Not quite pioneering... I read a thread about alternative ways of getting high of all kinds of substances that were practiced during the Soviet times. Like putting shoe polish on bread, letting it sit for a day. Scrape off the polish and you'll have a jolly good time after eating the bread. Or drinking octane 76 gasoline, some trained organisms can live with it... Heating washing powder for vapours; spraying some certain pesticide into beer; drinking wood stain (which gives a nice shine and tone to the skin); shaving the head, applying a rag with vodka or nitro solvent and a warm hat...
But there was this talk about a certain factory that produced various alcoholic beverages and that was heavily guarded, every leaving worker took a breathalyzer test (or just breathed towards the guard), trucks searched... The nurse of the factory provided a service that included pure alcohol and an enema for a certain fee. They wrote you still had to clean the test in fifteen minutes or the you'd fail the test... Worked like 100 grams orally but generally without a hangover! Supposedly the walls of the rectum absorb everything very well, no middle man (the digestive system) that dilutes everything...