Analytical Life Without NMR

We synthetikkers live in the gilded age of NMR. This analytical method is so fast and so rich in quantitative and structural details that we may forget what it’s like to produce materials that aren’t amenable to NMR rigged for liquid samples and H, C, F, B, Si, and P.

I’ve been busy making metal oxides and various complexes for sale that lend themselves to a very short list of analytical methods. When you make compounds for sale you have a responsibility to provide an unambiguous assay of purity for the lot.  Compounds that are poorly soluble, paramagnetic, or lack NMR active nuclei can be problematic for NMR assay in a production setting. Yeah yeah, I know- get a solid state NMR. Well, we don’t have one and it ain’t gonna happen in my lifetime. Meanwhile, I have 200 g of new product that needs to get certed and into inventory.

Lately I have been taking cues from catalog company web-sites and exploring other methodologies. Complexometric titrations for metals assay, AA, gravimetric AgX for halides, Karl Fischer for water, Loss On Drying (LOD) for volatiles (water, solvents), combustion analysis (C, H, & N), Glow Discharge MS (the Big Hammer) for refractory metal oxides, XRD for anything that could be in the xtal database, melting points, TGA, and I’m turning back to FTIR. 

I haven’t been using FTIR in a quantitative way, just looking for a “Conforms to Structure” result. But nonetheless, in the preparation of new compounds for the product list it is a life saver. I can convince myself that the desired ligands are there and use other methods to try to quantitate their wt %.

I always feel better if we can come up with 3 methods that corroborate the composition. You don’t always have to come up with methods that are on the specification either. It is reasonable to report results on a Certificate of Analysis that are “Report Only” and show general conformance rather than some percentage quantity.  Examples might be appearance, color, or even an NMR spectrum.

I have only recently begun to use XRD and am a mere novice in its intracies. I have sent solid solutions where components that I knew to be there were not detectable. I have also sent samples that came back with % compositions of several xtal phases. For characterization of production lots, it has utility in the detection of certain components. Amorphous phases and random, solid solutions are a blind spot for the method. On the other hand, there is ca one half million compounds in the database so it can detect xtal phases down to ~ 1%.

I have learned an expensive lesson in regard to ICP MS. The method is quite blind or unreliable with certain elements. Sulfur and halides in particular. A sample can be loaded with sulfur (often as sulfate) and the assay will come back with a wildly low value. An ICPMS assay of rare earth metal oxides can support a claim for 99.99 % total rare earth oxides. A GDMS of the same sample may show that it is 99.8x % in metals and even lower if you include halides, sulfur, and phosphorus. 

To be fair to purveyors of ICP MS, it is quite sensitive but standards at the lower limit of detection may not be available. Sub ppm numbers without an explanation of conditions and error are to be taken with skepticism.  Everything looks like a dogs lunch once you get down to the sub ppm level.

A Plurality of Moieties

I caught myself writing like a patent lawyer today. It was a little unnerving.

In the instant example … blah blah … the preferred embodiment … blahty blah blah … a plurality of moieties … blah blah … the said R group … yawn … including, but not limited to …

It is surprising how easy it is to fall into the style of writing that characterizes patent applications.  It is easy to poke fun at our lawyerly brethren for this.  But the stylistic manner and the use of precise vocabulary with elaborate sentence construction is the result of generations of bitter experience in court. A long time ago, lawyers figured out that you have to say precisely what you mean to get what you want.  

Judges and juries have to arrive at conclusions based on something, so if your fate rests on their interpretation of ambiguous language, you may be in for disappointment.  Precise language is meant to prevent misunderstanding and place rewards and liabilities where they belong.

For chemists who are busy inventing things, it is useful to actually study the form and the language in a handful of patents.  This will give a sense of how intellectual property is actually staked out and claimed.  It is useful for the chemist to provide some guidance to the attorney in drafting claims and maximizing the value of the patent.

I deleted the “plurality of moieties” in the final draft. Just couldn’t do it.

Linkography

A friend sent this hilarious Bill Gates movie link.  Thanks JT.

When it all comes tumbling down, these are the first 100 things to disappear.

Interested in the Taxonomy of Logical Fallacies? I guess I should actually read this.

Just wanna know how damned dangerous blogging really is? Satisfied??

Farewell to Bobby Fisher.

Lookin’ to get rid of some of that Radwaste you’ve got buried in the back yard? Lots of links here.

Michael Crichton’s “Next”- Somebody Call a Wildfire Alert!

I’m halfway through Crichton’s 2006 genetics saga Next. Slogged all the way to chapter 35 of 94. I hate to say it, but I’m bored out of my skull. I ran into the same issue with his last book, State of Fear. The question is this- Should a fellow spend perfectly good heartbeats in finishing the book, or move on to a better read? Ahh, I’m moving on.

Next reads like a made-for-TV drama. Thin character development and short chapters are ideal for the 12-minutes-of-ads-per-half-hour-of-programming world of television. Between chapters I fully expect to see a testimonial about erectile dysfunction or a teaser for a NASCAR race pageant. The chapters are so short and the narrative jumps around so much that it becomes difficult to keep track of what each character is doing. It is attention deficit narrative- ADN.

Crichton has become a TV writer and to expect anything different seems unrealistic. I’m sure it’s a good living. Hmmm, I wonder if he is on strike…?

I keep hoping for another Andromeda Strain and we keep getting ER

Breaking Bad

The AMC channel on cable is running a series called Breaking Bad. It is about a high school chemistry teacher who, for various reasons, begins to make high quality methamphetamine with a former student. It is actually quite interesting to watch. Never before have I seen so many details of chemical synthesis on an entertainment tv program.

The 2nd episode portrays a lecture on chirality to a chemistry class. The technical details seem well researched and the dramatic situations are unexpected and novel. I have to say that it is quite well done.

