July 03, 2009

Reactions - Ian Fleming

Ian Fleming is an Emeritus Professor in the Department of Chemistry in the University of Cambridge, and worked on a range of topics in the general area of synthetic organic chemistry. He is best known as a pioneer in applying organosilicon chemistry to control the regio- and stereo-chemistry of a variety of organic reactions.

1. What made you want to be a chemist?

A short answer is: because it was transparently interesting. But it is much harder to identify why I found it so. When I was eleven or so, I had a chemistry set - an almost useless one - which I augmented with purchases from a chemist's shop over the road from my school, with a Bunsen burner, conical flasks, glass tubing, funnels etc., and with a few items my father brought home from his work as a metallurgist, like copper sulfate, and concentrated hydrochloric and sulfuric acid. The first few years of school chemistry seemed to me obvious. The chemistry master, Mr Timbrell, had written an excellent book with the School Certificate syllabus in it; I read it, understood it and remembered it. I repeated what I could of it at home, and at school sat at the back of the class playing chess while he droned on and on. The subject really came alive when we got to organic chemistry in the sixth form, taught by Stan Featherstone, who arranged for me to stay after school and carry out experiments from Mann and Saunders' textbook. I had made about 50 organic compounds by the time I left school, more than all the ones I made as an undergraduate, so I was an experienced practical chemist early on. My other subject was biology, which I fully expected to be a part of my career, but when I met biochemistry at Cambridge I soon realised that the only part I found interesting was metabolic pathways - the chemistry. At the same time, in my second year, we met organic reaction mechanisms, first from Peter Sykes and then more compellingly from Malcolm Clark, and molecular orbital theory from Christopher Longuet-Higgins. The subject began to have a satisfying intellectual structure, and I was hooked. From then on, and especially in the next four or five years, I was able to order all my organic chemical knowledge into a coherent framework, to which I've been adding all the time. So a second short answer is: Stan Featherstone, Malcolm Clark and Christopher Longuet-Higgins.

2. If you weren't a chemist and could do any other job, what would it be - and why?

Realistically, of course, I would have been something close to a chemist: a biochemist or even maybe a doctor, but that is not interesting. Moving away from science, and choosing something from within my competence, I might have liked to be a photojournalist, because you get to see extraordinary things and people. I might equally have answered a film director, if I were allowed to interpret the words "could do" in the question to mean that I had magically been given the talent.

3. What are you working on now, and where do you hope it will lead?

I am rewriting my textbooks - I've finished and published the sixth edition of the Spectroscopic Methods book that Dudley Williams and I wrote, and am now putting the finishing touches to two versions of a book to replace my Frontier Orbitals book, which is now an astonishing 33 years old. I have a 300-page "student" edition at the same level as the Frontier Orbitals book, and a 550-page "library" version, with all the references and much more material, for those who want more. As before, it treats the subject without mathematics for the benefit of all those organic chemists like me who have little mathematical aptitude but want to understand the subject in a physical way. The new versions will be called Molecular Orbitals and Organic Chemical Reactions, with less emphasis on the Frontier Orbitals. My next task will probably be to look again at an even older book of mine: Selected Organic Syntheses.

4. Which historical figure would you most like to have dinner with - and why?

Samuel Johnson was arguably the wisest man ever, and good company. But a great many other names come to mind: Queen Elizabeth I, Henry James, Virginia Woolf, Orson Welles, Shakespeare, Billy Wilder? What a dinner party.

5. When was the last time you did an experiment in the lab - and what was it?

Some of my later co-workers may remember my showing them how to get crystals - a lost art it seems, but I don't think that counts as an experiment. The last preparation I remember was the preliminary work for the indole syntheses that Mike Woolias developed, when I prepared the way for him, by establishing that the reaction worked. It involved an amino group displacing an aryl halide, long before Buchwald and Hartwig, and without any transition metals being necessary. I remember leaving a reflux going to open an epoxide with benzylamine in ethanol, while I went to the Oxford Synthesis Meeting in July 1973, and coming back to find that not only had the epoxide been opened but the intramolecular displacement of the ortho bromide had also taken place.

6. If exiled on a desert island, what one book and one music album would you take with you?

It's always difficult to restrict oneself to one. It would have to be big. War and Peace, perhaps, or is one allowed the whole of Shakespeare? For music, it would have to be the late Beethoven quartets.

7. Which chemist would you like to see interviewed on Reactions - and why?

David Evans of Harvard, because he is inspirationally thoughtful in teaching and research.

Lindau09: Twitter round-up #4

Here are the highlights from yesterday's tweets from the 2009 Lindau Nobel Laureate Meeting

7.43am Final day of lectures here in Lindau (although not the final day of the meeting), and this morning will be a GFP extravaganza!

8.02am Shimomura is first up - telling us about the chemistry of bioluminescence

8.19am Interesting fact of the day from Shimomura who tells us that krill is the most abundant animal on the earth

8.31am Chalfie - I'm the accidental Laureate that got into the middle of this - he works on sensory mechanotransduction

8.33am Chalfie has spent a lot of his career 'tickling worms' - C. elegans that is - to find out how they respond to touch

9.08am Students and postdocs are the real innovators in science according to Chalfie

9.13am Final lecture of the 1st session is given by Roger Tsien - who will tell us about some of the mistakes he made & where he got lucky

9.48am Tsien - 'normally there is nothing green inside a mouse'!

9.51am Tsien has yet to run a gel or do a PCR reaction in his life - if he had to hire himself, he wouldn't do it!!

10.01am Schrock takes the stage - co-recipient of the 2005 chem prize (http://bit.ly/axqQt) - apologises for not being at the whole meeting

10.34am Schrock shows some 14 electron Mo catalysts that have 4 different groups on the metal centre - chiral metal catalysts on the way?

10.42am Take home message from Schrock - air-sensitive catalysts are good (not bad) if they can do something other catalysts can't

10.46am Final formal lecture of Lindau 09 given by Werner Arber, Laureate in Physiology or Medicine from 1978 (http://bit.ly/g1V74)

10.52am Arber is using a computer slideshow for his talk on 'Molecular Darwinism' - but all the slides are drawn by hand!

July 02, 2009

Lindau09: Island hopping

Tomorrow the Lindau Meeting shifts to another island in Lake Constance. Early in the morning, delegates will climb aboard a boat and be ferried across the lake to the island of Mainau - a trip taking more than a couple of hours. Here we will be treated to a panel discussion about 'Global Warming and Sustainability' with quite a distinguished line-up. As well as Laureates Molina and Schrock, the panel also includes Rajendra Pachauri, Chairman of the Intergovernmental Panel on Climate Change (IPCC) - which won the Peace Prize in 2007. Other participants include the author Bjorn Lomborg, and Professors William Moomaw and Thomas Stocker.

Because it is unlikely I'll have good web access tomorrow, I figured I should briefly post about Thursday's activities before I go. The first session of lectures amounted to a green fluorescent protein (GFP) extravaganza, with talks from Shimomura, Chalfie and Tsien (last year's recipients of the chemistry prize). We were treated to some very colourful slides, including a green bunny and the incredible hulk! It was nice to hear both Chalfie and Tsien talk about Doug Prasher's contribution to the area - the 'missing' Laureate in GFP research.

Both Chalfie and Tsien had stories to tell about getting their seminal papers published. Editors at a certain high-profile journal objected to Chalfie using the word 'new' in the title of his paper, saying that all work they published was new! Perhaps more amusing, however, was when someone from the art department got in touch with Chalfie about his cover image - they really liked the picture, but there was one colour they didn't really like to use on the cover, so could they get rid of the green...?! 'No', said Chalfie.

Tsien's story about publishing the crystal structure of GFP was one of referee trouble (at the same journal Chalfie struggled with). The first referee said that it was a competent crystal structure, but the protein was not very interesting! The second referee said it was all well and good but the paper didn't answer the most important question about GFP - it's biological role in the jellyfish! The manuscript was rejected and when Tsien appealed, the editor sent it to a third referee. Many months passed, however, and the third referee never replied. Then, on the internet, Tsien found a comment from someone saying that they had solved the crystal structure of GFP and it was coming out the following month in a different journal - Tsien forwarded this to the editor and the paper was accepted the next day! Moral of the story - be careful what you say on the internet...

Both Chalfie and Tsien had some great quotes - I include a few below (I can't guarantee that I have the wording exactly correct, but the meaning remains unaltered):

Chalfie:

It's very hard to tell if an animal is touch-sensitive if it is dead!
I'm the accidental Laureate that got into the middle of this.
Students and postdocs are the real innovators in science.

Tsien:

Biology has the most interesting grand questions in all of science currently doable by individuals.
I was no smarter the day after I received the Nobel prize than the day before, but it made me a lot more famous!
Prizes are ultimately a matter of luck, so avoid being motivated or impressed by them.

After the coffee break, the final two lectures at this Lindau Meeting were delivered by Richard Schrock (Chemistry 2005) and Werner Arber (Physiology or Medicine 1978). Schrock gave us a tour through his Mo and W metathesis catalysts, showing some recent work on being able to make Z-olefins, rather than the more thermodynamically stable E isomers. He was also eager to point out that although his catalysts are air and water sensitive (in contrast to the Ru catalysts of Grubbs and others), this does not matter if (i) you're making a billion-dollar drug or (ii) there is no other way of doing the same reaction. Anyone out there in pharma-land wish to comment on part (i)?

