Hacker News Reader

> Join us for our continued lecture series, covering topics such as

Please share/blog these! I too have several degenerate chemistry undergrad stories.

> The poor efficacy of DMSO in assisting drug translocation through skin

Yep. During one particularly sleep-deprived finals week, and after recently learning about DMSO's transdermal transportation abilities, my friend and I tried making caffeine skin patches. It worked...vaguely increasing alertness. However, it itched and burned worse than just about anything I've ever experienced.

Also I can concur that chloroform isn't some instant knock-out juice. But one time, a lab mate and I were running massive columns and had accumulated several hundred liters of DCM (dichloromethane) fractions in flasks (yes, it was a loong day). Despite the walk-in hoods running at full bore, by the end of the day, coworker and I were loopy, giggly idiots. Was it above OSHA PEL? Possibly, but probably not. I think the disinhibition was a combination of energy drinks, fatigue+boredom of running hundreds of fractions, and suggestibility, as much as it was the fumes. But my lab manager did walk in at one point and immediately recoiled from the fumes (which we were nose-deaf to at that point).

You have to really dilute DMSO if you're going to put it on your skin.

I mean, pure DMSO on the skin feels fine, albeit not the safest.

Can you not taste the garlic in your mouth for hours after?

Not everybody does.

But my lab manager did walk in at one point and immediately recoiled from the fumes (which we were nose-deaf to at that point).

I don't know whether it's true or not, but I remember a chemistry lecturer telling me that you don't need to worry about terrible smells in the lab, our noses are sensitive to extremely miniscule levels of chemicals. It's when the levels are so high that they have overpowered our senses and knocked out our sense of smell, that's when you need to worry! A wonderfully paradoxical piece of advice...

Hydrogen sulfide is a severe example: it initially smells strongly of rotten eggs but quickly damages the nose until it is undetectable and further exposure can be lethal. For most other chemicals, smells only fade to the background during prolonged lab work through mundane desensitization.

More or less, but with caveats. It's true that many smells (eg H2S, HCN) are detectable before toxic levels, and then become un-smellable at higher levels (saturates and depletes olfactory receptors). But you should still worry about certain terrible smells, because that's often the first sign that something is going wrong. Containment failure, reaction runaway, maybe someone dumped the wrong thing in the wrong waste barrel and now it's reacting, etc.

There's also things which are toxic at the same levels as olfaction, and of course there toxins which are dangerous by the time you have smelled them, or you lack the gene to smell. Most really smelly things aren't acutely toxic like that though. Take DMS (dimethyl sulfide, byproduct of Swern oxidation. Smells like boiling cabbage at low concentration, and liquid ass at high concentration. If you are running a Swern in a fume hood, you are likely quite well-contained even if you've made the whole lab smell like a cesspit.

When we ran cyanation at the kilo scale, you better believe we had HCN detectors all over the place, wore full-face respirators, etc.

I pass along this amusing advice, no doubt familiar to you, but probably not to the general HN readership.

"Gattermann (Ann. 357, 318 (1907)) recommends that the operator smoke during the preparation [of HCN], for he found that a trace of hydrogen cyanide is sufficient to give the tobacco smoke a highly characteristic flavor. This preliminary warning is useful in case of leaky apparatus or a faulty hood" - from Org Syn http://www.orgsyn.org/demo.aspx?prep=CV1P0314

Yup, similar to frostbite. Normal skin temp is around 86°F. as it is cooled, it goes from cool to cold sensation, to very painful at around 55°F. Below that, you don't feel anything as it continues to cool to the point where it freezes solid (which wouldn't be a problem if the freeze-thaw cycle didn't create so many little spiny ice structures that break the cell walls; a type of frog has 'anti-freeze' in it's makeup so it can freeze and re-thaw). So, when your skin stops being painful, that's when you really need to warm it up NOW.

> a type of frog has 'anti-freeze' in it's makeup so it can freeze and re-thaw

Nit: it can't actually recover from freezing solid. It just has lowered the freezing point of the remaining liquid to below the temperatures it's going to encounter.

