Investigations into the polymorphic properties of N,N-dimethyltryptamine by X-ray diffraction and differential scanning calorimetry

Alain Gaujac, James L. Ford, Nicola M. Dempster, Jailson Bittencourt de Andrade, Simon D. Brandt

DOI:10.1016/j.microc.2013.03.009

Very interesting! So they confirm that dmt crystals are polymorphic, have at least two types, and that color changes with stored dmt can be related to changes between those two structures.

This would confirm the fact that, through analysis, we have seen that DMT seems to only partially oxidize even if its significantly changing color, so changes in color can be related to the different crystal structures being formed even if mostly its still just DMT.

This hints to me that NMT changing color but not having an N-oxide probably maens that the changes in color is also related to its potential polymorphic structure?

And back to DMT, the fact that the stored DMT turns into the higher melting/boiling point type, this can also partly explain why some people feel the old DMT to be less active, maybe they are just not using enough heat or in general the efficiency of vaporization is affected?

Excellent find shaolin and excellent food for thought, as per endlessness' speculations.

..excellent find and thank you Shaolin..

this was speculated on this in this thread, with an interesting old paper doing x-ray crystallography of DMT post#18

..some people have reported subtle differing subjective effects (in the onset) between the low and high melting point forms..

very nice indeed.

I m.p. tested some spice a while back, 41-44C; coincides with form II.
it was stored in the fridge for over a year.

Some more research on DMT pretty fresh off the press. I think the study below just hints at the possibility of DMT existing in different forms, but thought this may be of interest to some.

Gaujac, A., Ford, J.L., Dempster, N.M., de Anrade & J.B. Brandt, S. D. (2013) Investigations into the polymorphic properties of N,N-dimethyltryptamine by X-ray diffraction and differential scanning calorimetry. Microchemical Journal, 110, 146-157.

The powerful psychoactive features of N,N-dimethyltryptamine (DMT) have sparked the imagination of many research disciplines for several decades. One of the key chemical features associated with compound identity is the determination of melting points. The descriptions of both melting points and morphology associated with DMT free base have long been a source of interest and discussion, especially when considering that these values encountered in the scientific literature range dramatically between 38–40 °C and 73–74 °C, respectively. Such variations in reported melting points suggest that DMT may exist in two or more polymorphic forms and it was the aim of this study to examine the potential polymorphism of DMT via X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC), including fast scan DSC. DMT samples were prepared following extraction from Mimosa tenuiflora inner barks or by laboratory synthesis and then its crystals were recrystallized from solutions of the alkaloid using either hexane or acetonitrile. Irrespective of source, crystals originating from synthesis were predominantly white crystals obtained using crystallization from hexane, whereas yellow samples following recrystallization with acetonitrile. Irrespective of source or solvent, two polymorphs appeared to exist with melting points, determined by DSC, of 57 °C to 58 °C for Form I and 45 °C to 46 °C for Form II. Estimates for their enthalpies were 91.9 ± 2.4 J g− 1 for Form I and 98.3 ± 2.8 J g− 1 for Form II. Form II converted to Form I during DSC; conversion was thus prevented by fast scanning rates of 100 °C min− 1. A transition temperature (Tg) in the range − 21 °C (2 °C min− 1) to − 13 °C (100 °C min− 1) was determined depending on DSC scanning rate. Its closeness to the melting point indicates a tendency of Form II to convert to Form I on storage, a phenomenon that was also facilitated by grinding. This study indicates that the presence of differently colored DMT free base crystals obtained from recrystallization might also point towards the existence of polymorphs rather than just the presence of impurities.

From:

http://www.sciencedirect...le/pii/S0026265X13000544

& another study...

Gaujac, A., Dempster, N., Navickiene, S., Brandt, S.D. & Andrade JB. (2013) Determination of N,N-dimethyltryptamine in beverages consumed in religious practices by headspace solid-phase microextraction followed by gas chromatography ion trap mass spectrometry. Talanta, 106, 394-398.

A novel analytical approach combining solid-phase microextraction (SPME)/gas chromatography ion trap mass spectrometry (GC-IT-MS) was developed for the detection and quantification N,N-dimethyltryptamine (DMT), a powerful psychoactive indole alkaloid present in a variety of South American indigenous beverages, such as ayahuasca and vinho da jurema. These particular plant products, often used within a religious context, are increasingly consumed throughout the world following an expansion of religious groups and the availability of plant material over the Internet and high street shops. The method described in the present study included the use of SPME in headspace mode combined GC-IT-MS and included the optimization of the SPME procedure using multivariate techniques. The method was performed with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in headspace mode (70min at 60°C) which resulted in good precision (RSD<8.6%) and accuracy values (71-109%). Detection and quantification limits obtained for DMT were 0.78 and 9.5mgL(-1), respectively and good linearity (1.56-300mgL(-1), r(2)=0.9975) was also observed. In addition, the proposed method showed good robustness and allowed for the minimization of sample manipulation. Five jurema beverage samples were prepared in the laboratory in order to study the impact of temperature, pH and ethanol on the ability to extract DMT into solution. The developed method was then applied to the analysis of twelve real ayahuasca and vinho da jurema samples, obtained from Brazilian religious groups, which revealed DMT concentration levels between 0.10 and 1.81gL(-1).

