Unmasking the Truth

From left to right, a full hazmat suit with HEPA-filtered respirator; a simple surgical mask used in a stationary, sterile OR; a simple surgical mask used in public, and an N95 particle filter mask used in construction.

As the COVID-19 pandemic of February and March 2020 unfolded like the slow-motion train wreck that it was and still is, each week brought a new, unexpected scene. For several weeks, we shopped for our groceries as we always had, but walked past shelves denuded of toilet paper, Clorox wipes and Purell. Politicians from the left urged us on TV to walk around in Chinese communities unprotected during their New Year celebration. As happened frequently to progressives, they dropped the ball with respect to pandemic control because they thought inclusiveness or racial justice were more important objectives than people getting sick and dying.

Nancy Pelosi encouraging people to visit Chinatown in San Francisco.

Governor Whitmer locking down Michigan and requiring face masks.

The Surgeon General of the United States went on Fox News and declared that face masks do not work https://www.foxnews.com/media/surgeon-general-explains-masks-public-coronavirus.

A few weeks later politicians were ordering the public to lock ourselves down in our homes and many governors ordered their constituents to wear masks in public. Again, they did so with such casual disregard for the economic consequences of that action it became difficult to understand if they had any priority than to issue orders and see that they were obeyed. That week, we began walking past the same supermarket shelves masked up like we were all planning to rob the store, as toilet paper made its return and then meat disappeared. Mask advocates invoked “the science” as if there was something obvious in the peer reviewed literature that formed the basis of this policy. There isn’t. There have been hundreds of studies of the patient risks during masked or unmasked medical procedures. There are no studies whatsoever as to the health outcomes of ordinary citizens wearing surgical masks as protective devices in a pandemic.

The use of the word “Mask” is an over simplification, because this controversy is really about three different things, each of them being separately defined and regulated as medical devices. A surgical mask is a disposable fabric filter designed to provide a protective barrier preventing the breath aerosols and droplets of the wearer from falling into a sterile surgical field. An N95 mask is a polymer enhanced version of the surgical mask that has been tested to retain 95% of particles of 0.3 microns diameter or more, and is more commonly called a dust mask, because they have found widespread use in the farming and construction industry to protect the wearer not from pathogens, but from inhalation of dusts, spores, and silica particles. The third device is a respirator, or a “rebreather” and this is a fully contained breathing system that allows the user to be enclosed in an impermeable suit with a mechanically driven HEPA filter cleaning all airborne particles and infectious agents from the breathable airstream. We currently have a controversial situation because health authorities have been requiring the population to employ device one, the surgical mask, as if it were a full respirator.

It’s informative to review the history of the first known COVID-19 patient identified in the United States, a 35 year old man who traveled directly from Wuhan, China in mid-January and presented in an emergency room in Washington on January 19, 2020. Quoting from the Bloomberg news article about his diagnosis, 

“The test came back positive that afternoon, Jan. 20, the first confirmed case in the U.S. By 11:00 p.m., the patient was in a plastic-enclosed isolation gurney on his way to a bio-containment ward at Providence Regional Medical Center in Everett, Washington, a two-bed unit developed for the Ebola virus. As his condition worsened, then improved over the next several days, staff wore protective garb that included helmets and face masks. Few even entered the room; a robot equipped with a stethoscope took vitals and had a video screen for doctors to talk to him from afar.”

It is clear from this account the medical staff in Everett understood that if they were to protect themselves from respiratory particles coming from a COVID-19 patient, full-containment respiratory self-breathing suits were required. They had them and they wore them. A simple surgical mask was not going to cut it. American health authorities fully understood that respirators were critical to protect medical staff. But the few in stock around the nation were simply for theater, something cool to flash for CNN during their coverage of Ebola outbreaks. They were not even a miniscule fraction of the number required to manage a pandemic. So when this one arrived, medical workers were forced to rely on the N95 and procedure masks, already well established to be inadequate for their protection. History would bear witness to this inadequacy, as more than 100 Italian doctors not only contracted COVID-19 but also died of it. There are only 336,000 doctors in all of Italy, so using a case fatality rate of 1%, fully 1/3 of all Italian doctors became infected using these inadequate masks as PPE. 

1. Germs collect far from the user’s face in the remote filter.; 2. Respiratory droplets and pathogens of the medical professional collect on the inside of the mask; 3. A variety of environmental pathogens, allergens and particulate pollutants collect on the front of the mask, in addition to the users own pathogens collecting on the inside.

