Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade
Identifieur interne : 000429 ( Pmc/Corpus ); précédent : 000428; suivant : 000430Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade
Auteurs : Farnoush Faridbod ; Mohammad Reza Ganjali ; Rassoul Dinarvand ; Parviz NorouziSource :
- Sensors (Basel, Switzerland) [ 1424-8220 ] ; 2008.
Abstract
Many research studies have been conducted on the use of conjugated polymers in the construction of chemical sensors including potentiometric, conductometric and amperometric sensors or biosensors over the last decade. The induction of conductivity on conjugated polymers by treating them with suitable oxidizing agents won Heeger, MacDiarmid and Shirakawa the 2000 Nobel Prize in Chemistry. Common conjugated polymers are poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(terthiophene)s, poly(aniline)s, poly(fluorine)s, poly(3-alkylthiophene)s, polytetrathiafulvalenes, poly-napthalenes, poly(
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PubMed Central: 3673421
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en">Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade</title><author><name sortKey="Faridbod, Farnoush" sort="Faridbod, Farnoush" uniqKey="Faridbod F" first="Farnoush" last="Faridbod">Farnoush Faridbod</name><affiliation><nlm:aff id="af1-sensors-08-02331"> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</nlm:aff></affiliation></author><author><name sortKey="Ganjali, Mohammad Reza" sort="Ganjali, Mohammad Reza" uniqKey="Ganjali M" first="Mohammad Reza" last="Ganjali">Mohammad Reza Ganjali</name><affiliation><nlm:aff id="af1-sensors-08-02331"> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</nlm:aff></affiliation></author><author><name sortKey="Dinarvand, Rassoul" sort="Dinarvand, Rassoul" uniqKey="Dinarvand R" first="Rassoul" last="Dinarvand">Rassoul Dinarvand</name><affiliation><nlm:aff id="af2-sensors-08-02331"> Medical Nanotechnology Research Centre, Medical Sciences/University of Tehran, Tehran, P.O. Box 14155-6451, Iran</nlm:aff></affiliation></author><author><name sortKey="Norouzi, Parviz" sort="Norouzi, Parviz" uniqKey="Norouzi P" first="Parviz" last="Norouzi">Parviz Norouzi</name><affiliation><nlm:aff id="af1-sensors-08-02331"> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</nlm:aff></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">PMC</idno><idno type="pmc">3673421</idno><idno type="url">http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3673421</idno><idno type="RBID">PMC:3673421</idno><idno type="pmid">NONE</idno><date when="2008">2008</date><idno type="wicri:Area/Pmc/Corpus">000429</idno><idno type="wicri:explorRef" wicri:stream="Pmc" wicri:step="Corpus" wicri:corpus="PMC">000429</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en" level="a" type="main">Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade</title><author><name sortKey="Faridbod, Farnoush" sort="Faridbod, Farnoush" uniqKey="Faridbod F" first="Farnoush" last="Faridbod">Farnoush Faridbod</name><affiliation><nlm:aff id="af1-sensors-08-02331"> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</nlm:aff></affiliation></author><author><name sortKey="Ganjali, Mohammad Reza" sort="Ganjali, Mohammad Reza" uniqKey="Ganjali M" first="Mohammad Reza" last="Ganjali">Mohammad Reza Ganjali</name><affiliation><nlm:aff id="af1-sensors-08-02331"> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</nlm:aff></affiliation></author><author><name sortKey="Dinarvand, Rassoul" sort="Dinarvand, Rassoul" uniqKey="Dinarvand R" first="Rassoul" last="Dinarvand">Rassoul Dinarvand</name><affiliation><nlm:aff id="af2-sensors-08-02331"> Medical Nanotechnology Research Centre, Medical Sciences/University of Tehran, Tehran, P.O. Box 14155-6451, Iran</nlm:aff></affiliation></author><author><name sortKey="Norouzi, Parviz" sort="Norouzi, Parviz" uniqKey="Norouzi P" first="Parviz" last="Norouzi">Parviz Norouzi</name><affiliation><nlm:aff id="af1-sensors-08-02331"> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</nlm:aff></affiliation></author></analytic><series><title level="j">Sensors (Basel, Switzerland)</title><idno type="eISSN">1424-8220</idno><imprint><date when="2008">2008</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en"><p>Many research studies have been conducted on the use of conjugated polymers in the construction of chemical sensors including potentiometric, conductometric and amperometric sensors or biosensors over the last decade. The induction of conductivity on conjugated polymers by treating them with suitable oxidizing agents won Heeger, MacDiarmid and Shirakawa the 2000 Nobel Prize in Chemistry. Common conjugated polymers are poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(terthiophene)s, poly(aniline)s, poly(fluorine)s, poly(3-alkylthiophene)s, polytetrathiafulvalenes, poly-napthalenes, poly(<italic>p</italic>-phenylene sulfide), poly(<italic>p</italic>-phenylenevinylene)s, poly(3,4-ethylene-dioxythiophene), polyparaphenylene, polyazulene, polyparaphenylene sulfide, poly-carbazole and polydiaminonaphthalene. More than 60 sensors for inorganic cations and anions with different characteristics based on conducting polymers have been reported. There have also been reports on the application of non-conducting polymers (nCPs), i.e. PVC, in the construction of potentiometric membrane sensors for determination of more than 60 inorganic cations and anions. However, the leakage of ionophores from the membranes based on these polymers leads to relatively lower life times. In this article, we try to give an overview of Solid-Contact ISE (SCISE), Single-Piece ISE (SPISE), Conducting Polymer (CP)-Based, and also non-conducting polymer PVC-based ISEs for various ions which their difference is in the way of the polymer used with selective\ membrane. In SCISEs and SPISEs, the plasticized PVC containing the ionophore and ionic additives govern the selectivity behavior of the electrode and the conducting polymer is responsible of ion-to-electron transducer. However, in CPISEs, the conducting polymer layer is doped with a suitable ionophore which enhances the ion selectivity of the CP while its redox response has to be suppressed.</p></div></front><back><div1 type="bibliography"><listBibl><biblStruct><analytic><author><name sortKey="Bakker, E" uniqKey="Bakker E">E. Bakker</name></author><author><name sortKey="Buhlmann, P" uniqKey="Buhlmann P">P. 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<front><journal-meta><journal-id journal-id-type="nlm-ta">Sensors (Basel)</journal-id><journal-id journal-id-type="iso-abbrev">Sensors (Basel)</journal-id><journal-title-group><journal-title>Sensors (Basel, Switzerland)</journal-title></journal-title-group><issn pub-type="epub">1424-8220</issn><publisher><publisher-name>Molecular Diversity Preservation International (MDPI)</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="pmc">3673421</article-id><article-id pub-id-type="publisher-id">sensors-08-02331</article-id><article-categories><subj-group subj-group-type="heading"><subject>Review</subject></subj-group></article-categories><title-group><article-title>Developments in the Field of Conducting and Non-conducting Polymer Based Potentiometric Membrane Sensors for Ions Over the Past Decade</article-title></title-group><contrib-group><contrib contrib-type="author"><name><surname>Faridbod</surname><given-names>Farnoush</given-names></name><xref ref-type="aff" rid="af1-sensors-08-02331"><sup>1</sup></xref></contrib><contrib contrib-type="author"><name><surname>Ganjali</surname><given-names>Mohammad Reza</given-names></name><xref ref-type="aff" rid="af1-sensors-08-02331"><sup>1</sup></xref><xref ref-type="corresp" rid="c1-sensors-08-02331"><sup>*</sup></xref></contrib><contrib contrib-type="author"><name><surname>Dinarvand</surname><given-names>Rassoul</given-names></name><xref ref-type="aff" rid="af2-sensors-08-02331"><sup>2</sup></xref></contrib><contrib contrib-type="author"><name><surname>Norouzi</surname><given-names>Parviz</given-names></name><xref ref-type="aff" rid="af1-sensors-08-02331"><sup>1</sup></xref></contrib></contrib-group><aff id="af1-sensors-08-02331"><label>1</label> Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran</aff><aff id="af2-sensors-08-02331"><label>2</label> Medical Nanotechnology Research Centre, Medical Sciences/University of Tehran, Tehran, P.O. Box 14155-6451, Iran</aff><author-notes><corresp id="c1-sensors-08-02331"><label>*</label> Author to whom correspondence should be addressed; E-mail: <email>ganjali@khayam.ut.ac.ir</email>; Tel: +98-21-61112788</corresp></author-notes><pub-date pub-type="collection"><month>4</month><year>2008</year></pub-date><pub-date pub-type="epub"><day>03</day><month>4</month><year>2008</year></pub-date><volume>8</volume><issue>4</issue><fpage>2331</fpage><lpage>2412</lpage><history><date date-type="received"><day>01</day><month>2</month><year>2008</year></date><date date-type="accepted"><day>02</day><month>4</month><year>2008</year></date></history><permissions><copyright-statement>© 2008 by MDPI (http://www.mdpi.org).</copyright-statement><copyright-year>2008</copyright-year><license><license-p>Reproduction is permitted for noncommercial purposes.</license-p></license></permissions><abstract><p>Many research studies have been conducted on the use of conjugated polymers in the construction of chemical sensors including potentiometric, conductometric and amperometric sensors or biosensors over the last decade. The induction of conductivity on conjugated polymers by treating them with suitable oxidizing agents won Heeger, MacDiarmid and Shirakawa the 2000 Nobel Prize in Chemistry. Common conjugated polymers are poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(terthiophene)s, poly(aniline)s, poly(fluorine)s, poly(3-alkylthiophene)s, polytetrathiafulvalenes, poly-napthalenes, poly(<italic>p</italic>-phenylene sulfide), poly(<italic>p</italic>-phenylenevinylene)s, poly(3,4-ethylene-dioxythiophene), polyparaphenylene, polyazulene, polyparaphenylene sulfide, poly-carbazole and polydiaminonaphthalene. More than 60 sensors for inorganic cations and anions with different characteristics based on conducting polymers have been reported. There have also been reports on the application of non-conducting polymers (nCPs), i.e. PVC, in the construction of potentiometric membrane sensors for determination of more than 60 inorganic cations and anions. However, the leakage of ionophores from the membranes based on these polymers leads to relatively lower life times. In this article, we try to give an overview of Solid-Contact ISE (SCISE), Single-Piece ISE (SPISE), Conducting Polymer (CP)-Based, and also non-conducting polymer PVC-based ISEs for various ions which their difference is in the way of the polymer used with selective\ membrane. In SCISEs and SPISEs, the plasticized PVC containing the ionophore and ionic additives govern the selectivity behavior of the electrode and the conducting polymer is responsible of ion-to-electron transducer. However, in CPISEs, the conducting polymer layer is doped with a suitable ionophore which enhances the ion selectivity of the CP while its redox response has to be suppressed.</p></abstract><kwd-group><kwd>Conducting polymer</kwd><kwd>sensor</kwd><kwd>ion selective electrodes</kwd><kwd>non-conducting polymer</kwd><kwd>potentiometric membrane sensor</kwd></kwd-group></article-meta></front><body><sec><label>1.</label><title>Introduction</title><p>Potentiometric measurements are based on monitoring potential values under a zero current flow regime, in order to determine the analytical concentration desired components in an analyte. In these methods the potential difference between an indicator electrode (i.e. ion-selective electrode, redox electrode, metal-metal oxide electrode) and the reference electrode is measured as the analytical potential. The potential of an electrochemical cell is due to the changes in the free energy that occurs if the chemical phenomena reach an equilibrium; which is a concept that is typically applied in quantitative analysis in relation to electrochemical cells, in which case, the difference between the cathodic and the anodic potentials is the potential of the electrochemical cell and is calculated using the so-called Nernst equation. Another source of potential may be physical phenomena not involving explicit redox reactions but having non-zero free energy initial conditions. For instance ion concentration gradients across a semi-permeable membrane can is one of such phenomena. This can also be potentiometric phenomena, and is the basis of measurements that use ion-selective electrodes, according to which the below equation is used to determine the concentration of the analyte:
<disp-formula id="FD1"><label>(1)</label><mml:math id="mm1"><mml:mrow><mml:msub><mml:mtext>E</mml:mtext><mml:mrow><mml:mtext>mem</mml:mtext></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mtext>Constant</mml:mtext><mml:mo>−</mml:mo><mml:mtext>RT</mml:mtext><mml:mo>/</mml:mo><mml:msub><mml:mtext>z</mml:mtext><mml:mtext>i</mml:mtext></mml:msub><mml:mspace width="0.2em"></mml:mspace><mml:mtext>F</mml:mtext><mml:mo> </mml:mo><mml:mo>ln</mml:mo><mml:mo> </mml:mo><mml:msub><mml:mtext>a</mml:mtext><mml:mtext>i</mml:mtext></mml:msub></mml:mrow></mml:math></disp-formula>where z<sub>i</sub> and a<sub>i</sub> represent the charges and the activity of the ion of interest respectively. Potentiometric ion sensors represent well-established analytical tools. The ISE illustrated in <xref ref-type="fig" rid="f1-sensors-08-02331">Figure 1</xref> is a typical electrode in which the transduction between the ion and electron takes place at the internal reference electrode (Ag/AgCl) immersed in the inner filling solution (KCl), as follows:
<disp-formula id="FD2"><label>(2)</label><mml:math id="mm2"><mml:mrow><mml:mtext mathvariant="italic">AgCl</mml:mtext><mml:mo>+</mml:mo><mml:msup><mml:mi>e</mml:mi><mml:mo>−</mml:mo></mml:msup><mml:mo>↔</mml:mo><mml:mi>A</mml:mi><mml:mi>g</mml:mi><mml:mo mathvariant="italic">+</mml:mo><mml:mi>C</mml:mi><mml:msup><mml:mi>l</mml:mi><mml:mo>−</mml:mo></mml:msup></mml:mrow></mml:math></disp-formula></p><p>The identical reaction (2) ocurrs at the external reference electrode (RE), illustrating the reversible and stable connection between the ionic (<italic>Cl</italic><sup>−</sup>) and electronic (<italic>e</italic><sup>−</sup>) signals. The selectivity is the result of incorporation of specific ionophores in the ion-selective membrane. Potentiometric ion sensors (ISEs) are very attractive, especially due to their small-size and portability, and low cost. Neutral or charged carrier based ISEs, which are available for about 60 different analytes, have found widespread applications in routine uses like clinical analysis [<xref ref-type="bibr" rid="b1-sensors-08-02331">1</xref>-<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>]. On the other hand, to fully use the potentials of this technique, more durable and maintenance-free ISEs that are easily miniaturized are needed.</p><p>The works showing that the detection limit of conventional ISEs has the potentials to be lowered towards the sub-nanomolar concentration level [<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>], making them suitable for trace analyses has attracted more interest to these devices [<xref ref-type="bibr" rid="b2-sensors-08-02331">2</xref>]. The development of new and applicable membranes such as plasticizer-free membranes [<xref ref-type="bibr" rid="b9-sensors-08-02331">9</xref>], covalently attached ionophores [<xref ref-type="bibr" rid="b10-sensors-08-02331">10</xref>], stable carborane anions [<xref ref-type="bibr" rid="b11-sensors-08-02331">11</xref>], and monolithic capillary based ISEs [<xref ref-type="bibr" rid="b12-sensors-08-02331">12</xref>], can be regarded as a sign of the great interest in these analytical tools.</p><p>Fabrication of all-solid-state ISEs that do not require internal filling solutions is another common approach, which necessitates careful design of the solid contact between the ion-selective membrane and the electronic conductor [<xref ref-type="bibr" rid="b9-sensors-08-02331">9</xref>-<xref ref-type="bibr" rid="b11-sensors-08-02331">11</xref>, <xref ref-type="bibr" rid="b13-sensors-08-02331">13</xref>]. The introduction of the so-called coated-wire electrodes (<xref ref-type="fig" rid="f2-sensors-08-02331">Figure 2b</xref>) about three decades ago, can be regarded as an important step towards solid-state ISEs [<xref ref-type="bibr" rid="b14-sensors-08-02331">14</xref>]. These devices, however, suffered from the ill-defined transduction of the ionically conducting ion-selective membrane and the electronic conductor, which made them rather instable. Scientists overcame this by simply using a hydrogel based electrolyte instead of the liquid internal electrolyte of the classical ISE (<xref ref-type="fig" rid="f2-sensors-08-02331">Figure 2a and 2c</xref>) [<xref ref-type="bibr" rid="b15-sensors-08-02331">15</xref>]. Hydrogel-contact ISEs suffer, however, from shortcomings originating from the water uptake/release and the resulting volume changes of the hydrogel layer which is a function of the salt concentration of the hydrogel. Another approach to solid-state ISEs is based on the modification of the coated-wire electrodes (<xref ref-type="fig" rid="f2-sensors-08-02331">Figure 2b</xref>), through the application of an intermediate layer of suitable redox and ion-exchange properties at the wire membrane interface [<xref ref-type="bibr" rid="b13-sensors-08-02331">13</xref>], in which case, even the application of a monolayer of redox-active compound allows a well-defined pathway for ion-to-electron transduction [<xref ref-type="bibr" rid="b16-sensors-08-02331">16</xref>]. Monolayers, however, suffer an inherently low frequency redox capacitance to provide stability condition which depends on the low frequency redox capacitance of the conducting polymer. The low-frequency impedance response of conducting polymers is similar to ideal capacitance resulting from reversible oxidation of the polymer bulk connected with ion transport. The small current that passes through the electrode during potentiometric measurements inevitably results in oxidation/reduction of the conducting polymer, i.e. charging/discharging of the bulk capacitance [<xref ref-type="bibr" rid="b17-sensors-08-02331">17</xref>].</p><p>The above mentioned may be one of the reasons behind the increasing interest in the application of conducting polymers as ion-to-electron transducers in this group of ISEs [<xref ref-type="bibr" rid="b9-sensors-08-02331">9</xref>-<xref ref-type="bibr" rid="b11-sensors-08-02331">11</xref>]. The ion-to-electron transduction process in this case is quite identical with the mechanism of this process at the internal reference electrode of the conventional or hydrogel-contact ISE and can be summarized as:
