Successfully designing and making effective of use of the next generation of liquid fuels, which will be derived from a range of biomass and fossil sources, requires an understanding of the interactions between structurally similar and dissimilar fuel components when utilised in current engine technology. Interactions between fuel components can influence the release of energy and production of harmful emissions in compression ignition combustion through determination of the autoignition behavior of the fuel. This paper presents experimental studies carried out in a single-cylinder engine supplied with a range of binary mixture fuels to investigate the effect of fuel component interactions on autoignition in direct injection compression ignition. A range of binary mixtures consisting of toluene and n-heptane and also 1-octene and n-octane were tested so as to observe respectively the effect of an aromatic compound and an alkene on n-alkane combustion and emissions. The engine tests were carried out at constant injection timing and they were repeated at constant ignition timing and at constant ignition delay, the latter being achieved through the addition to the various fuels of small quantities of ignition improver (2-ethylhexyl nitrate). Increasing the presence of toluene in the toluene/n-heptane binary mixtures resulted in an increased ignition delay time and generated a distinct two stage ignition process. An increased level of 1-octene in the binary mixtures of 1-octene/n-octane was also found to increase ignition delay, though to a much lesser extent than toluene in the case of the toluene/n-heptane mixtures. Interactions between the fuel components during the ignition delay period appear important in the case of the toluene/n-heptane mixtures but not those of 1-octene/n-octane. At constant injection and constant ignition timings, the combustion phasing and the level of emissions produced by each binary mixture were primarily driven by the ignition delay time. With ignition delay equalised, an effect of adiabatic flame temperature on NOx production was visible. (C) 2013 The Combustion Institute. Published by Elsevier Inc. All rights reserved.