Ohhh, I was wondering why your DMT was reading 189 rather than 188! TIL!



Here's a question: how high does your mass spec go? Assuming the oligomers survive the trip through the column intact, the indole stacks could be, I dunno, tens of molecules long even? That feels like an extreme upper limit, but hey, it's a thought.

Also, would you notice a peak at 197 if it was in extremely low concentration, say 1% or even 0.1%? How about minute traces of oligomers coming through at 385, 573, 761, etc?

We also haven't ruled out the possibility of other indole impurities causing goo, either by inducing oligomerization themselves, or by simply interfering with DMT crystal formation. Same goo, different causes.

I guess what I'm getting at is, what's the smallest amount of impurity you can reasonably identify (and quantify) in a sample using your equipment?

the scan range is 50-2000m/z, but z can be multiple charge states. A single quad ITMS can be used to analye protein digests and peptides. Small molecules can easily be detected down to the low-mid ng range.

Oligomers readily stand out, with 189 mz difference between the signals. the largest one I've seen is 567, effectively a trimer. Granted, the sample was synthetic, but the conditions for extraction were similar... high pH. Dropwise titration may likely eliminate conditions that favor oligomer formation.

We have experimentally seem that high pH does indeed drive oligomers on natural product. One strategy we are pursuing is to add NaOH with solvent present, and stop adding NaOH once the emulsion begins to bubble/break. Unfortunately high pH is needed to break up emulsions well (in practice pushing beyond the titration point), but this approach does minimize NaOH while meeting the no emulsion constraint. We are also throwing other measures to see if they can help (e.g. K+ ions to hopefully disrupt pi-pi bonds with pi-cation bonds). I have a MHRB extraction going with added KCl. Na+ can also disrupt pi-pi bonds - and could be important in the max ion TEK use of NaCl, however, in water K+ has supposedly more activity because of less interaction with water. We shall see what we get.

I have other strategies to characterize oligomers as well. Since they have additional pi-bond conjugation, they fluoresce differently (I've shown this using a simple UVA flashlight). I've been using fluorescence detection lately, and will employ charged aerosol detection, once I sort out the air compressor kinks. Oligomers give larger droplet particle sizes.

Below is a sample of relatively clean dmt, 96% pure.

I am still learning a lot from those of you versed in chemistry that have really made this thread take off. Thank you all.

My additions are generally for extra data. I have yet to put the time into studying chemistry to actually keep up.

Anyway, from the last two pulls, I chose to re-x. I also decided to have a little fun and try to get some bigger xtals.

As you see, this re-xed product is a beautiful golden color. This is actually more colorful than before putting the spice into fresh nathphta.

In this process, after dissolving a decanting the dissolved spice in the nathphta, I allowed some of the solvent to evaporate before placing the glass in the freezer. After it was in the freezer for about an hour, then pulled it out and allowed more solvent to evaporate with a fan. I then placed the glass back in the freezer. I pulled it out one more time to allow to evaporate then placed in the freezer for 12+ hours.

So here's an example of a different polymer. This is straight DMT freebase, but is a beautiful golden yellow.

Looking forward to the more extensive conclusions drawn by the chemists.

One love

Just to clarify...we're talking about dmt polymers, which are multiple dmt molecules.. not polymorphs, which refers to a single dmt molecule's semi-folded orientation, about its alpha-carbon. Polymorphs of dmt include the example that pic, to waxy amorphous solid. DMT polymers do not readily crystallize.
That color is typical, even with synthetic.

Thank you benzyme. I have certainly seen this color myself as well. I've just never seen this happen when I re-x with pretty white DMT.

And apologies, my camera isn't that great, however, there is no waxiness. It just fell out of the glass after it was done drying residual solvent.

Tend to learn a lot from you, so thank you again.

One love

Thank you as well. I'm also here to learn, and post what I've learned, as well as data. I'm counting on that data and theories being peer-reviewed and scrutinized, that is how knowledge bases are created.

Hello again polymer research team. If I may chime in with a question-proposition, I guess its for IridiumandLace.

