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Invisiblecloudtop
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Re: Discussion of Psilocybin pathway... [Re: fastfred]
    #5906324 - 07/27/06 06:45 PM (17 years, 6 months ago)

First and foremost it appears as though the lighting is quite different (as discerned through comparison of skin tone in the pictures). Secondarily, the angles/perspectives are different -- monstermitch, is the fruit black/blue throughout or is the hue predominantly on one side? How long of a delay was there between the two photos? Did you notice a fading of the effect?

I'm curious to see the distinct bruising effects in an CO2-saturated vs. oxygen-saturated atmospheres. Also, how would the bruising of psilocin-rich fungi vs. psilocybin-rich fruits be interpreted in light of your possible pathway, fastfred? I had initially believed the bruising of cubensis to be the result of phosphorylation of psilocin into psilocybin...but the same bruising is said to occur with Panaelous which tend to be psilocin-rich.

Back to the literature.


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Invisiblemonstermitch
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Re: Discussion of Psilocybin pathway... [Re: cloudtop]
    #5906372 - 07/27/06 07:02 PM (17 years, 6 months ago)

the lit one was taken one minute prior to the other one.

the up the stipe shot is the right side of the lit one.

no fading at all.
I ate it a few hours later and it worked very well.




and a random pic:


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Invisiblefastfred
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Re: Discussion of Psilocybin pathway... [Re: cloudtop]
    #5906463 - 07/27/06 07:29 PM (17 years, 6 months ago)

> I'm curious to see the distinct bruising effects in an CO2-saturated vs. oxygen-saturated atmospheres.

That's a really good idea. Somebody want to try that? Someone was just talking about a supercritical CO2 extraction in another thread.

The whole bluing thing is an interesting issue. It's known that the psilocybin is enzymatically dephosphorylated by enzymes present in the mushrooms. It might just be oxidized psilocin, but I think psilocybin is also dephosphorylated into psilocin and then oxidized. So I think that either one will produce a bluing reaction.

Apparently some mushrooms which contain actives don't bruise blue so that throws some more questions into the mix. If a psilocybin rich / psilocin poor mushroom also doesn't happen to have a dephosphorylase enzyme then it wouldn't bruise blue.

I don't think that psilocin content alone accounts for the bruising, so I favor the enzymatic dephosphorylation theory.


-FF


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OfflineMr E Guest
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Re: Discussion of Psilocybin pathway... [Re: fastfred]
    #6933747 - 05/18/07 08:45 AM (16 years, 8 months ago)

FF, in your psilocin pathway diagram the molecular stucture you dub "psiloceen" (psilocene would be more consistent with chemical nomenclature, btw, and psilocone(!) would be even more accurate) is a tautomer of psilocin rather than an oxidation product.

It has all the atoms (count them!) in virtually the same places, with just the 4-OH hydrogen shifted onto the opposite side of the benzene ring (the 7- position, pretty much at 6 o'clock compared to the 12 o'clock of the 4-position) and a couple of double bonds swapped around.

This form of the psilocin molecule is energetically very unfavorable and would therefore be unlikely to occur in anything other than vanishingly small proportions of any given sample of psilocin.

However, it does illustrate a possible route for the oxidation of psilocin as the 7-position hydrogens would quite readily be replaced by an oxygen atom to give a structure known as a quinone. Perhaps we could call the resulting structure "para-psiloquinone" as it's less of a mouthful than 3-(2-dimethylaminoethyl)indol-4,7-dione.

Molecules containing the quinone structure are often intensely coloured, which might give a lead in identifying the as-yet-uncharacterised blue pigment produced (as we well know!) upon bruising - and even spontaneously in some species - of psilocin containing mushrooms.

Note also that the 5-position of the psilocin molecule can be changed in a similar manner to form a different isomer, "ortho-psiloquinone".

This post is in danger of turning into a rambling chemistry essay, so to conclude I would note that structures closely related to 5-H- or 7-H-"psilocone" are more than likely transient intermediates in the enzymatic production of the mysterious blue pigment.