Finally, Countess Bernadotte wrapped up this part of the meeting, thanking the Laureates, the young researchers, the organisers and even the media - very nice to get a mention! We then headed off with Schrock to film with two students, although extracting a Nobel Laureate from adoring fans who want photos and autographs is not an easy task... but eventually we made it to the shoot location in a nearby hotel. Once that was finished, my headache finally got the better of me and I headed out of the heat and back to where I am staying - and now because it's a really early start tomorrow (and I'm not a big fan of those), I'm off to bed...

Stuart


Stuart Cantrill (Chief Editor, Nature Chemistry)


PS: There are lots of other people blogging from the meeting - check out some of these posts and have a poke around at each place for other Lindau entries here, here, here, here and here (apologies to those posts/bloggers I may have missed - feel free to leave links in the comments to this post).

Lindau09: Twitter round-up #3

Here are the highlights from yesterday's tweets from the 2009 Lindau Nobel Laureate Meeting

Wednesday 01 July

8.02am Day 3 begins here in Lindau and first up is Rudy Marcus (http://bit.ly/3tUJT) - sole recipient of the chemistry Nobel Prize in 1992

8.38am Next speaker is Kurt Wüthrich (http://bit.ly/dBaqV) who won a half-share of the 2002 chemistry prize

8.43am Wüthrich uses his belt to represent the human genome... 1.8 m of DNA - although he says his belt is not quite that large (yet)

9.16am The final talk before the coffee break is Sir Harry Kroto (http://bit.ly/Kd08W) speaking about science, society and sustainability

9.22am Kroto just explained chemistry and life in 30 seconds (I think he may have skimmed over a few important bits)

9.40am Kroto - if no-one finds a use for C60 soon, I may have to give the prize back...!

10.23am Coffee break over and Robert Huber - Laureate in '88 (http://bit.ly/2lwtV5) - is speaking about the destruction of molecules

11.13am Coming to the stage now is Walter Kohn - co-recipient of the Nobel Prize for Chemistry in 1998 (http://bit.ly/dvcaL) with Pople

11.20am Kohn is showing us a film he made called 'The Power of the Sun' - narrated by, if I am not mistaken, John Cleese!

11.44am Kohn would not be surprised if our two major forms of energy are solar and wind after the transition from fossil fuels

11.51am Final speaker today is Peter Agre - Laureate in Chemistry in 2003 (http://bit.ly/J6Hxl) on canoeing in the arctic

12.02pm Agre points out that one of his companions on his Arctic trips deserves a Nobel Prize for baking bread using camp fire & stones!

You can read Stu's full take on yesterday's proceedings in his post Lindau09: And now for something completely different.

Lindau09: And now for something completely different

Wednesday morning at the Lindau meeting saw a full slate of talks from half-a-dozen Chemistry Laureates: Marcus (1992), Wüthrich (2002), Kroto (1996), Huber (1988), Kohn (1998), Agre (2003) - and some of the highlights are covered below...

Marcus joked that he was going to speak for a couple of hours, but finished exactly on time after 35 minutes, giving us a tour of catalysis in many different forms, such as the 'on-water' work by Sharpless through to single-molecule enzyme catalysis. The next lecture was from Wüthrich, who started off by telling us that 'NMR' does not stand for 'no meaningful results' and then proceeded to take off his belt - and fortunately he stopped there! He then went on to use his belt to illustrate the human genome.

The final talk of the first session was from Kroto, who spoke on themes of science, society and sustainability. His lecture was a barrage on the senses (albeit a very entertaining one), with slides popping up at a high rate of knots, with occasional sound effects to boot. We were shown examples of artwork that Kroto had produced, including stamps, and even a new design for the flag of Japan. He then moved on to topics such as creationism and religion in general, Web 2.0 opportunities for science and scientific education, and the fact that he may have to give his prize back if no one finds a use for C60 in the near future! Kroto left the stage to the longest and loudest applause of the meeting so far.

After the coffee break, Huber was the first speaker, although the computer on which the presentations were loaded would not play ball. Problems finally solved, he went on to tell us about protein degradation. Kohn was next up and apart from a brief intro and wrap up, his 'lecture' consisted of showing a film he had made, called 'The power of the sun' - narrated by John Cleese of Monty Python fame. No ex-parrots in sight unfortunately! The final talk of the day was given by Agre, who told us about his canoeing trips in the arctic and sub-arctic. Although he tied his talk to environmental themes and climate issues, such as the changing migration paths of caribou and the impact on native hunters, it was hard not to think that we were just seeing his holiday snaps (very pretty ones, nonetheless!).

Lectures over for the day, I went to help out the film crew once more. The first shoot was a conversation between one of the young researchers (Tyler) and Ernst. As the storm clouds gathered in the distance and the thunder got louder, lightning crackled across the sky and the heavens opened - making filming impossible. With lots of camera equipment and a Nobel Laureate in tow, we tried to take the most direct (and driest) route back inside the conference venue. Our way was barred by the conference stewards, who probably assumed we wanted to film the afternoon discussions (which is not allowed - in fact, no press are allowed in those sessions at all) - whereas all we wanted to do was get inside to then go and find a new location. Tyler came to the rescue — his German being better than any of ours — and finally persuaded the stewards to let us in... he pointed out that we had a Laureate with us, who probably shouldn't get soaked in a thunderstorm. So, there you have it, getting the call from Stockholm can open doors for you!

Two shoots later, with Ciechanover and Tsien, it was time to wind down for the day and plan our activities for Thursday - just one shoot I need to be at today, so may have a little free time later this afternoon to explore Lindau. There may not be a post tomorrow, as we're off to the island of Mainau and away from the wireless access here in the Inselhalle, but they'll be a couple of more Lindau posts at some point.

Stuart


Stuart Cantrill (Chief Editor, Nature Chemistry)

July 01, 2009

Weird Words of Science: Azote

I was playing Scrabble online the other day and when a z materialized on my rack near the end of the game was desperate enough to try "azo". Good news, what I thought was chemist's shorthand, the dictionary thinks is a word. "Azo" has been part of my vocabulary since I was very young. My dad's graduate work was on azides - molecules that contain three linked nitrogen atoms (N3) tagged at the end and that are notoriously unstable (a fancy chemistry term for "could explode at any time" - at a dinner for his PhD adviser some 25 years later the number of people around the table lacking fingers was astounding). Azo compounds are molecular relatives of the azides - molecules that have an two linked nitrogens in the middle (R-N=N-R). Some azo compounds are brightly colored and generally they are more stable than azides.

As a rule of thumb, if you see "azo" in a compound's name, it's likely to have nitrogen in it somewhere. Why? French chemist Lavoisier dubbed the fraction of air that cannot support life "azote" from the Greek azotos: without + life. We now know that roughly 80% of the air we breathe is nitrogen gas - hence the connection between azo and nitrogen.

Lavoisier's alternate terms was "mephitic air" -- another Greek import, this time from the name of the goddess who prevented noxious smells from arising from sewers: Mephitis. Ironically, while many nitrogen compounds smell awful (dead fish anyone?), nitrogen gas, Lavoisier's mephitic air, is odorless. That goddess has lent her name to smellier pursuits though - the striped skunk's Latin name is Mephitis mephitis. I can personally attest to the smell.


Photo used under Creative Commons license. Credit to Kevin Bowman.

Comment 1 (Lindau09: Art meets science)

I first heard about anthropogenic climate change in a graduate course I took from Rowland (who also taught me general chemistry!). I'm always fascinated with the naysayers who want to tag warming as a "liberal fantasy" - since the first research came out of the military at the end of WW II?!

Lindau09: Reflections on day 2

Tuesday morning at Lindau saw three talks from Laureates - Aaron Ciechanover (Chemistry 2004), Mario Molina (Chemistry 1995), and Erwin Neher (Physiology or Medicine 1991). Unfortunately I was called away just at the start of the first talk to shuttle our van around Lindau and only made it back half-way through Molina's talk. Jason - one of my colleagues here - had it even worse, however, as he headed over to Zurich (almost a 300-km round trip!) to pick up essential equipment for the film crew.

After the coffee break, we were treated to the first of two panel discussions here at the meeting - this one was about the role and future of chemistry for renewable energy. Sitting on the panel were Laureates Ertl, Grubbs, Kohn, Kroto, Marcus, Molina and Rowland - quite a line-up! The moderator framed various problems at the opening of the discussion, in particular (i) the fact that fossil fuels will not last forever, (ii) anthropogenic climate change as a consequence of carbon dioxide and other greenhouse gases, and (iii) security problems with nuclear energy technologies. Each Laureate was invited to respond in an opening statement and some snippets are included below.

Ertl reminded us that we cannot create (nor destroy) energy and that our problems simply boil down to how we can harness the power of the sun to produce useful energy that can be stored in a practical fashion - he suggested that silicon photovoltaics are potentially a promising way forward. Grubbs reminded us that he was the only organic chemist on the panel (the first time I've heard him describe himself as an organic chemist!) and that materials science is a crucial and enabling technology for renewable energies, in terms of making energy storage and transport more efficient. Kohn summed up the situation by telling us that tough problems must be tackled by viewing them from many different perspectives.

