to a reference electrode. The selector element of the
potentiometric indicator electrode is an ion-selective membrane.
This membrane can be either an inorganic salt or an organic
polymeric matrix that contains receptor molecules. The receptor
molecules introduce the selectivity into the membrane by strong
and selective binding of the target analyte. They play a key role in
the development of potentiometric sensors.
Anion complexation and the design of anion receptors is far
less developed than the ®eld of cation receptors [1]. This is
re¯ected in the large arrears in the development of potentiometric
anion sensing. The ®rst publications on cation and anion recep-
tors appeared almost at the same time: in 1967 Pedersen [2]
reported the complexation of alkali metal cations by crown
ethers, and in 1968 the ®rst synthetic receptor for inorganic
anions was reported by Park and Simmons [3]. However, the ®eld
of cation recognition developed much more rapidly and there are
now many neutral host molecules for cations [4]. The slow
development of anion recognition can be related to some inherent
differences between anions and cations [5]:
i) Anions are relatively large and therefore require (macro-
cyclic) receptors with a much larger binding site. The
Ê ) as a
smallest anion, Fÿ, has the same ionic radius (1.33 A
moderately sized cation (K‡ ).
ii) Anions have many different shapes, e.g., spherical halides,
linear SCNÿ , trigonal planar NOÿ ÿ
3 , and tetrahedral H2 PO4 .
iii) Anions are more strongly hydrated than cations of equal size,
whereas the solvation by organic solvents is generally less
favorable [6].
iv) Several anions are present only in a narrow pH window, e.g.
H2 POÿ 2ÿ
4 and CO3 anions in an acidic and basic environ-
ment, respectively.
Nevertheless, during the past decade several types of poten-
tiometric anion sensors have been described in the literature. This
review describes the various aspects of the development of these
novel sensors. First, the transduction elements of the sensor will
be discussed (Section 2). Subsequently, the receptors (Section 3)
which determine the selectivity of the sensor, and the membrane
matrix (Section 4) which has a large in¯uence on the durability of
the sensor, will be reviewed.
2. Potentiometric Transduction Elements
In order to measure the electrochemical potential of the ion-
selective membrane, the membrane is integrated within the
transduction element. The most widely applied transduction
system is the two-electrode set-up as depicted in Figure 2. The

Electroanalysis 1999, 11, No. 14 # WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 1040±0397/99/1410±1035 $17.50‡:50=0
1036
Fig. 1. Working mechanism of a chemical sensor.
Fig. 2. Two-electrode setup for potentiometric ion-selective electrodes.
indicator electrode contains the ion-selective membrane and can
be either a conventional ion-selective electrode (ISE), a coated-
wire electrode (CWE), or a device based on an ion-sensitive ®eld
effect transistor (ISFET).
In conventional ISEs the membrane is placed between the
sample solution and the internal reference solution of the ISE
(Fig. 3a). The constant composition of the latter solution results
in a stable potential at both the inner boundary of the membrane
and the interface of the internal Ag=AgCl electrode. This results
in a high stability of the sensors. Most commercial potentiometric
ion-selective devices are based on conventional ISEs. However,
the presence of the internal reference solution normally requires
relatively large electrode dimensions of the conventional ISEs.
In CWEs the ion-selective membrane is directly deposited on
the internal electrode (Fig. 3b). This can be either a noble metal
wire, a graphite rod, graphite or silver paste. Silver coated with a
thin layer of AgCl is most often applied. The absence of an
internal electrolyte results in a thermodynamically ill-de®ned
electrode-membrane interface [7]. The function of the internal
reference solution container of ISEs can be taken over in CWEs
by a (poly(hydroxyethyl methacrylate) or polyvinyl alcohol)
hydrogel soaked with NaCl solution, between the electrode and
the membrane [8]. The stability can also be improved by the
addition of a silver complex to the membrane (e.g., a thioether-
functionalized calix[4]arene has been used as strong silver
Fig. 3. Potentiometric transducers. a) conventional ion-selective elec-
trode; b) coated-wire electrode; c) micromachined ion-selective elec-
trode.
Electroanalysis 1999, 11, No. 14
M.M.G. Antonisse, D.N. Reinhoudt
binding ligand [9]). The silver ions will form a redox couple with
Ag0 of the wire. The main advantage of CWEs over conventional
ISEs is the possibility of cheap mass production. The silver
electrodes and the membranes can be screen-printed on paper,
polyimide (Kapton) or epoxy supports. This procedure is con-
venient to disposable devices and special medical purposes [8b,
10, 11]. Furthermore, the small size allows the construction of
sensor arrays [11, 12]. A disadvantage of the CWE is that the
membrane easily becomes detached from the electrode and that
due to the small membrane volume leaching of membrane
components, e.g., the plasticizer, quickly deteriorates the sensor
characteristics. The leaching can be reduced with the micro-
machined silicon sensor depicted in Figure 3c [13]. The mem-
brane is deposited in a pyramidal hole etched in the silicon chip.
The reduced membrane-sample contact area improves the dur-
ability and protects the membrane from mechanical damage.
The third transducer type, the ISFET, already has been very
successful in the development of cation selective sensors, and
recently also anion micro-sensors were reported. The ISFET was
reported for the ®rst time by Bergveld [14], who removed the
metal gate electrode from a metal oxide semiconductor ®eld
effect transistor (MOSFET) and exposed the gate insulator oxide
directly to an aqueous sample. In the ISFET two n-type regions,
the source and the drain, are implanted in the semiconducting
p-type bulk silicon (Fig. 4). An external electrical ®eld (VGS )
applied to the surface of the ISFET (positive potential at the gate
side) will deplete the number of holes in the p-type bulk near the
surface between source and drain [15]. Above a certain threshold
voltage (VT ) of VGS electrons are attracted which will bridge the
potential gap between source and drain. This is the so-called
channel formed by the inversion layer. Changes in the gate
potential will result in changes in the density of electrons in the
inversion layer and consequently a change can be measured in the
drain current through the inversion layer. In practice the drain
current is kept constant because the change in the drain current is
compensated by a change of the potential of the reference elec-
trode (feedback mode) [16].
Potentiometric Anion Selective Sensors
Fig. 4. Schematic representation of ISFET-based chemically modi®ed ®eld effect transistor (CHEMFET).
ISFETs are pH sensitive devices. Depending on the acidity of
the solution the SiO2 gate insulator can be protonated or
deprotonated, which results in a pH dependent surface potential
[15b]. However, for ISFETs with SiO2 gate oxide the sensor
response is nonlinear and sub-Nernstian (20±40 mV=pH). The
pH sensitivity and the sensor drift are increased, respectively
decreased by applying a layer of Si3 N4 , Al2 O3, or Ta2 O5 on top
of the original SiO2 [17].
Sensitivity for ions other than H‡ can be obtained by
deposition of an ion-selective membrane on top of the gate
region, creating a so-called MEMFET (membrane ®eld effect
transistor). Janata et al. [18] demonstrated this principle for the
®rst time, developing a K‡ selective MEMFET based on a
plasticized PVC membrane with valinomycin as cation receptor.
