## Chemistry of lost gold

(by drrubidium) Sep 17 2014

Funny story... back in 2011, the United Arab Emirates (UAE) seems to have misplaced 50 kg of gold belonging to Crown Financial Solutions.  How much is 50 kg? That's 50 of these shiny bars...

Shiny bars that are worth a lot. [source]

For those adverse to the metric system, 50 kg of gold is about 110.2 lbs. Basically, the UAE just lost a solid gold Kate Moss (which is actually a thing). How much is 50 kg of gold worth?  A cool \$2.4 million by 2011 values when gold was \$1354.50 per ounce.  Today? The price of gold right now is about \$1235.82, so the missing bars are worth about \$2.2 million.

50 kg, 110.2 lbs, \$2.4 million, \$2.2 million... bah! How many atoms of gold are we talking here?!

Elemental gold [source]

If we assume that we've got a total of 50 kg pure gold, this problem is easy peasy! All we need is Au's molecular weight from the periodic table and Avogadro's number.

The UAE misplaced 150,000,000,000,000,000,000,000,000 atoms of gold. Fear not! There's something like 10^78 - 10^82 atoms in the observable universe, so 10^26 is a drop in the bucket. A very expensive drop...

______

Chemistry is everywhere. Even divorce.

______

*Damn sigfigs mean this answer should be rounded by a lot.

## In which I do acts of whimsy... FOR SCIENCE!

(by drrubidium) Aug 25 2014

The DIY Science Zone is back for GeekGirlCon 2014! You know what that means!

• There will be an fun place at GGC '14 for attendees to get their hands dirty with science!
• This zone will be staffed by a crew of talented scientists and science educators!
• We need to raise \$6000 and will do acts of whimsy to show our gratitude! As of 13 September 2014, \$5453.50 has been raised.

What acts of whimsy will I be doing? To celebrate the first \$100, I wore a tiara at work. Since we crossed the \$500 mark, I'll be running the CASA Donut Dash on September 14th in this Wonder Woman ensemble.

...but that's not all! Last year, I subjected myself to Nickelback to raise money for the DIY Science Zone.  This year, it's Pink Floyd.

Me too, bro

That's right, I don't like Pink Floyd.  But! I will listen to Pink Floyd - FOR SCIENCE!  For every \$1000 the pro-Pink Floyd ("Go PF") camp raises, I'll listen to an entire band album.  I can be saved from listening to Pink Floyd, if the anti-Pink Floyd ("No PF") camp offers up counter donations.  It's Go PF vs. No PF!  Here's how you can make be listen to Pink Floyd or save me from it:

Go PF or No PF, the winner will be science!  No donation is too small and every dollar helps!  Thanks to all our wonderful donors. Yes, even the Go PF ones...

UPDATE!  Go PF camp has raised \$595 to get me to listen to Pink Floyd.  The NO PF camp? \$275.  Gotta say, last year, Nickelback fans were all about throwing money at the zone. Pink Floyd fans? Um...

__________

gif from Buzzfeed

## I went to SPACE!!!

(by drrubidium) Aug 04 2014

Pre-launch....

Post-launch... okay, okay... post CGI

## Off to #dragoncon I go!

(by drrubidium) Jul 23 2014

This is the year of multi-genre con madness! First, Emerald City Comicon, then CONvergence, now Dragon Con, and soon GeekGirlCon!  Why multi-genre cons? Because they've got big audiences of hardcore fans that are passionate about every aspect of the genre they love. That's prime science outreach territory!  Breaking Bad fans want to know about meth synthesis methods. Song of Ice and Fire Fans want to know about poisons. Zombie fans want to know how to survive.  Oh, and I'm a HUGE fan. Of zombies, Star Trek, Star Wars, BSG, GoT, Locke & Key, Firefly, all the camp that is the SyFy Original Movie, and much, much more!

Dragon Con's Science Track, led by the fabulous Stephen Granade, has great programming on deck for this year's con!  Check-out the full schedule here.  I'll be participating in the following...

