Strange crystals in Rue extract (acid phase)?

[merkin]

Yeah, I'm knee deep in settling rue liquids

Now I used phosphoric acid instead of vinegar pretty much this entire process. Now I have been through a couple of based-decant-acidify-base-decant-wash-decant-acidify steps.

The pic is a liquid from its 3rd acid round and I was waiting for the seeming endless gunk to appear and settle before filtering again and maybe doing the first manske when I noticed these crystals all over the bottom of the flask. Normally the 'fallout' forms a dark greyish sludge on the bottom.

Any idea what they are? The pH is 2.79 and I actually saw them before on filtering a previous beaker but I thought they were dirt. They are sharp little clusters and appear reddish in the solution but black when dry. I don't have a dry pic but I'll try to get one when I filter this.

They taste *extremely* bitter and are very easily crushed or dissolved. When decanting the liquid they stayed firmly glued to the glass -

 

[downwardsfromzero]

I wonder if you've inadvertently discovered the phosphate equivalent of the Manske?

What do the crystals look like under UV light? And how about a solution of them under UV?

Perhaps you could recrystallise them from fresh phosphoric acid solution and repeat the UV tests. If you have a reagent testing kit it would be worth seeing what colour they give.

It would be a good idea to send a sample to Endlessness or Benzyme, perhaps.

 

[Elrik]

I suspect down may be right that it is harmala phosphate.
Its funny, just recently I've been pondering characterizing harmala sulfate because we really don't know how common salts of these alkaloids behave, beyond the hydrochlorides.
I'm dubious about using UV fluorescence as a test here, even trace quantities of harmaline glow bright. The liquid stuck between crystals could have enough harmaline to glow in solution.

As a beginning I would try to recrystallize them in water or water+alcohol to get the crystals cleaner. I'd get some dissolved and react it with a small quantity of calcium chloride or calcium acetate solution to see if calcium phosphate precipitates. Magnesium sulfate [epsom salts] could be similarly used. I'd also try basing some with sodium carbonate to do a mini-manske on the acetate made from any solids to see if they then match normal manske harmalas in crystal structure, fluorescence of a very dilute solution, and taste.
There is no mistaking the taste of harmalas. :shock: :surprised

If it is harmala phosphate pay attention and report any data, particularly a rough estimate of solubility in cold and hot water and if phosphoric acid or phosphates need to be added to push the crystals out of water. I suspect the acid wont be needed.

Now I have more reason to explore harm[al]ine sulfates properties.

 

[downwardsfromzero]

If precipitating phosphate with magnesium ions, add a suitable dash of ammonium sulfate/chloride first as magnesium ammonium phosphate is rather less soluble than (edit: at least some stoichiometries of) magnesium phosphate alone (iirc).

Elrik - That's what I was also thinking with the fluorescence test. It would require multiple recrystallisations to ascertain the absence of harmaline for exactly the reason you state. The phrase "wild goose chase" springs to mind in that respect :d

As far as easy tests go, simply applying strong heat to a sample of multiply recrystallised material would indicate the presence of organic material.

I'll try adding sodium dihydrogen phosphate to a sample of harmala alkaloids soon. We'll see what drops out in the fridge.

 

[merkin]

You guys stepped right out of my pay grade there! I'm strictly a recipe-following nexian and some of that stuff you wrote goes right over my head!

Anyway, sadly, I discarded most of them in my haste to complete my THH mission. I kept a few to get a pic when they were dry.

So I tried some of the suggestions:

1. It didn't dissolve at all in distilled water (cleaning their residue off the vacuum flask was also a little difficult)

*edit* Actually, after just resting for a few hours it did actually dissolve in the dist water!

2. The distilled water definitely took on the UV glow but that may just have been from the acid liquid they came out of
3. Under UV light (cheap LED torch) they didn't glow at all, unlike the manske mixed harmalas HCl
4. Not really sure how to recrystallise them to clean them (I need a tek to follow, lol)

Here are some more pics - First: the dried crystals and same under the UV - the filter paper contains the dried liquid they grew in and that obviously fluoresces brightly.

Second: the crystals not dissolving in distilled water and the same under the UV light

Third: Two pics of the Marquis reagent (all I have) test on the crystals and a comparison of the Manske mixed HCl under the UV to compare previous.

Last: Another pic of the crystals - the ones in the sun give a better idea of the color - sort of a bronze

Hope that helps!

