It was the line "either purchased or prepared by known chemical procedures" that Sasha reminded me of some years ago when questioning why I had included the results of Clement et al's two papers in several publications.
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Resolving controversy around plethora of alkaloids in Acacia Rigidula & Berlandieri
- Thread starter fractalicious
- Start date
fractalicious
Dave
Got you on the references if they do not exist or are not reliable or can't be reproduced or synthesized well that pretty much is a tell all that results inaccurate.:d
Thanks for the enlightenment, for sure, from frac
Thanks for the enlightenment, for sure, from frac
fractalicious
Dave
So in the day you had to actually have your own standards about or buy or synthesize them, rather than to get the information on these signatures electronically referenced from a national database???
Keeper Trout said:
Not exactly, it is still that way. Analysis requires actual reference standards rather data bases although there are automated analytical devices with sets of preprogrammed spectra. Even then positives generally require confirmation with a known standard.
There have been spectral data bases and reference compendiums around for many years. They are immensely valuable when trying to identify an unknown.
Its a bad idea to try to rely on that though for more than getting started with preliminary identifications.
Its always sound practice to actually run a known sample and also the suspected sample in the same system to be able to directly compare their spectra (even in thin-layer chromatography its always preferred to run a spot of a known standard alongside the unknown).
Its certainly possible to make good ID assignments based on the peaks in gc-ms (especially if you have a good idea of what is most likely and you just want to check it) but errors are also quite possible. Known reference standards run in the same system are really important in that regard.
For quantitative estimates having known dilutions of the alkaloid in question are required if a researcher is not doing isolations to the point of purity.
It is not cost effective for any chemical supplier to make a stockpile of every known natural alkaloid since most of those items would never recoup their manufacturing costs once they went into the catalog. Controlled substances are a different story and those are commercially available since they are required for analysis by forensic chemists.
Sometimes is simple to modify an alkaloid into another one but to accomplish the synthesis of many molecules a significant cost is incurred for each compound.
Researchers commonly keep their isolated and purified alkaloids for use as future reference standards and share them with other professional workers who have need. A lot of the published cactus chemistry could never have occurred without that.
There have been spectral data bases and reference compendiums around for many years. They are immensely valuable when trying to identify an unknown.
Its a bad idea to try to rely on that though for more than getting started with preliminary identifications.
Its always sound practice to actually run a known sample and also the suspected sample in the same system to be able to directly compare their spectra (even in thin-layer chromatography its always preferred to run a spot of a known standard alongside the unknown).
Its certainly possible to make good ID assignments based on the peaks in gc-ms (especially if you have a good idea of what is most likely and you just want to check it) but errors are also quite possible. Known reference standards run in the same system are really important in that regard.
For quantitative estimates having known dilutions of the alkaloid in question are required if a researcher is not doing isolations to the point of purity.
It is not cost effective for any chemical supplier to make a stockpile of every known natural alkaloid since most of those items would never recoup their manufacturing costs once they went into the catalog. Controlled substances are a different story and those are commercially available since they are required for analysis by forensic chemists.
Sometimes is simple to modify an alkaloid into another one but to accomplish the synthesis of many molecules a significant cost is incurred for each compound.
Researchers commonly keep their isolated and purified alkaloids for use as future reference standards and share them with other professional workers who have need. A lot of the published cactus chemistry could never have occurred without that.
wow..i wish i hadn't been so busy the last week..here we are with K. T. at the nexus!..
it's like entheogen heaven..
thanks for that valuable info Trout..hope you're well..!
on Clements et al., it does seem odd to 'dodge' questions on such an apparently 'big' discovery..would be great to finally see some more thorough testing of american species..
with the archeological evidence suggested of ritual use of acacia flowers by native americans (Pendleton & Pendleton 2011), and findings of alkaloids in flower (White 1951) and flavonoids (Petrie 1924) i suggest it would also be good, wherever possible, to also test flowers..it's also possible that flowers have different constituents to foliage or bark..
a note on phenethylamines in acacias..there are a handful of informal reports of the bioassaying of species known to contain principally PEAs (e.g. A. harpophylla) both orally and by vapour..no negative side-effects were reported, but the reports are scant..
