HomeLatest ThreadsGreatest ThreadsForums & GroupsMy SubscriptionsMy Posts
DU Home » Latest Threads » Forums & Groups » Topics » Science » Science (Group) » The Chemistry of the Clas...

Thu Sep 10, 2020, 09:47 AM

The Chemistry of the Class of Poisons Putin Utilized to Poison Navalny: Novichok A234.

The paper I'll discuss in this post is this one: Novichoks – The A group of organophosphorus chemical warfare agents (Marcin Kloske Zygfryd Witkiewicz, Chemosphere Volume 221, April 2019, Pages 672-682).

I came across this paper as a result of a news item in Science: How German military scientists likely identified the nerve agent used to attack Alexei Navalny (Richard Stone, Science September 8, 2020.)

An excerpt:

On 2 September, German Chancellor Angela Merkel revealed that Alexei Navalny, a Russian opposition politician, had been poisoned with a nerve agent “identified unequivocally in tests” as a Novichok—one of a family of exotic Soviet-era chemical weapons. Merkel, a chemist by training, did not reveal the nature of the tests, conducted in a military lab in Munich. But scientists familiar with Novichoks have a good idea how the toxicological sleuths went about it—and are impressed by how fast the culprit was unmasked.

Navalny fell ill on 20 August after drinking a cup of tea at a Siberian airport. He lapsed into a coma and was flown to Berlin 2 days later; in a statement yesterday, the hospital treating him said he is out of the coma and “responding to verbal stimuli.” Navalny’s supporters have accused Russian operatives of slipping poison into the tea—a charge that seems credible in light of Russia’s recent record of using toxic substances to silence critics.

Novichok A234 was the weapon of choice for settling a score with a former Russian spy, Sergei Skripal, in Salisbury in the United Kingdom in March 2018. In a botched operation, two Russian intelligence officers left a trail of evidence in the attempted assassination of Skripal, whose daughter Yulia also fell ill after exposure to A234. They survived, but a woman who later came across a perfume bottle containing the substance died.

The Salisbury scandal brought Novichoks out of the shadows. After a Russian chemist in 1992 divulged some details about the exquisitely toxic nerve agents—there are at least seven of them—the U.S. government and allies clamped down on open discussion; Novichoks were classified as secret. A234’s brazen use in the United Kingdom led to a public reckoning...


Personally, I don't think that the uncovering of Novichoks in Nalvany was particularly challenging. It is really an issue of seeing the symptoms, knowing some history, and utilizing some bioanalytical high resolution mass spectroscopy to confirm the suspicions.

I have no idea whether Vladmir Putin, who owns our "President" outright - has read a translation of Edgar Allan Poe's The Cask of Amontillado but in choosing his poisons, Polonium-210 in the case of Alexander Litvinenko, Novichok A234 in the case of Sergei Skripal, and now, for Navalny Novichok again, by using poisons to which he, and he alone, has unique access, so there can be no ambiguity about who is doing the killing, he seems to take Poe's remarks on revenge in the story seriously:

I must not only punish but punish with impunity. A wrong is unredressed when retribution overtakes its redresser. It is equally unredressed when the avenger fails to make himself felt as such to him who has done the wrong. It must be understood that neither by word nor deed had I given Fortunato cause to doubt my good will. I continued, as was my in to smile in his face, and he did not perceive that my to smile now was atthe thought of his immolation.
.

The full Chemosphere paper is a rather interesting review of the chemistry and history of these chemical warfare agents that are uniquely Soviet/Russian, although they got their start in Germany.

An excerpt from the text:

Organophosphorus-based chemical warfare agents (OP CWAs) are the most toxic substances amongst synthetic chemical ones. Notwithstanding the foregoing, as well as the Chemical Weapons Convention (CWC) spirit of the law (Witkiewicz et al., 1996), still exists the threat of the use of chemical warfare is almost growing day by day (Crowley et al., 2018; Guidotti and Trifirò, 2016; Kenyon et al., 2005; Mangerich and Esser, 2014; Robinson, 2008, 1998; Rogers, 2014; Simonen, 2017; Stock, 1998; Üzümcü, 2014). CWAs may be used, not only on the battlefields, during military operations, but still is growing the possibility of its terrorist's use. CWAs could be the tool for political opponents' killings. The threat is still to be expected (Croddy et al., 2011; Tucker, 2007). In March 2018 an attempt was made to murder Sergei Skripal with a new poisonous agent called Novichok. In fact, it is a group of chemical compounds with very high toxicity. The information about these substances is incomplete, often contradictory. Therefore, this paper describes the available information about this group of chemical compounds belonging to OP CWAs.


