82-02.fm

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1 w y wz 8«( 2y) 00~00, 2005 J. of the Korean Society for Environmental Analysis Calix[6]arene w k š w *Á x Á Á«ƒm w yw, *w w yw Cesium Ion Selective Solid Contact Electrodes Based on Calix[6]arene Won-sik Han*, Hyun-jin Lee, Seon-Kyoung Son, and Young-soon Kwon Dept. of chemistry, Catholic university of Korea, Yokkok 2-dong, Kyonggi-do, Korea *Dept. of chemistry, Hanseo university, Seosan Chungnam , Korea Cesium ion selective solid contact electrodes have been fabricated from Pt substrate and () electro-conductive layer and PVC matrix, Calix[6]arene as ionophore, KTpClPB as lipophilic additive and DBS as plasticizer. The limited response range of this electrode was M of cesium ion in sample solution with a mean Nernstian slope of mv/decade between ph 5.4 and The stabilization time was 2.7 hrs. with the response time of 109 sec. The selectivity coefficients for monovalent cations were determined. Especially when the electrodes were directly applied to the artificial human serum, we could get the satisfying results. Lifetimes of at least 3 months were estimated. Key words: Ion selective solid contact electrodes, Cesium, Cailix[6]arene 1. w h w y ƒ j w ƒ w yw š š w ƒ š. p, w ƒw y w ƒ ù y œ w w ƒ w w v ƒ š w k v w. 1,2,3) ƒ w ù, l œ œ l ƒ w, x. xw ü œ š ú j x w. t ƒ p p œ sw. p, -137 ü ƒ y» w ù. ƒ ùp ù e w yw w»». ƒ w ƒ w d wš w w ƒ v š w. y Calix[6]arene w y w w 4,5) Harris 6) Calix[6]arene ester w k 10 M¾ d 4 w. ionophore Calix[6]arene hexaacetic acid hexaacetyl ester w k š w wš w û ¾ d t w x ww. To whom correspondence should be addressed.

2 Calix[6]arene w k š x 2.1.»» Aniline (C 6 H 5 NH 2, 99.5%), bis(2-ethylhexyl)tetrakis (4-chlorophenyl)borate(KTpClPB, 98%), bis(2- ethyhexyl) adipate(doa, 99%), sodium hydroxide (NaOH, %), 2-nitrophenyloctylether (NPOE, 99 %), tetrahydrofuran(thf, 99.9%), Tris(hydroxymethyl) aminomethane(tris, 99.9%) Aldrich w, Cs ionophore I(calix[6]arene hexaacetic acid hexaacetyl ester) Fluka w. x w š x mw k w xw. d EDS l Ion analyzer (model 235, Mettler-Toledo Ltd. England) w d w Mettler-Tolede Inrab 413 Double-juncion e Orion (Orion Research. U.S.A.) d w. y Bi-potentiostat(EG & G model 362) X-Y recorder(eg & G RE0150) w PVC yw PVC yw, e ƒ, ƒ, THF w. PVC w e ƒ KTpClPB w. ƒ DOA, DOS, NPOE, DBS, DOP w ƒ yw g. yw THF 5 ml ww z 3 ml THF { w PVC layer w. x w calix-[6]- arene hexaacetic acid hexaacetyl ester w s d š x w. 7,8) 2.3. d ƒ ü ùkü 25 ±0.2 o C Ion analyzer w d w. d Mettler-Toledo Inrab 413 w d w. d y z y ƒ 0.2 mv w k ƒ 1 w w w œ x ü Cs ion x œ x 2.0 mm CaCl 2 /0.8 mm MgCl 2 /4.5 mm KCl/0.05 mm NH 4 Cl/4.7 mm glucose/2.5 mm Urea w, œ x w CsCl w, Cs ion 10 1 M 10 6 M y j d w. 3. š () () d w wš,» w yw (cocktail solution) d w cesium ion selective SCEs w. Ionophore calix[6]arene hexaacetic acid hexaacetyl ester w ionophore w w 10 M l 1 10 M¾ 7 Cs w d w. 6ƒ ƒ w yw sw y g»» š w yw. yw yw cesium g e ƒ KTpClPB g, ƒ 0.18 g, PVC 0.09 g ƒw ƒ w ùkü. Table 1 ùkü, w ƒ, () d ƒ, ƒ DOA DBS w»» ƒ ƒ w DOA ƒ w mv/decade»» 10 M 6.38 ùküš DBS ƒ w mv/decade»» M ùküš. () d ƒ, ƒ NPOE DOP w»» ƒ ƒ w š NPOE ƒ w mv/decade»» 10 M 6.02 ùküš DOP ƒ w mv/decade»» 10 M 5.92 ùküš. 14ƒ»» ƒ ƒ (1, 2, 11, 13 ) kw w w w d w. w d FIM(Fixed Interference Method) w d w,

