nice read on psychoactive shrooms

[Rev]

http://forum.thenook.org/index.php?showtopic=29560

From the Bulletin de L'hambra vol. 43:1-7 (2004)

PSYCHOACTIVE MUSHROOMS: BETWEEN MYCOCHEMISTRY AND MYCOMYTHOLOGY

Gianluca Toro

Introduction

The beginning of the interest in the biochemistry of psychoactive mushrooms can be traced back to the discovery of the ritual use of mushrooms in Mexico by R.G. Wasson and the investigations carried out by A. Hofmann ending in the identification of the active principles psilocybin and psilocin. But even if the chemo-taxonomical research is in constant and rapid development, as the publications on the subject demonstrate, (here weren't a true progress in the study of mushroom chemistry and in the identification of new active principles (Stijve & Glutzenbaum 1999).

Indeed, a certain attitude is common according to which some mushrooms species are considered trivial regarding their edibility, because of their reduced dimensions and/or rarity; but this fact often hides a scarce knowledge of either the biochemical or the toxicological aspects involved or quite a complete lack of precise investigations (SAMORINI1990).

On the other hand, it must be stressed that the diffusion of the recreational use of psychoactive mushrooms in the world has brought to an increase in the number of new active species identified as such, but there are some aspects to consider in order to understand the data available.

First of all, one have to take into account the bluification phenomenon generally valid for the psilocybian mushrooms when they are handled; this is due to an enzimatic oxidation of psilocin forming a blue compound. Every mushroom that stains blue could be a good candidate for being a new psilocybian mushroom and this could be a general rule, but the association between bluification and presence of psilocybian alkaloids is not always vailid, because some psiiocybian mushrooms doni stain blue and the reverse, species that show bluification are not psilocybian (Ibid.). Then, some species could be mistaken for others or be casually found among the active species during the recollection for the subsequent chemical analysis. In fact, the identification of small brownish mushrooms is generally difficult and there's also a specific expression (found in american texts) identifying all this mushrooms species in general, that's to say "Little Brown Mushrooms" (LBM) (Stuve Et Al.1984, Gartz 1996). As for the chemical-analytical methodology, the problem with determinations carried out in the past was the low selectivity and sensibility of the methods leading to false-positive identification of psilocybian alkaloids in some species. For example, serotonin and its precursor 5-hydroxytryptophan may have been mistaken for psilocybin during analysis on some species of Panaeolus (Stijve & Kuyper 1985). In particular, problems arise due to the lack of confirmatory procedures, when exact quantitative results are not reported and when the concentrations detected are very close to the detection limit of the method (STUVE & KuYPER 1988). Nowadays, with the development reached by modern analytical chemistry, chemical analysis are more reliable, but the errors of the past normally take some years to be corrected (Sijve & Glutzenbaum 1999). Other sources of errors could be the contamination of reagents, for example.

Other aspects are represented by the fact that sometimes these data are based on indirect, uncontrolled and poorly or not referenced reports and by the continuous and untiring research for new psychoactive mushrooms that leads to speculations and that are frequently reported in Internet. We have not to let apart the role of imagination and suggestion and the possibility of a hoax to exploit the gullibility of unwitting lay persons. So it is important to maintain reservations on sensational scientific discoveries in non-scientific literature. Different important aspects (and limitations) are of taxonomical and chemical nature. In fact, some mushroom species present different number of biochemical races (due to a genetic variability) so that it is not simple to exactly identify the taxonomical characters and to carry out reliable chemical analysis. In general, the identification of new psychoactive compounds in mushrooms maybe a difficult and long analytical work that can discourage the researchers (Ibid.).

We'll consider some not precisely yet identified and not well studied compounds one could find in some species of mushrooms. If confirmed, they could contribute to the total psychoactive action modulating for example the main effects of the psilocybian alkaloids psilocybin, psilocin, baeocystin and nor-baeocystin; such compounds could act in a sinergic way, the total effect being the sum or the product of the effects of the single compounds.

