Hedione is usually one specific stereoisomer of methyl hihydrojasmonate. i understand stereoisomerism very poorly have no idea how this would effect the efficacy of the product. Put simply, all methyl dihydrojasmonate is not the same and this is a form that could potentially be useless for us. Im currently waiting for a response from a chemistry major on the likely phytoactivity of commericial hedione products. There's very little experimentation done on MDHJ, ive only seen 3 studies that have used any form of MDHJ, 2 studies on tobacco and nicotine biosynthesis, and one study on the california poppy and alkaloid biosynthesis. so this puts us in a bit of a scientific blind spot.
Methyl Jasmonate is being used extensively in cancer studies as a potential cure for cancer. It often causes cancer cell apoptosis without having any effect on healthy cells.
This thread has been brought to my attention by Shaggy... as I'm sometimes a bit lazy, I'll more or less copy-past two emails I wrote regarding the subject including a few modification (in blue, so that Shaggy knows what he missed ).
Email 1:
Hedione, patented in 1959 by Firmenich, is the racemic mixture of methyl dihydrojasmonate (aka (+/-)-methyl dihydrojasmonate) containing roughly equal parts of all four stereoisomers.
Someone might have come to the wrong conclusion because the compound is often listed as (-)-epimer, although being a mixture, because the natural form, jasmonic acid, is usually depicted as (-)-epimer (see comment at the end). The newer 'version' from 1993 is called Hedione HC and contains only the cis-isomers; the latest 'member' of the family, synthesised in 1996, is termed Paradisone and is the enantiopure form of the 1R,2S-(+)-methyl epidihydrojasmonate (the active highly fragrant cis-isomer).
As said, the 'normal' form of jasmonic acid is mostly 1R,2R-(-)-Z-jasmonic acid which has a weak jasmine odour and a moderate bioactivity. Paradisone on the other hand corresponds to the intensely aromatic and highly bioactive form (notably, it's the dihydro-derivative which is somewhat less active but more stable than natural JA) and is obviously the most expensive one too. This very active form corresponds also to the real natural isomer which, due its sterical hindrance and keto-enol tautomerism, tends to epimerise during isolation and storage to the usually described derivative 1R,2R-(-)-methyl dihydrojasmonate or in short (-)-methyl dihydrojasmonate (in case of essential oils and plant extracts, it would be (-)-jasmonic acid). In fact, many older studies on jasmonic acid and/or methyl jasmonate used a racemic mixture comprising mainly of the stable two trans-isomers; one of the reasons why Firmenich got so famous for Hedione and more so the newer versions which are the ones way more difficult to synthesise. The favoured form under common conditions is a roughly 5:95 ratio favouring the less or even inactive form. This means that many commercial products, although synthesised at a given ratio will be converted once in contact with water; Hedione is therefore often a mix of 10:90 (+/-)-cis- to (+/-)-trans-isomers.
Why the most active isomer in plants is also the one with the strongest odour, I do not know... maybe because it's the natural one?
Remains to be said that all isomers show some activities in certain tests, most of all the two naturally occurring 1R-enantiomers, usually have the same net effect, and will produce the same results just to varying degrees but the 1R,2R-epimer (may that be jasmonic acid or Paradisone) shows always the strongest activity. Notably, the methyl ester renders the molecule more active than the free acid but the lack the double bond in the pentyl side-chain greatly reduces it. Unfortunately, there is neither much data on dihydro-derivatives nor on the used enantiomers. Hence, different publications show, depending on the enantiopurity of the dihydro-derivative as much as that of the reference jasmonic acid (which are both usually not known nor cared about!), an activity of 10 to 50% or zero activity. Comparing the commonly used concentration of (-)-jasmonic acid (the less active enantiomer usually used) with that of JAZ Rose Spray (likely the 'degraded' racemate of methyl dihydrojasmonate) implies an activity of 0.1 to 1% of the latter.
(And here I cut some stuff out)
Email 2:
Forgot to mention:
1R,2S-(+)-epijasmonate is also termed 3R,7S-(+)-iso-jasmonate, depending on the used nomenclature .
As mentioned (and I'm sure you don't really remember, although this is the important part) the epijasmonates (resp. iso-jasmonates) transform into the trans-enantiomers. As the former are more active than the latter (though you find some publications which state the opposite but that's based on a mistake and has been copied several times...he even copied the mistake from himself and stated the opposite a page later...such an idiot... ) this means the following for the price/activity calculation:
1R,2S-(+)-Methyl dihydroepijasmonate (1) has full bioactivity and a very strong odour
1R,2R-(-)-Methyl dihydrojasmonate (2) has still some bioactivity and a moderate odour
1S,2R-(-)-Methyl dihydroepijasmonate (3) has a very weak activity but no odour
1S,2S-(+)-Methyl dihydrojasmonate (4) is usually bare of any activity and odour
It looks like if many results prior to 2007 are flawed as they assumed (-)-jasmonic acid to be the active form due the non-availability of (+)-iso-jasmonic acid and also traces of that on in the former (especially in tests using the really-really active isoleucine-adduct). That means, we don't know how active the four above substances really are ;( .