From:

http://www.ncbi.nlm.nih.gov/pubmed/23598143

Neat, is might be as polymorphic in crystalline structure as it is in its effects.

Thanks for posting this. I always wondered why that was! Turns out that a lot of those yellow dmt oxides might not be oxides after-all .

I'll have to read the paper for the data!

edit -

@Endlessness - To vaporize the crystal it should be a sequential thermodynamic process. So essentially once DMT reaches a liquid phase it will still vaporize at the same temperature. Perhaps for users of the GVG they may notice some lag time but likely not very much of one.

A classic example of how color tells us very little about the materials we are dealing with. I wonder how it's absorbance changes. Maybe due to hydrogen bonding of the indole and amine group? Fun things to think about.

Old thread I know, but seems only appropriate to mention this here. First the quote:

DMT samples were prepared following extraction from Mimosa tenuiflora inner barks or by laboratory synthesis and then its crystals were recrystallized from solutions of the alkaloid using either hexane or acetonitrile. Irrespective of source, crystals originating from synthesis were predominantly white crystals obtained using crystallization from hexane, whereas yellow samples following recrystallization with acetonitrile. Irrespective of source or solvent, two polymorphs appeared to exist with melting points, determined by DSC, of 57 °C to 58 °C for Form I and 45 °C to 46 °C for Form II.



So...
It's pretty much just white clear crystal obtained via crystallization of already pure DMT from hexane, but it becomes yellow when crystalized from acetonitrile. I assume these were from multiple synthesis methods as it says 'irrespective of source' but mentioned they originated from synthesis.

The conclusion reads:

The data provided in this paper have shown that DMT can be
recrystallized from the solvents hexane and acetonitrile to give crystals
that are a mixture of two polymorphs. The fact that two clearly
exist explains the variation in melting points reported previously in
the literature. It seems possible that use of the latter solvent gives
crystals with a greater amorphousness and a yellow coloration. This
solvent dependency was independent of the source of DMT, whether
it was extracted from natural products or synthesized in the laboratory.
The XRPD data correlated with the fast scan DSC data (Figs. 2–5a at
100 °C min−1) and confirmed that all four samples studied contained
at least two polymorphic forms of DMT with varying ratios of concentration,
the proportion of which appears unrelated to sample color.]

I think it's important to note that this yellow form from acetonitrile gives no indication of the percentage of DMT polymorphs present, nor does it have any relevance to DMT texture or colour when obtained from hexane (and likely similar solvents in light naphtha). The text mentions that mostly white DMT is obtained from crystallization with hexane and I have never observed or heard of anyone on this forum recrystallizing pure DMT and obtaining a product that appears yellow and amorphous with hexane, heptane, or other light naphtha. So from this I think it's important to note:

1: Yellow DMT, if not crystallized from acetonitrile, is not yellow because of different polymorphs. It's much more likely to be an impurity, and can be cleaned out. Remember that DMT n-oxide is not pulled by light naphtha or similar such as hexane or heptane.

2: Pure white DMT likely still contains different polymorphs anyway, each with possible different melting points.

Anyone take issue with this? I want to help try to avoid assumptions of purity based on a misunderstanding of polymorphs and crystallization methods. Some may just assume that because they can't get rid of the yellow colour that their DMT is pure and it is because of different polymorphs, which appears not to be the case. I also want to make clear that I know the original posts weren't implying so either.

Pardon the necroposting...
I have some observances, and theories. First, I've noticed that lower-melting polymorphs (m.p. 41-44 C) tend to readily turn yellow with exposure to air. I don't think this is due to any impurity, but a matter of autooxidation. This doesn't mean N-oxide formation, but rather, loss of electrons from the 2-3-positions on indole. I suspect this occurs when the molecule is oriented in a way where the terminal amine is folded closer to the pyrrole amine, about the alpha carbon (polymorphism is possible because of partial rotatability about the alpha carbon of tryptamine). The lower-melting polymorph is often a waxy, orange amorphous solid.
Also, the higher-melting polymorph (60s C),(a quasi-trans orientation, if you will) tends to yellow very slowly, and retains tight, white granular crystalline structure. That orientation, with the terminal amine furthest from the pyrolle moiety, has something of a shielding effect. Diisopropyl/Isopropyl-subbed tryptamines tend to limit the folding, due to steric hindrance; those tryptamines don't readily turn the telltale orange/ochre color of tryptamine or dmt.

As far as limiting the influence of polymorphism on crystal formation..I don't think there is anything that can be done, aside from controlled, linear cooling. It's also concentration dependant, and proportional to solubility.

MS analysis of either polymorph shows identical spectra...145->189 m/z ion transition, with no other impurities. Electrons have negligible mass, so an autooxidized product will not be apparent from mass spec.

