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Negative Valve Overlap (NVO) is a potential control strategy for enabling Low-Temperature Gasoline Combustion (LTGC) at low loads. While the thermal effects of NVO fueling on main combustion are well-understood, the chemical effects of NVO in-cylinder fuel reforming have not been extensively studied. The objective of this work is to examine the effects of fuel molecular structure on NVO fuel reforming using gas sampling and detailed speciation by gas chromatography. Engine gas samples were collected from a single-cylinder research engine at the end of the NVO period using a custom dump-valve apparatus. Six fuel components were studied at two injection timings: (1) iso-octane, (2) n-heptane, (3) ethanol, (4) 1-hexene, (5) cyclohexane, and (6) toluene. All fuel components were studied neat except for toluene - toluene was blended with 18.9% nheptane by liquid volume to increase the fuel reactivity.