 

[Jees]

I wonder if you've inadvertently discovered the phosphate equivalent of the Manske?...

Me too, but he decanted his base liquid away (and washed FB's) before acidifying again. This would have lowered the potential salt content (resulting from residual base + acid) to a low degree where manske becomes very unlikely. He did not add any salt himself for promoting manske effects.

Secondly, I've done manskes on rue with addition of NaCl and phosphoric acid, always the same fine needles as with vinegar, no flowers like this.

Merkin, what was the amount of rue you processed and in how much liquids did you perform the A/B cycles please?
What base did you use?
Was your phosphoric acid pretty clean?
Was the rue batch good looking? No mix with other seeds? Just guessing here.

It is something curious.

 

[merkin]

Jees - this was just acid-base etc before the first Manske - it hadn't been done at that stage yet. The Manske done later was very much as always with vinegar - the golden colored needles, angel hair. (so basically those crystals appeared in the later stages and when the acidified liquid was settling - usually as a grey mud before that).

3 batches of 80g Rue seeds, using sakkedelic's microwave process, slowly combining after settling and decanting every day or so. The A/B cycles were batches of roughly 600-800ml of liquid, varying a bit due to using water to wash out beakers etc when transferring and then splitting down to about 500ml if beaker got too full.

The base was KOH to pH 12-12.5 each time.

Phosphoric Acid is Chem Supply 85% CP

Yeah the rue has a few sticks and stuff here and there, I wouldn't call it too dirty although there was a stone at one point, but I definitely didn't see any other seeds.

 

[Elrik]

Nice equipment for someone that just follows teks, your room looks like one that makes teks :thumb_up:
I like to do serial decantation. When you decanted there was still quite a bit of liquid left in each beaker, at this point I'd stir them and combine them together into one tall-form beaker or glass and draw off more liquid after settling.
If you ever happen to get a centrifuge, that helps. I like to centrifuge out the solids after decanting as much as I can. After pouring out the liquid I then put some vinegar in the tubes and shake them to get the solids out as acetate for the next step. Once all of the alkaloid base is dissolved I like to centrifuge the acetate solution, this always deposits a dark brown to black impurity that could not have been filtered out easily before centrifuging. Even if the crystals had gone through a manske cycle or two before getting based I still can remove some black solids. I've never decided if its solidified red pigment or just stained protein.
Just a thought, in case you ever get that toy.

As a further aside that could hijack your thread , I do wonder if the teks go too far in basing.
In my last extraction I based to 10,3 before centrifuging a sample and basing the clarified liquid to 11,0 to confirm no additional solids were formed by more base. They were not, and my yield was 5,1% of manske crystals.
I'm now doing another extraction from the same lot of seeds, this time I based to 9,8 [the pKa of harmaline] before doing the centrifuge test. Again I got no additional precipitate with more base. I'll be curious to see if the yield I get differs significantly.

 

[Jees]

Thanks for the reply merkin.

...When you decanted there was still quite a bit of liquid left in each beaker, at this point I'd stir them and combine them together into one tall-form beaker or glass and draw off more liquid after settling...

I agree,
I thought all base was out and FB's washed before acidifying again, this I made up from OP.
With this amount of strong base left + acidifying again, you might have some amount of salt due base+acid, you might have an early and unwanted manske effect after all in your acid stage. Too weird it makes flowers, my harmala phosphates were the typical golden needles.
Still feeling puzzled...
I suggest, get rid of that base liquid before acidifying, and see if the flowers still occur. To get rid of base liquid I keep the recipient still and suck the top layer off instead of tipping over/decanting, to remove top layer few mm above the FB alks.

 

[downwardsfromzero]

Merkin, did you use distilled water throughout?

Calcium or magnesium phosphate ought to be eliminated as a possibility.

Another thing could be an organic acid of some kind, but at the third acidification this would seem unlikely - besides, you mentioned it tasted very bitter. Now this brings me to a further clarification point: in my experience, some people describe things which are acidic as being 'bitter'.

Spoiler

I would call this sour, like the taste of lemon juice and most unripe fruits, or vinegar.

[Is there only one spoiler allowed per post? OK.]
Things that I would describe as bitter-tasting include:

Spoiler

coffee, wormwood, acetone, chicory leaves, radiccio leaves

I'm trying to establish if there are qualitative differences in taste perception and the descriptions that are used, so if you could consider these questions before looking behind the spoilers, that would be great - what else tastes bitter? How would you describe the taste of lemon juice?

