Studies on Diazetetraene Cobalt( ) Metallic Complex as Neutral Carriers for the Preparation of Salicylate2Selective Ion Electrodes

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1 , ACTA CHIMICA SINICA Vol 60, 2002 No 12, ( ) Ξ Ξ ( ) {3,3 2[1,22 ( ) ] 22,42 ( ) } [ Co ( )2EBIBP] (Sal - ), Hofmeister, Sal - µ I - > SCN - > NO 2 - > SO > NO 3 - > ClO 4 - > Br - > Cl -,,,, Studies on Diazetetraene Cobalt( ) Metallic Complex as Neutral Carriers for the Preparation of Salicylate2Selective Ion Electrodes CHAI, Ya2Qin XU, Wen2Ju YUAN, Ruo Ξ (Institute of Analytical Science, College of Chemistry and Chemical Engineering, Southwest Normal University, Chongqing ) Abstract Anion2selective electrode based on 3,3 2[ ethenebis(imidogenmethin) ]2bis22,42pentanedione cobalt ( ) metallic complex [ Co ( ) 2EBIBP] as the neutral carrier is described, which displays an anti2hofmeister selectivity sequence with a preferential potentiometric response to salicylate The selectivity sequence observed is Sal - µ I - > SCN - > NO - 2 > SO 2-4 > NO - 3 > ClO - 4 > Br - > Cl - The response mechanism is discussed in view of the alternating current impedance technique and the UV spectroscopy technique These deviations result from the direct interaction between the central metal and the analyte ion, and steric effect associated with the structure of the carrier The electrode can be applied to medicine analysis and the result has fair agreement with the result given by precipitation method Keywords diazetetraene metallic complex, ion2selective electrode, salicylate, neutral carrier [5,6 ], Hofmeister [1,2 Hofmeister ], SCN - NO 2 - [7 10 ] - :ClO 4 > SCN - > I - Sal - - > NO 3 > Br - - > NO 2 Schiff > Cl - > SO [3,4], Hofmeister I - [11,12], B 12 [13 15 ( ) ], Ξ E2mail : edu cn Received April 15, 2002 ; revised August 12, 2002 ; accepted September 2, 2002 (No )

2 No 12 : 2193,, 2, Hofmeister ( ) ( ) ( 1), ( ), ( ) PVC (ph 515, 0101 mol/ PVC L) (Sal - ) mol/ L (NaSal),, mol/ L, 52 mv/ p c Sal,, t 95 % 5 s mol/ L 10) 2 1 ( ) Sal - Figure 1 Structure of M2EBIBP metallic complex ( 2) 1 NaSal ph h, 0126 mv ( n = 36) mol/ L NaSal, 0158 mv ( n = 1 1 ph MP230 ( Mettler2Toledo ) PHS23C ( ) ; I - ( PE Lambda 17) ; IM6e ( ZAHNER elektrik ) ; NHC ( D26450 Heraeus ) ( ) [ Co ( )2EBIBP ] [16 ], [ ( %) : C 49189, H 5134, N 8132 ; ( %) : C 2 PVC Figure 2 Potentiometric response characteristics of membranes with various carriers 49152, H 5128, N 8125] 2 2 ph ( ) [Ni ( )2EBIBP] ph 410, 515, 616, 715 [17 ] Co ( ) Sal -, KMnO 4 ( 3), ph 515, 1 2,, OH -, OH -,, ph : PVC = , 6512 ( w/ w ) PVC [18], : Ag, AgCl KCl [19 21 ] ph (011 mol/ L) PVC KCl ( ),Hg 2 Cl 2,Hg 515 Sal -, Sal -, PVC

3 2194 Vol 60, 2002 ( ) Sal - ( 5), Sal - 16 nm, ( ) Sal - Sal - Co ( )2EBIBP Co ( ) 3 ph Figure 3 ph effect on potentiometric response characteristics of the electrode incorporating Co( ) 2EBIBP carrier 2 3 ( ) Sal -, 3362Sal - [21] ( 1) ph mol/ L 1, Co ( )2EBIBP Sal - 4 ( ), Hofmeister, : Sal - µ I - > SCN - > NO2 - > SO > NO - 3 > ClO - 4 > Br - > Cl Hofmeister, [22 ] ( ) Sal -, Sal - ( ) Co ( ), ( ) [16] Co ( ) ( ) Sal - Figure 4 Suggested coordination scheme of Co ( )2EBIBP with Sal - 5 ( ) NaSal (011 mol/ Ni ( ) L) ( ) ( ) ( ) Sal - Figure 5 UV absorption spectra of chloroform solution of 4 ( ) NaSal Co ( )2EBIBP ( ) and Co ( ) 2EBIBP treated with NaSal (011 mol/ L), (0 1 mol/ L) solution ( ) Carrier 1 ( ) (log K pot Sal -,j - ) Table 1 Selectivity coefficient (log K pot Sal -,j - ) for Co ( ) 2EBIBP electrode Interfering ion Sal - I - SCN - NO - 2 SO 2-4 NO - 3 ClO - 4 Br - Cl - Co ( )2EBIBP Sal

4 No 12 : ( ) PVC ph 515 NaSal ( 6), (APC),, 013 g 10 ml 011 mol/ L NaOH Warburg Sal -,, 011 mol/ L 50 ml, NaSal , 2 6 ( ) PVC [23 (ph 515),, ] , mol/ L,, 2 2, , , APC Sal -, ( ) Sal -, mg 2 h 5 ml, 0101 mol/ L (ph 515), [24 ] 3, 3, 6 ( ) Aspirin PVC Figure 6 Impedance plots of PVC membrane with Co ( )2 APC EBIBP carrier 2 Table 2 Determination of aspirin in pharmaceuticals Tablet Potentiometry a / % Titrimetry [23 ] / % a Mean of five determinations Sample Table 3 Determination of salicylate in human urine Potentiometry a Added/ (mmol L - 1 ) Found/ (mmol L - 1 ) Recovery/ % a Mean of four determinations Colorimetry [24 ] Found/ (mmol L - 1 ) Recovery/ % References 1 Morf, W E The Principles of Ion2selective Eletrodes and of Membrane Transport, Akademiai Kiado, Elsevier, Amsterdam, New York, Sollner, K ; Shean, G M J Am Chem Soc 1964, 86, Pranitis, D M ; Telting2Diaz, M ; Meyerhoff, M E Crit Rev Anal Chem 1992, 23, Hofmeister, F Arch Exp Pathol Pharmakol 1888, 24, Daunert, S ; Bachas, L G Anal Chem 1989, 61, Daunert, S ; Wallace, S ; Florido, A ; Bachas, G Anal Chem 1991, 63, Matais, R ; Cousin, J ; Soia, F Biophys Acta 1977, 467, Wuthier, U ; Pham, H V ; Zund, R ; Welti, D ; Funck, R J J ; Bezegh, A ; Ammann, D ; Pretsch, E ; Simon, W Anal Chem 1984, 56, Schulthess, P ; Ammann, D ; Simon, W ; Caderas, C ; Stepanek, R ; Krautler, B Helv Chim Acta 1984, 67, 1026

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