<disp-formula id="FD3"><label>(3)</label><mml:math id="mm3"><mml:mrow><mml:msup><mml:mtext>M</mml:mtext><mml:mo>+</mml:mo></mml:msup><mml:mspace width="0.2em"></mml:mspace><mml:msup><mml:mtext>A</mml:mtext><mml:mo>‐</mml:mo></mml:msup><mml:mo>+</mml:mo><mml:mtext>e</mml:mtext><mml:mo>↔</mml:mo><mml:mtext>M</mml:mtext><mml:mo>+</mml:mo><mml:msup><mml:mtext>A</mml:mtext><mml:mo>‐</mml:mo></mml:msup></mml:mrow></mml:math></disp-formula>where M<sup>+</sup> is metal ion (e.g. Ag<sup>+</sup>) or oxidized conducting polymer unit, e<sup>-</sup> is electron, M is metal (e.g. Ag) or neutral conducting polymer unit, and A<sup>−</sup> is anion (e.g. Cl<sup>-</sup>).</p><p>Because of the priceless electrical and electrochemical characteristics of conducting polymers, they have found many applications since their discovery. One of them is their wide use in the fabrication of electrochemical sensors such as potentiometric, amperometric and conductometric sensors [<xref ref-type="bibr" rid="b10-sensors-08-02331">10</xref>, <xref ref-type="bibr" rid="b18-sensors-08-02331">18</xref>]. They can be used to convert chemical information such as concentration or activity into electrical signals in the solid state. Combination of the properties of the conjugated polymer transducers with those leading to selective molecular recognition is a very important step in the way of obtaining durable chemical sensors. This wide application and great interest is mostly due to the their potential to exhibit improved response properties and also their high sensitivity to small perturbations which are great advantages in comparison to the inert polymers were which used only to enhance the mechanical strength of the membranes. Apart from their unique conductivity and ion transport properties leading to the mentioned advantages, conducting polymers also enjoy the benefits of being compatible with biological molecules in neutral aqueous solutions or even they can be used to bind biomolecules to a biosensor [<xref ref-type="bibr" rid="b18-sensors-08-02331">18</xref>-<xref ref-type="bibr" rid="b22-sensors-08-02331">22</xref>].</p></sec><sec><label>2.</label><title>Conducting Polymer Based Sensors</title><p>Detailed classifications divide “conducting polymers” into several types, including doped conjugated and redox polymers, polymer composites and polymer electrolytes. These compounds have shown to be very promising for the purpose of building different chemical sensors [<xref ref-type="bibr" rid="b23-sensors-08-02331">23</xref>-<xref ref-type="bibr" rid="b25-sensors-08-02331">25</xref>]. There are several reasons behind their being suitable as transducers in solid-state ISEs. First, they are able to form an ohmic contact to materials of high work functions, like carbon, gold and platinum. Second, due to the solubility of several CPs, they can be deposited from solutions. Third, they have ability to be electroactive materials of mixed electronic and ionic conductivity, which gives them the unique potential to transduce ionic signals into electronic ones.</p><p><xref ref-type="fig" rid="f3-sensors-08-02331">Figure 3</xref> illustrates some CP monomers and CPs commonly used as ion-to-electron transducers in construction of all solid state potentiometric sensors. Conducting polymers have been used in the construction of ISEs according to general approaches, which have led to the development of solid contact ion selective electrodes (SCISEs), and single-piece ion selective electrodes (SPISEs) and conducting polymer based ion selective electrodes (CPISEs). In SCISEs, the conducting polymer is electro polymerized on the surface of the electronic conductor and then, coated with the ion-selective membrane. The selective membrane determines the selectivity, and the conducting polymer only acts as an ion-to-electron transducer of the sensor. This way, both the ion-exchange and redox characteristics of the conducting polymers are successfully combined with the selectivity of the ionophore-based ion-selective membranes. In SPISEs, the selective membrane contains conducting polymer due to the solubility and the consequent dispersability of conjugated polymers in an organic solvent. In both the above mentioned ISEs, the plasticized PVC containing the ionophore and ionic additives govern the selectivity behavior of the electrode and the conducting polymer is responsible of ion-to-electron transducer. In CPISEs, the conducting polymer layer is doped with a suitable ionophore which enhances the ion selectivity of the CP while its redox response has to be suppressed. Thus, the redox sensitivity limits the use of CPISEs in direct measurements. The further explanation about these different types of ISEs will be discussed below.</p><sec><label>2.1.</label><title>Solid-contact ion selective electrode (SCISE)</title><p>To construct an SCISE (<xref ref-type="fig" rid="f4-sensors-08-02331">Figure 4</xref>) the CP can be electropolymerized on an electronic conductor and then coated with the ion-selective membrane. In the case of the electrodes prepared in this way, the PVC ion selective coating determines the ion selectivity, while the CP film acts as the ion-to-electron transducer. Bobacka <italic>et al</italic>. have recently used a number of CPs, like polypyrrole (PPy), poly(3-octyl-thiophene, POT), and poly(3,4-ethylenedioxythiophene, PEDOT) for the construction of SCISEs [<xref ref-type="bibr" rid="b9-sensors-08-02331">9</xref>-<xref ref-type="bibr" rid="b11-sensors-08-02331">11</xref>]. Due the special nature and design of the SCISEs, these devices have also been miniaturized to yield solid state ion-selective microelectrodes [<xref ref-type="bibr" rid="b26-sensors-08-02331">26</xref>].</p></sec><sec><label>2.2.</label><title>Single-piece ISE (SPISE)</title><p>This approach uses the solubility, and the consequent dispersability, of conjugated polymers in organic solvents such as tetrahydrofuran (THF), which is a commonly used as the solvent to dissolve the membrane components during the preparation of plasticized PVC-based ISEs. So, in case the CP is also dissolved as an additional membrane component it can be physically integrated within the ion-selective membrane, resulting in the so-called single-piece electrode (SPISE) [<xref ref-type="bibr" rid="b27-sensors-08-02331">27</xref>]. The presence of the CP in the membrane composition, however, definitely influences the electrode selectivity which changes the role of the CP from SCISE where they have a mere physical role, to SPISEs (<xref ref-type="fig" rid="f4-sensors-08-02331">Figure 4</xref>) where the CP also has a role as a membrane composition, which necessitates the careful optimization of this species in the later approach. It should be noted that, no matter which of the two above-mentioned approaches is used, it is still the plasticized PVC containing the ionophore and ionic additives that governs the selectivity behavior of the electrode.</p><p>On the other hand, since the life time of the plasticized PVC membranes is affected by leaching of the membrane components from the membrane into the sample solution, many efforts have been made to achieve plasticizer-free membranes and covalently bound ion recognition sites, in which case CPs also offer unique possibilities.</p></sec><sec><label>2.3.</label><title>Conducting polymer-based ISE(CPISE)</title><p>Conducting polymers (e.g. PPY) are known to possess mixed ionic/redox responses, which introduces some considerations, in case one tends to develop ISEs with a CP polymeric matrix or in other words a conducting polymer-based ISE (CPISE), including the fact that the ion selectivity of the CP should be enhanced while its redox response has to be suppressed. This can be achieved through doping the CP with metal-complexing ligands, the ion selectivity of which depends on the metal-complexing ligand used [<xref ref-type="bibr" rid="b28-sensors-08-02331">28</xref>]. Although the redox sensitivity limits the use of CPISEs in direct measurements, such ISEs have been successfully used as potentiometric indicator electrodes in non-classical titrations [<xref ref-type="bibr" rid="b29-sensors-08-02331">29</xref>]. For instance in the case of the PPy electrodes, the applicability of the CPISE in titrations was demonstrated by determination of Ca<sup>2+</sup> in mineral water [<xref ref-type="bibr" rid="b30-sensors-08-02331">30</xref>].</p><p>In another attempt to construct a CPISE valinomycin and a lipophilic anion were incorporated in undoped POT to build K<sup>+</sup> selective ISEs by dissolving the ingredients in chloroform, and casting the CPISE membrane [<xref ref-type="bibr" rid="b31-sensors-08-02331">31</xref>], resulting semi-conducting organic polymer with a reduced redox response (compared to PPy) due to the low electronic conductivity of the undoped POT and the high K<sup>+</sup>-selectivity of valinomycin. This is an indication that the selectivity of CP-based membranes can be greatly enhanced by addition of suitable ionophores and ionic sites [<xref ref-type="bibr" rid="b31-sensors-08-02331">31</xref>]. POT has also been used, in a similar way, to prepare Cl<sup>−</sup> sensors using tridodecylmethylammonium chloride (TDMACl) [<xref ref-type="bibr" rid="b32-sensors-08-02331">32</xref>]. Ca<sup>2+</sup>-selective CPISEs have also been constructed through the direct addition of a neutral ionophore (ETH 1001) to the soluble PANI [<xref ref-type="bibr" rid="b33-sensors-08-02331">33</xref>] or by simply using the Ca<sup>2+</sup>-selectivity of the phosphoric acid dopants, incorporated into the membrane [<xref ref-type="bibr" rid="b34-sensors-08-02331">34</xref>,<xref ref-type="bibr" rid="b35-sensors-08-02331">35</xref>]. In the case of the phosphoric acid dopants either bis(2-ethyl-hexyl)phosphoric acid [<xref ref-type="bibr" rid="b34-sensors-08-02331">34</xref>] or bis[4-(1,1,3,3-tetramethylbutyl)phenyl]phosphoric acid (DTMBP-PO<sub>4</sub>H) [<xref ref-type="bibr" rid="b35-sensors-08-02331">35</xref>] were used as the protonating acid. Some of conducting polymer can be made soluble by treating them with functionalized organic acids, e.g. sulfonic acids and organophosphates [<xref ref-type="bibr" rid="b35-sensors-08-02331">35</xref>], which make them at the same time electrically conducting and soluble. <xref ref-type="table" rid="t1-sensors-08-02331">Table 1</xref> shows the characterizations of the most reported conducting polymer based ion selective electrodes.</p><p>A brief description of potentiometric sensors assimilating conducting polymers is presented. There are several reports of ion-selective sensors based on conducting polymers including about nine reports about H<sup>+</sup> sensors including different conducting polymers often doped with different agents [<xref ref-type="bibr" rid="b36-sensors-08-02331">36</xref>-<xref ref-type="bibr" rid="b44-sensors-08-02331">44</xref>]. Hutchins and colleagues reported in 1993 a pH sensor with a linear dynamic range of 10<sup>-11</sup> to 10<sup>-2</sup> M concentration of H<sup>+</sup>. A Li<sup>+</sup> assay was reported by Bobacka <italic>et al</italic>. in 1994 using a potentiometric sensor that included a conducting poly (3-octylthiophene) polymer, which was also investigated with Ca<sup>2+</sup> and Cl<sup>-</sup>[<xref ref-type="bibr" rid="b60-sensors-08-02331">60</xref>]. There is a single report of Na<sup>+</sup> sensor by Cadogan <italic>et al</italic>. in 1992, where the detection limit for sodium ions was reported to be 3×10<sup>-5</sup> M [<xref ref-type="bibr" rid="b45-sensors-08-02331">45</xref>]. Eight K<sup>+</sup> selective sensors were developed during 1999-2007, among which the best detection limit was 10<sup>-7.4</sup> M, reported by Pawlowski <italic>et al</italic>. in 2006 [<xref ref-type="bibr" rid="b46-sensors-08-02331">46</xref>-<xref ref-type="bibr" rid="b53-sensors-08-02331">53</xref>]. In the same year Paczosa-Bator <italic>et al.</italic> obtained a slope of 29.1 for the calibration curve for a Mg sensitive conducting polymer doped with ATP [<xref ref-type="bibr" rid="b55-sensors-08-02331">55</xref>]. Over a three year period (2003-2006) seven Ca<sup>2+</sup> ion sensors based on different conducting polymers were reported [<xref ref-type="bibr" rid="b56-sensors-08-02331">56</xref>-<xref ref-type="bibr" rid="b62-sensors-08-02331">62</xref>]. MMA/DMA copolymer was incorporated as a conducting polymer in a Ca<sup>2+</sup> sensitive sensor by Sutter <italic>et al</italic>. in 2004. The detection limit was determined to be 10<sup>-9.3</sup> M. A sensor for strontium ions which included polymers of polyaniline with polycarbonate was fabricated in 2002 [<xref ref-type="bibr" rid="b64-sensors-08-02331">64</xref>]. In 2006 and 2007 two Cu<sup>2+</sup> electrochemical sensors based on a common conducting polymer were reported while the doping agents were not the same [<xref ref-type="bibr" rid="b65-sensors-08-02331">65</xref>, <xref ref-type="bibr" rid="b66-sensors-08-02331">66</xref>]. Poly(3,4-ethylenedioxythiophene) films doped by hexacyanoferrate anions was one combination used as a conducting polymer for Cu(II) selective sensor. Five papers on Ag<sup>+</sup> sensors based on conducting polymers were published [<xref ref-type="bibr" rid="b67-sensors-08-02331">67</xref>-<xref ref-type="bibr" rid="b70-sensors-08-02331">70</xref>]; three of them were in 1995, in which Vazques and coworkers made a sensor detecting 10<sup>-5.3</sup> M of Ag<sup>+</sup>. Khan <italic>et al</italic>. in 2004 developed a novel ion selective membrane electrode for assay of Hg(II) reaching a detection limit of 5×10<sup>-5</sup> M. A polypyrrole/polyantimonic acid combination was used as conducting polymer [<xref ref-type="bibr" rid="b73-sensors-08-02331">73</xref>]. Pandey <italic>et al</italic>. in 2002 developed a polypyrrole based sensor for Zinc capable of determining Zn ions in the linear range of 10<sup>-1</sup> to 10<sup>-5.6</sup>[<xref ref-type="bibr" rid="b72-sensors-08-02331">72</xref>]. Lead ions were determined in one case in 2007, in which Kissiel <italic>et al</italic>. reported a linear dynamic range of 10<sup>-2</sup> to 10<sup>-5</sup> M for a calibration curve with a slope of 29.9 for Pb ions [<xref ref-type="bibr" rid="b63-sensors-08-02331">63</xref>].</p><p>Some anions also have been under investigation by conducting polymer based electrochemical sensors during the last decade. The first halogen (F<sup>-</sup>) was determined together with H<sub>2</sub>PO<sub>4</sub> with a modified polyaniline sensor by Shiskanove <italic>et al</italic>. in 2005 [<xref ref-type="bibr" rid="b77-sensors-08-02331">77</xref>]. Six publications have probed chloride ion sensors during 1999 to 2004 [<xref ref-type="bibr" rid="b78-sensors-08-02331">78</xref>-<xref ref-type="bibr" rid="b83-sensors-08-02331">83</xref>]. The best detection limit was achieved by Michalska <italic>et al</italic>. in 2003. They obtained a detection limit of 4×10<sup>-7</sup> M utilizing a polypyrrole as conducting polymer. Another halogen (Br<sup>-</sup>) was investigated once in 1997 by Wang <italic>et al</italic>. achieving a detection limit of 6×10<sup>-5</sup>M for Br<sup>-</sup>[<xref ref-type="bibr" rid="b84-sensors-08-02331">84</xref>]. In 1994 Galal <italic>et al</italic>. reported an iodide selective sensor and there was another report on an iodide sensor in 1999 by Wolf <italic>et al</italic>. in which I<sup>-</sup> was determined down to 5×10<sup>-4</sup> M [<xref ref-type="bibr" rid="b85-sensors-08-02331">85</xref>,<xref ref-type="bibr" rid="b86-sensors-08-02331">86</xref>]. A potentiometric sulfide selective electrode based on two different conducting polymers with a fine performance was developed by Atta <italic>et al</italic>. The detection limit of their proposed electrode was 8×10<sup>-7</sup> M of sulfide ions [<xref ref-type="bibr" rid="b76-sensors-08-02331">76</xref>]. Hutchins <italic>et al</italic>. also investigated a NO<sub>3</sub><sup>-</sup> selective electrode in 1995 [<xref ref-type="bibr" rid="b75-sensors-08-02331">75</xref>]. The linear dynamic range of the latter report was 8.0×10<sup>-5</sup> to 2.5×10<sup>-2</sup> M of NO<sub>3</sub><sup>-</sup>. In 2002 Song <italic>et al</italic>. reported a CO<sub>3</sub><sup>2-</sup> sensor incorporating poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) as conducting polymer [<xref ref-type="bibr" rid="b74-sensors-08-02331">74</xref>]. Another organic compound, dodecylsuphate (DDS), was determined by a conducting polymer based sensor in which the detection limit was investigated to be down to 5×10<sup>-6</sup> M of DDS [<xref ref-type="bibr" rid="b86-sensors-08-02331">86</xref>].</p></sec></sec><sec><label>3.</label><title>Non-conducting Polymer PVC-Based ISEs</title><p>The electrodes with mobile charged sites, illustrating ionophores (organic or inorganic) compounds which bind to cations and anions, are broadly used in complex biological and environmental samples [<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]. Nowadays, the response mechanism of these electrodes has been extensively investigated [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>], revealing that the scientific interest should be principally concentrated on the research and the design of new ionophores [<xref ref-type="bibr" rid="b3-sensors-08-02331">3</xref>].</p><p>In this way, the fabrication highly ion-selective electrodes (ISEs) become feasible [<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>,<xref ref-type="bibr" rid="b5-sensors-08-02331">5</xref>]. The recent publication of several review studies [<xref ref-type="bibr" rid="b3-sensors-08-02331">3</xref>-<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>] with reference to ISEs delineates their great significance. This relatively modern field has been subject to extensive research in the period of 1999-2007 when more than 100 ISEs just employing Schiff bases as ionophore [<xref ref-type="bibr" rid="b5-sensors-08-02331">5</xref>].</p><sec><label>3.1.</label><title>ISE membrane components</title><p>Each polymeric membrane ISE comprises four basic components:
<list list-type="order"><list-item><p>The polymeric matrix</p></list-item><list-item><p>The ionophore (membrane–active recognition)</p></list-item><list-item><p>The membrane solvent (plasticizer)</p></list-item><list-item><p>Ionic additives</p></list-item></list></p><p>The ISE nature and characteristics are considerably influenced by the nature and the amount of each component. As far as the polymeric membrane is concerned, it separates the test solution from the inner compartment, containing the target ion solution [<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>].</p><sec><label>3.1.1.</label><title>The polymeric matrix</title><p>Initially, to construct the liquid ISE membrane porous materials were soaked in a solution of a water-immiscible, nonvolatile, viscous organic liquid containing the dissolved ionophore. Recently, polymers have been utilized as homogeneous membrane matrices. For the preparation of a sensing membrane, a typical composition is as follows: 33% (w/w) PVC as the polymeric matrix, 66% plasticizer for the matrix homogenization and 1% ionophore. Regarding the first polymeric ISE membranes, their manufacture involved valinomycin as the neutral ion carrier in silicone rubber or PVC without the addition of lipophilic ionic sites. In such polymeric membranes, the polymer could provide the required physical properties (e.g. elasticity and mechanical stability). It should be stressed that these ISEs exhibited a Nernstian response, owing to the possible ionic impurity presence in the used PVC as well as in the presence of the other membrane components. Moreover, membranes with no ionic sites did not respond to the target ion concentration, as they incorporate almost completely pure membrane ingredients [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p><p>Aside from PVC, other polymers can be also employed in membrane fabrication. The suitability of the polymer to be employed in a sensing membrane (when the required solubility is displayed) is defined by the glass transition temperature (T<sub>g</sub>) of the polymer (Tg is the temperature at which an amorphous solid, such as glass or a polymer, becomes brittle on cooling, or soft on heating). The T<sub>g</sub> value should be below the room temperature. As a consequence, the designed membranes are fluid enough under the ambient conditions, they allow the diffusion of the membrane components, they present reasonable ionic conductivities and they illustrate the proper mechanical properties to be handled for routine processes. If the polymers are characterized by high T<sub>g</sub> values (e.g. the T<sub>g</sub> value of the high molecular weight PVC is 80 °C), the use of plasticizers will be necessary. On the contrary, if the polymers are characterized by low T<sub>g</sub> values, such as soft polyurethanes with a low content of crystalline units, silicone rubber, poly(vinylidene chloride) and polysiloxanes, the use of plasticizers is not obligatory. In this way, the risk of the plasticizer leaching is avoided. Nevertheless, when no plasticizer is incorporated in the membrane, the ion selectivity modification by varying the plasticizer is no longer an alternative.</p><p>Different polymer types have been examined to be applied to membrane preparation. The majority of the examinations focused on the PVC derivatives with 1.8 % carboxylate groups. The respective sensing devices, based on several neutral carriers, presented similar characteristics to those of the PVC matrices. The reason is that the COOH groups remain principally undissociated. The aminated PVC or the related polymers are at least partly protonated upon contact with the aqueous samples, having been used to fabricate the so-called ionophore-free H<sup>+</sup>-selective liquid membrane electrodes. The neutral-carrier-based Na<sup>+</sup>-selective ISEs with a vinyl chloride-vinyl alcohol copolymer (OH-PVC) matrix illustrated reduced protein-induced asymmetry effects.</p><p>The ISE membrane biocompatibility is of vital importance with regard to the clinical applications. For the in-vitro measurements, the protein deposition on the membrane surfaces causes membrane asymmetries and instabilities [<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]. Then, frequent recalibration and skilled personnel are required. In contrast, in the <italic>in-vivo</italic> measurements, attention should be paid to the components leaching as they may have inflammatory, toxic and/or thrombogenic properties. Polyurethanes can decrease the inflammatory response and display excellent adhesive properties. A way to improve their biocompatibility is to covalently bond hydrophilic poly(ethylene oxide) to the surface of the polyurethane membranes. With respect to the blood compatibility, its improvement is possible by covalently attaching heparin to the membrane surface. Photocurable polymer matrices are usually used for the development of miniaturized electrodes by standard photolithography, as applied to the microelectronics technology. Such matrices, tested for the ISE membrane suitability, are the acrylates and the methacrylates, the methacrylated siloxane resins, the epoxyacrylates, polystyrene and the acrylates of urethane oligomers. Concerning the miniaturized electrodes, it is recommended to covalently attach all the membrane components, including the ionophore. To the polymer matrix, not only charged but also uncharged ionophores have been covalently bonded, seemingly with no essential loss in the electrode performance [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p></sec><sec><label>3.1.2.</label><title>The ionophore (membrane–active recognition)</title><p>The ionophore or the ion carrier is the most vital component in a polymeric membrane sensor in terms of selectivity and selectivity. The ionophore or the membrane–active recognition can be an ion exchanger or a neutral macrocyclic compound [<xref ref-type="bibr" rid="b3-sensors-08-02331">3</xref>]. It has molecule–sized dimensions and it contains cavities or semi-cavity to surround the target ions. The binding between the ionophore and the target ion is the molecular-level phenomenon, sensed by the ISE. Therefore, the various ISE selectivities towards the other ions are regarded to derive from the difference in the binding strengths between the selected ionophore, to be used in the sensor, and the different ions. The ISE function involves the phase transfer of the aqueous ions into an organic medium of the ISE, which is typically the plasticized PVC (as it will be discussed later). Actually, the transferred ions interact with the membrane components. In case that the incorporated ionophore is a simple ion-exchanging species, (e.g. a lipophilic ionic additive), the ion transfer process from the aqueous phase into the polymeric membrane of the sensor will be controlled by the lipophilicity of the exchanged ions, such as a phase transfer equilibrium. The selectivity behavior of an ion-exchanger based ISE, where the ionophore does not have any chemical recognition abilities, certainly reflects the relative lipophilicities of the studied ions. In other words, higher ion lipophilicity results in a greater sensor response towards the ion. After a number of studies conducted with ion-exchanging ISEs and liquid–liquid extraction assays, a lipophilicity-dependent selectivity pattern was concluded. This pattern, however, is valid only when the response is a function of the ion lipophilicity. For the cations, the corresponding pattern is:
<list list-type="simple"><list-item><p>Cs<sup>+</sup> > Ag<sup>+</sup> > K<sup>+</sup> > NH<sub>4</sub><sup>+</sup> > Na<sup>+</sup> > Li<sup>+</sup> > Ca<sup>2+</sup> > Pb<sup>2+</sup> > Cu<sup>2+</sup></p></list-item></list></p><p>In parallel, the respective pattern for the anions is as follows:
<list list-type="simple"><list-item><p>ClO<sub>4</sub><sup>-</sup> > SCN<sup>−</sup> > I<sup>−</sup> > salicylate > NO<sub>3</sub><sup>-</sup> > Br<sup>−</sup> > NO<sub>2</sub><sup>-</sup> > Cl<sup>−</sup> > HSO<sub>3</sub><sup>-</sup> > acetate > SO<sub>4</sub><sup>2−</sup> > HPO<sub>4</sub><sup>2−</sup></p></list-item></list></p><p>These patterns are known as the Hofmeister series [<xref ref-type="bibr" rid="b87-sensors-08-02331">87</xref>]. On the other hand, the incorporation of a selectively binding ionophore into the ion-sensing membrane reduces the total free energy for the transfer of the ionophore-bound ions to the organic phase in comparison with that of the simply aqueous ions. When the ionophore binds to an ion strongly, its influence on the ion phase transfer equilibrium is higher. The complex formation constant (K<sub>f</sub>) of an ionophore and one or more of the ions is sufficiently strong, a difference is expected in the observed/calculated selectivity for the ionophore-based sensor, compared with the lipophilicity series depicted above. Likewise, if the ionophore-ion complexes are stronger, a greater difference is expected in the magnitude of the selectivity coefficients versus the lipophilicity series [<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>,<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p></sec><sec><label>3.1.3.</label><title>The membrane solvent (Plasticizer)</title><p>The additives, which increase the plasticity or fluidity of the material to which they are added, are called plasticizers. Normally, the composition of the solvent polymeric membranes, used in the ion-selective devices, is about 30-33% (w/w) PVC and 60-66% of a membrane solvent. Such a composition exhibits optimal physical properties, ensuring relatively high mobilities for their constituents. The membrane solvent has to be physically compatible with the polymer (i.e. have plasticizer properties), so as to give a homogeneous organic phase. Additionally, it may affect the selectivity behavior. In contrast, the selectivities of the carrier-based ISEs are significantly influenced by the membrane solvent. For example, a plasticizer change from the polar <italic>o</italic>-NPOE or nitrobenzene (NB) to the apolar dibutyl phthalate (DBP) reduced the M<sup>2+</sup>-selectivity of the ISE with the ionophore 2,3,8,9-tetraazacyclododeca-1,3,7,9-tetraene. This influence can be attributed to the plasticizer polarity, which can be estimated from the interaction of the charged species with a continuum of the given dielectric constant (Born model) [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p><p>Nonetheless, the plasticizer selection is performed in line with its compatibility with the ionophore (solubility reasons) as well as the final ISE application. The names/abbreviations of the most common plasticizers employed in the ISE fabrication are as follows: benzyl acetate (BA) [<xref ref-type="bibr" rid="b88-sensors-08-02331">88</xref>], bis-(1-butyl-pentyl)ad ipate (BBPA) [<xref ref-type="bibr" rid="b89-sensors-08-02331">89</xref>], bis(2-ethylhexyl) adipate (DOA) [<xref ref-type="bibr" rid="b90-sensors-08-02331">90</xref>], bis(2-ethylhexyl) phthalate (dioctyl phthalate, DOP) [<xref ref-type="bibr" rid="b91-sensors-08-02331">91</xref>], bis(2-ethylhexyl) sebacate (BEHS) [<xref ref-type="bibr" rid="b92-sensors-08-02331">92</xref>], bis(<italic>n</italic>-octyl)sebacate (DOS) [<xref ref-type="bibr" rid="b93-sensors-08-02331">93</xref>], bibenzyl ether (DBE) [<xref ref-type="bibr" rid="b94-sensors-08-02331">94</xref>], dibutyl phthalates (DBP) [<xref ref-type="bibr" rid="b95-sensors-08-02331">95</xref>], dibutyl sebacate (DBS) [<xref ref-type="bibr" rid="b93-sensors-08-02331">93</xref>], didecyl phthalate (DDP) [<xref ref-type="bibr" rid="b96-sensors-08-02331">96</xref>], 2-nitrophenyl phenyl ether (<italic>o</italic>-NPPE) [<xref ref-type="bibr" rid="b97-sensors-08-02331">98</xref>], <italic>o</italic>-nitrophenyl octyl ether (<italic>o</italic>-NPOE) [<xref ref-type="bibr" rid="b98-sensors-08-02331">99</xref>,<xref ref-type="bibr" rid="b99-sensors-08-02331">100</xref>] and tri-<italic>n</italic>-butyl phosphate (TBP) [<xref ref-type="bibr" rid="b100-sensors-08-02331">101</xref>].</p></sec><sec><label>3.1.4.</label><title>Plasticizer-Free Polymer Membrane ISEs</title><p>PVC has been utilized as a polymer matrix for more than 30 years [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>], despite the fact that there are many drawbacks related with its usage. Plasticizer leakage is one them. Diminished sensor lifetimes, unstable responses and sample perturbation are caused by the plasticizer exudation from the sensing membranes. Furthermore, the decreased plasticizer content can reduce the ionophore solubility and the ion exchanger within the membrane, leading to a considerable sensitivity and selectivity reduction. A usual disadvantage of the plasticized-PVC observed in the ion-selective field effect transistors (ISFETs) is its poor adhesion to the gate oxide surfaces, which results in a shortened lifetime of the sensing device [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p></sec><sec><label>3.1.5.</label><title>Ionic additives</title><p>The permselectivity of the ISE membranes is a prerequisite in order to attain a theoretical response. The permselectivity ensures that no significant amount of the counter ions may enter the membrane phase. To achieve this so-called Donnan exclusion with the electrically neutral carriers, the counter ions (ionic sites) confined to the membrane must be present. Despite the fact that the neutral-carrier-based ISE membranes could function properly, even when they contain only a very small amount of ionic sites, the addition of a lipophilic ion salt is advantageous for various other reasons. The anionic interference decrease, observed in the presence of lipophilic anions (e.g. thiocyanate) is the basic reason for the addition of a tetraphenyl borate salt to the membrane of a cation-selective electrode. Simultaneously, the electrical resistance of the membrane is diminished, which is especially important in microelectrodes. The ionic additives are ion exchangers, which themselves induce a selective response if no or only an insufficient ionophore amount is present. It becomes pretty obvious that their concentration must be carefully adjusted [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p><p>The most important salts used as lipophilic additives are potassium tetrakis(<italic>p</italic>-chlorophenyl) borate (KTPClPB) [<xref ref-type="bibr" rid="b101-sensors-08-02331">102</xref>,<xref ref-type="bibr" rid="b102-sensors-08-02331">103</xref>], sodium tetrakis-[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl] borate (NaHFPB) [<xref ref-type="bibr" rid="b103-sensors-08-02331">104</xref>], sodium tetraphenyl borate (NaTPB) [<xref ref-type="bibr" rid="b104-sensors-08-02331">105</xref>], tetrakis(4-fluorophenyl)borate (cesibor) [<xref ref-type="bibr" rid="b105-sensors-08-02331">106</xref>], tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB) [<xref ref-type="bibr" rid="b97-sensors-08-02331">98</xref>] as cationic additive and hexadecylpyridinium bromide (HDPB) [<xref ref-type="bibr" rid="b106-sensors-08-02331">107</xref>], hexadecyltrimethylammonium bromide (HTAB) [<xref ref-type="bibr" rid="b106-sensors-08-02331">107</xref>], trioctylmethylammonium chloride (TOMACl) [<xref ref-type="bibr" rid="b107-sensors-08-02331">108</xref>] as anionic additive.</p><p>A variety of tetraphenyl borate derivatives were recently employed as anionic additives. Their disadvantage is that their chemical stability is limited, especially in the presence of acids, oxidants and light. The decomposition of these compounds is attributed to the H<sup>+</sup> ions attack on the phenyl substituents. The introduction of electron withdrawing substituents may increase the stability. The best available anionic additives are sodium oleic acid (OA) [<xref ref-type="bibr" rid="b95-sensors-08-02331">95</xref>] and potassium tetrakis[<italic>p</italic>-chlorophenyl]-borate (KTpClPB) [<xref ref-type="bibr" rid="b102-sensors-08-02331">103</xref>], on account of their chemical stability and lipophilicity. Ganjali <italic>et al</italic>. reported the use of the first fatty acid (e.g. oleic acid), as an appropriate lipophilic additive, for inducing permselectivity to some PVC membrane selective electrodes. Suitable cationic additives are considered to be the lipophilic tetraalkylammonium salts, like the hexadecyltrimethylammonium bromide (HTAB) [<xref ref-type="bibr" rid="b106-sensors-08-02331">107</xref>]. The hydrophilic counter ions of these lipophilic additives are exchanged with the primary ion as soon as the ISE is conditioned in the respective solutions.</p><p>To avoid the ionic sites leakage, their covalent bonding to the polymer matrix can be of interest (e.g. in sulfonated PVC). It should be nonetheless mentioned that the polymer could display a modified selectivity behavior, owing to the direct interaction of the sulfonate group with the cations [<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>,<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p></sec></sec><sec><label>3.2.</label><title>Non-conducting Polymer Membrane Sensors for the Hydrogen Ion and the First Main Group Cations</title><p>The macrocyclic ligands can form selective and stable complexes with the metal ions of compatible dimensions [<xref ref-type="bibr" rid="b94-sensors-08-02331">94</xref>] and can potentially be applied to their separation and determination [<xref ref-type="bibr" rid="b109-sensors-08-02331">110</xref>-<xref ref-type="bibr" rid="b111-sensors-08-02331">112</xref>]. For these reasons, continuous interest has been focused on the design and synthesis of new functionalized macrocycles for specific applications. Polymeric carrier-based ion-selective electrodes (ISEs), which are selective towards the alkali and the alkaline earth metal ions such as sodium, potassium and lithium, have been the focus of numerous studies [<xref ref-type="bibr" rid="b7-sensors-08-02331">7</xref>].</p><p>Potentiometric detectors based on ISEs are also considered suitable for this determination, since they offer advantages such as high selectivity, sensitivity, good precision, simplicity, portability, nondestructive analysis, ability to monitor the ion activity without extensive sample preparation and low cost. Because of the importance of developing new ionophores in the construction of liquid membrane ISEs, many cyclic and acyclic macromolecules have been introduced as ionophores.</p><p>A large number of H<sup>+</sup>-ISEs, based on different ionophores, have been introduced, during the past decade. They also exhibit excellent selectivities, which are absolutely comparable with, or in some cases, are even better than those of the glass electrodes. The names of some of the ionophores that were used in these sensors are 4,5-dibromofluorescein octadecylester (ETH 7075) [<xref ref-type="bibr" rid="b112-sensors-08-02331">113</xref>], alkyldibenzylamine [<xref ref-type="bibr" rid="b113-sensors-08-02331">114</xref>], porphyrin [<xref ref-type="bibr" rid="b114-sensors-08-02331">115</xref>], 1,1(-bis(11-mercaptoundecyl) ferrocene [<xref ref-type="bibr" rid="b115-sensors-08-02331">116</xref>], tertiary amine containing different alkyl chains [<xref ref-type="bibr" rid="b116-sensors-08-02331">117</xref>], <italic>N,N,N,N</italic>-tetrabenzylethanediamine [<xref ref-type="bibr" rid="b117-sensors-08-02331">118</xref>], <italic>p</italic>-<italic>tert</italic>-butylcalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene-oxa-crown-4 [<xref ref-type="bibr" rid="b118-sensors-08-02331">119</xref>], <italic>N,N′</italic>-dialkylbenzylethylenediamine [<xref ref-type="bibr" rid="b119-sensors-08-02331">120</xref>], tridodecylamine (TDDA) [<xref ref-type="bibr" rid="b120-sensors-08-02331">121</xref>,<xref ref-type="bibr" rid="b121-sensors-08-02331">122</xref>], alkyldibenzyl amines [<xref ref-type="bibr" rid="b122-sensors-08-02331">123</xref>], and tribenzylamine [<xref ref-type="bibr" rid="b123-sensors-08-02331">124</xref>].</p><p>During the past decade, there were four reports on Li<sup>+</sup> ion selective electrodes based on NASICON-type ceramics, 16-crown-4 derivatives, and 1,10-phenanthroline derivatives [<xref ref-type="bibr" rid="b124-sensors-08-02331">125</xref>-<xref ref-type="bibr" rid="b127-sensors-08-02331">128</xref>], four reports on Na<sup>+</sup> based on calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene triesters, cetylpyridinium-nitroprusside ion pair, dibenzopyridino-18-crown-6 and silacrown ether [<xref ref-type="bibr" rid="b128-sensors-08-02331">129</xref>-<xref ref-type="bibr" rid="b131-sensors-08-02331">132</xref>], more than 13 reports on K<sup>+</sup> based on rifamycin, benzo-15-crown-5, gamma-cyclodextrin, benzo-15-crown-5 fluoroionophore, dibenzo-18-crown-6, 5-dicarboxylic acid, decyl-18-crown-6, 4-acryloylamidobenzo-15-crown-5, bis(15-crown-5 ether) derived from xanthene-4,5-dicarboxylic acid, 2,2(-bis[3,4-(15-crown-5-)-2-nitrophenylcarbamoxymethyl] tetradecane, styrene/4(-vinylbenzo-24-crown-8) copolymer, valinomycin, bis(crown ether) ionophore containing two benzo-15-crown-5 moieties and cis-and trans-bis(crown ether)s [<xref ref-type="bibr" rid="b132-sensors-08-02331">133</xref>-<xref ref-type="bibr" rid="b144-sensors-08-02331">145</xref>], for Rb<sup>+</sup> there was one report which is based on crown ethers incorporating anthraquinone, benzoquinone, and 1,4-dimethoxybezene [<xref ref-type="bibr" rid="b145-sensors-08-02331">146</xref>] and 11 reports on Cs<sup>+</sup> ion selective electrodes based on upper-rim calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]crown, calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene dibenzocrown ether, lipophilic calix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arene tetraester derivatives, pyrone compound, quadruply-bridged calix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arenas, biscalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arena-25,25′,27.27′-bis(1,3-dioxypropane)-bis(5,11,17,23-<italic>p</italic>-<italic>tert</italic>-tetrabutylcalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene-26,28-diol), calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene derivative [25-(3-bromo-proploxy)-5,11,-17,23-tetra-kis(<italic>tert</italic>-butyl)-26,27,28-tris(1-propyloxy)calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene], poly(tetrafluoro-ethylene-co-ethylene-co-vinyl acetate), 1,3-alternate thiacalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]biscrown-6,6, Cs-12-molybdo-phosphate, sodium tetrakis-[3,5-bis(trifluoromethyl)phenyl] borate [<xref ref-type="bibr" rid="b146-sensors-08-02331">147</xref>-<xref ref-type="bibr" rid="b156-sensors-08-02331">157</xref>].</p><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for alkali cations is shown in <xref ref-type="fig" rid="f5-sensors-08-02331">Figure 5</xref>.</p><p><xref ref-type="table" rid="t2-sensors-08-02331">Table 2</xref> shows the characterization of the best reported alkali cation selective sensors based on non conducting polymer.</p><p>Some of the above ionophores used in construction of non-conducting polymer ISEs for first main group cations are shown in <xref ref-type="fig" rid="f6-sensors-08-02331">Figure 6</xref>.</p></sec><sec><label>3.3.</label><title>Non-conducting Molymer Membrane Sensors for the Second Main Group Cations</title><p>During the past decade, there were nine reports on Be<sup>2+</sup> ion selective electrodes, mostly based on benzo-9-crown-3 and its derivatives [<xref ref-type="bibr" rid="b101-sensors-08-02331">102</xref>, <xref ref-type="bibr" rid="b157-sensors-08-02331">158</xref>-<xref ref-type="bibr" rid="b164-sensors-08-02331">165</xref>], three reports on Mg<sup>2+</sup> based on the synthetic neutral carrier ETHT 5504, araldite zirconium(IV) selenomolybdate and benzo-15-crown-5 [<xref ref-type="bibr" rid="b165-sensors-08-02331">166</xref>-<xref ref-type="bibr" rid="b167-sensors-08-02331">168</xref>], more than eight reports on Ca<sup>2+</sup> based on polyaniline functionalized with bis[4-(1,1,3,3-tetra-methylbutyl)phenyl]phosphate, bilirubin (1,3,6,7-tetramethyl-4,5-dicarboxyethy-2,8-divinyl-[b13]-dihydrobilenone, dibenzo-18-crown-6, [2-(2-hydroxyphenyl)imino]-1,2-diphenylethanone, ETH 1001 and ETH 129, dimethyl 1-(4-nitrobenzoyl)-8-oxo-2,8-dihydro-1H-pyrazolo[5,1-a]isoindole-2,3-dicarboxylate, x-furyl dioxime [<xref ref-type="bibr" rid="b98-sensors-08-02331">99</xref>, <xref ref-type="bibr" rid="b168-sensors-08-02331">169</xref>-<xref ref-type="bibr" rid="b174-sensors-08-02331">175</xref>], For Sr<sup>2+</sup> there were eight reports based on lipophilic diamides containing pyridine rings, dibenzo-24-crown-8 and 4-<italic>tert</italic>-butylcalix[<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>]arene, 5,11,17,23, 29,35-hexakis-(1,1,3,3-tetramethylbutyl)-37,38,39,40,41,42-hexakis(carboxymethoxy)-calix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arene, 5,7,12,14-di-benzo-2,3,9,10-tetraoxa-1,4,8,11-tetraazacyclotetradecane, 1,10-diaza-5,6-benzo-4,7- dioxacyclohexa-decane-2,9-dione [<xref ref-type="bibr" rid="b173-sensors-08-02331">174</xref>-<xref ref-type="bibr" rid="b182-sensors-08-02331">181</xref>] and three reports on Ba<sup>2+</sup> ion selective electrodes [<xref ref-type="bibr" rid="b183-sensors-08-02331">182</xref>-<xref ref-type="bibr" rid="b185-sensors-08-02331">184</xref>]. The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for alkaline cations is shown in <xref ref-type="fig" rid="f7-sensors-08-02331">Figure 7</xref>.</p><p><xref ref-type="table" rid="t3-sensors-08-02331">Table 3</xref>, shows the characterization and properties of the reported alkaline cation membrane sensors.</p><p>Chemical structures of some of the above ionophores used in construction of non-conducting polymer ISEs for second main group cations are shown in <xref ref-type="fig" rid="f8-sensors-08-02331">Figure 8</xref>.</p></sec><sec><label>3.4.</label><title>Non-Conducting Polymer Membrane Sensors for the Third Main Group Cations</title><p>The development of ISEs for trivalent cations is difficult, owing to the high hydration energy and their existence as free M<sup>3+</sup> in narrow pH ranges. Due to the many industrial applications of these elements, their potentiometric monitoring is of great interest. A limited number of selective membrane sensors were developed for the cations of the IIIA Group.</p><p>During the past decade, there were five reports on Al<sup>3+</sup> ion selective electrodes based on furyl (ethanedione, di-(2-furyl)), bis(5-phenylazosalicylaldehyde)-2,3-naphthalene diimine, hydroxythio-xanthones, xanthone derivative, and <italic>N,N</italic>-bis(salicylidene)-1,2-phenylenediamine (salophen) [<xref ref-type="bibr" rid="b186-sensors-08-02331">185</xref>-<xref ref-type="bibr" rid="b190-sensors-08-02331">189</xref>], two reports on Ga<sup>3+</sup> sensors based on clorogallium(III), 2,9-dimethyl-4,11-diphenyl-1,5,8,12-tetraaza-cyclotetradeca-1,4,8,11-tetraene (DDTCT) [<xref ref-type="bibr" rid="b191-sensors-08-02331">190</xref>, <xref ref-type="bibr" rid="b192-sensors-08-02331">191</xref>], two reports on In<sup>3+</sup> ISEs based on 1-benzyl-3-methyl-4-benzoyl-5-pyrazolone, 15-crown-5-dicyclohexano-18-crown-6 [<xref ref-type="bibr" rid="b193-sensors-08-02331">192</xref>, <xref ref-type="bibr" rid="b194-sensors-08-02331">193</xref>], and seven reports on Tl<sup>3+</sup> ion selective electrodes based on quinoline-carbonitrile calix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arene or calix[<xref ref-type="bibr" rid="b5-sensors-08-02331">5</xref>]arene derivatives, 1,21,23,25-tetramethyl-2,20:3,19-dimetheno-[H,2]H,23H,25H-bis-[<xref ref-type="bibr" rid="b1-sensors-08-02331">1</xref>,<xref ref-type="bibr" rid="b3-sensors-08-02331">3</xref>]dioxocino[5,4-i:5′, 4′-i]benzo[1,2d:5.4-d']bis[<xref ref-type="bibr" rid="b1-sensors-08-02331">1</xref>,<xref ref-type="bibr" rid="b3-sensors-08-02331">3</xref>]benzodioxocin, 2′-amino-1,3,5′-trioxospiro[indane-2,4′(5′H)-3′-cyano indeno(1.2-b)]pyran, dibenzyldiaza-18-crown-6, tetrachlorothallate(III)-2,3,5-triphenyl-2-H- tetrazolium ion pair, and <italic>N′</italic>-dioctylethylenediamine-<italic>N′</italic>-disuccinic acid [<xref ref-type="bibr" rid="b195-sensors-08-02331">194</xref>-<xref ref-type="bibr" rid="b201-sensors-08-02331">200</xref>]. The statistical diagram of the reported potentiometric membrane sensors based on non-conducting polymer for third main group cations is shown in <xref ref-type="fig" rid="f9-sensors-08-02331">Figure 9</xref>. According to the literature survey, there are no reports on potentiometric sensors based on conducting polymers for third main group.