Hope this is understandable! And that nobody has said all this elsewhere months ago...


Edited by Mr E Guest (07/09/07 07:28 PM)


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OfflineMr E Guest
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and another thing... [Re: Mr E Guest]
    #6933942 - 05/18/07 09:45 AM (16 years, 8 months ago)

We are dealing with living systems here. Not only is the PSOP enzymatically dephosphorylated, the resulting PSOH is then enzymatically transformed via one or more steps to the blue pigment. At least one of these steps will be oxidative.

It may well be that two (or more) molecules of psilocin are joined together to form a molecule related to indigotin, the blue dye in denim. It may also be that the enzymatic coupling product is colourless and then turns blue upon oxidation in air, again just like in the use of indigotin.

Only chemical analysis of the blue psilocin-derived pigment will tell. And complicated enzymatic studies. PhD thesis, anyone?


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Invisiblefastfred
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Re: and another thing... [Re: Mr E Guest]
    #6935787 - 05/18/07 06:14 PM (16 years, 8 months ago)

You might call it a tautomer, but I don't think any real ratio between them exists. Not being interconvertable I wouldn't call them tautomers.

> This form of the psilocin molecule is energetically very unfavorable

Why would you say that? It's based off the oxidation product for serotonin. Being so similar I would think that they would have similar oxidation products.

> Molecules containing the quinone structure are often intensely coloured,

I've heard much talk of a quinone structure, but what exactly would you propose?


-FF


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OfflineMr E Guest
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Re: and another thing... [Re: fastfred]
    #6943122 - 05/20/07 02:47 PM (16 years, 8 months ago)

Quote:

fastfred said:
You might call it a tautomer, but I don't think any real ratio between them exists. Not being interconvertable I wouldn't call them tautomers.



The two structures are (theoretically) interconvertible:

Quote:

It has all the atoms (count them!) in virtually the same places, with just the 4-OH hydrogen shifted onto the opposite side of the benzene ring (the 7- position, pretty much at 6 o'clock compared to the 12 o'clock of the 4-position) and a couple of double bonds swapped around.(*)



-----------------------------------------------------------------------
Quote:

> This form of the psilocin molecule is energetically very unfavorable

Why would you say that?



Because it involves the dearomatization of the benzene ring.
--------------------------------------------------------------
Quote:

It's based off the oxidation product for serotonin. Being so similar I would think that they would have similar oxidation products.



The structure you propose is not an oxidation product. It is a minor rearrangement - call it isomer rather than tautomer if you prefer - of the psilocin molecule, as stated ((*)) above.
-----------------------------------------------------------------------
Quote:

> Molecules containing the quinone structure are often intensely coloured,

I've heard much talk of a quinone structure, but what exactly would you propose?



This is what I was attempting to describe here:

Quote:

However, it does illustrate a possible route for the oxidation of psilocin as the 7-position hydrogens would quite readily be replaced by an oxygen atom to give a structure known as a quinone. Perhaps we could call the resulting structure "para-psiloquinone" as it's less of a mouthful than 3-(2-dimethylaminoethyl)indol-4,7-dione.



And here:

Quote:

Note also that the 5-position of the psilocin molecule can be changed in a similar manner to form a different isomer, "ortho-psiloquinone".




Quote:

I would note that structures closely related to 5-H- or 7-H-"psilocone" are more than likely transient intermediates in the enzymatic production of the mysterious blue pigment.





Unfortunately I don't have a molecular structure drawing program which would make an explanation far easier. Maybe you could recommend me one?

[edit]I've just seen the thread from last year where the Swedish guy (forgot his name, sorry) says the same stuff as me but with molecular diagrams. He's an organic chemist, too.


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Be joyful. This could be the only chance you get.

All of the above posts are the fevered imaginings of a deluded mind, itself entirely the fictional creation of a somewhat peculiar author with a bizarre sense of humour.


