Author Archives: gaussling

About gaussling

Gaussling is a senior scientist in the chemical business. He occasionally breaks glassware, spreads confusion and has been known to generate new forms of hazardous waste. Gaussling also digs aerospace, geology, and community theatre.

The Asymmetry of BS Assertions

Unfortunately, when someone utters something in conversation that is wildly divergent from reason, they make the claim in mere seconds. A proper rebuttal, though, can take paragraphs of content to dredge up facts and compile reasoning to refute the reckless assertion. Spouting nonsense is much easier than attempting to convincingly invalidate it. Many people avoid contradicting someone with doubtful assertions because either they don’t want to be disrespectful or they’re afraid to push the matter.

As a result, fools sermonizing nonsense often wander off with a false sense of victory because nobody pushed back. We all have friends and family that somehow went into the weeds and picked up some wild ideas.

One way to deal with fools spouting nonsense is to turn around and leave. Other times a gentle change of the subject can lead someone to a better topic. To expect someone to have an epiphany about some closely held yet nonsensical notion leading to a higher plane of awareness standing right there is unreasonable. Most of us fools will stand our ground and argue. Yes, that includes me. Despite being in a hole, I also have been known to keep digging the hole, though not so much anymore.

Wherein I digress.

College is a great place to pick up debating skills. My research group in grad school was a quite assertive and international group of people. Today most of them are either full professors or VPs of R&D at some pharma company. Since I decided against pharma early on, I was thankfully able to avoid the east coast. At that time there wasn’t much non-biopharma elsewhere. To thrive, I need to be around some interesting topography like here in the west.

In grad school I learned to pitch back as much guff as I received. By assertive I don’t mean quarrelsome, usually. I mean debate. Knowledge and reasoning had to be there, as it should be. Most of these “energetic discussions” were at the chalkboard where we preposed reaction mechanisms by pushing electrons. Fermented beverages were often present. Since it was a natural product and stereochemistry group, we had to be able to render our chalk structures in pseudo “3-D.” Our research professor was a master at this. He could draw complicated alkaloids and diastereomeric transition states with chalk to show stereochemical mechanisms as well as anyone.

Back to the BS people spew.

Back to the topic of the post. I’ve lost much of the desire I once had to debate people who espouse outright stupidity. An example would be a MAGA follower. My working theory is that once someone has tasted the Trump Koolaid, they are likely lost for good. They’ll live their lives out as Trumpers and go to their graves that way. Some Trumpers do have a revelation and recover, but most don’t.

Attempting to educate MAGA people for the sake of truth and accuracy is a waste of time. Is this a pessimistic view of life? Yes.

Consciousness is Slanted by the Limitations of Our Senses

As wondrous as our physical and chemical senses are, they are severely constrained in a few fundamental ways. Our vision is limited to our retinal response to a narrow, 1-octave wide band of electromagnetic radiation. As it happens, this band of light can be absorbed non-destructively by or stimulate change in the outer, valence level of inorganic and organic molecules. Electrons can be promoted to higher energy levels and in doing so temporarily store potential energy which can then do work on features at the molecular level. In the retina, this stimulates a polarization wave that propagates along the nervous system.

Owing to the constraints of the optics of the band of light we can sense, we cannot see atoms or molecules with the naked eye. This is because the wavelengths in the narrow range of visible light are larger than objects at the atomic scale. Instead, we perceive matter as a continuous mass of material with no indication of atomic scale structures. No void can be seen between the nucleus and the electrons. For the overwhelming majority of human history, we had no notion of atoms and molecules.

Democritus (ca 460-370 BCE) famously asserted that there exist only atoms and vacuum, everything else is opinion. The link provides more detail. The point is that atoms and vacuum were proposed more than 2000 years ago in Greece. The words of Democritus have survived over time but I’ll hazard a guess that the words were not influential in the rise of modern atomic theory in the 19th and 20th centuries. A good question for another day.

In all chemistry, energy is added to the valence level of a molecule as electronic, rotational, vibrational or translational energy.

Thumbnail Sketch of the Interaction of Light and Matter

Radio waves are a band of long wavelength that can interact with electrically conductive materials. Electromagnetic waves having a wavelength greater than 1 meter are considered to be radio waves. As a radio wave encounters a conductor, the oscillating electric field of the wave causes charge to oscillate in the conductor and at a rate matching the radio wave. Radio waves, whether in electronic devices or in space, are formed by the acceleration of charged particles. Recall that when you cause a charged particle to change it’s direction of motion, e.g., by a magnetic field, it is undergoing an acceleration. It is useful to know that radio waves are non-ionizing.