</p><p><xref ref-type="table" rid="t4-sensors-08-02331">Table 4</xref>, shows the characterization and properties of the reported third main group cation membrane sensors.</p><p>Chemical structures of some above ionophores which are used in construction of non-conducting polymer ISEs for third main group cations are shown in <xref ref-type="fig" rid="f10-sensors-08-02331">Figure 10</xref>.</p></sec><sec><label>3.5.</label><title>Non-conducting Polymer Membrane Sensors for the Fourth Main Group Cations</title><p>Tin and lead ions are the only cations of this group which have the reported membrane sensors. During the past decade, there were two reports on Sn<sup>2+</sup> ion selective electrodes based on dibenzo-18-crown-6 and 6-(4-nitrophenyl)-2,4-diphenyl-3,5-diaza-bicyclo[3.1.0] hex-2-ene [<xref ref-type="bibr" rid="b202-sensors-08-02331">201</xref>,<xref ref-type="bibr" rid="b203-sensors-08-02331">202</xref>], and more than 40 reports on Pb<sup>2+</sup> ion selective electrodes based on quinaldic acid derivatives, capric acid, piroxicam, 2,2′-dithiodibenzoic acid, anthraquinone derivatives, 4<italic>-tert</italic>-butylcalix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arene, <italic>meso</italic>-tetra-kis(2-hydroxy-1-naphthyl)porphyrin, atropisomers, dibenzodiaza-15-crown-4,4,5-diaza-9-(4-methyl-phenyl)imino fluorine, 1-phenyl-2-(2-quinolyl)-1,2-dioxo-2-(4-bromo) phenylhydrazone, oximino-phenyl-2-ketomethyl quinoline, 1-furoyl-3-(2hydroxyethyl)thiourea, dibenzyl phosphate, tetrabenzyl pyrophosphate and diphenylphosphinic anhydride, tetraphenylporphyrin, 1-furoyl-3-phenylthiourea, 4,7,13,16-tetrathenoyl-1,10-dioxa-4,7,13,16-tetraazacyclooctadecane, 4′-vinylbenzo-15-crown-5-1,5-bis[2-(<italic>N,N</italic>-dialkylcarbamoylmethoxy)phenoxy]3-oxa-pentanes, 1-4,1,5-bis[2-(<italic>N,N</italic>-dialkylcarbamoyl-pentadecyloxy)phenoxy]-3-oxapentanes, dithiophenediazacrown ether derivatives, <italic>N</italic>, <italic>N′</italic>-bis-thiophene-2-ylmethyleneethane-1,2-diamine, calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene amide derivatives, 1,8-dihydroxy-2,7-bis(prop-2′-enyl)-9,10, 5,5′-dithiobis-(2-nitrobenzoic acid), bis[(1-hydroxy-9,10-anthraquinone)-2-methyl]sulfide, 1-furoyl-3,3-diethylthiourea, diporphyrin xanthene, bis(acetylacetone)-<italic>p</italic>-phenylenediamine lead(II) complex, <italic>N,N′</italic>-bis(5-methylsalicylidene)-<italic>p</italic>-diphenylenemethane diamine, <italic>N,N′</italic>-bis(3-methyl-salicyl-idine)-<italic>p</italic>-phenylmethane diamine, 1,10-dibenzyl-1,10-diaza-18-crown-6, <italic>N,N′</italic>-bis-thiophene-2-ylmethyleneethane-1,2-diamine, <italic>N,N′</italic>-bis(salicylidene)-2,6-pyridinediamine Schiff's base as a neutral carrier, <italic>N,N′</italic>-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane [<xref ref-type="bibr" rid="b204-sensors-08-02331">203</xref>-<xref ref-type="bibr" rid="b240-sensors-08-02331">239</xref>]. The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for fourth main group cations is shown in <xref ref-type="fig" rid="f11-sensors-08-02331">Figure 11</xref>.</p><p><xref ref-type="table" rid="t5-sensors-08-02331">Table 5</xref>, shows the characterization and properties of the reported fourth main group cation membrane sensors.</p><p>Chemical structures of some of the above ionophores used in the construction of non-conducting polymer ISEs for fourth main group cations are shown in <xref ref-type="fig" rid="f12-sensors-08-02331">Figure 12</xref>.</p></sec><sec><label>3.6.</label><title>Non-conducting Polymer Membrane Sensors for the Transition Metal Cations</title><p>Among the 29 transition metals, liquid membrane sensors have been reported only 14 of them. Construction and application of ion selective electrode as a potentiometric sensor for determination of the ions in the real samples, offers interesting advantages such as simplicity, speed, relatively fast response, low cost, wide linear dynamic range and ease of preparation and procedures.</p><p>A literature survey reveals that during the past decade, more than 170 ion selective membrane sensors for transition metal cations have been reported. One report for Y<sup>3+</sup> based on <italic>S-N</italic> Schiff's base [<xref ref-type="bibr" rid="b241-sensors-08-02331">240</xref>], one report for Zr<sup>3+</sup> based on bis(diphenylphosphino) ferrocene [<xref ref-type="bibr" rid="b242-sensors-08-02331">241</xref>], one report for vanadyl ion based on <italic>N,N′</italic>-bis-(salicylidene)-2,2-dimethylpropane-1,3-diamine [<xref ref-type="bibr" rid="b243-sensors-08-02331">242</xref>], 12 reports on Cr<sup>3+</sup> ion selective electrodes based on 2,3,8,9-tetraphenyl-1,4,7,10-tetraazacyclododeca-1,3,7,9-tetraene, a new tridentate <italic>S,N,O</italic> Schiff's base 4-hydroxysalicylade-2-mercaptoanil, 2-hydroxybenzaldehyde-<italic>O,O′</italic>-(1,2-dioxetane-1,2-diyl) oxime, <italic>N</italic>-(1-thien-2-ylethylidene)benzene-1,2-diamine, 18-crown-6 (18C6), dibenzo-18-crown-6 (DB18C6) and calix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arene, tri-<italic>o</italic>-thymotide, oxalic acid bis(cyclohexylidene hydrazide), ion-pair [Cr(oxalate)<sub>3</sub>]<sup>3-</sup> anion and tricaprylmethylammonium cation, tetraazacyclo-tetradecane, tetratosyltetraaza 12C4, tritosyltriaza 9C3, 4-dimethylaminoazobenzene, 4-amino-3-hydrazino-6-methyl-1,2,4-triazin-5-one, and 1,5-diphenylcarbazide [<xref ref-type="bibr" rid="b99-sensors-08-02331">100</xref>, <xref ref-type="bibr" rid="b244-sensors-08-02331">243</xref>-<xref ref-type="bibr" rid="b255-sensors-08-02331">254</xref>], two reports on Mn<sup>2+</sup> PVC membrane sensors based on [<italic>N,N′,N″,N‴</italic>-1,5,8,12-tetraazadodecane-bis(salicylaldiminato) 14,16-dimethyl-1,4,7,10,13-pentaazacyclohexadeca-13,16-diene [<xref ref-type="bibr" rid="b256-sensors-08-02331">255</xref>,<xref ref-type="bibr" rid="b257-sensors-08-02331">256</xref>], 11 reports on Fe<sup>3+</sup> ion membrane sensors based on 2-[(2-hydroxy-1-propenylbuta-1,3-dienylimino)-methyl]-4-<italic>p</italic>-tolylazo-pheol, a mu-bis(tridentate) ligand 2-phenyl-1,3-bis[3′-aza-4′-(2′-hydroxyphenyl)-prop-4-en-1′-yl]-1,3-imidazolidine, benzo-18-crown-6 crown ether, ion-pair between [Fe(oxalate)<sub>3</sub>]<sup>3-</sup> anion and tricaprylyl-methylammonium cation, formylsalicylic acid derivatives, 1,4,8,11-tetraazacyclotetradecane, 5,10,15,20-tetrakis(pentafluorophenyl)-21H, 23H-porphyrin, 2,4,6-tri(2-pyridyl)-1,3,5-triazine (TPTZ) [<xref ref-type="bibr" rid="b258-sensors-08-02331">257</xref>-<xref ref-type="bibr" rid="b268-sensors-08-02331">267</xref>].</p><p>Ten reports on Co<sup>2+</sup> ion selective electrodes based on 5-((4-nitrophenyl)azo)-<italic>N</italic>-(2′,4′-dimethoxyphenyl)salicylaldimine, <italic>N,N′</italic>-bis(salicylidene)-3,4-diaminotoluene, benzo-substituted macro-cyclic diamide, 2,3,4-pyridine-1,3,5,8,11,14-hexaazacyclohexadeca-2-ene, dibenzopyridino-substituted macrocyclic diamide, oxime of 1-(2-oxocyclohexyl)-1,2-cyclohexanediol, OXCCD, (2-mercapto-4-methylphenyl)-2-benzamido-3-phenyl-thiopropenoate, dibenzopyridino-substituted macrocyclic diamide, 1-phenyl-3-methyl-4-benzoyl-5-benzoxypyrazole, benzo-substituted macrocyclic diamide (18-membered macrocyclic diamide) [<xref ref-type="bibr" rid="b269-sensors-08-02331">268</xref>-<xref ref-type="bibr" rid="b280-sensors-08-02331">279</xref>].</p><p>Fourteen reports on Ni<sup>2+</sup> ion selective electrodes based on 5,10,15,20-tetraphenylporphyrin, 2,5-thiophenyl bis(5-<italic>tert</italic>-butyl-1,3-benzoxazole), 5,11,17,23,29,35-hexakis-<italic>t</italic>-octyl-37,38,39,40,41,42-hexakis(<italic>N</italic>-phenylthiocarbamoylmethoxy) calix[<xref ref-type="bibr" rid="b6-sensors-08-02331">6</xref>]arene, <italic>N,N′</italic>-bis-(4-dimethylaminobenzylidene)-benzene-1,2-diamine [Ni(Me<sub>4</sub>Bzo<sub>2</sub>[<xref ref-type="bibr" rid="b14-sensors-08-02331">14</xref>]aneN<sub>4</sub>)]Cl<sup>2-</sup>, benzylbis(thiosemicarbazone), 1,3,7,9,13,15, 19,21-octaazapentacyclooctacosane (pentacyclooctaaza), 3,4:11,12-dibenzo-2,5,10,13-tetraoxo-1,6,9,14-tetraazacyclohexadecane, dibenzodiaza-15-crown-4, Schiff's bases, <italic>N</italic>-(2-hydroxybenzyl)-<italic>N′</italic>-(2-hydroxybenzylidene)ethylenediamine and <italic>N</italic>-(2-hydroxybenzylidene)-Al′-(2-picolyl)ethylene-diatmine, thiophene-derivative Schiff's base, <italic>N<sup>1</sup>,N<sup>2</sup></italic>-bis((naphthalen-1-ymethylene)ethane-1,2-diamine [<xref ref-type="bibr" rid="b281-sensors-08-02331">280</xref>-<xref ref-type="bibr" rid="b294-sensors-08-02331">293</xref>].</p><p>More than 30 reports on Cu<sup>2+</sup> ion selective sensors based on <italic>N</italic>-[2-thienylmethylidene]-2-propanolamine, mixed complexes of Cu<sup>2+</sup> and Ni<sup>2+</sup> with <italic>N</italic>-[2-thyenilmethylidene]-2-aminopyridine, naphthol-derivative Schiff's base, bis-2-thiophenal propanediamine, thiophene-derivative Schiff's base, diphenylisocyanate bis(acetylacetone) ethylenedinnine, 2,2′- [4,4′diphenyl-methanebis(nitrilo-methylidyne)]-bisphenol, 2-(1′-(4′-(1″-hydroxy-2″-naphthyl)methyleneamino)butyliminomethyl)-1-naphthol, derived from 2,3-diaminopyridine and omicron-vanilin 2,2-[1,2-ethandiyl-bis(nitrilomethylidine)-bis]metacresole(l),2,2-[1,2-ethandiyl-bis(nitrilomethylidine)-bis]-<italic>p</italic>-cresol(II) and 2,2′- [1,2-ethandiyl-bis(nitritomethylidine)-bis]-<italic>o</italic>-cresol(III), 2-{1-(<italic>E</italic>)-2-((<italic>Z</italic>)-2-{(<italic>E</italic>)-2-[(<italic>Z</italic>)-1-(2-hydroxyphenyl)ethylidene]hydrazono)-1-methylpropylidene)hydrazono]ethyl)phenol, <italic>N,N′</italic>-bis-pyridin-2-ylmethylene-naphthalene-1,8-diamine, copper(II) complex of 2,4-dimethyl-1,5,9,12-tetraaza-cyclopentadeca-1,4-diene, 1,2,5,6,8,11-hexaazacyclododeca-7,12-dione-2,4,8,10-tetraene, Cu-II-cyclo-hexaneone thiosemicarbazone complex, 6,7,8,9,10-hexahydro-2H-1,13,4,7,10-benzodioxatriaza-cyclopentadecine-3,11(4H,12H)-dione, dithiomacrocycle (4-phenyl-11-decanoyl-1,7-dithia-11-1-aza-cyclotetradecane-4-sulfide), 2-(1′-(4′-(1′-hydroxy-2″-naphthyl)methyleneamino)butylimino-methyl)-1-naphthol, aza-thioether crowns containing a 1,10-phenanthroline sub-unit, 2,2′-[1,9-nonane-diylbis(nitriloethylidyne)]-bis-(I-naphthol6-methyl-4-(1-phenylmethylidene)amino-3-thioxo-1,2,4-triazin-5-one, bis(acetylacetone)propylenediimine, 4-amino-6-methyl-1,2,4-triazin-5-one-3-thione, 2-mercaptobenzoxazole, 9,10-anthraquinone derivative, synthesized macrocyclic diamide, copper(II) salicylaniline Schiff's base, naphthol-derivative Schiff's base, synthesized macrocyclic diamide, copper(II) complex of ethambutol, diphenylisocyanate bis(acetylacetone) ethylenedinnine, 2-quinolyl-2-phenylglyoxal-2-oxime (phenylglyoxal-alpha-monoxime), 1,10-phenanthroline sub-unit, bis-2-thiophenal propanediamine, 2,2′-dithiodianiline and dibutyl phthalate, cephaloridine [<xref ref-type="bibr" rid="b295-sensors-08-02331">294</xref>-<xref ref-type="bibr" rid="b333-sensors-08-02331">332</xref>].</p><p>Thirty nine reports on silver selective electrodes based on Schiff's base-<italic>p-tert</italic>-butylcalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene, a dioxime-type Schiff's base, <italic>N,N′</italic>-bis(2′-hydroxyimino-1′-phenyl-propylidene)-1,3-propanediamine, PHO<sub>3</sub>, derived from alpha-isonitrosopropiophenone and 1,3-diaminopropane, calix]4[arene derivative, Schiff base <italic>p-tert</italic>-butylcalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene derivatives containing N and O as binding sites, [bis 5-(4-nitrophenyl azo)salisylaldimine] 1,8-diamino, 3,6-dioxooctane, 2,3-butanedione-thiosemicarbazide, bis(dialkyldithiocarbamates), 2-aminothiophenol based dipodal, calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene compound of 5,11,17,23-tetra-<italic>tert</italic>-butyl-25,27-dihydroxy-calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene-thiacrown-4, calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arenes in the partial cone conformation, 7,8:16,17-dibenzo-6,9,15,18-tetraoxo-1,5,10,14-tetrathiacyclooctadeca-7,16- diene [Bz<sub>2</sub>Oxo<sub>4</sub>C<sub>18</sub>dieneS<sub>4</sub>] tetrathia macrocyclic carrier, calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene derivatives with four imine units, silver ethylmercurythiosalicylate (silver thimerosal), diaza-18-crown-6, containing two oxime donor groups, hexathia-18-crown-6, diphenyl selenide, benzyl phenyl selenide and dibenzyl selenide, 2,2′-dithiobis(benzothiazole), meso-tetraphenylporphine [H<sub>2</sub>T(4-OCH<sub>3</sub>)PP], 3-(2-pyridylethylimino)-2-butanoneoxime, 25,27-dihydroxy-26,28-bis[5-(4-methyl-6-hydroxypurimidine)thiaamyloxy] calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]-arene, <italic>N,N′</italic>-bis(2-thienylmethylene)-1,2-diaminobenzene, methyl-2-pyridyl ketone oxime (MPKO), phenyl-2-pyridyl ketone oxime and bis[2-(<italic>o</italic>-carboxythiophenoxy)methyl]-4-bromo-1-methoxybenzene, octahydroxycalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene derivative, macrocycle, Me-6(14) diene·2HClO<sub>4</sub>, aza-thioether crowns containing a 1,10-phenanthroline sub-unit 2-mercaptobenzimidazole, octaacetyl-resorc[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene, calix-[<xref ref-type="bibr" rid="b2-sensors-08-02331">2</xref>]furano[<xref ref-type="bibr" rid="b2-sensors-08-02331">2</xref>]pyrrole, exocyclic sulfur and selenium ligands based on calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arenes and crown ethers, <italic>O,O,O</italic>-tris(2-ethylhexyl) phosphorothioate and <italic>O,O,O</italic>-tributyl phosphorothioate with a thiophosphoryl (P=S) group, cyclam (1,4,8,11-tetraazacyclotetradecane) nitrogen containing calixarene derivatives, bis-pyridine tetramide macrocycle, calixarene derivative containing nitrogen atom, bis(dialkyl-dithiophosphates) [<xref ref-type="bibr" rid="b334-sensors-08-02331">333</xref>-<xref ref-type="bibr" rid="b373-sensors-08-02331">372</xref>].</p><p>Ten reports on Zn<sup>2+</sup> selective sensors based on <italic>N,N′</italic>-bis(acetylacetone)ethylenediimine, 5,6-benzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>,<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>,<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>]hexacos-5-ene, C2(B)22 cryptand, benzo-substituted macrocyclic diamide, dibenzo-24-crown-8, bis(2-nitrophenyl)disulfide, hematoporphyrin IX, sulipride drug <italic>N</italic>-[(ethyl-1 pyrrolidinyl-2)methyl]methoxy-2 sulfamoyl-5 benzamide, 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadecane-5,14-diene [<xref ref-type="bibr" rid="b374-sensors-08-02331">373</xref>-<xref ref-type="bibr" rid="b383-sensors-08-02331">382</xref>].</p><p>Fifteen reports on Cd<sup>2+</sup> PVC membrane sensors based on incorporating nitrogen and sulfur containing tridentate dicyclohexano-24-crown-8, [1,1′-bicyclohexyl]-1,1′,2,2′-tetrol, 1-furoyl-3-benzyl-3-phenylthiourea, dibenzo-24-crown-8, 5-[((4-methylphenyl)azo)-<italic>N</italic>-(6-amino-2-pyridinyl)salicyl-aldimine], 5-[((4-methylphenyl)azo)-<italic>N</italic>-(2-diamino-2-cyano-1-ethyl cyanide) salicylaldehyde], cetylpyridiniumtetraiodo cadmate or cetylpyridinium-tetrabromo cadmate, dioctyl phthalate and sodium tetraphenyl borate, 3,4:11,12-dibenzo-1,6,9,14-tetraazacyclohexadecane, dicyclohexano-18-crown-6, tetrathia-12-crown-4, 8-hydroxyquinoline, 8-hydroxyquinoline, monoaza-18-crown-6, <italic>N,N′</italic>-[bis-(pyridin-2-yl)formylidene] butane-1,4-diamine and <italic>N</italic>-(2-pyridinylmethylene)-1,2-benzenediamine [<xref ref-type="bibr" rid="b384-sensors-08-02331">383</xref>-<xref ref-type="bibr" rid="b396-sensors-08-02331">395</xref>].</p><p>Twenty five reports on Hg<sup>2+</sup> ion selective sensors based on tetraethylthiuram disulfide were chosen as a chemical modifier, bis[5-((4-nitrophenyl)azo salicylaldehyde)], <italic>p-tert</italic>-butylcalix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]crown with imine units, sulfur Schiff's base 1-(2-hydroxy-1,2-diphenylethylidene)thiosemicarbazide, ethylenediamine bisthiophenecarboxaldehyde, ethyl-2-(benzoylamino)-3-(2-hydroxy-4-methoxy-phenyl)-2-propenoate, bis(2-hydroxybenzophenone) butane-2,3-dihydrazone, dithiosalicylic acid, 4-(4-<italic>N,N</italic>-dimethylphenyl)-2,6-diphenylpyrilium tetrafluoroborate, 2-amino-6-purinethiol and 5-amino-1,3, 4-thiadiazole-2-thiol, polyaniline Sn(IV) phosphate, 5,5′-dithio-bis(2-nitrobenzoic acid) and tricyclazole, <italic>N,N</italic>-dimethylformamide-salicylacylhydrazone, tribromomercurate-rhodamine B ion-pair complex, diamine donor ligand, pentathia-15-crown-5, 1-(2-nitro-4-methylphenyl)-6-methyl-6-methoxy-1,4,5,6-tetrahydro-pyrimidine-2-(3H)thione, dibenzodiazathia-18-crown-6-dione, 25,27-dihydroxy-26,28- bis[(1-naphthalene) selenopropoxy] calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene, 2,3,4,9,10,1,1-dipyridine-3,10-diaza-1,5,8,12-tetrathiacyclotetradeca-2,9-diene, calixarene derivative containing a thiazole azo group, salicylaldehyde thiosemicarbazone, ethyl-2-benzoyl-2-phenylcarbamoyl acetate, 1,3-diphenylthiourea hexathia-18-crown-6-tetraone [<xref ref-type="bibr" rid="b397-sensors-08-02331">396</xref>-<xref ref-type="bibr" rid="b421-sensors-08-02331">420</xref>]. The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for transition metal cations is shown in <xref ref-type="fig" rid="f13-sensors-08-02331">Figure 13</xref>.</p><p><xref ref-type="table" rid="t6-sensors-08-02331">Table 6</xref> shows the characterization and properties of the reported transition metal cation membrane sensors.</p><p>Chemical structures of some above ionophores which are used in construction of non-conducting polymer ISEs for trantion metal cations are shown in <xref ref-type="fig" rid="f14-sensors-08-02331">Figure 14</xref>.</p></sec><sec><label>3.7.</label><title>Non-conducting Polymer Membrane Sensors for the Rare Earth Cations</title><p>The main problem in the field of ISEs globally was finding a selective sensor for lanthanides. The world researchers tried to construct a selective sensor for the lanthanide ions with the aid of ionophores having cavity like crown ethers but they were not quite successful. The only way to design an ISE for the lanthanide ions is using ionophores having semi cavity, heteroatoms (mostly S and N as donor atoms), and high flexibility. Such an ionophore can easily form a template with reference to the size of the cation. Furthermore, this ionophore is able to form a stronger complex with one of the cations than with the other ones. This phenomenon can be attributed to the type, the number and the site of its donor atoms, its flexibility as well as the size and the charge density of the cation [<xref ref-type="bibr" rid="b422-sensors-08-02331">421</xref>].</p><p>The literature survey reveals that during the past decade, more than 70 ion selective membrane sensors have been reported for lanthanide ions. Sixteen reports on lanthanide PVC membrane sensors based on 1,3,5-trithiacyclohexane, monoaza-12-crown-4,5,14-N,N′-hydroxyphenyl-4,15-dioxo-1,5,14,18-tetraazahexacosane, <italic>N</italic>-[hexahydrocyclopentapyrol-2((1H)yl)amino]carbonyl]-4-methyl-benzene sulfonamide (gliclazide), bis(2-mercaptoanil) diacetyl, bis(thiophenol)phenylen-1,3-diamine, dicyclo-hexano-18-crown-6, <italic>N,N</italic>′-adipylbis(5-phenylazosalicylaldehyde hydrazone), bis(2-methyl-benzaldehyde)butane-2,3-dihydrazone, 2,2′-dithiodipyridine, <italic>N</italic>-2,4-dimethylphenyl-<italic>N′</italic>-ethyl-formamidine, <italic>N</italic>-[hexahydrocyclopentapyrol-2((1H)yl)amino]carbonyl]-4-methyl benzene sulfonamide, 3-hydroxy-<italic>N′</italic>-(pyridin-2-ylmethylene)-2-naphthohydrazide, 8-amino-<italic>N</italic>-(2-hydroxybenzylidene)-naphthylamine, <italic>N</italic>′-(1-pyridin-2-ylmethylene)-2-furohydrazide, <italic>N</italic>-(2-pyridyl)-<italic>N</italic>′-(4-methoxyphenyl)-thiourea [<xref ref-type="bibr" rid="b91-sensors-08-02331">91</xref>, <xref ref-type="bibr" rid="b423-sensors-08-02331">422</xref>-<xref ref-type="bibr" rid="b437-sensors-08-02331">436</xref>].</p><p>Nine reports on cerium ion selective sensors based on 1,3,5-trithiane, 1,3,5-trithiane, azomethine of piperonylidine-4-[2.2]<italic>para</italic>-cyclophanylamine, <italic>N</italic>-[(<italic>Z</italic>)-2-chloro-2-(1-hydroxy-1,1,1-triphenylphosphor-anyl)-1-ethenyl]-4-ethyl-1-benzene sulfonamide, 2-aminobenzothiazole and oleic acid, <italic>N,N</italic>-bis[2-(salicylideneamino)ethyl]ethane-1,2-diamine, 1,4,7-trithiacyclononane and oleic acid, [4-(4′-nitro-benzyl)-1-phenyl-3,5-pyrazolidinedion)], <italic>N′</italic>-[(2-hydroxyphenyl)methylidene]-2-furohydrazide [<xref ref-type="bibr" rid="b438-sensors-08-02331">437</xref>-<xref ref-type="bibr" rid="b446-sensors-08-02331">445</xref>].