tryptophan to psilocybin in fungi

[Guest Thelema]

does anyone out there know the chimistry of how certain fungi convert tryptophan into psylocybin? Im looking for the exact chemical reaction that changes one into the other.

[This message has been edited by Thelema (edited 30 October 2002).]

[spiders]

They seek tryptophan precursors purely to produce their own psychoactive alkaloids - the stronger their source of tryptophans the stronger their alkaloid production

[waterdragon]

so if one wanted to enhance the fruit strength of an outdoor patch, one would add 'what substances' to the surrounding area? in theory.

[Guest reville]

Perhaps a tryptamine containing wood or grass

Acacia wood? Petalostylis wood? AQ1 phalaris?

Lots of things contain tryptamine which is a proven increaser of potency (Work by Jochen Gartz), no sense in wasting rarer DMT containing substances just go straight for the tryptamine sources

Chipped petalostylis cassioides or labichioides would be a nice one to try at 0.5% tryptamine.

[eccles]

if you really seriously want to know, I could search the literature for a paper on the biosynthesis of psilocybin, and post it up here...

that is what I have been doing the last couple of days for mescaline - some interesting stuff out there...

the first volume of Lloydia (journal of natural products) in 1973 started off with FOUR papers on mescaline/peyote... one about peyote alkaloids, one about mescaline (by our good friend A T Shulgin , and another couple, and they were all good. I will have to borrow that book... and scan the articles and put them up on the web maybe (till someone yells at me hehe)

[eccles]

well I have found one paper, but it is from 1968. The sequence is just what you'd have expected just from looking at the two molecules, but they don't seem to mention any of the enzymes involved, which is what I assume you actually wanted.

If you want me to email you the article my email address is

[email protected]

[eccles]

there actually seems to be sod-all around man...

a few articles, all from the late 60's... (and one from the 80's).

None of which I can actually access from here (I am not in a library so I can only access the electronically available ones)

but it doesn't sound like something that wouldn't have been sussed out before.

[Guest Thelema]

thanks eccles, yeah you guessed right, im really after the specific enzymes involved.

ill keep looking.

[Guest reville]

When we get the opportunity it would be good to look at the other tryptamines in mushrooms to try and guess the pathway.

It doesnt seem to go via DMT as this hasnt been found, so 4OH DMT must be created some other way. perhaps via NMT?i couldnt really say.

The articles id like to see but havent chased down are by jochen gartz who along with a couple of other dd some intereting work with psilocybe species in the 1990's (published) ive found their work several times in abstartct frorm but not had access to the papers.

Were you all aware that if you feed MIPT and DIPT to mycelia they can prduce 4PH MIPT and 4OHY DIPT? i guess theyd do the same to NMT,DPT and others.

Is 4OH tryptophan stable? or active?

[eccles]

I'll see what I can get for you Rev.

some will not be available, but surely some will.

but not tonight, I am working on a silly set of instructions to go with an assay kit for biochem!

[spiders]

I can get hold of Gartz papers, as well as Buchanan and Chang/Mills.

I am also aware of a study of cubensis that did find trace levels of DMT - ill try and find that as well...

[Guest reville]

Originally posted by bluemeanie:

I can get hold of Gartz papers, as well as Buchanan and Chang/Mills.

I am also aware of a study of cubensis that did find trace levels of DMT - ill try and find that as well...

If you can put those papers into pdf or text format that'd be fantastic!

If DMT really is the precursor to 4 OH DMT then mutagenesis on monokaryotic mycelia might create DMT strains or even strains with

other precursors which would be very interesting even just for the study of the biochemical pathways.These mutants must arise spontaneously anyway but are not detected as the copy of the gene on the other mating type would mask and compensate for the inactive copy.The only way youd find them naturally is if the same spore race was cultivated continuously and mated with itself enough times for a double dose of the mutant gene to occur in a fruiting isolate. Itd be normal but completely orally inactive, Ive never sen anyone post to this effect but then again the cahnces of it happenning are very slim given the odds needed.

Im not sure how you'd select them in a lab though as im not sure if monokaryotic mycelia is capable of synthesising tryptamines.

Perhaps you could also create such as strain by transforming it with a retrovirus that inserts itself specifically into the gene for the enzyme that 4 hydroxlates tryptamines thus inactivating it, or by using the technology that is used to excise and replace with an inactivated copy of the same gene.

but for this youd firts have to have charcterised the gene and so far i dont think it has been looked for let alone found.

And we havent yet answered the question as to why so many mushrooms in so many genera produce psilocin in the first place? They do produce it in rather large quantities and almost exclusively in the fruiting bodies, which are ephemeral, or as a secondary metabolite in aged mycelia.