Discussion of species

As for Boletus erythropus, in Internet sites is reported that it "contains unidentified hallucinogens (possibly psilocin/psilocybin)" and that more than 100 g fresh are ingested for psychoactive effects; in this species, the non-psychoactive tryptamine was identified and it is expected the presence of putrescine (Smith 1977, Stijve 2003a). Boletus satanas is responsible for a gastroenteric syndrome that, according to L. Giacomoni, it could be also a psychotropic one (Giacomoni 1985); probably, it contains indolic and isoxazolic derivatives. It is curious the popular name given in the italian dialect of Trentino, where it is called brisa matta, recalling the idea of madness (BRESADOLA1965).

There were also some species of Clitocybe (C. gallinacea and C. subilludens) reported to contain ergot alkaloids; this would be a very surprising fact among mushrooms, because until now these are typical compounds produced by some infesting species, for example the well known C. purpurea, but at least for C. subilludens from North America this datum was disproved (HEIM 1963, SAMORIN11990).

Other data comes from species of Coprinus. Generally, they are edible when young and without alcohol; with alcohol, they cause the so called "coprine intoxication". This intoxication is due to the accumulation of acetaldehyde and the clinical features of this syndrome are sensation of warmth, flushing, sensation of tingling of limbs, nausea and vomiting, tachycardia, palpitations, anxiety, vertigo, confusion and hypotension (Benjamin 1995).

At the beginning of 1900, there were some records concerning intoxications probably caused by ingestion of C. comatus (Krieger 1911). In one case, the symptoms were similar to those of alcohol intoxication; there were muscular incoordination, difficulty in standing, inability to walk, drowsiness, lack of control of the emotions, incoherent or inappropriate speech and for a person the furniture seemed bent, pliable and in motion. The author of the above cited reference compared these symptoms with those reported for a case of ingestion of Panaeolus campanulatus, possibly psychoactive, finding them similar; so he concluded that C. comatus was not responsible for the intoxications and that among mushrooms of this species (collected for eating) P. campanulatus was also casually picked up ("except by mistake it [C. comatus] has never before been reported as poisonous").

It is interesting to put in evidence how the author considered the idiosyncrasy an important factor in this kind of intoxication. Moreover, a certain Prof. Dearness proposed an explanation for such cases, writing that "in the process of disintegration, nocuous products undoubtedly do develop from innocent compounds" and that "it is quite conceivable that the strength of poisonous principles may vary in the same species of mushroom or that even some alkaloid may be normally present in one set of conditions and be absent in another". In recent times, in Poland young people are used to ingest 30-40 fresh carpophores of C. atramentarius without alcohol for supposed hallucinogenic properties. The quantity reported is hardly collected for an edible use and this fact could explain why the presumed psychoactivity of this species was not discovered; It would be interesting to investigate if this use in Poland is recent or has a traditional origin (Samorini 2002).

R. HEIM (1963) includes (but don't confirm) C. narcoticus, along with Panaeolus papilionaceus e P. campanulatus, in the group of mushrooms causing "cerebral mycetism", that's to say a psychodispieptic hallucinogenic effect. C. narcoticus, C. radicans and C. stercoreus have a strong "narcotic" smell. In Internet, C. narcoticus, C. niveus and C. patouillardii are reported to be consumed for their psychoactive properties (more than 50 g fresh). As for chemical data, the presence of tryptophan and tryptamine was found in C. atramentarius, C. comatus and C. micaceus (Worthen Et Al. 1961).

Passing to the rare mushrooms producing (3-carbolines, such compounds were isolated in Cortinarius infractus, namely infractine, 6-hydroxyinfractine and infractopicrine, responsible for its bitter taste that makes it not recommended as for edibility (Steglich Et Al.1984; Azema, Giacomoni 1987). Basing on the fact that these compounds have a structure similar to that of harmaline (another (3-carboline considered psychoactive), some authors affirmed that it is an hallucinogenic species (Azema 1987). But in the genus Cortinarius toxic compounds similar to orellanine are very common and they are present also in C. infractus, even if as traces; so, it's better to consider this mushroom as toxic and not hallucinogenic (SAMORINl 1990,1993).

