Better Gadgets

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The National Nuclear Security Administration (NNSA) announced on 3-2-07 that the US would be pursuing the Reliable Replacement Warhead (RRW) program.  The program makes a lot of sense on many levels. But the timing of the press release is a bit odd.  Certain sandy states will no doubt notice the irony of the program. While the US is browbeating them into abandoning their dreams of a fissile future, we on the other hand are pursuing better and safer nukes.  Of course, we’ll argue that it is a smaller and safer stockpile, and I’m sure that is true. But I’ll wager that the next generation nuke will be designed for better efficiency as well. 

Maybe we’ll launch them from the new Cheney Class of submersible aircraft carriers…

New Failure Modes

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Chemistry can be very humbling.  A person can be absolutely sure of how a new reaction or process will turn out and yet be absolutely dead wrong.  Process research is an engine that consumes dollars and churns out new failure modes in one big pile and positive results in a smaller, steaming heap. 

I have been working with ionic compounds that have weakly coordinating anions.  I’m finding that my finely honed intuition built from years of shame, suffering, and cruel humiliation is turning up flat wrong more times than I care to admit. A house of cards.

More than a few of these compounds seem to participate in the formation of a liquid phase in the right combination of solvents.  If I were keen on monkeying with ionic liquids, this would be just dandy.  But the product is a solid and I want to purify it by xtallization.  I’m tempted to categorize these liquid phases as clathrates, but I’m unclear if the definition will acommodate such a thing. In each case, a normally miscible solvent pair is required to split out the new phase when the weakly coordinating ion pair is dissolved in the more polar solvent. 

There is a happy ending to this.  I was able to isolate solid product from a 2-solvent system, but sadly, I would be hunted down and shot like an egg-sucking dog if I disclosed it.  Bummer.

Clancy’s World of Spooks

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It is like a disease. I find myself drawn to Tom Clancy novels.  I picked up Rainbow Six the other day. Other than his Op-Center series, I think I’ve read most of his books.  Clancy is one of the most successful writers in this genre.  Airport bookshops have been good for him.  When I was in the travelling phase of my career, his books were great for passing the time in airports.  Millions of us have read his books.

And millions of us have read Clancy’s idealized interpretation of how the clandestine world operates.  I won’t indulge in a superficial crtitque of the genre or his writing. But I would like to suggest that a population of readers who have followed the characters and themes of his immensely popular books might have developed certain impressions or even, shall we say, expectations, of the those who practice this tradecraft.

After reading his highly detailed and richly woven stories, one might develop the idea- subconsciously, mind you- that the clandestine services were capable of doing anything they set out to do.  Could it be that decades of Clancy’s stories have adjusted the expectations of countless readers in tems of what was possible in the world of the black arts? Could it be that such fiction has inadvertantly prepared our minds in such a way as to accept the assertions of government leaders when they tell us that hostile states have certain threatening capabilities? Surely, with all of the assets and talent at our disposal, when our elected leadership says that a threat exists, can’t we be certain that the conclusion was based on well placed human assets and has been through a series of tests and filters to verify the accuracy and magnitude of the threat? 

For those in power, the notion of “expertise” is not only useful, it may even be critical.  We all want to know that our safety is in the hands of experts. It is a comfort thing. Leaders need to be able to assure the population that experts are on the job and all will be well. 

I would suggest that there is no such thing as “expertise” as an intellectual destination.  There is only a continuum of confusion.  And some of us are more confused than others.

UV-Vis Spectrum of POM Pomegranate Juice

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Below is a link to a UV-Vis spectrum of POM brand Pomegranate Juice.  The graph shows two spectra- one is a simple dilution of POM-brand pomegranate juice. The other, lower extinction, spectrum was a simple dichloromethane (DCM) extraction of undiluted pomegranate juice as it comes out of the bottle. The extraction was done with a 1:1 v/v ratio of DCM to juice. Notably, the DCM extract contained no visible color. The layers emulsified and had to sit for ~10 minutes to separate. The DCM extract was dried over a bit of magnesium sulfate and filtered.  The undiluted extract was submitted directly to analysis. The dashed curve is the spectrum of the extract.