</p><p>Two reports for Pr<sup>3+</sup> membrane sensors based on <italic>N</italic>-(pyridin-2-ylmethylene)benzohydrazide [<xref ref-type="bibr" rid="b447-sensors-08-02331">446</xref>,<xref ref-type="bibr" rid="b448-sensors-08-02331">447</xref>]. Four reports for Nd<sup>3+</sup> ion selective sensors based on N-(2-furylmethylene) pyridine-2,6-diamine, 2-{[(6-aminopyridin-2-yl)imino]methyl}phenol, 5-pyridino-2,8-dithia[<xref ref-type="bibr" rid="b9-sensors-08-02331">9</xref>](2,9)-1,10-phen-anthrolinephane, benzyl bisthiosemicarbazone [<xref ref-type="bibr" rid="b449-sensors-08-02331">448</xref>-<xref ref-type="bibr" rid="b452-sensors-08-02331">451</xref>].</p><p>Six reports on Sm<sup>3+</sup> PVC membrane sensors based on isopropyl 2-[(isopropoxy-carbothioyl)disulfanyl]ethanethioate, Et<sub>4</sub>todit, <italic>N</italic>-[2-4-[[[(cyclohexylamino)carbonyl]amino]sulfonyl]-phenyl]ethyl]-5-methylpyrazine carboxamide, <italic>N</italic>-[2-[4-[[[(cyclohexylamino)carbonyl]amino] sulfonyl]-phenyl]ethyl]-5-methyl pyrazine carboxamide, 3-{[2-oxo-1(2H)-acenaphthylenyliden]amino}-2-thioxo-1,3-thiazolidin-4-one, [1-phenyl-3′(2-nitrophenyl)-spiro[oxirane-2.4-pyrazoline]-3,5-dione] (PNSOP) [<xref ref-type="bibr" rid="b95-sensors-08-02331">95</xref>, <xref ref-type="bibr" rid="b453-sensors-08-02331">452</xref>-<xref ref-type="bibr" rid="b456-sensors-08-02331">455</xref>].</p><p>Four reports for Eu<sup>3+</sup> ion selective sensors based on <italic>N,N</italic>-diethyl-<italic>N</italic>-(4-hydroxy-6-methylpyridin-2-yl)guanidine, bis(thiophenol)butane2,3-dihydrazone, 4-(2-hydroxybenzylideneamino)-6-methyl-3-thioxo-3,4-dihydro-1,2,4-triazi n-5(2H)-one, <italic>S-N</italic> hexadentate Schiff's base, bis(thiophenol)butane-2,3-dihydrazone [456-<xref ref-type="bibr" rid="b460-sensors-08-02331">460</xref>].</p><p>Four reports for Gd<sup>3+</sup> membrane sensors based on <italic>S-N</italic> Schiff's base (2-[{3-[(2-sulfanylphenyl)imino)- 1-methylbutylidene}amino]phenyl hydrosulfide, antibiotic omeprazole, bis(thiophenal) pyridine-2,6-diamine, and <italic>N</italic>-(2-pyridyl)-<italic>N′</italic>-(4-nitrophenyl)thiourea [<xref ref-type="bibr" rid="b104-sensors-08-02331">105</xref>, <xref ref-type="bibr" rid="b461-sensors-08-02331">461</xref>-<xref ref-type="bibr" rid="b464-sensors-08-02331">464</xref>].</p><p>Two reports on Tb<sup>3+</sup> ion membrane sensors based on <italic>N,N</italic>-bis(pyrrolidene) benzene-1,2-diamine, 4-amino-3-{2-[4-amino-6-methyl-5-oxo-4,5-dihydro-1,2,4-triazin-3(2H)-yliden]hydrazono}-6-methyl-3,4-dihydro-1,2,4-triazin-5(2H)-one [<xref ref-type="bibr" rid="b465-sensors-08-02331">465</xref>,<xref ref-type="bibr" rid="b466-sensors-08-02331">466</xref>].</p><p>Four reports on Dy<sup>3+</sup> ion membrane sensors based on <italic>N,N</italic>-bis(pyrrolidene) benzene-1,2-diamine, a new asymmetrical Schiff's base [(<italic>E</italic>)-<italic>N</italic>-(2-hydroxybenzylidene)benzohydraide], 6-hydrazino-1,5-diphenyl-6,7-dihydropyrazolo-[3,4-d]pyrimidine-4(5H)-imine [<xref ref-type="bibr" rid="b467-sensors-08-02331">467</xref>-<xref ref-type="bibr" rid="b470-sensors-08-02331">470</xref>].</p><p>Four reports on Ho<sup>3+</sup> PVC membrane sensors based on <italic>N</italic>-(1-thien-2-ylmethylene)-1,3-benzothiazol-2-amine, <italic>N,N</italic>′-bis(2- pyridinecarboxamide)-1,2-benzene [<xref ref-type="bibr" rid="b471-sensors-08-02331">471</xref>-<xref ref-type="bibr" rid="b474-sensors-08-02331">474</xref>].</p><p>Three reports on Er<sup>3+</sup> membrane sensors based on <italic>N</italic>′-(2-hydroxy-1,2-diphenylethylidene) benzohydrazide, pyridine-2-carbaldehyde-2-(4-methyl-1,3-benzothiazol-2-yl)hydrazone, and <italic>N</italic>-(2-hydroxy-1,2-diphenylethylidene) benzohydrazide [<xref ref-type="bibr" rid="b102-sensors-08-02331">103</xref>, <xref ref-type="bibr" rid="b475-sensors-08-02331">475</xref>-<xref ref-type="bibr" rid="b476-sensors-08-02331">476</xref>].</p><p>Three reports on Tm<sup>3+</sup> ion membrane sensors for thiophene-2-carbaldehyde-(7-methyl-1,3-benzothiazol-2-yl)hydrazone, 2,2′-dianiline disulfide [<xref ref-type="bibr" rid="b477-sensors-08-02331">477</xref>-<xref ref-type="bibr" rid="b479-sensors-08-02331">479</xref>].</p><p>Five reports on Yb<sup>3+</sup> ion membrane sensors for 3-hydroxy-<italic>N</italic>-[(2-hydroxyphenyl)methylene]-2-naphthohydrazide, 6-methyl-4-{[1-(1H-pyrrol-2-yl)methylidene]amino}-3-thioxo-3,4-dihydro-1,2,4-triazin-5(2H)-one, <italic>N</italic>-(6-picolyl)-<italic>N</italic>′-(4-methoxyphenyl) thiourea, cefixime and <italic>N</italic>-(2-pyridyl)-<italic>N</italic>′-(2-methoxyphenyl)-thiourea [<xref ref-type="bibr" rid="b480-sensors-08-02331">480</xref>-<xref ref-type="bibr" rid="b484-sensors-08-02331">484</xref>].</p><p>Two reports on Lu<sup>3+</sup> ion membrane sensors based on <italic>N</italic>-(thien-2-ylmethylene)pyridine-2,6-diamine [<xref ref-type="bibr" rid="b485-sensors-08-02331">485</xref>,<xref ref-type="bibr" rid="b486-sensors-08-02331">486</xref>].</p><p>Five reports on Th<sup>4+</sup> PVC membrane sensors based on 2-(diphenylphosphorothioyl)-<italic>N′,N</italic>′-diphenylacetamide, zirconium phosphoborate, thorium oxinate, Th(C<sub>9</sub>H<sub>6</sub>NO)<sub>4</sub>·2H<sub>2</sub>O, thorium oxinate, Th(C<sub>9</sub>H<sub>6</sub>NO)<sub>4</sub>·2H<sub>2</sub>O, 5,11,17,23-tetra-<italic>tert</italic>-butyl-25,26,27,28-tetrakis(diphenylphosphinoylmethoxy)-calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene [<xref ref-type="bibr" rid="b487-sensors-08-02331">487</xref>-<xref ref-type="bibr" rid="b491-sensors-08-02331">491</xref>].</p><p>However, there are no reports on lanthanide ion selective sensor based on conducting polymers. The statistical diagram of the reported potentiometric membrane sensors based on non-conducting polymer for lanthanide ions is shown in <xref ref-type="fig" rid="f15-sensors-08-02331">Figure 15</xref>.</p><p><xref ref-type="table" rid="t7-sensors-08-02331">Table 7</xref> shows the characterization and properties of the reported lanthanide ions membrane sensors.</p><p>Chemical structures of some above ionophores which are used in construction of non-conducting polymer ISEs for rare earth cations are shown in <xref ref-type="fig" rid="f16-sensors-08-02331">Figure 16</xref>.</p></sec><sec><label>3.8.</label><title>Non-conducting Polymer Membrane Sensors for Inorganic Anions</title><p>The anion selective electrodes, just like the cation selective ones, are an important group of the ion selective electrodes. The number of the anion selective electrodes is lower than that of the cationic sensors, due to reasons like the relative larger size of the anions, their various shapes and their high hydration energy. Nevertheless, a relatively large number of sensors for the anionic species have been published during the past decade.</p><p>For an anion-selective electrode, a strong interaction between the ionophore and the anion is required in order to complex the anion in a selective fashion. The potentiometric response of the membranes, doped with these complexes, is believed to be based on the coordination of the analyte anion axial ligand to the metal center of the carrier molecule.</p><p>Literature survey reveals that during the past decade more than 70 anion selective membrane sensors have been reported based on non-conducting polymers.</p><p>Three reports on bicarbonate PVC membrane sensors based on urea-functionalized calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arenas, 4-(<italic>n</italic>-hexadecyl)-3-nitro-1-trifluoroacetylbenzene, and long chain <italic>S</italic>-alkyldiphenylthiocarbazone [<xref ref-type="bibr" rid="b492-sensors-08-02331">492</xref>-<xref ref-type="bibr" rid="b494-sensors-08-02331">494</xref>].</p><p>Four reports on nitrite membrane sensors based on Co(II)-salen, Co(II)-salophen, (tetraphenyl-porphyrinato) cobalt(III) acetate, and methyl violet [<xref ref-type="bibr" rid="b495-sensors-08-02331">495</xref>-<xref ref-type="bibr" rid="b498-sensors-08-02331">498</xref>].</p><p>Twelve reports on nitrate ion selective sensors based on urea-calixarene, cyclic bis-thiourea, polypyrrole, silver bis(bathophenanthroline) nitrate [Ag(bath)<sub>2</sub>NO<sub>3</sub>], poly(3-octylthiophene) and poly(aniline) as ion-to-electron transducers, tetradecylammonium nitrate and (npoe) 2-nitrophenyloctyl, tris(2-aminoethyl)amino triamide, tert-octylammonium bromide dissolved in dibutylphthalate, tetra-decylammonium nitrate, <italic>N,N,N</italic>-triallylleucine betaine chloride, doped polypyrrole films, tetraoctylammonium bromide [<xref ref-type="bibr" rid="b499-sensors-08-02331">499</xref>-<xref ref-type="bibr" rid="b510-sensors-08-02331">510</xref>].</p><p>Three reports for dihydrogen phosphate based on cobalt rod, uranyl salophenes, and calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene anion [<xref ref-type="bibr" rid="b511-sensors-08-02331">511</xref>-<xref ref-type="bibr" rid="b513-sensors-08-02331">513</xref>].</p><p>Ten reports on monohydrogen phosphate based on vanadyl salen, vanadyl salophen, macrocyclic dithioxamide, molybdenum acetylacetonate, oxo-molybdenum methylsalen, vanadylsalen complex (VS), Binuclear organotin, polymeric membrane electrodes, heterocylic macrocycles, and oxo-molybdenum methyl-salen [<xref ref-type="bibr" rid="b106-sensors-08-02331">107</xref>, <xref ref-type="bibr" rid="b514-sensors-08-02331">514</xref>-<xref ref-type="bibr" rid="b522-sensors-08-02331">522</xref>].</p><p>Three reports on phosphate ion sensors based on bis(pentafluorobenzyl) tin(IV) dibromide, cobalt-wire phosphate ion-selective, and organic tin compounds [<xref ref-type="bibr" rid="b523-sensors-08-02331">523</xref>-<xref ref-type="bibr" rid="b525-sensors-08-02331">525</xref>].</p><p>Two reports on cyanide membrane sensors based on aquacyanocobyrinic acid heptamethyl ester (ACCbs) reagent (orange color) at pH 9.5 to give dicyarrocobester (DCCbs) (violet color) and thin electroplated membranes of silver chalcogenides [<xref ref-type="bibr" rid="b526-sensors-08-02331">526</xref>,<xref ref-type="bibr" rid="b527-sensors-08-02331">527</xref>].</p><p>About 30 reports on thiocyanide PVC membrane sensors based on (<italic>N,N′</italic>-bis-salicylidene-1,2-ethylenediamine), 2.2-[(1,3-dimethyl-1,3-propanediylidene)dinitrilo]bis-benzenethiolato cadmium(II), butane-2,3-dione bis(salicylhydrazonato) zinc(II), dinuclear copper complex, <italic>N,N′</italic>-ethylene-bis(4-methylsalicylidineiminato)nickel(II), zinc-phthalocyanine complex, [Cu(L)] (NO<sub>3</sub>)<sub>2</sub> (L=4,7-bis(3-aminopropyl)-1-thia-4,7-diazacyclononane), meso-tetraphenylporphyrin-rhodium(III), linear poly-amines, poly(vinyl chloride) membrane electrode based on calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene, bis-[(3-ferrocenyl)-(2-crotonic acid)] copper(II) complex [Cu(II)-BFCA], <italic>N,N′</italic>-bis-(benzaldehyde)glycine metallic complexes of Cu(II), Ni(II), Zn(II) and Co(II), bis-taurine-salicylic binuclear copper(II) complex, tribenzyltin(IV) dithiocarbamate [Sn(IV)-TBDTB], rhodium(II) phthalocyanine (RhPc), a copper-1,8-dimethyl-1,3,6,8,10,13-azacyclotetradecane complex, (octabromotetraphenylporphyrinato) manganese(III) chloride, nickel and iron phthalocyanines, tricoordinate Schiff's base copper(II) complex, 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphyrinatomanganese(III) chloride [Mn(TMP)Cl] and 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinatomanganese(III) chloride [Mn(C<sub>l8</sub>TPP)Cl], two zinc(II) ions and two molecules of the bis-<italic>N,O</italic>-bidentate Schiff base 2,2′-[methylenebis(4,1-phenylene-nitrilomethylidyne)]bisphenol, bisbenzoin-semitriethylenetetraamine binuclear cobalt(II) metallic complex [Co(II)<sub>2</sub>-BBSTA], <italic>N,N′</italic>-bis-(furaldehyde)-1,2-phenylenediamine-dipicolyl copper(II) complex [Cu(II)-BFPD], benzaldehyde semicarbazone copper (II) complex [Cu(II)-BASA], bis-benzoin-semitriethylenetetriamine binuclear copper(II) [Cu(II)(2)-BBSTA], manganese(III) tetraphenyl-porphyrin derivatives, Cu(Il)-1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane complex, nickel(II)-azamacrocycle complex, and nickel(II)-1,4-,8,11,15,18,22,25-octabutoxyphthalocyanine [<xref ref-type="bibr" rid="b528-sensors-08-02331">528</xref>-<xref ref-type="bibr" rid="b556-sensors-08-02331">556</xref>].</p><p>One report on sulfite ion selective sensors based on bis-urea calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]diquinones [<xref ref-type="bibr" rid="b557-sensors-08-02331">557</xref>]. More than ten reports for sulfate PVC membrane sensors based on schiff base complex of Zn(II), strontium Schiff's base complex (SS), zinc-Schiff base, <italic>N,N′</italic>-ethylenebis(5-hydroxysalicylideneiminato) chromium(III) chloride, 1,3,5-triphenylpyrylium perchlorate, alpha,alpha′-bis(<italic>N′</italic>-phenylthioureylene)-<italic>m</italic>-xylene, and 2,5-diphenyl-1,2,4,5-tetraazabicyclo[2.2.1]heptane [<xref ref-type="bibr" rid="b558-sensors-08-02331">558</xref>-<xref ref-type="bibr" rid="b569-sensors-08-02331">569</xref>].</p><p>There are four reports on F<sup>-</sup> ion membrane sensors which are based on gallium(III)-Schiff base, organotin compounds, uranyl salophenes derivatives, Zr(IV)-octaethylporphyrin (OEP) dichloride (Zr(IV)[OEP]Cl-2) [<xref ref-type="bibr" rid="b570-sensors-08-02331">570</xref>-<xref ref-type="bibr" rid="b573-sensors-08-02331">573</xref>], three reports on Cl<sup>-</sup> electrodes based on ruthenium(III) Schiff's base, Schiff's base complex of cobalt(II), liquid polymer nano-PEBBLEs [<xref ref-type="bibr" rid="b574-sensors-08-02331">574</xref>-<xref ref-type="bibr" rid="b576-sensors-08-02331">576</xref>] and 11 reports on ClO<sub>3</sub><sup>-</sup>based on synthesized platinum(II) complexes, 1,4,7,10,13-penta(n-octyl)-1,4,7,10,13-pentaazacyclo-pentadecane, calcium bis [4-(1′,1′,3′,3′-tetramethylbutyl)phenyl]phosphate, phosphadithiamacrocycle, octylammonium chloride, complex of uranyl, phosphorus(V)tetraphenylporphyrin, gold(I) organic complex, two nickel-hexaazamacrocycle complexes, some recently synthesized Ni(II)-hexaazacyclotetradecane complexes, and doped poly(3,4-ethylenedioxythiophene) [<xref ref-type="bibr" rid="b577-sensors-08-02331">577</xref>-<xref ref-type="bibr" rid="b587-sensors-08-02331">587</xref>]; five reports on bromide based on iron(III)-salen (IS), Zn(II) macrocyclic complex, new mercury(II) complex, bis(4-hydroxyphenyl) 1,4-diaza-1,3-butadiene-Hg(II), benzo-derivative xanthenium bromide [<xref ref-type="bibr" rid="b588-sensors-08-02331">588</xref>-<xref ref-type="bibr" rid="b592-sensors-08-02331">592</xref>]; and 18 reports on iodide membrane sensors based on salen-Mn(II), Schiff's base complex of Fe(III), cerium-salen, [5,10,15,20-tetrakis(4-<italic>N,N</italic>-dimethylaminobenzene)porphyrinato] Mn(III) acetate, cobalt-salophen, silver-tin oxide, halide-selective receptor, urea derivative, porphyrin, titanium, acetylacetonate, homogeneous crystalline membrane, thiopyrilium ion derivative, PVC-DZT-Hg(II) compound, triphenyllead chloride, bis(1,3,4-thiadiazole) complexes of Hg(II), copper phthalocyanine, 1,4,8-tri(<italic>n</italic>-octyl)-1,4,8,11-tetraazacyclotetradecane complexes of a cyclam derivative, and copper (II) complex [<xref ref-type="bibr" rid="b593-sensors-08-02331">593</xref>-<xref ref-type="bibr" rid="b610-sensors-08-02331">610</xref>] and 23 reports for triiodide membrane sensors based on Schiff's base 2,2′[4,4′-diphenylmethane bis(nitromethylidyne)] bisphenol, with copper(II) and Schiff's base 2,2′[4,4′-diphenylmethane bis(nitromethylidyne)] bisphenol, with iron(III), bis(2-hydroxy-acetophenone)butane-2,3-dihydrazone (ICT), bis(salicylaldehyde) ethylendiamine mercury(II) complex MS), <italic>N,N′</italic>-1,2-propylene-bis-(5-methylsalicylidene iminato) copper(II), a charge-transfer complex, of (1,3-diphenyldihydro-1H-imidazole-4,5-dione dioxide), with iodide, bis(2,4-dimethoxy-benzaldehyde)butane-2,3-dihydrazone with iodine, 2-(((2(((<italic>E</italic>)-1-(2-hydroxyphenyl)methylidine) amino)phenyl)imino)methyl) phenol with iodine, complex of (1,3-diphenyldihydro-1H-imidazole)-4,5-dione dioxime with iodine, complex of bis(2,4-dimethoxybenzaldehyde)butane-2,3-dihydrazone with iodine, bis-<italic>N,O</italic>-bidentate Schiff's base, bis(2-hydroxyacetophenone)butane-2,3-dihydrazone, 7,16-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, 2,4,6,8-tetraphenyl-2,4,6,8-tetraazabicyclo-[3.3.0]octane, 1,6-bis(<italic>N,N</italic>-diethylthiocarbamoylimino)-1,6-diphenyl-2,5-dithiahexane, mercury-salen, phenothiazine derivatives, tetra(<italic>p</italic>-chlorophenyl)porphyrinato manganese(III) acetate, tetrachloro-phenylporphyrinato manganese(III) acetate, ketoconazole-triiodide, two different charge-transfer complexes and amino crown ether, clotrimazole-triiodide ion, complex of iodine and bis(2-hydroxyacetophenone)butane-2,3-dihydrazone, complex of 2-(((2-(((<italic>E</italic>)-1-(2-hydroxyphenyl) methylidine)amino)phenyl)imino)methyl) phenol [<xref ref-type="bibr" rid="b88-sensors-08-02331">88</xref>, <xref ref-type="bibr" rid="b611-sensors-08-02331">611</xref>-<xref ref-type="bibr" rid="b630-sensors-08-02331">630</xref>]. There is also one report on periodide membrane sensors based on metaperiodate bis(triphenylphosphoranylidene)ammonium [<xref ref-type="bibr" rid="b631-sensors-08-02331">631</xref>] and one report for arsenite PVC membrane sensor based on 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrinato cobalt(II) [<xref ref-type="bibr" rid="b632-sensors-08-02331">632</xref>].</p><p>The statistical diagram of the reported potentiometric membrane sensors based on non-conducting polymer for inorganic anions is shown in <xref ref-type="fig" rid="f17-sensors-08-02331">Figure 17</xref>.</p><p><xref ref-type="table" rid="t8-sensors-08-02331">Table 8</xref> shows the characterization and properties of the reported inorganic anion membrane sensors.</p><p>Chemical structures of some above ionophores which are used in construction of non-conducting polymer ISEs for inorganic anions are shown in <xref ref-type="fig" rid="f18-sensors-08-02331">Figure 18</xref>.</p></sec></sec><sec sec-type="conclusions"><label>4.</label><title>Conclusions</title><p>The main problem with symmetric ion selective PVC membrane electrodes is the leakage of the internal solution to the outer surface of the membrane, causing changes in the surface potential. Therefore, the detection limit of this kind of electrode is about 10<sup>-6</sup> M. Since the lifetime of the plasticized PVC membranes is affected by leaching of the membrane components from the membrane into the sample solution, many efforts have been made to achieve plasticizer-free membranes and covalently bound ion recognition sites, in which case CPs also offer unique possibilities.</p><p>Construction of all-solid-state ISEs that do not require internal filling solutions is a common approach, which necessitates careful designs of the solid contact between the ion-selective membrane and the electronic conductor. These devices, however, suffered from the ill-defined transduction of the ionically conducting ion-selective membrane and the electronic conductor, which made them rather instable. Scientists solved overcame this simply by using a conducting polymer instead of the liquid internal electrolyte of the classical ISE. Conducting polymers are able to form an ohmic contact to materials of high work functions, like carbon, gold and platinum. Secondly, due to the solubility of several CPs, they can be deposited from solutions. Thirdly, they have ability to being electroactive materials of mixed electronic and ionic conductivity, which gives them the unique potential to transduce ionic signals into electronic ones.</p><p>These kinds of electrodes have lower detection limits, high mechanical resistance and reproducibility rather to the PVC based membrane electrodes. 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xlink:href="sensors-08-02331f1"></graphic></fig><fig id="f2-sensors-08-02331" position="float"><label>Figure 2.</label><caption><p>Structure of ion selective electrode electrodes; a) conventional ISE with an internal reference electrode and internal filling solution; b) coated wire or graphite coated ISE; c) ISE with a hydrogel contact.</p></caption><graphic xlink:href="sensors-08-02331f2"></graphic></fig><fig id="f3-sensors-08-02331" position="float"><label>Figure 3.</label><caption><p>Common used CP monomers and CPs as ion-to-electron transducers in construction of all solid state potentiometric sensors.</p></caption><graphic xlink:href="sensors-08-02331f3"></graphic></fig><fig id="f4-sensors-08-02331" position="float"><label>Figure 4.</label><caption><p>different types of conducting polymeric based ISE; a) electronic conductor; b)electronic conductor with a high work function (the work function is the minimum energy needed to remove an electron from a solid to a point close to the solid on the macroscopic scale outside the solid surface); c) conducting polymer; d) ion selective membrane; e) ion selective membrane containing conducting polymer; f) conducting polymer doped with ionophores.</p></caption><graphic xlink:href="sensors-08-02331f4"></graphic></fig><fig id="f5-sensors-08-02331" position="float"><label>Figure 5.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for alkali cations.</p></caption><graphic xlink:href="sensors-08-02331f5"></graphic></fig><fig id="f6-sensors-08-02331" position="float"><label>Figure 6.</label><caption><p>Structures of some ionophores used in construction of ion selective membrane sensors for some of first main group cations</p></caption><graphic xlink:href="sensors-08-02331f6"></graphic></fig><fig id="f7-sensors-08-02331" position="float"><label>Figure 7.