Y’all gonna need some time to splice those plasmids into the appropriate bacteria and determine fermentation feed and parameters!
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The key to understanding the acid thing probably lies in the fact that almost everything is a little soluble in everything else, @Sapper502! However, there is a major difference between dissolved and dissociated.
Any acid (or base, or salt, or anything, really) may be dissolved (i.e. homogeneously dispersed in a solvent at the molecular level, becoming “solute”) to some degree in a non-polar solvent like heptane or in a polar solvent like water.
The acid in water will also dissociate (i.e. “ionize” or break apart to form charged particles: cations (+), usually the naked hydrogen “proton” & anions (-), the rest of the molecule, known as the “conjugate base”) to some degree, based on its pKa (the dissociation constant). Only ionic bonds, like those in acids, bases and salts, can dissociate in water or other polar solvents.
Acid dissolved in heptane does NOT dissociate at all; it remains whole molecules of the acid compound. The acidic hydrogens in the molecules are still relatively positively charged, while the conjugate base is or contains relative negative charge. In other words, the acid molecules are still polar, and they float around like tiny electronic “magnets”, which gather near any polar regions on other dissolved molecules. This statistically slows down the rotation, vibration, and translation (movement) of these other compounds (e.g. THCa), effectively shielding their polar regions and exposing their non-polar regions to other non-polar regions in the solution… or, in this case, to the non-polar “backsides” of THC molecules that are stuck to the mol-sieve by their hydroxyl group sides.
As you can imagine, dissolved bases in the non-polar solvent would grab onto the carboxyl groups of THCa molecules even “harder” than acid does. So why don’t we use alkaline solutes in heptane?
Well, the bases grab too hard! Strong enough base, like sodium hydroxide, could even react with the THCa, especially when the water is later introduced to wash the base out of the heptane, before solvent recovery! This could even cause the THCa to stay in solution, since the net effect of the associated base molecule is neutralization, or zero charge, aka: non-polarity! Just as easily, the base molecules could remain stuck to the THCa while it is stuck to the THC, which is stuck to the zeolite. Worse still, the hydroxide groups on the base molecules could very rapidly (especially when base molecules are small) adhere/adsorb to all those OH sites on the zeolite, blocking the bulkier THC-OH from adsorbing in the first place!
An acid, especially a bulky (bigger than the 3Å pores), weak, multi-protic organic acid like citric acid, is perfect. It will weakly associate with the carboxylic acid groups and make the non-polar regions of the THCa more readily available to adsorb to the non-polar “bums” of THC sticking out from the zeolite… and because it has 2 extra weak protons sticking out, it could ostensibly hold up another 1 or 2 more THCa molecules passing by! Note: Because the triprotic citric acid does not dissociate in heptane, all 3 of its O=COH groups will retain equal affinity for other carboxylic acid groups… unlike dissociation, where the 1st, 2nd, and 3rd protons have progressively weaker dissociation constants (pKa), thereby weaker ability to generate acidity (pH).
Just think about all this stuff as little static electrical magnets made of + & - regions on otherwise neutral (non-polar) “non-magnetic” blobs. The carboxylic groups (negative O=C-O region & positive H) on two different organic acid molecules (e.g. citric acid & THCa) can weakly stick together, like so:
(HOC:O)…citric… (O:COH)×2
(+ - * : - ) •••~~••• (- : * - + )×2
(- : * - +) ~ ~ ~ ~ ( HOC:O…thc )×2
(O:COH)…thc
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Aye! Thank you sensei!
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What was your loss rate Rowan?
0% losses
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https://cen.acs.org/materials/Zeolite-membrane-finds-holey-purpose/98/i6?utm_source=Facebook&utm_medium=Social&utm_campaign=CEN Check this out they’re trying to use it to separate H20 from methanol for methanol production
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This technology already exists. Hitachi Zosen can offer dewatering membrane skids for solvent purification. They face no issues with azeotropes and can easily bring ethanol or methanol up to 99+% in a single pass. The largest ethanol refinery in Japan was built with this technology. Their US based partner is Membrane Technology and Research Inc.