For the sake of simplicity (relative simplicity), I base bioactivity on odour intensity; in fact, it could well be that only compound 1 has an activity at all and the 10% of compound 2 are just the few percent which epimerised. Also, I ignore the 95:5 epimerisation ratio, feel free to calculate yourself :
1: 100% active
2: 10% active
3: 1% active
4: 0% active
That means, Hedione, the equal parts mix, has an activity or 27.5% (just after synthesis)
Hedione HC, the mix of 1 and 3 has about 50% activity
Paradisone (compound 1) has 100% activity
Now you buy that stuff, put it into solution, and get hit by the train called Murphy's Law... epimerisation occurs (the more water and the more pH deviates from 7, the faster) and product 1 slowly turns into product 2 and product 3 into 4.
Hedione becomes a mixture of 2 and 4, which has a total activity of 5%.
Hedione HC first turns into something like Hedione and then obviously into the same 5% mix as above.
Paradisone on the other hand slowly turns into a mix of 1 and 2 and finally becomes 2, or 10% activity.
Do the maths and you will see that with Hedione, you spend less and lose only 5 times whereas with Heidone HC you spend more and lose 10 times only to find yourself with the same stuff as if you had bought standard Hedione.
With Paradisone, you spend a lot of money only to lose 10 times but at least ending with something having 10% activity.
The logic conclusion is: buy compound 2 if it's not too expensive because that way you buy 10% activity and keep the 10% no matter what. Consistency or spraying every time the exact same thing is most important. Alternatively, go for Hedione as that one only loses 5 times, certainly contains an active ingredient (1) and isn't expensive .
But again, the % activity are a rough estimate and the pure compound 2 may not be active at all but only Paradisone!! Without proper testing (which hasn't been done), we'll never know...
(Again, I cut some stuff out)
Hope that helps and wasn't too much confusion... If so, don't worry, you aren't the only ones; so far, I found three papers (one done by Firmenich itself, one sponsored by Firmenich, and one written by one of the 'gods' of jasmonic acid chemistry and signalling, imagine that!) wherein they used the wrong stereochemical nomenclature, drew the wrong enantiomer, or mixed the biological activity up.
Why these three? As said, they're flawed... if you perceive reading such papers as funny, then you're an even worse science nerd than I am .... Is there anyway you could post attachments of those three papers?...
Why these three? As said, they're flawed... if you perceive reading such papers as funny, then you're an even worse science nerd than I am .
And no, I won't attach any papers as I'm not sure that they're open access. Besides, there are more recent ones regarding jasmonic acid (search pubmed or sciencedirect for review articles for example by Wasternack) and you'll easily find enough on Hedione and chirality yourself (for example first hit on google).
It's weird, but nearly every article states different ratios for the enantiomers and often enough, it's not referenced from where they got the results... maybe epimerisation occurred during storage, sample preparation, or analysis?
I don't know If this has been discussed. But I've seen products make trichomes larger, producing more trichomes, will just say I take attorney try to come and make it big does it have the same thc content? Just say I turn 1 gram of resin glands in 2.dose the am I just building more wax on the resin gland or am I actually increase in the amount of THC in the overall product. Another words is making more or bigger resin glands dilute the potency of the THC present NSAID glands
I want to increase trichome production on my buds. To this end I read several studies available on the internet. From a study entitled “Interactive effects of jasmonic acid, salicylic acid, and gibberellin on induction of trichomes in Arabidopsis” by Traw and Bergelson, I learned that that, “…gibberellin and jasmonic acid had a synergistic effect on the induction of trichomes, suggesting important interactions between these two compounds.”
http://www.citeulike.org/group/2438/article/853395
From this PGRs thread, I leaned that a good economical source of jasmonic acid was Jaz Rose Spray (thank you Spurr). I already had some gibberellic acid that I bought a while back. Now I had everything to start my experiment.
The strain I used were six Bubblicious from Nirvana in their fourth week of flower, all in the same cabinet. I broke them into three groups. With two, I did nothing, Two others I removed from the cabinet and administered a spraying of Jaz Rose Spray (jasmonic acid). And the last two I removed from the cabinet and administered a dose of Jaz Rose Spray and gibberellic acid, as described by Traw and Bergelson. After the four plants had dried, I returned them to the cabinet.
Ten days later this is what I see:
The plants that received no treatment are progressing as Bubblicious always does, with light visible trichs on the buds, but very little frosting on the sugar leaves.
The plants that received jasmonic acid treatment only, show heavy visible trichs on the buds, as well as a light frosting of trichomes on the sugar leaves.
The plants that received the mix of jasmonic acid and gibberellic acid also show heavy visible trichs on the buds, a light frosting of trichomes on the sugar leaves AND a great deal of FOXTAILING. Foxtailing is considered a disagreeable trait by most gardeners.
Because of my strong attachment to my freedom, and a lack of technical prowess, I will not be posting any pics.
I hope this provides fodder for people more expert than me to examine more carefully the effect of jasmonic acid on trichome production.