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for alkaline earth cations</p></caption><graphic xlink:href="sensors-08-02331f7"></graphic></fig><fig id="f8-sensors-08-02331" position="float"><label>Figure 8.</label><caption><p>Structures of suitable ionophores used in construction of ion selective membrane sensors for some of second main group cations.</p></caption><graphic xlink:href="sensors-08-02331f8"></graphic></fig><fig id="f9-sensors-08-02331" position="float"><label>Figure 9.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on non-conducting polymer for third main group cation.</p></caption><graphic xlink:href="sensors-08-02331f9"></graphic></fig><fig id="f10-sensors-08-02331" position="float"><label>Figure 10.</label><caption><p>The structures of the suitable ionophores used in construction of third main group cation membrane sensors</p></caption><graphic xlink:href="sensors-08-02331f10"></graphic></fig><fig id="f11-sensors-08-02331" position="float"><label>Figure 11.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for fourth main group cation</p></caption><graphic xlink:href="sensors-08-02331f11"></graphic></fig><fig id="f12-sensors-08-02331" position="float"><label>Figure 12.</label><caption><p>Some structures of the suitable ionophores used in construction of lead and tin ion membrane sensors.</p></caption><graphic xlink:href="sensors-08-02331f12"></graphic></fig><fig id="f13-sensors-08-02331" position="float"><label>Figure 13.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for transition metal cation.</p></caption><graphic xlink:href="sensors-08-02331f13"></graphic></fig><fig id="f14-sensors-08-02331" position="float"><label>Figure 14.</label><caption><p>Some structures of the suitable ionophores used in construction of transition metal cation membrane sensors.</p></caption><graphic xlink:href="sensors-08-02331f14"></graphic></fig><fig id="f15-sensors-08-02331" position="float"><label>Figure 15.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for lanthanide ions.</p></caption><graphic xlink:href="sensors-08-02331f15"></graphic></fig><fig id="f16-sensors-08-02331" position="float"><label>Figure 16.</label><caption><p>Some structures of the suitable ionophores used in construction of lanthanide cation membrane sensors.</p></caption><graphic xlink:href="sensors-08-02331f16"></graphic></fig><fig id="f17-sensors-08-02331" position="float"><label>Figure 17.</label><caption><p>The statistical diagram of the reported potentiometric membrane sensors based on conducting and non-conducting polymer for inorganic anions.</p></caption><graphic xlink:href="sensors-08-02331f17"></graphic></fig><fig id="f18-sensors-08-02331" position="float"><label>Figure 18.</label><caption><p>Some structures of the suitable ionophores used in construction of some anion membrane sensors.</p></caption><graphic xlink:href="sensors-08-02331f18"></graphic></fig><table-wrap id="t1-sensors-08-02331" position="float"><label>Table 1.</label><caption><p>The characterizations of a number of reported conducting polymer based ISEs.</p></caption><table frame="box" rules="all"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ions</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Conducting Polymer</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Dynamic Linear Range (M)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Detection Limit (M)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref</bold></th></tr></thead><tbody><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">electrochemical polymerization of ortho-methoxyaniline and ortho-methylaniline</td><td align="left" valign="top" rowspan="1" colspan="1">pH 2-11</td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">63.8</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b36-sensors-08-02331">36</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">poly(1-aminoanthracene) film</td><td align="left" valign="top" rowspan="1" colspan="1">pH 1-12</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-12</sup></td><td align="left" valign="top" rowspan="1" colspan="1">52.5</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b37-sensors-08-02331">37</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">cobaltabis(dicarbollide) [3,3′-Co(1,2-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>)] <sup>(-)</sup>-doped polypyrrole (PPy)</td><td align="left" valign="top" rowspan="1" colspan="1">pH 3-12</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-12</sup></td><td align="left" valign="top" rowspan="1" colspan="1">50</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b38-sensors-08-02331">38</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline and its substituted derivatives</td><td align="left" valign="top" rowspan="1" colspan="1">pH 2-9</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">62.4 ±0.9</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b39-sensors-08-02331">39</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-5</td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline (PANI)</td><td align="left" valign="top" rowspan="1" colspan="1">pH 2-9</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">52.7</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b40-sensors-08-02331">40</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-6</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole with the dopant anion cobalt bis(dicarbollide) [3,3′-Co(1,2-C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>)<sub>2</sub>] <sup>(-)</sup></td><td align="left" valign="top" rowspan="1" colspan="1">pH 2-9</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">59.8</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b41-sensors-08-02331">41</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-7</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole (P-Py)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">45.5</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b42-sensors-08-02331">42</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-8</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">58</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b43-sensors-08-02331">43</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">H<sup>+</sup>-9</td><td align="left" valign="top" rowspan="1" colspan="1">poly(aniline) ultrathin films</td><td align="left" valign="top" rowspan="1" colspan="1">pH 3-9</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">55-59</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b44-sensors-08-02331">44</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Na<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole (PPy), doped with NaBF4</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">3.0×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">59.2</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b45-sensors-08-02331">45</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7.4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">65.9</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b46-sensors-08-02331">46</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-octylthiophene) and valinomycin</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">49</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b47-sensors-08-02331">47</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup> - 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">53.5</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b48-sensors-08-02331">48</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline (PANI)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">58.2</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b49-sensors-08-02331">49</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-5</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b50-sensors-08-02331">50</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-6</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">56.4</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b51-sensors-08-02331">51</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-7</td><td align="left" valign="top" rowspan="1" colspan="1">hexacyanoferrate(II)/(II) doped polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">24.3</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b52-sensors-08-02331">52</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>-8</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole doped with di(2-ethylhexyl) sulfosuccinate</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup> -10<sup>-1.5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b53-sensors-08-02331">53</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup> and Cu</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-octylthiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-1</sup> and 10<sup>-7</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5.8×10<sup>-5</sup>and 6.8× 10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">58 and 54</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b54-sensors-08-02331">54</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Mg<sup>2+</sup> and Ca<sup>2+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">29.1 and 28.6</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b55-sensors-08-02331">55</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline functionalized with bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-phosphate</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-1</sup> to 10<sup>-4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">8×10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">27.8 ± 0.2</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b56-sensors-08-02331">56</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline and di(2-ethylhexyl)phosphate</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-1</sup>-10<sup>-3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">27.0 ± 0.4</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b57-sensors-08-02331">57</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole based</td><td align="left" valign="top" rowspan="1" colspan="1">0.1-10<sup>-10</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">27.3</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b58-sensors-08-02331">58</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline and di(2-ethylhexyl)phosphate</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-3</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">28.6 ± 1.1</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b59-sensors-08-02331">59</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Li<sup>+</sup>, Ca<sup>2+</sup> and Cl<sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-octylthiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup>, 10<sup>-7</sup>-10<sup>-1</sup> and 10<sup>-6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">3×10<sup>-4</sup> 6×10<sup>-7</sup> and 9×10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">56.5, 30 and 62.6</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b60-sensors-08-02331">60</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup> and K<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-9</sup>-10<sup>-1</sup> and 10<sup>-6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-9</sup>and 4.4× 10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">48.8</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b61-sensors-08-02331">61</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Sr<sup>2+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline/polycarbonate</td><td align="left" valign="top" rowspan="1" colspan="1">1 × 10<sup>-10</sup> to 1×10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b62-sensors-08-02331">62</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Pb<sup>2+</sup> or Ca<sup>2+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-2</sup>and 10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-5</sup> and 5.0×10<sup>-4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">29.9 and 27.3</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b63-sensors-08-02331">63</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Pb<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-8.5</sup>-10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">58.2</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b64-sensors-08-02331">64</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) films doped by hexacyanoferrate anions</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">30</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b65-sensors-08-02331">65</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2-(<italic>o</italic>-arseno-phenylazo)-1,8-dihydroxynaphthalene-3,6-disulphonic sodium salt (Arsenazo-1)</td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">59</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b66-sensors-08-02331">66</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) (PEDOT)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">56</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b67-sensors-08-02331">67</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-octylthiophene) (POT)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5.5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">49</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b68-sensors-08-02331">68</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5.3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">60.7</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b69-sensors-08-02331">69</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) doped with silver hexabromocarborane</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">40.5±1.6</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b70-sensors-08-02331">70</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-5</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) and polypyrrole doped with sulfonated calixarenes</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5.1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">55.7</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b71-sensors-08-02331">71</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Zn<sup>2+</sup> and K<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">tetraphenylborate (TPB) ion doped polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5.6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">58</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b72-sensors-08-02331">72</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Hg<sup>2+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrolel/polyantimonic acid</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">29.6</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b73-sensors-08-02331">73</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">CO<sub>3</sub><sup>2-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">[poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene)</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-4</sup> to 1×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">2.6×10<sup>-4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-29.5</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b74-sensors-08-02331">74</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">NO<sub>3</sub><sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">doping of polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-5</sup> -0.50</td><td align="left" valign="top" rowspan="1" colspan="1">2×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-56 ±1</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b75-sensors-08-02331">75</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">S<sup>2-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-methylthiophene) and poly-(dibenzo-18-crown-6)</td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-8</sup>-1.0×10<sup>-3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">2.0×10<sup>-9</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-35.7</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b76-sensors-08-02331">76</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">F<sup>-</sup>, H<sub>2</sub>PO<sub>4</sub><sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">polyaniline modification</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-3</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">-45 and -39</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b77-sensors-08-02331">77</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-octylthiophene) and tridodecylmethylammonium chloride</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5.0 × 10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-58</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b78-sensors-08-02331">78</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-octylthiophene) (POT)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-55.1</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b79-sensors-08-02331">79</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">poly(pyrrole) layers doped with chloride (PPyCl)</td><td align="left" valign="top" rowspan="1" colspan="1">2×10<sup>-5</sup> -2×10<sup>-3</sup> and 10<sup>-5</sup>- 2×10<sup>-3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">N.M</td><td align="left" valign="top" rowspan="1" colspan="1">-58.1 and -33.1</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b80-sensors-08-02331">80</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">4×10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-55.9</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b81-sensors-08-02331">81</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup>-5</td><td align="left" valign="top" rowspan="1" colspan="1">polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">1.4×10<sup>-4</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-49.8</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b82-sensors-08-02331">82</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup>-6</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3,4-ethylenedioxythiophene) (PEDOT)</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">7×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-44.4</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b83-sensors-08-02331">83</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Br<sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">poly(methylthiophene-methylpyrrole) copolymer</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">6×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-50</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b84-sensors-08-02331">84</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sup>-</sup>- 1</td><td align="left" valign="top" rowspan="1" colspan="1">poly(3-methylthiophene) conducting polymer</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-7</sup> -5× 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-8</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b85-sensors-08-02331">85</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">dodecyl sulfate</td><td align="left" valign="top" rowspan="1" colspan="1">dodecylsulfate-doped polypyrrole</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup> -7×10<sup>-3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-57.5</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b86-sensors-08-02331">86</xref></td></tr></tbody></table></table-wrap><table-wrap id="t2-sensors-08-02331" position="float"><label>Table 2.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for alkali cations.</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Cation</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Most Important Interfering ions (log K<sub>sel</sub>> -2)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="center" valign="top" rowspan="1" colspan="1">Li<sup>+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">lipophilic crown-4 derivatives</td><td align="left" valign="top" rowspan="1" colspan="1">58</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Na<sup>+</sup>, K<sup>+</sup>,NH<sub>4</sub><sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b124-sensors-08-02331">125</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Li<sup>+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">1,10-Phenanthroline Derivatives</td><td align="left" valign="top" rowspan="1" colspan="1">58.7</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-4</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Na<sup>+</sup>, K<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b127-sensors-08-02331">128</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Na<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1-methyl-1-vinyl-14-crown-5</td><td align="left" valign="top" rowspan="1" colspan="1">55.0</td><td align="left" valign="top" rowspan="1" colspan="1">3.16×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b131-sensors-08-02331">132</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">K<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">styrene/4(-vinyl-benzo-24-crown-8) copolymer</td><td align="left" valign="top" rowspan="1" colspan="1">58</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b139-sensors-08-02331">140</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Rb<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">crown ethers incorporating anthraquinone, benzoquinone, and 1,4-dimethoxybezene</td><td align="left" valign="top" rowspan="1" colspan="1">54.7</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-5</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Na<sup>+</sup>,K<sup>+</sup>,Mg<sup>2+</sup>,NH<sub>4</sub><sup>+</sup>,Li<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b144-sensors-08-02331">145</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cs<sup>+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene derivative [25-(3-bromo- proploxy)-5,11,-17,23-tetrakis(tert-butyl)-26,27,28-tris(1- propyloxy) calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene]</td><td align="left" valign="top" rowspan="1" colspan="1">58</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b152-sensors-08-02331">153</xref></td></tr></tbody></table></table-wrap><table-wrap id="t3-sensors-08-02331" position="float"><label>Table 3.