I don't think we encounter DMT oxide. There is no hard evidence for that as far as I can see. The only thing I've seen was an assumption that the oil was an oxide because (1) the orange color matched literature descriptions and (2) a "zinc reduction" turned it into xtals. BUT polymerized DMT can also be orange, and the 'zinc reduction' result is also compatible with simpler de-polymerization in acid of DMT, where zinc is not helping reduce anything. In fact, regarding (2), one can turn the oil into xtals with an acid treatment alone, no zinc is needed as later experiments showed. Further, benzyme analyzed oil from a synthesis and found no oxides, instead he found mass peaks in multiples of DMT (compatible with aggregation/oligomers/polymerization).

Therefore, it seems that calling the oil an oxide was a mistake. This highlights that it is important to confirm hypothesis with an analytical result (even if a couple observations match a particular hypothesis there can still be other explanations).

There is yet more evidence against the DMT oxide claim. Brennendes Wasser made DMT oxide with peroxide (confirmed analytically) and found that it is an orange wax that with a cherry flavor that is not active. That is not what we encounter in extractions where the orange oil does not smell like cherries (it smells like xtal DMT) and is active. Before these analytical results, people assumed that DMT oxide converted to DMT with heat, but that seems to be false based on Brennendes Wasser's results. Instead of a DMT oxide conversion with heat, they simply never had DMT oxide to begin with and made another false assumption to hold their previous false assumptions together.

Relevant threads discussing this with analytical data and experimental results without zinc:

https://www.dmt-nexus.me...aspx?g=posts&t=95617
https://www.dmt-nexus.me...mp;m=1091320#post1091320
https://www.dmt-nexus.me...aspx?g=posts&t=88183

An aggregating/polymerization model also helps understand things better in my opinion:

The strongest results we have found so far to minimize polymer is that acid treatment helps, and also that dilute DMT basing also helps (e.g. see Jees's results above), and that a light saturated hydrocarbons seem to help (e.g. using lighter fluid with C6-8 instead of heavier painter's naptha with C9+).

This sheds new light on the max ion tek I think. The long acid treatment (8h) can break down natural DMT aggregation. Also, the extract is diluted to 1L or so for 100g of bark (~0.3% DMT). The justification was to be near the top of the jar/bottle so pipetting is easier. However, this dilution also minimizes polymer formation, helping DMT move into the solvent and boosting xtal yield. In a few ways, max ion is also a min polymer tek, it hits a sweet spot for good partition and min polymer. Since partition cannot be increased by aqueous DMT concentration because of polymerization, a dilute DMT solution (~0.3%) helped by ~6 to 8% NaCl salt ions seems to hit a sweet spot to get a good partition into warm light naptha while avoiding polymerization.

I think it is time to kill the DMT oxide idea, and look at our TEKs with polymerization in mind. It can explain some of the observations in them (e.g. not heating the solvent to avoid oil contamination and get xtals is just a loss of yield from not picking up the less soluble DMT polymer - such TEKs yield less than max ion).

Polymer also explains some modern e-mesh results. A higher temp is needed to get full effects from polymerized DMT because the vaporizing temp goes up. Similarly, during several heat cycles of a loaded crafty starting with excess xtals, DMT polymerizes and the temp needs to be dialed up to keep on getting effects.

Hi,
my zinc is grey as hell, yours seems white? Zinc oxide is white, is that what you have please? I believe zinc oxide is unable to cause a reduction as zinc does.
Nevertheless the color change is clear, it must have done something.

I disagree. In 2018 Brennendes Wasser demonstrated that FB DMT can undergo photooxidation to DMT-n-oxide, and in 2021 presented a reliable method for synthesizing it from an EtOH solution using H₂O₂. Despite being a relatively stable molecule on its own, it is clearly capable of oxidizing in the presence of oxygen radicals.

Oxygen radicals are everywhere. They form in the presence of UV light, they occur in aqueous solutions, and they're a natural by-product of plant metabolism. It stands to reason that there is at least some DMT-n-Oxide present in our extractions.