Also A. muscaria produces (3-carbolines, namely 1,2,3,4-tetrahydro-1-methyl-|3-carboline carboxylic acid (MATSUMOTOETAL. 1969).

Hygrocybe conica, popularly known as witch's hat, was at the center of the interest for the question of its edibility, with some legends and confusion. It is variously considered edible (in particular when cooked), not recommended, toxic (or slightly toxic) or dangerous. This is probably due to the presence of different strains, so that some specimens are edible, some are not. In the '30s, 4 deaths in China (Tonkin) were (perhaps mistakenly) attributed to it (HEIM 1963); this sort of legend had a so long life that many authors now consider H. conica with suspicion. It was placed among mushrooms causing choleriform mycetism (IBID.).

This species was claimed even to be hallucinogenic in some Internet sites selling spores and spawn kits for hallucinogenic mushrooms like P. cubensis. Perhaps, the same name witch's hat is evocative of some psychoactive properties, in reality referring only to the form of the cap.

Some ingestions provoked an odd sensation of lightheadedness and numbness (ARORA 1986). No tryptamines were found, only L-3,4-dihydroxyphenylalanine (L-DOPA) and muscaflavin, biogenetically derived from L-DOPA. L-DOPA is responsible for the black coloration after bruising or ageing (Steglich & Preuss 1975, Stijve 2003b); this fact could be misunderstood by person searching for hallucinogenic mushrooms, interpreting the blackening phenomenon for a blueing one.

The "false chanterelle", Hygrophoropsis aurantiaca, is said to produce hallucinations (MORGAN 1995). This mushroom was reported variously as poisonous, edible, non edible or innocuous (Stijve 2003c).

Hypholoma fasciculare causes a muscarinic (and perhaps also phalloidinic) syndrome but hallucinations were also reported, especially auditive ones. The toxins are not yet well identified and there aren't psychotropic indolic compounds. It is possible that the toxin is a yellow pigment with the structure of styryl-6-pyrones, such as yangonin (GlACOMONi 1985).

It seems that J. Gartz isolated from the psilocybian species Inocybe aewginascens an evasive analogue of psilocybin named aeruginascin and responsible (according to the author) of the cheerful properties of this species of Inocybe; so it is possible that aeruginascin could modify the pharmacological action of psilocybin. The chemical structure is not yet identified and nothing is known on the pharmacology of this new compound, but it would seem a characteristic compound typical of this species; other researchers failed to identify it (Gartz 1989,1995; STUVE &GLUTZENBAUM1999).

"Lepiota peele" or "Lepiota bigwoodf was perhaps the most debated possible hallucinogenic mushroom; the pertaining informations were widespread in commercial magazines of the youth counterculture (Peele 1982, Anonymous 1983, Arora 1986, Akers 1992, Stijve 2003d).

During the late 70's, S. PEELE. the mycological entrepreneur of FMRC (Florida Mycological Research Center) in Pensacola (Florida) reported the use of this mushroom as a psychoactive species, after an encounter with some persons in local cattle pastures in Flonda collecting this species, preferred to P. cubensis. a dose of 5-6 carpophores corresponding to a standard dose of LSD.

Peele identified the species as a Lepiota but Peele's Lepiota was never properly described in any journal so the validity of the species has never been established; we have only descriptions, some photographs and spore prints available in FMRC. This mushroom was finally identified as Lepiota humei, a species first collected in the Gainesville area (Florida) in 1938 and described in 1943.

