I think a common misconceptions is that DMT-N-Oxide is present in our plant extraction as an active oil. There is no hard evidence for that that I can find.

Instead, there is evidence that the active yellow/orange/red oils many of us encounter are simply DMT in oil form. As I understand it, DMT can form different weak intermolecular bonds and has many forms (polymorph). There are at least two different crystal structures identified in the literature, and then there are DMT oils (I believe).

There is nothing fundamentally wrong with the polymerized DMT oil, and many nexians have learned to enjoy it. However there are some drawbacks:

- DMT oil is harder to dissolve in Naphtha. This causes either (1) a loss of yield, or (2) the need to use hot naphtha which may pick up some unwanted plant matter and decrease purity (worst situation being grasses with gramine).
- Harder to vaporize. Not a big issue with flame, but could be inconvenient for fine-tuned electronic vaping where folks baby and nurture their wattage vs time curves 🙃
- Indistinguishable from actual plant oils, leading to dosing questions.
- Hard and messy to handle.

With this in mind, this thread is to collaborate in coming up with a minimum DMT polymerization TEK.

From what I can tell, the polymer forms during the basing step. If the water is very concentrated with ions and DMT, aggregates and polymer form overtime (I believe). There is no polymer formation during the acid step (positively charged molecules cannot aggregate).

An acid step done on DMT oil can break up DMT polymer (some folks added Zn unnecessarily and then incorrectly concluded they were reducing DMT-N-OXIDE; instead they were just breaking up the polymer with the acid and the Zn was doing nothing - in my opinion). Dissolving DMT oil in naphtha doesn't seem to change the DMT polymer state much.

Ok, so here is an outline of a TEK that tries to minimize DMT polymer:

Some ionic strength is good. For reference this Tek will target the "Max Ion TEK" ionic strength of ~1.9M. This is a great TEK and I'm using it is a reference point, but will make small changes try to minimize polymerization.

First part of the experiment will be focused on releasing the DMT salt from the plant matrix. This will be done with citric acid and freeze/thaw/warm temperature cycles. Will avoid boiling as it can break down the plant too much into stuff that will be absorbed by naphtha. This is already a known process (not new).

Second part of the TEK will be a little different than usual. To minimize polymerization, naphtha will be added first. Then, NaOH will be added in two steps. First to lightly FB DMT and allow it to move into the Naphtha as it forms and (hopefully) before it has a chance to polymerize. Finally, a 3rd NaOH addition will be done to full strength to break up any emulsions and push any remaining the DMT into the Naphtha.

Outline: (9/22 edit: moved to new outline/logic shown in post #10)
- Mix 100g of powdered bark, 1L of water, and 60g of citric acid
- Freeze/thaw/warm to 50C three times.
- Add Naphtha. This is not a defat step. This naphtha will be present to grab onto DMT as soon as it forms in the next step to try to minimize DMT aggregation/polymerization in the alkaline water. This is really the only thing that is "new" 😅
- Add 50g of NaOH and mix (citric acid and plant neutralization along with gentle basing will occur, expect a milky emulsion). Don't mix to quickly so solution stays bellow 50C.
- Add 25g of NaOH and mix (strong basing, expect good separation).
- Separate Naphtha, do a few more pulls, reduce solvent volume, and freeze as usual.

If anyone has any thoughts or knows why this could be wrong let me know. Otherwise I'll test this out in the next few weeks. Cheers.

Good stuff Loveall! Thank you.

Query: based on what you've stated, if I wanted polymerization (say to obtain "goo" on purpose), would you recommend leaving out all NaOH?
Thanks

One love

Keep the NaOH, free base is what polymerizes. To try max the goo, I would concentrate the DMT in water, add NaCl to 25% or so (double the max ion Tek), and let that base sit in the fridge for a few days. Then pull with hot Naphtha. It should be a lot of goo. You may even see some goo floating on the water before the pull in this extreme situation.

Gotcha. I didn't think that one quite through all the way lol.

In the next few days I'll start a new extraction with the attempt to maximize goo and report back soon.

Thank you very much. Looking forward to hearing your results.

One love

One thing that is not explicitly outlined in the method ('tek') is whether the NaOH is added as solid material, or pre-dissolved to some desired concentration. I would suggest the latter, principally in order to avoid localised high temperatures.

