Methods have been developed for the analyses of the minor high-boiling bases of smoke. Fused silica glass capillary columns coated with Superox-4 were prepared and used successfully for the GC analyses of the basic fraction of smoke, containing compounds covering a wide range of volatility and polarity (nicotine to norbarman). The Superox-4 capillary column also produced an excellent separation of the numerous Nacylalkaloids, which have been reported in tobacco and tobacco smoke. Several new N -acylalkaloids are reported. The described methodology should be a great asset in future isolation and identification studies of these and other, as yet to be characterized, minor bases of smoke and leaf.© 1984, Walter de Gruyter. All rights reserved.