Friday Fun: Masthead Surprise

Ever stop and read a magazine masthead? Y'know, the page where they list all the editors, staff, and Board members?

Sometimes you find fun* surprises.

 National Geographic Magazine

*Please state your answer in the form of a question...

Calimari Calligraphy: Same Ink, 160 Million Years Later

Old news: Geologists, digging up ancient British sea bed, unearth a fossilized cephalopod.


Big news: Its pigment sacs contain the same ink squid still use today!

Fossilized Ink Sac
Source: British Geological Soc. | Nat Geo

This archaeology, with a dash of chemistry for good measure, went to press in PNAS earlier today. As Nat Geo, Discovery News, and msnbc tell it, a stroke of luck brought the multi-national (Japan, India, USA, UK) team a fully intact ink sac, which still contained eumelanin, the ubiquitous black pigment found in skin, hair, and feathers throughout the biological world (for more on the structure and function of melanins, click here).  


Quoth the lead author, John D. Simon (UVA-Charlottesville), to Discovery: 

"Out of all of the organic pigments in living systems, melanin has the highest odds of being found in the fossil record" 

In other words, this collection of highly-oxidized tyrosine and indoleacetic acid residues, chained into polymeric pigments, stays preserved - and structurally sound - for 160 Million Years. Could we say that about most of the materials we make today? Moreover, by comparison of various spectral techniques, the authors wager that the ancient melanin composition looks nearly identical to what squid use today to scare off predators.

IR Data, "flipped"
Source: PNAS Supp Info

Well, I'd like to see some data, wouldn't you? Digging through the Supporting Info, I see loads of evidence: degradation studies, EPR, IR, Mass Spec, CHN analysis, Carbon-13 NMR, UV, pyrrolysis TIC, and X-Ray photoelectron spectroscopy (Whew!). 


Let's examine two of these a little closer. For the IR data, I've switched the view around 180 degrees, to present the peaks the way you'd normally see 'em in the lab. Note the top 2, calcium carbonate and hydroxyapatite, with their nice, sharp C=O and P=O stretching bands. When the researchers looked in the partially-fossilized sediment, they found mostly these two...but look at the dye! Even after all those millennia, the absorbances for the fossil dye line up almost perfectly with the modern-day sample.

Total Ion Chromatogram, Current (top) vs. Fossil (bottom)
Source: PNAS Supp Info

How about a little heat? If you cook the ink at 600 Celsius, then pass it quickly through a mass spec, plotting ion current vs. time, you get the next spectrum, the TIC. It shows the same breakdown products, a variety of small heterocycles and fatty acids, and something I wasn't familiar with: diagenetic products. These products, formed from reactions that occur during fossilization, show up here as sulfur heteorcycles. Since the samples have had quite a bit of time underground, they show much more diagenetic decomposition. 

The Chemistry Popularity Conundrum

Last week (October 16-22) was National Chemistry Week in the US. Did you celebrate? By all rights, it could have been the biggest one yet, since we’re deep into the tenth month of the International Year of Chemistry (#IYC2011). Did you see any news specials? Did Time or Newsweek run an exposé?

Credit: time.com

Probably not, but why not? When scientists cracked the human genetic code, front pages everywhere relayed the tense horse-race between Venter’s TIGR and Collins’s Human Genome Project. Whenever physicists flip the switch at the Large Hadron Collider, the public dreams of mini-black holes and cheating Einstein’s relativity. Chemistry, however, always seems to be the black sheep of the gang; DuPont’s slogan for nearly 50 years was “Better Things for Better Living . . .Through Chemistry,” until the final portion of the tagline was dropped in the mid-‘80s.

What creates the chemistry image problem? It’s true that many of the “pure chemistry” accomplishments of the last 30 years have gone largely unnoticed: ask someone at a local restaurant about triblock copolymers, organocatalysis, brevetoxin, or dye-sensitized solar cells. Applied chemistry fares a bit better, from polymers to paints, lasers to ligands, but the public still attributes many interface discoveries to other fields – drug chemistry gets lumped into “Health and Medicine,” or water-splitting tossed in with “New Energy.”

Don't let the test-tube on the front fool you.
Credit: amazon.com

The phenomenon even reaches general science books. On a whim, I opened up National Geographic’s The Science Book (bonus tagline – Everything You Need to Know about the World and How it Works) at a book store last week. A hefty volume, coming in at 432 pp., thus you might expect the “central science” to occupy at least 30% . . . right?

Wrong. Page count: biology, ecology, and sociology – 142 pages.  Physics, math, and ‘technology’ – 111 pages. Chemistry? 26 pages.

Total.

Does this all come down to poor public relations? Biology sells itself on some big questions: origin of life, evolution, ending disease, and genetic engineering. Physics moves out onto an even wider plane: does God exist?, fundamental particles, dark energy, string theory, and black holes. Ask most people about the word chemical, however, and their connotation is tangibly negative, associating the word with poisonous, pollution, ersatz stand-ins for “genuine” flavors or fragrances, artificial, corrosive, or toxic.

Prof. David MacMillan, Princeton

Not that none have addressed the issue – just recently, David MacMillan, editor of Chemical Science and accomplished organic chemist, called for increased outreach:    

‘One major thing chemists need to work on is their ability to promote their work to other scientists and the public. This is something we are really not good at in general and if we improved, it would really open doors for us and improve society’s perception of chemistry and its impact.'

