30 HUAXUE) 5 (FENXI 2002 5 Chinese Journal of Analytical Chemistry 513 517 3 (, 361005) (, 361005) [ Ru(bpy) 3 Cl 2 ] ( ECL), ECL, 0. 05 molπl (ph = 9. 0), (METH) ECL 6. 8 10-11 6. 8 10-3 molπl, 2 10-16 mol/ L, ;METH (APM) ; ECL, :,,,,,,,, 1 1987 Noffsinger [ Ru (bpy) 2 + 3 ] ( ECL) [1 ], Ru (bpy) 2 + 3, [2,3 ] (FIA), ECL,,ECL FIA (HPLC) (METH),,,,,,,METH ( GC) [4 ], 2( GC2MS) [5 7 ] (polarization fluoroimmunometry) [8 ],HPLC [9 ] (CZE) [10 ],, ECL, :,,,, METH (APM) 2 2. 1 Ru(bpy) 3 Cl 2 6H 2 O Aldrich, ; ; 2001206220 ;2002201207 (No. 2987022)
514 30 2. 2 7524B ( ) 1. 0 cm 1. 5 cm,,50 m, 1. 5 L [11 ] (22. 1 mm 2 ),,AgΠAgCl ( KCl ) FIA HL22 ( ), 30 L 7021 GD21 ( ) Model AFRDE5 Bi2Potentiostat ( Pine Instrument Company, USA) 2. 3 6. 8 10-3 molπl ; 1. 0 10-2 molπl, 0. 05 molπl (ph 6. 5 ph 11. 0), 0. 1 mmolπl Ru (bpy) 3 Cl 2,,, ( Echrom 98, ) 3 3. 1 3. 1. 1 METH APM ( CV) ECL METH APM CV 0 1. 9 V ( vs. SCE) METH APM ( 1), 1. 06 V ( vs. SCE) 1 CV Fig. 1 Voltammetric response at glassy carbon electrode ( GC) a.0. 1 mmolπl Ru ( bpy) 2 + 3 + ( buffer) ; b. 0. 1 mmolπl Ru(bpy) 2 + 3 + ( buffer ) + 0. 1 mmolπl (amphetamine) ;c. 0. 1 mmolπl Ru (bpy) 2 + 3 + ( buffer) + 0. 1 mmolπl ( methamphetamine ) (buffer) :0. 05 molπl NaH 2 PO 4 2NaOH(pH 9. 0) ; ( scan rate) : 100 mvπs 2 CV Fig. 2 Voltammetric response of some amine compounds a. (buffer) + 0. 1 mmolπl (codeine) ; b. (buffer) + 0. 1 mmolπl (cocaine) ; c. ( buffer) + 011 mmolπl (morphine) ;d. (buffer) + 0. 1 mmolπl (caffeine) ( buffer) : 0. 05 molπl NaH 2 PO 4 2NaOH (ph 9. 0) ; (scan rate) :100 mvπs Ru (bpy) 2 + 3 METH APM Ru (bpy) 2 + 3, METH, METH APM Ru (bpy) 2 + 3, Ru (bpy) 2 + 3, METH APM
5 : 515 METH ECL APM, + 1. 0 V( vs. AgΠAgCl), Ru (bpy) 2 + 3 METH ECL Ru (bpy) 2 + 3 1. 30 V, APM ECL, Ru (bpy) 2 + 3,Ru (bpy) 3 + 3,,,,Ru (bpy) 2 + 3 Ru (bpy) 3 + 3 ECL,,ECL, 3. 1. 2 CV, ( 2) : + 0. 9 V + 1. 1 V,, + 0. 9 V CV [12 ], Ru (bpy) 3 + 3 [13 ], Ru (bpy) 3 + 3, Ru (bpy) 2 + 3 3,,, Ru (bpy) 2 + 3 ECL 3. 2 ECL Noffsinger [1 ],ECL,, > >, ECL < < CH 2 CH CH 3 CH 2 CH CH 3 NHCH 3 Methamphetamine 3 NH 2 Amphetamine Fig. 3 Molecular structures of methamphetamine and amphetamine :METH ECL APM 2 METH, APM ( 3),, METH Ru (bpy) 3 + 3, Ru (bpy) 2 + 3 3,,ECL,,, Ru (bpy) 3 + 3, ECL, ( 4) ECL :6 ECL > >, > > METH > APM - OH - CH 3, 10 Greenway [14 ] ECL 8, - CH 3 N,,,,, Ru (bpy) 3 + 3, ECL,,, Ru (bpy) 3 + 3, 4 Fig. 4 Molecular structures of codeine morphine cocaine and caffeine
516 30 3. 3 3. 3. 1 METH 0. 13 1. 40 mlπmin ECL, : Ru (bpy) 2 + 3 Ru ( bpy) 3 + 3, METH, Ru (bpy) 3 + 3,,,, 0. 40 mlπmin 3. 3. 2 ph ph 2ECL,,METH ECL, ; 0. 2 molπl,, 0. 05 molπl, 0. 05 molπl ph (5. 8 11. 0),, ph 9. 0 METH,,, H +,OH - O 2, Ru (bpy) 2 + 3 Ru (bpy) 2 + 3,, ph Ru (bpy) 2 + 3 3 ph = 9. 0 3. 3. 3 ( ) ( ) ( 220 ) ECL,,,, ECL ; ;, :,,,, ECL, Ru (bpy) 2 + 3,,,,METH 3. 3. 4,METH, 6. 8 10-11 6. 8 10-3 molπl, y = 0. 2762 x + 3. 5269, y (mv) lg H, x (molπl) lg C, R 2 0. 99,( SΠN = 2) 2 10-16 molπl, METH 1. 0 10-8 molπl 2. 9 %( n = 6), 1 1 ( n = 6) Table 1 Determination results and recoveries of samples( n = 6) Sample Found Π10-3 (molπl) Content ( %) RSD ( %) Added Π10-3 (molπl) Found Π10-3 (molπl) Recovery ( %) 1 # 8. 54 87. 2 0. 8 2. 8 6. 84 15. 79 106. 2 1. 7 2 # 8. 13 76. 8 1. 2 4. 1 6. 84 13. 91 94. 5 3. 1 3 # 9. 50 92. 6 0. 6 2. 8 6. 84 16. 09 100. 0 3. 7 4 # 9. 49 88. 5 1. 1 1. 8 6. 84 17. 02 105. 7 2. 4, GC2MS,,, [15 ],, ECL 3. 4 6, : ECL,, ECL, :
