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Heavy-duty engine experiments were conducted to explore reactivity controlled compression ignition (RCCI) combustion through addition of the cetane improver di-tert-butyl peroxide (DTBP) to pump gasoline. Unlike previous diesel/gasoline dual-fuel operation of RCCI combustion, the present study investigates the feasibility of using a single fuel stock (gasoline) as the basis for both high reactivity and low reactivity fuels. The strategy consisted of port fuel injection of gasoline and direct injection of the same gasoline doped with a small volume percent addition of DTBP. With 1.75% DTBP by volume added to only the direct-injected fuel (which accounts for approximately 0.2% of the total fueling) it was found that the additized gasoline behaved similarly to diesel fuel, allowing for efficient RCCI combustion. The single fuel results with DTBP were compared to previous high-thermal efficiency, low-emissions results with port injection of gasoline and direct injections of diesel.