Zirconium(IV)-porphyrins as novel ionophores for fluoride-selective polymeric membrane electrodes

Malinowska, Elżbieta; Górski, Łukasz; Meyerhoff, Mark E.

doi:10.1016/s0003-2670(02)00635-9

Cited by 86 publications

(94 citation statements)

References 25 publications

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“…It should be noted that at this pH, a significant fraction of the fluoride ions are protonated ([A − ]/[HA] = 0.72) and this influences the LDL observed, since free unprotonated fluoride is the species that is sensed by the membranes. Nonetheless, as with other metalloporphyrin-based electrochemical and optical sensors for fluoride reported previously [9,14,16,17], the tradeoff of using such a low pH for practical measurements of total fluoride concentration more than outweighs the greater loss in LDL owing to hydroxide interference that occurs when the pH of the test solution is raised to a higher value.…”

Section: The Influence Of Ph On Electrodes Parametersmentioning

confidence: 95%

“…Incorporation of the t-butyl-substituents in the para position of TPP (see Fig. 1 [9,14]. For the electrodes with Zr[tBTPP], the slopes were acceptable for at least 30 d, with a decrease of only 2.7 mV/decade over this period.…”

Section: Lifetime Of Electrodesmentioning

confidence: 97%

“…Many of the previously reported fluoride-selective electrodes based on metalloporphyrins do not exhibit fast and reversible EMF response due to dimerization or aggregation equilibria of metalloporphyrins within the organic membrane phase [9,14]. To prevent dimer formation, sterically hindered metalloporphyrins have been suggested [14,18].…”

Section: Response Time and Reversibilitymentioning

confidence: 99%

“…Similarly, thus far, relatively few useful fluoride-selective polymeric membrane electrodes have been reported [8][9][10][11][12][13][14][15]. Most suffer from practical problems such as high level of interference by lipophilic anions [11,12,15], super-nernstian response slopes, sluggish and not fully reversible response properties [8,9,10,14] and short use lifetimes of the electrodes [14].…”

Section: Introductionmentioning

confidence: 99%

“…Most suffer from practical problems such as high level of interference by lipophilic anions [11,12,15], super-nernstian response slopes, sluggish and not fully reversible response properties [8,9,10,14] and short use lifetimes of the electrodes [14]. Recent research has suggested that membranes formulated with Al(III) octaethylporhyrin (Al [OEP]) and Al(III) tetraphenylporphyrin (Al[TPP]) [14] exhibit very high potentiometric selectivity towards fluoride anions, and this has led also to the design of highly selective optical fluoride sensors with sub-micromolar fluoride ion detection limit [16,17].…”

Section: Introductionmentioning

confidence: 99%

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Polymeric membrane electrodes with improved fluoride selectivity and lifetime based on Zr(IV)- and Al(III)-tetraphenylporphyrin derivatives

Pietrzak

Meyerhoff

Malinowska

2007

Analytica Chimica Acta

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Novel aluminum(III)-and zirconium(IV)-tetraphenylporhyrin (TPP) derivatives are examined as fluoride selective ionophores for preparing polymer membrane-based ion-selective electrodes (ISEs). The influence of t-butyl-or dichloro-phenyl ring substituents as well as the nature of the metal ion center (Al(III) vs. Zr(IV)) on the anion complexation constants of TPP derivative ionophores are reported. The anion binding stability constants of the ionophores are characterized by the so-called "sandwich membrane" method. All of the metalloporphyrins examined form their strongest anion complexes with fluoride. The influence of plasticizer as well as the type of lipophilic ionic site additive and their amounts in the sensing membrane are discussed. It is shown that membrane electrodes formulated with the metalloporphyrin derivatives and appropriate anionic or cationic additives exhibit enhanced potentiometric response toward fluoride over all other anions tested. Since selectivity toward fluoride is enhanced in the presence of both anionic and cationic additives, the metalloporphyrins can function as either charged or neutral carriers within the organic membrane phase. In contrast to previously reported fluoride-selective polymeric membrane electrodes based on metalloporphyrins, nernstian or near-nernstian (−51.2 to −60.1 mV decade −1 ) as well as rapid (t < 80s) and fully reversible potentiometric fluoride responses are observed. Moreover, use of aluminum (III)-t-butyltetraphenylporphyrin as the ionophore provides fluoride sensors with prolonged (7 months) functional life-time.

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Section: The Influence Of Ph On Electrodes Parametersmentioning

confidence: 95%

Section: Lifetime Of Electrodesmentioning

confidence: 97%

Section: Response Time and Reversibilitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Polymeric membrane electrodes with improved fluoride selectivity and lifetime based on Zr(IV)- and Al(III)-tetraphenylporphyrin derivatives

Pietrzak

Meyerhoff

Malinowska

2007

Analytica Chimica Acta

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A Unique Fluoride Nanocontainer: Porous Molecular Capsules Can Accommodate an Unusually High Number of “Rather Labile” Fluoride Anions

et al. 2015

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The present work refers to the challenging issue of fluoride anion recognition/binding in water by taking advantage of the unique possibilities offered by the porous molecular nanocontainers of the {Mo 132 } Keplerate type allowing the study of a variety of new phenomena. Reaction of the highly reactive carbonate-type capsule with aqueous HF results in the release of carbon dioxide and integration of an unprecedentedly large number of fluoride anions-partly as coordinated ligands at both the pentagonal units and the linkers, partly as a disordered water/fluoride assembly inside the cavity. The internal assembly and some of the fluoride ligands are easily released, which provides interesting options for future studies regarding coordination chemistry and catalysis under confined conditions.

show abstract

A Unique Fluoride Nanocontainer: Porous Molecular Capsules Can Accommodate an Unusually High Number of “Rather Labile” Fluoride Anions

et al. 2015

View full text Add to dashboard Cite

The present work refers to the challenging issue of fluoride anion recognition/binding in water by taking advantage of the unique possibilities offered by the porous molecular nanocontainers of the {Mo132} Keplerate type allowing the study of a variety of new phenomena. Reaction of the highly reactive carbonate-type capsule with aqueous HF results in the release of carbon dioxide and integration of an unprecedentedly large number of fluoride anions--partly as coordinated ligands at both the pentagonal units and the linkers, partly as a disordered water/fluoride assembly inside the cavity. The internal assembly and some of the fluoride ligands are easily released, which provides interesting options for future studies regarding coordination chemistry and catalysis under confined conditions.

show abstract

Zirconium(IV)-porphyrins as novel ionophores for fluoride-selective polymeric membrane electrodes

Cited by 86 publications

References 25 publications

Polymeric membrane electrodes with improved fluoride selectivity and lifetime based on Zr(IV)- and Al(III)-tetraphenylporphyrin derivatives

Polymeric membrane electrodes with improved fluoride selectivity and lifetime based on Zr(IV)- and Al(III)-tetraphenylporphyrin derivatives

A Unique Fluoride Nanocontainer: Porous Molecular Capsules Can Accommodate an Unusually High Number of “Rather Labile” Fluoride Anions

A Unique Fluoride Nanocontainer: Porous Molecular Capsules Can Accommodate an Unusually High Number of “Rather Labile” Fluoride Anions

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