Microwave energy causes dipolar molecules to rotate back and forth by torsion as the waves pass. This rotational energy can be transferred to translational and vibrational energy through collisions, raising the temperature. The molecule does not need fully separated charges like a zwitterion, but molecules may have less than full charge on one side and a less than a full opposite charge on the other side, like water. This is a dipole. Water has a strong dipole and is susceptible to absorbing energy from microwaves.

Water molecule with dipole indicated.

Infrared radiation causes individual chemical bonds and entire frameworks to vibrate in specific ways. The Wikipedia link for this topic is quite good. When a molecule absorbs heat energy, it is partitioned into a variety of vibrational modes which can bleed off into other energy modes, raising the temperature.

Ultraviolet light is energetic enough to break chemical bonds into a pair of “radicals”- single valence electron species. These radicals are exceedingly reactive over their very short lifetime and may or may not collapse back into the original bond. Instead they can diffuse away and react with features that are not normally reactive, leading to the alteration of other molecules. UV light is very disruptive to biomolecules.

X-rays are more energetic than ultraviolet light and can cause destructive ionization of molecules along their path. They can dislodge inner electrons leaving an inner shell vacancy. An outer shell electron can collapse into the inner vacancy and release energy that can eject a valence level electron, called an Auger electron. This alters the atom by ionization and giving a change in reactivity. X-rays are also produced by the deceleration of electrons against a solid like copper though lighter targets can also produce x-rays.

Gamma radiation originates from atomic nuclei and their energy transitions. They are the highest energy form of electromagnetic radiation and cover a broad range of energies at <0.01 nanometer wavelengths. Many radioactive elements emit only gamma rays as a result of their nuclei being in an unstable state. Some nuclei can emit an alpha or beta particle resulting in an unstable nucleus that will then emit a gamma to relax.

The wavelengths of radio waves are too long and too weak to interact with biomolecules. Some radio waves come from the synchrotron effect where charged particles like electrons will corkscrew around magnetic field lines of a planet and release energy in the form of radio waves. In the case of Jupiter and it’s moon Io, a stream moving charged particles are accelerated by a magnetic field, the particles will emit mainly in the 10 to 40 MHz (decametric) range of radio waves as they spiral around the magnetic field lines into Jupiter. Jupiter’s volcanic moon Io sends charged particles into the planet’s polar regions where the magnetic field lines bunch up. This leaves a visible trace of borealis-like gas that glows. That radiation is emitted in the shape of a conical surface. It is only detectable here when the cone sweeps past earth as Io obits Jupiter.

Image from NASA. “This is a representation of the Jupiter-Io system and interaction. The blue cloud is the Io plasma torus, which is a region of higher concentration of ions and electrons located at Io’s orbit. This conceptual image shows the radio emission pattern from Jupiter. The multi-colored lines represent the magnetic field lines that link Io’s orbit with Jupiter’s atmosphere. The radio waves emerge from the source which is located at the line of force in the magnetic field and propagate along the walls of a hollow cone (grey area). Juno receives the signal only when Jupiter’s rotation sweeps that cone over the spacecraft, in the same way a lighthouse beacon shines briefly upon a ship at sea. Juno’s orbit is represented by the white line crossing the cone.”
NASA/GSFC/Jay Friedlander
Jupiter’s volcanic moon Io funnels charged particles into the planet’s polar regions where the magnetic field is strongest. This leaves a visible trace of borealis-like trails that glow. Source: NASA.

An atomic nucleus can absorb or emit gamma rays. For instance the gamma emitter Antimony-124 emits a 1.7 MeV gamma that can be absorbed by a Beryllium-9 nucleus which photodisintegrates into a 24 kiloelectron volt neutron and two stable He-4 nuclei. This nuclear reaction can be used for surveying for beryllium ore deposits by detecting neutron backscatter.

Ok, done with that.

So, not all electromagnetic radiation plays nicely or at all with any given chemical substance. The narrow visible band of light is uniquely well suited to interact non-destructively, mostly, with living things. Chemistry is about the behavior of the outer, valence level of electrons around and between atoms and molecules.

The retinas in our eyes send signals to the brain continuously that result in a very curious thing- our perception of color registers instead of just a grey scale. Not just the colors of the rainbow, but also more nuanced perceptions like pastels, brown and in their many textures- all with binocular vision!

The constraints on human vision depend on the chemical composition and anatomical structures of the retina as well as the construction of the brain. As the description of the various bands of electromagnetic radiation suggest, there is much to the universe that our senses cannot detect. We do not directly view the radio, microwave, infrared, ultraviolet, x-ray or gamma ray views of the universe.