If oxide enhances polymerization and polymerized spice has a yellow to red aspect, an `easy` experiment could be adding excess white (unpolymerized) spice to small amounts of red spice and incubate. Even better would be to use converted n-oxide (H2O2 reacted white DMT) as a primer instead of yellow-red. If this hypothesis is right then the white plus red mix would turn yellow-red faster than unmixed white spice over the same time period or incubation? A control unreacted mix could be done that is left in a freezer, that could be used to compare with the reacted mix.

Good cameras could be used to gather visual evidence, perhaps even quantify color change using ImageJ. Quantification could be done with a spectrophotometer, assessing white and red individual spectrum prior then spectrum after incubation. Longitudinal readings using the photometer would show changes overtime, with higher concentrations of red spice showing faster spectrum conversion rates?

I was just linked to this paper
I've also seen dimers of tryptamine in spectra. As I had mentioned before, acidic hydrolysis will cleave the dimers into the monomers.

(from the article)

I'm getting good results with KCl and light hydrocarbon (ronsonol lighter fluid).

Extract is behaving different. Xtals formed before clouding 🤔. Bizzare yet interesting. No traces of yellow oil at all, not a drop. Never got this result before. Image below, the Xtals are forming under ronsonol lighter fluid a few minutes after warm pulls.

I'll keep on refining this, but it is looking good for me.

Of the several items we have been discussing, this combo seems to be working:

- Hot and long citric acid treatment to break up any natural bark DMT aggregation (same as max ion). This natural aggregation could be a huge incoming variable otherwise depending on the plant's mood.
- Use KCl at ~8% to help disrupt pi-bonding. I think this is an improvement over NaCl recommended in max ion. K+ is better at disrupting indole ring to indole ring pi bonds than Na+ because it interacts less with water and more with DMT due to its size. I think the good results of max ion are related to pi bond distribution from Na+ (not just increased ionic strength and better partition coefficient), and K+ can do an even better job.
- Dilute DMT before basing to ~3% or so. This matches max ion. Max ion adds this dilution to get to the narrow neck of the container for easy pippeting, but I believe it also helps and is also important to avoid DMT molecule proximity and pi bond formation.
- Add light carbon solvent before basing (new)
- Add NaOH until emulsion breaks (bubbles pop) after shaking. This is newish, idea is to not over-base, but base enough to break emulsion (which is a necessary). Max ion seems to not want to over base either by simply recommending a pH of 12. The new thing here is that by adding the solvent first DMT has room in the solvent as basing is occurring so it doesn't spend any extra time in basic water where it could slowly form pi bonds in free base form.

Essentially, this is a re-interpretation of the techniques in max ion focusing on pi bond management. With this perspective in mind, a couple steps are re-optimized to avoid DMT aggregation.

After putting it all together I'm getting zero yellow oil for the first time. Without being aware of these modulators and controlling them, a random goo to xtal result would be expected, which is what I have seen for years. Even worse, a temptation to use cold naphtha could arise leaving behind the less soluble DMT goo, exchanging a xtal result for an unnecessary loss of yield.

For long storage I think an e-juice that has a PG soluble DMT salt would be ideal. Hopefully it would become an aerosol and should be effective (like modern nicotine salts in PG). Free base aggregates over time, especially in my e-juice where it changes color after only a few weeks.

Work continues...

Here is the result from the KCl and lighter naptha approach. Much better than my usual result with NaCl and heavy painter's naphtha as far as whiteness goes.

👍🏻

Pretty sparkles! 🤩

And nice practical application of the deduced pi-stacking insights to obtain such a beautiful result (as ever!) by adding KCl and pre-basing NPS, Loveall

What would you imagine the difference might be from using lighter naphtha, compared to the heavier one you had been using? Is poorer solubility another advantage in avoiding aggregation as the molecules are more dilute?

Not sure. I would guess the smaller hydrocarbons can get in between DMT molecules and interact more with them to disrupt pi stacking. Just a guess. The idea comes from benzyme undoing aggregation from a synth using boiling ether if I recall correctly. Also, cyb mentions using lighter fluid during his extractions in the forum and getting good results. but I don't think that made it to the max ion TEK itself. Going off memory so I could be wrong.

