Bloggenvolk

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It would could be fun to meet other bloggers at the ACS meeting in Chicago.  Eventually we’re going to have to have some kind of official (ACS sanctioned) function where bloggers can get together at these meetings.  We’re all driven to write about chemistry in one way or other and I’d say, for the most part, we’re all smitten with this science.  Chemistry bloggers are science writers.  We write because we are driven to do it.

It would have to be done in a way that is not threatening to anyone.  Basically we’re all anonymous writers.  I suppose that fact could be viewed as kind of creepy in some way- I don’t want to run into some wacko either.  But wouldn’t it be fun to sit with other bloggenvolk at the convention hall and chat?  I think it could be lots of fun. The pseudonym stuff wears thin. 

Eventually it’ll happen. This mode of communication isn’t going to disappear anytime soon.

Active Denial System- RF Radiation Weapons

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It appears that some of our clever friends and neighbors at the local military/industrial complex have been busy designing millimeter-wave radio frequency weapons.  Last year the DoD announced the development of a new form of weapon billed as non-lethal to fill the “gap between shoot and shout”.  The device consists of a powerful rf source and what must be a fairly narrow beamwidth antenna for illuminating unruly people.  The website includes video clips of test subjects and their descriptions of what it feels like to be on the receiving end of this radiation weapon. 

I refer to it as a radiation weapon because that is precisely what it is.  Millimeter wave radiation is directed at a person or a crowd and in short order the recipients in the beam feel their skin temperature rise to discomfort. Whether it truly raises skin temperature or the sensation is an artifact of surface electrical currents in the skin is unclear. The fact is that it can cause instantaneous discomfort and anxiety about burning to a crisp.  Obviously, the purpose is to discourage aggressive behaviour in individuals or of crowds and do so in a non-lethal manner. 

So, really, what is wrong with this?  In a sense it is like a shock collar on a dog.  An occasional burst of juice causes the unruly dog to suspend the offensive behaviour.  The dog learns the lesson and is not physically harmed by it. 

I’ll admit to being quite uncomfortable with this “technology”.  The potential for abuse and exploitation is staggering.  If a short burst of rf energy will cause people to scatter or desist their behaviours, what will a long exposure do?  And, just what happens to someone on prolonged exposure?

What is the difference between negative reinforcement and torture?  Is it the difference between a 5 second exposure and 60 seconds?  And, when will a tin-pot dictator acquire this capability now that we have proudly trotted ours out?  Whereas ours will have controls for non-lethal operation, would a terror group or arms merchant bother to have safety protocols to guard against overexposure? Maybe a stripped down version absent interlocks will be the weapon of choice among African dictatorships.

How long will it take for civilian units to come on stream? What US city will be the first to acquire one of these things for crowd control and when?  LA?  DC?  NYC?? 2015? 2020?  Pretty soon every SWAT commander will be clamoring for one “just in case”.  Whose march on the Capital Mall in DC will trigger the first use of such a device on civilians? 

Can the energy be reflected back to the source or in some other direction?  Is a metal trash can lid or aluminized mylar blanket an effective countermeasure?  Maybe we’ll see rock throwing 12 year olds in Gaza with a stone in one hand and a trash can lid in the other after its inevitable introduction in the middle east.

Microwave/millimeter technology is ubiquitous.  No nuclear materials. No ammunition.  Just a powerful rf source and an antenna. No doubt arms merchants are already lining up buyers for this weapon of mass agony.

What a lamentable development for mankind.  Our ability and willingness to commit violence from a distance is one of our greatest downfalls.

Tvashtar’s Plume

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While we ground pounders were conducting our tedious lives deep in earths gravity well, the Pluto-Kuiper Belt probe “New Horizons” made it’s closest approach to Jupiter on Wednesday, 28 February, 2007. Swinging past this enormous ball of gas for a gravity assist, the probe trained its LORRI imager on the moon Io and caught an amazing picture. The photo shows the volcano Tvashtar ejecting a plume 290 km from the surface.  On the left one can also see a plume of ejecta from the volcano Prometheus. 

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.