 

[Elrik]

I find that people almost universally mistake astringency for bitterness. It wouldn't surprise me if some other flavors are mistaken for bitter.
I have never in my life tasted bitter coffee, for instance. I'd be worried if I did! Yet people often cite coffees 'bitterness' as a common fact.
Quinine, genuine Calea, Andrographis, and distinctly bitter varieties of Gynostemma are bitter. Harmalas are bitter and something else, acrid? The stem ends of heirloom cucumbers or poorly grown broccoli can at times be bitter. It's a very different sensation than astringency or sourness.
I'm told beer is bitter. I don't know, I last drank a beer as a teenager and I was drunk at the time.

I think the lack of bitterness in industrialized diets is proof of a toxic diet.

 

[merkin]

Lots of good suggestions and questions! I feel quite humbled and a little embarrassed having my technique so carefully examined. Yes, I am most definitely not a pro at this and some results could definitely be as a result of that and impatience (this rue-> harmala thang can take a while!)

To answer (in reverse order)

Generally I used RO drinking water when 'washing' the bases, use distilled when mixing solutions and when small amounts needed (distilled water is expensive)

Definitely bitter, I would call vinegar sour, limes a bit more on the bitter side of sour. Brocolli I would classify as mustard-y lol. Actually my kitchen chemistry (as in food prep) is a lot better than my other 'kitchen chemistry' (as in substance preparation).

As for decantation etc, yes - I would combine those three beakers (limited no of beakers) together, wait again for settling then decant away to roughly a similar level on the combined one. Then I would add RO water to top up the beaker and settle, decant (siphon) and do it again. Then I would add some 10% phosphoric solution till everything became that red clearish color again. Then I would filter it immediately, then wait for settling (dark stuff, grey mud), then filter it again. Then I would start adding strong KOH to base it again and repeat. Those crystals appeared while waiting for a filtered acidified liquid to settle.

That centrifuge process sounds great, perfect in fact, but honestly my 'gear' is simple. I have a bit of a fetish for lab glass, the aesthetics of it I guess, and the rest came from other attempts at self prepared inebriates. The pressure pump (THC shatter) and the stirrer/heater + sep funnel (used as a slow dropper usually) from my quest to make clean GHB (without charcoal filtering and residual lactone flavours) and it taught me how important the right gear is for chemical processing. The other "pro" thing was a decent pH meter from China (for the VDS protocol) and glass pipettes with plastic thumbscrew pumps for pulling NPS. The vacuum flask I got to try and do Harmala filtering easier/better. Soon learnt not to filter the bases until after Manske!

Anyway, thanks for all the comments guys, its all very interesting to me and some good lessons towards improving my tek in general. I reckon if my high school science teacher had have demonstrated a single Manske to produce those golden clusters I would have followed a very different career path!

 

[Elrik]

I also use drinking water for large volume crude work like the seed [or cactus] boils, washing base, etc. it seems to cause no harm. It's when I'm trying to get the product pure that I go to distilled water.
And all of my stock solutions of acids, bases, dyes, etc. are in distilled water with the exception of one bottle of salt saturated tap water.

In a recent harmala extraction I kept the fifth boil separate from the rest and processed it by itself to know if doing five boils was worthwhile. The first 4 boils combined gave a respectable yield of crude red-brown manske crystals. The fifth boil processed, just by basing with carbonate and doing one manske, to beautiful pure gold harmalas that anyone would be proud of. All done with tap water except for using saturated salt water made with distilled water for the manske, because it was what was on my shelf.
Distilled water clearly isn't essential.

For the curious, that fifth 'boil' [really an hour simmering and 3 hours slow cooling, like the previous boils] represented 5,2% of the total extracted alkaloid. 660mg of golden manske crystals from 250g of seed. Just enough extra that I did 5 boils on the next extraction, too.

 

[merkin]

Cool, thanks Elrik, I was thinking the same about the water. Good to know it wasn't that important.

Jees - not that it matters much, but the reason for the decanted level in the beakers was quite simply the limits of the tool I cobbled up for siphoning - The Siphonater version 1.1 - 1.0 was straight glass tube -- then I added a little hook on the end of the glass tube so that it draws from above rather than always sucking up the precipitate when it gets near the bottom

I did not realise the importance of draining it more thoroughly before acidifying. I will use a pipette to reduce it some more next time. This Tao of Rue certainly forces a measure of patience on a person and I need to respect that.