.. on toxicity associated with livestock ingesting A. berlandieri..it is also possible that the toxicity is not directly a result of the alkaloids, but rather dietary interaction through vast amounts other compounds being ingested..
[similar to how it has recently been shown that acute Phalaris toxicity is caused by excessive Nitrate levels which are allowed to build up by a compound in the phalaris (not yet identified), and of course are a result of grazing many kilos of high nitrate plants]
..PEAs are certainly a different kettle of fish to DMT in terms of known and/or possible toxicity, but may well have benefits too..
.
it's like entheogen heaven..
thanks for that valuable info Trout..hope you're well..!on Clements et al., it does seem odd to 'dodge' questions on such an apparently 'big' discovery..would be great to finally see some more thorough testing of american species..
with the archeological evidence suggested of ritual use of acacia flowers by native americans (Pendleton & Pendleton 2011), and findings of alkaloids in flower (White 1951) and flavonoids (Petrie 1924) i suggest it would also be good, wherever possible, to also test flowers..it's also possible that flowers have different constituents to foliage or bark..
a note on phenethylamines in acacias..there are a handful of informal reports of the bioassaying of species known to contain principally PEAs (e.g. A. harpophylla) both orally and by vapour..no negative side-effects were reported, but the reports are scant..
.. on toxicity associated with livestock ingesting A. berlandieri..it is also possible that the toxicity is not directly a result of the alkaloids, but rather dietary interaction through vast amounts other compounds being ingested..
[similar to how it has recently been shown that acute Phalaris toxicity is caused by excessive Nitrate levels which are allowed to build up by a compound in the phalaris (not yet identified), and of course are a result of grazing many kilos of high nitrate plants]
..PEAs are certainly a different kettle of fish to DMT in terms of known and/or possible toxicity, but may well have benefits too..
.
Great to hear from you, Nen. I wish I was in Oz.
That is an interesting bunch of thoughts I need to look into. Thanks for that mind food I need to digest.
I had thought Anderton, Bourke and coworkers linked chronic Phalaris toxicity to a bisindole? It looks like a complex phenomenon of several sorts of toxicities so if what you mention accounts for the acute phase the picture may be finally resolving? Amazing its taking so many years.
Same with the berlandieri and rigidula picture. Sasha brought these problems to my attention around 1999 I think. Its incredible only in 2013 is a little light showing on those questions. That part wouldn't be happening if Fractilicious hadn't contacted Forbes and made that first post above.
This is a great set of inquiring minds here.
Berlandieri actually is a nutritious browse most of the time and causes no problems outside of prolonged drought periods. Your suggestion is sound since the problem seems be the result of something(s) building up over months of time.
That is an interesting bunch of thoughts I need to look into. Thanks for that mind food I need to digest.
I had thought Anderton, Bourke and coworkers linked chronic Phalaris toxicity to a bisindole? It looks like a complex phenomenon of several sorts of toxicities so if what you mention accounts for the acute phase the picture may be finally resolving? Amazing its taking so many years.
Same with the berlandieri and rigidula picture. Sasha brought these problems to my attention around 1999 I think. Its incredible only in 2013 is a little light showing on those questions. That part wouldn't be happening if Fractilicious hadn't contacted Forbes and made that first post above.
This is a great set of inquiring minds here.
Berlandieri actually is a nutritious browse most of the time and causes no problems outside of prolonged drought periods. Your suggestion is sound since the problem seems be the result of something(s) building up over months of time.
A friend told me he had smoked some pure PEA freebase a couple of years or so ago.
He said he got a huge rush and a bit of a headache with perceptible effects ending rapidly.
He said he got a huge rush and a bit of a headache with perceptible effects ending rapidly.