The teacher is a kind of anti-hero. We can identify with him to a point. But where we depart from him is where he breaks bad. The scenes of a chemist working in a respirator and tighty-whities may frighten some viewers. Caution is advised.

et Al. A Gathering in Memory of Albert I. Meyers.

Colorado State University has announced “a gathering in memory of a remarkable life” in honor of University Distinguished Professor Albert I. Meyers. It will be held Friday, February 22, 2008, at 10:30 a.m. in the Arizona Room at the Hilton Fort Collins. You may recall that this hotel is 2 blocks south of the Chemistry Building.

RSVP:       csn (at) lamar dot colostate dot edu

This event is being managed by the Director of Development at the College of Natural Sciences at CSU. (I am hesitant to post names and phone numbers that can be collated by web crawlers)

I’ll definitely be there.

Cloverfield

Just back from seeing the movie Cloverfield. Holy cow! Fast and intense flick. Not for dates.  Ninety five minutes of home video. NYC trashed by another dyspeptic monster. Creature feature. Angry shrimp-grass hopper hybrids the size of golden retreivers. Rather well done in my estimation. Best seen on a theater screen.  Not for little kids- it’ll scare the doo-doo out of them.

Gaussling’s Curio Shop of Links

Ever notice how the seats in the gate waiting areas at the airport usually have arm rests next to every position? There is a reason for that. The Blog Architectures of Control, Design with Intent is devoted to the design of artifacts in our public spaces that encourage or discourage certain kinds of use. 

The use of the apostrophe is detailed in this site. According to author, yours truly could be an actual moron.

Concerned that the government isn’t adequately monitoring schizophrenics?

I knew that Leonard Euler had a number, but I didn’t know he had a disk too.

Looking for something new in the Vampire genre? Try “the Nymphos of Rocky Flats“. The adventures of Felix Gomez, Vampire and PI.  So far, friends who spent their careers at the Rocky Flats nuclear weapons plant near Denver have been strangely neutral on the book. I smell conspiracy.

The Black Art of Procurement

The act of consumating a business deal can be very exciting and fulfilling. It can also be a moment fraught with anxiety. [A variety of unwholesome metaphors could be brought in at this point, but I’ll resist.]  A business deal requires a buyer and a seller. The buyer has to satisfy needs that have an inverse relationship with the seller. The buyer wants a low price and high value per $. The seller wants a high price and a nominal value per $.

All buyers have a list of requirements: First, the buyer has to bring home a service or a product. Second, the buyer needs some kind of assurance that the transaction won’t go afoul by slow or non-delivery, poor quality, or shabby service. The buyer often has a third need, one that may or may not be evident from the beginning to the seller. Most buyers have a need to demonstrate that they have gotten a bargain. It is not enough to have merely purchased a thing- most people have a real need to bring back a kind of buyers trophy.

What many sellers may not appreciate is the kind of pressures that may be on a buyer in the B2B world.  The value of a buyer to his/her employer is the ability to get the lowest price under the best terms. The ability to put the squeeze on vendors is a highly prized attribute among buyers.  Some organizations actually consider their purchasing department to be a kind of profit center.

A company that is involved in technology development for their own use or for licensing may have several kinds of buyers. They may have a conventional purchasing department for paper clips, hardware, and commodity chemicals. This department is charged with sourcing and buying fairly ordinary things.

But the same company may also have a procurement group that focuses on the sourcing and purchasing of specialty items. In the fabulous world of chemical industry, a procurement manager may specialize in items that must be custom made or are otherwise scarce, highly technical, patented/licensed, or just plain expensive.

Some materials are particularly critical to a company. It may be a key chemical feedstock, a special reagent, a catalyst, or something that is difficult to make or is highly specialized. The procurement of specialized materials often requires the attention of a chemist. So, it is not at all uncommon to find chemists involved as procurement managers in the chemical industry. In fact, many high level procurement people I know were chemists early in their careers. 

Procurement people are quite important players in a company. They have heavy responsibilities and are always under pressure to perform. They deal in dollars and days. Their performance is easily monitored by their superiors by the simple metrics of dollars and delivery times. To put the delivery puzzle together, they have to negotiate and enforce specifications, price schedules, supply contracts, secrecy agreements, delivery schedules, and often international multimodal logistics. 

If a procurement person flubs a detail, like delivery of raw material on a certain date, a process shutdown at the plant could be the result. Depending on the magnitude of the fiasco, this could be a career ending injury for the manager.

We live in the age of just-in-time delivery of feedstocks. Raw material inventory sitting in a warehouse is equivalent to having a big pile of money sitting there. Extended warehousing of raw material inventory means that some amount working capital is is not only unavailable, but is not earning interest in an account somewhere.

Every query a buyer issues is an opportunity to work on lowering prices. Some materials are purchased regularly while others are more episodic. Some companies have a policy of buying under contract and others are satisfied to issue a spot purchase order as needed. Some buyers may have favorite vendors and others may not. Shopping for the best price usually means that multiple vendors are tagged for quotations.

Sourcing information is increasingly dependent on the internet.  Mysterious job shops in Asia or the Ottoman Empire are as easily found on a web search as are the venerable giants BASF or DuPont.  A lot of filtration has to be done by the buyer to sort out the authentic from the wannabe’s. It has been my experience at trade shows and on the web that many Asian suppliers are so anxious to cash in on the export trade that they will say yes to virtually every query.  They are not dishonest, really. They just have a severe can-do attitude. I’d do the same thing.

In the end, a seller needs to remember this about procurement people- Always do your best to make them look good in front of their bosses. That means offering a decent price and an honest assessment of delivery dates. A good price followed by poor delivery will harm a relationship as fast as anything. Be honest, earnest, and on time and your buyer will be good to you.