Chemical Process Development

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Lots of semi-batch process development and safety work going on in my lab. We use our reaction calorimeter for a variety of studies now. Naturally we want to know about energy accumulation with a given feed rate or any unforeseen induction or initiation problems in a reaction. We can also home in on recommendations for safe feed rates of reactants into a reaction mass.

What I am beginning to learn from the RC1 work is that running a reaction at low temperature is frequently done for sketchy reasons. Unless there are selectivity or side product issues, you really have to question why the reaction is specified to be run at low temperature. I think some of it comes from habit gained in grad school.  Low temperature may introduce dangerous situations with abrupt initiation by accumulation of unreacted reagents. Or it may lead to overly long feed time with the associated costs of added plant time and labor.

There are reagent incompatibilities like nBuLi in THF above – 15 C or so. But you’ll find that MeTHF is a bit more tolerant of temperature than is THF.

The precise temperature management capabilities (Tr) of an RC1 including the ability to lock on a temperature or precision ramping gives insight on solubility questions or on freezing points. The instrument also provides heat capacity data for engineering calculations. it is a very useful apparatus.

A Big Bronx Cheer for the 2014 Jeep Cherokee!!

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The makers of Jeep have resurrected the standard Jeep Cherokee in, well, how else can I say it … a very stupid way. They have abandoned the classic boxy utility vehicle lines of the old Cherokee in favor of the now popular fat and squat ellipsoidal lines of contemporary design. In other words, it looks like a jelly bean or rugby ball.  The classic 4.0 Liter Cherokee had power to spare and it had the fantastic visibility of an inverted fish tank. It had troubles too, namely bad electric connectors and perhaps an under-designed cooling system. But at least it had the classic squared-off Jeep lines and lots of traction.

But the greatest sin of all was abandoning the 4.0 L straight-6 engine for the 3.2 L engines. Jeep?? WTF!! What were you thinkin’? I would love to meet the committee of marketing pencil necks and constipated MBA’s responsible for this one. It’s a travesty.

So Long Year 2013. Hello 2014!

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Update:  I sit and write at a desk piled with pdf printouts of patents, journal articles, a Phi-Tec 1 handbook, and a great heap of process safety data and reports. I help coworkers find and study patents for their R&D due diligence. The bigger task is running a thermo lab for determining the thermokinetic safety of bulk chemical processing. These two topics, patents and thermodynamics, would induce instant unconsciousness for most folks. An acute boredom-stroke followed by involuntary somnolence and collapse to the floor. Oddly enough, I rather dig these topics- especially the thermodynamics. A single fellow covering these two widely differing topics is entirely a(n) historical artifact, unlikely ever to be repeated.

Several months following throat cancer treatment, my energy and curiosity are back although I still cannot eat solid food due to impaired salivary glands and taste buds.  The head-and-neck-onco-doc says it’ll take 1.5 to 2 years for the spitter to come back online. It is like serving a sentence in the Nestle warehouse living on Boost. I enjoy food vicariously watching the Food Network. This is what the term “food porn” means- watching others enjoy a sensory and emotional experience with food.

The year 2014 will see me spending more time with the urology oncologist. At the last appointment he promised to help keep me on the top side of the grass as long as possible. I have to hold him to it.

An American Parliamentary Republic? Why not?

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Here is an idea for debate. Why not pitch our flawed constitution overboard? Replace it with one that supports a parliamentary form of government rather than the fractious, unworkable presidential system we have now. Who else in the world uses this system of government? Why is it that most other forms of government in the world are parliamentary in structure?

Make the US government more responsive to the citizenry by rendering the election cycle time dependent on confidence in the leadership.

The US constitution needs a rewrite. Among the distortions in the constitution-

  1. The metaphysical equation of money with speech.
  2. The foggy language of the 2nd amendment that engenders armed fanaticism
  3. The indistinct barrier between the secular and theocratic civic influences. Keep religion and other magical thinking out of governance. Preserve freedom from religion.
  4. The near impossibility of getting a bad president or governor out of office.
  5. Clearer language is needed on what is actually meant by the right to petition congress. Currently this has lead to an intractable cancer of corruption between government and the movers of wealth. (Consider the F-35 strike fighter or the lack of tight control over Wall Street investment banks)
  6. Apparently the rules for the waging of foreign wars are indistinct because current constitution or presidential structure seems to allow the US much flexibility and low accountability with invasions and sending ordinance across borders.

