Electrochemiluminescence Detection of Primary Amines Using Tris(bipyridine)ruthenium(III) after Derivatization with Divinylsulfone

Aliphatic primary amines are industrial chemicals with a wide variety of applications. For the determination of these substances, HPLC has recently been used; it has several advantages over other analytical methods, including high selectivity and sensitivity. On the other hand, an electrochemiluminescence (ECL) method has been developed as a highly sensitive method for HPLC detection.)-3 However., there is still no established methodology for the determination of aliphatic primary amines. The Tris(bipyridine)ruthenium(II) (Ru(bpy)32+) ECL system is useful for a selective, sensitive determination of oxalates4'5, indoles1'6, and trialkylamines2'' in biological and pharmaceutical samples. We previously reported that by using this system alicyclic tertiary amines8 were detectable at the pmol level, althouth the CL intensity of aliphatic primary amines was very low compared with that of the tertiary amines; and they could only be detected at a level of about 1000-times lower than that of tertiary amines.' In this paper we discuss the CL detection of some primary amines using a cycloaddition reaction of the amines with divinyl sulfone (DVS) caused by electrogenerated Ru(bpy)33t Furthermore, precolumn derivatization HPLC of the amines using LC postcolumn reaction detection with this CL system is described.