The relative significance of multiple pathways in peroxyoxalate chemiluminescence reactions

被引:11
作者
Lee, JH [1 ]
Lee, SY [1 ]
Kim, KJ [1 ]
机构
[1] KOREA UNIV,DEPT CHEM,SEOUL 136701,SOUTH KOREA
关键词
chemiluminescence; peroxyoxalate chemiluminescence; multiple pathways;
D O I
10.1016/0003-2670(96)00100-6
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
Chemiluminescence (CL) from fluorophores generated by the reaction of bis(2,4-dinitrophenyl)oxalate (DNPO), H2O2, and several bases have been examined for the identification of multiple pathways. When the intensity of PO-CL (peroxyoxalate chemiluminescence) vs. time was measured under low base concentration in acetonitrile, two distinctive emission maxima, a fast decaying peak and a slowly decaying peak, were observed. The fast decaying first peak was predominant over the slowly varying peak at high concentration of DNPO and H2O2 and at low base concentration, and might be formed by the direct reaction of hydroperoxy oxalate ester (X) and fluorophore. When another set of the intensity vs. time was measured at high base concentration in ethylacetate containing 5% tert-butylalcohol, there also appeared two different peaks, a slowly decaying peak and a sharply decaying peak. The slowly decaying peaks in both sets of experiments were produced by base-catalyzed nucleophilic reaction of DNPO with X. The sharply decaying peak in the latter experiment could be dependent on the relative basicity of the donor, X, and acceptor, base. Based on the those observations a scheme is suggested that describes three reaction pathways.
引用
收藏
页码:117 / 126
页数:10
相关论文
共 28 条
[1]   MULTIPLE INTERMEDIATES GENERATE FLUOROPHORE-DERIVED LIGHT IN THE OXALATE PEROXIDE CHEMILUMINESCENCE SYSTEM [J].
ALVAREZ, FJ ;
PAREKH, NJ ;
MATUSZEWSKI, B ;
GIVENS, RS ;
HIGUCHI, T ;
SCHOWEN, RL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (20) :6435-6437
[2]  
Burr J. R., 1985, CHEMI BIOLUMINESCENC, P245
[3]   NATIVE PEROXYOXALATE CHEMILUMINESCENCE FROM THE REACTION OF BIS(2,4-DINITROPHENYL) OXALATE AND HYDROGEN-PEROXIDE PERTURBED BY NONFLUOROPHORES [J].
CAPOMACCHIA, AC ;
JENNINGS, RN ;
HEMINGWAY, SM ;
DSOUZA, P ;
PRAPAITRAKUL, W ;
GINGLE, A .
ANALYTICA CHIMICA ACTA, 1987, 196 :305-310
[4]   CHEMI-LUMINESCENCE FROM REACTIONS OF BIS(PENTACHLOROPHENYL)OXALATE, HYDROGEN-PEROXIDE AND FLUORESCENT COMPOUNDS - KINETICS AND MECHANISM [J].
CATHERALL, CLR ;
PALMER, TF ;
CUNDALL, RB .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1984, 80 :823-836
[5]  
CHANDROSS EA, 1963, TETRAHEDRON LETT, V12, P761
[6]   OXALATE HYDROGEN-PEROXIDE CHEMILUMINESCENCE REACTION - A F-19 NMR PROBE OF THE REACTION-MECHANISM [J].
CHOKSHI, HP ;
BARBUSH, M ;
CARLSON, RG ;
GIVENS, RS ;
KUWANA, T ;
SCHOWEN, RL .
BIOMEDICAL CHROMATOGRAPHY, 1990, 4 (03) :96-99
[7]   PROPERTIES OF BASES IN ACETONITRILE AS SOLVENT .4. PROTON ACCEPTOR POWER AND HOMOCONJUGATION OF MONO- AND DIAMINES [J].
COETZEE, JF ;
PADMANAB.GR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1965, 87 (22) :5005-&
[8]   INVESTIGATION OF THE QUENCHING OF PEROXYOXALATE CHEMILUMINESCENCE BY AMINE SUBSTITUTED COMPOUNDS [J].
DEVASTO, JK ;
GRAYESKI, ML .
ANALYST, 1991, 116 (05) :443-447
[9]  
Givens RS, 1989, CHEMILUMINESCENCE PH, P125
[10]   LOW-LEVEL INTERFERENCES IN PEROXYOXALATE CHEMILUMINESCENCE [J].
GOOIJER, C ;
VELTHORST, NH .
BIOMEDICAL CHROMATOGRAPHY, 1990, 4 (03) :92-95