Loveall, nice to see the subject of to-goo-or-not-to-goo is still rocking.

Not about bark extraction, about 14 days ago there was this initiative to minimize time present in base + minimizing ionic strength. It was to freebase deems-fumarate by pulling with naphtha.
About a gram of the D-fumarate got dissolved in about 100 to 150 ml of luke warm water, kept the vessel at around 50degC during the pull. Then 100ml of naphtha was added and placed in a stirrer on fairly high speed. Only then a base of 8mol caustic was dripped in slowly, really drop wise. It was cool to see the miniature white cloud of each drip immediately got grabbed by the naphtha, this embodied the minimal-time-in-base objective. In the end pH 14 was reached without the watery layer ever becoming clouded as a whole. The expectations were to have only white FB flakes in the freeze stage of the naphtha.

Before freezing a very tiny thin yellow layer did form at the bottom, preventing to call it a 100% white success. In the end it looked as a very typical naphtha pull, white with a little hint of yellow, but sure no goo to see.

Some questions arise:
* would it have helped to add tiny acid anyway, initially? I suppose not.
* definitely overshoot with the base, perhaps this added to higher ionic strength than necessary.

No report of yield, it was an eye indicative test.
Next time more care will be taken, a larger watery layer and lesser base overshoot.

All in all I liked the idea of starting in salt stage, adding naptha there already, then base slowly. Haven't thought to do same on a bark soup, thanks for mentioning.

***

About this wiki:
https://wiki.dmt-nexus.m..._Freebase_Conversion_TEK
Type 1 and 2 both use the same starting materials, but end significantly different.

It surprised me that Type 2 yielded all goo while type 1 nothing of a goo. Checking out type 2 it indeed formed a block of goo in a split nano-second. (Voidmatrix, if you like goo this is the way to go)
Checking out Type 1 this took too long for the milk to crystalize, I doubt efficacy yield wise. Pulling with naphtha looked a faster method so left type 1 tek.

Happy trials...

Thanks for the feedback Jees! I enjoy the spice in all its forms and this is a good exercise to further grow and refine my chemistry knowledge.

One love

Very cool report Jees, thank you.

In the Tek you link, method 1 uses a lot less sodium carbonate (seems to just titrate and add a little bit more) and crystals form in the water, while method 2 uses a lot of excess sodium carbonate and makes goo in the water. That makes perfect sense and I think is consistent with our current thinking.

pH of 11 should be enough to free-base most of the spice (pKa+2.2).

With the plant stuff very high pH is kind of "required" because of emulsions, so some goo may be inevitable. Maybe instead of freezing the first Naphtha pulls from a heavy plant basing, a mini A/B is needed where a gentler pH is used when basing the second time, them simply pull with the same naphtha and freeze that. Maybe that is a better approach than having Naphtha present during the base (or maybe both changes can work together), or maybe being careful with the pH and keeping it at 11 is good if Naphtha is always present (?).

I don't know, but there are things to try 🙂.

I'm gonna mix Naphtha and acid plant soup. Them add base incrementally, colors will change and emulsion will form. Add enough base to just break up the emulsion, see if goo is minimal 🤞

Good experiment. It may be possible to minimise goo by drying the naphtha with something like saturated brine before cooling. Damp naphtha was one of the other factors implicated in goo formation.

I think this could be useful. Testing indicates that acid can break down polymer, but you have to have enough acid. Mild conditions don't seem to de-polymerize oils to white xtals.

We've assumed that in the plant DMT is a salt and not polymer form, but things may be more complicated. I imagine the plant could have polymer "hybrid" grouping with salts at the "ends".

Also, NaOH lysing time seems beneficial to wrestle the DMT from the plant, so it may be a good idea to keep it and deal with the polymerization we things it causes.

One way, to put all this together would be:

1) Lyse 100g bark in 250ml of ~10% NaOH. Downside is polymer increasing, but we take care of that next.
2) De-polymerize in a warm acid environment where DMT concentration is low (dilute to 1L and go for a low pH towards 2).
3) Add naptha
4) Slowly base while shaking until emulsion breaks (and no basing beyond that).