Further, it's been shown that DMT behaves strangely in the presence of its oxide. The oxide seems to inhibit the DMT from crystallizing, even in very trace amounts. The resulting homogeneous mixture presents as a sticky goo, tinted anywhere from pale yellow to dark reddish-orange by the oxide present.

I would further postulate that DMT is capable of forming a complex with the oxide, such that the FB facilitates the oxide dissolving into NPS where it would otherwise be insoluble. This may be particularly pronounced at temperatures above ~60°C, where DMT melts into a liquid that as far as I can tell, is more or less fully miscible in hot heptane.

This could explain why my pulls get redder and dirtier the hotter they are. Using ascorbic acid I pull at 60°C to avoid decomposing the ascorbate, and compared to pulling at 90°C using citric acid, my yields with ascorbic acid are both cleaner and smaller.


I think you're begging the question. How does this explain what happened in the vial I was holding? I had to agitate it to dissolve the DMT into the citric acid. To reduce incidental oxygen I also replaced the air in the bottle (as much as was practical) with relatively inert gas. It sat there for 20 minutes before I added the zinc, re-replaced the air, and shook it once. The color change was immediate. Something got reduced in that jar, and the amount of trace impurities and free oxygen were not enough to explain the significant amount of zinc oxide that crashed out upon basing.


If this were strictly true, it should work with acetic acid and it would be common knowledge that you can turn orange goo into white xtals by simply cooking it in vinegar. All your experiments demonstrating "acid depolymerization" that I could find included citric acid, ascorbic acid, or both; they're both reducing agents, whereas acetic acid is not.


I can't seem to find this post? Can you link it? If they were dealing with a large amount of DMT FB complexed with a small (or trace) amount of DMT-n-oxide, the presence of the oxide could have been obscured by a large amount of FB polymerized with it.


I think completely discounting the possibility of the presence of DMT-n-Oxide in an oxidizing atmosphere is likewise a mistake. It's also a fallacy to assume my hypothesis is wrong just because others observed the same phenomenon and reached a similar conclusion but an incorrect mechanism.

I have a sneaky suspicion that we're both correct. I propose that even small amounts of DMT-n-Oxide can trigger the polymerization of DMT, which causes them to stubbornly move in tandem through aqueous and nonpolar phases where the oxide would not go if it was pure. The resulting mixture:

• Is active
  
  • Because it's still largely n,n-DMT
  
  
• Is yellow to orange to red
  
  • Tinted by the dark red oxide
  
  
• Fails to crystallize, remains oily/gooey
  
  • Either due to polymerization, or because the amorphous oxide interferes with the formation of a DMT crystal structure, or both. Probably both, considering DMT is persnickety about crystallizing and doesn't mind spending a few days as a supercooled liquid anyway
  
  
• Is difficult to separate
  
  • It persists until the oxide is reduced to DMT by zinc or a reducing acid, is incrementally removed through repeated A/B workups, or the polymer is degraded by a prolonged boil in NPS

This could even explain the vaping issue you pointed out; the oxide or oxide-FB-polymer could raise the boiling point of the mixture, to the point that it won't boil until the last of the oxide has decomposed.

That being said.....

I'm not making any hard assumptions here, I'm proposing a hypothesis and laying out my evidence for it. I assume you're doing the same, so, let's work together! I have an analytical balance with a 10μg resolution and some **very** pure DMT to work with. In a few weeks I'll have all the apparatus I need to easily extract virtually all of the NPS-soluble substances from an aqueous solution. I'm willing to produce some DMT-n-oxide for the cause, if you'll help me devise an experimental protocol to help us settle the question of whether our polymerish goo contains DMT-n-oxide or not.

That's a trick of the light. My zinc isn't as finely powdered as I would have liked, so it was a little shiny. Zinc oxide is soluble in acid, and a significant amount of white zinc oxide crashed out when I basified this solution.

I do have some fine zinc powder on the way though. When it arrives I'll test to see how fast it gets attacked by various organic acids and report back.

IridiumAndLace, good point, maybe there could some oxide with the DMT polymer. Let's see if we can determine if that is the case.