^..yeah, i haven't been too keen to emphasise PEA species in the acacia thread..
tryptamines i tend to know and trust..
re the acute form of Phalaris toxicity, here's what i dug up for the Phalaris=The Way of the Future thread:
tryptamines i tend to know and trust..
re the acute form of Phalaris toxicity, here's what i dug up for the Phalaris=The Way of the Future thread:
nen888 said:
nen888- Cool stuff. Its great how the acute and chronic poisonings are finally being understood rather than force fitting tryptamines as the culprit.
One comment I'd like to add is that there is no real reason to think Forbes is not honestly reporting his experiences.
There are some valid questions raised about their sources of reference standards that need clarification but his comment about being unaware of controvery or that anyone could not contact Clement are likely quite genuine.
Clement was listed as the corresponding author (ie the person all correspondence should be directed to) so all contact attempts would have gone to her. I do not know but suspect that Forbes was a grad student of hers at the time? There would be little reason for him to learn of this back then or since if no one pointed it out to him.
I still have some questions on the discrepancies in the reference standard comments stated above by Forbes and those in Clement et al 1997 but that seems likely to require a conversation to resolve.
One comment I'd like to add is that there is no real reason to think Forbes is not honestly reporting his experiences.
There are some valid questions raised about their sources of reference standards that need clarification but his comment about being unaware of controvery or that anyone could not contact Clement are likely quite genuine.
Clement was listed as the corresponding author (ie the person all correspondence should be directed to) so all contact attempts would have gone to her. I do not know but suspect that Forbes was a grad student of hers at the time? There would be little reason for him to learn of this back then or since if no one pointed it out to him.
I still have some questions on the discrepancies in the reference standard comments stated above by Forbes and those in Clement et al 1997 but that seems likely to require a conversation to resolve.
Thanks everybody for all the excellent thread here
I can´t be at the Nexus much due to current life circumstances but I´m very happy for all these developments!
BTW, regarding n-methyl-PEA, it seems I detected it in Mimosa hostilis too. Gardner (was it 2012 publication maybe? shaolin posted the paper somewhere in the nexus) was studying mimosa due to it also being toxic to livestock, which is relevant here. Though in the rootbark I analysed it seemed to be present only in trace amounts, and I didnt have a reference standard at the moment but by retention time in the chromatography column it was where it should have been (based on other analysis done in the past with same machine and with other PEAs with reference standards).
Then again, I also detected hordenine in the rootbark (and so did gardner, from comparing the spectra he sent me with my own tests, though he didnt identify the peak in the publication).
In any case the whole toxicity to livestock thing may have several factors involved, being one or several alkaloids or other mechanisms as mentioned by trout in SST and as nen mentioned above.
Anyways that was just a small note, keep this thread going, cant wait to read it as it develops
I can´t be at the Nexus much due to current life circumstances but I´m very happy for all these developments!
BTW, regarding n-methyl-PEA, it seems I detected it in Mimosa hostilis too. Gardner (was it 2012 publication maybe? shaolin posted the paper somewhere in the nexus) was studying mimosa due to it also being toxic to livestock, which is relevant here. Though in the rootbark I analysed it seemed to be present only in trace amounts, and I didnt have a reference standard at the moment but by retention time in the chromatography column it was where it should have been (based on other analysis done in the past with same machine and with other PEAs with reference standards).
Then again, I also detected hordenine in the rootbark (and so did gardner, from comparing the spectra he sent me with my own tests, though he didnt identify the peak in the publication).
In any case the whole toxicity to livestock thing may have several factors involved, being one or several alkaloids or other mechanisms as mentioned by trout in SST and as nen mentioned above.
Anyways that was just a small note, keep this thread going, cant wait to read it as it develops
This is a great thread. Good to see you endlessness, hope your travels are going well. See you in a couple of months buddy.