Like in CWEs, the inner membrane boundary potential in
MEMFETs is ill-de®ned due to the absence of an internal
reference solution. Furthermore, CO2 or neutral organic acids,
like ascorbic acid and benzoic acid, diffuse through the mem-
brane and cause local pH changes at the hydrated layer between
the gate oxide of the ISFET and the membrane [19]. By covering
the ISFET surface with a thin pH insensitive layer of AgCl [19b]
or polyacrylate [20] this effect can be eliminated. The stability
can also be improved by the introduction of a poly(2-hydroxy-
ethyl methacrylate) (polyHEMA) layer between the ISFET and
the ion-selective membrane [21]. In chemically modi®ed ®eld
effect transistors (CHEMFETs) [22] the polyHEMA is covalently
attached to the ISFET by prior treatment of the surface with (3-
methacryloxypropyl)trimethoxysilane. Soaking of the layer with
a pH buffered solution of the primary ion, results in elimination
of the CO2 interference and an improved stability due to the
constant boundary potential at the inner interface of the mem-
brane. Suggestions in the literature [7, 23] as would this approach
fail because ``a small deviation from the osmotic equilibrium
results in transport of water across the polymer which causes drift
or a mechanical failure of this structure'' are mere speculations
and conclusively contradicted by the experimental results,
showing no drift (additional to the inherent drift of ISFETs) on
the time-scale of the measurements. Furthermore, the stability of
CHEMFETs (electrochemical and mechanical) was proven by the
good sensor characteristics even after exposing the sensors to tap
water for over more than half a year [24].
In contrast with more mature ®eld of cation selective sensors,
there is still only a limited number of anion microsensors, based
on CWE or ISFET transducers. The majority of the sensors with
selectivity deviating from the Hofmeister series is based on the
conventional ISE. Recently some anion micro-sensors with
coated wire or ISFET transducer elements were developed,
however, are still mainly in combination with solid-state or ion-
exchange membranes.
1037
3. Selectivity of Anion-Selective Membranes
3.1. Introduction
The selectivity of potentiometric anion sensors is introduced
via an ion-selective membrane deposited on top of the transducer
element. Because sensors are often designed for certain appli-
cations and well-de®ned conditions, this membrane does not
necessarily have to be speci®c for the analyte as long as strong
interferents are absent or present only in low concentrations. The
®rst anion sensors were based on solid-state inorganic mem-
branes, for example LaF3 or AgCl. For polymeric membranes,
anion selectivity is most easily obtained with positively charged
ion-exchange membranes. The selectivity of these membranes is
governed by the partion coef®cients of anions. The relative par-
tition is (besides by the solvation of the membrane) determined
by the relative dehydration energies which is given by the Hof-
meister series [25].
ClOÿ ÿ ÿ ÿ ÿ ÿ ÿ
4 > SCN  I > salicylate > NO3 > Br > NO2
 Clÿ > HCOÿ ÿ ÿ 2ÿ
3 > H2 PO4  F  SO4
This sequence shows that anion sensors based on ion-exchange
membranes can only successfully be applied for the determina-
tion of the relatively most lipophilic anions in solution. In
practice this means that an anion in the series from ClOÿ4 to NO3
ÿ
can be detected if the other ions in this series are absent or are
only present in much lower quantities. Hydrophilic anions may
be present in the sample in higher concentrations.
To obtain sensors selective for hydrophilic anions, it is
necessary to add receptor molecules to the membrane that
selectively bind the target anion (Fig. 5). The presence of such
selective receptor molecules favors the penetration of the target
anion into the membrane, and selectivities can be achieved even
over much more lipophilic anions present in the sample solution.
To obtain a Nernstian sensor response, the receptor should
effectively buffer the free primary ion activity. Depending on the
Fig. 5. Mechanism of an ion-selective membrane with receptor mole-
cules.
Electroanalysis 1999, 11, No. 14
1038
charge of the receptor, this is achieved in different ways. With
neutral anion receptors the constant ion activity is achieved by
the establishment of a constant ratio between the concentration of
the anion-receptor complex and the free receptor. According to
the equation for the association constant of the complex forma-
tion, this results in a constant concentration of the free anion. In
order to achieve a nearly constant ratio between free receptor and
complex, the amount of lipophilic positive sites, added to the
membrane to compensate the charge of the complexed anions,
should be 0.5 equivalent of the total receptor concentration (for
monovalent anions). When the anion receptor is positively
charged there is no need to add cationic sites in order to get a
sensor response towards anions. The receptor will form a salt
with the anion in the membrane. The change in free ion con-
centration in the membrane as a consequence to a variation in the
sample composition is effectively buffered by the solubility
(product) of the salt. A drawback of a membrane with charged
receptors is that the membrane selectivity is lower as would be
expected based on the ratio of the association constants, and
therefore lower as would be obtained with a neutral receptor of
equal selectivity [26]. However, recently both theoretically and
experimentally it was proven that the addition of lipophilic
negative sites in the membrane enhances the selectivity by
increasing the free receptor concentration [27]. In the latter case
the selectivity coef®cient Ki;Potj is given by Equation 1, which
simpli®es to Equation 2 for the limiting case of the concentration
anionic sites being almost equal to the concentration of the
charged receptor.
kj bjL
Ki;Potj ˆ
ki biL
‰Rÿ ŠbiL ‡ 1 ÿ ……Rÿ ŠbiL ‡ 1†2 ‡ 4biL …LT ÿ ‰Rÿ Š††1=2
 without sensitivity for NOÿ
‰Rÿ ŠbjL ‡ 1 ÿ ……Rÿ ŠbjL ‡ 1†2 ‡ 4bjL …LT ÿ ‰Rÿ Š††1=2
…1†
kj bjL
lim…‰Rÿ Š ! LT † Log Ki;Potj ˆ Log ‡ Log …2†
ki biL
with ki the partion coef®cient, biL the stability constant of the ion
receptor complex, [Rÿ ] the concentration of negative sites, LT the
total concentration of receptor molecules, and the subscripts i
and j indicating the primary and interfering anionic species,
respectively.
For the anion binding by the receptors applied in the anion-
selective membranes several binding principles have been
explored. Charged receptors, like bisquaternary ammonium sites
or charged metal complexes, attract anions via Coulomb inter-
actions. With neutral receptors, the anion can be bound by Lewis
acidic coordination of metal centers, or by hydrogen bond for-
mation. These latter interactions are weaker than Coulomb
interactions and depend strongly on the directionality and on the
electron density of the anion. Nevertheless, combination and
preorganization of several binding sites can lead to strong anion
binding receptors. Furthermore CO2ÿ 3 and carboxylate selective
sensors have been developed that are based on reversible covalent
bond formation.
3.2. Sensors with Inorganic Salts as Selector Element
In 1966 Frant and Ross [28] discovered that a single crystal of
LaF3 contacted to an electrode could be used for Fÿ sensing. The
Electroanalysis 1999, 11, No. 14
M.M.G. Antonisse, D.N. Reinhoudt
mechanism of this ®rst anion-selective sensor is based on the
mobility of the ¯uoride ions in the LaF3 crystal lattice. Upon
contact with the aqueous solution, the anions distribute over the
crystal-water interface leaving positively charged vacancies in the
lattice. This charge separation results in a boundary potential
which depends on the activity of Fÿ in the sample. By chemical
vapor deposition (CVD) of LaF3 on a Si3 N4 -insulator layer of
ISFETs also with these transducers high Fÿ selectivity was
Pot ÿ
obtained (Log KF; j < ÿ3.7) over more lipophilic anions like Cl
and NOÿ 3 [29].
