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Not really going to make too much difference either way I would think., but if you smoke before searing you may get more smoke penetration, which is a good thing.
No sear for Me...rubbed mine down with favorite rub..in the fridge overnight, on the smoker reached 150 F, foiled it.. till it reached 205 F. set in cooler for one hour..unwrapped and it fell apart..nice and juicy..no pics so I guess it never happened.
The smoke ring is caused by A nitric acid build up in the SURFACE of meat.. Nitric acid is formed when nitrogen dioxide (a gas..not visible smoke) from wood combustion in smoke mixes with water in the meat. So yes...Basically it is a chemical reaction between the smoke and the meat. This reaction however is mostly tasteless discoloration, and really has nothing to do with smoke penetration...Smoke particulates (ash, soot, etc.) are much to big to penetrate the surface of meat..They lay on the surface....HTH