Our daily understanding of the universe is mostly framed by what we can see with the unique biochemistry and anatomy of the retina. It’s not a bad thing with its limitations, but for an appreciation of the true scope of the universe we would have to find ways to view in the other electromagnetic radiation bands. And, we do. With radio telescopes and satellites that pickup x-ray and UV energy to give images. Now with JWST, we’re peering deeper into the universe as revealed by infrared energy. The longer wavelengths of infrared can pass through clouds of dust particles that previously blocked our view in the optical spectrum.

The structures of the atom and molecules are characterized by the very large fraction of “empty” space they contain2. Electrons seem to be point charges with no measurable size. Yet they have mass, spin and the same magnitude of charge but opposite that of the much heavier proton. And, the proton is not even a fundamental particle but a composite particle. It’s like a bag with three hard objects in it.

The universe is wildly different from what our senses present to us. All matter1 is made of mostly empty space. What we see as color doesn’t exist outside of our brains. Our sensation of smell is the same. Cold is not a thing. It is just the absence of heat energy. Finally, our consciousness exists only in our brains. It is a natural phenomenon that is highly confined, self-aware and may be imaged through its electrical activity or F-19 MRI with fluorinated tracers. This wondrous thing is happening on the pale blue dot floating in the vastness of empty space. So far, we can’t find anywhere else in the observable universe where this occurs.

It is good to remember that we search for extraterrestrial intelligence to a large extent with radio telescopes. On earth, the use of radio communication is a very recent thing, tracing back to the beginning of radio in 1886 in the laboratory of Professor Heinrich Rudolf Hertz at the University of Karlsruhe. Hertz would generate a spark and find that another spark would occur separately.

By 1894, Marconi was working on his scheme to produce wireless transmissions over long distances. The wider development of radio transmissions/receiving is well documented, and the reader can find a rabbit hole into its history here.

In order for the discovery of radio transmission to occur, several other things must have been developed first. The discovery of electricity had to precede the development of devices to generate stable sources of electricity on demand and with sufficient power. Then there is the matter of DC vs AC. Some minimal awareness of Coulombs, voltage, current, electromagnetism, conductors and insulators, and wire manufacturing is necessary to build induction coils for spark generation.

James Clerk Maxwell had developed a series of equations before the discovery of wireless transmission by Hertz. Hertz was very familiar with the work of Maxwell from his PhD studies and post doc under Kirchhoff and Helmholtz. Hertz was well prepared in regard to the theory of electromagnetism and was asking the right questions that guided his experimental work.

Radio transmission came to be after a period of study and experimentation by people like Marconi, Tesla and many others who had curiosity, resources and drive to advance the technology. As the field of electronics grew, so did the field of radio transmission. It’s not enough to build a transmitter- a receiver was required as well. Transmitter power and receiver sensitivity were the pragmatics of the day.

This was how we did it on earth. It was facilitated by the combined use of our brains, limbs, opposable thumbs and grasping hands. Also, an interest in novelty and ingenuity during this period of the industrial revolution was popular. While people who lived 10,000 years ago could certainly have pulled it off as well as we did, the knowledge base necessary for even dreaming up the concepts was not present and wouldn’t be for thousands of years. The material science, mathematics, understanding of physics, and maybe even cultures that prized curiosity and invention were not yet in place.

In order for extraterrestrials reaching out to send radio signals that Earthlings could detect, they would have to develop enough technology to broadcast (and receive) powerful radio transmissions. If you consider every single mechanical and electrical component necessary for this, each will have had to result from a long line of previous developmental work. Materials of construction like electrical conductors could only arise from the previous development of mining, smelting and refining as a prelude to conductor fabrication to produce a way of moving electrical current around.

Radio transmission requires electrical power generation and at least some distribution. None of this could have been in place without the necessary materials of construction, mechanical and electrical components already in place. Most of the materials would have to have been mined and smelted previously. Electrical power generators need to be energized by something else to provide electricity. On earth we use coal or natural gas to produce steam that drives generator turbines to make electricity. Also, there is nuclear and hydroelectric power. ETs would face a similar problem for the generation of electrical power.

If you follow the timeline leading to every single component of an operating radio transmitter, you’ll see that it requires the application of other technologies and materials. It seems as though a radio transmission from extraterrestrial home planets need something like an industrial base to get started.