There are more problems with the constitution. Maybe the reader has thoughts on this? The problems of presidential systems have been studied and this Slate article summarizing the issues is worth reading.

The Squamous Chronicles. Just pissin’ and moanin’.

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It’s been 16 days since radiation ended. My throat (oropharanx) seems better though the internal blistering has not totally subsided. Fatigue and boredom grind the soul like a rock in my shoe. I’ve collected new books on poetry and science but to no avail. Concentration remains elusive.

Eating is tedious. The g-tube pump is slow and I am not tolerating the nutrient fluid (i.e., “food”) all that well. Food tastes awful and swallowing is problematic.

My other cancer- prostate- is next on the firing line. I won the cancer lottery with an aggressive form that has spread to a lymph node but not to any bones according to the Tc bone scan.  I am under hormone ablation therapy which slows down the spread for a few years anyway. We may start radiation in January. The docs won’t say anything about life expectancy. The urologist is disinclined to treat it surgically. At the UC hospital, they have a tumor board meeting every Tuesday where they discuss cases. It’s nice to know that multiple folks are looking at it.

The Squamous Chronicles. Pointers for the home stretch.

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A few observations for those facing irradiation of the throat.

  • Don’t wait too long with your decision to get a gastric tube put in.
  • Get started with a high calorie regimen early. By week 3 of 6, swallowing suddenly became very painful.
  • Beware the constipating drugs.  For me it has been the anti-nausea drugs and the narcotic pain killers. It is very easy to get behind the curve on this. Find a parallel bowel control regimen and stick with it.
  • Some meds that promote bowel movement are too strong. For me it is Dulcolax.
  • Mucositis is more than just a nuisance. Viscous mucus it produces will trigger gagging and vomiting. Pumping acidic vomit through a raw throat is exactly as fun as it sounds. Mucinex (aka guaifenesin) goes a long way towards keeping this in check. Out of about 20 nurses and docs I’ve had contact with, only one nurse seemed to know this trick.
  • The so called magic mouthwash, Benedryl/Lidocaine/liquid antacid was too viscous for the mucositis.
  • After 63 Gy of therapeutic  x-rays and what I’ll estimate as ca 450 mGy from 35 CT x-rays, a surgical scar will be very sunburned if it was in the beam. It is important to keep it moisturized and covered.  The pharmacy can compound  an ointment composed of 2 % lidocaine in Aquaphore. This works very well.

It is important to let go of some of the independence and allow people to help you. The people around you want to help but feel unable to do anything substantial. Let them drive you around or bring food even if you can’t eat it. They’ll tell you about others they know who have had cancer and perhaps died of it. Even though it may not really be comforting to you, they are reaching out the best way they know how. You have to allow them this because they are under stress as well.

Attacking Syria for nerve gas use in Ghouta

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In the news there are reports of pending action by the US in Syria. Maybe I have a blind spot. Maybe there is some fundamental principle I am missing here. But how is it that a mass killing by gas elicits a response from the US when a larger mass killing by bullets and high explosives does not? Where are sympathetic Arabs in the region? How are they exempt from delivering bombardment as justice for the dead?

Obviously, gas attacks lie across a firebreak of some kind. What is the Syrian death toll now- 90,000 + by bullets and bombs? And that does not trigger international action? Apparently, grisliness is not a deciding factor.

This isn’t about justice at all. It is a smack down on setting a precedent with NBC warfare- nuclear, biological, and chemical. It is a genie we cannot allow out of the bottle … in the land of the genie.