Peace
Macre
Peace
Macre
sleepypelican
Rising Star
there is an energy shot on the market that claims to contain an extract of from the leaves of Acacia Rigidula "yeilding 200mg of alkaloids including R-Beta-Methylphenylethylamine, Methylsynephrine, N-Methyl-B-phenylethylamine, Phenylehylamine". there are other ingredients, but that is what is stated as coming from acacia rigidula.
^..interesting..sleepypelican said:
thanks..
I'd suggest that the products on the market with N-Me-synephrine or synephrine or ephedrine or similar are all adding that from some sort other than Acacia rigidula. Sida, Ephedra and pharmaceutical compounds appear to be common choices in combination with rigidula in herbal products. (There must be close to two dozen products on the market right now. Caffeine is a common ingredient as well.)
I posted a reference to a recent analytical paper that sheds much light on this subject.
No amphetamines of any type were found in the plant (collected from three different counties in Texas) but they were common in the herbal products claimed to contain this species.
I posted a reference to a recent analytical paper that sheds much light on this subject.
No amphetamines of any type were found in the plant (collected from three different counties in Texas) but they were common in the herbal products claimed to contain this species.
FluffyClouds
Rising Star
What I find extremely interesting is that the plant contains amphetamines, mescaline ,nicotine ,dmt,etc all in one plant.
Example:
The cactus containing mescaline contains many other active compounds.
-----
The point that I'm trying to get across is this, maybe if one were to eat some of the plant's fruit?. As all the combined substances, creating something amazing?.
Example:
The cactus containing mescaline contains many other active compounds.
-----
The point that I'm trying to get across is this, maybe if one were to eat some of the plant's fruit?. As all the combined substances, creating something amazing?.
FluffyClouds
Rising Star
Senegalia berlandieri - Wikipedia
Vachellia rigidula - Wikipedia
Apologies for bumping an older thread but an article was brought to my attention that might raise further questions about data integrity in those results from Clement.
Readers with interest might want to check out an interview with Clement:
In particular one paragraph jumped out at me:
"The early season guajillo was unremarkable to Clement and her team. "The extraction was clean (bright green extract, easily partitioned with acid and base extraction)," Clement reported. "The analysis was relatively straightforward; we found terpenes, a few simple phenols and scant traces of β-phenethylamine, but no detectable N-methyl-β-phenethylamine, which had previously been reported." However, work on late season guajillo was a different story. "The initial methanol extract was a very dark green, almost black color," she noted, adding the team realized these extracts had to be handled much more carefully due to extreme vulnerability to degradation. "After we began using an argon blanket, this degradation was no longer a problem; argon is a much more forgiving inert atmosphere than nitrogen." The end result was positive identification of N-methyl-β-phenethylamine; N,N-dimethyl-β-phenethylamine; and tyramine in these fractions. "
Notice both what is said and what is not mentioned?
For instance, in light of those wealth of novelties consider this single sentence in that paragraph "The analysis was relatively straightforward; we found terpenes, a few simple phenols and scant traces of β-phenethylamine, but no detectable N-methyl-β-phenethylamine, which had previously been reported."
It is worth comparing her statement to the published details contained in that paper.
I've also noticed that all of Forbes' papers on the subject hav become unavailable at the A&M website, also at the A&M Uvalde website and at the Journal of Animal Sciences website (at least one of which, Pemberton et al, PubMed still lists as being available including free full text but following their link now leads to a missing page note).
If I've missed something please let me know!
Readers with interest might want to check out an interview with Clement:
In particular one paragraph jumped out at me:
"The early season guajillo was unremarkable to Clement and her team. "The extraction was clean (bright green extract, easily partitioned with acid and base extraction)," Clement reported. "The analysis was relatively straightforward; we found terpenes, a few simple phenols and scant traces of β-phenethylamine, but no detectable N-methyl-β-phenethylamine, which had previously been reported." However, work on late season guajillo was a different story. "The initial methanol extract was a very dark green, almost black color," she noted, adding the team realized these extracts had to be handled much more carefully due to extreme vulnerability to degradation. "After we began using an argon blanket, this degradation was no longer a problem; argon is a much more forgiving inert atmosphere than nitrogen." The end result was positive identification of N-methyl-β-phenethylamine; N,N-dimethyl-β-phenethylamine; and tyramine in these fractions. "
Notice both what is said and what is not mentioned?