In a similar fashion, deposition of AgBr [30] and AgCl [30b,
31] yield Brÿ and Clÿ selective ISFETs, respectively. The silver
salts can also be suspended in an inert polymeric membrane
matrix (elastomeric poly¯uorinated polyphosphazene) on top of
the gate yielding ISFETs with almost Nernstian responses for
Clÿ , Iÿ , and CNÿ [32]. ISEs selective for Brÿ or Iÿ were con-
structed with heterogeneous membranes made of silicone rubber
[33] or poly(methyl methacrylate) [34], respectively. Bakker [35]
developed Clÿ sensitive electrodes by using membranes that
contain strong silver complexes with organic ligands. In the
absence of silver ions in the sample, these cations will be released
slowly from the membrane, forming an AgCl precipitate at the
membrane interface.
ISEs for NOÿ 3 detection have been developed based on solid,
crystalline membranes of silver diethyldithiocarbamate and silver
sul®de [36]. Although the NOÿ ÿ
3 selectivity over ClO4 (Log
Pot
KNO3 ;ClO4 ˆ 0) is improved compared with common ion-
exchange membranes, the selectivity coef®cient is lower in the
presence of Fÿ and SO2ÿ 4 as interfering ions. Coating of the gate
area of ISFETs with a ®lm of alkali metal-free lead phosphate
glass results in anion sensitive sensors with selectivities that
follow the Hofmeister series (SCNÿ > Iÿ > Brÿ > NOÿ 2 ) but
3 [37]. Electrodes of hydroxyapatite
(Ca10 (PO4 )6 (OH)2 ) are sensitive towards phosphate and high
selectivity over NOÿ ÿ
3 and ClO4 is reported [38]. At pH 5 a
response of ÿ34 mV=decade is observed, suggesting sensitivity
towards bivalent HPO2ÿ although this is not the predominant
4
species at pH 5. Electrodes of hydroxyapatite with graphite in
epoxy resin show at the same pH a response of ÿ55 mV=decade.
Cobalt wire electrodes are responding to H2 POÿ 4 in a sub-
Nernstian manner (ÿ47mV=decade) with Log KHPot2 PO4; j between
ÿ2 and ÿ3 vs. halides and NOÿ 3 [39]. The response is probably
not due to a special host-guest interaction at the CoO surface of
the electrode as was ®rst proposed, but originates from slow
oxidation of Co0 followed by the formation of Co3 (PO4 )2 [40].
Di Natale et al. [41] developed an array of 20 sensors of
different composition including solid state Clÿ and Fÿ selective
electrodes and several chalcogenide glass electrodes. The mea-
surements of about 180 different solutions were used as the input
for an arti®cial neural network. Although no sensor was present
that is speci®c for SO2ÿ 4 , it was possible to detect this anion on
the basis of cross-selectivities.
3.3. Sensors with Quaternary Ammonium or
Guanidinium Sites
As mentioned in Section 3.1, sensors with polymeric ion-
exchange membranes with cationic sites that do not selectively
bind any speci®c anion, follow a selectivity pattern according to
the Hofmeister series. Lipophilic anions, like ClOÿ ÿ
4 and NO3 , are
favored over the more hydrophilic anions, like H2 PO4 and Clÿ .
ÿ
There is much interest in the development of sensors for NOÿ 3
Potentiometric Anion Selective Sensors
because of the importance of this anion in environmental and
agrocultural samples. Lipophilic tetraalkylammonium ions as
ion-exchange sites are used for nitrate selective sensors based on
ISE-, [42] CWE-, [43] or ISFET-transducers [44]. According to
the Hofmeister series, selectivity is obtained over other, more
hydrophilic natural occurring anions like Clÿ and NOÿ 2 (Log
Pot
kNO 3; j
ˆ ÿ2:3 and ÿ1.2, respectively). Sensors with a selectivity
for lipophilic organic anions like anionic surfactants [45] or
carboxylate anions [46] are based on the same principle, viz. the
incorporation of tetraalkylammonium or bis(triphenylphos-
phoranylidene)ammonium salts in the ion-selective membrane.
Brzozka [47] investigated ion-exchange membranes sensitive for
Au(CN)ÿ
2 as an analytical method for gold. Increased lipophili-
city of the tetraalkylammonium ion-exchange sites improved the
selectivity for Au(CN)ÿ ÿ corresponding pentaaza derivative 6 shows the same sensor
2 vs. hydrophilic anions, like Cl
ÿ ÿ
IO3 . Similar results were reported for Cl selective ion-exchange
membranes [48].
Meyerhoff et al. [49] developed heparin sensors based on ion-
exchange membranes with methyltridodecylammonium chloride
sites. For poly-ions like heparin the response is small according
to the Nernst equation, because the slope is proportional to the
reciprocal of the charge. However, when a heparin-free mem-
brane is exposed to a solution with a low concentration of
heparin, Clÿ ions from the membrane are exchanged by heparin
ions. The inward ¯ux of heparin creates a nonequilibrium,
steady-state potential, which is given by Equation 3.
 
RT z Da d m
DEMF ˆ ln 1 ÿ chep;bulk
F Rt Dm da
DEMF is the nonequilibrium potential change at sample heparin
concentration chep;bulk ; Rt refers to the concentration of ion-
exchange sites in the membrane, and D and d are the diffusion
coef®cient and diffusion layer thickness in the membrane (m) and
aqueous sample (a).
Receptor molecules with charged nitrogen atoms that pre-
ferentially bind a speci®c anion, due to complementarity in size
or in geometrical positioning of the charged binding sites, can
exhibit a sensor selectivity that deviates from the Hofmeister
series. Incorporation of diquaternary ammonium salt 1 in an ion-
selective membrane results in Iÿ selectivity over ClOÿ 4 and SCN
ÿ
[50]. Apparently the I ion can interact simultaneously with both
quaternary nitrogen atoms. The distance between these qua-
ternary nitrogen atoms plays an important role, because the
normal Hofmeister selectivity is obtained when these sites are
separated by a propylene spacer. Several mono-, di- and tri-
alkylguanidines have been tested for possible speci®c anion
interactions [51]. However, these sensors show only Hofmeister
selectivity. Bachas et al. [52] have shown that guanidinium
derivative 2 exhibits selectivity for HSOÿ 3 . Receptor 3 has a
different structure and this results in loss of the HSOÿ3 sensitivity.
