There are numerous methods of extraction. The industry standard (at least in my experience) is the use of ketones to separate the capsaicin crystals from the pepper. Capsaicin and sugar have a strong semi-atomic bond to each other, and the ketones put the capsaicin in solution whilst leaving the sugar behind. However, the down side is having to remove the ketones from the solution (unless you enjoy blindness, central nervous system shutdown, renal failure and, oh yeah, death) so they can be consumed by bipeds. This process is also well-known for having a chemical or metallic taste, ick. There are various other forms of extraction methods, including the one you hinted at regarding vinegar and a semi-fermentation. This process is an interesting one, and there is information on how to do it on various websites. There are also distillation methods as well. But, before I put everyone to sleep, I'll stop here. If you are going to enter the world of extracts I caution you to take pre-emptive measures to ensure your own safety. The stuff you will be creating is not for the faint of heart, and can be quite dangerous if not done correctly. I understand you have a pretty good chemistry background, but even so, never underestimate the power of our friend capsaicin, especially when in a concentrated form. Best of luck with your endeavor.