Fri 2030: Zombies and Vampires and Mummies — Oh My! | Location: 202 - Hilton
The undead fascinate us, but what does “undead” mean? Are all undead monsters created equal? Panel scientists will examine life, death, and undeath.
Raychelle Burks, Lali DeRosier, Emily Finke, and Kristopher Hite

Sat 2200The (Non) Science of SyFy Movies | LocationGrand Ballroom West - Hilton
SyFy movies contains some…unique ideas about science. Our scientists discuss the real science, with special guest star SHARKNADO.
David Shiffman, Rachel Pendergrass, Raychelle Burks, Lali DeRosier, and Lisa Hoopes
(Note that this will run in a ballroom while other panels continue in the track room)

Sun 1000The Hands-On Science Power Hour! | LocationAtlanta - Sheraton
Give us an hour and we’ll give you a science buffet! We’ve got twelve hands-on experiments for you to try. How many can you do in an hour?
(Note that this will run in a ballroom while other panels continue in the track room)

Sun 1300Ask a Scientist! Location: Atlanta - Sheraton
You’ve got science questions? We’ve got science answers! Ask our panel of expert scientists anything you want to know about science.
Mika McKinnon, John Cmar, Pamela Gay, Raychelle Burks, David Shiffman, Stephen Granade (moderator)

Sun 2200: The Solve for X Science ShowLocation: Grand Ballroom East - Hilton
Puppet show, PowerPoint karaoke, quiz game, storytelling: the scientists are loose, and nobody knows what could happen next.  Find out more here

____________

Top image created using clip art in PowerPoint

(by drrubidium) Jul 14 2014

That's right. Next month.

THE HELL YOU SAY!

A lot of institutions start the fall term in August. That's next month.

For many of us, that means a return of a life-force diminishing activity. Yes, I mean 'grading'.

Since everything is made better with a soundtrack*, I'm sharing my ever-expanding Grading Soundtrack below.  Feel free to drop a relevant^ track in the comments.

________________

*This is a totes false assertion, but it feels true.  Which, by the way, is how Fox News operates.

^Nickelback, Rush, and Pink Floyd are NOT relevant.

________________

Tom Hiddleston gif from here

Kristen Wiig gif from here

## Because she didn't die

(by drrubidium) Jul 08 2014

This post is the second in my Case Book series on old or odd crimes, which began with The suspicious case of Miss Sapwell. The events described herein occured a few years ago in China (Yan et al., 2012).

Tiny metallic objects, opaque to x-ray, were spread bilaterally across her chest. A shotgun blast? The metallic objects resembled birdshot, but there was too many of them. There was also no external trauma - no lacerations and no blood.  She had not been shot, yet there they were, a collection of tiny metallic rounds. Whatever they were, and however they got there, these objects were making her terribly ill.

She had come to the hospital complaining of a persistent cough, chest pain, shortness of breath, and fatigue.  Looking at her chest x-ray, a radiologist knew what was causing her respiratory symptoms - those metallic objects in her lungs.  What were they? How did they get there?  The radiologist was baffled.  The patient was hospitalized, but released on the say-so of another doctor.  The only care instruction she was given was bed rest.  Two months later, she was back in the hospital and she was worse.

In addition to her previous symptoms, which had advanced, there were new ailments to be treated.  Abdominal pain, weight loss, ulcers in her mouth, and bleeding gums.  No x-rays were taken during this second visit, which would see her hospitalized for 10 days.  She was released by the same doctor as last time.  Three months later, that very same doctor found her dead in bed.  That doctor was her husband.

Her husband was not a suspect upon her death.  Chiefly because no one thought a crime had been committed. Her long illness, worsening month-by-month, was well documented - along with the attempts to treat whatever it was that ailed her.  Her decline, while perhaps bit mysterious, was not considered suspicious.  The death was ruled "natural", no autopsy was performed, and she was buried the day after she died.

She would not stay buried. Infidelity would cast her death in a new and unnatural light. Her doctor husband - the one that had discharged his sick wife (twice) and found her dead - was caught having an affair with a nurse in his hospital. Their affair had been going on for several months and its discovery provoked her family to request an forensic autopsy*.  While the affair brought suspicion, an autopsy would provide answers. Two months after her death, she was exhumed and examined.

An internal exam cleared-up the mystery of those metallic objects observed in her chest x-ray.  Those metallic objects were mercury globules.

elemental mercury

Seven months after her first hospital visit and two months after her death, her lungs were full of mercury globules.  These globules weren't just in her lungs, they were also in her pulmonary arteries.  High mercury concentrations were found in her liver, heart, and kidneys.  Her x-ray and presenting systems are nearly textbook for mercury poisoning (mercurialism) of a very particular exposure type. She had been injected with mercury. An injection site wound was found during her autopsy beneath the crease of her left elbow.

Intravenous elemental mercury poisoning is extremely rare. This mode of poisoning is also not a reliable murder weapon.