As a first experiment, PEELE ingested 3 specimens. After one hour, he felt himself "changed" and had difficulties in reading; he noticed a slight lightness but no feeling of intoxication. Moreover, he experienced a visual display of undulating black lines and large, floating balls of colour, sufficient for him to place this species among the psychoactive ones. According to PEELE, the species does not contain psilocybin, suggesting the possible presence of an active compound not previously found in mushrooms or new at all.

So, a collaboration with J. Bigwood at the Evergreen State College in Olympia (Washington) started at the beginning of the '80's; Peele request was that any possible new compounds would not be named. Peele noticed that the mushroom mycelium came up from the ground, feeding on the grass ("mat condition") and thus on a substrate that was not the usual one; this would allow the mushroom to produce compounds not normally produced. According to PEELE, the mushroom has no effect when there isn't the "mat condition".

On the other nand, Bigwood cultivated the mushroom and did experiment in rats, never seeing any effects but finally in 1983 he isolated and synthesized the new active compound, with a short life of 1-2 days, then breaking down to other non-active products; the only way to slow down this process was to put the mushroom in chlorinated water but this is incompatible with the drying and storing processes for later analysis. The mushroom would be active when fresh but it looses its potency very quickly; on the other hand, the mycelium would excrete a psychoactive yellow liquid, named "the golden goop". For Bigwood, hallucinogenic effects would occur even by smoking dried samples.

According to P. Stafford, Bigwood told him that in Peele's Lepiota were present many alkaloids, above all lysergamides and N,N-dimethyltryptamine. In particular, Bigwood identified a compound produced by the human brain, found for the first time in a plant tissue. At the end. someone had broken into the laboratory and sabotaged the standards; from that moment on, the research still remains unfinished.

Other ingestion experiment was carried out in the '90s with gradually increased amounts of fresh mushrooms on an empty stomach; 5-6 carpophores didn't produced toxic or hallucinogenic effect (AKERS 1992).

Returning to the chemical aspect of Peele's Lepiota, a report was announced in 1983 but never published (Anonymous 1983). Anyway, according to researches carried out by T. Stijve in 1982-1983 (Stijve 2003d), the species does not contain: amatoxins (such as in other Lepiota species), phallotoxins, orellanine. muscarine, muscimol, ibotenic acid, psilocybin. psilocin, baeocystin, bufotenine, 5-methoxytryptamine, N.N-dimethyltryptamine, tryptamine, P-carbolines, ergot alkaloids and adrenochrome. It were found only low levels of urea and free tryptophan.

At the end, it seems that this species is not hallucinogenic; this is confirmed by people who actually ingested this mushroom and by the fact that there was no further great interest in the following years, even if L humei is reported in some Internet sites as psychoactive.

Regarding Lycoperdon spp., their entheogenic use has not been fully and precisely demonstrated; chemical studies are scarce and the presence of entheogenic compounds remains to be proved (Ott 1996). The effect reported after their ingestion is generally a more or less narcotic one, but probably at least some species can be dream-inducing.

For example, it seems that L mixtecorum and L marginatum have a divinatory use (Orr 1996). They are called by the Mixtec people of Oaxaca, Mexico, gi V wa (first quality mushroom) and gi'/ sawa (second quality mushroom), respectively. The effect is similar; it is a narcotic one, and possibly dream-inducing, with voices to whom a person can ask questions. But in a field study, these effects were absent at the doses recommended by an informant; maybe at larger doses there could be narcosis. On the other hand, according to Giacomoni, probably such puffballs contain some indolic compounds responsible for a narco-psichodisleptic syndrome (Giacomoni 1989). Then, it seems that in the concoctions of basque witches there was possibly L. pyriforme, with narcotic properties (it could induce a short and, in some cases, potent narcosis); also L perlatum has shown narcotic properties (Morgan 1995). Other species such as L. pedicellatum and L. umbrium are suspected to be active and among mexican Tarahumara Indians of Chihuahua, a Lycoperdon species perhaps was a substitute for peyote (Lophophora williamsii) (Ratsch 1998).