By requiring persons in states or countries under lockdown to wear surgical masks in public, health authorities have pushed the device beyond its design specifications. When used for hours by a wearer traversing crowded public spaces, the mask becomes akin to a collection device for sampling all available environmental pathogens. Respiratory droplets from dozens of people containing a variety of bacterial and viral pathogens are collected and retained a few mm from the lips and nose of the wearer, and maintained in a moist environment that enhances pathogen survival. Remember, a surgical mask is designed for the wearer to stand virtually immobile in an operating room environment, to wear the mask for a few hours at most, and to dispose of it antiseptically as if it were highly contagious. Current lockdown policies require users to wear this device while they traverse public spaces, intersecting the exhaled breath paths of numerous strangers. Because of the scarcity of masks, most of the general public do not dispose of their masks regularly or at all, but wear them repeatedly. A review of laboratory acquired infections over the past eighty years has shown that a self-contained rebreathing device is necessary to prevent the wearer from inhaling aerosolized live pathogens. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2493080/ and https://cmr.asm.org/content/cmr/8/3/389.full.pdf. The extreme cost, lack of availability, and cumbersome nature of this equipment that would have been necessary and sufficient to protect both emergency hospital workers and the general public from infection with SARS-CoV-2 is what led to the politically establishment of surgical mask misuse.

This situation has let to massively conflicting information about the use and effectiveness of surgical masks in public. Comments seen on Twitter include, “If masks work, then why don’t they just give all the prisoners masks instead of letting them out of jail? If masks work, then why do we have to stand 6 feet apart? If standing 6 feet apart works, then why do we need to wear masks?” Social media contributed further confusion as well by the creation of outright falsehoods masquerading, again, as science. Here’s one example:

There is no scientific study to document this. A designed study of this type is unethical. Accidental exposures of this type can be studied.  A study of the COVID-19 seroprevalence in NYC health care workers suggests that the true contagion probability is 1 or 2% even after repeated exposures. Only 7% of NYC health care workers had seroconverted or caught the illness even after weeks of repeated, daily exposures of this type. https://www.forbes.com/sites/lisettevoytko/2020/05/07/fewer-ny-healthcare-workers-are-being-infected-with-covid-19-compared-to-public-cuomo-says/#193104176619

There is no scientific study to document this. Exposing any healthy subject to a COVID-19 positive patient, whether masked or not, is unethical. Instances where a completely unprotected health worker was exposed to a masked COVID-19 patient would be too rare to be meaningful.

There is no scientific study to document this. It is possible that in a jurisdiction where all EMTs apply PPE to suspected COVID-19 patients before delivering them to PPE-protected health service providers in hospitals, and those providers never are exposed to any other source of the virus, one could derive a statistic. The scenario is improbable.

And finally, there is the homemade cloth version of a surgical mask. Many masks are homemade cotton cloth improvisations that filter droplets less well than polymer fiber masks, and retain more moisture. The inferiority of cloth masks to standard medical masks has been documented. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4420971/ Since there is clear scientific evidence that cloth masks have a negative impact on the spread of disease and the health of the user, public health authorities ought to be forbidding their use. Instead, the industriousness and creativity of cloth mask wearers are extolled, and they are made out to be heroes of the revolution. 

At this point in the pandemic, the face mask has transcended it’s potential medical function and has become a simple political statement. 99.99% of mask wearers are healthy. The only impact the mask can have on their health is to catch and sequester a pathogen near their mucous membranes. Yet the mask is now a political symbol of subservience to authority and of polite contrition in the face of incomprehensible mandates by those paid to provide guidance. Masks are going to be with us for a long time. Fortunately, it is now summer where I live, and whenever I’m not wearing my mask, I can flip it up on the dashboard where the temperature is often 140 degrees fahrenheit under direct sunlight. Studies have shown that corona viruses and almost all respiratory viruses cannot survive more than a few minutes under these conditions. 

               

There will never be an actual end to this pandemic, unless you define that as some time in the future when SARS-CoV-2 does not kill any substantial fraction of the people catching a seasonal respiratory virus. Considering the many unusual cardiovascular and immune dysregulatory aspects of corona virus, I think that day will be a long time coming. In the words of T.S. Eliot, it will die not with a bang but with a whimper. Even with an effective vaccine, life will not be without risk. It never has been. At some point, you just have to take that diaper off your face and get back to living.