Instead selectivity for salicylate is observed with selectivity
Pot
coef®cients (Log KSal;j ) over the most interfering anions benzo-
ate, acetate, and ClOÿ4 of ÿ1.7, ÿ2.4 and ÿ2.6, respectively [53]
Protonated cyclic aza diamide 4 (n ˆ 1) selectively binds
HPO2ÿ
4 [54]. At pH 7.2 the slope for this divalent anion is almost
1039
Nernstian with selectivity over thiocyanate (Log
Pot
KHPO 4 ;SCN
ˆ ÿ2:3). Sensors with protonated cyclic triaza dia-
mide 5 are capable to distinguish planar anionic metal cyano
complexes like Ni(CN)2ÿ and Pt(CN)2ÿ and complexes with
4 4
octahedral structures (e.g., Fe(CN)3ÿ 4ÿ
6 and Fe(CN)6 ) [55] The
and
selectivity for both types of anions. Umezawa et al. [56] reported
sensors for nucleotides. ATP4ÿ sensitive sensors were obtained
with protonated pentaazamacrocycle 6. Although the high charge
of ATP4ÿ results in a Nernstian slope of only ÿ15 mV=decade,
the selectivity over the polyphosphates ADP3ÿ and AMP2ÿ and
even over the lipophilic ClOÿ 4 anion is a factor of 30. Receptor 6
does not discriminate between different nucleotide bases like
ATP and GTP. Ditopic receptor 7 has, besides a (protonated)
triamine moiety for phosphate binding, a cytosine moiety which
is complementary to guanine [57]. The additional selective
interaction between the guanidine moiety of GTP4ÿ and the
cytosine moiety is re¯ected in a selectivity for GTP4ÿ over
ATP4ÿ.
…3†
Electropolymerized, oxidized polypyrrole membranes are
positively charged and can act as ion-exchange membranes [58].
Depending on the salt present during the polymerization of the
aqueous pyrrole solution and during the conditioning, the sensors
are selective for Clÿ [59] or NOÿ 3 [60]. These sensors reveal a
selectivity deviating from the Hofmeister series, probably
because the size of the larger anion prohibits exchange with the
small anion included during the polymerization; even with
selectivity of Clÿ or NOÿ ÿ
3 over the highly lipophilic ClO4 .
However, the sensor characteristics are strongly dependent on the
membrane preparation procedure, like polymerization and con-
ditioning times, and the polymer ®lm deteriorates when exposed
ÿ
to light [60]. Besides the instantaneous Nernstian response,
sensors based on polypyrrole membranes show drift towards a
long term equilibrium potential when exposed to a new analyte,
which is due to changes in the oxidation level of the ®lm [61].
3.4. Sensors with Organometallic Receptors
Receptors with Lewis acidic metal centers as anion binding
sites are often applied for anion sensors with selectivities
deviating from the Hofmeister series. The metal center can be
either ionic (complexed in an organic ligand), or can be cova-
lently bound as part of an organometallic structure. Depending
on the organic ligand and the metal center this class of receptors
applied in ISEs contains both charged and neutral receptors. As
described in Section 2.2, with positively charged receptors lipo-
philic anionic sites should be added to the membrane to optimize
the sensor selectivity, whereas in the case of neutral receptors
cationic sites should be added.
The type of ligand and metal center in¯uence the sensor
selectivity due to differences in the electron-accepting character
of the complex. For example, with Au3‡ -triisobutylphosphine
Electroanalysis 1999, 11, No. 14
1040
sul®de sites, SCNÿ selective electrodes are obtained [62]. The
selectivity over ClOÿ ÿ Pot
4 and Br (Log KSCN; j ˆ ÿ1:8 and ÿ0.4,
respectively) is strongly deviating from the Hofmeister series.
Membranes containing a N-thiocarbamoylimine-dithioether sil-
ver complex show selectivity for Iÿ over ClOÿ ÿ
4 , SCN , or other
halides [63]. HPO2ÿ 4 sensitive electrodes were obtained with
plasticized PVC membranes that contain a Ni2‡ mixed ligand
complex with one diketonate and one N-alkylated ethylenedia-
mine ligand [64]. ISEs that are highly selective for Iÿ , even with
respect to lipophilic anions like ClOÿ ÿ
4 and SCN , are obtained
2‡
with the tetraazaannulene Ni complex 8 [65]. Due to the saddle
shape of 8, the two axial positions of the metal center are not
equivalent and a pentagonal coordination is preferred.
Sometimes ligands are used that have also been applied as
receptor in cation-selective sensors, like for example crown
ethers or calixarenes. Electrodes with electropolymerized
binaphthyl-20-crown-6 potassium complex respond to HSÿ
with a slope (ÿ110 mV=decade) strongly deviating from the
theoretically expected Nernstian slope of 59 mV=decade [66].
Bis(thioamido)- and tetrakis(thioamido)-functionalized calix[4]-
arenes strongly bind heavy metal ions, and have been applied as
receptors for Pb2‡ selective CHEMFETs [67]. These calix[4]-
arene derivatives in membranes without the addition of lipophilic
ionic sites or with a small amount of positive sites give anion
sensitive sensors with a selectivity generally following the Hof-
meister series except with an increased sensitivity for Iÿ [68].
Schiff's base ligands are frequently used to complex anion
binding metal ions. Cammann et al. [169] reported CNÿ selective
electrodes using biscopper complex 9. CNÿ binding is favored
because this anion ®ts well into the cavity and can coordinate to
both copper centers. The sensors show selectivity of one order of
magnitude over ClOÿ ÿ
4 and SCN . The Schiff's base complexes of
Ba , Cu , or Pb were used as ion-exchange sites in ClOÿ
2‡ 2‡ 2‡
4 Co3‡ cobyrate derivatives, structurally related to vitamin B12
selective CWEs [702]. Sensors with the neutral complex of Co2‡
and a salophene are selective for Iÿ over ClOÿ ÿ
4 and SCN (Log
Pot
Ki; j ˆ ÿ2:4 and ÿ2.2, respectively) [71].
In our group anion-selective CHEMFETs were developed with
neutral anion receptors based on an uranyl cation immobilized in
a salophene ligand. Bound by this ligand the uranyl cation prefers
a pentagonal, bipyramidal coordination, with the two oxygen
atoms at the apical positions and four of the equatorial positions
occupied by the salophene ligand. The ®fth equatorial position
can coordinate to nucleophilic guest species. This can be a
nucleophilic moiety (e.g., CˆO or SˆO) of a neutral molecule
[72], or an anionic species [73, 74]. The salophene building
block can be modi®ed with lipophilic docyl substituents for
improved solubility of the uranyl salophenes in the polymeric
membrane matrix. The hard Lewis acidic uranyl cation favors
interaction with hard Lewis basic anions, and consequently the
parent salophene 10 gives H2 POÿ 4 selective CHEMFETs. The
Electroanalysis 1999, 11, No. 14
M.M.G. Antonisse, D.N. Reinhoudt
sensors have an almost Nernstian response slope of
ÿ56 mV=decade, and show selectivity over more lipophilic
anions, like Brÿ and NOÿ Pot
3 (Log KH2 PO4 ; j ˆ ÿ1:7 and ÿ1.3,
respectively). By variation of the ratio between the concentrations
of receptor and lipophilic cations in the membrane the stoichio-
metry of the anion receptor complex was studied and appeared to
be 2 : 1 receptor to anion [75].
