With the evolution of ion-selective ionophore-based liquid/polymer membrane electrodes (ISEs) over the past 25 years, many cations of physiological and industrial significance can be measured effectively by direct potentiometry. However, there is a noticeable lack of analogous electrodes for many common anions. 1 Although commercial electrodes based on anionexchangers such as quaternary ammonium salts can be analytically useful, their selectivity patterns are always correlated solely with anion lipophilicity, resulting in the classical Hofmeister series (ClO 4 ->SCN -> salicyl a t eTherefore, highly hydrated anions such as fluoride, bicarbonate, chloride, and nitrite are difficult to monitor due to significant interference from more lipophilic anion species that may be present in the sample. Recently, examination of a variety of compounds that have strong yet reversible interactions with target anions has resulted in new ionophores with decidedly non-Hofmeister selectivity toward anions. 3,4 Many research groups are studying a wide variety of new ionophores that demonstrate these characteristics such as mercury 5 , silver 6 , and tin 7 organometallic compounds, fluorinated (poly)ethers 8 , metallophthalocyanines 9 , metallocenes 10 , and trifluoroacetyl derivatives. 11 The pioneering work of Simon et al., in which the behavior of lipophilic vitamin B 12 derivatives as ionophores was examined, led to one of the first nitrite selective liquid/polymer membrane electrodes. 12 Metalloporphyrins, which are one carbon larger but structurally analogous to the cobyrinate ring of vitamin B 12 , also exhibit unique anion ionophore properties when incorporated into plasticized polymer membranes. Mn(III) [13][14][15][16][17][18][19][20] , Co(III) 13,16,[21][22][23][24][25][26] , Ru(II) 16 , and Sn(IV) 25,27-29 porphyrin-based ISEs have been shown to exhibit useful selectivity for thiocyanate, nitrite/thiocyanate, thiocyanate, and salicylate, respectively. More recently, the nature of the ionophore-anion interaction mechanism has been correlated to the charge of the central metal ion.25 Metal(II) porphyrins were found to serve as neutral carriers, metal(IV) as charged carriers and metal(III) porphyrins as either neutral or charged depending on the existance and number of bound axial ligands. The use of lipophilic ionic additives, either cationic (quaternary ammonium salts for neutral carriers) or anionic (tetraphenylborate salts for charged carriers) can help to determine the dominant mechanism within the polymer membrane responsible for EMF response. 30 These ionic sites have also been found to improve general electrode performance by reducing the membrane resistance, decreasing counter-ion interference, and enhancing selectivity. 25,[30][31][32] In this work, porphyrins containing group XIII ions as metal centers are examined as unique ionophores in the preparation of anion ISEs. Electrodes based on indium(III) porphyrins in poly(vinyl chloride) (PVC) membranes have been shown previously to exhibit enhanced responses toward...