… no lethal consequences from intravenous injected metal are to be expected…

Elemental mercury, when injected, as opposed to inhaled, caused few of the effects typical of mercurialism (because only a part of mercury is transported into the central nervous system; most of it is deposited in internal organs, lungs, kidneys, aortic valve, as well as at the site of injection), e.g. mercurial tremors and leg pains; however pleuritic chest pain was frequent, whereas renal and central nervous system symptoms were less common. (Lech & Goszcz, 2008, p21)

Mercury made her ill, but something else hastened her demise. Toxicology results showed she had been exposed to cyanide, which is a far more lethal poison than mercury upon injection. Cyanide causes histotoxic hypoxia - cells are unable to use available oxygen and death results.  She was injected with an extraordinarily high dose of cyanide - 1 gram of sodium cyanide dissolved in normal saline. A 100 miligrams of sodium cyanide delivered in the same fashion would have been more than than enough to bring about her quick death. Cyanide, however, wasn't the only injection she received the day of her death.  Shortly before the cyanide, an injection of meperidine (trade name Demerol®) was also administrated.

Meperidine is a narcotic analgesic used to treat moderate-to-severe pain.  As with the cyanide to follow, meperidine was mixed with a glucose solution prior to injection. With the first two injections - mercury and mepheridine - she was told it was just glucose.  She was told it would make her feel better. She'd a headache a week before her first trip to the hospital.  Her doctor husband told her an injection of glucose would help her headache.  He injected her with 40 milliliters of a glucose solution and 3 milliliters of mercury.  Within a week she was so sick she had to be taken to the hospital, but death did not ensue.  She got worse, and there was the second trip to the hospital, but she didn't die.  He got tired of waiting.  Five months after poisoning her with mercury, he "treated" her again with glucose - merperidine. This drove her to a state of semi-consciousness.  It was then that he injected her with cyanide.

He appears to have obtained the mercury, meperidine, and cyanide at the hospital he worked as a physician. The same hospital he took his ailing wife to. The same hospital the nurse he was having an affair with worked.  Several days before her death, he visited the hospital laboratory and obtained 20 grams of sodium cyanide for ‘‘chemical analysis for his study’’ (Yan et. al., 2012).  Upon being confronted with his wife's autopsy results and evidence of his affair, he confessed all - the timeline, poison dosages, his duplicity.

His lies and his position seem to have provided a sufficient smokescreen for her protracted murder.  Why hadn't the radiologist diagnosed mercury poisoning?  Her doctor husband twice checked her out of the hospital... why didn't that raise an alarm?  Bells didn't ring over his procurement of 20 grams of sodium cyanide using, quite frankly, a thin story - why? Did the hospital not notice the missing mercury and bottle of meperidine?  If his affair hadn't been discovered, he might have gotten away with murder.

_______________________________________

*Her head was not examined at the request of her family (Yan et. al., 2012)

_____________Select References_____________

• Lech, T.; Goszcz, H. Chronic, long-term presence of mercury due to a single injection of elemental mercury in human, Int J Biochem Biotechnol, 2012, 1, 19-23.
• Vallant, B.; Deutsch, J.; Muntean, M.; Goessler, W. Intravenous injection of metallic mercury: case report and course of mercury during chelation therapy with DMPS, Clin Tox, 2008, 46, 566–569
• Yan,P,; Huang, G.; Daoquan, L.; Li, L. Homicide Due to Intravenous Metallic Mercury Injection Followed by Sodium Cyanide Injection, Am J Forensic Med Pathol, 2012, 33, 273-275

Casebook image from IGAS

Mercury image from Keuka College

Meperidine image from chemspider and Demerol bottle from hospira

## My @CONvergenceCon shenanigans!

(by drrubidium) Jun 25 2014

I'm super excited to be attending CONvergence (July 3-6) as part of the Skepchick crew.

Skepchicks is running the SkepchickCon, the science track at CONvergence.  This science fiction and fantasy con is chockablock full of great programming! SO MUCH TO DO!!!  When I'm not fangirling, I'll be putting on my somewhat-serious-face and participating in the following panels...

Thursday, July 3

12:00-4:00pm Invisible ink (I'll be helping experimenters in a Skepchicks activity/party room. They'll be other activities too!)

5:00 Hookers & Purls (I'm co-hosting a crafty salon for crocheters & knitters!  Dropping into a session like this is how I learned to knit in early 2013. Since then, I've been hooked. Sorry, not sorry, for that pun.)

8:30pm Green Is Not Diversity

Friday, July 4

2:00pm Greeter in the Skepchicks activity/party room

3:30pm I'm getting my game on!

11:30pm The Zombie Environment

Saturday, July 5

8:30pm Getting Away with Murder

10:00pm Volunteer in the Skepchicks party room

Sunday, July 6

The rest of the time, I'll be attending panels, gaming, crafting, and skipping around the con. Woohoo!

