A very simple molecular cation, 4-(4-dimethylaminophenyl)-2,6-diphenylpyrylium, has been demonstrated to have a function of molecular half-adder and half-subtractor according to the detectable spectroscopic changes of the molecular system in response to the inputs of acid and base. Distinct algebraic operations can be performed in this reconfigurable molecular logic system.
A polyethylene glycol (PEG)-supported NADH model as a novel organic reductant was designed and synthesized. The reductions of various α,β-unsaturated ketones by the PEG-supported NADH model were examined,and the results showed that the reductions completely and quickly proceed with no catalyst at ambient temperature. The main advantages of this liquid-like PEG-supported NADH model are easy workup,and an optimal potential for recycling use and solvent-free for use in reactions.
Heterolytic and homolytic C D bond dissociation energies of three NADH models: BNAH-4,4-d 2 , HEH-4,4-d 2 and AcrD 2 in acetonitrile were first estimated by using an efficient method. The results showed that the heterolytic C D bond dissociation energies are 65.2, 70.2, and 81.9 kcal/mol and the homolytic C D bond dissociation energies are 72.66, 70.69, and 74.95 kcal/mol for BNAH-4,4-d 2 , HEH-4,4-d 2 , and AcrD 2 , respectively. According to the bond dissociation energy differences of isotope isomers, an interesting conclusion can be made that the primary kinetic isotope effects are dependent not only on the zero-point energy difference of the isotope isomers, but also on the types of C D bond dissociations, and the C D bond homolytic dissociations should have much larger primary kinetic isotope effects (26.9 28.8) than the corresponding C D bond heterolytic dissociations (3.9-5.4).