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for alkaline earth cations.</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="top" rowspan="1" colspan="1"><bold>Cation</bold></th><th align="center" valign="top" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="center" valign="top" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="top" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="center" valign="top" rowspan="1" colspan="1"><bold>Most Important Interfering ions (log K<sub>sel</sub>> -2)</bold></th><th align="center" valign="top" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="center" valign="top" rowspan="1" colspan="1">Be<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">2,3,5,6,8,9-hexahydro-1,4,7,10-benzotetra oxacyclododecine-12-carbaldehyde-12-(2,4-dinitrophenyl)hy</td><td align="left" valign="top" rowspan="1" colspan="1">29.9</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup> -1.0 × 10-<sup>1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Na<sup>+</sup>, Ca<sup>+2</sup>, Li<sup>+,</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b150-sensors-08-02331">151</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Be<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">2,6-diphenyl-4-benzo-9-crown-3-pyridine</td><td align="left" valign="top" rowspan="1" colspan="1">29.6</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup>-1.0×10</td><td align="left" valign="top" rowspan="1" colspan="1">Mg<sup>+2</sup>,Ca<sup>+2</sup>,K<sup>+</sup>,Na<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b151-sensors-08-02331">152</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Mg<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">synthetic neutral carrier ETHT 5504</td><td align="left" valign="top" rowspan="1" colspan="1">28.6</td><td align="left" valign="top" rowspan="1" colspan="1">1.0× 10<sup>-5</sup>-1.0 ×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b165-sensors-08-02331">166</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Mg<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">araldite zirconium(IV) selenomolybdate</td><td align="left" valign="top" rowspan="1" colspan="1">23</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-5</sup>-1.0 ×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b166-sensors-08-02331">167</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ca<sup>+2</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">[2-(2-hydroxyphenyl)imino]-1,2-diphenylethanone</td><td align="left" valign="top" rowspan="1" colspan="1">28.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b172-sensors-08-02331">173</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ca<sup>+2</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">dimethyl 1-(4-nitrobenzoyl)-8-oxo-2,8-dihydro-1H-pyrazolo[5,1-a]isoindole-2,3-dicarboxylate</td><td align="left" valign="top" rowspan="1" colspan="1">29.5</td><td align="left" valign="top" rowspan="1" colspan="1">8.0×10<sup>-7</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b98-sensors-08-02331">99</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Sr<sup>+2</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">5,7,12,14-dibenzo-2,3,9,10-tetraoxa-1,4,8,11-tetraazacyclotetradecane</td><td align="left" valign="top" rowspan="1" colspan="1">29.0</td><td align="left" valign="top" rowspan="1" colspan="1">3.98×10<sup>-6</sup> -1.0 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ca<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b180-sensors-08-02331">179</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Sr<sup>+2</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">1,10-diaza-5,6-benzo-4,7-dioxacyclohexadecane-2,9-dione</td><td align="left" valign="top" rowspan="1" colspan="1">30.0</td><td align="left" valign="top" rowspan="1" colspan="1">1.6 × 10<sup>-6</sup> -3.0 × 10<sup>-3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b181-sensors-08-02331">180</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ba<sup>2+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">dimethyl 1-acetyl-8-oxo-2,8-dihydro-1H-pyrazolo[5,1-a]isoindole-2,3-dicarboxylate</td><td align="left" valign="top" rowspan="1" colspan="1">29.7</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup> -1.0 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b185-sensors-08-02331">184</xref></td></tr></tbody></table></table-wrap><table-wrap id="t4-sensors-08-02331" position="float"><label>Table 4.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for third main group cations.</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Cation</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Most Important Interfering ions (log K<sub>sel</sub>> -2)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="center" valign="top" rowspan="1" colspan="1">Al<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">xanthone derivative</td><td align="left" valign="top" rowspan="1" colspan="1">20.0</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup>-1.6 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Hg<sup>2+</sup>, Ba<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b189-sensors-08-02331">188</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ga<sup>3+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">chlorogallium(III)</td><td align="left" valign="top" rowspan="1" colspan="1">30</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup> −10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b191-sensors-08-02331">190</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">In<sup>3+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">1-benzyl-3-methyl-4- benzoyl-5-pyrazolone (PMBP)</td><td align="left" valign="top" rowspan="1" colspan="1">18.7</td><td align="left" valign="top" rowspan="1" colspan="1">3.2×10<sup>-5</sup> - 1.0× 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ga<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b193-sensors-08-02331">192</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Tl<sup>3+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">2′-amino-1,3,5′-trioxo- spiro[indane-2,4′(5′H)-3′-cyano-indeno(1 .2-b)]pyran</td><td align="left" valign="top" rowspan="1" colspan="1">59</td><td align="left" valign="top" rowspan="1" colspan="1">0.1-1.0 × 10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Rb<sup>+</sup>, Cs<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b198-sensors-08-02331">197</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Tl<sup>3+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N′</italic>-dioctylethylene-diamine-<italic>N′</italic>-disuccinic acid</td><td align="left" valign="top" rowspan="1" colspan="1">56</td><td align="left" valign="top" rowspan="1" colspan="1">6.4 × 10<sup>-7</sup>- 10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Rb<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b201-sensors-08-02331">200</xref></td></tr></tbody></table></table-wrap><table-wrap id="t5-sensors-08-02331" position="float"><label>Table 5.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for fourth main group cations.</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Cation</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Most Important Interfering ions (log K<sub>sel</sub>> -2)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="center" valign="top" rowspan="1" colspan="1">Sn<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">dibenzo-18-crown-6(DB18C6)</td><td align="left" valign="top" rowspan="1" colspan="1">27.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup> - 1.0 × 10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b202-sensors-08-02331">201</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Sn<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">6-(4-nitrophenyl)-2,4-diphenyl-3,5-diaza-bicyclo[3.1.0] hex-2-ene</td><td align="left" valign="top" rowspan="1" colspan="1">28.8</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-5</sup> - 1.0 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b203-sensors-08-02331">202</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Pb<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">anthraquinone derivative</td><td align="left" valign="top" rowspan="1" colspan="1">29.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-7</sup> - 1.0 × 10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b208-sensors-08-02331">207</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Pb<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">1-phenyl-2-(2-quinolyl)-1,2-dioxo-2-(4-bromo)phenyl-hydrazone</td><td align="left" valign="top" rowspan="1" colspan="1">28.7</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup> - 1 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b223-sensors-08-02331">222</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Pb<sup>2+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">diporphyrin xanthene(ADPX)</td><td align="left" valign="top" rowspan="1" colspan="1">28.2</td><td align="left" valign="top" rowspan="1" colspan="1">2.6 × 10<sup>-6</sup> - 1.0 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b230-sensors-08-02331">229</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Pb<sup>2+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">N,N′-bis(salicylidene)-2,6-pyridinediamine</td><td align="left" valign="top" rowspan="1" colspan="1">29.4</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup>-1.0 × 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup>, Ag<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b235-sensors-08-02331">234</xref></td></tr></tbody></table></table-wrap><table-wrap id="t6-sensors-08-02331" position="float"><label>Table 6.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for transition metal cations</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Cation</bold></th><th align="left" valign="middle" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="left" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="left" valign="middle" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="left" valign="middle" rowspan="1" colspan="1"><bold>Most Important Interfering ions (log Ksel > -2)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="center" valign="top" rowspan="1" colspan="1">Y<sup>3+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">A new Schiff's base with sulfur and nitrogen donor atoms (2-({(<italic>E</italic>)1,2-diphenyl-2-[(2-2-sulfanylphenyl)imino]ethylidene} amino)-1-benzenethiol, DSAB)</td><td align="left" valign="top" rowspan="1" colspan="1">19.2</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup>-1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Sc<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b241-sensors-08-02331">240</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Zr<sup>4+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">bis(diphenylphosphino) ferrocene</td><td align="left" valign="top" rowspan="1" colspan="1">59.7</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b242-sensors-08-02331">241</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Vo<sup>2+</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N,N</italic>′-bis-(salicylidene)-2,2-dimethylpropane-1,3-diamine (NNPD)</td><td align="left" valign="top" rowspan="1" colspan="1"></td><td align="left" valign="top" rowspan="1" colspan="1"></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b243-sensors-08-02331">242</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cr<sup>3+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">tetraazacyclotetradecane, tetratosyltetraaza 12C4, and tritosyltriaza 9C3</td><td align="left" valign="top" rowspan="1" colspan="1">20±1</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup> - 1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Fe<sup>3+</sup>, Ni<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b251-sensors-08-02331">250</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cr<sup>3+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">1,5-diphenylcarbazide</td><td align="left" valign="top" rowspan="1" colspan="1">19.52 ± 0.40</td><td align="left" valign="top" rowspan="1" colspan="1">6.3×10<sup>-8</sup> - 1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b254-sensors-08-02331">253</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Mn<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N,N′,N″,N‴</italic>-1,5,8,12-tetraazadodecane-bis(salicylaldiminato)(H<sub>2</sub>L)</td><td align="left" valign="top" rowspan="1" colspan="1">30</td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Cd<sup>2+</sup>, Fe<sup>3+</sup>, Ni<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b256-sensors-08-02331">255</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Mn<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">14,16-dimethyl-1,4,7,10,13-pentaazacyclohexadeca-13,16-diene</td><td align="left" valign="top" rowspan="1" colspan="1">29.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.25×10<sup>-1</sup> 1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Zn<sup>2+,</sup> La<sup>3+</sup>, Hg<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b257-sensors-08-02331">256</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Fe<sup>3+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">benzo-18-crown-6 crown ether</td><td align="left" valign="top" rowspan="1" colspan="1">15.7±1</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b260-sensors-08-02331">259</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Fe<sup>3+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">2,4,6-tri(2-pyridyl)-1,3,5-triazine (TPTZ)</td><td align="left" valign="top" rowspan="1" colspan="1">30±1</td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-7</sup>-1×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">K<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b267-sensors-08-02331">266</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Co<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N,N′</italic>-bis(salicylidene)-3,4-diaminotoluene</td><td align="left" valign="top" rowspan="1" colspan="1">30 ± 0.2</td><td align="left" valign="top" rowspan="1" colspan="1">7.9×10<sup>-8</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>, Ni<sup>2+</sup>, Cd<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b270-sensors-08-02331">269</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Co<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">dibenzopyridino-substituted macrocyclic diamide</td><td align="left" valign="top" rowspan="1" colspan="1">27.5</td><td align="left" valign="top" rowspan="1" colspan="1">7.0×10<sup>-7</sup>-1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b273-sensors-08-02331">272</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ni<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">N,N′-bis-(4-dimethylamino-benzylidene)- benzene-1,2-diamine</td><td align="left" valign="top" rowspan="1" colspan="1">30 ± 1</td><td align="left" valign="top" rowspan="1" colspan="1">2.0×10<sup>-7</sup>-1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>,Hg<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b286-sensors-08-02331">285</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ni<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">benzylbis(thiosemicarbazone)</td><td align="left" valign="top" rowspan="1" colspan="1">29.0±0.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup>-1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b288-sensors-08-02331">287</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ni<sup>2+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">1,3,7,9,13,15,19,21-octaazapentacyclooctacosane (pentacyclooctaaza)</td><td align="left" valign="top" rowspan="1" colspan="1">30.0</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-6</sup> -1×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ba<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b289-sensors-08-02331">288</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ni<sup>2+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">dibenzodiaza-15-crown-4</td><td align="left" valign="top" rowspan="1" colspan="1">28.6</td><td align="left" valign="top" rowspan="1" colspan="1">7.1×10<sup>-7</sup>-1.2×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>, Pd<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b291-sensors-08-02331">290</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">bis-2-thiophenal propanediamine (TPDA)</td><td align="left" valign="top" rowspan="1" colspan="1">29.1</td><td align="left" valign="top" rowspan="1" colspan="1">6.0×10<sup>-8</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b299-sensors-08-02331">298</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">new thiophene-derivative Schiffs base</td><td align="left" valign="top" rowspan="1" colspan="1">29.3± 0.7</td><td align="left" valign="top" rowspan="1" colspan="1">6.0×10<sup>-8</sup>- 1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Zn<sup>2+</sup>, Hg<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b300-sensors-08-02331">299</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">diphenylisocyanate bis(acetylacetone) ethylenedinnine (DIBAE)</td><td align="left" valign="top" rowspan="1" colspan="1">29.8</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b301-sensors-08-02331">300</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-4</td><td align="left" valign="top" rowspan="1" colspan="1">1,2,5,6,8,11-hexaazacyclododeca-7,12-dione-2,4,8,10-tetraene</td><td align="left" valign="top" rowspan="1" colspan="1">29.5± 0.3</td><td align="left" valign="top" rowspan="1" colspan="1">2.0×10<sup>-7</sup> - 1×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b309-sensors-08-02331">308</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-5</td><td align="left" valign="top" rowspan="1" colspan="1">Cu-II-cyclohexaneone thiosemicarbazone complex</td><td align="left" valign="top" rowspan="1" colspan="1">29.2</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-9</sup> -1×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b310-sensors-08-02331">309</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>-6</td><td align="left" valign="top" rowspan="1" colspan="1">bis-2-thiophenal propanediamine (TPDA)</td><td align="left" valign="top" rowspan="1" colspan="1">29.1±.1</td><td align="left" valign="top" rowspan="1" colspan="1">6.0×10<sup>-8</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b329-sensors-08-02331">328</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">25,27-dihydroxy-26,28-bis[5-(4-methyl-6- hydroxypurimidine)thiaamyloxy] calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]arene</td><td align="left" valign="top" rowspan="1" colspan="1">61.4</td><td align="left" valign="top" rowspan="1" colspan="1">5×10<sup>-8</sup>-1×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b353-sensors-08-02331">352</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">2-mercaptobenzimidazole (MBI) and 2-mercaptobenzothiazole (MBT)</td><td align="left" valign="top" rowspan="1" colspan="1">60.2 and 57.8</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b355-sensors-08-02331">354</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">cyclam (1,4,8,11-tetraazacyclotetradecane)</td><td align="left" valign="top" rowspan="1" colspan="1">59±2</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b364-sensors-08-02331">363</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Zn<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">5,6-benzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>,<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>,<xref ref-type="bibr" rid="b8-sensors-08-02331">8</xref>]hexacos-5-ene</td><td align="left" valign="top" rowspan="1" colspan="1">29.1 ± 0.4</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b375-sensors-08-02331">374</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Zn<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">benzo-substituted macrocyclic diamide</td><td align="left" valign="top" rowspan="1" colspan="1">28</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-9</sup>-1.0×10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Li<sup>+</sup>, Na<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b377-sensors-08-02331">376</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cd<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">tetrathia-12-crown-4</td><td align="left" valign="top" rowspan="1" colspan="1">29.0 ±1.0</td><td align="left" valign="top" rowspan="1" colspan="1">4×10<sup>-7</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b384-sensors-08-02331">383</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Cd<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">N,N′-[bis(pyridm-2-yl)formylidene] butane-1,4-diamine and N-(2-pyridinylmethylene)-1,2-benzenediamine</td><td align="left" valign="top" rowspan="1" colspan="1">29.5</td><td align="left" valign="top" rowspan="1" colspan="1">7.9×10<sup>-8</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Cu<sup>2+</sup>, NH<sup>4+</sup>, Cr<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b395-sensors-08-02331">394</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Hg<sup>2+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">ethylenediamine bisthiophenecarboxaldehyde</td><td align="left" valign="top" rowspan="1" colspan="1">30.0 ± 0.4</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Ag<sup>+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b401-sensors-08-02331">400</xref></td></tr><tr><td align="center" valign="top" rowspan="1" colspan="1">Hg<sup>2+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">diamine donor ligand</td><td align="left" valign="top" rowspan="1" colspan="1">25 ± 0.1</td><td align="left" valign="top" rowspan="1" colspan="1">1.25×10<sup>-7</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b412-sensors-08-02331">411</xref></td></tr></tbody></table></table-wrap><table-wrap id="t7-sensors-08-02331" position="float"><label>Table 7.