The advantage of the uranyl salophene building block is that
additional hydrogen bond binding sites can be introduced close
to the uranyl center and this made it possible to improve or
change the selectivity in anion binding. For example, the meth-
oxy substituents in receptor 11 can accept hydrogen bonds from a
H2 POÿ 4 anion coordinated at the uranyl center. CHEMFETs with
this receptor show improved H2 POÿ 4 detection limits and selec-
tivity over halide anions compared to the sensors with the parent
salophene 10 [76]. Also hydrogen bond donating amido sub-
stituents can be introduced (receptor 12). Due to the reduced size
of the binding cleft and the capability to donate hydrogen bonds,
this receptor is a stong binder of Fÿ, which is a hard Lewis base
and stong hydrogen bond acceptor. With this receptor it is pos-
sible to detect Fÿ at the (sub)millimolar level, even in the pre-
sence of a large excess of the very lipophilic perchlorate (Log
Pot
KF;ClO 4
ˆ ÿ1:7). Uranyl salophene derivative 13 gives CHEM-
FETs selective for acetate. In spite of the high hydrophilicity of
acetate, they are selective for acetate in the presence of Clÿ , Brÿ,
and NOÿ Pot
3 (Log MKAcO; j ˆ ÿ1:2, ÿ1.2, and ÿ0.3, respectively).
The selectivity over H2 POÿ 4 is a factor of 250. Apparently, the
phenyl substituents of 13 which give a favorable interaction with
the methyl group of the acetate anion, unfavorably interact with
the tetrahedral H2 POÿ 4 anion and consequently reduce the bind-
ing strength of the H2 POÿ 4 anion with the uranyl center.
(14), give well-functioning anion sensors. In vitamin B12 the
cobalt cation is bound at the four equatorial coordination sites by
the nitrogen atoms of the corrin cycle. At the axial positions
cyanide and the dimethylbenzimidazole ribonucleotide part (the
proximal base) of the corrin ring are coordinated. This results in a
monovalent complex. For sensor applications more lipophilic
derivatives like 15 have been synthesized [77]. Derivative 15
lacks the proximal base and this leaves one of the axial coordi-
nation sites free for anion complexation [77b]. These sensors
have high NOÿ 2 selectivity over more lipophilic anions like NO3
ÿ
ÿ Pot
and ClO4 (Log KNO2 ; j ˆ ÿ3:6 and ÿ2.4, respectively). The
optimal sensor characteristics with this positively charged
receptor are observed with about 60 mol % (vs. receptor) of
lipophilic borate anions in the membrane [78]. With corrin 16, in
which an imidazole ring is present as proximal base, sensors
become Iÿ selective, because this ion might interact with both the
cobalt center and the (protonated) imidazole ring [79].
Potentiometric Anion Selective Sensors 1041

In porphyrins the Co3‡ ion is also coordinated via the equa- Nernstian slopes of ÿ80 mV=decade [91]. The interference of
torial sites. The axial positions of the monovalent complex are lipophilic anions to the sensor response of this charged receptor
could be reduced by the addition of borate salts to the membrane,
although the response slopes remained super-Nernstian [81a].
Gao et al. [92] applied the In(III)-TPP complex for the NOÿ 2
selective sensors. Sensors with MoO3‡ TPP are responding to
OHÿ with an almost Nernstian slope in the range 10ÿ11 ±
10ÿ1 Mÿ1 [93]. The selectivity over lipophilic ClOÿ 4 (Log
Pot
KOH;ClO 4
ˆ ÿ4:7) is high. Another way to in¯uence the selec-
tivity of metalloporphyrins is the introduction of either electron-
donating or -withdrawing substituents at the porphyrin ring
which change the electron density of the metal center [94], or
substituents that have a steric interaction with the anion coordi-
nating to the metal [95].
Phthalocyanines (18) related to porphyrins also form com-
available for anion binding. ISEs with Co3‡ porphyrin 17 are plexes with various metal ions. Cobalt phthalocyanine in plasti-
sensitive towards NOÿ 2 with two orders of magnitude selectivity cized PVC membranes of ISEs exhibit selectivity for NOÿ 2 [96]
over NOÿ 3 [80]. After conditioning of the sensor in NOÿ 2 solu- and H2 POÿ 4 [97]. CWEs with electropolymerized cobalt phtha-
tions, one of the axial coordination sites strongly binds a NOÿ 2 locyanine detect NOÿ ÿ
2 [98], H2 PO4 [99], or S
2ÿ
[100]. Electro-
anion. This results in a neutral anion receptor in which a second des modi®ed with poly(acrylate) membranes with covalently
anion can coordinate to the other axial position [81]. The main linked cobalt phthalocyanine detect Fÿ and CNÿ in acetonitrile
interfering ions in the NOÿ 2 response are OH
ÿ
and SCNÿ [101]. Although the cobalt phthalocyanines are often referred to
[81b,82]. HodinaÂr and Jyo [83] used this receptor for SCNÿ as neutral receptors, the Co2‡ center is easily oxidized and the
sensors with selectivity over ClOÿ 4 . One of the advantages of active receptor is the charged Co3‡ phthalocyanine [96]. The
metalloporphyrins is that various types of metal cations can be redox couple Co2‡ =Co3‡ is the origin of the ascorbic acid
incorporated [84]. Due to the differences in the electron-accept- (Vitamin C) response of cobalt phthalocyanine pressed pellet
ing character of the metal cores, metalloporphyrins can induce solid electrodes [102]. Several other phthalocyanines with mag-
sensor selectivity for several anions (Table 1). Charged Mn3‡ nesium, lead, or copper centers are sensitive for NOÿ3 , although in
porphyrins induce a less pronounced deviation from the Hof- the latter two cases the reproducibility is low [103].
meister series than Co3‡ porphyrins, and exhibit small preference
for Clÿ over NOÿ ÿ ÿ
3 and selectivity for SCN over ClO4 [80, 85].
The oxo-bridged manganese porphyrin (MnTPP)2 O exhibits less
OHÿ interference of SCNÿ sensors [86]. The selectivity for
SCNÿ over ClOÿ 4 is improved with (FeTPP)2 O as anion receptor
Pot
(Log KSCN;ClO 4
ˆ ÿ2:3) [87]. Sn4‡ porphyrins are charged anion
receptors [81a] and they are strongly selective for salicylate [88].
PVC membranes with 1 wt.% of Sn(IV)-TPP show a Nernstian
response, but with larger amounts the slopes are super-Nernstian.