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That article explains a very elegant inorganic mol-sieve metamaterial to remove a limiting reaction product (water) at extremely high efficiency, without being permeable to the smaller H2 gas molecules! Fascinating! Thank you!
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I don’t know how I missed this thread but this is freaking awesome!
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Has anyone tried this with CBG?
I missed this …but sections 69 to 83 are very interesting in that
they give considerable insight to the environment of the TRICHOME STORAGE AREA. These variations enzyme solution chemistry clearly demonstrate the type of aqueous environment the enzyme, e.g., THCA synthase is normally active in. Remember it has been shown that the synthase is actively secreted along with its substrate CBGA into the storage area.
- As every one expects it can operate in “organic modified”
Aqueous environment. - Most important are the numbers mentioned for pH values: pH=4-8. I have been stressing this issue for more than a year
Based on pH measurements of dried biomass soaked in water and measurements of fresh trichomes squished with water…
4.5 is a common number. As you all should know by now the pKa of THCA is close to 3. And when you start thinking about extraction with butane at -50C…some strange bells should be going off in your head. THCA-:THCA (H) ratio of 10 to 1.
so we know the organic modifier must be terpenes and something like Palmitamide as an additional complexing agent…along with the terpene antifreeze (polyol). The exact n1(THCA-)-n2(THCA[H})-n3(ternary complexing agent) is unknown and simply too complex to think about in water contaminated Butane.
@johnbigoilco , @Dukejohnson, @ Dred_Pirate…etal.- guys and the medusa
Problem need to think clearly about this…
It is this complex, not identified as yet, that is present in your BHO extracts…that further interacts with the butane contaminants.
Medusa…. Is formed from this “complex”…in butane…in the presence of thousands of ppb other organics from plant AND butane contamination problem.
Medusa can not be pure….but the ripened chalk…is pure…
As some claim ripened chalk can test out by HPLC as 99% plus pure. Why/ how the butane contaminants can catalyze this precipitate -medusa form is unknown. Can we say anything about Medusa form other than it ripens to chalk over a period of weeks?
Everyone should try to understand the modified aqueous environment to the trichome storage area. Curious?
Read 69-83 of the above patent.
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Always posting stuff way over my head! Ill have someone smarter then I take a look and see what they come back with.
Ive seen clear thca stones go to chalk in 24 hours once removed from the mother liquor.
Do you think the PKA is stable? as in, if we agree the PKA is aprox 3, will it always be that in most cannabis material? Or will the PKA change based on how the plant was grown? Does having nutrient lockouts effect the PKA of the Trichome head? Is there a reason dried material seems to be more prone to “medusa” over Fresh frozen material? Is the PKA of dry and ff material the same?
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I think the PKA is referencing pure THCA in its normal form. Correct me if I’m wrong someone please but the PKA should stay the same. What could vary is the other ingredients that come along with the THCA which will also have their own PKAs that will affect the total solution.
@moronnabis
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Well…yes THCA has its own pKa property…for the carboxylic acid moiety.
If it were to interact with an amine …which also has its own pKa.
It is all dependent on the pH, what exact complexes can be made.
All told, all weak acids and weak bases act together to effect a buffer action with regards to pH of the total solution.
But they also act together h-bonded solution networks.
Or ion pairs…I have posted paper references on all the different forms of carboxylic acids In both protic and aprotic solutions. (Often using Salicylic Acid as a model for cannabinoic Acids).
Now this post is about the Trichome storage area environment…
Which based on the data posted in that patent…suggest basically a protic environment slightly modified by organics (terps?)…
And notes enzyme rates at different pH…4-8.
So here we appreciate THAT mixture or solution…say pH 4.5 protic, trichome volume playing field…with terpene and polyol antifreeze.
As soon as you freeze the H20 solid at -50 and extract that mess with Butane…surprise…it all goes into solution.
However what ever held that protic solution together in the trichome protic environment at the trichome concentration of cannabinoic acid….let us just amuse ourselves with a Hydrotrope action, which is concentration dependent….is all obtained by concentration levels in the Trichome Volume Element.