What if there were intelligent extraterrestrials who were not anatomically suited to constructing radio transmitters for their own Search for Extraterrestrial Intelligence or just for local use? Perhaps they are +very intelligent but not far along enough yet to have developed radio. Or, what if they were just disinterested in radio? What if they used radio for a short window in time and have been using something else not detectable from earth, like what we do with optical cable? The point is that we would never hear them by radio, yet they would be there.

Surely there is a non-zero probability of this happening. This dearth of signal may be so prevalent that we will conclude that we are alone in our local region of space. Perhaps funding will be cut and we’ll quit looking. We can take that finding to fuel our sadness of being alone in the cosmos. Or we could use it to appreciate just how unique life is and take better care of ourselves.

1. Not including dark matter, if it really exists. I remain skeptical.

2. I’ve come around on this business of the atom being almost entirely empty space. This is a firmly established bit of folklore in chemistry. It makes sense only if we look at the electron as a solid or material object buzzing around the nucleus which it is not. The electron is a point charge manifestation of the electromagnetic force. It is a disturbance in the electric field. It doesn’t fly like a ball, it propagates in the manner of a wave. It has none of what humans think of as material substance, rather it is purely a quantum mechanical manifestation. It is shaped by 3-dimensional probability density standing waves surrounding the nucleus. This probability density is defined by a spherical harmonic wave series. We chemists know this harmonic series as s, p, d and f “orbitals”. Electron probability density extends from the nucleus to the frontier orbitals of the atom with s, p, d, and f orbitals occupying space according to its unique wave equation.

Zombie Oil & Gas Wells in Texas

Much has been written about the gas & oil industry in the US. My aim only is to highlight the leaking, not actively producing, oil & gas wells.

Many states have a problem with orphaned and zombie wells. Big ole Texas has a problem with orphaned and “zombie” oil wells also. Over time, oil and gas companies have been abandoning uncapped oil and gas wells in their eternal haste to produce “Black Gold, Texas Tea.” Inactive or non-compliant wells with delinquent organizational reports (Form P-5) for more than 12 months are called “orphan” wells in Texas. The state of Texas does have procedures for the disposition of orphan wells. Wells may be abandoned because of low output or the owners going bankrupt. It is possible to take over an orphaned well, though why would someone takeover a depleted orphan well or a low output well?

What’s worse, even the capped wells have begun to leak because of the corrosion and decay of well casings and plug material. The leak may be far down the hole or near the surface. These abandoned wells that are now leaking are called “zombie” wells. The zombie wells push up brackish water along with hydrocarbon liquids and vapors into the atmosphere and the surface soil as well as underground into the water table. Some underground flows are large enough that sinkholes form and fill up with polluted water.

The Oil & Gas division of the Texas Railroad Commission is responsible for “Regulating the exploration, production, & transportation of oil and natural gas in Texas.”

In a September 14, 2022, article in the Houston Chronicle, James Osborne writes

Source: Houston Chronicle

Following up, Amanda Drane writes in her July 17, 2023, article in the Houston Chronicle

Source: Houston Chronicle

The Texas Oil & Gas Association has stated-

Source: The Houston Chronicle.

As can be seen, the Texas Oil & Gas Association seems to feel that it has done its job with orphaned wells. The Teflon-coated Texas Oil & Gas trade association did what trade groups are supposed to do- shield their members from public blame and immense liability.

One component of crude oil & gas is hydrogen sulfide (H2S) which resides in both the liquid and vapor phases. This component is capable of both oxidation in the air to form a series of variously oxidized sulfur products as well as elemental sulfur itself. Hydrogen sulfide is extremely toxic and prone to cause olfactory fatigue in humans. The odor threshold is extremely low which could lead one to safely vacate the area, but the “nose numbing” effect on the sense of smell can lead to a false sense of security and continued exposure. Most cases of intoxication occur in confined spaces, however.

In a way, drilling for and striking oil & gas is like opening Pandora’s box. The well can produce valuable oil & gas, but along with it comes produced water with undesired dissolved minerals, petroleum and drilling residues. It seems clear that the State has a compelling interest in the final disposition of the well. The driller or party who owns the drilling rights to the well should be financially responsible for its clean shutdown. Bankruptcy should not absolve a company from responsibility for trouble the well brings.

This post is limited to the issue in Texas but it can exist anywhere oil & gas drilling has occurred. Obviously, the oil & gas industry represents a massive amount of economic activity and consequently it has enjoyed a privileged position in American industry in terms of regulations. It is doubtful this will change but that doesn’t mean that the beady eye of scrutiny should blink.

Even if hydrocarbon vapors and other gaseous substances blowing out of wells were not greenhouse gases, can’t a case be made for capping-off wells just to prevent pollution? There is a mentality out there that holds that if some pollution action is not mandatory, then it is not necessary. Their response to a problem is often that they “met regulatory standards.” That is, they would have done less if they could have.