3 64 w Á x Á Á«Table 1. Response characteristics of SCEs with various composition in PVC layer Ionophore 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g 0.001g DOA 0.18g g DBS g g DBP g g DOP g g DOS g g 0 0 NPOE g 0.18g g 0.18g PVC 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g 0.09g KTpClPB g g g g g g g g g g g g g g THF 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL 5mL Electroconductive layer Slope (mv/decade) Limit range(10 M) Table 2. The response characteristics of SCEs based on Cs ionophore in Tris buffered CsCl solution with 0.13M interference cation background (where, Rb is M). -logkcs,j () () DOA DBS NPOE DOP j=li j=na j=k j=rb w Table 2 ùkü. () () Li sw Cs w f ù 1 ü, j» ƒ ƒw w sw ü Cs k. p, Rb wƒ ƒ w ùkû Cs Rb j»ƒ w ionophore e w w». () DBS ƒ w 2 DOA w 1 w ùküš, () DOP w 11 NPOE ƒ w 13 w ùküš. Fig. 1 d ùkü w 2 11 w w z ùküš»» () () w š 2 w x wwš w. y () z, Fig. 1. The response characteristics of Cs ion selective SCEs in CsCl sample solution with different electro-conductive mer. - ù- () (4 electrode-dop) - þ- () (2 electrode- DBS). k 10 3 e z, 20 z l d w. e z ƒ w ƒ 2.7 z yƒ 0.2 mv w y ƒ ùkùš. x 10 1 M CsCl ü 3 y k z d w (Fig. 2) M CsCl 50 ml 10 1 M CsCl 50 ml ƒw z, ƒ d w w. ƒƒ ph M CsCl ph Tris ü

4 Calix[6]arene w k š 65 Fig. 4. Stabilization range of Cs selective () 2 electrode SCEs in ph buffer 10 1 M Tris solution with 10 3 M CsCl. Fig. 2. The stabilization time of Cs ion selective () SCEs in 10 3 M CsCl solution (2 electrode). Fig. 3. The response time of Cs ion selective () SCEs when 50 ml 10 1 M CsCl solution injection into 10 3 M CsCl ph Tris buffered sample solution Tris w ƒ z d y 109 (Fig. 3) ¼ ƒ š ù z 0.1 mv/sec. w ùküš T 90 1 ü d. Fig. 4 ph ü ùkü. ph 5.4 ph 10.3 ü w d scale w, ù» w ùkü. x ü w Cs w» w œ x ü Fig. 5. The response characteristics of () (electrode 2) SCEs in Tris buffered CsCl solution -þ-, and artificial serum -ù-. Cs w x w Fig. 5 ù kü. x w d, œ x w ùkü š. x w w»»ƒ Tris-CsCl ü w w š,»», mv/decade ƒw š, x ü cesium w.

5 66 w Á x Á Á«4. () () / d w Cesium ion selective Solid Contact Electrodes w. Ionophore calix[6]arene w ƒ DBS, DOP, DOA, DOS, NPOE, DBP w. d () wš ƒ DBS w w ùkü»» mv/decade ùkûš. w 10 M š d PVC d g ionophore : 0.18 g DBS : 0.09 g PVC : g KTpClPB. y 2.7 hr, 109 sec. ü. ph w d w ph 5.4 ph 10.3 w w w š j»ƒ w Rb w ƒ ƒw y w (Rb >K >Na > Li ). œ x ü mv/ decade w»», 10 M 5.40 w š x ü Cs ion w ƒm w. š x 1. H. Freiser, Ion selective electrodes in Analytical chemistry; Plenum Press, New york, Worth, H.G.J., Analyst, 1988, 113, Solsky, R.L., Anal. Chem., 1988, 60, Gusche, C.D., Calixarenes, RSC Monographsin Supramolecular Chemistry No. 1, The Royal Society of Chemistry, Cambridge, Arnaud-Neu, F., Collins, E. M., Deasy, M., Ferguson, G., Harris, S. J., Kaitner, B., Lough, A. J., McKervey, M. A., Marques, E., Ruhl, B. L., Schwing-Weill, M. J., and Seward, E. M., J. Am. Chem. Soc., 1989, 111, A. Cadogan, D. Diamond, M. R. Smyth, G. Svehla, M. A. Mckervey, E. M. Seward and S. J. Harris, Analyst, 1990, 115, W.S. Huang, B.D.Humphrey and A.G. MacDiarmid, J. Chem. Soc. Faraday Trans. 1, 1986, 82, A. Michalska, A.H ulanichi and A. Lewenatam, Microchemical journal, 1997, 57, 59.