Aluminum(III) Porphyrins as Ionophores for Fluoride Selective Polymeric Membrane Electrodes
dc.contributor.author | Mitchell-Koch, Jeremy T. | en_US |
dc.contributor.author | Pietrzak, Mariusz | en_US |
dc.contributor.author | Malinowska, Elzbieta | en_US |
dc.contributor.author | Meyerhoff, Mark E. | en_US |
dc.date.accessioned | 2007-05-02T14:17:29Z | |
dc.date.available | 2007-05-02T14:17:29Z | |
dc.date.issued | 2006-03 | en_US |
dc.identifier.citation | Mitchell-Koch, Jeremy 14T.; Pietrzak, Mariusz; Malinowska, Elzbieta; Meyerhoff, Mark 14E. (2006). "Aluminum(III) Porphyrins as Ionophores for Fluoride Selective Polymeric Membrane Electrodes." Electroanalysis 18(6): 551-557. <http://hdl.handle.net/2027.42/50662> | en_US |
dc.identifier.issn | 1040-0397 | en_US |
dc.identifier.issn | 1521-4109 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/50662 | |
dc.description.abstract | Aluminum(III) porphyrins are examined as potential fluoride selective ionophores in polymeric membrane type ion-selective electrodes. Membranes formulated with Al(III) tetraphenyl (TPP) or octaethyl (OEP) porphyrins are shown to exhibit enhanced potentiometric selectivity for fluoride over more lipophilic anions, including perchlorate and thiocyanate. However, such membrane electrodes display undesirable super-Nernstian behavior, with concomitant slow response and recovery times. By employing a sterically hindered Al(III) picket fence porphyrin (PFP) complex as the membrane active species, fully reversible and Nernstian response toward fluoride is achieved. This finding suggests that the super-Nernstian behavior observed with the nonpicket fence metalloporphyrins is due to the formation of aggregate porphyrin species (likely dimers) within the membrane phase. The steric hindrance of the PFP ligand structure eliminates such chemistry, thus leading to theoretical response slopes toward fluoride. Addition of lipophilic anionic sites into the organic membranes enhances response and selectivity, indicating that the Al(III) porphyrin ionophores function as charged carrier type ionophores. Optimized membranes formulated with Al(III)-PFP in an o -nitrophenyloctyl ether plasticized PVC film exhibit fast response to fluoride down to 40 14ΜM, with very high selectivity over SCN − , ClO 4 − , Cl − , Br − and NO 3 − ( k pot <10 −3 for all anions tested). With further refinements in the membrane chemistry, it is anticipated that Al(III) porphyrin-based membrane electrodes can exhibit potentiometric fluoride response and selectivity that approaches that of the classical solid-state LaF 3 crystal-based fluoride sensor. | en_US |
dc.format.extent | 118943 bytes | |
dc.format.extent | 3118 bytes | |
dc.format.mimetype | application/pdf | |
dc.format.mimetype | text/plain | |
dc.publisher | WILEY-VCH Verlag | en_US |
dc.subject.other | Chemistry | en_US |
dc.subject.other | Polymer and Materials Science | en_US |
dc.title | Aluminum(III) Porphyrins as Ionophores for Fluoride Selective Polymeric Membrane Electrodes | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Biological Chemistry | en_US |
dc.subject.hlbsecondlevel | Chemical Engineering | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbsecondlevel | Materials Science and Engineering | en_US |
dc.subject.hlbtoplevel | Health Sciences | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.subject.hlbtoplevel | Engineering | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Chemistry Department, University of Michigan, Ann Arbor, MI 48109, USA ; | en_US |
dc.contributor.affiliationother | Department of Chemistry, Emporia State University, Emporia, KS 66801, USA | en_US |
dc.contributor.affiliationother | Department of Chemistry, Warsaw University of Technology, Warsaw, Poland | en_US |
dc.contributor.affiliationother | Department of Chemistry, Warsaw University of Technology, Warsaw, Poland | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/50662/1/551_ftp.pdf | en_US |
dc.identifier.doi | http://dx.doi.org/10.1002/elan.200503450 | en_US |
dc.identifier.source | Electroanalysis | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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