Hmm, that's really interesting! I have questions!



Can you elaborate on this? I'm not familiar with autooxidation, just regular autoxidation (which is what I've been suggesting all this time). If no oxide is being formed, where do those electrons go? And why is air required?

Also, could the presence of trace impurities cause one polymorph to be favored over another?

And, for that matter, how would polymorphism relate to the behavior of DMT in solution (either aqueous or nonpolar)?

The idea of polymorphs is intriguing, and admittedly requires fewer assumptions compared to polymerization. But I'm still struggling to explain my zinc experiment result in the absence of an ozidation-reduction reaction.

https://www.dmt-nexus.me...mp;m=1041499#post1041499





I explained why your zinc experiment gave your observed result, I gave a more indepth explanation of redox chemistry in this post if you are interested:

https://www.dmt-nexus.me...mp;m=1041499#post1041499





So the reason why you see zinc salts, is that zinc spontaneous is reduced in the presence of water to produce zinc ions, acid is necessary to catalyze this reaction for solubility of ions and dissolving the passivating zinc hydroxide layer. When you add base, you will precipitate zinc hydroxide. So the presence of DMT-n-Oxide or dmt in your reaction has no effect on this primary reaction, which is obvious with the effervescent hydrogen. The zinc hydroxide is the other product. You can test this yourself by repeating what you did in the absence of your dmt extract, you will see the same precipitation occur.

I apologize to you guys, i have nowhere near the chem knowledge that is on display here and the minimum polymer thread.

If a commoner like me understands this correctly, it seems highly unlikely that polymorphs truly coexist in an extraction using a single NP solvent, or at least an exclusively petroleum distillate extraction. Am I correct?

In other words, aren’t the goos more likely to simply be contamination in these circumstances?

I think Mindlusion is saying you can get DMT goo when it precipitates a certain way out of the solvent.

Could also be contamination, but you don't need it to get goo and I haven't encountered it. The goos I get are simply DMT and can become white xtals.

Not judging your technique, but removing pure loaded solvent could be a problem for some (traces of that black-yellow tar), leads me to think contamination is sometimes confused with a more complex process.

Btw, i’m not trying to negate the existence of polymorphs, both conditions can exist: polymorphs and poor technique.

Given the rudimentary tools and varying skills, I wouldn’t rule out some amount of misclassification between the two.

I play it safe though, and try to use good tools & technique, while also trying to glean something useful from the esoterica.

Seems Max Ion and some of the little I could understand from the pi bond discussion worked for me.

Thanks

Polymorphism doesn't exist in the solution phase. Polymorphism only makes sense in the context of a solid or the phase change between liquid and solid. So it doesn't make sense at all to talk about polymorphs existing in the solvent phase. As benzyme said, polymorphs can arise due to hindered rotation about certain bonds in the molecule due to steric blocking, in the solvent phase however you have a much freer and faster rotation. The conditions during the phase change (solvent, temperature) are crucial in what polymorph forms, or what mixture of the two forms. There is a detailed paper on this specfically you can read here: https://www.sciencedirec...6265X13000544?via%3Dihub

in other words, pure white crystalline DMT can appear as amorphous yellow goo, and still be 100% the same pure DMT. The assumption that yellow means impurity is wrong, yellow just means that more lower frequency light is absorbed, because of imperfections in the crystal lattice

---------

makes total sense to me,
after extraction my dmt is always white like snow then after a couple of weeks and after moving it around it gets orange like earwax.
Still it is potent as hell soi dont think its loosing potency while it changes structure.

How do you take it? Under a flame I think it remains just as potent, but precise electronic devices seem to be more sensitive to me, needing higher temps for the more gooey DMT in my subjective experience.

Thank you for your response. I will take a look at the paper, but doubt I have the background to understand it.

And thank you for your comments on the Minimum Polymer thread. I actually used some of the practical comments of yours in my recent Max Ion run ( https://www.dmt-nexus.me...mp;m=1140838#post1140838 ).

From what i can understand, and have witnessed myself - in the past two days - I believe that impuriies can lead to yellow.

So, i can agree (like I did in my reply to Loveall above) that ‘The assumption that yellow necessarily means impurity is wrong’.

I've had that dispute with people on reddit; they attributed the yellow color to impurities.
Then I came back with fluorescence spectra and mass spectra...

I showed white crystals, that turned orange, actually...just sitting at room temp, no sunlight exposure, over the period of two weeks. Same structure too, verified under a stereo microscope. m.p. 66-67 C.

The fluor spectra for both white and orange were identical, same with the mass spectra.
It's really a job for NMR, since autooxidation points to a loss of electrons, which as I mentioned, lack any appreciable mass.

And this is not to say that an impurity won't strip electrons from dmt, it certainly could...but the discoloration is an inherent property of indole's 3-carbon, and it's tendency to losing its electrons. I've seen pure tryptamine turn yellow with exposure to air in just 20 mins.