This looks a lot like the max ion TEK, except that the NaOH lysing step is moved to before the de-polymerization acid stage. Max ion limits alkaline lysing/polymerization to 2h, and the DMT is dilute, so that may take care of excess polymerization already. Still, if some DMT polymer does form, or if longer alkaline lysing is beneficial if done before De-polymerization, there could be an improvement to an already excellent TEK by simply moving this step.

Edit: Early results in this work flow here. Future results will be posted here.

Carrying a blazing torch for method development as ever, Loveall!

It'll be interesting to see what results you get. We'll get at least an indication whether the hydroxide anions are what catalyses the oligomerisation, or if DMT is itself a sufficiently strong base to autocatalyse the reaction.

Another factor could even be cation size. Would potassium hydroxide produce less polymerisation as the larger potassium cation is a weaker Lewis acid than sodium? Would lithium hydroxide produce more polymerisation? Side note, ammonium cations are considered to be in the same size range as potassium.

Hi Loveall,
could A/B be as effective as the proposed STB+A/B concerning "lysing" cells, can an acid replace lye just as well? We would need a stronger acid than a weak acid (preferably not muriatic acid because of practical drawbacks) but what about phosphoric acid? Any better candidates out there?
Thanks.

I think that is a great question. Perhaps avoiding strong base altogether general is good, polymerization seems reversible in some experience, but if gets too bad it may be hard to undo. There is also salt from the neutralization which was not present in our de-polymerization experiments. Also, when I tested the strong base earlier, I did get some yellow color on the xtals.

There is also the possibility that DMT has a small degree of polymerization in the plant. It's a salt, so unlikely - but who really knows? Concentrated acid could help break up any natural polymerization should it exist.

Oxalic is the only other acid I can think of. Phosphoric could be a good choice. Citric too (see attached list ordered by pKa). A mixture of acids could each go after different parts of the plant and work better together.

There is also the microwave assisted extraction option. It can lyse cells, especially when drying wet bark. I've been trying to learn about it. There is also the freeze/thaw.

So now I'm thinking of a hybrid A/B min polymer

- High concentration strong organic acid mix (15%), extract/lyse with microwave and/or freeze/thaw.
- Dilute by a factor of 2 (so salt concentration is not high after neutralizing)
- Base with Ca(OH)2 with Naphtha present. This limits the pH. Ca++ salts would be at ~7% and help break emulsions, and do the salting out effect.

ACY had an extraction along these lines (was a drytek with less water) and got white xtals from acacia confusa. Perhaps DMT in that plant has a higher degree of natural polymerization (groups of 4 or so indole rings facing each other surrounded by charged amine+ tails and encapsulated by plant anions. A sort of polymerized DMT micelle. Maybe when doing A/B on acacia we are not only cleaning it, but also de-polymerizing it (?). Q21Q21's published TEK also has this sort approach for mimosa (using vinegar instead of citric and limiting potential alkaline polymerization by using lime).

In our published TEKs there are statements such as vinegar helps DMT become a salt and be soluble in water. I'm confused by that because DMT is already a salt. Perhaps acid helps break up any natural polymerization should it exist. That could make DMT more soluble in both water and naphtha, and also more white/xtaline like we have been observing if starting with what we think is polymerized DMT.

Here is a potential practical test with actual numbers. I haven't done this yet, but plan to try something similar to this:

-Extract: Mix 100g of bark with 500ml of 15% citric acid solution. Microwave at 300W for 30 minutes. Replace any lost water, stir, and repeat microwave run two times for a total of three runs.
-Dilute: Add water to reach ~1L of volume in the extraction vessel. Ideally, the vessel narrows near the top to make pipetting easier in the next step.
-Pull: Add ~150ml of naphtha and shake solution. Add lime and continue shaking. Solution expected to go from light red, to milky, to dark red (after ~ 50g of lime). Settle, allow layers to separate (hopefully they do), and remove solvent layer with a pipette or turkey baster. Repeat naphtha pull 4 more times (warmer pulls at 50C may be better but if polymerization is very low room temp may be fine, IDK).

Formic?

In respect of using oxalic acid: Calcium oxalate is practically insoluble, so emulsions would be the same at best and salting out unaffected/ineffective.

Lime would have to be mixed with water into a paste first, otherwise (as a powder) it will disperse into the naphtha, which is a pain.

I believe formic has a higher pKa/pH than both Oxalic/Phosphoric.