And God Made Who??

There is a video on Truth Social posted by Trump or one of his lackies made by a fan with a soundtrack that sounds suspiciously like the radio broadcaster Paul Harvey from the days of old. It is a hagiography, a Valentine to #45 repeating over and over that God chose Trump to rescue America from a long list of troubles nagging at conservatives. Good heavens, there are even Marxists out there!

God took the time to plan this out for the sake of right-thinking Americans. The Big Guy who set the galaxies spinning and is the author of quantum entanglement and irritable bowel syndrome is also mucking about in Republican politics here on the pale blue dot.

This was released just prior to the Iowa caucuses to wheedle the Republican faithful to take heed and turn out to vote ’cause it’d please the Big Guy.

Jeepers. Would’ya get a load of that?

Tempest in a Teapot Over Austin

I am a little annoyed by the breathless attention given to Defense Secretary Austin for his “failure” to release a notice of his absence due to illness. Yes, he is the SecDef after all and he is an important player in our national defense establishment and US foreign policy. But if any organization has an extensive chain of command it is the Defense Department. His position can be covered by his direct-reports while he is out. To say that the Pentagon depends on a single person every moment of the day for critical decisions only he personally can make is to say that SecDef represents a single-point failure for the entire military apparatus of the US. This is absurd. 

Could it be that the news media are hyperventilating over this? Are they so daft as to believe that this was some kind of close call? It seems likely that in the Pentagon’s PR office handbook on protocol there is a paragraph on notifications like this. Well, they muffed it. Some poor fool will get their tit in a wringer over this. Big Freaking Deal. Move on.

I imagine that in 6 AM staff meetings in newsrooms across the country, staffers buzzing on 4 cups of Folgers coffee were trying to come up with fresh news “stories”. In some eager beaver’s mind they imagined that a breach of protocol at the Pentagon involving SecDef was going to attract attention. And if one broadcaster does it, they all have to. Are you listening NPR? I think some 4th estate swimmers dove into the pool and scraped their noses on the bottom.

Tempest in a Teapot. Source: Wikipedia.

A Bit of Fentanyl Chemistry

A recent raid on a clandestine drug lab in the Hatzic Valley east of Vancouver, BC, netted 25 kg of “pure” fentanyl and 3 kg which had already been cut for street use. Precursor chemicals used to manufacture the fentanyl were also seized. Along with the drug, the raid also seized 2,000 liters of chemicals and 6,000 liters (about 30 drums) of hazardous chemical waste, according to an RCMP news release 2 November, 2023.

The police said that the seizure represented 2,500,000 street doses.

In August of 2023 the police in Hamilton, Ontario, announced the results of Project Odeon. This was a large-scale sweep of illicit drug production in the Hamilton and Toronto area. From January 1, to July 30, 2023 there were 606 incidents related to suspected opioid overdoses and 89 suspected drug related deaths in the Hamilton area. Twelve people were charged for a total of 48 criminal charges. The police disclosed the following items that they seized-

  • An operational fentanyl drug lab at 6800 Sixteen Road, Smithville.
  • A dismantled fentanyl drug lab at 4057 Bethesda Road, Stouffville.
  • Approximately 3.5 tons of chemical byproduct from fentanyl production.
  • 800 gallons of chemicals commonly used in the production of fentanyl
  • Lab equipment commonly used in the production of fentanyl
  • 64.1 kg of illicit drugs, including 25.6 kg of fentanyl, 18 kg methamphetamine, 6 kg of ketamine
  • A loaded, Glock firearm and ammunition and four extended magazines
  • Over $350,000 of seized proceeds, including cars, jewelry, furniture and cash

Fentanyl is a synthetic drug first prepared in 1959 in Belgium by Paul Janssen (1926-2003). Janssen was the founder of Janssen Pharmaceuticals, now a subsidiary of Johnson & Johnson. In addition to fentanyl, the Jenssen team developed haloperidol, the ultrapotent carfentanil, and other piperidine based congeners. Piperidine itself is a DEA List 1 substance in the US.

Carfentanil is just modified fentanyl. Graphics: Will O. de Wisp

The elephant in the room with fentanyl is its extraordinary potency as an opioid. In pharmacology, potency is a quantitative measure of the amount of dose needed to elicit a specific effect on an animal or human in terms of dose weight per kilogram of body mass. Potency is subject to variability across a population and rises to an asymptote which can be difficult to pin down. For these reasons potency is reported at 50 %. For highly potent drugs like fentanyl, the measure is expressed as milligrams or micrograms of dose per kilogram body weight (mg/kg or mcg/kg body weight). One milligram per kilogram is one part per million (ppm).

