A Novel Potentiometric Sensor for Thiocyanate Based on an Amide‐Linked Manganese Diporphyrin Xanthene

The synthesis of a new compound, amide-linked manganese diporphyrin xanthene (Mn2Cl2ADPX), and its application for preparation of thiocyanate selective electrodes was described. The electrode was prepared with a PVC membrane combining Mn2Cl2ADPX as an electro active material, 2-nitrophenyl octyl ether (o-NPOE) as a plasticizer in the percentage ratio of 3 : 65 : 32 (Mn2Cl2ADPX: o-NPOE: PVC, w : w : w). The electrode exhibited linear response within the concentration range of 2.4×10−6 to 1.0×10−1 M SCN−, with a working pH range from 3.0 to 8.0 and a fast response time of less than 60 s. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The Mn2Cl2ADPX based electrode shows obviously better response characteristics than that of monoporphyrin manganese in terms of working concentration range and slope. Selectivity coefficients for SCN− relative to a number of interfering ions were investigated. The electrode exhibits anti-Hofmeister selectivity toward SCN− with respect to common coexisting anions. The electrode was applied to the determination of SCN− in body urine with satisfactory results.

[1]  D. Nocera,et al.  A convergent synthetic approach using sterically demanding aryldipyrrylmethanes for tuning the pocket sizes of cofacial bisporphyrins. , 2002, Inorganic chemistry.

[2]  K. Sollner,et al.  Liquid Ion-Exchange Membranes of Extreme Selectivity and High Permeability for Anions , 1964 .

[3]  Kouichiro Tsuge,et al.  Cyanide and Thiocyanate Levels in Blood and Saliva of Healthy Adult Volunteers , 2000 .

[4]  P. Bühlmann,et al.  Ion‐Selective Electrodes for Thiocyanate Based on the Dinuclear Zinc(II) Complex of a Bis‐N,O‐bidentate Schiff Base , 2004 .

[5]  G. Rechnitz,et al.  Selectivity studies on liquid membrane, ion-selective electrodes , 1969 .

[6]  A. Adler,et al.  A simplified synthesis for meso-tetraphenylporphine , 1967 .

[7]  J. F. Staden,et al.  Spectrophotometric determination of thiocyanate by sequential injection analysis , 2000 .

[8]  M. Meyerhoff,et al.  Further studies on the potentiometric salicylate response of polymeric membranes doped with tin(IV)-tetraphenylporphyrins , 1992 .

[9]  Y. Yamamoto,et al.  Determination of thiocyanate in human saliva and urine by ion chromatography. , 1992, The Analyst.

[10]  A. Gold,et al.  Effect of Meso Substituents on Exchange-Coupling Interactions in μ-Oxo Iron(III) Porphyrin Dimers , 1986 .

[11]  G. Shen,et al.  A novel ethacrynic acid sensor based on a lanthanide porphyrin complex in a PVC matrix. , 2000, The Analyst.

[12]  D. Nocera,et al.  Xanthene-bridged cofacial bisporphyrins. , 2000, Inorganic chemistry.

[13]  M. Ghaedi,et al.  Bis(2-mercaptobenzoxazolato)mercury(II) and bis(2-pyridinethiolato)mercury(II) complexes as carriers for thiocyanate selective electrodes , 2003 .

[14]  C. Hill,et al.  Isolation, purification, and characterization of high-valent complexes from a manganese porphyrin based catalytic hydrocarbon activation system. Crystal and molecular structure of .mu.-oxo-bis[azido(tetraphenylporphinato)manganese(IV)] , 1982 .

[15]  M. Kochanny,et al.  Regiospecific aryl nitration of meso-substituted tetraarylporphyrins: a simple route to bifunctional porphyrins , 1989 .

[16]  E. Kılıç,et al.  Using of hydrogen ion-selective poly(vinyl chloride) membrane electrode based on calix[4]arene as thiocyanate ion-selective electrode , 2006 .

[17]  A. Abbaspour,et al.  Thiocyanate-selective electrode based on unsymmetrical benzoN(4) nickel(II) macrocyclic complexes. , 2002, Talanta.

[18]  W. Butts,et al.  Automated method for determining serum thiocyanate, to distinguish smokers from nonsmokers. , 1974, Clinical chemistry.

[19]  A. Amr,et al.  Novel thiocyanate-selective membrane sensors based on di-, tetra-, and hexa-imidepyridine ionophores , 2003 .

[20]  R. Yu,et al.  Substituted metalloporphyrin derivatives as anion carrier for PVC membrane electrodes , 1995 .

[21]  Y. Chai,et al.  Highly Thiocyanate‐Selective PVC Membrane Electrode Based on Lipophilic Ferrocene Derivative , 2005 .

[22]  M. Meyerhoff,et al.  Salicylate-selective membrane electrode based on tin(IV) tetraphenylporphyrin. , 1989, Analytical chemistry.

[23]  R. Yu,et al.  Metalloporphyrin Derivatives as Neutral Carriers for PVC Membrane Electrodes , 1994 .

[24]  L. Bachas,et al.  Anion-Selective Electrodes Based on Electropolymerized Porphyrin Films , 1991 .

[25]  L. Singh,et al.  Molybdate sensor based on 5,10,15,20-tetraphenylporphyrinatocobalt complex in a PVC matrix , 1999 .

[26]  S. Tangestaninejad,et al.  Thiocyanate-selective electrodes based on nickel and iron phthalocyanines , 1999 .

[27]  R. Yuan,et al.  Highly thiocyanate-selective membrane electrodes based on the N,N′-bis-(benzaldehyde)-glycine copper(II) complex as a neutral carrier , 2005 .

[28]  G. Shen,et al.  Fluoroborate ion sensitive PVC membrane electrode based on chloro[tetra(m-amino-phenyl)porphinato]-manganese as neutral carrier , 2000 .

[29]  B. Gong,et al.  Fluorimetric method for the determination of thiocyanate with 2′,7′-dichlorofluorescein and iodine , 1999 .