Edited by Mr E Guest (07/09/07 07:27 PM)


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Invisiblefastfred
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Re: and another thing... [Re: Mr E Guest]
    #6951469 - 05/22/07 11:17 AM (16 years, 8 months ago)

Thanks for the input E. For continuity here is the link to the earlier thread...
http://www.shroomery.org/forums/showflat.php/Number/3128800

As far as drawing structures I usually just use paintshop pro or photoshop and manipulate images pulled from the web. There is one good structure program that I've used though. Go to the pubchem search the structure you want to start with and then click on sketch.
http://pubchem.ncbi.nlm.nih.gov/search/

I think my structure is sound because of how indoles oxidize and also how the very similar serotonin oxidizes. One thing to remember is that psilocin oxidizes first into a blue product under normal conditions but it will turn black in a day or so. The presence of a good oxidizer will also oxidize it straight to black. So there is obviously more than one oxidation product or the first product is then oxidized further, possibly dimerizing or forming an o-quinnoid.




-FF



Edited by fastfred (05/22/07 06:22 PM)


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Offlinejohnuk
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Re: and another thing... [Re: fastfred]
    #7014800 - 06/06/07 06:50 AM (16 years, 7 months ago)

Great thread guys. Haven't had a chance to go through it all in detail yet though.

Why does the IPA cause bluing do you think? Could it be disrupting cell walls or causing some form of osmotic pressure change?

Also, FF, do you have a link to that supercritical CO2 discussion? Thanks!


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Invisiblefastfred
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Re: and another thing... [Re: johnuk]
    #7015923 - 06/06/07 02:53 PM (16 years, 7 months ago)

> Why does the IPA cause bluing do you think?

I think that the IPA probably increases the turgor pressure on the cell walls through osmosis resulting in them leaking. Then again I'm not much of an expert on osmosis.

> Also, FF, do you have a link to that supercritical CO2 discussion? Thanks!

http://www.shroomery.org/forums/showflat.php/Number/5906229


-FF


Edited by fastfred (06/06/07 02:59 PM)


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OfflineMr E Guest
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Re: and another thing... [Re: fastfred]
    #7153973 - 07/09/07 10:23 PM (16 years, 6 months ago)

I've drawn those structures (finally!) and a picture of the tautomeric (not oxidative) relationship between psilocin and 7-H psilocone ("psilocybeen"), although I now see what you're getting at with the absent hydrogen atom on the indolic nitrogen. It's a couple of the double bonds you've drawn in the wrong places, making your "psilocybeen" a cross between a tautomer and a free radical.




Cheers, PubChem Structure Search sketch function is great!

Oh, and by the way:

In Neils Jensen's dissertation "Tryptamines as Ligands and Modulators of the Serotonin
5-HT2A Receptor and the Isolation of Aeruginascin from the Hallucinogenic Mushroom
Inocybe aeruginascens" ,

http://deposit.ddb.de/cgi-bin/dokserv?idn=973960833&dok_var=d1&dok_ext=pdf&filename=973960833.pdf
http://webdoc.sub.gwdg.de/diss/2004/jensen/jensen.pdf

he states that,

"[...]psilocybin has a relatively simple chemical structure. It is biosynthetically derived from the amino acid tryptophan by enzymatic decarboxylation, indole hydroxylation, N-methylations, and O-phosphorylation [...]. Feeding experiments with putative intermediates,analogues of them, and radioactive precursors supported the view that the biosynthetic pathway starts with a decarboxylation and that O-phosphorylation is the final step. However, there is still uncertainty  about the sequence of N-hydroxylation and the N-methylation steps. Some authors even suppose a biosynthetic grid with multiple routes to psilocybin."

and

"These findings prove that the 4-hydroxylating and 4-O-phosphorylating enzyme systems are capable of tolerating N-methyl and N-ethyl substitutions as well as that the N-methylating system is capable of tolerating 4-hydroxy groups. The major pathway in vivo has not been established yet due to the instability of 4-hydroxylated indole derivatives in solution, the uncertainties of precursor uptake into living mycelium, and the possible interference with pathway regulating mechanisms."