Next was Kroto, who said that we need to recognise the scale of the problem - telling us that it takes a million years to produce the quantity of fossil fuels we currently consume each year. Water splitting is what we should focus on in his opinion - and recounted someone telling him that if 'stupid' trees can do it, then we should be able to do it too! The problem is that trees really aren't that stupid after all - nature has had a long time to figure out photosynthesis. Sir Harry went on to criticise how science is funded, and pointed out that breakthroughs often come from blue-sky research and that governments and funding agencies should continue to fund such work.

Marcus was next and brought up the point that not only is solar energy conversion an important societal challenge, but is also a very interesting and stimulating intellectual challenge. Large numbers of researchers and good collaborations are required - and he suggested that a mini Manhattan Project is in order (obviously with a very different goal, but using the same principle of bringing together leading scientists and engineers from around the world to tackle a pressing problem).

Molina and Rowland rounded out the opening statements, with Molina suggesting that society needs to double or triple its investment in renewable energy - and although it may look self-serving for a scientist working in this area to say this, it is wholly justified. Finally Rowland lamented the fact that he had to say something original after following six other Laureates! Nevertheless, he did, saying that we should focus on getting rid of carbon dioxide from the atmosphere and also look at other nuclear fusion approaches, although he was less optimistic about these.

Finally, the moderators presented questions to the Laureates that had been prepared by the students - and much discussion ensued about the best way to tackle the energy problems we face as scientists and as a society.

That concluded the open scientific activities for the day and then I went off to my other career here, that of a helping hand with the film crew. First off we filmed a couple of the young researchers chatting with Peter Agre and then headed off to one of the hotels to film a discussion between Molina, Rowland and three students moderated by Olive from the Climate Feedback blog.

After that, there was another production meeting to discuss the filming schedule for today and that will kick into high gear after lunch - and stories will follow tomorrow...

Stuart


Stuart Cantrill (Chief Editor, Nature Chemistry)

Lindau09: Twitter round-up #2

Here are the highlights from yesterday's tweets from the 2009 Lindau Nobel Laureate Meeting

Tuesday 30 June

8.50am And speaking now is Mario Molina (http://bit.ly/qA6Zf) - the third of the 'ozone hole' Laureates to speak at the meeting

8.57am Molina - no silver bullet for solving climate problems, need to implement a number of different measures to tackle the problem

9.16am Next 'guest' Laureate is Erwin Neher (http://bit.ly/IvcoH), who was awarded the Nobel Prize in Physiology & Medicine, not chemistry! Neher is going to tell us about how chemistry helps neuroscience

10.10am Incredible Laureate line-up for panel discussion: Ertl, Grubbs, Kohn, Kroto, Marcus, Molina, Rowland - let's see where this goes...

10.21am Ertl reminds us that we cannot create energy, just convert it from one form to another (pesky laws of thermodynamics!)

10.26am Grubbs points out he's the only organic chemist on the panel - and says that new materials are vital for energy storage/transport

10.42am Kroto reminds us that some of the most important breakthroughs come from blue-sky research and so we must continue to fund it! Met with applause from the audience.

10.52am Molina says that society must double or triple its investment if we are to make headway in tackling the energy problem

11.01am Rowland suggests we should concentrate on the problem of removing carbon dioxide from the atmosphere

11.05am Question - can we combine chemical & biological systems to address energy problems? Maybe, but it seems nature has a big head start

11.12am Kroto - does the amount of money poured into the Manhattan project compare with the funding of nuclear fusion projects?

11.16am Ertl - still lots of open questions in nuclear fusion, but that's no reason not to continue...

11.18am What do you say to people who don't believe in climate change? Listen to Prof. Molina says Ertl!!

June 30, 2009

FEATURE: Join Us for a Capital National Meeting

With summer here at last, we're getting ready for the upcoming 238th ACS National Meeting in Washington, DC (Aug. 16-20, 2009), and we hope you'll join us! The meeting theme is "Chemistry and Global Security: Challenges and Opportunities," with plenty of special programming and exhibitors focused on that theme - a very timely topic in a very appropriate setting!

Social Networking Tools and the Washington Meeting

You can keep in touch with the latest Washington, DC meeting information and connect with other meeting attendees using your favorite social networking tools. Start discussions and connect with other attendees on the ACS Network and the ACS Facebook page. Follow @ACSNatlMtg on Twitter and be sure to tag your own ACS National Meeting tweets with #ACS_DC. Read "C&ENtral Science" blog posts about ACS meetings and share your comments.

Lindau09: Art meets science

On day 1 of the Lindau Meeting, art and science collided in more than one way... here's what I got up to.

First port of call was the Inselhalle on the island of Lindau (which is connected to the mainland by road and rail). The island is a pleasant 20-30 minute walk from our hotels on the mainland, or just a few minutes drive in the space-age VW van we have been kindly given for the duration of the meeting. It has a few thousand miles on the clock but has a genuine new car smell - so much so, I though it was brand new.

Anyway the morning began in a packed lecture hall and the first Laureate to speak was the 2007 Nobel Prize recipient, Gerhard Ertl. So, the conference kicked off with some hardcore catalysis - the kind that takes place on solid surfaces. We were treated to some pretty patterns associated with complex reactions - such as the BZ reaction.

Art featured much more heavily in the second lecture of the day, which was delivered by the 1991 awardee, Richard Ernst. He told us that there is much beyond traditional science, such as arts and humanities and that we should have 'passions' outside of science to make us more complete individuals. His lecture ranged from the cultural history of central Asia - including, in particular, Tibetan art, of which he is a collector - to science education for monks and nuns in south India: 'Science meets Dharma'. Ernst talked us through some fascinating pieces of art - and then moved on to art restoration and chemical techniques for pigment analysis, nicely weaving together his interests in art and science.

The first session of the day was rounded out by Ryoji Noyori whose theme was very much that chemistry is the key to our future. The moral to his story was that while nature gives us many wonderful molecules, the synthetic chemist can make so many more, and as we develop newer and better methodology, we can make them selectively and efficiently. He ended by saying that education is key and that the young researchers at the meeting are crucial for our (chemical) future.

After the coffee break, the first two speakers were Sherwood Rowland and Paul Crutzen - co-recipients of the 1995 Nobel Prize (along with Mario Molina). If you ever had any doubts about anthropogenic climate change, then you need to listen to these eminent scientists speak. The first day was then rounded out by Hartmut Michel - who received the Nobel Prize in 1988 - telling us about cytochrome c oxidase.

That was it for lectures, but then in the afternoon I turned runner/boom operator for the film crew shooting the Nature videos. I went from Laureate chauffer - driving SIr Harry Kroto and his wife to the location of the filming - to 'microphone stand' - which my colleague Sam assures me is the technical term for a boom operator... - I think he might be winding me up...

Anyway, after a successful shoot, Prof. Kroto and his wife had a much smoother ride back to their hotel when someone else drove the VW van, and then finally the team got together for some well-deserved tex-mex as the sun slowly set. Discussions about filming for today ensued, and then we made our way back to our hotels to recharge for today - which you can find out about tomorrow! More then...

For other NPG blogging, check out the Climate Feedback blog and Olive's post about the renewable energy panel discussion earlier today.

Stuart


Stuart Cantrill (Chief Editor, Nature Chemistry)

Chemistry is not above the law


The US supreme court ruled a few weeks ago that the chemists that perform tests in forensic analysis are not immune from cross examination by defense attorneys.  It’s not surprising that the American judicial system did not inherently allow for this, since it’s a very biased and fucked up system.  With this tool in the briefs of attorneys, it sets up a very real and very likely chance that a number of methods used in forensic science, as conducted in the state crime labs, will not hold up to scrutiny.  Not because they’re necessarily invalid (though, we shall see about that), but because they’ve not been done with the appropriate controls – an argument mentioned in the majority arguments by Scalia:

He cited one report, for example, that said “there is wide variabiility [sic] across forensic science disciplines with regard to techniques, methodologies, reliability, types and numbers of potential errors, research, general acceptability, and published material.”

Putting the chemist or lab technician on the stand to be tested by cross-examination, the majority said, will help “weed out not only the fraudulent analyst, but the incompetent one as well.

While this is a good thing for people who are accused of crimes they didn’t actually commit, it provides a way for a young, naive lawyer to get unfortunately schooled in a cross examination.  Without knowing the fundamental questions one should ask (and know before you ask) this could be a strategic blunder, making the forensic evidence look all the more compelling.

So, then, what should a young lawyer who suddenly learned they have this new power look for?  Frankly, I don’t know – but I can say there are somethings they should be aware of:

TLC (thin layer chromatography) is not a quantitative method because commercially obtained plates do not contain a consistent density and quality of silica, which means any TLC results are suspect without a co-spot.  Even so, co spotting can be misleading, unless you’re using the correct visualization method, to make sure you don’t have any overlapping spots.  In effect – I’d thing TLC evidence would be the easiest to toss out and make fun of as a method to corroborate a story.  It may be good enough to test purity for a rough guess, but it’s not accepted in the journals as proof – because it’s not.

MS  (mass spectrometry) can be misleading since calibration of the instrument must be done correctly.  Any competent technician will give the method of calibration.  I would guess that state labs use old equipment and they very would could be passing off aberrant noise as a peak of some sort.

Actually, I have to assume most of the stuff they’re doing is done on really old equipment – though that in itself isn’t reason to suspect the results.  Questions regarding the validation of that equipment, however, is appropriate.  Most scientific instrumentation loses some degree of precision as it ages, rendering it less accurate at the extremes of its detection ranges.  External companies are often used (and are usually necessary) to validate the instruments to some specification (I assume NIST standards) and provide proof of that validation.  Equipment that lacks this validation may not necessarily provide reliable evidence.  If a case could result in a very long incarceration of someone who may be innocent, the calibration – even in a reasonable range of detection, should be a concern.