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Science Guy

Kirk_Science Guy

The Eastern Market district of Detroit is on the wrong side of the freeway. The Fox Theatre, the big new stadium where the Tigers play – they’re over on the other side. Here in the Market, each block is an uncertain and dangerous piece of terrain. Coming around a corner or under a bridge, you are likely to be accosted by a strange and bedraggled person – what we call the homeless. Yes, that can happen on any big city street – but usually you are in the company of the crowd. Here you are alone with the outcasts. They often confront you, ask unusual questions, and make demands. To negotiate these streets is to be a wanderer in a children’s fairy tale. You meet the trolls, beggars and princes in disguise, and must always be thinking. If you persevere and show courage and imagination, you may find your reward. The stench of excrement, from both people and other things, is common. It mingles with the waste vapors of the cars on I-75. Supposedly, that stuff is making the world warm up, but with the temperature around 5 degrees on this January day, I think maybe it’s not true. Or, if it’s true, I wish it would hurry up.

I am almost to the door of the slaughterhouse, when my sleeve is suddenly grabbed by a person that I did not see. He was behind a telephone pole. He eyes the bright white Styrofoam box that I’m carrying, and demands to have what’s in it. It’s a test. I think quickly, and decide that I should give in to his demand. I open the box, and offer it to him. I can hear his hand scrabbling around among the contents – then he draws a piece out. He stares at it for a second – then he screams. He lets go of my arm, and I slip in the door. He must have thought I had food or something. It was dry ice.

At first, I can’t see anything – so stark is the contrast between the dim interior and the daylight outside. In my mind, I keep seeing the startled, wide-open mouth of the nameless creature who confronted me. There were only three teeth – two on the bottom and one on the top. But the tongue was surprisingly healthy and pink. Not as anemic as his station in life might have predicted. Just around the corner, I can see the place I’ve been seeking. It is an Islamic slaughter house, where a bearded man with a knife dispatches the animals one after another, in accordance with the Koran, the USDA, and also the FDA, simultaneously. Today, we’re killing sheep.

The floor is wet and stained pink with blood, although they stop to spray it down with the hose when the inspector makes them. Little bits of pale and bleached flesh catch in the cracks and pockets of the rough concrete where he stands with his arms folded across his chest. Big, black, smiling as he jokes with the men, he points to the debris at his feet when it gets too thick to suit him. Someone quickly rinses it away. He didn’t like me when I first came in, cold from the winter air and not certain where I was. He wants to know what’s in the box. It’s another test, but this time I think I should respond with my best version of the truth. I tell him about the dry ice in my box, the vesicular glands, and where they are in the sheep. “Like it was where your prostate would be?” “That’s right,” I answer, mumbling a few words about our research.

Semen is one of those things that you can’t mix up until right before you plan to use it. It’s like the epoxy cement at the hardware store that comes in two separate tubes. Neither one is any good as a glue unless you mix them into each other with a small stick. Then within minutes, they harden up like a rock. In order to make semen, you have to mix a stream of fluid from the vesicular glands of the prostate with another one that comes from the epidydimus. (That’s a sperm storage bag that hangs on the side of each testicle like a little French beret.) Why you have to mix semen just before use is not as well understood as epoxy cement. That’s one reason why I’m here.

I study COX. No, not penises – COX stands for cyclooxygenase – an enzyme. COX is an enzyme apparently up to no good. It makes people have headaches, menstrual cramps, and achy joints. COX comes in two varieties – the regular blue jeans version, COX-1, and one for special occasions, called COX-2. No one had really heard much about it until Merck made an inhibitor for COX-2, and named it Vioxx. People soon started sueing Merck, claiming that Vioxx caused them to have heart attacks. I used to be able to send my colleagues e-mails and use the letters COX anywhere I wanted to. Now that makes spam filters throw the e-mails in the trash, and no one ever gets them. I used to be able to search for COX on Google and get reasonable information – now I get solicited by attorneys and linked to nasty web sites. There is no better place to get COX than sheep seminal vesicles – their prostate glands. They’re loaded with it. That may in some way be related to the fact that semen is stored in separate compartments. If I’m lucky, today I’ll get enough of them to study that.

Prostate hits home with our representative from the government; he grabs his pants. “Had a friend had to have his taken out – got to wear diapers now. That why you want ’em? For research?” A thread of fear catches in his throat – you can see it in his eyes. This man does not want to wear diapers, all the fault of some odd lump of a gland that goes bad deep inside his bowels. “Right,” I answer, knowing it’s not exactly right but close enough for partial credit. Smoky mist curls out from under the lid by my wrist. Dry ice. Coldest thing anyone here has ever heard of. One hundred ninety degrees below zero. He leaves me a place to stand where I won’t get hit by the hose. I’m starting to get some respect.

