Ambiguous bromine

At first sight bromine seems to be ‘just another halogen’, a helpful counter-anion or leaving group in SN2 or cross-coupling reactions. Of course this isn’t the whole story, as Matt Rattley — a chemistry student at the University of Oxford and the author of the winning essay on bromine for last year’s contest — points out in his article (subscription required).

Bromine was isolated independently by Carl Jacob Löwig from a mineral water spring, and Antoine Balard from seaweed, in 1825 and 1826. Having identified that he’d obtained a substance between chlorine and iodine, Balard first thought it was idodine chloride before recognizing it as a new element. It seems unclear who exactly from Balard or Gay-Lussac thought of the name brôme but we know it comes from the Greek bromos, stench — a fair description of gaseous bromine. In addition to its rather unpleasant smell, bromine is also toxic — as Rattley puts it, bromine’s orange-brown colour is convenient because “avoid it you should”. In the sunlight, elemental bromine (Br2) splits into radicals that readily attack other species, including lung tissues.

Brominated compounds have been used throughout history for a variety of purposes, with varying degrees of success — find out in the article how one was dangerous (likely lethal, really) to ancient Egyptians in the seemingly mundane form of a lipstick. More successful applications include that of potassium bromide, which acts on the nervous system, as an efficient epilepsy remedy, an anticonvulsant and a sedative during the late-19th and 20th centuries. It still is used in veterinary medicine, but bromide’s chronic toxicity has since put a stop to human uses. Other instances have also exploited toxicity — Rattley mentions the insecticide chlorenapyr, whose rather peculiar structure comprises three different halogens — while in others no particular problems arose. A polybrominated dye for example has been widely used to stain various cell components for imaging purposes.

In light of such diversity, it certainly doesn’t seem unreasonable to think that bromine will continue to feature prominently both in research and practical applications.

Anne

Anne Pichon (Associate Editor, Nature Chemistry)

The four worlds of carbon

Our element of the month is carbon. Carbon is so ubiquitous, with its various allotropes and as part of the many, many compounds and living organisms it makes up, that it’s hard to know where to start. Well, why not in New York City? As Simon Friedman from the University of Missouri Kansas City — interviewed here in Reactions — puts it in his article (subscription required) “The organic chemist’s view of carbon can be like the New Yorker’s view of the world, which to them ends at the edge of Manhattan.” And so he goes on to explain.

The first world of carbon is undeniably organic chemistry, with the incredibly varied species — such as drugs, pesticides, dyes — that it endeavours to synthesize. Yet beside the undisputed, elegant role carbon assumes in organic chemistry, it is also a key component of steel. It is true that iron is by itself a useful material, but it is carbon doping that converts it into steel, an altogether much stronger, much more durable material that can be used to build robust structures. Read Friedman’s article to find out how carbon atoms achieve this.

Another world of carbon — also related to materials and their bulk properties — that has become an inherent part of our lives is plastic. It’s hard to fully grasp just how omnipresent plastics are, from invaluable and advanced items (for example, lenses implanted within the eye) to an unfortunate mountain of junk items filling up landfill sites and even covering a vast area of the Pacific Ocean. Some forms of carbon really are forever, or close enough that we must think carefully about whether this is a good thing or not before (over)using them.

Finally, the last thing you can do with your carbon-based molecules is burn them for energy. We’ve been relying on oil, coal and natural gas for energy — yet in terms of usage of carbon this is more than a little upsetting. I particularly like how Friedman expresses this sentiment: “to the organic chemist, simply burning carbon for its energy must surely be akin to burning your books when you are cold, or eating next year’s seeds when you are hungry”.

Anne

 

Anne Pichon (Associate Editor, Nature Chemistry)

Element of the month: Counting on copper

Readers of this blog will be familiar with last year’s essay competition — as Stuart mentioned here a few days ago, the winning  essay on copper, written by Tiberiu Moga, appears in this month’s ‘in your element’ feature.

Copper has been part of our lives pretty much for ever — the Copper Age started around 5,000 BC (give or take a couple of thousand years depending on whether you count the Copper–Stone Age or not), made its way into epic poetry (read the article to find out how it features in the Kalevala) and copper-based materials are still virtually everywhere, from the humble penny to electrical wiring. So what exactly does copper do, apart from giving her copper(II) carbonate-green colour to the Statue of Liberty? Scientifically speaking, lots of things.

Moga is a Medical Doctor student at the University of Toronto, and previously studied both chemistry and biology at Dartmouth College — he is thus particularly interested in copper’s biological functions and catalytic role in the synthesis of new medicines. He identifies three processes that cover most of its abilities: Lewis-acid catalysis, single-electron-transfer processes, and two-electron-transfer reactions.