Here is benzyme's mass spec result (first post), I don't see a DMT oxide peak was present (from a synthesis),

https://www.dmt-nexus.me...aspx?g=posts&t=88183

He was able to convert the red oil back to xtals using solvent alone (presumably the solvent he used broke up the polymerization). I only got partial breaking de-polymerization in solvents, but I used heavy painter's naphtha while benzyme used a very light hydrocarbon (CAS 101316-46-5, with 30-50C boiling point I think). I have since switched to lighter fluid which is generally a lighter hydrocarbon than naphtha and I'm getting less oil in my extractions from what I can see.

As I understand BW's thread he never sees DMT oxide from extractions. He also tested heat (100C oven I believe) and did not get any oxide. You are right that he got oxide after two days of direct exposure to sunlight, but we don't do that in extractions. I assume that if you send your DMT oil for analysis you would get the same result as he did and see no oxide (as long as you don't expose DMT to direct sunlight by extracting outside on a sunny day), but I could be wrong.

Regarding your zinc experiment, I believe zinc salt forms when metal zinc reacts with acid to release hydrogen gas. Zinc salts can also change the color of the solution I think, and also crash when basing (ammonia basing being a possible exception). You could have formed zinc salts without reducing anything. I could be wrong thought.

You make a good point about me not having a de-polymerization result with vinegar alone. I think diluting the DMT in acid could be very useful to de-polymerize better (e.g. do a large volume A step instead of a mini A). I may try that with vinegar at some point.

I considered that, but barring any trace side products, the only zinc salt that could have formed was zinc citrate, which is freely soluble in water. (I didn't observe any bubbling of hydrogen gas, but it could simply have been reacting too slow for bubbles to be visible.) Zinc oxide is water soluble under acid conditions but insoluble in alkaline solutions. The sheer amount of zinc oxide that crashed out actually threw me, because it turned the aqueous phase cloudy and I couldn't tell when I was done pulling from it.

One issue I immediately spot with benzyme's analysis is that they were running the GC/MS at 200°C. We know that DMT-n-oxide decomposes above 100°C, so it's possible all they saw in the mass spec was degradation products, maybe even DMT that had been reduced right there in the column. Formic acid in the eluent, perhaps?

I'm not making a case against DMT aggregation/polymerization; I agree there's excellent evidence of that. I'm suggesting that this aggregation may be triggered or mediated by the presence of DMT-n-oxide (and/or other indole impurities). I'm picturing, for instance, a clump of DMT molecules all stuck together, with a molecule of oxide in the middle lending a tiny bit of charge to promote pi-bonding and hold the clump together.

So far, most or all of the proposed teks for breaking these polymers could also be explained by the reduction (or removal) of the oxide. If we can make that oxide reduction particularly efficient, we'll no longer need to worry about the polymer, because it won't form.

Edit: I finished my extraction and re-x for the vial of spice I posted about the other day. The dish looked awfully empty, and I was worried I had lost half my spice somewere. Scraping was an experience though, it turned out the crystals were just exceptionally dense. From ~1.3g of crude spice, I ended up with 1.2200g of pure white DMT, so dry and crisp that it hardly even sticks to the glass. Not a trace of goo, and some of the xtals even came out whole.

I think I'm definitely going to pursue using zinc as a reagent in my future extractions. I don't know how much it'll increase yields, but even if it just increases purity, I sense a new tek in here somewhere...

Sorry, but I did not follow your exposition very well. If oxides trigger polymerization wouldn`t they become part of the polymer? Or does your current model implies some sort of non-covalent interaction between oxides and NN-DMT?

I have so many questions regarding the polymer model, like, where the additions occur? At both ends? Which atoms would be the ends by the way? What about oxides, they add better or worse than NN-DMT?

Very beautiful white crystals by the way.

When reducing with zinc we indeed form a lot of zinc salts and IridiumAndLace will have formed it for sure, it needs passing a high enough pH level (say 11) for these zinc salts to go again into solution so to retrieve the alks 'alone'. The precipitated and retrieved zinc salts I got below this pH level (say under 10) where off white and hard when dry, so this can be misleading.