What is interesting about the extract is that the absorption maxima do not align with the maxima of the whole juice.  The DCM soluble fraction is quite different electronically from the balance of the components. Indeed, the extinction drops off to 0.026 by 350 nm and drops to near zero thereafter.  It is important to note that the absorbance of the extract is based on a much more concentrated solution, so a direct comparison of absorbances with the highly diluted whole juice is not valid. Focus instead on the wavelength of the maxima.

I ran the spectrum of the whole juice as a 500 to 1 dilution in distilled water.  No attempt was made to buffer the pH of the water or to filter the juice. I fully realize that there are experimental control issues to contend with here- i.e., pH dependence, turbidity, oxidative degradation due to air exposure, etc. 

POM Pomegranate Juice UV-Vis

According to the literature, pomegranate juices contain varying amounts of polyphenolic, tannin-type species not just from the juice, but also material that is released from the rind in the pressing process.  So further experiments should try to obtain juice that is pressed in a way to discourage the inclusion of materials from other plant tissues.

According to one source, the components of pomegranate juice can stabilize the level of PSA in men who have prostate cancer.  Whether it works via the anti-oxidant properties or some other more specific interaction is unclear.

Just what is the point of running these spectra?  My original interest related to the visible part of the spectrum. I wanted to know what the visible spectrum of this intensely colored juice looked like.  What is evident is that for all of the extinction in the visible part of the spectrum (>350 nm), the UV band is much more intensely “colored”. That is, the extinction is much higher in the UV range (<350 nm). Why UV-Vis spectra?  Because, silly, I don’t have an NMR. But I do have a UV-Vis spectrometer.

Well, that’s not quite true. I can run a proton NMR of the crude material, but given that pomegranate juice is a plant fluid, all I’m going to see is a forest of peaks.  Actually, more to the point, others have isolated components from this fruit.  My interest is in the reduction capacity of the pigments.

Extracting structural data from a UV-Vis spectrum is not really possible. UV-Vis spectroscopy is about electronic transitions and a wide variety of species overlap appreciably, so structural determinations of components in complex mixtures is out of the question.  Furthermore, pomegranate juice is sensitive to oxidative degradation and is likely to be quite sensitive to pH (next on the agenda), so it’s thermal and O2 exposure history may be important (i.e., has it been Pasteurized, etc).  So it’s back to the drawing board.  

Worlds in Collision- Idiots Out Wandering Around

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I had the great privilege of doing my post-doc along side some smart and colorful folks.  Fellow post-docs from various parts of the world. In particular I was fortunate to have worked with some folks who came to the USA as Soviet scientists in 1990. Later all but one went back as Russian scientists.  This one in particular was a stunning beauty from near Lake Baikal in Siberia.  She was a first-rate experimentalist who was built like a fashion model from Paris.  She had “The Look”.

I recall the time she and I went to the Symphony.  She was dressed in a short and slinky green dinner dress with a plunging neckline below those electric eyes and high cheekbones.  I was a freshly divorced and mildly oafish- an ethnic Iowegian- chronically depressed and wrapped accordingly in a poorly fitting blue sport coat with tattered khaki slacks.  Just call me “Goober”.  OK. That’s Dr. Goober.  Of course, this was Texas so I fit right in …

As we entered the lobby, I could hear the necks creaking as heads craned in our direction with the odd slapping noise as jaws dropped to the floor. My colleague had that affect on people. Well, I’m not actually stupid. I could tell we were at the receiving end of many furtive glances.  But they were not admiring glances. They were questioning glances. As if to ask “What is that goddess doing with that imbecile?”  Now, being recently divorced and not unaccustomed to being stomped in the head by women, I took it in good humor and in stride.  For this lovely Russian beauty and I were dear friends and colleagues and it was my great privilege and pleasure enjoy the concert with her that evening in that stunning auditorium in San Antonio.

Today she is the Director of Chemistry for a startup pharma company. And me, well I’m a blogger.  Some months after this occurance, I attended a Gynocology convention with a friend who was doing her residency in OB-GYN. But that is another story.