The bearded guy – I guess he’s the Imam – does his little thing with some muttering, and another sheep goes down. There’s a thick, musty vapor in the air, like wet hay starting to mold. It’s the blood. Sheep blood spills out onto the cement, warm and steaming. The air is wet, heavy, full of pungent odors that course through sheep veins. Molecules that have been making the quiet commute from kidney to liver to lung and back suddenly find themselves dumped without ceremony onto the floor. (Well, actually there was a little bit of a ceremony – I’m just not sure either the sheep or myself understood it.) Derailed from their routes, metabolites and pheromones are released to float free around my feet, into my clothing. The knives flash silver, pressing gently into the sheep as the ribbons of flesh open up and the hide peels away. The belly parts smoothly down the center and out falls a huge and hideous snake; a python disguised as a digestive system, all neatly coiled into loops and ripples of gray-green, bulging here and tapering there into fine lengths of sausage. The surface shines like a polished rock. It is deftly cut free and scooped with two hands into the tray before me, slithering to a stop. And not a drop of blood on it. The seminal vesicles look like peach pits, the color of raw shrimp, tucked in behind the limp sac of a bladder. It takes a few minutes to carefully cut them free, pry them up out of the fat while severing each little thread of tissue holding them in place. Once in the dry ice they blanch white, freezing in an instant. They roll around in the box like marbles. The sheep goes on down the line, its body disintegrating into pieces. The bigger ones fall into trays and hang from the ceiling on hooks. But the scent of life breaks free in a swarm of potent little vectors that waft up toward the ceiling.

In a few hours the sheep are all gone and my box is half full. The inspector is munching a donut, taking care not to let any crumbs fall onto the floor and contaminate it. No, the floor is the place for entrails, and rumpled wooly hides caked with dried sheep dung – woe to anyone who might drop a couple of donut sprinkles down there. He’s telling me about his education now, and how he rose up from the ranks of janitors and night watchmen to become a federal inspector for the U.S.D.A. He has even confided some tips on how I might be able to follow his example and become an inspector too. I think he must like me, perhaps because I’m not afraid of dead sheep. Or perhaps it’s because he hopes that one day I may help mediate a dispute that he might have with his prostate gland. To be honest, I like him too. It’s because he let me take the glands without being a pain in the ass about it. I nod to him and step out through the heavy metal door.

A cloud of steam exits along with me, boiling into vapor as it strikes the cold air. Thin January sunlight is shining brightly into my eyes. Walls of faded and crumbling red brick line the street. The thick, sweet aroma from inside fades quickly. In its place are the cold, dead smells of a city in winter. There is exhaust in the wind, and garbage on the sidewalk. My hands are warm, the skin soft and greasy from the sheep. Although I washed them, they seem to have absorbed something that doesn’t wash away. I clutch the box under one arm, and turn to make my way back to where I parked my truck. A half inch of snow was dumped here in the night by a storm that now races away across lake Ontario. The cold winter wind is playing with the snow like an idle child, pushing it into fine white lines where there are cracks and making white triangular piles behind the tires and the phone poles. My friend with the frostbitten fingers is nowhere in sight. The same mysterious forces that pushed us together for an instant at the slaughterhouse door have now pulled us apart. Once I am safely back inside my pickup, I can begin to feel badly. I feel badly for this city, which seems stricken by some disease or evil spell that mires it down in perpetual ruin. And about him, his life, and how the guy with the box tricked him. And about the sheep, who went so quietly, but left the essence of their lives stamped into my skin. It only lasts a moment, as I nudge aside the box lid and peek at the frozen tissue. There is a new compound, KMN10404, back at the lab. It is an elegant, tiny little construct, with an oxygen, a nitrogen, and then three carbon atoms tied together into a neat little pentagon. It’s an isoxazole…maybe it will be christened Isoxx. I already know it’s a COX inhibitor, and at least 1000 times more potent than Motrin. I won’t know if it’s like Vioxx or not until I get back and grind up my little frozen marbles. Already I’m speeding down I-75 and out of Detroit. I know my place in the world, and it is not as the fixer of dead cities or the rescuer of the homeless. I am just a science guy.

