The Effect of Mixing Alcohol and Caffeine in the Presence of Carbon Dioxide.

[NNadir]

I don't generally drink hard liquor, and limit myself to wine and beer, and then in moderation, but I do have a caffeine "problem." However, recently, because everybody said I should, I watched "The Big Lebowski," and although I didn't actually get it until I rewatched "The Big Sleep," at the advice of a correspondent I watched while consuming a "White Russian," a concoction of heavy cream, vodka and Kahlua, a coffee liqueur.

I don't actually have a sense of humor, but if I did, with this in mind, mixtures of caffeine and ethanol that might have been carbonated (but wasn't), I might find this paper, across which I stumbled funny in a way: The Polar Cosolvent Effect on Caffeine Solvation in Supercritical CO2–Ethanol Mixtures: A Molecular Modeling Approach (Ioannis Skarmoutsos, Ioannis D. Petsalakis, and Jannis Samios Industrial & Engineering Chemistry Research 2021 60 (31), 11834-11847.)

It begins with a little lecture on the possible health consequences dangerous drug (in this case not alcohol) to which I'm addicted, although the text notes I'm not alone:

Caffeine (1,3,7-trimethylxanthine) is the most consumed alkaloid worldwide and can be found in significant concentrations in natural products such as coffee and cocoa beans, tea and yerba mate leaves, and kola nuts.(1) Because of its therapeutic properties, caffeine is also a basic ingredient in the formulation of a variety of medicinal products.(2) When consumed in moderate amounts, it can stimulate the central nervous system, exhibiting in this way an analgesic activity, reducing fatigue and increasing attention.(3) However, large doses of caffeine can adversely affect cognitive responses and may also cause insomnia, heart palpitations, stomach irritation, and hypertension.(4?6) Consequently, the extraction of caffeine from raw natural products is necessary to use it in medicines, energy drinks, and other beverages but also to control its concentration.(7) The extraction can be achieved using organic solvents,(8) such as dichloromethane and hexane. However, these solvents are considered harmful to human health and the environment. On the other hand, supercritical carbon dioxide (SC CO2) is an inexpensive, nonflammable, and nontoxic solvent. For these reasons, it is considered to be an attractive alternative to these conventional organic solvents.(9?11) Supercritical-fluid (SCF) extraction, a well-established separation technology, has received wide attention in recent decades and has been successfully employed in a variety of applications including food processing, extraction of active principles for pharmaceutical formulations, wastewater treatment, enhanced oil recovery operations, and as an analytical chromatographic tool.(12?15)

The low solubility of polar substances in nonpolar SCFs, such as SC CO2, is an obstacle to the development of viable extraction operations using supercritical CO2. Although SC CO2 is quite efficient for the selective extraction of caffeine,(16) the solubility of caffeine in this solvent is lower than that in liquid organic solvents.(11,17?19) Due to this, the use of a large amount of CO2 during the extraction process is required, causing a substantial increase in operating costs...

The solution?

Just add alcohol...

If I had enough of a sense of humor to find this amusing - I don't - it would be funny in a dorky kind of way, which would not be a problem for me, because some people who have been supercritical of me have noted, with some element of truth, that I am a dork.

Cool paper though...

There's a lot of sophisticated molecular modeling in this paper which concludes as follows:

The effect of the addition of a small amount of ethanol cosolvent in supercritical CO2 on the solvation structure and dynamics of caffeine in the mixed supercritical CO2–EtOH solvent has been investigated using a systematic multiscale molecular modeling approach, employing DFT quantum chemical calculations and classical MD simulations. The results obtained have clearly revealed the existence of preferential interactions between the caffeine and ethanol molecules in the system. A deeper investigation of the local solvation structure around caffeine has revealed the existence of HB interactions between caffeine and ethanol molecules, whereas the average number of EtOH–EtOH hydrogen bonds per ethanol molecules inside the solvation shell of caffeine is maintained in comparison with the bulk supercritical mixture. The latter finding has been further investigated, revealing that the ethanol molecules inside the solvation shell of caffeine continue forming hydrogen bonds with other ethanol molecules, even when they also form hydrogen bonds with caffeine. These findings further support a previously proposed hypothesis that the main reason for the enhanced solubility of caffeine in SC CO2–EtOH mixtures is the strong interaction between the polar caffeine molecule and the ethanol aggregates formed in the binary SC CO2–EtOH mixture.

This means that if you ever find yourself watching "The Big Lebowski" while consuming a White Russian and still plan on sleeping that evening, stick the thing in a can of pressurized carbon dioxide and heat it gently.

Another alternative would be not to watch "The Big Lebowski," and/or not have a White Russian while doing so.

On the serious side, any technology that minimizes the use of dichloromethane and hexane, which simultaneously sequestering carbon dioxide for use is a good thing.

I absolutely love learning about supercritical carbon dioxide in particular, and supercritical fluids in general.

As for "The Big Lebowski" it was mildly amusing and might have been funny even, at least if I had a sense of humor, regrettably though, I don't.

[eppur_se_muova]

1. "Nature's own effervescence" ... and, uh, natural moonshine !

Madison Ave. felt "supercritical carbon dioxide" didn't have much consumer appeal, obviously. Maybe they'll refer to the improved process as "sparkling liqueur".

[Hugh_Lebowski]

2. Other than my mom, you're like last person I know in the world I'd recommend watch Big Lebowski

Based on what I know of you, I'd have fallen on the floor if you said you loved it.

[NNadir]

4. Well, dude, I certainly mean no offense to anyone who IS a Lebowski. I have to confess...

...that among the Lebowski's I know, you're the best, better than the movie, at least in my opinion, but again, I don't have a sense of humor.

[Hugh_Lebowski]

6. No offense taken, like I said, I would NOT expect you to like it ...

It's a 'niche' kinda movie, you have to not only have a sense of humor in general, but even one of a specific sort.

[Jim G.]

3. I Have An Above Average Sense Of Humor

And I've seen 'The Big Lebowski' a couple times & I didn't think it was all that either.

[Hugh_Lebowski]

5. I think one has to have a sense of humor of a particular bent, not just sense of humor period

It's also best to watch it the first time really baked

I think how much one thinks Pulp Fiction is funny would track closely to thinking Lebowski is funny, cause I think the humor is in similar vein.

Napoleon Dynamite is another movie like this ... it's very much loved and hated in equal measure ... if it's 'your kind of humor' it's hilarious. Others watch it, never laugh, and think it's the worst movie of all time.

[Earth-shine]

7. I must have a below-average sense of humor.

I thought The Big Lebowski was great from beginning to end.