(Basing with ammonia is in my anekdotal experience not excluded from this process but I've found ammonia turning the zinc salts back into solution to happen more fast and easy compared to lye or carbonates.)

In this post pictures set (omit the text) only zinc salts (product of vinegar + zinc) were in the vessel (no alks!) to see how they develop under a range of pH. The pH levels may not be absolute numbers, they may drift up or down as the composition changes (presence of alks, other salts,..) but the general idea remains to go just pH high enough after reduction to get them zinc salts liquid again to be discarded with the liquid.

Firstly, massive kudos to IridiumAndLace for the elegant idea regarding DMT aggregation. You've given me a 'lightbulb moment' there, so thanks for increasing my understanding.

Ruffles - The thinking regarding polymerisation is a little different from what you may have learned in the example of polyethene or polypropene. Rather than the strong sigma bonds that are formed when the pi bonds of the alkene monomers in the examples given are broken, in the case of DMT it is being posited here that a pi charge-transfer aggregation is being formed.

What we may be seeing here is intermolecular interactions occuring through differing charge distributions and some quantum mechanical shenanigans. IridiumAnd Lace has supplied the rather nice idea that the increased polarity of a single DMT-N-oxide molecule may be sufficient to induce the pi-stacking oligomerisation of a significant number of non-oxygenated DMT freebase molecules on either side of it. The charge of the oxide makes it 'sticky', and the stickiness oozes through the stack like having a stripe of honey in the middle of a stack of sliced bread.

The idea is that that one oxygen atom inductively pulls the charge concentration away from the indole portion of the molecule slightly, causing the electron-rich pi clouds of the neighbouring DMT molecules to become attracted to the ever so slightly more positively charged indole portion of the N-oxide. This results in the outside face of each surrounding DMT molecule to become ever so slightly positively charged and the process continues repeatedly until some such level of aggregation that the entropic effects resisting the increased order outweigh the energy gained form the pi-transfer aggregation.

Probably a picture would help, but for now try imagining the bread and honey analogy - except that the oozing of the honey is running in completely the opposite direction compared to the electron redistribution.

One possibility is indole ring pi stacking. Color under UV changes for DMT xtal vs DMT oil as benzyme observed, consistent with this.

I believe the literature mentions this aggregation can occur when the molecules come in close proximity in solution. Hence why the DMT FB concentration in water is could be very important. To break this aggregation up hot low boiling point solves seem good when in FB. Also, time as a salt in an acidic environment helps break up the aggregation.

DMT in the plants may come aggregated already. Perhaps more so in acacias vs MHRB. Acacias Amy benefit more from a longer acid step and light hydrocarbon solvents. This is just speculation though.

I don't see any signs of DMT oxide in any analysis of plant extracts. It's never there, even if oil is analyzed. It only shows up after peroxide or UV treatment. If it shows up in plant extraction analytical results, I'll be happy to learn and be proven wrong.

IridiumAndLace's result was good using zinc though. If she did see an experimental benefit to Zinc, Could there be an alternative explanation to DMT oxide reduction?

I've assumed that high ionic strength increases polymerization when basing because it lowers DMT solubility pushing molecules together. I've also seen FB DMT polymer oil quickly form and float in concentrated water solutions and very high NaCl concentrations.

However, what about at intermediate ionic strengths? Maybe I was wrong to assume that less ionic strengh is better to minimize polymerization in general.

It turns out that cations may interfere with pi bond stacking, through a cation-pi bond mechanism. The nature of the cation makes a big difference, in particular K+ >> Na+. I wonder about Ca++ too.

So does a moderate ionic strength in the water help break down polymer? The MAX ion TEK has NaCl concentration at 6-8%, is that a good range for Na+ to interfere with DMT pi pi bonding? Is higher NaCl concentration detrimental since the Na+/Cl- form shells around water pushing DMT together?

How about using a different cation other than Na+ that is better at forming a "protective" cation-pi interaction? K+ seems promising based on the info in the wikipedia link above (add KCl instead of NaCl). How about Ca++ (add CaCl2 instead of NaCl)? How about Zn++ (add zinc metal and an acid)? How about basic amminoacids like Arg and Lys?