Sensors based on the Sn4‡ complex of octaethylporphyrin (OEP)
did not exhibit this high salicylate selectivity and sensitivity. The Organotin derivatives have been extensively investigated as
super-Nernstian response is attributed to a complicated salicylate anion receptor for sensors. ISEs with trialkyltin chlorides or
binding mechanism in which ®rst water is coordinated to Sn4‡ acetates (alkyl ˆ octyl or butyl) respond to Clÿ with selectivity
and salicylate anions are held in a second sphere bound by over NO3 ÿ and ClOÿ 4 [104]. The neutral tetracoordinated tin
hydrogen bonds in a 1 : 3 porphyrin-anion stoichiometry [89]. In center converts into the pentacoordinated complex upon the
the second step the water ligands are exchanged by salicylate and binding of Clÿ [105]. This can lead to exchange of the initial
one salicylate anion is released. ISEs with Sn(IV)-TPP have also ligands. Addition of lipophilic nucleophiles to the membrane
been used for the detection of 2-hydroxybenzhydroxamate, a enhances this process and results in improved response times and
drug for the prevention of kidney stones [90]. The In3‡ complex slopes [106]. Although the initial anionic ligand does not in¯u-
of TPP and OEP used in Clÿ selective electrodes show super- ence the selectivity, derivatives without such ligands, e.g., 1,2-
(trimethylstannyl)benzene or hexabutyldistannane, do not induce
any sensor sensitivity [107]. The selectivity can be modi®ed by
Table 1. In¯uence of the metal center of porphyrins on the sensor the type of the organic ligand. While bis( p-chlorobenzyl)tin or
selectivity
bis(p-¯uorobenzyl)tin dichloride were applied in HPO2ÿ 4 selec-
Metal center Detected anion Reference tive electrodes [108], tris(benzyltin)chloride was used to intro-
3‡ ÿ duce salicylate selectivity [109]. Binuclear bis(tribenzyltin)oxide
Mn Cl [80]
SCN- [85]
was used to introduce HPO2ÿ 4 selectivity [110]. Chaniotakis et al.
Fe3‡ SCNÿ [87] [111] have developed several di- and tristannyl derivatives (e.g.,
Co3‡ NOÿ 2 [80] bis(phenyldibromostannyl)methane and tris(3-(chlorodimethyl-
SCNÿ [83] stannyl)propyl)tin chloride) which are selective for H2 POÿ 4 . In
MoO3‡ OHÿ [93] sensor membranes the response slopes are sub-Nernstian (ÿ40 to
In3‡ Clÿ [91] ÿ45 mV=decade), but there is selectivity over SCNÿ and ClOÿ 4.
NOÿ [92]
2 Mercury is the Lewis acidic site in Clÿ selective receptor 19.
Sn4‡ Salicylateÿ [88]
The ortho-positioning of the two mercury substituents improves

Electroanalysis 1999, 11, No. 14

1042 M.M.G. Antonisse, D.N. Reinhoudt

the selectivity compared to mono or meta-derivatives [112]. For phosphine oxide disulfoxide [120]. The resulting macrocycle
an almost Nernstian slope of ÿ57 mV=decade for Clÿ the addi- binds anions via hydrogen bond formation or ion-dipole inter-
tion of a small amount (1 mol %) of lipophilic ammonium sites is actions and gives sensors sensitive towards ClOÿ4 with selectivity
necessary, although this also results in a somewhat lower selec- according to the Hofmeister series. In receptor 25 the methylene
tivity over more lipophilic anions like Iÿ and SCNÿ . Various hydrogen atoms interact with anions due to their electron de®-
mercury(II) complexes with organic ligands have been applied in cient character caused by the electron-withdrawing effect of the
several anion-selective sensors. The Hg2‡ complex of triisobu- adjacent CF2 moieties [121]. However, sensors with 25 show a
tylphosphine sul®de is applied in Iÿ selective ISEs [113]. Bis(4-
methylpiperidinedithiocarbamato)- or bis(alkyldithiocabamato)-
mercury(II) are used for SO2ÿ ÿ
3 =HSO3 sensors [114]. The
potentiometric response of these sensors is induced by the
reduction of Hg2‡ to Hg‡ by SO2ÿ ÿ
3 or HSO3 , which results in
free organic ligand as negatively charged sites in the membrane
[114b]. Prolonged exposure to reducing agents deteriorates the
response due to conversion of all Hg2‡ . Main interferents of the
sensors are other reductive anions like Brÿ, NOÿ ÿ
2 , and N3 .
Although the metallocenes have been investigated thoroughly
and show strong anion complexation in solution [115], ISEs with
these receptors give generally a poor anion response [116].
However, hafnocene and zirconocene dichloride show selectivity
towards salicylate with benzoate as the main interferent. selectivity that follows the Hofmeister series, although the sen-
sitivity for Fÿ is somewhat increased.

3.5. Sensors with Anion Binding Based on Hydrogen

Bonding or Ion-Dipole Interactions
Compared to the receptors that bind anions by Lewis acidic
centers, the application of receptors that bind anions via hydro-
gen bonding or ion-dipole interactions is far less developed.
Recently Umezawa et al. [117] reported the application of
bis(urea) derivative 20 (R ˆ hexyl) as receptor in ISE mem-
branes. Remarkably H2 POÿ 4 could not be detected as would be
expected on the basis of the high association constants for this
ion in solution; and instead a moderate Clÿ sensor was obtained.
The potentiometric selectivity coef®cient vs. Brÿ (Log
Pot
KCl;Br ˆ 0:4) re¯ects the almost equal sensitivity for Clÿ and
Brÿ. Receptor 21, in which two thiourea moieties are linked via a
m-xylene spacer, introduces SO2ÿ 4 sensitivity [118]. The slope is
Nernstian from 10ÿ6 to 10ÿ2 M Na2 SO4 (ÿ28.1 mV=decade) and
compared to the Hofmeister series the interference of Clÿ , Brÿ,
or NOÿ Pot
3 is strongly reduced (Log KSO4 ; j ˆ ÿ0:1, 1.1, and 1.6,
respectively). Lipophilic derivatives of cytosine (22) and thymine
(23) were synthesized as receptor sites for potentiometric dis-
crimination between AMP2ÿ and GMP2ÿ [119]. The hydrogen
bond donating and accepting atoms of 22 are at complementary
positions compared to GMP2ÿ. This results in preferential bind-
ing of GMP2ÿ, and there is a small selectivity for this anion
when the receptor is applied in ISE membranes (Log
Pot
KGMP;AMP ˆ ÿ0:4). However, with thymine derivative 23 there is
no selectivity for AMP2ÿ over GMP2ÿ.
3.6. Sensors with Tri¯uoroacetophenone Receptors
In contrast to the receptors described in the previous sections,
where selectivity results from noncovalent interactions with the
anion, tri¯uoroacetophenone derivatives (26) form a covalent
bond with CO2ÿ 3 (Scheme 1) [122]. The electrophilicity of the
carbonyl group of tri¯uoroacetophenone is enhanced by the
presence of the adjacent tri¯uoromethyl group, and 2:1 receptor-
anion adducts are formed with CO2ÿ 3 . Several sensors have been
developed with near-Nernstian slopes towards CO2ÿ 3 and a
selectivity over Clÿ , Brÿ, and NOÿ3 [123]. Because derivatives 26
act as neutral receptors, addition of lipophilic ammonium sites
improves the sensor characteristics [122, 123d]. The selectivity is
further enhanced by the introduction of electron-withdrawing
substituents at the benzene ring para to the tri¯uoroacetyl sub-
stituent [124]. However, this also results in increased suscept-
ibility for hydration. The main interfering species for these
sensors are lipophilic organic carboxylate anions. Consequently,
the tri¯uoroacetophenone derivatives are also suitable for the
development of salicylate [125] and benzoate [126] selective
ISEs. Hexyl-4-tri¯uoroacetylbenzoate has been applied in SO2ÿ 4
sensitive ISEs [127]. However, the selectivity is low and super-
Nernstian slopes of ÿ87 mV=decade are obtained.