GMP protocols probably will provide a better guide than I could.  I assume if it’s a standard by which drugs are made, it should be a standard by which evidence is measured….

Lindau09: Twitter round-up #1

For those of you who don't follow our Twitter feed, I'm going to summarise Stu's output from the 2009 Lindau Nobel Laureate Meeting on a daily basis

Mon 29 June

8.03am And here we go with the scientific part of the meeting after the opening ceremony yesterday - first up is Ertl http://bit.ly/txc5R

8.23am Ertl compares the reaction between carbon monoxide and oxygen to the 'reaction' between hares and lynxes and the fur trade - clever!

8.34am Ertl talks about spiral patterns in reactions & complexity - such as in the BZ reaction; see here for more info http://bit.ly/1nDFsB

8.35am And now it's Richard Ernst (http://bit.ly/RFJ34) who will talk about passions and activities beyond science

9.03am Ernst says that 'NMR is useless' for pigment analysis - use Raman spectroscopy instead; he does this at home!

9.13am Third lecture of the morning is from Ryoji Noyori (http://bit.ly/it8MF) talking about chemistry as the key to our future

9.16am Noyori: "close involvement with society is the destiny of science"

10.19am Second session of the morning begins with Sherwood Rowland (http://bit.ly/qA6Zf) talking about green house gases & climate change

10.31am What does it take for a molecule to be a greenhouse gas? - well, one requirement is a minimum of 3 atoms (for IR absorption)

10.48am Now on stage is Paul Crutzen (http://bit.ly/qA6Zf), who says that Rowland is a hard act to follow, but that he has better slides!

11.48am Final speaker of the open scientific sessions today is Hartmut Michel (http://bit.ly/2lwtV5) - talking about cytochrome c oxidase

11.56am So, open talks on day 1 are over. The afternoon will see closed-session discussions between the young researchers & Laureates

If you want to ask Stuart questions as he tweets, get on Twitter and direct your queries @NatureChemistry!

Comment 1 (Chemists take on immunology)

his conclusion is that our models for the hydrophobic effect and for how water molecules behave in proteins are basically wrong

How so?

June 29, 2009

Lindau09: Setting the scene

So, the NPG team and film crew arrived on Saturday afternoon in Germany and after checking in to our hotels on the mainland, we made our way over to the island of Lindau to meet some prospective students for the series of videos that we are producing. Much discussion ensued over dinner later in the evening and the plan for the films started to crystallise - calls were made and appointments set.

Sunday morning began with some filming of some of the students chosen to speak with the Laureates in the films. This involved finding locations on the scenic island of Lindau where there was enough sun, but not too much - and as little background noise as possible. You really don't notice how noisy 'background noise' can be until you need to film! Cobbled streets and roller-suitcases make for quite a din!

Sunday afternoon then saw the opening ceremony at Lindau, which began with a very eloquent and moving address to the assembled delegates from Countess Bettina Bernadotte, President of the Council for the Lindau Nobel Laureate Meetings. Two new members were admitted to the Honorary Senate of the Foundation Lindau Nobelprizewinners Meetings at Lake Constance - José Barroso, President of the EU-Commission and Kapil Sibal, Indian Minister for Human Resource Development.

The ceremony drew to a close after a discussion on the stage with five of the young researchers who are attending the meeting, during which they described what is required to succeed in science - with answers ranging from good collaborations, support, ambition, and perhaps even a little bit of luck.

We've now just had the first scientific session, with talks from Ertl, Ernst and Noyori - I'll gather my thoughts and then tell you all about it a little later, but now the second session is moments away. For live updates, you can follow on Twitter!

Stuart


Stuart Cantrill (Chief Editor, Nature Chemistry)

June 27, 2009

Bad Writing


One of the most confounding things I have discovered is how horrible some of the smartest people I know write.  While they can effectively spin yarns on the research they do with both clarity and poise yet they cannot put pen to paper and produce a single cogent product worthy of reading.  The single gravest sin, as I see it, is that they write like they speak and have no sense for punctuation.

While it’s probably too late to teach grammar, it’s never too late to convert someone’s hideous writing style to something more in line with a readable manuscript.  Allow me to suggest a few cardinal sins in writing a scientific paper, if I may:

  1. Using similes and metaphors.
  2. Writing in the passive voice.
  3. Switching verb tenses.
  4. Using unnecessary words.

Each of these rules, in particular the first one, are inviolable offenses.  The first one, of course, is self explanatory.  There should be no reason to use a figure of speach since they do not translate well and are usually corny.  The other three, on the other hand, require a bit of ‘esplanin.

The active voice in scientific writing can be difficult because it requires you to overcome a rule which was ingrained at some point into your head: the use of pronouns.  I had to go back and check if this advice was kosher with the Whitesides’ method and it appears as though it is – surprisingly.  The sentences taken:

Passive: It was observed that the solution turned red.
Active: We observed that the solution turned red.
Sexually Active: I fucked the solution until it was red.

Writing in the active form, while it may force a pronoun every here and again, forces you to keep your sentences short and to the point.  Alternatively, that sentence could have simply stated:  The solution turned red.  The fewer words, the better (if I may generalize) almost to the point that you’re generating paragraphs of bullet points.  After all, the point of a scientific document is to state all pertinent details in a readable narrative.

Verb tense somehow gets fucked up every now and then, even in the hands of seasoned writers.  As it typically happens, multiple drafts end up with multiple tenses and before you know it you have added a reagent in both the present and past tense.  How can I really do more than tell you to avoid it?  I dunno.  Just try.

Using unnecessary words is as noisome as it is common.  “For instance,” “also,”  “additionally,”  and “then” are added to sentences for no apparent reason.  Let me give you an example of a sentence:

In order to look at the binding of substrate 1 we initially studied the spectra of both uncomplexed and complexed substrate and then preformed a titration on both substrates at room temperature to give a Kd of 3.1 nM.

Too many fucking words.  Allow me to truncate:

After analysis of reactant and product spectra, titration of substrate 1 gave a Kd of 3.1nM at room temperature.

DONE.  In the top sentence, some of those words are screaming “DELETE ME!”  “In order to…” is meaningless and look, a superfluous “then!”  Why?  Why fill your sentences with so much shit when you can have such a nice pretty sentence that says everything you want it to.

The problem with effective writing is infrequently the use of too few words.  To the contrary, it is using too many which have no point.

June 26, 2009

Showing their metal

Sadly it’s my final day in Paris, but the conference has finished in fine style with a selection of talks largely focusing on organometallic chemistry and catalysts. I have a soft spot for organometallic chemistry, and so too did the audience it seems, since the lecture theatre was full, even though many attendees were probably slightly hungover from last night’s conference dinner.

But then again, who would miss the chance to see Richard Schrock? He gave a fascinating talk describing the development of his (and Amir Hoveyda's) stereogenic-at-metal catalysts for asymmetric metathesis reactions (Nature subscribers can read the first report of this work here; JACS subscribers can read the latest paper on the subject here). I was also interested to hear that he has developed catalysts that provide Z-products from metathesis reactions, which has led to the preparation of the first cis- syndiotactic polymer (described in another JACS paper). And there’s more to come - a paper reporting enantio- and endoselective enyne metathesis is currently in press.

So how do you follow that? With Steve Buchwald, of course. He dished out some great advice for those wanting to do C-N bond formations (and I know there are many of you). So, if you’re bewildered by the array of ligands for these reactions, he reckons that one of Xphos, RuPhos (named after his cat, Rufus, by the way) or BrettPhos (which is discussed in this JACS paper) will always do the job. He’s also come up with some useful precatalysts, which he reckons should overcome the problems some people have encountered when using this chemistry (see this JACS paper for a description of the precatalysts).

Not long now before I have to dash off to catch my train home, but there’s just time to mention Jose Barluenga’s talk that discussed the use of Fischer carbene complexes and late transition metal catalysis in organic synthesis (the latter including a rather nice modular approach for making indoles - Angewandte subscribers can read about this here). Perhaps most intriguing was his discussion of a metal-free coupling of tosylhydrazones with boronic acids to make diphenymethane compounds. These were preliminary results, so I’ll be intrigued to see the paper when it’s published.

Right, I’m off to the Gare du Nord. A bientot!

Andy


Andrew Mitchinson (Senior Editor, Nature)

Reactions - Lei Zhu

Lei Zhu is in the Department of Chemistry & Biochemistry at Florida State University, and works on supramolecular chemistry and bioinorganic chemistry of zinc.

1. What made you want to be a chemist?

In high school, I enjoyed all subjects in science. The experimental part of (high school) chemistry was much more visual than those of others which swayed me to what I do now.

2. If you weren’t a chemist and could do any other job, what would it be - and why?

My career choice second to chemistry would be investigative journalism. It is not too different from science – one draws conclusions based on evidence.

3. What are you working on now, and where do you hope it will lead?

We develop fluorescent molecules that report zinc gradients in biological systems. Also, we are interested in photophysics and coordination chemistry embodied in the compounds that we design. In addition to advancing fundamental understanding of the chemical systems, I hope that our work will lead to better sensors and catalysts, and ultimately, lots of wonderful surprises.