ACS attempts much the same with their Chemistry Ambassadors program, and the Interactive Periodic Table of Videos surely adds some demonstration “Wow!” factor. But the days of science-themed programs (Mr. Wizard, NOVA, How it’s Made, even the tongue-in-cheek Look Around You) seem to have waned, and Mythbusters can’t save the whole genre single-handedly. Linus Pauling, Noam Chomsky, Carl Sagan, Stephen Hawking, Steven Pinker, E.O. Wilson, and Oliver Sacks have held down much of the science PR fort, but we still haven’t found the next great chemistry “populizer.” So, what are we to do?

Can these guys hold down the science program genre forever?
Credit: dsc.discovery.com

Well, I’m not the first to tackle this question. Luckily, many have gone before me: see Dr. Free Ride’s post on Scientopia (“navel-gazing” sounds so apropos) or the CHEMisperceptions Blog Roundtable from early 2011 hosted at ScienceGeist. Start there, and glance through the situations and stories these authors present. See where you stand.

And think. Just think.

Think about how you’ll answer the dreaded “So, what do you do?” question at the next holiday party. Think about a show you wish were on TV, DVD, or radio that covered breaking-edge reactions or materials, but isn’t. Think about how you might tell such a story. Think about what types of jobs you, as a chemist, might envision working in 10, 20 years . . . if they even exist right now! Think of the reactions, equations, elements, polymers, or drugs (heh) that really ‘get you up’ in the morning.

When you’ve thought awhile, narrow down your list to one or two things you truly enjoy. Write a short blog post or a newspaper article. Send an email. Take some pictures. Tell your kids. Teach a short course. Write a book. Produce a show. Anything you can do that creates new, high-quality content to help improve the stead of science in the world will do.

Idealistic?  Sure.   

Dreamy?  You got me.

Possible?

. . . I’d like to think so.

(Note: You don’t have to start from nothing - there’s quite a few folks already working on the problem. For general chemistry blogs, start at CENtral Science. Work your way around to Chemistry Blog, Discover Magazine, SciAm Blogs, and Popular Science. Chemjobber, The Curious Wavefunction, and ChemBark help capture some of the current chemical zeitgeist, while Totally Synthetic and BRSM cover my favorite topic, chemical synthesis. For health and medicine, try In The Pipeline or The Medicine Show. Want books? Napoleon’s Buttons, The Poisoner’s Handbook, Mauve, and Uncle Tungsten are a few favorites. On a personal note, although he’s not formally a chemist, Surely You’re Joking, Mr. Feynman! and What Do You Care What Other People Think? helped me appreciate how one can use scientific curiosity to change the world.)

Rare Earths, Common Problem

Rare earth elements have made quite a stir lately: just last month, both Discover and National Geographic have written full articles about these 17 unique metals, which comprise the top part of the periodic table “f-block” (plus scandium and yttrium). Pundits and scientists alike are anxious that the US won’t be able to compete in the high-tech sector with scarce domestic rare earth supply.

Discover’s Hugh Aldersey-Williams (July / Aug 2011, p. 62) takes the historic view, starting from the elements’ first discovery in Ytterby, Sweden (1787, yttrium) and wending through the myriad of uses for the rare earths in modern-day electronics, hybrid cars, lighting, and materials.  The NatGeo article (June 2011, p. 136) takes a decidedly more polemically charged stance, peeking over the fence at China’s 97% share of the world rare earths market. Reporter Tim Folger argues that China’s unmatched mining infrastructure, coupled with lax environmental restrictions and cheap labor, make it tough for US miners to compete, despite the importance of a regular supply – the world demand for technology items such as iPods, wind turbines, flatscreens, and military equipment may drive lanthanide demand to a projected 185,000 tons by 2015, of which the US can only account for 5,000 tons of production. Worse, Folger bases this estimate on the production of a single mine (Molycorp) in California.

So what’s the impact for synthetic chemists?

Many of our favorite reactions use these metals. Lanthanum and scandium triflate promote aldols, acetylation, imine addition, cyclopropanation, and guest-star in new reagents like Leighton’s “EZ-crotyl” (JACS 2011, 6517). Samarium diiodide, a 1-electron reducing agent with a penchant for carbonyls and halides, underlies the Evans-Tischenko and Barbier couplings.  Cerium ammonium nitrate (CAN), a stable, off-the-shelf oxidizer, plucks off TBS and PMB groups, and promotes oxidative fragmentations. Perhaps even more worrisome is that the cerium and samarium reactions usually use the metal-containing reagent in large excess.

How can we fix the problem? New labs might find themselves conducting cost-benefit analyses simply to see if the improved reactivity or selectivity offered by these metals is worth their increased price (the Hoveyda-Grubbs 2^nd-gen catalyst, a highly active precious metal catalyst based on still-rarer ruthenium, runs $671 USD / 2g).  Perhaps the NSF will step in to issue challenge grants to develop catalytic processes intended to wean us from rare earth excesses. Either way, we’ve got to figure it out soon; as the US has shifted to a service-based economy, we’ve lost many skilled laborers (steel workers, miners, heavy industry) and may not be able to increase our rare earth capacity quickly enough.

Updates (July 28, 8:15PM) - Ever-helpful editor @carmendrahl informs me of a fantastic rare earth cover story from C&EN.  Others showed me the WIRED post about the US stealth fleet.

(July 30, 7:40AM) - Here's a July 2011 story in Scientific American debating the potential for harvesting rare earths from ocean floor sediment. Says Duke researcher Cindy Van Dover: "Four thousand meters in the deep ocean is a long way down"

(August 27, 10:36PM) - Commenter gippgig refers to Science News cover story, see here