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Conversion of Harmine->Harmaline->THH by simple boiling (and storage?)

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endlessness

endlessness

Established member
Moderator Lab expert
It seems this conversion actually happens and has been documented in a couple of places. (edit: one home experiment with TLC testing seems to show no conversion happening)


McIlhenny et al 2009. Direct analysis of psychoactive tryptamine and harmala alkaloids in the Amazonian botanical medicine ayahuasca by liquid chromatography–electrospray ionization-tandem mass spectrometry. Journal of Chromatography A, 1216, 8960–8968

The data also suggest that prolonged heating/boiling of the ayahuasca preparations leads to inter-conversion of some of the components. This appears to occur to a significant degree for the changes seen in THH, harmine and harmaline levels between samples undergoing further heating to attain higher concentrations of the components (See Table 3). This phenomenon, an apparent acid-driven chemical reduction of harmine-to-harmaline-to-THH, has also been reported by Callaway et al. [28] and constitutes another source of potential variability of results among ayahuasca preparations.


(...) Solutions of the target compounds in water were stable for the period of time examined (6 months) when stored at −20 ◦ C and kept from exposure to light by use of amber vials. Similarly, ayahuasca samples were stable for the same period of time when retained under the same conditions. However, preliminary data (not shown) indicate that the ayahuasca preparations are susceptible to degradation and compound inter-conversion through
prolonged exposure to room temperature conditions and these changes are accelerated by exposure to light (data not shown) and changes in pH that occur as the preparations age. These and related data will be the subject of a forthcoming publication.
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and:

Callaway et al 2005. Phytochemical Analyses of Banisteriopsis Caapi and Psychotria Viridis. Journal of Psychoactive Drugs Volume 37, Issue 2, 2005

The average ratio of THH to harmine in the vegetals (traditional brews) was consistently near 1:1, from all sources (table 2), while this ratio was closer to 1:5 in a large survey of source plant material. It is presently unclear whether harmine and harmaline are being chemically reduced to THH during the acidic process of decoction, or if THH is simply more stable than the other two harmala alkaloids, which may be lost through decomposition, or a combination of both processes.
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Interesting enough, recently I tested some black caapi vine, just methanol soak, and it didnt seem to have any detectable harmaline. When I tested an extraction from the same vine, it did have detectable harmaline. Would be good to test this again, experimenting with different variables in the experimentation (like for example boil homogeneized plant material for longer or less, with acid or no acid, etc. McIlhenny et al never seemed to have published the other data about this interconversion of alkaloids. Edit: I tested this again with white caapi and the same happened, check caapi analysis thread. One more potential confirmation that this interconvertion is actually happening.

Some questions: Is the extended boiling done by indigenous people purposeful, because somehow intuitively or experientially they felt that brews with higher THH content was more beneficial? Shoud this be an invitation for extended boiling? Is it worth the energy spending in these days where ecological impact is an issue? Maybe the boiling also breaks down other components instead of just converting harmalas, so whats the cost/benefit like?

And some more chemically related: Due to the chemical bonds, is it less favourable for harmine to turn into harmaline, than to harmaline turn into THH ? Can one get an "optimum" ayahuasca alkaloid content by messing with cooking time/storage?

Regarding storage, while McIlhenny paper says storage affect alkaloid content, callaway paper says it did not affect content of one sample they monitored over 80 days, which only changed pH (becoming more basic) and started to ferment after a while, but alkaloid content stayed the same. Both papers seem to agree boiling does make that conversion, and no extra acid seemed to have been added on any brew.
 
Interesting, I have seen talk of something similar at the Ayahuasca forums but not in much detail. How do you feel about THH and It's benefit compared to the other Harmalas? Would you find it worth the extra time commitment when brewing?
 
Im not sure... For that question to be answered, it would have to be someone who would, for example, every week drink some aya in same setting and dosage, and after X number of weeks change the component ratio (or make a cycle, rotating over the different possibilities each week and repeating them over the months) , to account for natural effect variability.

