urushibara (Hive Bee)
04-29-03 05:02
No 430117
      bulk plant extractions and sugars  Bookmark   

I'm not sure exactly if this is the right place to post this, but it is about methods, so I thought it would best go here. It could just as easily apply to other plant alkaloid extraction processes, since sugars are universally present in plants. I am happy to see this moved to the tryptamines forum, but I think that here it will attract more comments from more knowledgable chemistry folk.

SWIM recently did an extraction from a fairly large quantity of acacia obtusifolia bark, and for the second time encountered a problem with what he believes to be sugars in the sap that are extracted.

The acidic extraction was done at a pH of about 3, and when the whole solution was reduced to 500ml (from about 20L) it became a thick soupy sticky consistency, which defeated all efforts to properly filter it.

It also made defatting almost impossible, since the sugars are also amphoteric and the separation of the nonpolar solvent very innefficien and lots of residual defatting solvent ends up in the final extraction.

SWIM was thinking that maybe other SWIMs had worked with larger quantities, and could inform SWIM of the best way to eliminate this problem.

These are the ideas that SWIM has had regarding this:

The problem seems to stem from the fact that sugars are in fact miscible in water. Thus, although he expects that no significant loss of product occurs, a mixture which is more than half sugars becomes very difficult to work with.

Thus first of all, he thinks that filtration should be done on the unreduced liquid, as in this state it flows freely and would not clog the filter quite so much as the sugars which coat and thicken preventing the flow of the solution. Using progressive filtration, starting with a strainer, then through a single layer of cloth, and then multiple layers of cloth and finally through coffee filters.

The other idea that is coalescing is that it might be possible to use salting out to drive the alkaloid salts out of the solution, thus separating them from the undesirable sugars. This would be done in a fair excess, well before the solution becomes too thick, it doesn't matter much if there is an excess of salt, as this will not completely confound the extraction, it will mean that more base will be required to achieve the high pH required for extraction.

After adding an excess of salt to the solution, the solution would be cooled, and the supernatant (above the precipitate) liquid should be now safe to discard. The alkaloids will drop to the bottom along with other substances which are less soluble in the water due to the full saturation of the solution with salt. Thus they should remain in the bottom of the container when pouring it off.

The liquid at the bottom should now be relatively free of the sugars, while other substances, such as tannins and mineral salts, along with the alkaloid salts which will make the defatting step much simpler.

The technique of salting out as used in the manske extraction has been demonstrated (by me) to work with other alkaloids, namely caffeine and hypericin, so there is no reason to suspect that DMT tartrate or whatever acid ion bound to it wouldn't likewise drop to the bottom of the container.

The elimination of the sugars would make the whole process a lot simpler.

I would like to hear other chem savvy folks comments on this idea. Even in small extractions, this would reduce the amount of material very dramatically, and make defatting a hell of a lot more effective.

SWIM, of course, depleted the last of his stock of obtusifolia bark in this most recent 'disaster', though perhaps he might have *some* alkaloids left in the bark that this extraction was done with, but probably not much, and the ratio of sugars to material is probably majorly depleted compared with fresh material. He's run out of funds to continue further experiments at this point, and is also imminently about to become homeless, but he will definitely pursue this experiment.

you can't keep peace with a gun
(Hive Bee)
04-29-03 17:19
No 430207
      correction  Bookmark   

okay okay, you don't have to tell me, sugars are not miscible in water. you can see it is true because the solution forms a skin of crusty sugary stuff.

They do go quite liquid at the boiling point of water though.

anyway, if anyone can suggest a means of separating the sugars out, that would be rather handy.

I just had an idea that perhaps boiling down the acidic extract until it starts to go excess sugary, and then cooling it down might work? at the point of syrup formation, the sugar is saturated, so cooling it down would make it more fully come out of solution.

I should see if tfse has any clues on isolating sugars.


you can't keep peace with a gun
(Hive Bee)
04-29-03 18:31
No 430220
      the fucking search engine!  Bookmark   

Okay, I did a bit more reading, about sugars, and I happened to find a nice post of stuff which was from strike I think, reposted by psyloxy, which talked about filtration and extraction.

Anyway, the end result is I worked out a solution to the problem of sugars in bulk extractions, which prevent boiling down past the saturation point of the sugars (this is a problem, because sugars don't boil, and they melt at around 200+C, which means the salts of the alkaloids are at risk of evaporating if the sugar increases the temperature of the solution this high).

The answer is: boil it down until it appears to lose vigour in boiling (this is the sign that the sugars are increasing the boiling temperature), then defat the solution, since defatting is fast and easy to do, this could be done quite quickly with a couple of empty 4L turpentine bottles, and done with turpentine, which should dissolve the sugars quite well.