For instance, in light of those wealth of novelties consider this single sentence in that paragraph "The analysis was relatively straightforward; we found terpenes, a few simple phenols and scant traces of β-phenethylamine, but no detectable N-methyl-β-phenethylamine, which had previously been reported."
It is worth comparing her statement to the published details contained in that paper.
I've also noticed that all of Forbes' papers on the subject hav become unavailable at the A&M website, also at the A&M Uvalde website and at the Journal of Animal Sciences website (at least one of which, Pemberton et al, PubMed still lists as being available including free full text but following their link now leads to a missing page note).
If I've missed something please let me know!
I dont understand, trout .. Isnt that paragraph about an earlier research, and not the one where they found the amphetamine-related compounds?
The amphetamine/meth/PMA etc compounds in acacia claim is def weird and raises questions. Who knows though, nature has surprised us before.. But you'd expect a follow up to try to repeat results, and AFAIK so far there is nothing..
The amphetamine/meth/PMA etc compounds in acacia claim is def weird and raises questions. Who knows though, nature has surprised us before.. But you'd expect a follow up to try to repeat results, and AFAIK so far there is nothing..
The Interview was a follow up about the more recent work of Pawar not being able to confirm N-Me-PEA in the course of investigating what they thought was an amphetamine in diet aids..
Did I miss an earlier analytical report?
Do you have a reference to an earlier paper?
There was at least one published follow-up that could not replicate the results. (Pawar et al 2014).
Did I miss an earlier analytical report?
Do you have a reference to an earlier paper?
There was at least one published follow-up that could not replicate the results. (Pawar et al 2014).
This is what I am currently aware of concerning the published analysis for the two Acacias:
Adams, Herman R. & Bennie J. Camp (1966) Toxicon, 4: 85-90. "The Isolation and Identification of Three Alkaloids from Acacia berlandieri."
Bennie J. Camp (1956) dissertation A&M, "The alkaloid of Acacia berlandieri, N-Methyl-B-phenylethylamine"
Camp, Bennie J. & Carl M. Lyman (1956) Journal of the American Pharmaceutical Association, Scientific Edition 45 (11): 719–721. “The Isolation of N-Methyl beta-Phenethylamine from Acacia berlandieri.”
Camp, Bennie J. & Carl M. Lyman (1957) The Southwestern Veterinarian 10: 133. [Have not yet obtained a copy.]
Camp, Bennie J. & Joan A. Moore (1960) Journal of the American Pharmaceutical Association, Scientific Edition. 49 (3): 158–160. “A Quantitative Method for the Alkaloid of Acacia berlandieri.”
Camp, Bennie J. & Michael J. Norvell (1966) Economic Botany, 20 (3): 274-278. "The Phenylethylamine Alkaloids of Native Range Plants."
Camp et al. (1964) Annals of the New York Academy of Sciences, 111 (2): 744-750. "The Chemistry of the Toxic Constituents of Acacia berlandieri." (Bennie J. Camp, Ray Adams & J.W. Dollahite)
Clement, B.A. et al. (1997) Phytochemistry, 46 (2): 249-254. “Toxic Amines and Alkaloids From Acacia berlandieri.” (Beverly A. Clement, Christina M. Goff & David A. Forbes)
Clement, B.A. et al. (1998 ) Phytochemistry, 49 (5): 1377-1380. “Toxic Amines and Alkaloids From Acacia rigidula.” (Beverly A. Clement, Christina M. Goff & T. David A. Forbes)
Forbes, T.D.A. & B.A. Clement (1998 ) Texas A&M University, Uvalde, BL-R8, "Chemistry of Acacia's from South Texas." (Essentially a short summary of Clement et al. 1997 & 1998.)