4. Which historical figure would you most like to have dinner with - and why?

That would be Charles Darwin on the Beagle. He was a wise man and may have had incredible dinner options over his voyages.

5. When was the last time you did an experiment in the lab - and what was it?

The last entry on my notebook is March 17 this year. I prepared a precursor of ligands that we study. It’s a reaction that we have done many times. It does not go wrong. I did it to escape from my office work. I do not have a project anymore because I’m unable to provide the continuity that’s required for a project to move forward in a timely manner. Most of my lab activities involve instrument maintenance.

6. If exiled on a desert island, what one book and one music album would you take with you?

I’d happily indulge in Chinese kung fu novels which occasionally do offer recipes for preparing marine delicacies. I’m not so much a music person. I’d trade music CDs for a couple of Dane Cook comedy show recordings.

7. Which chemist would you like to see interviewed on Reactions – and why?

Maitland Jones at NYU. He’s a person with ample life experience but a young and playful heart. Also, Frantz Andersen at SUNY New Paltz would be interesting. He’s a very good friend of mine from the days at UT Austin. Frantz always has shockingly amusing tales to tell.

June 25, 2009

Chemists take on immunology

Day two of my conference in sunny Paris, and the talks moved on this afternoon to biological chemistry. Long-term readers of this blog will know that I’m not a chemical biologist, so this will be a relatively brief overview of the topics discussed - but what topics!

Kim Janda largely focused on his work discovering antibodies for various therapeutic applications. I never knew that it might be possible to develop a vaccine for cocaine addiction, but Kim seems to be well on his way, with an antibody treatment that - in animal studies - reduces the amount of cocaine that passes through the blood-brain barrier, and which offers some protection against overdoses with the drug.

Carlos Barbas’s talk also strongly featured antibodies. I was particularly taken with his idea of using bifunctional antibodies in combination with prodrugs for anticancer therapy. The antibodies bind to tumours, but they also unmask anticancer agents from the prodrugs; this ensures that cytotoxic anticancer agents are targeted exclusively to tumours (which is good, because such agents are generally also toxic to healthy cells). He showed that a prodrug of the anticancer drug etoposide, when given to mice with appropriate antibodies, elicits a 75% reduction in tumour growth compared with controls, and with no signs of toxicity.

Thomas Carell gave a brilliant talk about his studies of DNA repair mechanisms, having isolated crystal structures of some of the enzymes concerned when in complex with damaged DNA. And here’s one of those mind-boggling statistics: apparently, in humans, every cell sustains 100,000 lesions to its DNA every day. So be thankful for your photolyases and Y-polymerases, which deal with the problem.

And finally, what was the dispute between George Whitesides and Jean-Marie Lehn yesterday? Well, George was discussing the problems of designing ligands for proteins - his conclusion is that our models for the hydrophobic effect and for how water molecules behave in proteins are basically wrong. But he also declared that the ‘lock-and-key’ model of enzyme-ligand interactions is bogus too: you don’t need a precise, tight fit, as implied by the model, but rather a ‘sloppy’ fit. Jean-Marie, however, defended the lock-and-key model, saying that, at the very least, it is the best way of explaining protein-ligand interactions for non-specialists. And then he went on to use the lock-and-key analogy in his slides.

More from Paris tomorrow…

Andy


Andrew Mitchinson (Senior Editor, Nature)

June 24, 2009

I love Paris

No, I don’t mean Ms Hilton. I’m at the Tenth Tetrahedron Symposium in Paris, celebrating 50 years of Tetrahedron Letters with a stunning programme of speakers - a real who’s who of organic chemists. If you ever have the chance to attend a conference in Paris, you’ve got to go, if only because it’s a foodie’s paradise. The three-course lunch was sensational, and the mini-desserts they’ve been dishing out during coffee breaks are to die for.

But I digress. Let me tell you about the chemistry. Catalysis was the unofficial theme of the morning’s talks. A highlight for me was Masakatsu Shibasaki’s discussion of his work developing asymmetric ‘two-centre’ catalysts (so-called because they contain two different metal atoms). I love hearing how original ideas extend into different directions, and this was a great example of that, as Masakatsu described how the discovery of catalysts for asymmetric Michael reactions led on to the development of catalysts for cyclopropanations, then for epoxide-formations and ultimately for making 2,2-disubstituted oxetanes (Angewandte Chemie subscribers can see the oxetane work here).

After lunch, a smorgasbord of treats awaited us (and not just the petits fours). Peter Vollhardt described unpublished work on the chemistry of phenylenes, including a fascinating description of haptotropism in their cobalt complexes. Michael Krische gave an overview of his work developing carbon-carbon bond-forming reactions via hydrogenations - appropriately enough for the venue, this work was inspired by seminal work from the French chemists Victor Grignard and Paul Sabatier. To my mind, this is a brilliant strategy for C-C bond formations - a minireview in Angewandte about catalytic carbonyl addition through transfer hydrogenation, written by Krische, can be found here (but subscribers only, I‘m afraid).

And that’s not to mention typically mesmerising talks from the likes of George Whitesides and Jean-Marie Lehn (who had a slight disagreement regarding a well-used model of molecular recognition - but more on that tomorrow).

I could go on - but for now, I’ll sign off with an ‘au revoir’.

Andy


Andrew Mitchinson (Senior Editor, Nature)

June 23, 2009

Releasing the Tension

My youngest son, Barnacle Boy, swims like a fish. When he was small, he could stay under water just a second longer than I though he should be able to -- I'd be ready to reach under and haul him to the surface, and then up he would pop. I began to wonder if he had gills.

Nowadays I'm certain he has no gills, though he can still hold his breath for a long time. He's not quite completely adapted to an aquatic life, though. He suffers from water in the ears. And he hates to hear himself sloshing...

The standard remedy for water stuck in the ears is "SwimEar" - an ad for which reads in part:

"Once water enters this tube...surface tension will cause this water to adhere firmly to the walls of the canal, thereby blocking it. Why is this water so difficult to remove? This is due to surface tension effect as well as the fact that it is extremely difficult to break the vacuum that is created behind the trapped water in the ear canal."

Despite the popping sensation you can get when your ears finally clear from water, there is no vacuum behind the water (really, I'm certain). As the ad implies, the trouble is that water is clingy, and therefore has a high surface tension. The high surface tension is what impedes the flow of water out of the ear canal -- think of getting the water out of a thin straw. The ear canal is behaving like a capillary. Reduce the surface tension and the fluid will release.

SwimEar is just a solution of isopropyl alcohol with a dash of glycerin added for comfort. (Ethanol, or ethyl alcohol, is what we drink - but to a chemist, an alcohol is a molecule that has a "tail" of (mostly) carbons and hydrogens topped off by a hydroxyl group: OH. Ethanol is CH3CH2OH, isopropyl alcohol is (CH3)2CHOH.) The isopropyl alcohol lowers the surface tension of the water (so will a bit of soapy water for that matter).

Comment 1 (On the road again)

Good luck at the conference, I will see you out there next year. The Nobel Laureates are an amazing group of people!

Eric T. @ JAZD Chemicals

June 19, 2009

On the road again

Tomorrow sees me hit the road (well, the rails, really) for the start of my conference season. First up is the 2009 International Symposium on Macrocyclic and Supramolecular Chemistry (ISMSC 2009) in Maastricht in The Netherlands. This brings back fond memories of my first trip to an ISMC conference (in the days before the macrocyclic and supramolecular chemistry meetings decided to merge) back in 1998. The venue was Turtle Bay on the Hawaiian island of Oahu. Brownie points for anyone who can spot me in this photo!

Next up, is a trip to the 2009 Lindau Nobel Laureate Meeting - and this year the meeting is dedicated to chemistry (with some climate concerns thrown in for good measure). The Lindau meetings bring together Nobel Laureates and young researchers from around the globe and is not your typical conference that consists of lectures and poster sessions. The laureates and researchers are thrown together for the best part of a week; for lectures, discussions and dinner - the social programme is integrated with the scientific one.

Last year at Lindau the focus was on physics and Nature produced a series of videos featuring conversations between students and Laureates - you can see all of them here. This year, we're doing a similar thing, so look out for some videos later in the year.

I'll be blogging from both meetings and perhaps tweeting too... so keep an eye out for what's going on.

Stuart


Stuart Cantrill (Chief Editor, Nature Chemistry)

June 17, 2009

Extreme makeover chemistry style

In revisiting a chemical reaction that's been in the literature for several decades and adding a new wrinkle of their own, scientists with Berkeley Lab and the University of California (UC) Berkeley have discovered a mild and relatively inexpensive procedure for removing oxygen from biomass. This procedure, if it can be effectively industrialized, could allow a number of of today's petrochemical products, including plastics, to instead be made from biomass........

Chemists synthesize herbal alkaloid

The club moss Lycopodium serratum is a creeping, flowerless plant used in homeopathic medicine to treat a wide variety of ailments. It contains a potent brew of alkaloids that have attracted considerable scientific and medical interest. However, the plant makes a number of of these compounds in extremely low amounts, hindering efforts to test their therapeutic value........

June 11, 2009

Sweet leads


Sugar of Lead Poison Bottle
Originally uploaded by john4kc


Horror of horrors - the Romans used lead to sweeten their fruit. No wonder Rome fell! Except that I was willing to read a 1883 paper (in German with healthy helpings of Greek and Latin) to discover that it may be lead and it may be sweet, but the lead doesn't lead it to be sweet.