Up to the moment, in literature there is a division of OP CWA(s) into G and V (sub)groups. These groups are well descripted in the sets of articles and books, as well as are quite well described in the undisclosed military literature. In this paper we describe G and V group in general terms, with strict Novichok characterization as one of OP CWA, capable to inhibit acetylcholinesterase (AChE). Novichoks are described as A-subgroup, without clearly stating that they are organophosphorus substances with physicochemical and toxic properties similar to substances belonging to groups G and V. This is probably, due to the fact that there is no P-C binding in its molecules. However, these substances are organophosphorus compounds because its molecules contain phosphor and carbon atoms. Therefore, we believe that it is necessary to introduce the novel OP CWAs division into three subgroups: G, V and A. In this article we present a justification for this opinion.


Some history:

The chemical warfare history is probably as old as the humankind. Already in 400 BCE, during the Peloponnese War, the Sparta army used sulphur vapours against the Athens army. Later, chemical substances were used many times and in various forms during military operations. The highest victim number was caused by the chemical warfare use during World War I, between 1914 and 1918. As a result of the poisonous substances use on both sides of the conflict, 85.000 soldiers died, more than 1.2 million were permanently blinded, burnt and mentally mutilated (Delfino et al., 2009; Mangerich and Esser, 2014; Ramirez and Bacon, 2004; Sheffy, 2005; Shiver, 1929; Szinicz, 2005)...

...Nerve agents poisoning symptoms are associated with the autonomic nervous system stimulation by acetylcholine accumulation, which is not decomposed by acetylcholinesterase. The cholinesterase inhibition is the reason for this.
In addition to their immediate effects, nerve agents also have delayed effects. They take the form of psychological, neurological and cancer effects. There is also susceptibility to infectious diseases, liver disorders, pathological changes in blood and bone marrow as well as eye damage.

Nerve agents have been discovered in Germany before World War II during the development of organophosphorus pesticides. On an industrial scale, they started to be produced during the War...

...In 1936, the OP CWAs, compounds with code names G (G-group) has been discovered in Germany. On December 23rd this year, during his work on insecticides, Gerhard Schrader discovered the first chemical compound belonging to the G group. It is nowadays known as tabun. After a drop of tabun spilled on the laboratory table, Schrader and his assistant had myosis, dizziness and shortness of breath. It took them three weeks to recover. The Wehrmacht had been interested in the discovery and further hidden research was carried out in a military laboratory. The tabun was initially coded Le 100 and later Trilon 83. In 1938 in the Schrader's team was discovered compound with code-name T-144 and Trilon-46, known as sarin. This name is derived from the names of the first developers: Schrader, Ambros, Ritter and Linde. Sarin has been shown to be about 10 times more toxic than tabun.
Through research on tabun and sarin at the Heidelberg Institute, Kuhn and Henkel received a soman whose name is derived from the Greek word 'to sleep' or the Latin 'mace'...

... The tabun test production has been started before the World War II beginning. The test production process and equipment used in it were complicated. The industrial scale production during WW II was located in Dyhrenfurth, currently Rokita Chemical Plant in Brzeg Dolny (Poland). Approximately 3000 employees were engaged at the plant. Of these, several hundred were injured and at least several dozen died. About 10,000 to 30,000 tons of tabun were produced before the plant was taken over by the Soviet army and was probably moved to Dzerzhinsk, Russia. The slave labour force was employed to take part in tabun production. One of the inmates was prisoner of the concentration camp at the Dyhrenfurth plant, professor Andrzej Waksmundzki; in the next years outstanding chemist, analyst and chromatographer...


"Milestones" in the development of chemical warfare agents, table 3 from the text:



Structures of some known nerve agents, including Sarin, which was used for a terrorist attack in Japan in 1995, and again in Syria, by Putin's client, in 2018:



The caption:

Fig. 1. OP CWAs structural formulas for G-group nerve agents: tabun, sarin, soman, ethyl sarin, chlorosarin, cyclosarin, and DFP.