Pawar, R.S. et al. (2014) Journal of Pharmaceutical and Biomedical Analysis, 88: 457-466. “Determination of selected biogenic amines in Acacia rigidula plant materials and dietary supplements using LC–MS/MS methods.” (Rahul S. Pawar, Erich Grundel, Ali Reza Fardin-Kia & Jeanne I. Rader)
Pemberton, I.J. et al. (1993) Journal of Animal Sciences, 71 (2): 467-470, "Technical note: an improved method for extraction and quantification of toxic phenethylamines from Acacia berlandieri." (I.J. Pemberton, G.R. Smith, T.D.A. Forbes & C.M. Hensarling) Not accessed by me yet.
There was also an education Ag poster aimed at ranchers that was circulating in the late 1990s asserting meth was a danger to animals feeding on these Acacias. I did not think to try to obtain a copy until too late as I can't even find evidence it existed now (Martin Terry sent me a link to it online)
Adams, Herman R. & Bennie J. Camp (1966) Toxicon, 4: 85-90. "The Isolation and Identification of Three Alkaloids from Acacia berlandieri."
Bennie J. Camp (1956) dissertation A&M, "The alkaloid of Acacia berlandieri, N-Methyl-B-phenylethylamine"
Camp, Bennie J. & Carl M. Lyman (1956) Journal of the American Pharmaceutical Association, Scientific Edition 45 (11): 719–721. “The Isolation of N-Methyl beta-Phenethylamine from Acacia berlandieri.”
Camp, Bennie J. & Carl M. Lyman (1957) The Southwestern Veterinarian 10: 133. [Have not yet obtained a copy.]
Camp, Bennie J. & Joan A. Moore (1960) Journal of the American Pharmaceutical Association, Scientific Edition. 49 (3): 158–160. “A Quantitative Method for the Alkaloid of Acacia berlandieri.”
Camp, Bennie J. & Michael J. Norvell (1966) Economic Botany, 20 (3): 274-278. "The Phenylethylamine Alkaloids of Native Range Plants."
Camp et al. (1964) Annals of the New York Academy of Sciences, 111 (2): 744-750. "The Chemistry of the Toxic Constituents of Acacia berlandieri." (Bennie J. Camp, Ray Adams & J.W. Dollahite)
Clement, B.A. et al. (1997) Phytochemistry, 46 (2): 249-254. “Toxic Amines and Alkaloids From Acacia berlandieri.” (Beverly A. Clement, Christina M. Goff & David A. Forbes)
Clement, B.A. et al. (1998 ) Phytochemistry, 49 (5): 1377-1380. “Toxic Amines and Alkaloids From Acacia rigidula.” (Beverly A. Clement, Christina M. Goff & T. David A. Forbes)
Forbes, T.D.A. & B.A. Clement (1998 ) Texas A&M University, Uvalde, BL-R8, "Chemistry of Acacia's from South Texas." (Essentially a short summary of Clement et al. 1997 & 1998.)
Pawar, R.S. et al. (2014) Journal of Pharmaceutical and Biomedical Analysis, 88: 457-466. “Determination of selected biogenic amines in Acacia rigidula plant materials and dietary supplements using LC–MS/MS methods.” (Rahul S. Pawar, Erich Grundel, Ali Reza Fardin-Kia & Jeanne I. Rader)
Pemberton, I.J. et al. (1993) Journal of Animal Sciences, 71 (2): 467-470, "Technical note: an improved method for extraction and quantification of toxic phenethylamines from Acacia berlandieri." (I.J. Pemberton, G.R. Smith, T.D.A. Forbes & C.M. Hensarling) Not accessed by me yet.
There was also an education Ag poster aimed at ranchers that was circulating in the late 1990s asserting meth was a danger to animals feeding on these Acacias. I did not think to try to obtain a copy until too late as I can't even find evidence it existed now (Martin Terry sent me a link to it online)