Thanks, you provoked me to look it up in more detail, and we're both oversimplifying, and it's even wilder than I thought. From [0]:

>> On an organismal level, they are completely frozen to death — their heart stops beating and breathing ceases. Image via Facebook

>> The frog’s death-defying trick actually comes down to one simple factor: nucleating proteins. When the frog’s skin begins to freeze, these proteins cause the water within the frog’s blood to freeze first, which in turn serves as a vacuum for most of the water out of the cells. Simultaneously, their bodies pump out large amounts of glucose to serve as stuffing material, which prevents the cells from collapsing.

>> Essentially, frogs fill their bodies full of sugar to keep themselves alive through winter. When warm temperatures melt the snow around their hibernacula, frogs slowly thaw back to life. Water melts and returns to the bloodstream, begins circulating, and restarts their heart and breathing. Within an hour or so the frog returns to normal life, completely unscathed.

Just wild!

[0] https://roaring.earth/frogs-literally-freeze-during-winter-a...

It's definitely wild!

But "completely frozen" isn't quite right: if you slowly lowered the temperature of a "frozen" frog enough the tiny bit of water still within the cells would freeze, and the frog would die.

They also froze hamsters and revived them with a microwave

https://youtu.be/2tdiKTSdE9Y

I noticed a similar effect getting 3rd degree burns. It was very painful for a moment, then much less painful as the nerves burnt away.

> But my lab manager did walk in at one point and immediately recoiled from the fumes (which we were nose-deaf to at that point).

Reminds me of NileRed's attempts to create enormously stinky substances [1][2]. In one of the videos he said he's basically smell-blind.

[1] https://www.youtube.com/watch?v=C_eYLWLsWPg

[2] https://www.youtube.com/watch?v=LmAG8-V_WQY

Excuse me sir, but are you implying that in 1993 at WrestleMania 9 when Giant Gonzalez knocked out the Undertaker using a chloroform soaked rag that it was all fake? If so then mister, I think you are full of crap. /s

It was real if it was real to you goddammit

Upvoted despite the Reddit flavoring

Professional wrestling got a lot more fun and cool when I realized it isn't "fake", because it isn't trying to be real because it's actually supposed to be modern day Shakespeare

I loved watching it as a kid and my friend convinced me to check out some modern stuff about 2 years ago and I have been having a blast watching it ever since.

Roland Barthes agrees. Check this essay he wrote in the 60s about wrestling.

https://archive.org/details/barthes-world-of-wrestling/mode/...

Same! Learning it was fake ruined it. And then realizing that it’s in on being “fake” and that it’s a soap opera made me appreciate it a lot.

And “fake” may cover the results of the matches but it doesn’t cover how intense it is on their bodies. Olympic wrestling is probably a far easier sport on the body.

I got into it pretty hardcore after hearing an NPR doc on the Montreal Screwjob.

> Harm reduction re: consumption of USP 99.9% ethanol

According to Ignition! by John Clark, high-purity ethanol used for rocket fuel undergoes a similar phenomenon when in storage tanks near rocket scientists and Navy personnel. Interesting to see that this also occurs in the proximity of undergrads. Study operators claimed that dissolving the ethanol in H2O, or, preferably, lime juice and/or soda water, merits further study.

But yes, I would also be interested in reading that continued series.

So far the correlation between personnel proximity and tank depletion is just that: a correlation. All attempts at establishing causality have been met with fuzzy recollections, outright denials, and conflicting reports.

More investigations are warranted.

The earliest HDDs were not sealed and required regular maintenance to clean the heads manually; you were supposed to use ethanol or isopropanol for that purpose. There was a story from late Soviet times about this - since they lagged quite badly when it came to computing, even in late 80s there was still plenty of hardware around like that. And for every such hard drive, there would be accounting to track the amount of ethanol issued, so the engineers had to make do with what they could skim after the cleaning.

But then around that time some better stuff began to trickle in - instead of 3-5 Mb HDDs, you could get a whopping 30 Mb! Those were sealed and required no cleaning... but the legend goes that, in one such place, it occurred to the engineers that accounting doesn't know that. So, instead, they submitted a request to procure more ethanol for cleaning, on the basis that a 30 Mb hard drive would obviously need 6 times as much for servicing as a 5 Mb one does. It was approved, and the arrangement lasted until the head of the department caught someone drunk and traced the source.