When matters of toxicity arise, it is important to remember the maxim that “the dose makes the poison”. This observation traces back to Paracelsus in the mid-sixteenth century.

Fentanyl acts much like morphine in regard to its affinity for one particular opioid receptor. Morphine is commonly the “standard” with which other opioids are compared. For instance, fentanyl is said to be 50-100 times more potent than morphine. Only 0.1 mg of fentanyl is equivalent to 10 mg of morphine. Carfentanil is more potent still at 10,000 times the potency of morphine.

Morphine is an agonist which activates the ÎĽ-opioid receptor. Activation of this receptor with morphine produces analgesia, sedation, euphoria, decreased respiration and decreased bowel motility leading to the earthly delights of constipation. Fentanyl is thought to interact with this receptor as well.

Original fentanyl synthesis by Janssen. Graphics: Will O. de Wisp

So, how is fentanyl synthesized? See the synthetic scheme above. I’ll just comment on the Janssen synthesis and some issues. I have no idea of how it is made out in there by the Mexican cartels and in ramshackle American trailer parks. The synthesis above has some steps that may be undesirable for backwoods or jungle operations like hydrogenation. In the first step, aniline will be needed to make the phenyl imine. It’s pretty toxic and stinks to high heaven. Next, lithium aluminum hydride is needed to reduce the imine double bond to an amine. This innocent looking grey powder is very hazardous and should only be used by an experienced chemist. It is also available as a solution in tetrahydrofuran. The next step is the formation of the amide with propionic anhydride. While the reaction entails a simple reflux, you still have to isolate the product. Once you have recovered the amide, the benzyl protecting group on the piperidine nitrogen must be removed. It allowed amide formation exclusively on the upper aniline nitrogen and has served its purpose. Finally, the piperidine nitrogen must be festooned with a phenylethyl group and phenylethyl chloride was used to afford the fentanyl product. 

An excellent review of the pharmacology and drug design of this family of opioids, see Future Med Chem. 2014 Mar; 6(4): 385–412.

In chemical synthesis generally, substances are prepared in a stepwise manner and with as few high yielding steps as possible. To begin, one must devise a synthesis beginning with commercially available raw materials as close to the target as possible. If the product has many fragments hanging off the core structure, it’s best to solve that problem early. Synthetic chemistry is almost always performed in a non-interfering solvent that will dissolve the reactants and allow the necessary reaction to occur. A low boiling point is preferable for ease of distillation. An important side benefit from a solvent is that it will absorb much of the heat of reaction which can be considerable. Left on its own, a reaction might take its solvent to the boiling point by self-heating, generating pressure and vapor. The benefit from evaporation or reflux boiling is that as a solvent transitions from liquid to vapor there is a strong cooling effect which helps to control the temperature. An overhead condenser will return cooled solvent to prevent solvent loss.

You can do any chemical synthesis in one step with the right starting materials. Unfortunately, this option is rarely available. The next best option is to take commercially available starting materials through a known synthetic scheme. People who run illicit drug labs are never interested in R&D. They want (and need) simple chemistry that can be done by non-chemists in buckets or coke bottles at remote locations. Chemical glassware can be purchased but sometimes the authorities will be notified of a suspicious order. This is especially true with 12 liter round bottom flasks.

The most difficult and risky trick to illicit drug synthesis is obtaining starting materials like piperidine compounds in the case of fentanyl and its congeners. In the case of heroin, acetic anhydride shipments have been investigated for a long time because it is used to convert morphine to heroin- an unusually simple one-step conversion. Solvent diethyl ether is similarly difficult to get outside of established companies or universities. Many other common drug starting materials are difficult to obtain legally in the US or EU by the criminal element. However, China is thought to be a major supplier of starting materials outside the US and EU. Countries with remote coastlines, loose borders, lackadaisical or corrupt law enforcement reduce the barriers for entry of drug precursors. China in particular has a large number of chemical plants that make diverse precursors for legitimate drugs. Unfortunately, some of these precursors can also be used for illicit drugs or existing technology adapted for this use. Precursors can be sold to resellers who can do as they please with them. Agents may represent many manufacturers and can mask the manufacturer’s identity and take charge of the distribution abroad. Shady transactions become difficult for authorities to detect and trace. The identity of illicit precursor chemicals are easily altered in the paperwork to grease the skids through customs. Resellers can repackage chemicals to suitable scale, change the paperwork and jack up the price for export. It has been my experience that many if not most Chinese or Japanese chemical manufacturers conduct business through independent export agents. However, behind the curtains there often a byzantine web of connections between companies and agents, so you may never know who will manufacture your chemical. As an aside, this complicates getting technical information from the manufacturer since the agent will not disclose a contact at that manufacturer.