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for lanthanide ions</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Cation</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Most Important Interfering ions (log K<sub>sel</sub>> -2)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="left" valign="top" rowspan="1" colspan="1">La<sup>3+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N</italic>-2,4-dimethylphenyl-<italic>N′</italic>- ethylformamidine (amitraz)</td><td align="left" valign="top" rowspan="1" colspan="1">19.8 ± 0.2</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-7</sup>-1.0 ×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b433-sensors-08-02331">432</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">La<sup>3+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">8-amino-<italic>N</italic>-(2-hydroxy- benzylidene)naphthylamine</td><td align="left" valign="top" rowspan="1" colspan="1">20.3 ± 0.3</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-7</sup>-1.0 ×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Pr<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b424-sensors-08-02331">423</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ce<sup>3+</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N,N</italic>-bis[2-(salicylidene- amino)ethyl]ethane-1,2-diamine</td><td align="left" valign="top" rowspan="1" colspan="1">20</td><td align="left" valign="top" rowspan="1" colspan="1">1.41× 10<sup>-7</sup>- 1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">La<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b443-sensors-08-02331">442</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Pr<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N</italic>-(pyridin-2-yl-methylene)- benzohydrazide</td><td align="left" valign="top" rowspan="1" colspan="1">21.1</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>−2</sup>-10<sup>−6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Sm<sup>3+</sup>, Er<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b447-sensors-08-02331">446</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Nd<sup>+3</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">5-pyridino-2,8-dithia[<xref ref-type="bibr" rid="b9-sensors-08-02331">9</xref>](2,9)- 1,10-phenanthrolinephane</td><td align="left" valign="top" rowspan="1" colspan="1">20.1</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Yb<sup>3+</sup>, Gd<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b450-sensors-08-02331">449</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Nd<sup>+3</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">benzyl bisthiosemicarbazone (BTC)</td><td align="left" valign="top" rowspan="1" colspan="1">19.7</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Gd<sup>3+</sup>, Sm<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b451-sensors-08-02331">450</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Sm<sup>3+</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">3-{[2-oxo-1(2<italic>H</italic>)-acenaphthyl- enyliden]amino}-2-thioxo-1,3-thiazolidin-4-one</td><td align="left" valign="top" rowspan="1" colspan="1">19.3</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b456-sensors-08-02331">455</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Sm<sup>3+</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">[1-phenyl-3′(2-nitrophenyl) spiro[oxirane-2.4-pyrazoline]-3,5-dione] (PNSOP)</td><td align="left" valign="top" rowspan="1" colspan="1">19.30</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Gd<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b456-sensors-08-02331">456</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Eu<sup>3+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">4-(2-hydroxybenzylideneamino)- 6-methyl-3-thioxo-3,4-dihydro-1,2,4-triazi n-5(2H)-one (HMTDT)</td><td align="left" valign="top" rowspan="1" colspan="1">19.7 ± 0.4</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup> -1.0× 10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b457-sensors-08-02331">457</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Gd<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N</italic>-(2-pyridyl)-<italic>N</italic>′-(4-nitrophenyl)- thiourea</td><td align="left" valign="top" rowspan="1" colspan="1">19.95 ± 0.3</td><td align="left" valign="top" rowspan="1" colspan="1">3.0 × 10<sup>-7</sup>-1.0 ×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b463-sensors-08-02331">463</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Tb<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">4-amino-3-{2-[4-amino-6- methyl-5-oxo-4,5-dihydro-1,2,4-triazin-3(2H)-ylidene] hydrazono}-6-methyl-3,4-dihydro-1,2,4-triazin-5(2H)-one (ATO)</td><td align="left" valign="top" rowspan="1" colspan="1">19.4 ± 0.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b465-sensors-08-02331">465</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Dy<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">6-hydrazino-1,5-diphenyl-6,7- dihydropyrazolo-[3,4-d]-pyrimidine-4(5H)-imine</td><td align="left" valign="top" rowspan="1" colspan="1">19.6± 0.3</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-1</sup>-1.0×10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b469-sensors-08-02331">469</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Ho<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N,N′</italic>-Bis(2-pyridine- carboxamide)-1,2-benzene</td><td align="left" valign="top" rowspan="1" colspan="1">19.6</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Er<sup>3+</sup>, Dy<sup>3+</sup>,Sm<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b472-sensors-08-02331">472</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Er<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N</italic>′-(2-hydroxy-1,2-diphenyl- ethylidene) benzohydrazide</td><td align="left" valign="top" rowspan="1" colspan="1">21</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b475-sensors-08-02331">475</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Tm<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">2,2′-dianiline disulfide (DADS)</td><td align="left" valign="top" rowspan="1" colspan="1">19.5 ± 0.3</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b478-sensors-08-02331">478</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Yb<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1">3-hydroxy-<italic>N</italic>-[(2-hydroxyphenyl)-methylene]-2-naphthohydrazide</td><td align="left" valign="top" rowspan="1" colspan="1">19.2</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Nd<sup>3+</sup>, Pb<sup>2+</sup>,Gd<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b480-sensors-08-02331">480</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Lu<sup>+3</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N</italic>-(thien-2-ylmethylene)pyridine-2,6-diamine (TPD)</td><td align="left" valign="top" rowspan="1" colspan="1">20.5 ± 0.4</td><td align="left" valign="top" rowspan="1" colspan="1">1.0 × 10<sup>-6</sup> - 1.0 × 10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Nd<sup>3+</sup>, Dy<sup>3+</sup>,Gd<sup>3+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b485-sensors-08-02331">485</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Th<sup>4+</sup></td><td align="left" valign="top" rowspan="1" colspan="1">2-(diphenylphosphorothioyl)-<italic>N′,N′</italic>-diphenylacetamide</td><td align="left" valign="top" rowspan="1" colspan="1">15.2</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">Mg<sup>2+</sup>, Cu<sup>2+</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b487-sensors-08-02331">487</xref></td></tr></tbody></table></table-wrap><table-wrap id="t8-sensors-08-02331" position="float"><label>Table 8.</label><caption><p>Characterization of a number of reported ion selective sensors based on nonconducting polymers for inorganic anions.</p></caption><table frame="box" rules="cols"><thead><tr><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Anion</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ionophore</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Slope (mV decade<sup>-1</sup>)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Linear Range (M)</bold></th><th align="left" valign="middle" rowspan="1" colspan="1"><bold>The most interfering ions (log K<sub>Sel</sub>> -2)</bold></th><th align="center" valign="middle" rowspan="1" colspan="1"><bold>Ref.</bold></th></tr><tr><th valign="bottom" colspan="6" rowspan="1"><hr></hr></th></tr></thead><tbody><tr><td align="left" valign="top" rowspan="1" colspan="1">HCO<sub>3</sub><sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">long chain S-akyl diphenylthiocarbazone.</td><td align="left" valign="top" rowspan="1" colspan="1">-54</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-2</sup>-10<sup>-5</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="left" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b493-sensors-08-02331">493</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">NO<sub>2</sub><sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">(tetraphenylporphyrinato) cobalt(III) acetate</td><td align="left" valign="top" rowspan="1" colspan="1">-58.4 - 60.8</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-1</sup> and 5.0×10<sup>-8</sup>-5.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">F<sup>-</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b496-sensors-08-02331">496</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">NO<sub>3</sub><sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1"><italic>N,N,N</italic>-triallylleucine betaine chloride</td><td align="left" valign="top" rowspan="1" colspan="1">-59.1</td><td align="left" valign="top" rowspan="1" colspan="1">1×10<sup>-6</sup>- 2.25×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b507-sensors-08-02331">507</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">HPO<sub>4</sub><sup>2-</sup> -1</td><td align="left" valign="top" rowspan="1" colspan="1">molybdenum acetylacetonate</td><td align="left" valign="top" rowspan="1" colspan="1">-29.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-1</sup>-1.0×10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b516-sensors-08-02331">516</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">HPO<sub>4</sub><sup>2-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">oxo-molybdenum methyl-salen</td><td align="left" valign="top" rowspan="1" colspan="1">-28.6</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-1</sup> -4.0×10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b517-sensors-08-02331">517</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">PO<sub>4</sub><sup>3-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">bis(pentafluorobenzyl) tin(IV) dibromide</td><td align="left" valign="top" rowspan="1" colspan="1">-70.8</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-5</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b523-sensors-08-02331">523</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">CN<sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">thin electroplated membranes of silver chalcogenides</td><td align="left" valign="top" rowspan="1" colspan="1">-90</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup>-10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b527-sensors-08-02331">527</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SCN<sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">(octabromotetraphenylporphy rinato)manganese(III) chloride</td><td align="left" valign="top" rowspan="1" colspan="1">-58.3</td><td align="left" valign="top" rowspan="1" colspan="1">4.8×10<sup>-7</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b544-sensors-08-02331">544</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SCN<sup>-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">manganese(III) tetraphenylporphyrin derivatives</td><td align="left" valign="top" rowspan="1" colspan="1">-59.5</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b553-sensors-08-02331">553</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SCN<sup>-</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">nickel(II)-azamacrocycle complex</td><td align="left" valign="top" rowspan="1" colspan="1">-57.8</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-7</sup>- 1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b555-sensors-08-02331">555</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SO<sub>3</sub><sup>2-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">bis-urea calix[<xref ref-type="bibr" rid="b4-sensors-08-02331">4</xref>]diquinones</td><td align="left" valign="top" rowspan="1" colspan="1">-51.5</td><td align="left" valign="top" rowspan="1" colspan="1">6.0×10<sup>-5</sup>-1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">ClO<sub>4</sub><sup>-</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b557-sensors-08-02331">557</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SO<sub>4</sub><sup>2-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">strontium Schiff's base complex (SS)</td><td align="left" valign="top" rowspan="1" colspan="1">-29.2</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-2</sup>-10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">SO<sub>3</sub><sup>2-</sup>, CO<sub>3</sub><sup>2-</sup>, Cl<sup>-</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b559-sensors-08-02331">559</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SO<sub>4</sub><sup>2-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">zinc-Schiff base</td><td align="left" valign="top" rowspan="1" colspan="1">-29.2</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-2</sup>-10<sup>-6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b560-sensors-08-02331">560</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">SO<sub>4</sub><sup>2-</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">alpha,alpha′-bis(<italic>N′</italic>-phenyl-thioureylene)-m-xylene</td><td align="left" valign="top" rowspan="1" colspan="1">-29.6</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-6</sup> - 10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">SCN<sup>-</sup> , Br<sup>-</sup>, NO<sub>2</sub><sup>-</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b563-sensors-08-02331">563</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">F<sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">organotin compounds</td><td align="left" valign="top" rowspan="1" colspan="1">-62.7</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b571-sensors-08-02331">571</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Cl<sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">ruthenium(III) Schiff's base</td><td align="left" valign="top" rowspan="1" colspan="1">-54.5</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-1</sup>-3.0×10-<sup>6</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b574-sensors-08-02331">574</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">ClO<sub>4</sub><sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">complex of uranil</td><td align="left" valign="top" rowspan="1" colspan="1">-60.6 ± 1.0</td><td align="left" valign="top" rowspan="1" colspan="1">1.0×10<sup>-6</sup> -1.0</td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b584-sensors-08-02331">584</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">ClO<sub>4</sub><sup>-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">some recently synthesized Ni(II)-hexaazacyclo-tetradecane complexes</td><td align="left" valign="top" rowspan="1" colspan="1">-59.3</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-1</sup>-5.0×10<sup>-7</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b586-sensors-08-02331">586</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Br<sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">iron(III)-salen (IS)</td><td align="left" valign="top" rowspan="1" colspan="1">-59.0</td><td align="left" valign="top" rowspan="1" colspan="1">7.0×10<sup>-6</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">SCN<sup>-</sup>, I<sup>-</sup>, Cl<sup>-</sup></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b588-sensors-08-02331">588</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Br<sup>-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">Zn(II) macrocyclic complex</td><td align="left" valign="top" rowspan="1" colspan="1">-59.2</td><td align="left" valign="top" rowspan="1" colspan="1">2.2×10-<sup>6</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b589-sensors-08-02331">589</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">cobalt-salophen</td><td align="left" valign="top" rowspan="1" colspan="1">- 58.9</td><td align="left" valign="top" rowspan="1" colspan="1">5.0 ×10<sup>-7</sup> 1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b597-sensors-08-02331">597</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sup>-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">thiopyrilium ion derivative</td><td align="left" valign="top" rowspan="1" colspan="1">-60</td><td align="left" valign="top" rowspan="1" colspan="1">8.0×10<sup>-7</sup> -1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1"></td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b604-sensors-08-02331">604</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sup>-</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">bis(1,3,4-thiadiazole) complexes of Hg(II)</td><td align="left" valign="top" rowspan="1" colspan="1">-59.0</td><td align="left" valign="top" rowspan="1" colspan="1">2.0×10-<sup>8</sup>-2.0×10-<sup>2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b607-sensors-08-02331">607</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sub>3</sub><sup>-</sup>-1</td><td align="left" valign="top" rowspan="1" colspan="1">bis (salicylaldehyde) ethylendiamine mercury(II) complex MS)</td><td align="left" valign="top" rowspan="1" colspan="1">-59.0</td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-8</sup>-1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b613-sensors-08-02331">613</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sub>3</sub><sup>-</sup>-2</td><td align="left" valign="top" rowspan="1" colspan="1">a charge-transfer complex of (1,3-diphenyldihydro-1H-Imidazole-4,5-dione dioxide with Iodide</td><td align="left" valign="top" rowspan="1" colspan="1">-59.3</td><td align="left" valign="top" rowspan="1" colspan="1">10<sup>-7</sup>-10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b615-sensors-08-02331">615</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sub>3</sub><sup>-</sup>-3</td><td align="left" valign="top" rowspan="1" colspan="1">2-(((2(((<italic>E</italic>)-1-(2-hydroxy-phenyl) methylidine)amino)-phenyl)imino) methyl) phenol with iodine (CTC)</td><td align="left" valign="top" rowspan="1" colspan="1">-59</td><td align="left" valign="top" rowspan="1" colspan="1">5.0×10<sup>-8</sup> -1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b88-sensors-08-02331">88</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">I<sub>3</sub><sup>−</sup>4</td><td align="left" valign="top" rowspan="1" colspan="1">mercury-salen</td><td align="left" valign="top" rowspan="1" colspan="1">-59.0±0.5</td><td align="left" valign="top" rowspan="1" colspan="1">5.0 ×10<sup>-8</sup>− 1.0×10<sup>-2</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b623-sensors-08-02331">623</xref></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">IO<sub>4</sub><sup>-</sup></td><td align="left" valign="top" rowspan="1" colspan="1">metaperiodate bis(triphenylphosphoranylide ne) ammonium</td><td align="left" valign="top" rowspan="1" colspan="1">-60.1</td><td align="left" valign="top" rowspan="1" colspan="1">8.0×10<sup>-3</sup> -2.7×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b631-sensors-08-02331">631</xref></td></tr><tr><td valign="bottom" colspan="6" rowspan="1"><hr></hr></td></tr><tr><td align="left" valign="top" rowspan="1" colspan="1">Arsenite</td><td align="left" valign="top" rowspan="1" colspan="1">PVC based 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrinato cobalt(II)</td><td align="left" valign="top" rowspan="1" colspan="1">-28.8</td><td align="left" valign="top" rowspan="1" colspan="1">7.9×10<sup>-5</sup>-1.0×10<sup>-1</sup></td><td align="left" valign="top" rowspan="1" colspan="1">-</td><td align="center" valign="top" rowspan="1" colspan="1"><xref ref-type="bibr" rid="b632-sensors-08-02331">632</xref></td></tr></tbody></table></table-wrap></floats-group></pmc></record>Pour manipuler ce document sous Unix (Dilib)
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