____________

CONvergence banner from con website

OITNB's Taystee gif from giphy

## The suspicious case of Miss Sapwell

(by drrubidium) May 06 2014

Some might call it a "girls' weekend", what Miss Marion Sapwell had planned for those few days in late July, 1960. Miss Sapwell, soon-to-be a bridesmaid in a friend's wedding, was travelling to Melbourne for a day or two of shopping and fun with the bride-to-be. Both women were nurses; Miss Sapwell at Wangaratta Base Hospital.

On Friday, July 22nd, Miss Sapwell drove the over 150 miles from Wangaratta to Melbourne and stayed the night with her friends, Mr. and Mrs. Etienne Mehari. Saturday should have seen Miss Sapwell and her affianced friend hitting the shops in Victoria's capitol. Instead, Miss Sapwell fell ill Saturday morning at the Mehari home.  A doctor made a house call, and by midday Saturday, Miss Sapwell was a patient at Melbourne's Box Hill Hospital.

An otherwise healthy woman of twenty-three, Miss Sapwell's sudden illness and presenting symptoms had Box Hill resident Dr. Robert Oliver suspecting poison.  Concerned with Miss Sapwell's rapid decline, and with his patient adamant she hadn't taken anything, Dr. Oliver called the Mehari home.  The couple had not seen Miss Sapwell take any pills or powders and even searched their home.  Nothing untoward was found.   Dr. Oliver thought Miss Sapwell had ingested a irritant or corrosive poison, but which one?  Another doctor would identify the poison, though too late to aid Miss Sapwell.  In the early hours of Sunday, July 24th, Miss Sapwell died.

In death, Miss Sapwell became a patient of Dr. James McNamara, assistant lecturer in forensic medicine at the University of Melbourne and assistant medical officer to the City Coroner.  Parchment-like abrasions on Miss Sapwell's skin, along with the state of certain internal organs, led Dr. McNamara to finger cantharidin as the cause of the young nurse's death.  Lynn Turner, deputy medico-legal chemist for Victoria, also determined the poison in question was cantharidin.

Cantharidin is produced by over 1500 species of beetles as a defensive measure, causing blistering to skin upon contact.  This vesicant action earned cantharidin-making beetles the moniker 'blister beetles'.  One particular beetle, Lytta (Cantharis) vesicatoria, is the source of cantharidin's much more popular name.  L. vesicatoria is the beetle known as 'Spanish fly'.

L. vesicatoria

While some Spanish fly preparations are simply dried blister beetles ground into a powder, fairly pure cantharidin can be easily isolated from these beetles.  Dissolved in alcohol, oil, or placed in various foods, cantharidin has been used as an aphrodisiac for thousands of years.  Incorrectly used, that is.  Catharidin does not increase sexual desire - though its physiological actions likely led to its aphrodisiac misnomer.

Within a certain dosage range, cantharidin causes pelvic vascular congestion.  Blood pooling in the pelvic vessels affects both men and women, with men often experiencing persistent erections (priapism).  For both women and men, pelvic congestion can be painful.

Ingesting a large dose of cantharidin causes significant internal damage.

…severe burning and blistering of the gastrointestinal and urinary tracts... abdominal pain, nausea, vomiting of blood, bloody diarrhea, painful and bloody urination, convulsions, rapid pulse, a drop in blood pressure, shock, and death.

[excerpt from Murder and Mayhem: A Doctor Answers Medical and Forensic Questions for Mystery Writers by D.P. Lyle, MD]

The kidneys, which would work to clear cantharidin out of the body, can also fall victim to its affects. Cantharidin causes acute swelling of the spaces between the kidney tubules (interstitial nephritis), which may lead acute renal failure.  Though consumption of cantharidin for medicinal has long been advised against, this irritant did find its way into treatments and tonics. Decades before Dr. McNamara named cantharidin as the chemical culprit in Miss Sapwell's death, there were no recognized legitimate medical use for cantharidin - save one.  Dilute cantharidin solutions (< 1% w/vwere - and still are - used topically to remove warts by causing the skin beneath a wart to blister.

Though there were blisters on Miss Sapwell's skin, Dr. McNamara asserted they were caused by cantharidin in Miss Sapwell's vomit coming in contact with her skin during her illness.  Miss Sapwell ingested a lethal dose of cantharidin (10 - 60 mg), which caused her death.  Who poisoned the young nurse?  Investigators focused on a single suspect based on a single word said by Miss Sapwell to Dr. Oliver. "Funny".  That is how Miss Sapwell described the taste of the coffee Mr. Mehari had served her Saturday morning.