Highly potent drugs like fentanyl must be taken in very small dosages which means that kilo-scale batch quantities of drug result in many individual sales per kilo. Small quantities of highly potent drugs are more easily smuggled than bulky drugs like weed with its strong odor.

There is a down-side to the illicit manufacture of drugs like fentanyl. It is quite toxic at very low dosages and must be handled with the greatest of care lest the “cook” and other handlers get inadvertently and mortally poisoned. Good housekeeping helps, but I have yet to see a photo of a tidy drug lab.

Fentanyl can be sold as a single drug but perhaps is cut with a solid diluent that some random yayhoo decided was Ok to use. Other drugs of abuse like heroin may be surreptitiously spiked with fentanyl to kick up the potency. In either case, a given dosage may or may not be safe even for a single use. There is no way for a user to know. Also, the concentration or homogeneity of mixed solids may be subject to wide variation. For more than a few people, their first fentanyl dose will be their last.

Passage Slowdown Through the Panama Canal and Some Rerouting at the Suez Canal

The year 2023 has been a bad year to be a canal user. Between a drought aggravated by El Nino and a shooting war by Houthi terrorists, transit costs and risks have risen steeply.

The two major canals for transoceanic shipping in the world are seeing events affecting their operation which are beyond their control. The Panama Canal is suffering a slowdown in transits due to a drought reducing the water level of Gatun Lake which feeds the canal lock system. The Suez Canal is being affected by hostile Iranian-backed Houthis in Yemen threatening shipping in and out of Israel moving through the Red Sea. They claim to be after ships to and from Israel, but it doesn’t appear that their target identification is very good.

The Suez Canal does not use locks so it can pass more ships per day. While the Panama Canal suffers from drought limiting its throughput, the Suez Canal has no new physical impediments. It is affected by ship operators who elect to bypass the Houthi threat by going around the Cape of Good Hope. Since 17 November, 2023, 55 ships have rerouted around the Cape of Good Hope and 2,128 ships have passed through the Suez Canal according to Reuters.

The Panama Canal auctions-off transit slots on a daily basis. During normal conditions before the drought, there were 36 transits per day. At the start of December, 2023, that rate was at 22 transits per day and the cost of a transit has risen accordingly. As of 15 December, 2023, the transit rate was increased to 24 transits per day through both the Panamax and Neopanamax locks.

The US produces more gasoline than it consumes and most of the excess is exported from the Gulf Coast. For buyers along the Atlantic basin, the US produces the cheapest gasoline. The Gulf Coast also supplies refinery products to the Pacific rim via the Panama Canal.

Within the US, gasoline prices have been low owing to excess inventories. Because of the Panama Canal slowdown, some refineries may have to reduce production to prevent further inventory buildup, potentially resulting in increased prices generally and heating oil in particular.

Panama Canal “slots are prioritized according to highest bid in auction processes, full containers, market and customer rankings,” according to Reuters.

Howdy Arabia

I heard a sarcastic moniker for Texas yesterday for the first time. It was “Howdy Arabia”. It was used by one of my favorite comedians, Trae Crowder, and refers to ultra-conservative xenophobic southern American culture. Crowder is from Tennessee and calls himself a progressive hillbilly or a liberal redneck. But Howdy Arabia has been around for a while as a Google search will show. The phrase “Y’all Qaeda” also bubbles up.

Why all of this intemperate 8th grade slander on an entire state? The abortion fiasco led by Texas Attorney General Ken Paxton happening in Texas presently is so foul and unnecessary that I can barely listen to it without becoming angry. Medical reality doesn’t seem to have a place in Paxton’s absolutist, linear brain. He is putting on a performance to display his Republican bona fides. His are the Bible belt constituents who elected him. In this sense, he is a duly elected official giving his voters what they want no matter the cost. It isn’t just Paxton- it is the entire GOP party apparatus at work.

Paxton is an aggressive, doctrinaire male exerting control over a woman’s body from a distance. He won’t be present as she suffers through this ordeal. He could have accepted the local court’s decision and allowed the woman to go forward with the procedure. Instead, he appealed to the Texas Supreme Court and ruled against the lower court’s decision. Further, he sent letters to local health care providers threatening severe legal consequences if they were to aid in the woman’s abortion. This is Republican Texas.