5 : 517 ECL,, CV References 1 Noffsinger J B, Danielson N D. Anal. Chem., 1987, 59 : 865 868 2 Brune S N, Bobbit D R. Talanta, 1991, 38 : 419 425 3 He L, Cox K A, Danieison N D. Anal. Lett., 1990, 23 : 195 201 4 Cox R A, Crifasi J A, Dickey R E. J. Anal. Toxicol., 1989, 12 : 224 226 5 Ellerbe P, Long T, Welch M J. J. Anal. Toxicol., 1993, 17 : 165 170 6 Yao Yanhong(),Kan Yuhe (),Wang Sihong (). The World of Chemistry ( ),1999, 11 : 568 570 7 Che Zongling(). J. Analytical Test ( ),1997, 16 (4) : 45 46 8 Cody J T, Schwarzhoff R. J. Anal. Toxicol., 1993, 17 : 26 30 9 Legua C M, Falco P C, Cabeza A S. J. Chromatogr. B, 1995, 672 : 81 88 10 Chen Wei ( ),Chen Xi ( ),Sun Zhenhua (),Wang Xiaoru(). Journal of Xiamen University ( Natural Science) ( ( ) ),2000, 39 (1) : 62 66 11 Chen X, Sato M J. Flow Inj. Anal., 1995, 12 (1) : 54 65 12 Sun Shigang(). Electrochemistry Study Methods (), Xiamen ( ) : Xiamen University Press( ), 1998 : 83 84 13 Leland J K, Powell M J. J. Electrochem. Soc., 1990, 137 : 3127 3131 14 Greeway M G, Knight A W, Knight P J. Analyst, 1995, 120 : 2549 2552 15 Sun Jing ( ),Zhao Jingzhen (). The Determination of Narcotic ( ). Center of Identification of Material Evidence of Police ( ),1990 : 1 8 Study of the Electrochemiluminescence Based on Tris( 2,2 2bipyridyl) ruthenium Χ and Some Nervous Amine Compounds Using Flo w Injection Analysis Chen Xi 3, Li Meijin, Li Zhen, Yi Changqing, Wang Xiaoru ( The Key Laboratory of Analytical Sciences of Ministry of Education, Department of Chemistry, Xiamen University, Xiamen 361005) Wang Bo ( Institute of Criminal Science and Technology of Xiamen, Xiamen 361005) Abstract A new electrochemiluminescence ( ECL) method for the detection of methamphetamine (METH) and some nervous amine compounds is described. The ph of mobile phase and applied potential on glassy carbon electrode obviously influance the intensity of the ECL of METH. The mobile phase was selected as 0. 1 mmplπl Ru (bpy) 3 Cl 2 in 0. 05 molπl NaH 2 PO 4 2NaOH (ph 9. 0) buffer. The studies of the effect of applied potential and flow rate on ECL showed that METH gives the brightest light emission at the potential of + 1. 55 V and at the flow rate of 0. 4 mlπmin. A linear relationship was obtained from 6. 84 10-11 6. 84 10-3 molπl with a correlation coefficient of R 2 = 0. 9906 and the detection limit was 2 10-1 molπl under the experimental condition. The effect of surfactants on ECL was studied. The work also included the study of ECL of related compounds such as codeine, cocaine, morphine and so on. Cyclic voltammetry showed that their different oxidation currents might lead to their different ECL intensity. The method was simple, economical, sensitive, useful and provided some evidences for scout cases. Keywords Electrochemiluminescence, flow injection analysis, tris (2,2 2bipyridyl) ruthenium Χ, methamphetamine, codeine (Received 20 June 2001 ; accepted 7 January 2002)