Scheme 1

4. Materials for Polymeric Ion-Selective

Membranes
The phosphadithia macrocycle 24 in membranes of potentio- In the ion-selective sensors described in the previous section,
metric sensors becomes easily oxidized to the corresponding the receptor molecules are dissolved in a polymeric membrane

Electroanalysis 1999, 11, No. 14

Potentiometric Anion Selective Sensors
Table 2. Membrane materials used for potentiometric anion-selective
sensors
Polymer Detected anion Reference
PVC=PVA NOÿ 3 [129d, 135]
Urushi Clÿ [138]
Acrylate NOÿ [147c]
3
Polysiloxane NOÿ [156a, 160, 162, 166]
Siloxane sol-gel Cl ÿ
3
[146]
Monolayer Cl , NOÿ
ÿ
[141, 143]
3
matrix (Table 2) to immobilize these selector molecules in close
proximity of the transducer. Generally, the membranes consist of
high molecular weight poly(vinyl chloride) (PVC) mixed with
plasticizing high boiling organic liquids like o-nitrophenyl octyl
ether (NPOE) or bis(2-ethylhexyl) sebacate (DOS). The plasti-
cizer lowers the glass transition temperature and increases the
polarity of the membrane to facilitate the partition of ions.
Because of the large in¯uence that the plasticizer can have on the
partitioning of the ions, several types of plasticizer have been
developed [128] and used to optimize the selectivity of the sensor
[129].
The use of plasticized PVC membranes has also some distinct
disadvantages. The gradual leaching of the plasticizer and the
electroactive components from the membrane into the sample
solution deteriorates the sensor characteristics like slope and
signal-to-noise ratio, thus limiting the durability of these mem-
branes [130]. This is mainly the case for microsensors like CWEs
and CHEMFETs. The conventional ISEs have a much larger
membrane volume and consequently the effects of leaching of the
plasticizer are observed after a longer period. Moreover, when
plasticized membranes are used on solid-state transducers, the
weak physical interaction between the membrane and the trans-
ducer surface is another disadvantage for long-term durability.
For ISFETs some improvement in the adhesion could be obtained
by covering the ISFET surface with a polyimide mesh [131] or a
hydrophobic polyacrylate ®lm [132]. Carboxylated PVC [133,
134,] and copolymers of PVC, poly(vinyl alcohol) (PVA), and
poly(vinyl acetate) (PVAc) [135] show improved adhesion to
solid-state transducers. However, the former polymer is less
suitable for anion sensors since interactions of the carboxylate
moieties with anion receptors can be expected [136]. The adhe-
sion of PVA can be further enhanced by pretreatment of the
ISFET wafer with SiCl4 [133, 137]. This results in covalent bond
formation between the polymer and the silicon surface. Urushi is
a naturally occurring lacquer which has a strong adhesion to the
ISFET surface. When a plasticizer is added, this matrix can be
well used for sensor membranes [138]. However, a disadvantage
of this material is the long curing time up to 10 days. The
addition of formaldehyde as cross-linking agent or increased
temperature reduces the curing time to 2±3 days [139].
Plasticizer-free membranes are preferred for the development
of sensors with long lifetimes. The latter type of membrane has
also advantages for large scale production of sensors which
requires the possibility that the membrane can be deposited on
wafer scale via photolithographic techniques. The use of plasti-
cizers has been circumvented by using Langmuir-Blodgett ®lms
of polyglutamate mixed with a receptor that were transfered onto
an ISFET to obtain Na‡ sensitivity [140]. However, the leaching
of receptor results in a rapid loss of sensitivity within three days.
Covering the ®lm with a phthalocyaninato-substituted poly-
siloxane membrane improves the durability and a 10 mV=decade
loss in sensitivity was observed over 180 days. Thin membranes
1043
made of the polyion complex of dioctadecyldimethylammonium
poly(styrene sulphonate) without the addition of plasticizers were
also applied for Clÿ selective ISFETs [141]. Grafting of the
ISFET surface with cationic quaternary ammonium moieties
[142], anionic phosphonate moieties [143], or crown-ether-
functionalized phthalocyanine molecules [144] was applied to
introduce NOÿ 2‡ ‡
3 , Ca , and Na sensitivity. Since complete cov-
erage of the ISFET surface cannot be obtained by this method a
large residual sensitivity towards pH changes is observed. A
novel approach is the application of membranes obtained with
sol-gel methods [145, 146,]. These membranes are formed by
reaction of a mixture of tetraethoxysilane, diethoxy-
dimethylsilane and the receptor yielding a viscous solution.
Deposition of this solution on top of an ISFET and heating for
two days results in a glassy membrane which is very well adhered
to the ISFET surface. Membranes with selectivities according to
the Hofmeister series are obtained with hibrid organic-inorganic
sol-gel matrices based on a biscarbamate with two triethoxysilane
functional groups, doped with lipophilic ammonium sites [146].
Although the adhesion of the above-mentioned membrane
materials to the ISFET surface is improved compared to plasti-
cized PVC membranes, the photolithographic deposition and
patterning of these membranes on wafer scale are still not
possible. Therefore photopolymerizable (meth)acrylates, like
bisphenol A epoxydiacrylates, hexanedioldiacrylate, and alkyl-
methacrylates, have often been investigated as membrane mate-
rial [147, 148,]. Also polyurethanes have been applied as sensor
membranes because of the good adhesive properties to solid-state
transducers and their biocompatibility [149]. Urethane oligomers
with acrylate moieties have been used to make these membrane
polymers photopolymerizable [147d, 150]. However, all poly-
acrylate membranes require a plasticizer, and besides the limiting
effect on the sensor durability, also the photopolymerization is
negatively in¯uenced by these additives [147c].
The siloxane polymers are very promising materials for the
development of durable ion-selective membranes. The intrinsic
elastomeric properties (Tg 4 ÿ 100  C) of these polymers make
the addition of plasticizers super¯uous [151]. Moreover, the
biocompatibility and the adhesion to silicon surfaces are better
than that of PVC membranes [149a]. Several commercial room
temperature vulcanizing (RTV) silicone rubbers, like Bayer's
Silopren and Dow Corning 3140 RTV, have been investigated for
this purpose. However, the polarity of the parent poly(dimethyl
siloxane) is very low and this restricts a suf®ciently high partition
of ions into the membrane phase. The result is a high membrane
resistance [152]. The addition of more lipophilic ionic additives
results in a slight decrease in membrane resistance [153]. How-
ever, the solubility of the common electroactive species is limited
[148, 154]. Homogeneous membranes could be obtained by
modi®cation of borate salts and receptor molecules with trisdi-
methylsiloxane or polymerizable trisethoxysilane substituents
[154, 155]. Another way to increase the polarity of the membrane
and thereby improve the solubility of the receptor is by the
addition of a plasticizer [153, 156, 157]. However, this greatly
eliminates the advantage of polysiloxanes with respect to dur-
ability, and indeed it was reported that the durability of such
membranes is only moderate due to the gradual leaching of the
plasticizer [156].