Idiots are elected by idiots.

Execution by Nitrogen Hypoxia

It came out that the state of Alabama is preparing to execute a prisoner by nitrogen hypoxia. Oklahoma and Mississippi are the only other states that have authorized this method of execution. The prisoner, Kenneth Eugene Smith, had previously selected nitrogen hypoxia as a secondary means of execution. This decision was backed by the US Supreme Court. The first attempt to execute Smith by lethal injection failed because of the inability of workers to find a vein after 4 hours trying.

Smith’s attorneys have made the argument that this new form of execution claim that Smith is a “test subject for this novel and experimental method.” According to the Death Penalty Information Center, some have claimed that “those who support the use of nitrogen hypoxia can only theorize that the method will be painless and quick, but opponents have likened it to human experimentation.”

Criticism of the nitrogen hypoxia method have raised safety concerns for witnesses. It’s been argued that nitrogen escaping from the condemned man’s mask could threaten the health of those nearby, particularly the preacher standing close for spiritual comfort.

Critics say that the state of Alabama has not adequately prepared for the execution and the safety of witnesses and workers nearby.

“They could start to hyperventilate because their body would detect that they’re in a low oxygen environment,” said Dr. Joel Zivot, an anesthesiologist and associate professor at Emory University School of Medicine. “And that severe hyperventilation can lead to a stroke.” The doctor expressed concern that the method is full of unknowns and seemed quite skeptical of the method.

Seems to me that on basic principles alone, this method should work just fine. It would’ve been nice to read that the state had a written procedure that specified the type of mask and the nitrogen flow rate. As for the safety of others, minimally there should be an O2 concentration meter present, which is the case. The air exchange rate in the room can be measured and increased, assuming this is possible in an Alabama prison. Best of all, supplied air hoods or masks are widely available. This would only require an air compressor in fresh air.

The Squamous Chronicles: 10 Years Later

It has been right at 10 1/2 years since I was treated for squamous cell throat cancer. This virally induced cancer is quite treatable with a high success rate. The treatment was simultaneous radiation and cisplatin. The x-radiation dose was 68 Gray in daily 2 Gray doses with 6 cisplatin infusions. The radiotherapy machine was an Intensity Modulated Radiation Therapy (IMRT). The source rotates around the stationary patient varying the beam size and intensity as it goes. The idea is to put the energy into the tumor and spare healthy tissue to the greatest extent possible. The neck is a very crowded place with many kinds of tissues you don’t want to zap too much.

Illustration showing variable intensity beam shaping from the IMRT on the right. Source: Semantic Scholar.

It took about 1 week for the radiation effects to show up. It began with a sore throat which quickly led to a stomach feeding tube. They snake a pointy-ended tube down your throat and poke it out of your belly. I had it in for about 6 weeks. I jammed my liquid food in with a 60 mL syringe.

Besides the considerable discomfort from the radiation, long term side effects were not terrible. My thyroid took a big hit as did my salivary glands and taste buds. Ten years of dry mouth has led to the loss of some teeth. And, there was difficulty in swallowing initially. This problem unexpectedly returned during my recent bout of pneumonia.

The cisplatin was given in 6 doses. The nursing staff in the infusion suite don considerable PPE while handling chemotherapeutic drugs due to the toxicity hazard. I had no noticeable symptoms from this treatment. But while in the infusion suite, I could hear numerous female patients who were groaning in misery and vomiting from their meds. It was heart wrenching.

Nine years ago I wrapped up radiation for my stage 4 prostate cancer. Though the dose was lower at 38 Gray, there were no real negative effects as with the throat radiation. This was followed by 2 years of chemical castration with Lupron. It is also called hormone ablation. Lupron interferes with the production of testosterone. It does not, however prevent the adrenal glands from producing it, but this is a minor source. The first effective treatment for prostate cancer was surgical castration done to halt testosterone production. This hormone accelerates the growth and spread of the cancer. These guys who take testosterone for body building have no idea about the other thing the hormone can do. Just my opinion.

Hormone ablation eventually becomes ineffective because over time the prostate cancer cells respond by increasing the number of androgen receptor proteins on the cell walls. After hormone ablation fails, more severe treatments are put into use.

My outlook is this- The throat cancer is unlikely to return, but the prostate cancer will eventually take me out. I’ve had plenty of time to ponder death since the cancer diagnoses. I’d much prefer to have a quick, fatal heart attack than a slow, wasting death from cancer. I jokingly mentioned this to my cardiologist. He replied that the heart attack might not kill me. Buzzkill.