moyshekapoyre
Rising Star
ijahdan said:
Any particular salt form? I thought it was as HCl salt that it was degrading? Or those photos were of FB crystals?
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Harmine, harmaline and THH from Syrian Rue. Verification and finetuning of the VDS-protocols
- Thread starter An1cca
- Start date
Any particular salt form? I thought it was as HCl salt that it was degrading? Or those photos were of FB crystals?
ijahdan
Rising Star
Just checked back through the thread and an1cca describes preparing samples for microscopy by first dissolving in vinegar, then adding a drop of ammonia, so this would yield freebase I suppose. He also describes thh in solution changing colour under uv light from blue to green, indicating oxidation. This can be reversed by adding more zinc. This suggests the oxidation also happens to the acetate salt form in solution. More research needed.
moyshekapoyre
Rising Star
Loveall said:
Not sure, didn't measure pH, but 2 extractions were done. The first was done with the usual amount of vinegar and yielded very little harmine (but significantly more harmaline than usual). The second was done with only a dash of vinegar, but the same result... very little harmine. So I'm thinking the seeds are simply changing due to the cold weather perhaps. I will try to get some unripe seeds.
And what is exactly "as always"? We cannot know. Some people use pH 8.75 as a separation point but this is not how VDS worked.moyshekapoyre said:
How do you determine whether you have harmine or harmaline please?moyshekapoyre said:
Since this is a VDS thread, we suppose you follow that procedure, but which one? VDS did both carbonates-separation and pH-depression style of separation.
Spill some beans please
moyshekapoyre
Rising Star
"As always" was an opaque reference of course, but the point was just that nothing has changed in my technique (which is the old way of using sodium carbonate to separate, but I may change to ammonia now), and so I had to assume that the seeds were the issue. I could upload my technique notes, but it is basically the same as what folks have been doing with rue before this VDS tek came out. One difference tho is that I do precip harmine at pH 7.5, so that part I already figured out thru experiment.
Thank you for clarifying that.
Of course in a fixed approach the seeds could be the difference.
In the plays we made with rue some things showed like the point where a component starts to precipitate is not pinned on a specific pH, this has been confirmed several times. Conditions determine that point. General conditions might cloak that vulnerability. For example I've managed to precip harmine at just above 6 by doing extra care to minimize salt content. Your fixed approach should eliminate this potential drift. But the results call for an extra examination if really all parameters where identical, maybe some just out of the corner of habitual eye sight? A nudge of salt is all it needs to elevate that pH point significantly. I fail to back this up chemically, maybe some none can? The salt comes from basing the acid as far as I supposed. pH point gets more sensitive to that salt when the concentration of alks rises. Just some observations, no more.
I believe you when you say the executes were identical, I was only pointing out to peculiar encounters.
Happy trials :thumb_up:
Of course in a fixed approach the seeds could be the difference.
In the plays we made with rue some things showed like the point where a component starts to precipitate is not pinned on a specific pH, this has been confirmed several times. Conditions determine that point. General conditions might cloak that vulnerability. For example I've managed to precip harmine at just above 6 by doing extra care to minimize salt content. Your fixed approach should eliminate this potential drift. But the results call for an extra examination if really all parameters where identical, maybe some just out of the corner of habitual eye sight? A nudge of salt is all it needs to elevate that pH point significantly. I fail to back this up chemically, maybe some none can? The salt comes from basing the acid as far as I supposed. pH point gets more sensitive to that salt when the concentration of alks rises. Just some observations, no more.
I believe you when you say the executes were identical, I was only pointing out to peculiar encounters.
Happy trials :thumb_up:
moyshekapoyre
Rising Star
Jees said:
Wow, verrry interesting. Thanks! I will consider that...
Btw i dont get notifications when replies are posted on this thread for some reason.
Your welcome moyshekapoyre.
Just to add extra that in normal boiling/extracting situations (where the concentration is "low") then the pH points where stuff precipitate are quite fixed. But in higher concentrations (like in possible separation actions) this starts to play a role. Not only pH points start to become lively, also the whole crystallization process gets affected with mechanics that are unseen at higher concentrations, which is where the VDS approach seem to hinge on.
The vds paper does not cover the use of strong bases (caustic etc) as these seem to make vds approach impossible. So in higher concentrations also kind of base starts to matter the crystallization points (pH points).
Again, for the stages where people are extracting seeds it is of no concern. But I thought it might be worth noting because you had some peculiarity in a separation act between harmine and harmaline. Do you recall what concentrations you worked with (gr extracts per volume of liquid) and what base you used?
But seeds low in harmine, perhaps yes, who knows.
Just to add extra that in normal boiling/extracting situations (where the concentration is "low") then the pH points where stuff precipitate are quite fixed. But in higher concentrations (like in possible separation actions) this starts to play a role. Not only pH points start to become lively, also the whole crystallization process gets affected with mechanics that are unseen at higher concentrations, which is where the VDS approach seem to hinge on.