Mr. Mehari was seven years older than Miss Sapwell in July 1960, living with his wife and young son in a residence above the chemist shop (pharmacy) managed by Mrs. Mehari. Working in the same general field as his wife, Mr. Mehari was employed with a firm of wholesale druggists (pharmacists).   The Merharis met Miss Sapwell through a letter of introduction brought with Miss Sapwell from  her native New Zealand when she first arrived in Melbourne to finish her nursing studies in 1959. The couple and Miss Sapwell had became friends.

In that summer of 1960, the police suspected that Mr. Mehari was no friend to Miss Sapwell. Two days after Miss Sapwell's death, on July 26th, police said Mr. Mehari came clean about the "funny" tasting coffee he served Miss Sapwell.

It’s no use denying it. I put something in it, but I can’t tell you what it was. I could not face my wife if she found out what I did… my marriage will be ruined if it comes out what I gave her.

[quote from "Young Nurse Poisoned in Home Where She Was Guest, Court Told"]

According to police, Mr. Mehari did not have murder on his mind when he'd slipped cantharidin in Miss Sapwell's coffee.  He sought a sexual encounter with Miss Sapwell, using the infamous 'Spanish fly' to enable an assault.  When Miss Sapwell fell ill, Mr. Mehari kept what he had given her to himself.

I was in an awkward position. I could not tell the doctor what I had given here because my wife, and I did think she would die.

[quote from "Young Nurse Poisoned in Home Where She Was Guest, Court Told"]

On the evening of July 26th, Mr. Mehari was charged with murder and Australia's Crown Prosecution would bring him to trial that November. During his trial, Mr. Mehari denied ever making any confessional-type statements to the police and leveled an accustion of his own - police misconduct.  Mr. Mehari claimed a detective struck him, that threats of criminal prosecution were made against his wife, and that detectives even mentioned his son.  Detectives denied any wrong-doing in court, with the Crown and the defense doing battle over Mr. Mehari's supposed statements to police.  Another battle was to come. A battle of experts, common in today's high-profile murder trials.

Dr. McNamara posited Miss Sapwell's death was the result of cantharidin poisoning, a view shared by state chemist Turner. Miss Sapwell's statements prior to her death, as reported by Dr. Oliver, also seem to clear the nurse of administering cantharidin to herself.  Why might Miss Sapwell have taken cantharidin, but not disclosed doing so - even in the terrible throes of her illness?  In 1960, the use of cantharidin as a supposed sexual stimulant was embarrassing, likely scandalous, but not as much as this chemical's other use.  Cantharidin has a long history as a abortifacient, though this does not appear to have been explicitly acknowledged during the trial.  Dr. McNamara seems to imply this use of cantharidin by testifying there was no "possibility of pregnancy" in Miss Sapwell's case.  Testimony from Drs. McNamara and Oliver bolstered the Crown's claim that Miss Sapwell was a poisoner's victim - something the defense seemed to agree with or, at least, not deny.  What the defense did deny was that Mr. Mehari was the poisoner and that cantharidin was the poison.

Mr. Mehari, represented by Mr. Frank Galbally during his trial, protested his innocence in court, refuting the claim he put anything in Miss Sapwell's coffee. He rebuffed the idea he wanted a sexual relationship with Miss Sapwell, reportedly testifying  "...he and his wife were very happy and he had no desire for such a relationship." Along with refuting who poisoned Miss Sapwell, the defense called their own expert to refute what poisoned her.

University of Melbourne Professor of Pharmacology Dr. Frank Shaw disagreed with Dr. McNamara's and state chemist Turner's opinion that cantharidin was the irritant poison in question.  According to Dr. Shaw, the "parchment-like abrasions " on Miss Sapwell's skin were completely unlike the blisters cantharidin would cause - something Dr. Shaw set out to demonstrate in dramatic fashion.

Professor F. H. Shaw… showed the court two blisters and a scar on his arm, but declined to reveal their cause.  Professor Shaw was invited by Mr. Galbally to show the scar and blisters to Lynn Turner, State medico-legal chemist, who game evidence of a post-mortem examination. He formed the opinion that the girl had died of cantharadin poisoning.  Turner, after inspecting the blisters on Professor Shaw’s arm, was unable to say if they were caused by cantharadin.

[excerpt from "Police Deny Violence at Questioning Before Murder Charge"]

a blister beetle's work

State chemist Turner's ability to confirm or dismiss skin blisters as being due to cantharidin was key for one reason.  A skin test was how state chemist Turner identified the poison as cantharidin.  Rather than this being an oversight, it simply demonstrates the testing methods available at the time of Miss Sapwell's death.