(Another version of this legend has a slight variation in that the engineers submitted a request for more than 6x, deliberately making a mistake in math to make it look like a clumsy attempt to get more. Accounting promptly "caught" it and gave them a stern lecture about how they're not getting even one drop over what the proper number required... i.e. 6x.)

If you liked that story, you'll love https://www.youtube.com/watch?v=bKoHMXggEHU

It could well be a similar phenomenon to how silencers on firearms absolutely do not make a gun sound like it sounds in the movies, but because it's become an established (and convenient) film trope, it persists in film.

Similarly - films depicting kidnapping people using chloroform as an instant knockout drug.

I remember reading (can’t find the source anymore) that ether would work as knock-out drug, and that indeed it was used as a plot device in crime books as chloroform is used in movies today. The problem is that ether can be highly toxic at relatively low dosage, and then it was replaced by chloroform in fiction to avoid giving dangerous ideas to people.

Is there any truth behind this theory?

Just some anecdotal evidence to support what you're saying.

When I was in college and a freshman, I was told the urban legend about the "ether bunny". The story about a freshman who finds out his roommate has been drugging and having sex with him using ether.

I wasn't very knowledgeable about these stories or urban legends in general so when I was home for Christmas vacation, I told my Dad about it, and he started laughing and said it was an old college urban legend but when he was told it (in the 1960's) as a freshman they used chloroform instead of ether. He mentioned some other details about the story that were changed due to the times, but that was one point that was clearly changed over time, possibly for the same reason.

However, drink 'spiking' for the same purpose is a thing, and people have been jailed for it.

Ether and chloroform both have relatively narrow therapeutic windows - the toxic dose is very close to the minimum active dose. But they were one of the few true anaesthetics at the time (late 1800s). Alcohol was also used for surgery but it's slower and inhibits clotting. In fact often it'd be a combination of all three, known as ACE [1]. This worked okay-ish, as the GABA-ergic synergy was able to suppress consciousness and memory without poisoning the patient's heart or liver (as) severely.

The other big issue was flammability.

Ether still takes enough time to reduce consciousness that you have a good minute or two (minimum) of struggle. It's not "towel over face, muffled screaming, then sleepytime". But an attacker with advantage of surprise and a decent grapple could usually get the target dosed before they could break free.

[1] https://en.m.wikipedia.org/wiki/ACE_mixture

I've heard that grayanotoxin was uses for surgery around that time frame as well.

Weirdly enough, ether can be drank. Erowid has a great many self-reported case studies of the effects of ether drinking

https://erowid.org/experiences/subs/exp_Ether.shtml

I've never consumed or inhaled it myself. However from someone who I know drank it, said the high is rapid and intense. Basically, it's enough to get you arrested for a public intox, and by the time you're at the police station, you're completely sober, save for your breath smelling like gasoline.

Another source about consumption of ether in 19th c Ireland : https://www.newscientist.com/letter/mg19125630-800-bring-bac...

https://www.mayoclinicproceedings.org/article/S0025-6196(11)...

https://en.wikipedia.org/wiki/Ether_addiction

As a final edit: It's probably a really bad idea to inhale or drink ether.. but it is definitely drinkable.

“The only thing that really worried me was the ether. There is nothing in the world more helpless and irresponsible and depraved than a man in the depths of an ether binge. And I knew we'd get into that rotten stuff pretty soon. Probably at the next gas station.” ― Hunter S. Thompson

Suppressed subsonic 300 blackout is pretty darn close to the movies: https://www.youtube.com/watch?v=1AUDVoGOCxw

It's quiet enough that those guys are not completely crazy for not having ear protection — but of course the microphone is not picking up the full volume of the shots either, any more than it does for unsuppressed, supersonic rounds.

Microphones generally are very bad at picking real volume of gunshots, silenced or not, subsonic or not, small, large and massive calibers alike

Not when you're standing right next to it with no ear protection. The peak is still going to be on the order of 115-125 dB at the muzzle even with the best can. This is well within hearing-safe territory (<140 dB per OHSA). But that is still louder than an auto horn!