Example where cyb mentions ronsonol: https://www.dmt-nexus.me...&m=370788#post370788

benzyme breaking up oligomer with sigma petroleum ether (I think it has low count carbon chains): https://www.dmt-nexus.me...mp;m=1123161#post1123161

That depends entirely on the boiling range of the pet ether used. Benz?

As we were discussing earlier, pi-stacking interactions (8-12 kJ/mol) are still only very weak interactions in this context, they are only slightly stronger than the weakest of intermolecular forces, induced dipole-induced dipole or van der waals (0.4-4 kJ/mol) and are dwarfed when compared to the stronger non-covalent interactions, such as dipole-dipole and ion-dipole interactions, like hydrogen bonds, these forces are ranging from 20-50 kJ/mol.

To suggest that pi-stacking or other kinds intermolecular forces are going to cause aggregation , in spite of , or in resistance to the intermolecular forces of solvation, especially in the ion-dipole conditions (aqeuous with acid) but even in the non-polar phase (van der waals) is to misappropriate the effect in the thermodynamic context of the system. It is like saying, water boils at 100C, and expecting to see the same thing on Neptune, forgetting the fact that water only boils at 100C at sea level on earth. Similarly, pi-stacking being a dominant force causing aggregation in gas-phase under vacuum, or in crystalline structures, is a different thermodynamic environment compared to aqueous ion solvation.

The only time it is really appropriate to talk about aggregation of DMT at all due to intermolecular forces, is at the very instance of precipitation, whether by crystallization in a non-polar solvent, or precipitation by addition of base into aqueous. In this case, the aggregation is driven more from the pressure of the surrounding liquid and gas pushing the molecules together, than it is from the intermolecular forces of dmt holding onto each other. This is why oils have a very low surface tension in general, compared to water (hydrogen bonds).

The confusion here comes from the general difficulty in obtaining crystals as opposed to goo, but the variables to consider are always concentration and temperature. Using aliphatics like heptane (or naptha) impurities like mysterious dimers, trimers, or other oligomers are insoluble, while pure dmt can be extracted in the hot solvent. It doesn't matter if you are started with red goo, or pure crystalline DMT. Sometimes recrystallization fails, and an oil falls out before the nice crystals do. This is just the nature of the material, and this inconsistency can be attributed to polymorphic properties of the molecule. The higher alkyl tryptamines are even worse in this regard, MIPT for example, has an even harder time to crystallize, likely due to the inhibited rotation of the carbon chain due to the steric blocking of the isopropyl, in DMT these effects are lessened, but still apparent. But it has nothing to do with the extraction or the method, it is a quality of the molecule itself. The only variables you should be concerning yourself with are the typical ones concerning crystallization. Concentration, temperature, the rate of cooling, etc.. even a minor change in these can drastically affect the process for some molecules. Redissolving and heating and using lots of solvent vs less is typically better when dealing with molecules that are dropping out as oil and failing to crystallize. Especially molecules with slow rotating bonds prone to polymorphism, heating helps break the energy barriers for bond rotation. Slow cooling to room temp before putting in the fridge or freezer, addition of a co-solvent like ethyl acetate, these are things that I do to get consistent crystallization.



Goo is not evidence for oxide, goo is a result that can happen with dmt of ANY purity. Crystallization is not always a given with molecules that have properties that say otherwise (i.e. polymorphism). It has never been argued that oxide is not a side product, particularly with sunlight, all amines react with oxygen and light, that is what gives aliphatic amines their characteristic yellow discolouration. Try distilling any amine, it will be colourless at first and then eventually discolor despite your best efforts. The reason why you don't see any DMT n-oxide as a product of extractions, is because it is not soluble in the non-polar phase, especially if you are extracting from basified aqueous water, which it is extremely soluble in and forms powerful ion-dipole hydrogen bonds (50 kJ/mol) many times more powerful than the solvation forces.



This is not possible. See thermodynamic argument above.



This is unscientific, you are fitting your theory to your observations, without any physical rational.



Zinc has a negative standard reduction potential. Meaning that it spontaneously is reduced in the presence of H+ (H2O). Simple proton is your oxidant, in this case. This is basic redox, the presence of Zn(OH)2 means nothing. A simple control experiment would have told you that too.