In a 1954 British Medical Journal article Poisoning by Cantharidin, the authors detail the testing methods available.

It was found that only three tests could be relied on for identifying cantharidin: (1) melting point ; (2) production of characteristic pain and blistering when the material was applied to the arm by the method described in Taylor (1948) only the production of a blister was regarded as a positive identification; (3) x-ray diffraction pattern of the crystalline material.

In a poisoning case, these tests would be in addition to medical observations.  In the case of Miss Sapwell's poisoning, state chemist Turner testified to performing test (2).

An analytical chemist showed a Criminal Court jury yesterday a scar on his arm which, he said, came from the application of a substance he found in the postmortem examination of a young woman.

[excerpt from Jury in "Murder Case Told Poison Made Scar on Analyst"]

No other tests appear to have been conducted on this "substance" identified by state chemist Turner as cantharidin.  None of the noted tests for cantharidin were done on any other items of evidence, as the Crown presented no such evidence during the trial.  Though Mr. Mehari admitted to having access to cantharidin through his work, no cantharidin was found in the Mehari home or in his possession.  The chemist shop over which the Meharis lived did not carry cantharidin.

The defense was not done countering the Crown's claims of death-by-cantharidin just yet.  Dr. Shaw took issue with the idea that cantharadin in vomit would cause blistering at all. Under questioning from Mr. Galbally,  Dr. McMamara did not directly contradict Dr. Shaw assessment, going on to state ""...a great deal more would need to be known."  That "funny" tasting coffee was also criticized by Dr. Shaw. Puting cantharidin in his own coffee, Dr. Shaw noted nothing odd in the drink's flavor, though it burned his tongue.  Dr. Shaw also pointed out that coffee, being chiefly water by volume, was also a poor medium for cantharidin, a sparingly water soluble molecule.

Was it cantharidin or not? According to the defense, if it wasn't cantharidin, then the lecherous motive ascribed to Mr. Mehari by the Crown was no more.   Mr. J. Flannagan, appearing for the Crown, stated "..it does not matter twopence whether it was cantharidin which killed the girl, or whether it was some other irritant poison."  The trial's judge, Mr. Justice Gavan Duffy, seemed to agree with both the Crown and the defense - to a point.

On November 30th, the last day of the trial and the start of jury deliberations, His Honor told the jury there was "no proof" the poison was cantharidin and that "[i]t does not matter whether it was cantharidin in the coffee, or some other poison."  His Honor left it for the jury to decide if Mr. Mehari had made those confessional statements to the police. The jury went to consider Mr. Mehari's fate, returning five hours later with a verdict. Mr. Mehari was not guilty of murder, but was guilty of manslaughter.  His Honor stated he thought Mr. Mehari did not "intend harm, but "... was simply careless of whether he would do injury."  On December 3rd, Mr. Mehari was sentenced to five years imprisonment.

It has been nearly 54 years since Miss Sapwell death. Advances in the fields of analytical chemistry and toxicology have given us new detection methods for an array of chemicals and sample types (e.g. urine, kidney tissue, etc.).  A chemist today would likely rely on a liquid or gas chromatography- mass spectrometry (LC-MC or GC-MS) method to determine if cantharadin played a role in a suspicious death like Miss Sapwell's.  Would an assured poison identification have changed the outcome of Mr. Mehari's trial? Or did it truly "not matter"?

Case book image from IGAS

L. vesicatoria from Vanderbilt University Center for Teaching blog

Bottle labeled cantharidin from l-milleri's Ebay site

Blisters on skin from University of Florida 'Featured Creatures' site

__________References___________

• Nurse Poisoned; Murder Charge (July 27, 1960) The Age, 1
• Young Nurse Poisoned in Home Where She Was Guest, Court Told (1960, November 22) The Age, 5
• Jury in Murder Case Told Poison Made Scar on Analyst (1960, November 23) The Age24
• Police Deny Violence at Questioning Before Murder Charge (1960, November 24) The Age12
• Defense Will Claim Girl's Death Not Due to Cantharidin (1960, November 25) The Age12
• Counsel to Address Jury in Alleged Poison Case Today (1960, November 29) The Age6
• Judge's Charge to Jury Today in Murder Hearing (1960, November 30) The Age6
• Mehari Remanded for Sentence After Manslaughter Verdict (1960, December 1) The Age7
• For Manslaughter... (1960, December 3) The Singapore Free Press, 1
• Craven, J.D. and Polak, A. (1954) Cantharidin Poisoning, Br Med J., 2(4901), 1386–1388
• Chen, L. and Huang, G. (2013) Poisoning by toxic animals in China—18 autopsy case studies and a comprehensive literature review, Forensic Sci Int., 232, 12-23
• Honkanen, R. (1993) Cantharidin, another natural toxin that inhibits the activity of serine/threonine protein phosphatases types 1 and 2A, FEBS Letters, 330, 283-286
• Moed, L.; Shwayder, T.; Chang, M. (2001) Cantharidin Revisted, Arch Dermatol, 137, 1357-1360
• Nickolls, L.C. and Teare, D. (1954) Poisoning by Cantharidin, Br Med J., 2(4901), 1384–1386
• Polettini, A.; Crippa, O.; Ravagli, A.; Saragoni, A. (1992) A fatal case of poisoning with cantharidin, Forensic Sci Int., 56, 37-43
• Sandroni, P. (2001) Aphrodisiacs past and present: a historical review, Clin Auton Res, 11, 303-307