In a time when mercury was regularly used as a remedy for maladies as serious as syphilis and as commonplaces as constipation, it doesn’t surprise me that lead compounds were in the pharmacopeia. (In all fairness, some modern antibiotics and most chemotherapy agents are at least as toxic as these less old remedies; they just have a better risk-benefit ratio.) Sugar of lead, or as it’s called in the 19th century medical literature, saccharum saturni, is lead acetate: Pb(CH3COOH)2. It was once prescribed for intestinal troubles, an odd choice, since one symptom of acute lead poisoning is an upset stomach. Lead poisoning is also known as painter's colic.

Sugar of lead really is sweet, roughly as sweet per spoonful as sugar. In the 18th and 19th century, lead shot was often dropped into bottles of port, purportedly to make it sweeter - though the more likely effect is anti-bacterial. Why? Lead does dissolve well in alcohol and juices (crystal decanters to store your port are a bad idea) - but I can't find anything that suggests solutions of lead ions are sweet.

The Romans were reputed to use lead acetate as a sweetener. They produced a syrup called sapa by boiling down mildly fermented grape juice in kettles made from lead alloys. (The hydrates of lead acetate are far less soluble in alcohol solutions - you are more likely to get a suspension of crystals in the syrup.) I am suggesting that it’s unlikely that the syrup was sweet because of the lead acetate it certainly contained. An 1883 analysis of sapa produced according to recipes dating from the classical Roman period, in kettles of similar metallic content to those found at Pompeii and other sites, suggested that the lead content of sapa was roughly 850 mg per liter. The equivalent amount of table sugar would be roughly a teaspoon - hardly enough to taste sweet in a liter of liquid. On the other hand, the sugars (glucose and fructose) in the concentrated grape must are the equivalent of 1 cup of table sugar per liter and would certainly swamp any sweetness coming from the lead acetate. It's still not all that sweet. To get a sense of how sweet this is, simple syrup, which has similar culinary uses to sapa, has about 4 cups of sugar in a liter.

I still wouldn't use sapa to poach my pears, but I think it unlikely that the sweet taste of sapa has much to do with lead.


Photo is c. 2009 John4kc. Used with permission.

June 05, 2009

Sweet Stones

I was wandering the Cape Anne historical museum this winter and noticed in a 19th century ship's medical kit a vial labeled "sugar of lead." This is lead acetate, which tastes sweet -- and is reputed to have been used as a sweetener is days past. Other metal salts are sweet as well - yttrium salts and beryllium salts can both taste sweet.

Beryllium was first identified in 1798 by chemist Louis Vauquelin as an oxide in beryl and emeralds (emeralds are beryls with a bit of chromium added!). Since the chloride salt of the new element tasted sweet, the editors of the journal which published Vauquelin's findings suggested he call the oxide (or earth) glucina from the Greek, glyks (γλυκυς) for sweet. The elemental symbol used was Gl.

Beryllium was suggested as alternative once other sweet metal salts were found, for the gemstones in which the element was first identified. It took until 1949 for this to become the official IUPAC name of the element with four protons.

Beryls were used to make "reading stones," magnifying glasses, then eventually ground into lenses for eyeglasses.

June 01, 2009

Anti-Archimedes

The recipe for pulled pork called for 1/2 cup of brown sugar to be dissolved into 1 1/2 cups of apple cider vinegar. What I had in the cabinet was solid as a rock - there was no way I was packing this into a measuring cup. (Yes, I know I could have done this in the microwave...) My scale came to the rescue. I hacked off chunks until I had the correct mass of brown sugar (110 grams more or less). I dumped the three large hunks into the vinegar in a 2 cup glass measure, and noted that the total volume was just about 2 cups. Nice job.

Then I stirred it to dissolve the sugar. And watched the volume decrease to just over 1 1/2 cups of solution! Have I just proved Archimedes wrong? The volume of sugar at first seemed to have displaced the equivalent volume of liquid, but then seemed to vanish...well not exactly into thin air, but vanish nonetheless. As my 15-year old might say, "What's up with that?"

Yes, Archimedes was correct, but his theory did not address substances that dissolve in the liquid. This is a good demonstration of how much "empty "space is in a liquid. The sugar molecules (and other things in brown sugar, which is not terribly pure as chemicals go) insert themselves between water molecules, without needing to push the water molecules further apart. To a good first approximation the volume of a solution made from a solvent and soluble solid is the volume of the solvent used, not the sum of the two volumes.

Try it...it's fun to watch, and it still intrigues me to think about the amount of unused space there is in a liquid that seems so substantial at the macroscopic level!


The pulled pork was a keeper...though the kids found the BBQ sauce too spicy for their taste. Try it on challah rolls!

May 26, 2009

Cold as Ice

This article in the Atlantic monthly caught my eye, if only because it included an experiment and less because of my refined palate. Wayne Curtis is writing about the unsung hero or villian of mixed drinks: ice.
"I went into the kitchen with another bartender, Stephen Cole, who hunted up a scale and thermometer. He placed the two kinds of ice into separate cups filled with water. We let them sit for 10 minutes. The cheater-ice water proved to be colder (34 degrees compared with 40 degrees), but the ice had lost a full quarter of its weight, compared with just a 14 percent loss in the chunk ice. A cheater-ice cocktail is thus chillier (numbing the taste buds) and more watery (making it flat)."
He describes a bar which stocks eight different types of ice - though the classification system is not quite what a physical chemist might use - or even Kurt Vonnegut. I suspect, however, a serious flaw in the experiment, and therefore in the conclusions drawn about the effect of ice type on a drink.

Take a mixture of ice and water that has been thermally isolated (put in a thermos!) and allow it to come to thermal equilibrium (let it sit until the temperature doesn't change any longer). When the contents of the thermos reach equilibrium, if there are both ice and water present, the temperature is 32 degrees (Fahrenheit). It does not matter how cold the ice was to start, how much water is present, how warm or cold the water was - it will be 32 degrees. Not 40. Not 34.

Also known to those who know how to read a phase diagram, ice at normal pressures will not start to melt until it reaches 32 degrees, and its temperature will not rise above 32 degrees until it has all melted. Curtis' experiment isn't quite as sophisticated as the thermos one I've sketched out, but assuming that the rate of heat loss to the room was small (air - or any gas - isn't a very good thermal conductor, so over the short term this is not a bad assumption), and that the ice and water used were pure, and that a very large amount of water was used relative to the ice - I find it untenable that the "cheater-ice" cocktail is different in temperature than the one made with less porous ice. More watery, yes, colder, no.



Photography by Sue Stafford. Used under Creative Commons license.

May 11, 2009

Weird Words of Science: Hypsometer


Every time I write an exam, I think about this story, where a physics professor asks on an exam how to measure the height of a building using a barometer. A student answered that he would tie a string to the barometer, lower it down, then measure the length of the string. Given no credit, he protests, and the professor offers him a second chance to provide an answer that is both correct and demonstrates some knowledge of physics taught in the course. The student goes on to give several answers (in some versions the student is averred to be Niels Bohr - though the origin of the story is apparently in a textbook on the teaching of math and science by Alexander Calandra, and unrelated to Bohr) all demonstrating a knowledge of physics, and none the one he seems to know the professor is fishing for (which has to do with the - probably unmeasurably small - pressure differential between the ground and the top of the building).

Here is a chemistry exam question I sometimes ask - how would you measure the height of a mountain with a thermometer? This is a well-known technique,not a trick question, the apparatus is called a hypsometer, from the Greek for "height-measure". The underlying science is that the boiling point of a liquid changes in a known way with altitude. Hypsometers were used before portable aneroid barometers became widely available, and were used in high altitude balloon measurements of pressure as late as the 1960s.

Bonus question: Is it easier to drink a liquid using a straw at the top of Mt. Everest or on the beach in Florida? (Disregard temperature differences and explain your answer for full credit!)

May 02, 2009

70s House Eco Renovation: From Green to "Green"

As we do an eco renovation of our house, we will take it from the color green to being eco green. This series of articles will document our progress and share what we learn along the way. We will provide reviews of the eco products we use and provide tips for those who like to DIY (do-it-yourself). We will document not just what we did, but why we did it. Our eventual goal is to reduce our energy and water consumption and bring our home to as close to carbon neutral as is practical. At the same time we want our home to be comfortable with the amenities we are accustomed. By Kenneth Barbalace

May 01, 2009

Nano-meter

The Nano Song from nanomonster on Vimeo.


This song certainly has rhythm as well as meter...and does give you a sense of what "nano" means. My non-musical attempt of a couple of years ago is not so jazzy!

April 24, 2009

Table Manners in Nature Chemistry


The second issue of Nature Chemistry appeared online today, with my musings about the shapes the periodic table can take, and why I think chemists like to keep their elements in boxes.

"Chemists have created hundreds of variations in search of the perfect periodic table. The periodic table has been mapped onto spirals, circles, triangles and elephants. The first such “alternative” periodic table, based on a sprial, was proposed by Gustavus Hinrichs of the University of Iowa in 1867, two years before Mendeleev published the forerunner to the current blocked tabular form. Still, open 50 random introductory chemistry texts and it is a fair bet that all 50 of them have IUPAC’s standard periodic table inside, or its generic sister. Chemists are stuck in the box." Read the rest of the column here (requires a subscription...).
Or if my Table Manners are not to your taste, this article in the same issue on syntheses of Moebius molecules might be.