70210

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I Know This Man

My son would probably not have reached his normal adult height if it had not been for the barbacoa burritos at Chella’s Restaurant on Liberty Street in Ann Arbor. I was there with him a lot. Several nights a week. People were friendly there – we were friendly back. I knew the owner, who was often behind the counter. Then one night last week, he showed up on TV.  And I thought to myself, “I know this man.”

Kirk Maxey and Adrian Iraola

Kirk Maxey and Adrian Iraola

His name is Adrian Iraola. He was standing in the middle of my big living room TV screen, and David Muir was saying “Watch as this meeting about inclusion and diversity takes a devastating turn…”

For me, something just snapped when I saw this man being hounded as if he had no right to stand up and make critical comments about the community of Saline Michigan BECAUSE HE CAME HERE FROM MEXICO!! We all came here from somewhere. There are no Americans who were always here from the beginning. The so called indigenous came more than 10,000 years ago by foot and by small boat, and spread across the land. Europeans came in trickles 400 years ago by boat, soon coming in larger numbers and bringing African slaves. Famines hit Ireland and Denmark, and the destitute came then in massive waves in the 1800s. Later influxes came mainly by air, as Hungarians, Estonians, Czechs, and Poles fled revolution and repression in their homelands. The collapse of the Soviet Union brought new surges of Russians and Ukrainians followed by Serbs and Romanians in the aftermath of the wars in the Balkans. These people melded into the mix of English, Irish, Italian, German, Swedish, and Danish who came before them, and they ARE AMERICA.

Adam Uzieblo and Kirk Maxey

Adam and Kirk

Adam Uzieblo was born in Warsaw and has a PhD in organic chemistry. When he came to America in 1981, he was forced to leave his wife and small son behind. He was hired as a synthetic chemist at Cayman Chemical in 1989, and has prepared thousands of complex prostaglandins and biochemicals over his decades long career. His family joined him five years later, and his son is now a skilled vascular surgeon practicing in the Detroit area. Adam is a member of the Board of Directors of Cayman Chemical. #Iknowthisman.

There is a lot to find disgusting about the Trump administration, but nothing compares to their racist, xenophobic paranoia regarding immigrants. These people ARE US – they are the new building blocks of America, fitting neatly into the spaces where those of us with a few or even many generations on US soil already live. The Gestapo wannabes of ICE and the HSA routinely humiliate and degrade anyone foreign as they travel into and out of the US. They abuse US citizens and green card holders based on crude racist stereotypes of skin color, language and ethnicity. It is a complete abandonment of our own human decency. I’m sick to goddamn death of it, and I’m not going to sit still for it a second longer.

Zahra Assar, Kirk Maxey, and Andrei Kornilov

Zahra, Kirk, and Andrei

Zahra Assar was born in Tehran, Iran in 1989, the same year that Adam came to work at Cayman. She has a BS in Chemistry from Sharif University of Technology and a PhD from Michigan State. She came to America in 2012 and joined Cayman in 2017 as a structural biologist while she was still defending her thesis. #Iknowthiswoman. Andrei Kornilov was born in Kiev, Ukraine and earned his PhD in Chemistry at the University of Kiev. He came to America in 1996, and is my coauthor on my most recent publication  #Iknowthisman

Toni and Kirk

Toni and Kirk

This is Toni, a Cherokee woman who manages the Twin Peaks mine near Mount Ida, Arkansas. We share a love of nature, quartz crystals and geology. Our relatives from many generations ago were from the southeastern US, moved westward to Oklahoma and then went their separate ways. #Iknowthiswoman

Cathy and Kirk

Cathy and Kirk

Cathy Miller was born in Taiwan and moved to America when she was 5. She graduated with a degree in Chemistry from the University of Michigan and joined Cayman Chemical in 1994. She has held positions in several departments, and is now part of the ISO-qualified forensics department that handles drugs of abuse. #Iknowthiswoman

In America, we are all immigrants. The only distinction is that some of us came recently and have more obvious traces of our past, like an accent or some unusual holidays or traditions of dress. Those of us who have been here longer need to be as welcoming, respectful, and appreciative of recent immigrants as possible, because they are literally the lifeblood of our country. They truly understand and appreciate freedom and liberty, some after having been deprived of their basic human rights elsewhere. Somewhere within the twisted guts of this foul administration is a perverted goon who thinks up new ways every day to mistreat decent, honest people crossing our borders. He’s the asshole who dreamed up snatching kids away from their parents and locking them in cages. We need to smoke that son of a bitch out and LOCK HIM UP!!!