## My adventures in green screen & sci-comm

(by drrubidium) Apr 28 2014

Thanks to the folks at ACS Reactions, I've gotten the chance to fight ninjas do a little green screen filming.  The first video, Zombie Apocalypse Survival Chemistry: Death Cologne, was based on a guest blog I wrote for Scientopia ('Chemistry for the zombie apocalypse') which I turned into a presentation most recently given at SciPop Talks!

The second video - Inside the Game of Thrones Poison, the Strangler - comes from a recent entry to this blog called 'Chemistry and King Joffrey'.

I even got to pontificate on why I love to blend science and pop culture.

Now I just need to write a post on chemistry & pirates, so the folks at ACS Reactions will CGI me onto a pirate ship...

## Chemistry and King Joffrey

(by drrubidium) Apr 15 2014

HBO's King Joffery on the Iron Throne

Fans of George R.R. Martin’s Song of Fire and Ice series and HBO’s Game of Thrones know two things...

1. don’t get too attached to any of the characters
2. not all weddings are happy occasions.

Sometimes the reason a wedding isn’t so happy is because people get dropped from the guest list during the event. The Red Wedding lost a few wedding guests in dramatic fashion.  In the fan-dubbed Purple Wedding, only one character is dispatched. However, that one character was important - and not just because he was the groom. He was also the king.  A nearly universally despised king, but a king nonetheless. King Joffrey meets his end at the hands of "the strangler" in Martin’s book A Storm of Swords. The strangler isn't a wedding quest with a criminally obvious nickname. No, the strangler is a poison made from a plant - plus sugar, spice, and everything not-so-nice - as described in Martin's book The Clash of Kings.

Do we have any poisonous plants here in the real world that could bring down a king? Oh yes – and more than one!  There are a number of plants that produce chemicals that can be both medicinal and murderous. Three plants are routinely cast in fictional and non-fictional murder plots - belladonna (aka “Deadly Nightshade”), poison hemlock, and Strychnos nux-vomica (aka “strychnine tree”).

right: belladonna | middle: poison hemlock | left: strychnine tree

These three usual suspects all produce alkaloids that can be weapons in the wrong hands. Alkaloids share a loosely similar chemical structure – at least one nitrogen atom in a heterocyclic ring.  Belladonna, poison hemlock, and Strychnos nux-vomica all make more than one alkaloid, but each has an alkaloid it's best know for.  For belladonna, it's atropine and  for poison hemlock, coniineStrychnos nux-vomica's  heavy-hitting alkaloid takes its name from the tree - strychnine.

left: atropine | middle: coniine | right: strychnine

Could any of our usual suspects be a real-world stand-in for the strangler?  To determine that, the strangler's modus operandi must be examined. In Martin’s book The Clash of Kings, this poison is described as making "...the muscles of a man’s throat clench tighter than any fist, shutting off his windpipe."  Taking some creative license with Martin's description, a real-world strangler stand-in must cause airway and/or neck muscles to clench (contract) and death by asphyxia.  This requirement lets two of our usual suspects off the hook.

Both belladonna and poison hemlock can be stone cold killers, but their stand-out alkaloids tend to relax and paralyze muscles. Belladonna's atropine affects smooth muscle in a relaxation-to-paralysis way, including airway smooth muscle.  Atropine, typically as a sulfate salt, has seen used as a bronchodilator - something that decreases airway resistance and increases airflow to the lungs.  Atropine can certainly kill you, usually by messing with your heart, but it doesn't kill like the strangler does.  Coniine also works to paralyze muscle, but it targets striated muscles - like skeletal muscle.  This includes the ribs' intercostal muscles and the diaphragm, which are the respiration system's heavyweights.

