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Compliance with future ultra-low nitrogen oxide regulations with diesel engines requires the fastest possible heating of the exhaust aftertreatment system to its proper operating temperature upon cold starting. Late post injections are commonly integrated into catalyst-heating operating strategies. This experimental study provides insight into the complex interactions between the injection-strategy calibration and the tradeoffs between exhaust heat and pollutant emissions. Experiments are performed with certification diesel fuel and blends of diesel fuel with butylal and hexyl hexanoate. Further analyses of experimental data provide insight into fuel reactivity and oxygen content as potential enablers for improved catalyst-heating operation. A statistical design-of-experiments approach is developed to investigate a wide range of injection strategy calibrations at three different intake dilution levels.