Synthesis of porphyrin-appended terpyridine as a chemosensor for cadmium based on fluorescent enhancement.

The design and synthesis of a porphyrin-appended terpyridine, 5-(4-([2,2':6',2'']-terpyridin-4-yl-carboxyamidyl)phenyl)-10,15,20-triphenylporphyrin (H(2)TPPTPy) and its application as potential fluoroionophore for recognition of metal ions are reported. For preparation of the fluoroionophore, a novel simple strategy with improved total yield has been applied for the synthesis of 2,2':6',2''-terpyridine-4'-carboxylic acid as a ligand. H(2)TPPTPy shows chelation-enhanced fluorescence effect with cadmium ion via the interruption of photoinduced electron transfer (PET) process, which has been utilized as the basis of the fabrication of the Cd(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Cd(II)-sensitive chemosensor were investigated. It shows a linear response toward Cd(II) in the concentration range of 3.2x10(-6) to 3.2x10(-4)M with a limit of detection of 1.2x10(-6)M. The chemosensor shows good selectivity for Cd(II) over a large number of cations, such as alkali, alkali earth and transitional metal ions except Cu(II) and Zn(II). The sensor has been used for determination of Cd(II) in water samples with satisfactory recoveries.

[1]  A. M. Díaz,et al.  A flow-injection renewable surface sensor for the fluorimetric determination of vanadium(V) with Alizarin Red S. , 2005 .

[2]  A. Harriman,et al.  Photoinduced Electron- and Energy-Transfer Processes Occurring within Porphyrin-Metal-Bisterpyridyl Conjugates , 1994 .

[3]  Xiaobing Zhang,et al.  A fluorescent chemical sensor for Hg(II) based on a corrole derivative in a PVC matrix. , 2006, Talanta.

[4]  S. Zakeeruddin,et al.  Determination of pKa Values of 4-Phosphonato-2,2":6",2""-Terpyridine and Its Ruthenium(II)-Based Photosensitizer by NMR, Potentiometric, and Spectrophotometric Methods , 2000 .

[5]  V. Miskowski,et al.  SPECTROELECTROCHEMISTRY AND DIMERIZATION EQUILIBRIA OF CHLORO(TERPYRIDINE)PLATINUM(II). NATURE OF THE REDUCED COMPLEXES , 1996 .

[6]  S. Fukuzumi,et al.  An yttrium ion-selective fluorescence sensor based on metal ion-controlled photoinduced electron transfer in zinc porphyrin-quinone dyad. , 2004, Journal of the American Chemical Society.

[7]  J. Waluk.  Hydrogen-bonding-induced phenomena in bifunctional heteroazaaromatics. , 2003, Accounts of chemical research.

[8]  Anthony W. Czarnik,et al.  Chelation enhanced fluorescence in 9,10-bis[[(2-(dimethylamino)ethyl)methylamino]methyl]anthracene , 1988 .

[9]  Lan-sun Zheng,et al.  p-Dimethylaminobenzaldehyde thiosemicarbazone: a simple novel selective and sensitive fluorescent sensor for mercury(II) in aqueous solution. , 2006, Talanta.

[10]  D. Akins,et al.  Aggregation of Tetraaryl-Substituted Porphyrins in Homogeneous Solution , 1996 .

[11]  S. Webber,et al.  pH-Induced Fluorescence Quenching of Anthracene-Labeled Poly(2-vinylpyridine) , 2004 .

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

[13]  R. Leblanc,et al.  Peptidyl fluorescent chemosensors for the detection of divalent copper. , 2003, Analytical chemistry.

[14]  R. Thummel,et al.  Fluorescence Quenching by Pyridine and Derivatives Induced by Intermolecular Hydrogen Bonding to Pyrrole-Containing Heteroaromatics† , 2002 .

[15]  U. Resch‐Genger,et al.  Redox Switchable Fluorescent Probe Selective for Either Hg(II) or Cd(II) and Zn(II) , 1999 .

[16]  H. Freake,et al.  Illuminating zinc in biological systems. , 2004, Chemistry.

[17]  B. Jaselskis,et al.  Fluorometric determination of submicrogram quantities of cadmium by reaction with the metallofluorochromic reagent, calcein , 1974 .

[18]  G. H. Nancollas,et al.  CALORIMETRIC STUDIES OF COMPLEX FORMATION OF TRANSITION METAL IONS WITH 2,2′,2′-TERPYRIDINE , 1977 .

[19]  R. Houghten,et al.  A traceless approach for the parallel solid-phase synthesis of 2-(arylamino)quinazolinones. , 2002, The Journal of organic chemistry.

[20]  E. V. Donckt,et al.  Determination by Fluorescence Spectroscopy of Cadmium at the Subnanomolar Level: Application to Seawater , 2000, Journal of Fluorescence.

[21]  G. Kirsch,et al.  A novel pathway for the synthesis of a carboxylic acid-functionalised Ru(II) terpyridine complex , 2003 .

[22]  T. Moore,et al.  Structural Effects on Photoinduced Electron Transfer in Carotenoid−Porphyrin−Quinone Triads , 1997 .

[23]  J. Temmink,et al.  Cadmium - environmental aspects. , 1993 .

[24]  T. Koike,et al.  Recent development of zinc-fluorophores , 1998 .

[25]  Ipcs,et al.  Cadmium; environmental aspects , 1992 .

[26]  Glenn E. M. Maguire,et al.  Fluorescent PET (photoinduced electron transfer) sensors , 1993 .