Could this also explain why dry TEKs prefer Ca(OH)2 over NaOH? Maybe Ca++ is better at disrupting polymerization in high DMT concentrated water than Na+?

In practice a test adding some CaCl2 or KCl in the acid step to de-polymerize and DMT oil or to extract with min polymer could be interesting.

To recap, the max ion tek already seems like a "min polymer" tek beaded on learnings and hypothesis so far:

1) Long acid treatment may break down any natural DMT plant aggregation
2) ~1M NaCl addition adds cation-pi interactions which could compete with the pi-pi aromatic ring interaction that causes aggregation
3) DMT solution is diluted to ~0.3%, less chances of DMT molecules to see each other and have pi-pi aromatic interactions
4) Target pH to 12. Avoiding very high pH is a good idea, otherwise water activity decreases and pi-pi interactions are more likely to occur as seen experimentally (this seems to out compete the increase in Na+ from the base).

I think considering polymerization may help understand the max ion tek a little better. One question I always had is why stop at ~1M salt concentration? Why not more to keep on improving the partition coefficient? Cyb mentions emulsion as reasons to not up the salt. Indeed, at very high ionic strength water activity decreases, and DMT oil forms because of aggregation (out competing the increase in Na+) - which could be the source of the emulsion. There may be a sweet spot for min polymer while the partition coefficient is still improved somewhat, which is where max ion landed through experiment. It is a thing of beauty how Max Ion, found near ideal DMT concentration, Na+ concentration, and OH- concentration to push up the partition coefficient while simultaneously (possibly) minimizing DMT aggregation with experimental feedback.

Maybe Max Ion is already good enough for min polymer. But to get the dense white shiny xtals consistently right off the bat, maybe there are a couple adjustments from the minimum polymer point of view:

- Use KCl (available in many hardware stores) instead of NaCl. Reason is K+ is better at forming cation-pi bonds because it interacts less with water. This could allow higher ionic strengh without DMT oil forming, boosting partition coefficient while still minimizing polymer. There is still a trade off between salting out and aggregation, but K+ could be more capable (lease aggregation allowing more ionic strength).
- Add solvent before basing. Add solvent slowly until emulsion breaks up, then stop. This helps DMT move out of the water before it can aggregate in pi-pi bonds as FB.
- Use the lightest hydrocarbon available (C5-8 ). It seems better than heavier painter's Naptha (C8+) at disrupting/dissolving pi-pi bonds aggregation. A boiling step before freeze precipitation seems to help break up any remaining pi-pi bonds (not a re-x, simply boil the naphtha pull before freezing).

I plan to continue testing these ideas. Open to new odeas too.

Thank you all for answering my questions and illuminating my limited mind, indeed I was thinking of `classical` polymers, something more as strand-like molecules with covalent bonds between the monomers. Your explanations dispelled fixed concepts and I kind of can see now that there are more `degress of freedom` regarding electrostatic interactions between molecules and the possible structures they would form.

Cation-pi and pi-pi interactions are kind of newish though (started in the late 80s?). Turns out they are kind of important though. They were just recently discovered as very important in nicotinic receptors. We are still just speculation here that they may play a part on how DMT presents itself (could be that this is false), more experiments should shed light on this, especially if K+ can break up FB oil in water for example (K+ should be superior to Na+ at disrupting pi-pi bonding with cation-pi interactions - see image below from Wikipedia).

Thanks for the thoroughness - as ever - in delving deeper into things, Loveall! The possibility of cation-pi interactions is thought provoking. Trapped sodium ions could provide that electrostatic 'stickiness' required to promote oligomerisation and high ionic strength would indeed promote this happening.

It turns out that indole is on the higher end of the range of susceptibility to cation-pi binding:


If it is indeed the sodium cations that are intercalated in the centre of the pi-aggregation oligomers, it should be relatively simple to detect the presence of sodium through its strong emissions in flame spectrometry.

High levels of pi-intercalated sodium could even explain the cases of caustic-seeming batches of DMT, perhaps.

Thanks DFZ.