When you extract that trichome volume element with your butane extraction volume element, there must be (guessing) a 1000 fold dilution of that volume element…so any concentration and pH dependent hydrotope like action that prevailed in the Trichome volume element is gone….AND
the entire solution now rearranges to the aprotic-nonpolar volume element of the Butane (butane contaniminated with water and a thousand other things, not exactly butane and 1000x diluted…moreover, the prevailing solvent is now aprotic and everything you ever knew or thought about pKa’s is out the window…that is we don’t think hydronium ions we think in terms of non disassociated acid monomers, dimers and heterologous [R-COO- _ RCOOH) dimers and homologous conjugates in solution and even R-COO- perhaps in solution shielded or complexed with water, amines, alcohols and amides….and the whole new solution as some sort of fragile h-bonded network.(zoo)
The pKa of R-COOH in this aprotic, non-polar butane-system may be as high as 10-11 This would mean all the COOH are neutral (H)…so where do the H come from if this is the case?
If not, some how the homologous conjugate dimers might crystallize. ??? Big question marks???
Honestly I am back to What is a medusa crystal/ We know THCA is a 99% pure chalk when it wants to be. The rest I have no idea considering possibilities of salts. Every THCA analysis should be accompanied by ICP analysis to make sure it is not an inorganic salt. And every hplc analysis should keep in mind possibility of amine salts or heterologous carboxylic acid dimers…if your final acid is not washed or precipitated from pH2 HCl…i.e., convincing
Non-organic acid wash…you probably have something else. Remember, redissolving what ever you have in HPLC mobile phase with formic acid
Will only result in rearrangement to THCA(H)…and you will get a nice little pure THCA(H) peak…because you put it in a protic mobile phase that forces that form.
The phenomena where THCA chalk precipitates out on the extraction column filter…should be totally exploited as a “feature”
…
To this aprotic butane “solution” noted above, the medusa people must think about how their methanol and amines may act…especially upon concentration as the butane evaporates.
This is the “Medusa playing field”. Fast crash and medusa phase changes emerge from the dynamics of this system.
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This is exactly what I’ve been talking about the past couple of months, albeit in simpler terms. Water is the common factor, which is why it is both an effective washing agent for these contaminants, and also the reason they can be so difficult to remove from the butane without pre-drying it to as close to anhydrous as possible. The latter is the key to making adsorbents work most effectively.
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I thought that was the other way around…is this prevailing thought…please advise,
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For us It seems dried material is more effected but I have a feeling it has to do with the terpene content. FF has a higher terpene content from my experience.
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Since writing this a year ago…naturally occurring Deep Eutectic Solvents (NADES) have come to my attention.
This concept may well apply to my use of the term Hydrotrope (or this case Lipotrope) . There is a separate forum on Deep Eutectic Solvents (DES) here on 4200…look it up.
The explanations presented above for “half decarbed “, and cannabinoic acid separations from neutral cannabinoids, and I mean the “theory” of what is happening using the zeolite structure as surface for binding isotherms….is somewhat lacking. As Photon points out, once you get past the non linear Raoult’s Law for adsorption isotherms you can get positive deviations from linearity and due to geometry secondary isotherms. And yes this is what is happening when highly concentrated alkane extracts are passed over solid supports for “selective” CRCs….and one continuum of :
Nobody knows shit about what is going on…other than “some things work”.
For a fundamental understanding of the separation chemistry of cannabinoic acids under dilute conditions one should attempt to study RP-HPLC separations of neutral cannabinoids and cannabinoic acids where the research focus is studying the effect of pH and buffer in the mobile phase. Acidification of THCA forcing the Intramolecular H bond to the adjacent hydroxyl form has profound effect on it chromatographic behavior. You don’t see it with CBDA…rescorcinolic acid form. @Termite says add “acid to the Heptane”….really….4200 response: WTF??
There is a WHOLEWORLD of polar protic chemistry =water that 4200 just ignores …let us call it “cannabinoids:the basics”….lol. There is no water in my biomass, there is no water in my solvents, and no I have no idea what the “effective pH” is.
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One of the humate mineral deposits we were looking at buying also had zeolite. I am watching this thread to see the practical applications for cannabis. I love it!
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