Topic
Reaction mechanisms research, explained
6 open-access reaction mechanisms studies, each with a flashcard deck and a quiz.
- Gas-phase rates of heme-model olefin epoxidation
FT-ICR and DFT show iron(IV)–oxo porphyrin cation radicals epoxidize olefins with rates that track substrate ionization energy.
- H2O2 is not born at the air–water droplet surface
Sensitive assays show microdroplet H2O2 comes from dissolved O2 reacting at solid–water interfaces, not from ultrahigh fields at the air–water surface.
- Why gold carbenes hit phenol para-C–H
DFT plus deuterium controls show (PhO)3PAu carbenes add at phenol para-C, then two waters shuttle the proton, beating O–H insertion.
- Direct SN2 rebound survives bulky alkyl iodides
Even with extra methyl groups on the alkyl iodide, Cl− and CN− still show a direct backward SN2 rebound channel at high collision energy rather than fully statistical dynamics.
- Why acetaldehyde kills the DERA aldolase
Crotonaldehyde, the acetaldehyde aldol product, covalently bridges catalytic K167 to nearby C47; a C47M mutant survives 300 mM acetaldehyde.
- Ultrasound microdroplets make H2O2 from dissolved O2
Water-in-hexadecane droplets under 40 kHz ultrasound produce H2O2 at 0.24 mM min−1, almost entirely at the oil–water interface via superoxide from dissolved oxygen.