Good point about forming insoluble calcium salts. Those that are soluble will suppress the pH from lime. Need to keep that in mind. Perhaps we won't get a good salting out effect or emulsion breakdown. We'll need to see.

I was imagining the lime cloudiness disappearing in the solvent disappearing while shaking. Will test it out. I have seen it before in dryteks though and know what you mean, valid concern - thanks.

DWFZ's note on Calcium salt solubility is interesting.

We got what looks like great de-polymerization results with a combo of acetic, citric, ascorbic acids. Not sure if all are needed, but that's what we got. When using less acid results where not as good.

When neutralized with lime, acetate and ascorbate salts are soluble, while citrate is not. That's fine, actually quite convenient if we want to end up with an ionic strength similar to Cyb's max ion tek without having to dilute with water.

Updated approach:

- Extract with a combo of acetic, citric, ascorbic.
- Basify with Ca(OH)2. Citrates crash, but acetates and ascorbates remain in solution. Choosing the citric to ascorbic + acetic acid ratio seems like a convenient way to adjust the ionic strength and Ca++ concentration. The pH will also be buffered and gentle, minimizing potential DMT polymer formation.

Microwave could be useful. The oscillating EM field shakes ions and rotates polarized molecules. Seems like a good environment to make sure DMT is not polymerized. Macro plant DMT salts with possible polymerization should break down into very simple salts with minimal polymerization.

We also have ACY's result on acacia mentioned above. He did a microwave drytek with a pinch of citric acid (for min polymer we would test 15%+ citric). Then added lime. Despite being a dry-tek ionic strength was low because calcium citrate is not very soluble. From a minimum polymer point of view this is ideal (low ionic strength and gentle pH). The DMT concentration was high before adding naphtha which goes against our hypothetical min polymer. However, there could be a way around that even with a dry TEK: add naptha before basing and base slowly to try to limit FB concentration in the alkaline MHRB water paste (since it moves into naphtha as it forms). We would also skip waiting for DMT to FB as ACY mentions: that goes against our min polymer hypothetical approach here. Would need the cloudy lime to clear up (or alternatively use a lime paste as used as DWFZ suggested).

With the lime/naphtha question it's mostly down to which step you want to add in: mixing up a lime paste or filtering fine lime particles out of naphtha (or waiting a while for the lime to settle out before decanting).


The mixed acid approach does seem promising - nice idea.

Not sure about rate of polymerisation (I've never used NaOH), but ime STB with KOH also produces the polymer.

Ok, I don't recommend this. Ca(OH)2 could not basify the acidic extract well and I had to break out the lye. Emulsions where a mess too.

However, the process did give white DMT. Whitest I've ever gotten.

I think the initial acid treatment may be important. The more aggressive, the more likely it is to get to a min polymer state and whiter DMT (?).

Does anyone know if natural DMT in the rootbark is aggregated in some kind of marco molecule with some degree of oligomerization/polymerization? Could different plants have different macro molecule states (eg acacia > MHRB). It has en reported that "PC abuse" gives good results for acacia, perhaps the PC de-polymerizes the DMT for that type of plant (?).

After learning from the last data turn, gonna try this approach:

- De-polymerization of natural DMT (?): 100g root bark, microwaved with 300ml of a "strong" 15% citric acid solution till 100ml evaporate (about 100 minutes at 200W).
- Allow to cool, add ~100ml naphtha
- Slowly mix in ~500ml of 10% NaOH (try to avoid polymerization by giving DMT FB the opportunity to move out of the water as it forms and not reach a high aqueous concentration)
- Pulls/freeze precipitate

Are you going to include a filtration step in there? I'm interested in experimenting with this technique myself, but I learned the hard way that putting basified MHRB solids into my separatory funnel is really, really unpleasant.

Incidentally, it was during that same experiment that I found that after repeated citric acid cooks (3-4 washes at pH 2 and 80°C for a total of 6-8 hours), I could only recover a negligible amount of DMT from the remaining solids via STB. It's possible that it may have (re)polymerized per your hypothesis though.

Do you think adding salt late in the process and doing another pull could yield additional product, per Cyb's Max Ion? Maybe once the DMT is dilute enough in the aqueous phase, ionic strength overtakes polymerization as the limiting factor for additional yields.