Then one would after each trip write down effects, ideally answer some kind of questionnaire like in our experience survey link below the banner, and then we could maybe draw out some conclusions. Ideally it would be blind, the person would not know which is which until after taking and completing the questionnaire.

Ive drunk aya that was boiled for many hours like traditionally, Ive also had brews brewed for shorter time, and had great experiences (and hard moments) on all of them, so I cant say for myself.


Regarding THH, one interesting thread that came up not so long ago is a member who posted having taken pure THH and that it did NOT orally activate DMT (indicating no or very low MAOI action), but did have some different effects on its own. Jace Callaway has shown THH to be responsible for serotonin receptor platelets to increase (maybe accounting for anti-depressive action), but I dont think he also tested the other harmalas to show that they dont have same effects, so again no conclusions as of yet.

We need more people experimenting 8)
 
I founds calleway's piece quite interresting.

I am just speculating changes could happen during fermentation
 
I just edited the first post, now papers are also linked there

Callaway paper says fermentation did NOT change alkaloid content.

Callaway 2005 said:
One sample from the UDV was put on a shelf in the dark for 80 days at room temperature of 23C. There was no significant change in either alkaloid profile or composition during this time. Howhever, the acidic pH of this beverage gradually changed to neutral as it began to ferment over time. Thus, it is not unusual to detect the sweet smell of ethanol in batches of vegetal that are more than a few weeks old. The fiberous material in all vegetals will eventually settle out to form a thick sludge on the bottom of the container. Both the supernatant and the sludge are rich in alkaloids
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Yes.

I have to re-read publications, anybody remember of the top of their heads if rue was ever found naturally with THH? Because some extracted rue I analysed did have some THH, and so did burnt's.
 
wikipedia says that it doess contain THH in some small amounts :

en.wikipedia.org

Peganum harmala - Wikipedia

en.wikipedia.org en.wikipedia.org


edit :

i think this is the paper where the reference is taken from, it was posted in another thread here on nexus.
 

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Endless what a great find.

This is fascinating. This should actually be straight forward to investigate with simple TLC.
 
..i believe McKenna et al. 1984 MONOAMINE OXIDASE INHIBITORS IN SOUTH AMERICAN HALLUCINOGENIC PLANTS PART 1 shows that THH is not very potent oral MAOI by in-vivo studies, but i've lost access to the full paper..but smoked, or with more potent MAOIs it may well do something interesting..
 
Nen, I guess you mean this publication.

Most of the synthetic tryptamine derivatives that were assayed as MAOIs did exhibit some activity, but the I50 values were usually several orders of magnitude iower than those for the B-carboline derivatives. Interestingly, DMT showed the most MAOI activity of all the typtamine derivatives tested: Its I50 was comparable to tetrahydroharmine (THH), one of the least active of the b-carbolines
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If DMT up to one gram orally is not active by itself without MAOI according to shulgin, similarly even up to a gram of THH would NOT activate oral DMT, then?

This would be in line with the experiment on this thread: Pure Synthetic THH does not activate oral DMT! - Pharmahuasca - Welcome to the DMT-Nexus
 
Wouldn't it be exciting to take pure Harmaline; boil in H20 for various legths and acidity levels before subsiquently testing solutions to see if THH has been created?

Blessings.
 
endlessness wrote:
Nen, I guess you mean this publication.