One of the best-known reactions involving copper as a Lewis acid is the popular ‘click’ azide–alkyne cycloaddition that connects the two groups to form an azole ring. This fast, reliable reaction is generally easy to carry out and makes for a highly efficient step in a wide variety of processes including, for example, natural product total syntheses.

Single-electron-transfer processes where copper adopts either a Cu+ or Cu2+ form are widespread in biosystems. Cellular respiration in organisms, for example, relies on a succession of these steps carried out by copper-containing enzymes to oxidize glucose, and extract its energy. Two-electron transfer reactions are also common — they go through a slightly more complex mechanism involving a halide ion.

Of course, this is by no means an exhaustive list. Copper is looking increasingly like a good alternative to palladium catalysts, and it’s also a useful building block — remember the copper nanotubes?

As it turns out, we’re still very much in a copper age, and it looks all set for the duration.

Anne

 

Anne Pichon (Associate Editor, Nature Chemistry)

DNA nanotechnology workshop: Unnatural assemblies

I’m just back from Shanghai, where I attended the 2nd DNA nanotechnology workshop, a very exciting meeting at which we also celebrated the prestigious Albert Einstein professorship of the Chinese Academy of Sciences being awarded to Ned Seeman, often called ‘the father of DNA nanotechnology’. The story goes that as a young crystallographer, worried about getting tenure, he went to the campus bar to have a few beers and mull things over. Seeman found inspiration in the Escher woodcut Depth to make crystals using DNA, so as to avoid the guessing game (and potentially praying)­ that everyone who ever tried to crystallize anything is only too familiar with. The rest, as they say, is DNA nanotechnology.

The idea of hybridization — mixing two separate DNA strands to make a double helix — was reported in 1956 by Alex Rich, in a paper that incidentally very nearly fitted into a single column (half a page) of the journal! The beauty of the assembly lies in the precisely controlled positioning it enables at the nanoscale, and by carefully designing strands you can fold them up into increasingly complex designer structures (origami).

The meeting — whose theme was “From structure to function” — undeniably showed that DNA nanotechnology now branches out in many directions. We saw a wide variety of DNA items, triangle, cube, tetrahedron, octahedron, and even curved architectures; used for example to position other species (from gold nanoparticles to proteins); or manipulated to form nanomechanical devices such as tweezers, chopsticks-renamed-pliers, or walkers. These behaviours can in turn be used for example for guest recognition, detection, or to construct logic gates; make up DNAzymes (single-stranded DNA sequences that act as enzymes). It would be impossible to try and discuss here all the elegant structures and systems presented at the workshop, but I would like to mention an unusual one. Fritz Simmel from Munich looked into autonomous behaviours, and coupled DNA tweezers with oscillating systems. You will find more details at PNAS, 108, E784-E793 (2011) but essentially, they used transcription and RNA degradation reactions to induce, under the right conditions, the periodic opening and closing of DNA tweezers, making for a synthetic transcriptional clock.

There was also quite a lot of talk of cell studies — which perhaps shouldn’t be surprising as we are, after all, discussing DNA here. When it comes to therapeutic applications though, as William Shih mentioned, it is great to have new drugs but the hurdle we need to get passed is their delivery — how to get them in the cells? And so he’s exploring how the shape, size and function of DNA items affects the rate at which they are internalized.

The wide variety of DNA assemblies presented leaves no doubt that the field will only continue to get more exciting, and I look forward to seeing these developments and further branching out. I have to say as well that, for me, all of this made all the more exciting by being hosted at the Shanghai synchrotron facility!

Anne

 

Anne Pichon (Associate Editor, Nature Chemistry)

Element of the month: Cool as helium

This month’s ‘in your element’ article (subscription required) is also a winning entry from last year’s competition. Christine Herman, known on Twitter at @CTHerman, a PhD student at the Department of Chemistry, University of Illinois at Urbana-Champaign, who also likes to write about science — for example she contributes to C&En’s Just Another Electron Pusher — shares why she loves helium.

In 1868, astronomers Jules Janssen and Norman Lockyer — who was about to found a certain Nature journal — both noticed (independently) a bright yellow line in the spectrum of the Sun that could not be accounted for by known elements. The suggestion that this line might come from an element present in the Universe but so far undiscovered on Earth seemed bizarre at first, but was to be later unambiguously backed up. Luigi Palmieri detected this element in 1882 in Mt Vesuvius’ lava, and William Ramsey managed to isolate it in 1895 by treating a sample of the uranium mineral (cleveite) with sulfuric acid, liberating helium that had been produced by the radioactive decay of uranium.