If it were used against insects or other microrgaisms you dexpect it to be in the vegetative sections that live the longest not in the short lived fruits - which seem to be eaten by insects anyway.

If it were used to repel vertebrates then its not a very effective deterrant! especially when you consider that if you ate them all the time you'd become tolerant very quickly and could probably eat with impunity (Don't try this at home kiddies )

I suppose that this theory about vertebrates does have some credibility in that Psilocin peaks in immature fruit bodies and decreases rapidly during sporulation, so it serves its protective role when needed then degrades.

Another thing thats interesting is that the species that contain Psilocin rarely contain any other toxic compounds that are so common in mushrooms, protein toxins like in amanita, or murscarine or even serotonin which is found in many non-psilocin producing members of the genus Panaeolus, along with tryptophan and 5 OH tryptophan.

And how could this enzyme that puts the 4OH on the tryptamines evolve in so many genera but not in any other living thing? You find Lysergic acid derivatives in many unrelated Fungi and also in the Convovulaceae, also you find tropanes in Erythroxylum, solanaceae and even in members of the Proteaceae (is nicotine a tropane? if so add clubmosses to this too). So these biosynthestic pathways arise independantly all the time, why is 4 hydroxylaton so unique to fungi?

so many questions?????????

[theobromos]

Tropanes in Convolvulaceae as well.

There are substituted indoles with the oxygen at the 4 position in Brassicaceae (the cabbage family) and some spider venoms. Mitragynine is an indole alkaloid with a methoxy at the indole 4 position. There are many other 4-substituted tryptamines in toads and corals.

[Guest reville]

really . i didnt see those in my new trouts notes.. id better go back and have look.

Theo we should capture you on a desktop application "ask Theo" for WIN 98,xp,2000

[Guest Thelema]

here's a thought

psilocybin peaks in the fruiting body just b4 natural sporulation

maybe its presence is determined specifically to INDUCE animals to eat it, that way providing a natural symbiotic way to transmit the spores far and wide through the faeces.

[Guest reville]

well that works well for hominids but cows?

i would think tripping would be an evolutionry disadvantage for grazing animal. And im sure it isnt tailore dto us... we're too unreliable.

[spiders]

Out of interest Gartz detected .30% L-tryptophan (as unconverted psilocybin) in the very interesting Psilocybe Weilli. According to reputable sources, the Weilli experience is quite unique and can last for a lot longer than the average psilocybin experience.

I think the Gyms may have similar chemical make-ups with tryptophans

[nabraxas]

just on a possible symbiotic relationship tween shrooms & animal- in wales, the liberty caps tend to grow predominately in fields grazed by sheep. it appears to be common local knowledge that the sheep totally avoid eating the shrooms- which is remarkable 'cus lib. caps are usually pretty small & tend to blend into the pasture.

[Guest Plantnursery]

well that works well for hominids but cows?

i would think tripping would be an evolutionry disadvantage for grazing animal. And im sure it isnt tailore dto us... we're too unreliable.

A gnome I know has seen cows eating a native psilocybe on numerous occasions.

[spiders]

Ive just been reading that panaeolus acuminatus yielded through alkaloid analysis, no psilocybin, no psiloscin, but .016% serotonin, .066%5-OH- tryptophan, and 029% tryptophan.

Also reading through some articles, it appears that Gartz, after finding that the introduction of tryptomine precursors into the substrate of cubensis increased alkaloid production, was going to attempt to grow a grassland psilocybe on grasses with known trytomine contents such as Canary Grass.

[Guest electro]

The synthetic pathway proceeds from tryptophan to tryptamine to N-methyltryptamine to N,N-dimethyltryptamine to psilocin to psilocybin.

http://www.erowid.org/plants/mushrooms/mus...rticle2-2.shtml

[Thelema]

interesting, so it adds the 4 at the end!

complete reversal of modern synthetic methods, which must add the 4 at the beginning of the synthesis!

Do you know the enzyme responsible for the 4-subs step?

[Guest electro]

no ..

i could find almost no information on the subject ... plenty of "what has been found" but really nothing much on the actual processes or enzymes in action.

[ 30. March 2005, 13:51: Message edited by: electro ]

[Thelema]

I wonder if the 4-enzyme "waits" until DMT is formed, or whether small amounts of 4OH Tryptophan, 4OH tryptamine and 4OH nmethltryptamine are also present in small amounts.

[Guest electro]

ive seen reports of 4-ho (or is oh) tryptophan being present