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17 Questions About Glyphosate

It’s important that as lawyers and special interests create false chemophobic “facts” someone should maintain a good website where those are noted and the actual scientific truth of the matter be stated as clearly and bluntly as possible. No Virginia, glyphosate does not cause cancer.

Thoughtscapism

Many worry about pesticides for health or environmental reasons, and the most common target of general concern is undoubtedly glyphosate, the active ingredient in the famous weedkiller RoundUp. I find that the best thing to do when something worries me, is to
1find out more about it.  I’ve delved into the details behind the 17 most common concerns I’ve encountered. Questions 1-11 are mainly about health, whereas 12-16 focus on environmental aspects, and lastly, 17 delves into the question of the integrity of research. I will do my best to present useful evidence-based resources on all the following topics. If you would like to listen to a summary of this series you can head on over to my guest appearance on the podcast Talking biotech with Kevin Folta – I was very honoured for the opportunity to join his great series.

After receiving valuable feedback from my readers, I decided to break these questions into blog posts of their…

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Putin’s Poisons

Putin Cobra Blog Image Kremlin 2018DECVladimir Putin is the current totalitarian ruler of Russia, which isn’t in itself an historically surprising circumstance. From the Tsars to the Bolsheviks and on through the present, a single despotic person has generally ruled over Russia, and frequently over a large part of the contiguous territories of Europe and Asia. Unlike Stalin, who was an imposing physical person and who murdered wantonly and in massive numbers, Putin is a small, pale, reptilian person who rules and murders much more after the fashion of a snake. There is a certain morbid fascination in watching a current head of state selecting and deploying a range of improbable toxins against a fairly random list of perceived traitors, enemies, journalists and spies. Poisoning is only an attractive option for murder when one wishes to have plausible deniability, yet Putin’s numerous deployments of poisons to date have been a comedy of errors and uncritical thinking, leaving in many cases a trail of tracks leading almost directly to him.

Russia’s brief flirtation with democracy ended in the year 2000 with the sudden resignation of Boris Yeltsin followed by the improbable election of Vladimir Putin with a reported 53% majority of the vote. At this time, the most recent known use of poisoning for assassination by Russian operatives was the 1978 killing of dissident Georgi Markov in London. Markov was jabbed in the thigh with a sophisticated umbrella tip injector that deposited a tiny pellet of the biological toxin ricin resulting in his death 3 days later.

Two years after Putin’s ascension to the Russian presidency, his regime was challenged by the 2002 Moscow theater hostage crises when at least 40 armed Chechen rebels seized several hundred hostages and demanded an end to the war in Chechnya. The Russian security forces responded by pumping an aerosolized solution of the μ opioid receptor agonists fentanyl, and/or carfentanyl into the building’s ventilation system, killing all of the rebels and at least 204 of the hostages. These drugs have been developed as useful anesthetic agents and are potentially reversible, but first responders from the FSB who stormed the theater wearing gas masks did not seem to have remembered to bring any of the lifesaving antagonist naloxone with them, resulting in the high civilian death toll.

Fentanyl and Carfentanil

Yuri Schekochikhin was a 53-year old investigative journalist  who was hospitalized suddenly in 2003 with symptoms of heavy metal poisoning, including a peripheral neuropathy.  He fell ill just a few days before he was scheduled to fly to the United States to discuss a corruption scandal involving Vladimir Putin with the FBI. Since Schekochikhin was treated at the Central Clinical Hospital in Moscow which is tightly controlled by the FSB, there was never a formal autopsy and his family was denied access to his remains. However, the clinical picture is consistent with an acute intoxication by the toxic heavy metal Thallium. From 2003 through 2004, this seems to have been Putin’s choice of poisons, as it was also implicated in the death of his former bodyguard Roman Tsepov in St. Petersburg. The journalist Anna Politkovskaya was also poisoned with a substance in her tea in 2004, which she survived, only to be gunned down in an elevator in 2006. Thallium was not a new or particularly innovative poison, as it had been tried several times in the preceding decades by a number of governments, including the French, Americans, South Africans and Iraq’s Saddam Hussein.

Thallium (2)

However, a new poison emerged that same year in the bitterly contested Ukrainian election contest between pro-Russian Viktor Yanukovych, the hand picked favorite of Putin, and Viktor Yuschenko representing the Western-leaning independence parties.