Again, this is wrong. Not because that DMT oxide is not there, and not because that people don't falsely assume their 'red goo' is DMT N-oxide, when it is infact mostly DMT, you are absolutely right about that, and I really appreciated Brennendes Wasser's post on the photochemical DMT N-oxide with the NMR-data, although to confirm it would need to be cleaned up a bit, but its good enough for me to bet on based on what I've done as well with it.
But this is not about that, this is wrong because your proposal is thermodynamically incongruent.

You can test this yourself very easily, take a mixture of freebase DMT, and DMT N-oxide. I actually tried this synthesis the first time when I was just a highschool student, and posted it on this forum back in 2010. I also advised Brennendes Wasser on this method with h2o2 when he was working on it recently. If you prepare DMT-N-oxide successfully with h2o2, you will find it has very different properties compared to DMT. If you then mix it with freebase DMT, and attempt extraction with boiling naptha, you will find that the freebase DMT dissolves, while the DMT N-oxide separates and collects at the bottom as an oil. The hot naptha can be decanted, and allowed to cool, with pure dmt crystals forming. I always kind of thought maybe the separation might be difficult, because DMT-n-oxide is something of a surfactant (hydrophobic tryptamine tail, hydrophilic O- tail, but clearly, its not enough to have a real effect.
You should in theory be able to separate this from photochemical DMT N-oxide, but the only way your going to end up with a significant amount of DMT N-Oxide to test this is if you intentionally try to make it, most people don't let their naptha evap in direct sunlight, in this case you will want to.

In 2019 when I was working with different tryptamines, I did make some 5meo-DMT N-oxide as a curiosity and to get a NMR spectrum, I was able to reduce it back to DMT using NaBH4/MeOH quantitatively. I can't find the electronic data, i might have saved the print out somewhere.. I don't remember it smelling like cherries, however..

And also, before I forget... you will definitely 100% see N-oxide in LCMS electrospray mass spec... its an extremely sensitive mass spec that catches ions... and DMT N-oxide is permanently ionized, you would detect the M+1 (pka ~ 4) ion without a doubt.. its not going to be obscured. What I want to ask benzyme is if he has mass spec according to each of the peaks hes seeing in in chromatograph...

--



Again, there is a lot of misappropriating organic chemistry concepts here, that is where the confusion is coming here.
First off, you can't be using polymerization interchangeably with non-covalent complexation or aggregates. Polymerization means a molecule that is forming new covalent bonds with units of itself. Complexation or aggregation involves non-covalent intermolecular interactions. DMT N-oxide does not trigger either of these things.




I respect that. I made a lot of errors when I was first learning and diving into organic chemistry, and I did it all here on this forum too. So I don't want to put a damper on anything, I know you're not making any hard assumptions but I think you have the cart before the horse on a few things, while overlooking some of the fundamental bedrock that theory is built on. You've made some good points here, I am trying to reel so it back in.
for example:



This is arguably the most accurate thing you could say, DMT is persnickety about crystallizing. And that is the source of this confusion, but none of it is related to polymerization or the extraction conditions or dmt n-oxide, that is all jut adding to the confusion. And it is not because it is a supercooled liquid. Thermodynamically it is different. A supercooled liquid would be liquid because of an activation barrier, but not because of melting point depressing or crystallization inhibiting polymorphs. A supercooled solution doesn't possess these properties, and so would crystallize instantaneously given a small push. DMT does not do this so easily, because it is not simply supercooled. Trace solvent, other factors can contribute as well to the lack of crystallization.

Thanks Mindlusion, that is awesome info. I'll focus on the xtalization part, sounds like that was the main driver of xtalization vs goo results.

In chat, you also mentioned using seed Xatals, I'll try that also.

When I got my best results (whitest DMT), I noticed cloudiness started immediately on the first pull after the warm naphtha was moved to cold jar. Then, after adding more pulls yhat cloudiness dissipated. I left it in the wintertime cold garage for a while before moving it to the freezer. Sounds like that is what really matters and not the KCl, acid used, etc.

I'll do more tests. Cheers and thanks 🙏

This is testable. A portion of DMT can be converted to the N-oxide and combined with the unoxidized material in carefully measured proportions. Subsequent manipulations will lead to observations of one kind or another. Use of an inert atmosphere would be advisable.