So, here is the scenario-  the US will begin a strike at 3 am with cruise missiles to soften up the target area and air defenses. Stealth fighters will fly in to attack everything that flies. Penetrator missiles will demolish air, missile, and command and control bases. But what to do about the nerve gas armaments? Are they bombed or isolated? Who recovers them right after the attack? Al Qaeda? Let’s hope not.

This whole thing is a troubling moral discontinuity. By policy we watch many tens of thousands murdered by bullets and high explosives, but act on policy that triggers when gas is used. There may not be an answer, but there certainly is a smell. The smell of death.

The Squamous Chronicles. Finish one and start another.

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8/27/13.  As of today, I have 3 more x-ray treatments culminating in a dose of 63 Gray to the throat. The pain has required narcotics pretty much continuously and the attendant constipative delights that go with that. Pills are difficult to swallow and the gag reflex is heightened. The final chemo was yesterday so I am done eating platinum.

I began hormone ablation treatment for an aggressive form of prostate cancer two weeks ago. While the throat cancer is substantially beatable, the prostate is a different story. Here is the deal fellas. While you can gauge with PSA numbers, it is the Gleason grading system that tells the tale. And to get that you must do a biopsy. In order of increasing severity, the Gleason score goes from 2 to 10. I pulled a 9.

Hormone ablation is delicate way of saying chemical castration. The spread of prostate cancer can be controlled somewhat for up to 2 years by shutting down testosterone production. This they do by injecting a synthetic peptide, Degarelix, into belly fat to control the dosing to the pituitary gland. Had my first hot flash a week ago. It was a eunuch sensation.

Interesting anecdote.  My medical oncologist described an MD patient who had been using sunscreen on the radiated area of his throat. He soon experienced an increase in surface burning of the throat on continued x-radiation. Turns out he was using a sunscreen that had titanium dioxide that was scattering/absorbing radiation on the affected surface. He stopped and the accelerated damage ceased.

Schneier on Security

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Schneier on Security is one of my favorite non-chemistry blogs. The particular link here is to a post on the NSA and It’s apparent commandeering  of the internet for its own, opaque purposes. Bruce Schneier developed the Blowfish encryption algorithm.

While I have previously criticized Libertarianism and its peculiar conflation of civilization with Austrian economic thinking, I am enough of a civil libertarian to be deeply alarmed by post-911 security paranoia with its narrow readings on the 4th amendment and attending case-law.

Ask yourself, how much of your life do you want to be subject to structural snitch features that trigger silent alarms when your face is recognized in a building, when you called the front desk of a business or agency, or when you download particular information from the internet or just do keyword searches on Google?

You can bet that hordes of NSA folk as well as contractors are working feverishly on what else they can do with this metadata and location data accumulating in datacenters.

Many friends have said half joking that they feel sorry for spooks who have to sift through their chatter and insignificant browser searches. But what if an NSA spook were standing over their shoulder while they did it? How would they feel then? Maybe fellow citizens who approve of this kind of activity should be flagged for participation and the rest of us left alone. Would they feel the same about it?

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The Squamous Chronicles. Radiation, biopsy, gastric tube and chemo.

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As of today, I am 18/30 of the way through radiation. Last week I was unable to eat much, resulting in a large weight loss (ca 10 wt %) and necessitating the placement of a gastric tube. This was done under general anesthesia, but while I was awake. A fluoroscope was used to view the procedure. This was a bizarre experience. I could feel the stomach being punctured and sutured to the abdominal wall.

As weird as this experience was, it was nothing compared to the prostate biopsy the next day. Eight corings of the prostate though the rectum wall producing 8 little meat sticks of sample. It felt like the snapping of a tight rubber band against the tissue. The doc tried to ask about my hobbies during the procedure for distraction. Glad that is over.

The biggest side effect of this has been fatigue. I’ve experimented with more exercise to good effect. Freshly juiced vegetables help compensate for the drug induced constipation. And a large influx of calories through the gastric tube all add up to an improved energy level. I have been juicing beets and swiss chard.

In general, owing to the radiation on the throat (they say) my taste buds are operating improperly. Everything tastes really bad.

This week, a day past the third 90 mg drip of cisplatin, I am experiencing hair loss.