 

Dioxin

Dioxin (2)

The dioxin molecule, pictured above, was already rather infamous following the accidental 1976 industrial release in Seveso, Italy that sickened thousands of people and killed birds and animals. However, sickened is the operative word here, since although dioxin is toxic, it isn’t very lethal. Yushenko’s poisoners did manage to inflict a painful and disfiguring case of chloracne on him, but he survived. He also provided an impressive number of pharmacokinetic samples to the doctors who treated him, allowing them to work out the metabolism and excretion routes of this compound using only a single, inadvertent human test subject. This peculiar and silly choice of toxins shows Putin for the amateur that he is, but also shows him struggling with an internal conflict. He wants his victims dead, but he cannot resolve whether he wants to kill them secretly and privately, or whether he wants the poison to make it clear that he is the killer and is behind the assassination of each person as the victims fall ill.

The botched poisoning of Viktor Yuschenko dramatized the incompetence that sometimes attends Putin’s attempts to poison for political purposes. However, rather than learning from this, the keystone cops theme expanded with the 2006 poisoning and eventual assassination of Alexander Litvinenko using the powerful radioactive alpha-emitter Polonium 210. In terms of the selection of the poison, this was a much more lethal and effective agent when compared to dioxin. Putin had been in power for 6 years, and must have felt secure enough to turn to the Kremlin’s secretive research institutes for poisoner’s advice. Polonium 210 is an almost ideal radioactive poison. Almost a pure alpha particle emitter, it cannot be detected inside a simple glass vial by conventional radiation detectors. It is estimated to be up to one trillion times more toxic that hydrogen cyanide, also known as prussic acid and the favored poison from more than one hundred years earlier. Once Litvinenko ingested the few micrograms of radioactive metal that killed him, his own body was sufficient to absorb almost all of the emitted radiation, and at first his doctors did not think he had radiation poisoning.

Polonium-210

Litvinenko was poisoned in a London sushi shop where he sipped the fatal dose of Polonium 210 in a cup of tea. The FSB agents Andrei Lugovoi and Dmitri Kovtun who carried out the assassination had already left a trail of radiation in the airliner which carried them from Moscow through Berlin to London. They had spilled it in their hotel room and sopped it up with a bath towel. Lugovoi accidently contaminated a strip club and a soccer stadium that he visited on the same trip, and a flat where he stayed in Hamburg, Germany. Due to its unique half life, unusual trace impurities, and the scarcity of nuclear facilities in the world capable of purifying it, the source of the Polonium 210 was directly traced to the Russian nuclear complex in Sarov, about a day’s drive from Moscow.

So while Polonium 210 brought Putin an extremely effective agent, it once again foiled any attempt at secrecy, as it practically fingerprinted Russia, his regime, and him personally as having plotted and carried out the murder.

This brings us to the much more recent and sensational poisonings of Sergei and Yulia Skripal in the town of Salisbury, England, and then the additional accidental poisonings of Charles Rowley and Dawn Sturgess, who blundered into residues of the poison used on the Skirpals in a discarded perfume bottle 4 months later. The poisonings first came to the attention of police on March 4, 2018 when the Skripals were noticed slumped over and unconscious on a public bench. These attacks represented the first open use of an advanced class of nerve gas agents specifically designed as chemical warfare agents in Russia before the collapse of the Soviet Union, called the Novichoks or “Newcomers.”

Novichok-234.JPGThis most recent application of chemical weapons for political ends by Vladimir Putin was my inspiration for writing this blog post, since my company Cayman Chemical has a deep working knowledge of the target of these agents, the essential neuronal enzyme acetylcholinesterase (AChE). Acetylcholine is a major neurotransmitter of the central and peripheral nervous systems, controlling many aspects of conscious activity including the activation of the heart, diaphragm and voluntary muscles. AChE acts to terminate these signals so that the system can return to a resting state. Simply put, AChE allows you the delicate motor control to breath in, then out, and to scratch your nose without punching yourself in the face. If AChE is inhibited or blocked, uncontrolled muscular contractions and spasms lead to cardiac and respiratory arrest, and death from circulatory and respiratory collapse soon follows.

ache together

Sarin and other classical chemical warfare agents, as well as the advanced Novichok agents deployed in the UK, all act by irreversibly inhibiting AChE, reacting with a critical serine residue in the AChE active site with displacement of the fluorine and formation of an enzyme-phosphonate ester.