Patent Sturm und Drang

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To patent or not to patent, that is the question. An innovation comes along and you’re left with this question. Ask (n) colleagues and you’ll get (n+1) opinions.  Ask a patent attorney and they will thrust a disclosure form in your face and firmly request documentation for an application.  When you’re a hammer, everything looks like a nail. You can’t blame attorneys for prosecuting things- it’s what they do.

A comment on attorneys.  Working with attorneys can be a very emotional experience.  The fact that you need one says that you are probably involved in something that is too big for you to handle alone. In the case of patent work, you don’t have to be an attorney to file for and receive a patent. But in order to take the USPTO to an appeals court, you do have to be a member of the patent bar.

Back to the emotional bit.  It is a thrill to see a good attorney working their heart out on your behalf.  Watching them navigate the procedures during the discovery phase and on into litigation is an amazing thing to see. To read the transcripts of your opponents deposition is to understand what power is about.  Conversely, watching the other sides attorney lunging for your throat (metaphorically, at least) with a procedural garrote, trying to lop off your reputation down to the bloody stump is terrifying indeed.  The legal profession is a brutal and bloody business when it is aimed at you.  But when they are working for you, they are jolly good chaps.

It has been my experience that the decision to patent is fundamentally a business decision.  Once you pull the trigger on this, you set yourself up for a lengthy series of legal expenses. And, you leave an indelible and credible paper trail in the public domain.  In some cases the expense and the sturm und drang is well worth the trouble.  If you are a large company, you might have actual attorneys on staff to do the deed.  If you are less than a large company, you will have to retain a law firm to do the prosecution.

When it comes to filing for a patent, is not uncommon for the client to heap everything onto the attorneys desk with a yellow sticky note saying “call me when it’s over”.  This certainly one way to do it.  But to do it this way is to neglect whay we even have attorneys at all.  An attorney is a hired gun.  They are your mechanical arm in the bewildering world of law. The attorney is working on the client’s behalf and the client really should be in the lead, backed up by an attorney, not the reverse. Easy to say but hard to do in practice.

In principle, the inventor and assignee should write the patent application, or at least the first draft.  To do this forces the inventor/assignee to think through what the invention really means for them.  After all, no one should know the art better than the inventor. And the inventor has some obligation to the assignee to assure that the art is fully captured in the appln.  

The attorney is best used in wordsmithing the application to it’s final form. The attorney can anticipate the consequences of the language that goes into the appln.  This is a huge contribution and is one of the main reasons you pay patent attorneys the big dough.  Having an attorney slog through the basics of the art, patch together the concepts from notebook pages, and synthesize the claims is an expensive indulgence the assignee probably can’t afford.  In short, the better researched and the tighter the copy you give the attorney, the more resources you”ll have for your  next patent appln.

Lanthanide Contractions and a Dog’s Lunch

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The rare earths are a curious group of elements from the commercial point of view.  There are a variety of lanthanide products available from a handfull of vendors, most of whom cater to a small group of users. Some of the catalog houses have respectable collections of them.  My friends at GFS offer lanthanides- specializing somewhat in cerium products.  Aldrich, Gelest, and Strem, of course, offer a variety of rare earths (RE). Hard to say if they are big sellers-I’m guessing they are on the slow side of the 80/20 rule.  I’m aware of a single American company that actually refines Scandium Oxide and manufactures Scandium Triflate as well. They are one of the few, if not the only, companys in North America that refines any RE’s. Most everyone else imports from Estonia, Russia, or China.

From my perusal of the literature it seems that the field partitions roughly into reagents for chemical transformations and oxides for material science.  The material science side is way beyond my reach, so I’ll pass on that segment.

The least expensive and most basic RE products are the oxides. If you spend some time shopping around for various RE’s, what you’ll find is a sliding scale of purity specs, 99%, 99.9%, 99.99%, 99.999%, etc.  If you look even closer to the specs, what you’ll find is some sleight of hand in regard to what the number of nines actually represents.  Most vendors will offer a number of 9’s that are TREO, Total Rare Earth Oxides. So if you are keen on Scandium Oxide, 99.99 % (or 4N), chances are that the 4 nines really represents the total of all of the RE oxides present.  In reality, 99.99 % TREO Sc2O3 will be 99.9 % in Scandium and the balance of the 4 nines is a dogs lunch of Ln Oxides. 