It’s perhaps no wonder that this noble gas wasn’t noticed earlier — it is, after all, colourless, odourless, tasteless, non-toxic, and escapes easily from the Earth’s atmosphere so that its concentration is only about 0.0005% by volume. It does however get trapped under the surface, usually with natural gas, and this is where we get the helium we need.

And need it we do, not just for balloons and squeaky voices at parties. You already know this if you’re, among other things, a paleontologist, a deep-sea diver or an arc welder; read Herman’s article to find out more.

She does make a fair point — helium is cool. So much so that many scientists in many fields (for example physics and medicine but also nuclear energy applications) use it as a cryogen. And if you go down to temperatures below 2 K, helium becomes downright bizarre and very intriguing: it adopts a superfluidic state that has no viscosity but a very high thermal conductivity. It is also enticing to chemists who, undeterred by its inertness, keep trying to combine it with various elements. Some of these — excited dimers rather than actual compounds — went on to find a use in lasers.

And, as if helium wasn’t exciting enough in its own right, antihelium observed last year made for the heaviest anti-particles produced so far. All in all, colourless, odourless, tasteless, non-toxic element 2 is very far from dull.

Anne

 

Anne Pichon (Associate Editor, Nature Chemistry)

 

 

Element of (last) month: A pinch of sodium

In the midst of the blog relaunch, a trip to China last December (which I plan on telling you about in a future post), and the end-of-year holiday period followed by a start-of-year busy period, I didn’t get the chance to write about our December in your element article. This is the first competition winning essay that we’ve published — I think I did mention last year’s essay competition a couple of times.

Margit Muller – PhD student in pharmacology at the University of Copenhagen – highlights how sodium is far from being as mundane as it may seem. Wise daughters from old fairy tales who tell their royal father they love him as much as sodium chloride (they might have said “salt” in the original version) know this, but let’s take a look at the chemistry arguments.

Since its discovery in 1807 by Sir Humphry Davy – who was on a rather impressive element-discovering spree – sodium has amazed chemists. Reports dating back to the 1850s already describe its spectacular reactivity, including its reaction with water that contributes to entice generations of (mischievous) school kids to chemistry according to some Reactions pieces. Among other applications, it is also what makes for pretty yellow flames in fireworks.

Read the article (subscription required) to find out just how crucial sodium is in biological processes, and how essential it is to maintain a good balance of sodium outside and within the cells. Membrane proteins are in charge of controlling specific sodium channels, which let Na+ ions in and out of cell as required and regulate all sorts of processes related to pretty much everything we do, from muscle contraction to neurotransmission. You have been warned, disturbing this sodium influx can have pretty serious consequences! For example, this is just what makes tetrodotoxin from pufferfish (or fugu) — one of the most toxic substances on earth — poisonous…

Anne

 

Anne Pichon (Associate Editor, Nature Chemistry)

Element of the month: Oxygen origins

Oxygen is everywhere. Really, few elements are more abundant in the universe — in fact just two, hydrogen and helium. It combines with most other elements from the periodic table to form an incredibly wide range of compounds which serve an incredibly wide range of purposes. Just looking at the Earth: oxygen-bearing compounds are found in the mantle, crust, oceans and seas, atmosphere and living organisms, not to mention natural and man-made materials such as silica, zeolites, textiles, ceramics and drugs. Oh, and oxygen also takes part in energy production, as well as a variety of processes that range from metabolic to geological.

Oxygen is most frequently encountered in the form of isotope 16O, much more stable than 18O and 17O — this is because 16O boasts 8 protons and 8 neutrons, a ‘magic number’ in the atomic world that confers special stability. In this month’s ‘in your element’ article (subscription required), Mark Thiemens from the University of California, San Diego, explains how determining the ratio of oxygen isotopes has greatly contributed to our understanding of the evolution of natural processes and life on Earth. For example, the ratio of 18O to 16O is different in the atmosphere and in oceans (this is called the Dole effect). This difference arises from the photosynthesis and respiration of land-based or marine organisms, which means it can be used to deduce the evolution of terrestrial and marine activities.

Yet, the role of oxygen in the formation of the solar system remains unclear. Some meteorites that are known to be among the oldest objects in the solar systems have an unexpected oxygen isotopic distribution. Despite progress in the field, described by Thiemens in his article (they involve measurements on solar wind samples!), this distribution still remains unaccounted for, and exactly how the current celestial objects were formed remains unsolved for now.