April 10, 2009

All that glitters...may be tin


While medieval alchemists were searching for the secrets of turning base metals, such as lead and tin, into gold, medieval artists had already figured out how to do this. Gold was often applied to manuscripts in medieval Europe and the Middle East to “illuminate” them, an illuminated page would have the functional equivalent of little mirrors scattered across it, making the most of dim interior lighting. In addition to being reflective, gold does not corrode or oxidize, so gold will not discolor with time. There is a fine collection of medieval illuminated manuscripts at a library near me, and as you turn the pages of Book of Hours that is half a millenia old (wearing gloves, of course), the golden decorations wink at you as brightly as the day they were applied.

Gold is expensive, and hard to handle, particularly in the thin sheets necessitated by the cost. One alternative is to use a tin base, then brush on a saffron oil glaze. Polish it up and you might not notice. The glaze blocks out the oxygen and moisture in the air, preventing many of the chemical reactions which can cause the metal to discolor. The resulting preparation is called auripetrum - Peter’s gold. Peter had a good idea - whoever he was.

Does anyone know more about the source of this name? I'd love to know.

March 25, 2009

A rose by any other name is poison ivy

In 1865 John Maisch published a short paper "On the Active Principle of Rhus Toxicodendron". For the unsensitized, rhus toxicodendron is the botanical name for poison ivy. Maisch isolated a fraction he considered to be the "active principle" responsible for the misery that is poison ivy and dubbed it toxicodendric acid. Are you itchy yet? (I am and Maisch surely was, he and various visitors to his lab suffered with outbreaks of poison ivy.)

By 1897 Franz Pfaff of Harvard had weighed in. Toxicodendric acid extracted from poison ivy turned out to be acetic acid - yes, vinegar, by another name, CH3COOH. He showed the itch was in the oil.

Weird Words of Science: Lemniscate Elemental Landscapes

In reading an older paper about periodic tables, the author referred to the "lemniscate table of Gooch and Walker" - but didn't provide a figure, and I had to admit lemniscate was an unfamiliar descriptor. (It's not in the abridged Oxford English Dictionary on my iPod, either - so I don't feel all that ignorant!) Even a Google search was not particularly enlightening.

The full OED came to the rescue - "ribbon like", from the Latin for a ribbon. The term dates to the 17th century when Bernoulli used it to describe a set of curves. The term was new, the curves were not - Bernoulli's lemniscate was a special case of a set already described by Cassini.

Once I located a figure of Gooch and Walker's table, I would agree "ribbon-like" is a good description and it is certainly reminiscent of Cassini's figure eight curves (to give credit where credit is due).








Figure of the periodic table from Outlines of inorganic chemistry‎ by Frank Austin Gooch, Claude Frederic Walker, Macmillan:New York, 1905. Figure of Bernoulli's lemniscate is from here.

February 12, 2009

It's Just a Phase



Allotropes are all the rage? Or at least sending Conan O'Brien over a very funny edge! The bit was inspired by this article in the NY Times science section. I'm not nearly this riveting when I lecture about allotropes, I've got to admit.

O'Brien gets the chemistry nearly right. My only quibble would be that he calls the different forms (the diagrams are the real thing, by the way) different phases, which they aren't really. They are technically allotropes, different structural forms within the same phase or state of matter. The quintessential example is the allotropes of solid carbon, graphite and diamond and a few others. All that said, when you draw a phase diagram for an element, you show the allotropes on it, and many chemists would characterize the change from one allotrope to another as a phase change.

Oxygen has some fascinating solid allotropes, including one that is a blue solid at room temperature!

December 18, 2008

Grapes of Wrath



My youngest came home from a father-son event with a new interest in healthy foods. I put grapes on the table with dinner. "There are grapes for dinner," he exclaimed. Who are you and what have you done with son? ran through my mind.

At the end of dinner he puts two grapes on his plate and carefully cuts them nearly in half. Then he ducks into the kitchen. "Come on, Mom!" Warm grapes? He'd eaten all the chicken, there was nothing left on his plate to veronique.

He hits the start button and suddenly the grapes start arcing, and one actually bursts momentarily into flame. I'm stunned. No metal, but the arcing is clear. We try various experiments - do you have to leave the grapes connected (no), does it work with other things (carrots), can you char a grape (yes).

What's going on? Hang on, we were producing plasmas in the kitchen. Not the kind that circulates in your veins, but the kind that stars are made out of. Plasma is often called the 4th phase of matter - the iconic triad being solid, liquid and gas. (There are many other phases in which substances can exist, in fact - such as liquid crystals and supercritical fluids.)

Plasmas are gases in which a large number of electron are "free", rather than associated with a molecule or atom.

I'm still trying to come to grips with the idea that I can create a (very tiny) ball of plasma in my kitchen.

(Read more in the paper : "Microwave Mischief and Madness" by H. Hosack, N. Marler, D. MacIsaac of Northern Arizona University, The Physics Teacher 40, 14 (2002).

December 10, 2008

Shell Games

I'm an unrepentant Trekkie, I'll admit it. Remember when Spock, Scotty, Uhura, Sulu, Chekov, Kirk and McCoy went back in time to San Francisco to rescue the humpback whales? Scotty got a local company to whip up some transparent aluminum to use to build a whale tank in the ship to bring the whales back to save the Earth.

In the latest issue of Nature, Robert Richie's group at Lawrence Berkeley Labs reports that they have created a composite material that mimics aluminum alloys in strength. Following nature's lead, they use ice as a template to build layers aluminum oxide and polymethacrylate into a strong ceramic similar in structure to nacre - the stuff of which shells are made.

The materials extraordinary strength relative to the component materials is due to the stacking of the layers, which make it difficult for macroscopic cracks to form. Could this type of process lead to transparent aluminum alloy?

November 13, 2008

Allotropes and architects: buckminsterfullerene

Responding to an earlier post on inert gases, a commenter wondered if buckminsterfullerene might act as an inhalation anesthetic - given that, like xenon, it's a large, polarizable ball of electron density. It might, if you could get enough to inhale. At room temperature, the vapor pressure is 5 x 10-6 torr. Very roughly, that's about a billionth of atmospheric pressure. For comparison's sake, the pressure of xenon necessary to induce anesthesia is about 500 torr, or 65% of normal atmospheric pressure. If you want higher pressures, you need higher temperatures: buckminsterfullerene sublimes (goes directly from the solid to the gas phase, like dry ice) just above 1000F. Not great to breathe...

While likely impractical as an anesthetic, buckminsterfullerene has asthetic properties. It's a highly symmetric molecule - having iscosohedral symmetry. Kroto and Smalley discovered the new allotrope of carbon, C60, in vaporized graphite and named it for the architect (Buckminster Fuller) who made famous the geodesic domes it resembled. Two more familiar allotropes of carbon are graphite and diamond.

Allotropes are differing forms of the same element. The roots of the word are Greek - allos for different and tropos for "turn of mind". A different turn of mind? It's what Smalley needed to propose the now iconic structure, over a beer at his kitchen table.


Another allotrope of carbon is lonsdaleite - named for Kathleen Lonsdale, an Irish crystallographer who determined the structure of benzene and my brother-in-law's godmother.

The Grecian Bends: Ladies' Corsets and Henry's Law

In an earlier post I suggested there was a connection between ladies' corsets and Henry's Law. A general statement of Henry's Law is that the solubility of a gas in a liquid depends on the pressure of the gas above the liquid. An everyday example is soda. A can of soda is pressurized by exposing it to carbon dioxide having equivalent of about 2.5 times atmospheric pressure at room temperature. When you quickly lower the pressure of carbon dioxide over the liquid, say by opening the can, the solubility decreases and the gas adjusts by rapidly coming out of solution. Fizzing results (and eventually the soda goes flat).

When a diver dives the pressure of the gases breathed increases, and the amount dissolved in the blood increases. Diving to just 50 feet increases the total pressure to roughly that of the carbonated soda! Rapidly ascending reduces the pressure, just like opening the can of soda, and the gas rapidly comes out of solution - the diver's blood can "fizz". Bubbles in the blood and body tissues are clearly not a great thing, and the physiological effects range from the relatively minor (bubbles in the skin layers) and joint pain, to potentially lethal embolisms in the brain and lungs.

This phenomenon was first observed by Robert Boyle in 1670 who noted the formation of bubbles in the eyes of a snake that had been placed in a high pressure environment, then rapidly decompressed. "I once observed a viper furiously tortured in our exhausted receiver… that had manifestly a conspicuous bubble moving to and fro in the waterish humour of one of its eyes." Before the effects was widely understood, many construction workers suffered from "caisson workers' disease" while working in pressurized environments (caissons) under rivers.

Dive tables - a schedule for ascending from a dive that reduces the chance of decompression sickness - were first created for use by British Navy divers in the early 20th century. How do whales and dolphins cope without dive tables? Half-mile deep, hour long dives are not uncommon - and a rapid ascent from depth could cause a massive case of the bends. They may not be immune - recently researchers have found evidence for chronic decompression injuries in sperm whales. The whale bone in the photo above shows evidence of dysbaric osteonecrosis (bone death caused by rapid decompression).

What does this all have to do with ladies' corsets? In the 1870s tight corsets and big bustles were all the rage. The posture forced upon women wearing these fashionable undergarments was called the Grecian Bend. As decompression injuries caused a similar posture, workers on the Brooklyn Bridge christened the syndrome "the Grecian bends", soon shortened to "the bends".