As others have noted, recording equipment doesn't register these levels reliably, so watching a recording does not reflect the actual experience.

Uh… the highest limit osha has on sound levels is 115db. 140 is a jet engine. A chainsaw is 110

That's for continuous noise like engines. OTOH "exposure to impulsive or impact noise should not exceed 140 dB peak sound pressure level".

Would be fun for a show like law and order to do an episode where someone is framed with chloroform and part of solving the crime is excluding the framed person because the chloroform TV trope isnt based in science.

A suppressed .300 blackout subsonic round sounds like the movies. It’s unreal. The slide and mechanics of the gun are louder than the round. A rather large round, at that.

It's not just silencers - movies and video games are generally bad at gunshots. For good reasons - if you make them as loud as they ought to be, even to the limits of the recording equipment (since you'd need to go well into the hearing-unsafe territory), they'll drown out everything else.

There are exceptions. The famous shootout scene from "Heat" does a surprisingly good job at conveying just how deafening gunfire really is close up, for a movie. Although even that is much milder than it would be IRL, due to use of blanks and the aforementioned equipment limitations.

https://www.youtube.com/watch?v=ZL9fnVtz_lc (shooting starts around 4:20)

That scene was pretty interesting but can’t help notice that all the automatic guns just fired endlessly. There were a few reloads but it’s astonishing how fast you go through 30 rounds and they were firing way longer uninterrupted. On another note that final shot was amazing cinematography.

> The poor efficacy of DMSO in assisting drug translocation through skin

Oh yeah, for the observer gallery: The reason DMSO (and DMF, DMAc, HF, to an extent haloforms, and polar aprotic solvents in general) are dangerous is that they can dissolve and transport small molecules (under 1000 daltons, possibly more) through your skin and into the bloodstream. They go straight through nitrile, vinyl, and latex gloves. You need to match the glove to the solvent. For these strong solvents, you want aliphatic polymers (LDPE) or laminates (mylar aka aluminized polyester).

Actually one of the best protection schemes is the shoulder-length polyethylene gloves used for ...ahem... bovine obstetrics, with nitrile over that for grip and to keep the cow glove in place. Looks hilarious but great for pouring nasty solutions or weighing dusty powders.

https://www.amazon.com/livestocktool-com-Disposable-Artifici...

The garlic like smell of DMSO just doesn't leave you if it gets into your skin. It's "safe" but really, really bad to have fingertips smelling of it for days. I wish I had those bovine gloves during my PhD...

> fingertips smelling of it for days

It's even more insidious than that -- it is not only your fingertips that smell, since it penetrates the skin so readily. Pure DMSO itself is odorless, but it is metabolized into DMS, which stinks unbelievably strongly of garlic. The DMS has a very high systematic half-life (38 hours!!!) and remains dissolved in the blood, meaning your blood itself will stink of garlic for days after exposure.

The gut punch, however, is that the victim is reportedly unable to smell it (probably because their olfactory tissue is literally awash in DMS), so they don't realize they smell like walking garlic bread.

isn't DMSO used as a (home?) remedy for joint pain?

I've thought about trying it but have visions of it leaching the dye from my clothing and transporting it into my bloodstream. the garlic wouldn't make me many friends, but dissolving poisons is scarier.

The weird death of Gloria Ramirez that I heard about years ago has apparently been linked to topical DMSO as a factor. https://www.youtube.com/watch?v=lXBCIzkannw

I recently had to use a mitomycin C (very toxic) solution in DMSO, I was really paranoid to not spill any.

Wow. That's not something you want to have an oopsie with.

Holy lord, how do I join your curriculum? The topics look like straight out of Derek Lowe's "Things I won't work with"

>Why attempting GHB synthesis via permanganate oxidation of THF is a bad idea

I'm interested . . . is it because of the risk of blow-ups?

The biggest issue is that it poses health risks, like being carcinogenic.

That's why the primitive anesthetic ACE (Alcohol, Chloroform, Ether) existed in many proportions, but never chloroform alone.

you're telling me that movies LIED to me my entire life, i'm shocked, SHOCKED i tell you!!!!