As for the genus Pluteus, in samples of P. ephebus [P. villosus) collected in Netherlands and Switzerland psiiocybine was not identified, but the test for the presence of tryptamines gave positive results. It is suspected the presence of a tryptamine analogue to psiiocybine and it is not sure that the grey-blue color of this mushroom is due to this compound (Stijve & Bonnard 1986).

In P. semilanceata, the popular (especially in Europe) psilocybian mushroom, Stuve (1984) found two not yet identified and not yet studied tryptamines, that could contribute to the effect of the mushroom, and also in samples of the Pacific Northwest an indolic compound with a mobility slightly slower than psilocybine was found in TLC (Repke & Leslie 1977). In other analysis, 8 new compounds were identified, some of them with a presumed steroidal structure (Calligaris 1993-1994). In samples from Sweden, phenethylamine (PEA) was identified with a maximum concentration of 146 ug/g on fresh material (Beck Et Al. 1998). This compound is formed by decarboxylation of the ubiquitous aminoacid phenylanaline and it was not identified in any other mushroom until today.

The effect of PEA is amphetamine-like, principally inducing tachycardia and general adverse reactions one could note after ingestion of P. semilanceata; the differences in effects between synthetic psilocybine and mushroom could be due to the presence of PEA in the latter. On the other hand, the concentration of PEA is highly variable in respect to that of psilocybine, so that adverse reactions are evident only in some cases. PEA is rapidely inactivated by MAO-B enzymes, forming phenylacetic acid, while psilocybine is first dephosphorilated to psilocin, which in turn is inactivated by MAO, giving 4-hydroxyindolacetic acid. But for psilocin this seems the minor metabolic pathway in rats, so that psilocin is a poor substrate for MAO. It is not precisely known if psilocin is a substrate for MAO-A or MAO-B, but one could speculate if there is a metabolic interaction between PEA and psilocin through competitive inhibition of MAO. Other not yet identified tryptamines are present in Leucoagaricus spp., some species of Psathyrella and Sarcodon atroviridis. In the first case, the presence of 6- and 7- ubstituted tryptamines is supposed; their presence in biological material is not well known and they are still laboratory curiosities (Stjive 2002-2003). As for Psathyrella spp., 2 fluorescent tryptamines (named psathyrelline I and psathyrelline II), that are not present in species of Panaeolus, Psilocybe and Stropharia, were put in evidence (STUVE 1985, 2002-2003); Psathyrella candollenana, P. gracilis and P. sepulchralis are reported in Internet to be used for psychoactive properties. In Sarcodon atroviridis there are not less than 4 tryptamines and tryptamine (STUVE 1995, 2002-2003), this latter present also in the species of the same genus, S. imbricatum (Smith 1977).

Conclusions

In evaluating a possible psychoactive effect of a mushroom not previously reported to be psychoactive, one have to consider that the informations appearing in some magazines and in Internet sites could be false, sensationalistic and based on misunderstandings. An important factor is the particular psychological situation of the person, for example the suggestibility and the psychological predisposition, leading to a psychoactive effects even if there isn't a real pharmacological action; briefly, if one think that a mushroom is psychoactive and ingest it, it is possible that this turns out to be psychoactive, even if it isn't.

As we pointed out, it is possible that the presumed identification of psychoactive compounds in mushrooms was due to an incorrect taxonomical identification, to the low selectivity and sensibility of some analytical methods and to errors in the procedure. On the other hand, it is possible that the psychotropic effect is really due to a new compound and that it's presence is not constant for the biochemical variability of the particular mushroom species, rendering the research difficult. In some cases, new compounds were discovered, but until now they are not yet identified and pharmacologically studied.

At the end, it is important to take into consideration the anthropological data available and maintain a scientific approach, with precise chemical analysis carried out with the higher sensibility and sensitivity and eventually some carefully controlled experiments of ingestion...for the braves!

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