I wasn't thinking of Na+ ions promoting aggregation and ending up in the extraction, interesting idea. I'm was not considering that Na could make it into the solvent. This is what I was thinking as a hypothesis:

- DMT aggregation occurs when indole to indole pi-pi bonds form. The planar molecules could stack together like a deck of cards (or other configuration). For example, in high pH and high DMT concentration water, DMT oil forms and floats at the top, possibly because the high concentration and lower water activity is an ideal environment for the indole rings to interact. Or, the plant may stack it's DMT molecules to store them in macro-molecules with pi-pi interactions.

- Maybe DMT could be de-agreegated (or stopped from aggregating) by breaking(disrupting) the pi-pi bonds with cation-pi bonds. That is where Na+, may be useful in the max ion tek (%~6-8% NaCl concentration). However too much Na+ and water activity decreases so much that pi-pi bonds begin to form again.

- Cation-pi bonds could be good if they protect DMT from aggregating with pi-pi bonds in water. Then, the cation-pi would break apart in Naphtha, with the Na+ returing to the water and the neutral DMT molecule remaining in the solvent.

- We want high solubility in the solvent to disrupt any pi-pi bonds that remain there. Lighter hydrocarbons that (a little bit more polar than the larger hydrocarbons) seem to be able to get in between DMT molecules and separate them. Especially with a boiling step before freeze precipitation. Other solvents could promote pi-pi bonding (e.g. xylene), so oils result from these (but they could be ideal to pull aggregated DMT that light naphtha cannot grab onto even when warm).

I think this also explains why in extractions with partially aggregated DMT in the water (e.g. STB I believe), one gets relatively white to orange xtals with cold Napthata: the aggregated DMT is harder to pick up and stays out of the way when the naphtha is colder. Them, with a warm solvent pull, DMT becomes yellow/orange and waxy/oily because the aggregated molecules can now be picked up.

Point being that the exceptional results from max ion are not just because of an improved partition coefficient (otherwise more pulls with other TEKs would apporach the same result). The Na+ addition (along with the long acid soak), minimize pi-pi bonded/aggregated DMT in the water.

If this is true, KCl could be even better than NaCl at disrupting pi-pi bonds (or maybe there is no difference if NaCl does a great job already). Using a light hydrocarbons and boiling it before freezing could also help ensure any remaining pi-pi bonds formed in the water are gone. Perhaps these changes to max ion (motivated by min polymer considerations) will give even whiter, denser xtals that vaporize at the lowest e-mesh settings and more easily complex with | High Pobability of Braindamage by Creepy non tested Drugs (forced by scammer 69ron) |.

Or... I could be completely wrong. Will run tests and see what happens.


PS: I've seen e-liquid change color from clear to yellow/orange over time. DMT in the e-juoce may slowly be aggregating. I don't think it is oxydizing, but not sure. Having something added that disrupts pi-pi bonding may avoid this issue for e-liquids. Or maybe a heat cycle to break them up.

Hmm, OK... I was also wondering if zinc might happen to fall into a magic range of charge density that promotes the depolymerisation of the pi stacks. It's like a calcium ion but with shielding from its 10 extra d-electrons, making it potentially similar to potassium from a cation-pi point of view. The increased nuclear charge overall brings zinc's ionic radius to practically the same as that of magnesium.

Of course, in aqueous conditions all these ions will be inside a hydration sphere at the very least, and in the case of zinc the hexaaquo complex is well established.


The consequence and indeed the relevance of any of these observations are something I'll have to sleep on.

Since last time I got .5g from a few pulls, I kept those jars. I did another single pull out of each jar (roughly 50ml NPS each) and this was the result, and as such will do some more pulls.

Not sure how much of the yellowing is a result from using preused NPS and how much is related to the polymorphism of DMT coming at the tail end of pulls.

One love

First, thanks so much to DFZ for that fantastic elucidation of my hypothesis. I really think I'm on to something with this oxide-mediated oligomerization idea. The resulting "goo" may only contain trace amounts of oxide, which is why a) it's commonly reported to be active, and b) oxides haven't been detected in extracts.