So perhaps that clears up that:grin: matter somewhat.

Did you read the whole paper, btw? #6437250


Edited by Mr E Guest (07/13/07 04:54 PM)


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Invisiblefastfred
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Re: and another thing... [Re: fastfred]
    #7154901 - 07/10/07 02:05 AM (16 years, 6 months ago)

E, could you put a couple line breaks between your pics so the thread isn't stretched out so wide?

I've combined the proposed structures into one pic...


I haven't looked at Jensen's paper you linked to yet.

As far as the biosynthetic route, I'm going to stick with Agurell and Nilsson's work. It's possible that there are other pathways, but I think (nor)baeocystin is just a dead end side reaction rather than a significant part of the pathway. Agurell seems like he did a lot of good work on the subject. In their second paper they talk about further experiments to be published. They even cite their yet-to-be-published work. I tried pretty hard to figure out if they ever published it, but couldn't find it. I'm assuming that they got much the same results and it just didn't turn out to be noteworthy enough to be published.

> that swedish guy whose name I've forgotten has already posted some excellent and plausible structures last year. You seem to be deliberately ignoring them.

If you find them please post a link. Pinback posted the same structures as above, we just never really discussed them much and I wasn't sure if he was seriously proposing them or just throwing out a few possibilities.

> If you come up with a name like "psilocybeen" you quite clearly have no idea what you're talking about. The "-cy-" compounds are all phosphorylated

The nomenclature of common names is not one of my strong points. There are so many different common names and spellings that I rarely pay any attention to them. "Oh my such good apple pie" is about as far as I try to fool with common names.

One other point is that psilocin has more than one oxidation product. Apparently is oxidizes blue/green and then to black over time. It can also be oxidized straight to black by strong oxidizers. Based on that observation I think there are quite a few possibilities. I've only really ever thought about the blue product before.

I'll have to look at things a bit more, but I'm not sure I see what you're saying about the bond locations.

Anyhow, hopefully this thread won't end up locked. RR doesn't really like any sort of chemistry discussion in advanced, so be careful not to anger him again.


-FF


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OfflineMr E Guest
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Re: and another thing... [Re: fastfred]
    #7167274 - 07/12/07 06:04 PM (16 years, 6 months ago)

It looked ok on my window...

Well done for condensing them structures into one pic, though. I tried on Photoshop pro and, being slightly clueless, failed to do so. I'm glad you think it was the (off-topic) chemistry that got that other thread closed (we should have been posting here with a lot of it, really) rather than how insulting we all got. :rolleyes:

The structures for psilocin oxidation products will all be speculative because, as far as I know, nobody has actually done an analysis yet. The quinone and dimeric structures I have seen are all based upon plausible reactions related to existing known compounds. Somebody (give me a lab...) will have to extract the blue and black pigments, purify them and analyse them.

>I'm not sure I see what you're saying about the bond locations.

Compare: the tautomeric structures for psilocin, the less favoured of the two having the same number of double bonds in the same positions as your proposed "psilocybeen" structure; the indolic nitrogen atom in your psilocybeen structure having only two bonds and no hydrogen atom (which would make it either a free radical or an anion); and the structure labelled "psilocone" alongside the quinone structures I illustrated - it has the same ketonic nitrogen and nitrogen atom sans hydrogen, but the nitrogen atom has three bonds (as it should if it is a neutral atom without an unpaired electron) and the rest of the double bonds are located accordingly.

>I haven't looked at Jensen's paper you linked to yet.

That's a shame, it's very interesting (especially if you're a biochemist...) and I found the link to it on one of your posts, although I had seen it before.


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All of the above posts are the fevered imaginings of a deluded mind, itself entirely the fictional creation of a somewhat peculiar author with a bizarre sense of humour.


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