The photograph of the whale bone is by Tom Kleindinst, Woods Hole Oceanographic Institution and is used with permission.

The image of the Grecian Bends is from the Library of Congress

Random Facts about Ludwig B.

Not that Ludwig B. - the other Ludwig B: Ludwig Boltzmann, an Austrian physicist.

Boltzmann's name is familiar to many science students through the eponymous constant: 1.381 x 10-23 Joules/mole-Kelvin, which appears in many equations. The constant (usually written as k) arises from the proportionality between the absolute entropy of a system (S) and the number of possible arrangements of that system (W). Boltzmann's expression of the entropy, S=k ln W, is inscribed on Boltzmann’s tombstone in Vienna, Austria. Boltzmann did not write it in this form, however, Planck did.

Boltzmann also has two other equations named for him, the first is a diffusion equation used in neutron transport theory and the second describes particles in a gravitational field. In 1904, Boltzmann gave lectures on mathematics at the World’s Fair in St. Louis. He was also a popular lecturer in philosophy at the University of Vienna. Boltzmann is considered the founder of statistical mechanics, and a strong proponent of the “atomistic” view that underscored the importance of understanding the behavior of atoms and molecules in order to understand the bulk.


Loosely, the entropy is a measure of the "randomness" in a system.

Weird Words of Science: isotope


The periodic table is the map of the chemical world. Columns collect atoms which share properties - all of the elements on the far right - He, Ne, Ar… - are all gases and all nearly chemically inert. The region at the bottom harbors elements more likely to be radioactive. Metals pool in the middle.

Each atom of an element has a characteristic number of protons - positively charged particles - in their nucleus. An atom with five protons is boron. One with 82? Lead.

Most atoms also have a number of uncharged particles - neutrons - in their nuclei as well. The sum of the number of protons and neutrons in a given nucleus is called its mass number. A boron atom with six neutrons has a mass number of 11: five protons and six neutrons. Take away a neutron and it’s still boron, but the mass number is now 10.

Atoms with different mass numbers but the same number of protons are termed isotopes. Most elements have several naturally occuring isotopes. The most abundant form of the element carbon has a mass number of 12. One percent of carbon atoms, however, have an extra neutron and a mass number of 13.

Scottish novelist and physician Margaret Todd coined the term for her distant relative Frederick Soddy at a dinner party in 1913. He had described his research to her and she responded that any good discovery need a Greek term to describe it. She suggested combining the Greek “iso” for same and “topos” for place - to emphasize that the mass number of an element doesn’t affect it’s place in the periodic table: argon-36 and argon-40 are both inert gases. Soddy went on to win the Nobel Prize in 1921 for his discovery - perhaps because his distant relation had coined him a such good term?

Protecting Groups


The whole family was at camp last week, living in tents, sleeping on cots, eating in the mess hall. Every camp has them, squirrels and chipmunks that survive on the crumbs of campers' treats (or sometimes the whole banana). We were warned - no food in the tents except in metal boxes.

The boys had the tent next door to ours. I came back from dinner one night to find a very happy squirrel just making off with a chip container from the kids tent. At which point I remembered the dried fruit I'd left in my pack after the morning hike. Whew...it was still there. The rodents had been attracted to the far more tasty snack leavings next door. The boys tent is serving as (a chemist would say) a protecting group.

Chemical protecting groups work similarly. Say you have two sites on a molecule that can react with a reagent, but you only want one to undergo the reaction. If you can put a protecting group on the site you want left unmolested, like a cover, you can run the reaction, change the other site and then take off the protecting group. (See the scheme for an example.)

It works wonderfully for many reactions, and is keeping my pack safe from marauders.

May 18, 2008

Writing in Santa Fe

In about 8 hours, I should be taking off for Santa Fe and the 2008 Santa Fe Science Writing Workshop. I'm bringing some of the work I've done on the blog, trying to shape a longer and coherent narrative. There are about 40 students coming - from a range of backgrounds. Scientists, journalists, students. My instructor will be Laura Helmuth - the science editor for the Smithsonian.

May 02, 2008

How to tell if you're really a chemist

You pronounce unionized as UN-ionized not union-ized.
When you hear the word mole, you don't think of an animal.
Milli is a prefix, not a girl's name.

This Sceptical Chemist blog post suggests a new test to tell if you're really a chemist. What do you see when you look at this illustration by Joon Mo Kang? If the first things you see are five bonds to carbon, and three bonds to a hydrogen, you're a chemist. If that's all you see - you are really a chemist.

A couple of chemists missed the point of the illustration so completely they wrote to the NY Times to let them know of their chemical illiteracy. Another blogger was also vexed by the nonsensical molecule.

I'll admit it -- I saw five bonds.

April 14, 2008

Neurodevelopmental Disorders in Children: Autism and ADHD

While the generally accepted causes of neurodevelopmental disorders like Autism and ADHD include genetic and environmental factors, a wide range of toxic chemicals in the environment have also been associated with these disorders.

April 08, 2008

Concentrated Chemistry: American Chemical Society National Meeting

The American Chemical Society national meeting is on in New Orleans this week. Somewhere on the order of 10,000 chemists will be here for at least some of the week - it's noticeable on the streets to be sure.

The Nature Chemistry group win the prize for most challenging travel. Read the teaser at the Sceptical Chymist - and place your bet on whether United Airlines will get them home again. A road trip to London isn't going to be the solution to return travel woes (unless that Bering Strait tunnel project gets off the drawing board much sooner than anticipated...).

The ACS has an oral history project going...and I'm signed up to be videotaped this afternoon.

My favorite t-shirt seen at the meeting: The name's Bond. Ionic bond. Taken, not shared.

March 06, 2008

Inert gases aren't always inert

Earlier this week I posted about the intoxicating effects of nitrogen gas at high pressures, which leads divers to substitute helium for nitrogen. An astute reader wondered in the comments why argon wasn't used, as it is substantially cheaper. It turns out that argon is even more potent intoxicant than nitrogen at high pressures! But aren't argon and helium inert gases?

The elements in the last column in the periodic table comprise what IUPAC (the International Union of Pure and Applied Chemists is to chemists what the IOC is to sports) calls Group 18, but what most of us learned in high school to call the noble or rare, gases. Helium, argon, neon, krypton, xenon and radon are indeed all gases under standard conditions, but the modifier misses the mark by a bit.

Rare? Take a deep breath, you've just inhaled about 100 mg of argon. Almost 1% of the atmosphere is argon; there is almost three times as much argon in the air as there is CO2. "Noble" generally means "unreactive" to a chemist. The noble metals, such as gold and platinum are resistant to oxidation - they don't rust - unlike the "base" metals such as iron and copper. Much like gold and platinum, under the right conditions these inert gases can be made to react. The first noble gas compound - xenon hexafluoroplatinate - was synthesized in 1962, but there were earlier clues that these gases might not be completely unreactive. The anesthetic effect of xenon had been observed in the 1930s, and reports of its use in clinical settings appeared in the late 1940s.

The mechanism by which nitrogen, argon and xenon behave as anesthetics isn't completely understood. The best theories at the moment suggest that the gases interact with ion channels - but whether they binding chemically or physically is not clear.

March 04, 2008

Breathing Deeply

The tunnels deep beneath New York that bring crystal clear water from the reservoirs upstate to the city are aging. Divers are busy assessing the infrastructure - and it's literally a high pressure job. In order to avoid time consuming daily decompressions, the divers are living in a high pressure environment for weeks at time, almost 20 times normal atmospheric pressure. As AP reports, the pressures require that the men breathe a helium-oxygen mixture. Unfortunately, the reason given in the article for breathing the squeaky voice inducing mix: "the nitrogen in regular air is too heavy at 600 feet and their lungs could not handle the pressure." is utter nonsense.

Nitrogen does not weigh more under pressure, and the total pressure of the gas in the divers lungs is high, regardless of the identity of the gas (oxygen gas weighs more than nitrogen does, in fact). The real reason has to do with Dalton's law of partial pressures, and the fact that at high pressures, neither oxygen nor nitrogen are benign substances.

Dalton's law says that the pressure of each gas in a mixture is a function of the percentage of that gas and the total pressure of all the gases. For example, at 30,000 ft, where the total pressure is 0.3 atm and the fraction of oxygen in the air is 21%, the partial pressure of oxygen is 0.063 (humans need a partial pressure of about 0.1 atm to oxygenate their blood).

At the depth of the NYC tunnels, the total pressure is just over 18 atm, so the partial pressure of oxygen would be 3.8 atm. Above a partial pressure of roughly 1.5 atm oxygen gas is seriously toxic. The partial pressure of nitrogen 600 feet below the surface is about 14 atm. Nitrogen narcosis, rapture of the deep, sets in at pressures above 4 atm. At these depths, nitrogen is essentially an anesthetic!

Introducing an inert gas into the breathing mix, such as helium, reduces the percentage of oxygen and nitrogen in the air, thus reducing their partial pressure and reducing the danger of oxygen toxicity and nitrogen narcosis. The need for the specialized breathing mix has nothing to do with the heaviness of the nitrogen and everything to do with the toxic effects of these gases at high partial pressures.


Eliminating nitrogen completely from the mix can also reduce the potential for developing the bends (bubbles of gas that form in the tissues when pressure is reduced) - but that has to do with Henry's Law and ladies corsets, and is another blog post!