Most of the synthetic tryptamine derivatives that were assayed as MAOIs did exhibit some activity, but the I50 values were usually several orders of magnitude iower than those for the B-carboline derivatives. Interestingly, DMT showed the most MAOI activity of all the typtamine derivatives tested: Its I50 was comparable to tetrahydroharmine (THH), one of the least active of the b-carbolines
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If DMT up to one gram orally is not active by itself without MAOI according to shulgin, similarly even up to a gram of THH would NOT activate oral DMT, then?
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..yes (thanks for link) ..but the effects of THH once in the bloodstream could be very interesting/desirable..chemist Jace Callaway wrote in E.R.:
"However, in a broad (as yet unpublished) survey of Banisteriopsis caapi, Psychotria viridis and subsequent teas, which included phytochemical analyses of all, plus subjective ratings of the teas, a strong correlation was found with teas that contained high amounts of THH and not DMT! This rating was from a large body of experienced users (regular União do Vegetal members who had consumed ayahuasca for 10+ years). In short, yes, there seems to be important activity from THH, but likely not the sort of activity that currently seems valuable to the
lay user in the U.S. or E.U.; e.g., more temporal, than whirly/swirly, if you know what I mean.

"I have tried THH, alone and in combination with MAOI, and there is a twinkling of sorts, but one might get a substantially similar reaction from Prozac. Also, there are two isomers possible from THH (+ and -, or d and l). I would suppose that one is more active than the other. Simply heating in boiling water will convert one to the other, so most teas will have both. the “d” form is the one reported to be found in the plant (d-leptaflorine), and I have often wondered about tales from the rainforests, where the tea is sometimes prepared just from soaking the macerated vine overnight (no heating, no admixtures), with visions resulting. Note: I suppose the desired vine should be a chemovare having high levels of THH.
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(see Trying to improve Acacia info p.15 for full article, in context of THH/DMT in Calliandra species..)

..on another note regarding prolonged boiling, as i commented in this thread [Concept for the formation of betacarbolines from tryptamines..] the prolonged boiling with acetic acid of some tryptamine containing acacias may result in the formation of more ß-carbolines..
.
 
Well you see, there have been very little to no controlled experiments regarding this. We dont know yet at what rate this happens. We're not even 100% sure this is happening but the data gathered does seem to indicate it. In my own tests, the differences in alkaloid profiles were very minimal, so it might take an excessively amount of hours to change anything significantly, but maybe not... And unless you have a control group (a disolution without boil) and some way to test the alkaloid content, you wont know if it worked or not, right?
 
chocobeastie said:
It might be worth some people checking/revisiting out professor 8's tek of harmaline to THH


I have tried the end result and I can say at 200mg it is the cleanest MAOI I have ever tried - *very* smooth. Maybe it is not THH and something else?
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Given that 1. this tek only assumed conversion 2. professor8 did not demonstrate any changes other than colour changes and subjective experience changes (both these "tests" being frown upon and are not acceptable here on the Nexus) and 3. there other reports that demonstrate not only THH conversion (with mass spec and TLC) and their bioassay did not have MAOI activity...

i'd safely say that this tek does not give THH - you just further cleaned your harmaline.
 
i'd safely say that this tek does not give THH - you just further cleaned your harmaline.
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I feel the effect is very different from Harmine and Harmaline. That is a subjective experience, which you say is not acceptable on the nexus? Come on! I would say that is where analysis begins! However, I do feel that professor 8 did jump the gun in saying that it for sure is THH without doing analytical tests. However, I can respect that he trusts himself and his product enough to do this!

As the quote from McIlhenny states:

"This phenomenon, an apparent acid-driven chemical reduction of harmine-to-harmaline-to-THH, has also been reported by Callaway et al. [28] and constitutes another source of potential variability of results among ayahuasca preparations."

So it does look plausable considering that an acid driven chemical reaction is thought to convert harmaline to THH.

I would also like to note, that Professor8 has not posted on this forum since he posted that tek. *scratches head*

there other reports that demonstrate not only THH conversion (with mass spec and TLC) and their bioassay did not have MAOI activity...
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Yes, but how many bioassays have been done? Perhaps there is something else going in Professor 8's tek that we are not aware of or unable to understand at this point.

At the very least, his work deserves replication and further work to try and find out what is going on here - which I for one am going to carry out! :)
 
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