Then it should be safe to boil it down further, without the risk of other chemicals in the solution causing a dangerous rise in boiling temperature, thus making it possible to reduce to a tidy small volume, which is essential if dealing with bulk quantities.

and proceed as normal after that, of course taking into account that it might take more naptha to extract if there's more freebase.

That should solve the problem I think.

you can't keep peace with a gun
(Hive Addict)
04-29-03 20:03
No 430237
      Precipitate the sugars?  Bookmark   

I believe you can precipitate the sugars out w/ lead oxide. I don't have the ref handy but remember it from the chromo work i did...
  You have carboxyl acids in that brew which you should probably remove w/ baking soda before you boil it down, that will help prevent the saponin's from jelling up on you...

Infinite Radiant Light - THKRA
(Hive Bee)
04-30-03 01:31
No 430288
      gelling?  Bookmark   

ah, so part of the problem is gelling. and yes, there is a soap-like feeling to it as well.

lead oxide... there wouldn't be other alternatives would there?

Wouldn't it be risking de-ionising the DMT raising the pH like that?

Would it help to defat before boiling it down further, since both the sugars and saponins will be washed off to a significant degree by a nonpolar (probably aromatic) solvent?

you can't keep peace with a gun
(Hive Addict)
04-30-03 01:48
No 430296
      correction...  Bookmark   

It's lead acetate.. it all comes out.. here's the cite from Practical Thin-Layer Chromatography Bernard Fried and Joseph Sherma, page 182:

     Add just enough lead acetatte to the soultion to cause complete precipitation, shake thoroughly and let the mixture stand a few minutes."

    Get the carb. acids out prior to defat cause the polar is not going to get those out of the solution. Then when you try to do the basic extraction, you end up saponifying everything and have the ugh of emulsions to deal with.. ( which is why i bought a centrifuge and even that isn't fool proof for extraction)

    So if you use the sodium carbonate (or bicarb) to precipitate the Carboxylic acids  and this to clean up the sugars, then you can go basic and extract  into non-polar layer. 

   This is the only ref. I've found for cleanup of sugars.

Infinite Radiant Light - THKRA
(Hive Bee)
04-30-03 02:05
No 430297
      degelling with NaCl  Bookmark   

Would salt also function to stop the saponins gelling?

just googled for info about saponins, found a couple if nice piccies, which helps understand their chemical structure - in essence they are terpenes, often with sugars bound to them - some are also steroids.

These two above are from withania somniferum

the saponin from quillaja, 'desert chilli', which is quite useful as a soap.

anyway, these chemicals act in a similar way to manufactured soaps, and it doesn't take much salt at all to drive them out of solution, soapmakers have to use distilled water to get liquid soaps to dissolve properly, otherwise it ends up cloudy and the soap molecules settle to the bottom if given enough time.

Also, clearly from looking at some typical saponin chemical structures, they clearly would be removed by defatting as well.

I'm not sure how to work out a proper technique for this, it is a concern that putting too much salt in would settle out alkaloids as well, but a tablespoon or two wouldn't bee too much in a solution which is being reduced to 500ml or a litre. Defatting will also remove them, so that should be done first I think, or maybe a tablespoon of salt and defatting at the same time.

you can't keep peace with a gun
(Hive Bee)
04-30-03 02:20
No 430298
      thanks clearlight  Bookmark   

Using lead acetate to make the sugars settle out would obviously be helpful. I suppose this chemical would have to be bought from a chemistry supplier (ugh) which is a bit of a pain.

I don't see how sodium carbonate or bicarb would precipitate the carboxylic acids, it would neutralise them, but they wouldn't drop out unless the solution was saturated. or would it be saturated?

Saponification is harder to do than you think, generally it takes about 3-4 hours at a fairly high temperature to get fats to saponify, and the fats would be removed quite effectively by defatting anyway.

I am thinking the best way to go would be to defat with lots of nonpolars, aromatics preferably, then add a tablespoon or two of NaCl (preferably rock salt for the purity factor), then filter the material, and it should be possible to boil it down quite a bit further after that.

you can't keep peace with a gun
(Hive Addict)
04-30-03 06:34
No 430338
      Saponification is fast...  Bookmark   

There is a link somewhere on this that i'll have to dig up that explains the whole procedure w/ removal of carbox's as the carbonate precipitate.

   Saponification happens really fast.. just ask anyone who's done a a/b wash on MHRB... I got so much suds there I washed the sep funnel with it!  It was pretty much instantaneous as soon as the NaOH hit it....which is why i happen to know something about it lol!

  I'd much rather have the tryptamine than the soap though...

Infinite Radiant Light - THKRA