What happens is that your body is slowly but surely paralysed while you're still fully conscious, starting at the feet and rising until eventually even the muscles surrounding the vital organs become affected. Death is caused when the diaphragm stops contracting and oxygen stops getting to the heart.

[excerpt from Chemistry World's Chemistry in its element on coniine]

Coniine, like atropine, isn't a good fit for the strangler role.  That leaves strychnine.

Like coniine, strychnine targets striated skeletal muscles - including those important respiration muscles.  Unlike atropine and coniine, strychnine does not relax and paralyze muscles.  Strychnine causes muscles to contract – violently and incredibly painfully. Within 10-20 minutes of ingesting a lethal dose of strychnine, the muscles of the face and neck convulse – fitting a bit with Martin’s description of the strangler.  Convulsions spread to all skeletal muscles, coming in waves. The periods of contraction grow longer, with breathing impossible during a convulsion. Death by asphyxia results. That death could be quick – say a few minutes from the start of convulsions - or a person may suffer in agony for 2-3 hours (or more!).

Muscle contraction and death by asphyxia - strychnine and the strangler have a bit in common.  Could strychnine play the strangler?  Back to Martin's description of the strangler from The Clash of Kings

It was made from a certain plant that grew only on the islands of the Jade Sea, half a world away. The leaves had to be aged, and soaked in a wash of limes and sugar water and certain rare spices from the Summer Isles.  Afterward they could be discarded, but the potion must be thickened with ash and allowed to crystallize.  The process was slow and difficult, necessaries costly and hard to acquire.

If we think of Joffery’s home as a sort of Europe, then the strychnine tree is definitely from half a world away being native to Southeast Asia. The most dangerous part of this tree isn’t its leaves, but the seeds of its fruit.  The leaves^ contain strychnine, but not nearly as much as the seeds.  It will take a lot of leaves, which seems like just the kind of hassle Martin is trying to convey in his recipe. Martin's recipe calls for the leaves to be dried (aged), followed by the extraction of strychnine with "a wash of limes".

What if Martin doesn’t mean lime, the fruit?  What if Martin means lime (aka "quicklime"), a product of treating limestone?  This type of lime is mainly calcium oxide and is alkaline.  This lime has been used as part of multi-step processes* to extract alkaloids from leaves – like the alkaloid cocaine from coca leaves or the alkaloid morphine from opium.  The non-fruit lime is just one interpretation* of Martin's recipe, but it could be part of a "slow and difficult" extraction process.  Sugar and spice is next, which is good considering that strychnine - like most alkaloids - has a bitter taste that will need to be disguised.  Leaving nothing to chance, a beverage that will also help disguise strychnine's bitterness should be used.   A beverage like red wine – which seems to be Martin's delivery beverage of choice and what King Joffrey is drinking at his end.

This strychnine concoction is nearly stage-ready, except… where’s the purple? The strangler is described as a purple poison.  Is strychnine purple?  No.  In fact, many alkaloids - strychnine, cocaine, caffeine, morphine – are white crystalline solids.  Here’s where Martin’s spices could help out again. Some spices pull double-duty as dyes.  If dried berries are in Martin's spice cabinet, purple strychnine wouldn't be just a fantasy.  Dyed strychnine isn't as weird as it sounds – some commercially available strychnine pellets for dispatching of rats, gophers, or other critters are dyed red or green.

In a pinch, purple strychnine could stand-in for the strangler.  To be sure, we have to try Martin’s recipe with the lots of Strychnos nux-vomica leaves and spices for color to see if we could make our purple poison. Given how nasty strychnine is, we’ll need to strictly follow lab safety protocols. For even greater safety, never let Martin plan your wedding.

____________

^In 2011, a suicide attempt via ingestion of Strychnos nux-vomica leaves was reported in literature.

*Another interpretation of Martin's recipe is that his lime is the fruit, working perhaps an acid extraction.  The ash in Martin's recipe could be wood ash or soda ash, both of which are alkaline and could neutralize the acidic brew. Update 04/28/14: I'm of the view that lime juice simply isn't acidic enough.  An acid extraction with hydrochloric acid (HCl) would do the trick, and the resulting salt would be water soluble.  Subsequent treatment with base (non-fruit lime, lye, sodium carbonate, or wood ash) would return our lethal alkaloid to us.

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Image of King Joffery from Wired

Image of belladonna plant from NC State University

Image of poison hemlock from NC State University

Image of strychnine tree from Caroline's Botanical Art Blog

All chemical structure images are from chemspider

Strychnine label from photobucket user Samantha Giedris

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