Some more text:

Novichoks has been discovered in the former Soviet Union as the development work on the third and fourth generation of chemical warfare agents (Averre, 1995; Kloske, 2018; Mirzayanov, 2009). These works included inter alia, the construction of binary munitions and delivery systems. The main research centre for CW was the State Institute for Scientific Research on Organic Chemistry and Experimental Technologies. Initially, only reconstructive research was being conducted on the works carried out in western laboratories. At the beginning of the 1970s, the highest authorities imposed on scientists the development of poisonous fourth generation substances on their own. These substances had to be:

a)
undetectable using standard chemical detection instruments fitted to the NATO member states armies in the 1970s and 1980s;
b)
able to penetrate the enemy soldier's body despite the application of individual protection measures;
c)
safer than previous generations of CWA during storage and combat use preparation;
d)
not mentioned in the lists (also precursors) of Chemical Weapon Convention.

As a result of these assignments, phosphonates and phosphates containing amidine and guanidine fragments in the molecule - Fig. 5 and formaldehyde oxime - Fig. 6, were invented. It is also worth mentioning that in the late 20th century, the German company Bayer developed an organophosphorus pesticide derivative, called Phoxim, whose use in agriculture was banned in 2007 due to its strong toxic properties - Fig. 7.


Figures 5, 6, and 7:



The caption:

Fig. 5. General OP CWAs chemical structures for amidine & guanidine X = F or S-alkyl; R1 = O-alkyl (phosphate derivative) or alkyl (phosphonate derivative); R2, R3, R4, R5 = H, alkyl, phenyl, -CN.




The caption:

Fig. 6. General organophosphorus derivatives of formaldehyde oxime formula; X1 = F; X2 = any halogen, CF2NO2, CN; X3 = any halogen, CN, R = O-alkyl (phosphate derivative) or alkyl (phosphonate derivative).




The caption:

Fig. 7. Phoxim structural formula


The programme under which Novichoks were developed was codenamed FOLIANT. The first public article on Novichok appeared in the weekly Moskovskie Novosti in 1992, on the eve of Russia ratifying the Chemical Weapons Convention. The authors were two chemists - Lew Fiodorov and Vil Mirzayanov. According to the authors, the Russian military-chemical complex was using funds received from the West for the implementation of disarmament agreements to build a modernised potential for conducting a chemical war. The authors revealed information allegedly in connection with their concern for the environment. They were working on measuring the concentration levels of harmful substances in facilities and outside facilities associated with the chemical weapon programme. These measurements were to prove whether foreign intelligence agencies could detect traces of BST production. The results of the measurements showed that the levels of toxic agents in the environment were about eighty times higher than the maximum safe concentrations. For unknown reasons only one article author - Mirzayanov was arrested and accused of state secrets treason


And so on...

Nice guy, the guy who owns your "President..."

Interesting paper, I think, scary but interesting.

I am not, for the record, in favor of banning chemistry, but like any technology, chemistry has a huge potential for abuse.

Have a nice, and where possible, safe, day.

3 replies, 590 views

Reply to this thread

Back to top Alert abuse

Always highlight: 10 newest replies | Replies posted after I mark a forum
Replies to this discussion thread
Arrow 3 replies Author Time Post
Reply The Chemistry of the Class of Poisons Putin Utilized to Poison Navalny: Novichok A234. (Original post)
NNadir Sep 10 OP
still_one Sep 10 #1
LunaSea Sep 10 #2
NNadir Sep 10 #3

Response to NNadir (Original post)

Thu Sep 10, 2020, 09:51 AM

1. but does it cure SARS co V 2?



Reply to this post

Back to top Alert abuse Link here Permalink


Response to NNadir (Original post)

Thu Sep 10, 2020, 10:00 AM

2. My god, what a board!

Chemical warfare and Edgar Allan Poe in a single post.
Where else you gonna find that?

Reply to this post

Back to top Alert abuse Link here Permalink


Response to LunaSea (Reply #2)

Thu Sep 10, 2020, 10:07 PM

3. It is not simple or straight forward to kill someone with these exotic poisons.

Every time Putin assassinates someone with something of this nature, considerable expense and the surreptitious handling of highly toxic materials is required. It is much simpler simply to shoot someone, stab them, strangle them.

Whenever Trump's owner kills someone I think of the opening lines of a "Cask of Amontillado."

Putin wants the world to know that it's him. He wants it clearly understood. It makes him more fearsome.

Reply to this post

Back to top Alert abuse Link here Permalink

Reply to this thread