sarin

Many years ago, we at Cayman Chemical were introducing research tools for inhibiting a different enzyme when we prepared the compound MAFP, shown below. This compound is a potent, selective inhibitor of the cytosolic phospholipase A2 (cPLA2) that releases free arachidonic acid in response to cell signalling in inflammation. The mechanism is precisely the same as a nerve agent, in that the MAFP molecule irreversibly binds to an active site serine in cPLA2 and forms a phosphonate ester by displacement of fluoride.

mafp

At the time, we were concerned that this compound might be dangerous, so we performed an LD50 study in mice (unpublished) and found that mice survived the highest dose of 10mg/kg. This and other binding data indicated that MAFP was selectively targeting the cPLA2 enzyme and was not binding to the AChE enzyme as the nerve agents do.

As we look to the future, expect Putin to continue to try to perfect his poisoning as he remains plagued by performance issues with both his toxins and his FSB subordinates.* Look also for further refinement of the Novichok agents, as they proved much too stable, and ironically killed only one of three non-targeted, accidental victims several months after the unsuccessful assassination attempt on the Skirpals. All fluorophosphonates, whether they be pesticides, research tools, or chemical warfare agents, have three functional domains as illustrated below. Improvements could be made to both the enabler and guide, making a newer Novichok evaporate more quickly, polymerize and degrade on environmental exposure, be more difficult to prep for mass spec analysis, and not hang around for 3 months in a perfume bottle. Just sayin’, Vlad.

warhead

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This brings me to the conclusion of my first blog post for 2019, which will be a remarkable year by any measure. The use of chemical warfare agents should be unheard of, as proscribed in the Geneva Convention, but instead their use sometime in the new year seems likely. Russia and its ally Assad have made them a standard military option in the Syrian civil war, and North Korea joined Putin last year in favoring nerve agents as a method of silencing opposition leaders. The heads of state in some of the most powerful countries in the world seem quite unqualified for such a position. In the United State, we have an ignorant, narcissistic, compulsive liar as our president, who seems likely to ignite conflicts through his sheer stupidity and incompetence. In Russia we have a megalomaniac serial killer who experiments on citizens of other countries with his super-poisons and Machiavellian schemes for world dominance. Strangely, even Great Britain, attacked within the last 12 months, continues to welcome Putin’s attendance at global strategic summits such as the recently concluded G-20 meeting in Argentina. The coordinated public shaming, shunning, and eventual removal from power of Vladimir Putin is the only safe and reliable antidote to any of Putin’s Poisons.

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New paper provides no evidence that polar bears ate whale carcasses to survive Eemian interglacial

The scientific press is increasingly publishing baseless speculation mixed together with actual research papers including data and experiments. Such speculative papers usually have a blatantly political message which seeks to shroud itself under the cloak of Science, when in fact ithis cannot justifiably be done.

polarbearscience

Contrary to what the misleading press release implies, an entirely speculative new paper by polar bear specialists Kristin Laidre and Ian Stirling (among others) presents zero evidence that polar bear consumed whale carcasses during the last warm Interglacial (Eemian, ca. 115-130kya). And contrary to the impression that Eemian conditions were very challenging for polar bears, simulations from the single paleo sea ice simulation paper these authors cite show the ice-free season over most of the Eemian was less severe than today in the polar basin, with no reason for polar bears to scavenge extensively on large whale carcasses.

LaidreFEE_Wrangel Island scavenging_smaller Polar bears are shown scavenging on the carcass of a dead bowhead whale that washed ashore on Wrangel Island, Russia. Credit: Chris Collins/Heritage Expeditions

This is yet another paper posing as science co-authored by Stirling that uses anecdotal accounts of behaviour to send a message about evolutionary capabilities of polar bears (Stirling…

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Saturated Fatty Acids

This is a great blog – etymology allows you to follow thousands of years of unguided, random history and find it all preserved in the words you’ve always been saying.

Chemtymology

Before chemists had a detailed understanding of molecular structure, newly discovered chemicals were named on the whims of the discoverers. By the end of the 19th century the number of organic molecules known to science had started to increase dramatically, and the list of unconnected names that had to be remembered was getting longer and longer. It became apparent that this mess had to be sorted out, and the process of developing the systematic naming conventions that we have today began. However, despite being less descriptive, many of the old names are retained in the language today and referred to as trivial or common names.

Saturated fatty acids are a good example of a class of compounds where the systematic names are quite simple and easy to remember, being generally based on the Greek for the number of carbons, but common/trivial names are often used preferentially. This balance of use…

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