2002 60 12, 2192 2196 ACTA CHIMICA SINICA Vol 60, 2002 No 12, 2192 2196 ( 400715) Ξ Ξ ( ) {3,3 2[1,22 ( ) ] 22,42 ( ) } [ Co ( )2EBIBP] (Sal - ), Hofmeister, Sal - µ I - > SCN - > NO 2 - > SO 2 4 - > 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 400715) 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 2 4 - [3,4], Hofmeister I - [11,12], B 12 [13 15 ( ) ], Ξ E2mail : yuanruo @swnu edu cn Received April 15, 2002 ; revised August 12, 2002 ; accepted September 2, 2002 (No 29705001)
No 12 : 2193,, 2, Hofmeister 2 1 2 2 ( ) ( ) ( 1), ( ), ( ) PVC (ph 515, 0101 mol/ PVC L) (Sal - ) 110 10-1 610 10-6 mol/ L (NaSal),, 210 10-6 - mol/ L, 52 mv/ p c Sal,, t 95 % 5 s 110 10-3 mol/ L 10) 2 1 ( ) Sal - Figure 1 Structure of M2EBIBP metallic complex ( 2) 1 NaSal ph 515 5 h, 0126 mv ( n = 36) 110 10-2 110 10-3 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 = 518 29, 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
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 5 5 0 1 mol/ L 1, Co ( )2EBIBP Sal - 4 ( ), Hofmeister, : Sal - µ I - > SCN - > NO2 - > SO 2 4 - > NO - 3 > ClO - 4 > Br - > Cl - 2 4 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 0 0-2 16-2 58-2 74-2 91-2 99-3 11-3 51-3 71 3362Sal - 0 0 0 62 1 04-1 82-0 95 2 24-1 17-1 96
No 12 : 2195 2 5 ( ) PVC ph 515 NaSal ( 6), (APC),, 013 g 10 ml 011 mol/ L NaOH Warburg Sal -,, 011 mol/ L 50 ml, NaSal 110 10-4, 2 6 ( ) PVC [23 (ph 515),, ] 110 10-3, 110 10-2 mol/ L,, 2 2, 111 10 6, 912 10 5, 815 10 5 APC Sal -, ( ) Sal -, 3 500 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 89145 0123 89125 0125 51104 0131 52140 0122 Sample 1 2 3 3 Table 3 Determination of salicylate in human urine Potentiometry a Added/ (mmol L - 1 ) Found/ (mmol L - 1 ) Recovery/ % 0 0 0 2 0 0 0 4 0 0 0 6 a Mean of four determinations 0 93 1 13 1 45 1 84 1 25 1 87 100 0 97 5 103 3 Colorimetry [24 ] Found/ (mmol L - 1 ) Recovery/ % 0 85 1 06 1 56 1 94 1 21 1 82 105 0 95 0 101 7 References 1 Morf, W E The Principles of Ion2selective Eletrodes and of Membrane Transport, Akademiai Kiado, Elsevier, Amsterdam, New York, 1981 2 Sollner, K ; Shean, G M J Am Chem Soc 1964, 86, 1901 3 Pranitis, D M ; Telting2Diaz, M ; Meyerhoff, M E Crit Rev Anal Chem 1992, 23, 163 4 Hofmeister, F Arch Exp Pathol Pharmakol 1888, 24, 247 5 Daunert, S ; Bachas, L G Anal Chem 1989, 61, 499 6 Daunert, S ; Wallace, S ; Florido, A ; Bachas, G Anal Chem 1991, 63, 1676 7 Matais, R ; Cousin, J ; Soia, F Biophys Acta 1977, 467, 357 8 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, 535 9 Schulthess, P ; Ammann, D ; Simon, W ; Caderas, C ; Stepanek, R ; Krautler, B Helv Chim Acta 1984, 67, 1026
2196 Vol 60, 2002 10 Schulthess, P ; Ammann, D ; Krautler, B ; Caderas, C ; Stepanek, R ; Simon, W Anal Chem 1985, 57, 1397 11 Yuan, R ; Song, Y2Q ; Chai, Y2Q Talanta 1999, 48, 649 12 Yuan, R ; Chai, Y2Q ; Liu, D Anal Chem 1993, 65, 2572 13 Badr, I H A ; Meyerhoff, M E ; Hassan, S S M Anal Chim Acta 1996, 321, 11 14 Liu, D ; Shen, G2L ; Yu, R2Q Analyst 1996, 121, 1495 15 Zhi, Z2Q ; Yuan, R ; Ying, M ; Song, Y2Q ; Shen, G2L ; Yu, R2Q Talanta 1998, 46, 943 16 Bodie, E D Inorganic Synthesis, Vol 18, Science Press, Beijing, 1983, p 46 (in Chinese) (Bodie, E D,,,, 1983, p 46 ) 17 Horning, E C Organic Synthesis Coll, Vol, Wiley, New York, 1955, p 140 18 Anker, P ; Wieland, E ; Ammann, D ; Dohner, R E ; Asper, R ; Simon, W Anal Chem 1981, 53, 1970 19 Li, Z 2Q ; Shen, G2L ; Yu, R2Q Anal Lett 1997, 30, 1455 20 Ma, S C ; Chaniotakis, N A ; Meyerhoff, M E Anal Chem 1988, 60, 2293 21 Liu, D ; Chen, W2C ; Shen, G2L ; Yu, R2Q Analyst 1996, 121, 1495 22 Chaniotakis, N A ; Park, S B ; Meyerhoff, M E Anal Chem 1989, 61, 566 23 Pharmacopeia Committee of the Ministry of Health of China, Chinese Pharmacopeia, Vol, Chinese Health Press, Beijing, 1985, p 4 (in Chinese) (,,,,, 1985, p 4 ) 24 Trinder, P J Biochem 1954, 57, 301 (A0204152 LI, L T ; LING, J )