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The fact is that Psychotria viridis et al were never used singly because they didn't produce any effect when taken orally.

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I cannot speak for P. Viridis, but Banisteriopsis Cappi does have an effect when taken by itself.... at least for me.  It is not the mind bending DMT experience, but there is an altered state of perception from the vine itself.  It is a subtle, I am in synch with everything, sort of feeling.

There are also DMT snuffs (Yopo, Vilva, and Cahoba) which do not require the use of an MAOI.

The plants containing DMT and those containing MAOIs could easily have been discovered independently.  There is no reason that two random, unknown plants had to be combined to form Ayahuasca.  It makes much more sense that two known plants were mixed and Ayahuasca was discovered.

I don't believe that the discovery was a pure accident.  They already knew about the various plants that alter our perceptions.  It is only natural that somebody eventually tried to make a 'superbrew' by mixing them together and got lucky.

I have read reports that MAOIs also increase the effects of smoked DMT.  I would assume the same would be true for snuffs.  If a shaman noticed this effect why not try to find a different method of consumption.  From what I have read, the snuffs are very painful and unpleasant.

Of course, maybe alien elves came out of the shadows and taught the shamans what to mix.  None of us were there (or remember being there) so we will really never know... 

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It is as if they knew about the molecular properties of plants and the art of combining them, and when one asks them how they know these things, they say their knowledge comes directly from hallucinogenic plants."

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