The vds paper does not cover the use of strong bases (caustic etc) as these seem to make vds approach impossible. So in higher concentrations also kind of base starts to matter the crystallization points (pH points).
Again, for the stages where people are extracting seeds it is of no concern. But I thought it might be worth noting because you had some peculiarity in a separation act between harmine and harmaline. Do you recall what concentrations you worked with (gr extracts per volume of liquid) and what base you used?
But seeds low in harmine, perhaps yes, who knows.
moyshekapoyre
Rising Star
So I wonder if too much salt would potentially make the harmine precipitation point closer to the harmaline point, or would it just raise both equally? If the former, then that could potentially be an explanation, but I will see if I can find the notes on how much liquid was used etc. Thanks again Jees!
An1cca
Rising Star
Moyshekapoyre, did your microscope already arrive? It comes in very handy while experimenting to check the nature of your precipitate. Needles=harmine, ferns=DHH, boulders=THH. Mixtures have diverse appearances. I posted a lot of them together with their respective GC/MS results earlier...
I suppose the pH point would rise (due salt) both, but in same amount that I dunno.
The conditions seen for pH rise were dual:
- high enough concentration;
- use of a weak base. (carbonates, ammonia)
If these conditions are not met, none of the VDS mechanics work (imho) and a regular pH split point of 8.75 between harmine and harmaline can be used. At pH 7 only 17% of harmine is freebased (hard) according to a theoretical calculator.
The conditions seen for pH rise were dual:
- high enough concentration;
- use of a weak base. (carbonates, ammonia)
If these conditions are not met, none of the VDS mechanics work (imho) and a regular pH split point of 8.75 between harmine and harmaline can be used. At pH 7 only 17% of harmine is freebased (hard) according to a theoretical calculator.
Attachments
Jees said:
According to the link below, at the low salt concentrations molecules are salting-in meaning that their solubility increases with salt content. At higher salt concentrations the opposite happens and they are salted-out (so there is a max. solubility where the salt goes from increasing solubility to decreasing it). When you minimized salt carefully I think you saw the earliest precipitate because you where minimizing the salting-in effect.
Here is a link and a quote which I don't quite understand 100%, I'm not an expert - just trying to learn
Salting in - Wikipedia
Wikipedia said:
moyshekapoyre
Rising Star
Jees said:
Base was sodium carbonate. Volume of liquid between 12 and 18 liters for about 60g of harmalas.
Still awaiting microscope.
Following up on Jees' comment where minimizing salt caused precipitates to form earlier when basing: There is a relatively recent (August 2017) write up on salting out/in here,
After reading it, I want to try CYB's max ion tek with Na2SO4 instead of NaCl. Has this already been tested? Maybe one day we can generate our own Dm plots/data
.
After reading it, I want to try CYB's max ion tek with Na2SO4 instead of NaCl. Has this already been tested? Maybe one day we can generate our own Dm plots/data
.moyshekapoyre
Rising Star
Ok, got the 60x microscope, but of course my THH is a powder so I will have to crystalize it...
Indeed, and give it some time like a few minutes while they grow, indicated by disappearing white-milky.An1cca said:
Aim not to disturb the glass in general, be gentle as possible, the crystals are extremely fragile (harmaline mostly) when they wobble around in that drop, they can break into parts by hitting onto each other and when moved they form pockets of heaped collected crystals instead of nicely spread out. Get the concentration right, too much and it forms a chaotic mess. Lower concentration so far until there's some free space between the crystals after they grew. It took me some time and for a while I thought it would never work. But in situ (in a drop) is a fun and ultimately the best way for identification.
:thumb_up:
May there be some reason to think sublimation could be an effective way of filtering freebase harmalas from undesirable alkaloids, in lieu of successive manskes?
I notice that An1cca has sublimated harmalas with a wine preserver. How long did it take? What type of set up did you have? Sublimation of THH seems like it would be ideal in light of what has been noted about heavy metal impurities in zinc.
I notice that An1cca has sublimated harmalas with a wine preserver. How long did it take? What type of set up did you have? Sublimation of THH seems like it would be ideal in light of what has been noted about heavy metal impurities in zinc.
An1cca
Rising Star
Nigredo, I would think that performing a Manske with your crude THH will already purify your material in a rather specific way. I managed to sublime the freebase from a washer that was mounted onto an adjustible soldering iron underneath a glass Mason jar that was pulled 'vacuum' with a Vacuvin winesaver. It's an interesting process and quite beautiful to see the snow-white THH condense on the glass. However, it was a small sale setup and more a proof-of-concept kind of thing. For small quantities only and quite lossy. A deeper vacuum and more contrallable heatsource could certainly increase yields. Hope this helps...