Absence of evidence isn't evidence of absence. It may simply be that nobody is looking for oxide, and it gets missed in analyses because the signals for oxide get lost in the noise. Oxide won't show up on a GC/MS because it degrades at a low temperature, and do we even have a reference IR spectra for it? If a sample contains even half a percent of oxide, would that be discernible from plant fats or other impurities on a TLC or spectrometer? I don't know, but I suspect not.

The goo/oil may only contain traces of oxide... But maybe a trace is all it takes. Like I said earlier, DMT is finicky about crystallizing; when cooling molten DMT, or doing an evap from a completely dissolved solution, even fairly pure DMT freebase seems perfectly happy remaining a gooey, sticky, resinous liquid for days or weeks at room temperature before spontaneously crystallizing. Agitating it (such as by scraping) helps when the freebase is quite pure. But if you have oxide present interfering with the DMT crystallization, it may remain a red/yellow goo indefinitely.


Oooh, this is a cool thought, and perfectly compatible with my hypothesis. The positively charged cations may help inhibit aggregation, possibly to the point that the oxide-freebase complex becomes too small and polar to dissolve into the NPS. That is to say, it starts behaving less like freebase and more like oxide. This gives larger, cleaner yields, but with the tradeoff of leaving some amount of aggregated freebase in the aqueous phase, bound to insoluble oxide. I propose that if we can reduce the oxide back to freebase, it'll liberate the remaining freebase and drive yields up even further. How much, depends on the amount of oxide present to begin with, and the degree of oligomerization under varying conditions.

See, my experimental result presents another obstacle to the "pure DMT polymer" hypothesis. After I filtered off the zinc, when I went to basify my solution, I accidentally basified it too fast. Not only did this result in the zinc oxide abruptly crashing out of solution, it also caused the DMT to crash out so fast that it formed large globules of clear molten DMT floating between the water layer and the NPS layer. (I was doing this at around 80°C, well above the melting point of DMT.)

Had this molten DMT been tinted yellow or orange, I might well have described it as "DMT oil". Had it fallen out of the NPS in the freezer but failed to crystallize, I would certainly call it "goo". Neither was the case; it was clear and virtually colorless, dissolved rapidly in the NPS, and crystallized out cleaner than any of my previous extractions.

Having that much DMT present in aqueous solution (high concentration), and then adding that large an excess of sodium ions, I don't know that I could have created a more ideal situation for the formation of DMT polymer. Except, of course, for the zinc ions present, which quickly crashed out anyway. Obviously, polymerization did not occur, and indeed the opposite seemed to happen even under these extreme conditions. The amount of zinc oxide that precipitated suggests that the zinc didn't just catalyze the breakup of the polymer, it reduced an oxide somewhere.

Once again, I think you're not wrong about the formation and behavior of DMT oligomers. I just think the inconsistency in these results compared to your hypothesis supports my idea that there's another factor in play driving polymerization. So far, DMT-n-oxide is doing a pretty good job explaining the experimental results.

Of course, all this is just speculation at this point, and likely will remain so until someone can do a lot more in-depth analyses of various DMT goos and extractions. But once all my new glassware arrives, I'll start doing some tests to see if I can at least use this new hypothesis to improve on Cyb's Max Ion tek.

I used LCMS, because it's what I have (I don't have GCMS), and it is amenable to heat-labile compounds; the capillary temp was set to 200 C to vaporize the mobile phase, for the short flowpath of the ion transfer tube. However, it does not degrade the analyte. That fact has allowed me to analyze heat-labile compounds like ergolines.
Also, formic acid is used in LCMS (not GCMS) as an ion-paring reagent...it generates protons in the mobile phase, for complexation at the ion source, with the analyte (positive mode electrospray generates greater ion counts than negative mode). All it does is add +1 to molecular masses of all analytes.

I've only noticed n-oxide from harsh conditions, like pyrolysis. UV-induced degradation may also cause n-oxide formation.

as for dimers... I notice them with addition of strong base...NaOH. The exothermic rxn it generates favors dimer formation; I've never seen dimers form from sodium carbonate. I just analyzed some that was basified with sodium carb, and extracted... no 378 m/z ion present.