As we all know, when you analyze for more and more 9’s, you eventually find most of the periodic table present in your material.  But if you really want 99.99% in Scandium, it can be relatively hard to sort from the TREO products.  You are forced to swim through spec sheets to find material that meets your need. BSC offers 4N in Scandium, and some others do as well.

One of the interesting applications of RE triflates is as a water tolerant acid catalyst.  Essentially all of the RE triflates have been reported, with the possible exception of Promethium. The lanthanides show a general decrease of ionic radius as one increases atomic number. This is the lanthanide contraction. It has been shown that the catalytic activity in certain acid catalyzed reactions (i.e., with a Ln(III) triflate) correlates with the charge-to-radius ratio in this group.  Not surprising, I suppose. 

So, for an ambitious person with designs of bringing rare earth reagents to the marrket, this is a classic “technology push” situation.  In order to convince people to buy RE triflates as acid catalysts, you first have to offer a value proposition.  They can use conc H2SO4 or they can use Yb(OTf)3 as an acid catalyst. Hmmm.  So which is cheaper in my application?  Given the sparse literature on Ytterbium Triflate chemistry, for instance, it could be hard to convince a customer to adopt your RE product beyond R&D use.

So, whaddaya hafta do to sell a boat load of this stuff? You probably have to come up with a killer application for the RE Triflate to convince people to buy it and try it. If you as the purveyor lack this application, they you have to rely on the customer to do it for you.  In the mean time, you could get very hungry.

30 Years of Star Wars

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It has been 30 years since the release of the movie Star Wars. Back then I had just started a job at the local movie house as a projectionist. We had two Phillips-Norelco 35 mm projectors with Xenon arc lamphouses and 6000 ft reels. We’d splice 3 x 2000′ shipping reels onto one reel so that there would be fewer changeovers. 

The theater owner put down a $10,000 non-refundable deposit on the print and paid 90 % of the ticket sales to the distribution company for the first 6 weeks. So for the first month and a half, we made our money on popcorn, cokes, and Junior Mints.

In 1977 Star Wars was THE blockbuster of all time. We had sell-out crowds every show for the first 2 weeks. The concession girls could barely keep up with the popcorn demand. Other theaters were popping corn for us in an attempt to keep up. We blew through 5 gallon syrup cylinders like spent cannon shells on a battleship in Guadalcanal.

I ended up running Star Wars 186 times. But it was far from routine.  The projector chewed up a bit of the end of reel three, the famous dumpster scene. Unfortunately, I was operating the night the print failed. The projector shredded about 20 feet of film (18 inches/sec) in several places and the resulting film break  caused the automation to switch on the houselights, close the curtain, and start a Neil Diamond 8-track tape playing for the audience. After 3 seconds of bewilderment, the crowd turned ugly and started shouting and storming to the lobby to complain. The film stopped at a very exciting point and the customers were none too happy.  I didn’t venture downstairs.

I was a casualty of Star Wars and actually had to be taken to the hospital during the run.  In trying to investigate the source of some troublesome image chatter, I got my finger caught on a sprocket and ran it between the teeth and the guard post.  Ended up with a meaty gash that required stitches.  Of course, I never told George Lucas…

The print grew progressively worse over time. The dumpster scene would chatter through the film gate in defiance of our best adjustments.  But despite this, few complained when they walked out of the theater. It remains a great movie.  Eventually, as a college student I moved up to a 4-plex theater with platters and automated Simplex 35’s.  This night job paid for much of my BA in chemistry. I read much of Solomons Organic Chemistry in the projection booth.

Solar System Simulator

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NASA has a great website with a solar system simulator in it.  For instance, it will simulate the positions of the various satellites of the planets.  It also gives the user a choice of sites from which to take in the view.  So, if you are going to look at Jupiter some evening through your backyard telescope, you should be able to identify the 4 brighter moons.