An alternative approach to enhance the polarity of poly-
siloxane membranes is the introduction of polar substituents to
the polysiloxane backbone. Attachment of the relatively polar
cyanopropyl moieties to the polysiloxanes has been successfully
applied for this purpose [158]. Impedance measurements showed
Electroanalysis 1999, 11, No. 14
1044
that a polysiloxane with only 3 mol % of cyanopropyl sub-
stituents has a 10±20 times lower membrane resistance than
membranes made of commercial poly(dimethylsiloxane) [159].
Recently, also commercially available tri¯uoropropyl-substituted
polysiloxanes have been used as membranes on CHEMFETs
with selectivity towards Na‡ , K‡ , or NOÿ 3 [160]. However, for
the detection of Mg2‡ , Cd2‡, Pb2‡ , or Ag‡ ions these mem-
branes are inferior in terms of sensitivity and durability compared
with their PVC counterparts.
To obtain suf®cient mechanical stability of the polysiloxane
membranes, the siloxane chains have to be cross-linked. For
silanol end-capped polymers, cross-linking is possible by a
condensation reaction of the end groups in the presence of a
catalyst [148, 161, 162]. However, this method does not allow
patterning of the membranes by photolithographic techniques.
Polysiloxanes with methacrylate substituents can be cross-linked
via photo-initiated radical polymerization [158a], and via
photolithographic patterning multi-ion sensing CHEMFET arrays
become possible [162, 163].
Previously, in our group photopolymerizable siloxane ter-
polymers were developed with methacroyl and cyanopropyl
substituents by cationic emulsion polymerization of octa-
methylcyclotetrasiloxane, a mixture of the cyclotetramer and
cyclotrimer of (3-cyanopropyl)methylcyclosiloxane, and 3-
methacroylpropyldichloromethylsilaan [161]. However, due to
the different reactivities of the monomers in the polymerization
(decreasing in the order dichlorosilane > cyclotrisiloxane>
cyclotetrasiloxane) and impurities in the commercially available
starting compounds, this reaction was not very reproducible and
batches of polymers were obtained that were inhomogeneous. We
have found that the polysiloxane production can be improved in
terms of quality and reproducability by synthesis via anionic
polymerization of a mixture of hexamethylcyclotrisiloxane, 3-
methacroylpropylpentamethylcyclotrisiloxane, and a R-propyl
substituted pentamethylcyclotrisiloxane initated by CsOH
(Scheme 2) [164]. The obtained polymers have a narrow mole-
cular weight distribution and there is good agreement between
the relative amount of siloxane moieties in the polymer and in the
monomer mixture.
Besides for cross-linking of the polymer backbone, the
methacroyl substituents are used for the covalent attachment of
the electroactive species [165]. For this purpose tetra-
phenylborate and several cation receptors have been modi®ed
with a methacroyl substituent. For durable anion sensors photo-
polymerizable ammonium sites were synthesized [166]. The
NOÿ 3 selective CHEMFETs obtained with these polysiloxane
ion-exchange membranes have an improved durabilty (>190
days) upon continuous exposure of the sensors to water compared
to sensors in which the ammonium sites are not immobilized.
Scheme 2
Electroanalysis 1999, 11, No. 14
M.M.G. Antonisse, D.N. Reinhoudt
The polarity of the polysiloxane membranes can be modi®ed
by changing the type or number of polar substituents at the
polysiloxane back-bone. Impedance spectroscopy has shown that
the benzoylaminopropyl or phenylsulfonylpropyl moieties result
in a lower membrane resistance than obtained with similar
amount of cyanopropyl, acetylphenoxypropyl, or acetylpropyl
substituents [167]. Moreover, the membrane resistance can be
lowered by increasing the degree of substitution, e.g., a mem-
brane with 25 mol% of cyanopropyl substituents has a similar
membrane resistance as the polysiloxane membranes with 10
mol% of phenylsulfonylpropyl moieties.
The variation in polar substituents can be used to optimize the
sensor characteristics like sensitivity and selectivity. First, the
substituents can in¯uence the solvation of the ions in the mem-
brane phase. This is re¯ected in differences in the selectivity
when NOÿ 3 selective ion-exchange membranes of polysiloxanes
with different polar moieties are compared. For membranes with
benzoylaminopropyl substituents more interference of Clÿ and
Brÿ is observed than with cyanopropyl substituted polysiloxanes
Pot
(Log KNO 3 ;Cl
ˆ ÿ1:6 and ÿ2.3, respectively) [166]. The halide
anions have a favorable hydrogen bond interaction with the
amido substituents and consequently the partitioning from water
to the membrane is increased. Secondly, the polar substituents
can in¯uence the functioning of receptor molecules in sensors
with selectivity deviating from the Hofmeister series. Highly
aromatic receptors like cobalt porphyrins or uranyl salophene
derivatives are only soluble in polysiloxanes with aromatic polar
substituents [168]. However, in the case of polysiloxane mem-
branes with aromatic benzoylaminopropyl substituents, the car-
bonyl oxygen atoms of amido substituents can interact with the
metal centers of these receptors and consequently inferior sensor
characteristics are observed compared to PVC membranes.
Sensors with the optimal sensitivity and selectivity for hydro-
philic anions like NOÿ 2 or F
ÿ
(based on receptor 17 and 12,
respectively) have membranes of polysiloxane with phe-
nylsulfonylpropyl subsituents. These moieties allowing easy
partitioning of the anions due to the high polarity, result in good
solubility of the receptor, and do not have any interactions with
these receptors.
5. Concluding Remarks
The examples in this review illustrate that although the
development of anion selective sensors lays behind the counter-
parts for cationic species, several potentiometric sensors have
been developed for anionic analytes. The progress in potentio-
Potentiometric Anion Selective Sensors
metric anion sensing is generally driven by the development of
novel anion receptors which introduce the selectivity in the
sensor. Most successful until now appear to be the receptors
based on Lewis acidic organo-metallic anion binding sites.
However, the introduction of organo-metallic binding sites is
dif®cult and can not easily be combined with geometric restric-
tions of the receptor to enhance the selectivity as is used in
several cation receptors. Moreover, the metal centers are often
labile in aqueous environment. Regarding these limitations, anion
recognition exclusively based on hydrogen bonding is very
promising. Hydrogen bonding moieties, e.g., amido or urea
moieties, are easily synthesized and the high directionality
of the interactions can be used to improve the selectivity.
For the applicability of the anion sensors durability of the
membranes is required, in particular when the sensors are in
contact for prolonged time with aqueous samples. Several novel
membrane materials which can substitute plasticized PVC as
membrane matrix can improve the sensor durability. They have
better adhesion when solid state transducers are used, and they
lack membrane components (e.g., plasticizers) which easily
leach. However, most of the materials have only been investi-
gated for cation selective sensors or anion sensors with selectivity
according to the Hofmeister series. The low partitioning of
anions and limited solubility of several anion receptors might
restrict the applicability of these materials. However, the siloxane
polymers with several types of polar substituents that we have
developed, are also successful for the development of anion
sensors.
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