Anne

 

Anne Pichon (Associate Editor, Nature Chemistry)

ICCOSS XX: Growing crystals in all shapes -and sizes

All good things come to an end… Among the many, and varied, aspects discussed at ICCOSS over the past few days, I wanted to bring your attention to halogen–halogen bonding, which seems to be becoming quite popular. When a halogen atom engages in such a bond, its charge distribution changes a little, leading to a ‘polar flattening’ of the atom. The more electronegative side of one atom naturally engages in a halogen–halogen bond with what has become the more electropositive side of the other. Can these interactions be relied on to assemble building blocks? Can they be tuned in a controllable manner by judicious choice of the halogen?

But the good old hydrogen bond was far from being left out. I enjoyed E. Arunan’s presentation about giving atoms a hydrogen bond radius. After all, covalent, ionic or van der Waals interactions have their covalent, ionic or van der Waals radii counterparts, so although by no means easy it may well be possible to do that for the hydrogen bond too.

Another exciting feature of the solid state is chirality – which turns out to be a lot more widespread that one might think. Bart Kahr had some surprising numbers for us: 8% of organic compounds naturally crystallise in a helical form, and about 25% can be made to do so! He showed a very nice movie of a crystal growing helically — but with an optical axis that moves during the growth process: twisting occurs at the tip, and at the same time the bulk untwists. This, he suggested, is probably associated with strains and stresses that are caused by the presence of an impurity.

From a theoretical perspective, R. Ramasesha showed us how he goes about modelling molecular materials for electronic applications – in a JACS paper from 1911 (very possibly the oldest paper cited at the conference) Moore and McCoy wrote that “it is possible to prepare composite metallic substances from non-metallic constituent elements”. This is exactly what organic electronics are.

But I’m not going to list all the topics discussed. Why not come and see for yourself at the next ICCOSS, held in Cardiff in July 2013!

I did want to mention the presentation by Hitoshi Kanazawa, Professor at Fukushima University, about 60 km from the Daichi nuclear power plant, who reported on the situation and how he and his group went around measuring radioactivity after the accident (this is not easy, as the values measured depend on where exactly you take the measurement, how far above the ground, the winds at that moment and so on). He also tried to find a way to rinse the radioisotopes but all attempts have so far remained unsuccessful. As we know, this accident has been a disaster, and sadly cleaning up will take for ever.

Hitoshi Kanazawa also had a very interesting poster – but I’ll refrain from telling you all about it, as the results are unpublished. I will only say that admiring some sample materials that he’d brought involved a syringe and a band aid, which certainly made for an enhanced poster experience.

And finally… for all of you out there who just love pretty crystals – I know it’s not just me – I have good news: our Ali Baba’s cave does exist. It is in Chihuahua State, Mexico – aptly named the Crystal Cave – connected to the NAICA mines. Dario Braga showed striking pictures throughout his presentation – these caves shelter crystals as big as trees! How did they form? You can find out at the website of the team of scientists and explorers who are studying – and protecting – these amazing crystals.

Anne

Anne Pichon (Associate Editor, Nature Chemistry)

Pacifichem 2010: Dispersion corrections and gelation

This morning I went to some physical chemistry sessions on computational quantum chemistry. I won’t attempt to summarize the various interesting points raised by the speakers as well as the members of the audience, but I’d like to highlight one conclusion from Stefan Grimme’s presentation: he showed that dispersion corrections should really be used routinely – rather than occasionally – in density functional theory (DFT) methods. Pavel Hobza, who next took the stage, wholeheartedly agreed, saying in particular that these corrections play an extremely important role when it comes to biomolecules.

After another few talks in that session – including a very engaging presentation from Mark Gordon about his favourite molecule, water – I nearly didn’t make it to the sessions held in a different hotel because the roads were getting flooded… [well, yes, after I mentioned the lovely weather and warm temperatures it’s only fair to let you know that we did have a lot of rain today]. But all went well and I managed to see some anion coordination chemistry, including a photo of beautiful crystals growing in a supramolecular gel, from Jon Steed’s lab (photo that appeared recently in a certain chemistry journal). Steed’s group first form a supramolecular bis(urea) gel for which the gelation can be reversed by adding an anion. They then use the gel as a matrix for the crystallisation of organic compounds, and subsequently remove it (by anion addition) to collect the crystals. Gels are often mentioned as promising host matrices for drugs, and this approach could serve for pharmaceutical polymorph screening.

The last talks of the conference will be held tomorrow morning — and this also marks the end of Chemistry Week, as December 15-20 had been officially proclaimed by the Governor and Lieutenant Governor of the State of Hawai’i.

It has certainly been a great meeting, with engaging presentations and discussions as well as very enjoyable evenings – for example, we were treated to some traditional chanting and dancing not only from Hawaii but also from the other Polynesian countries. And this is how I got to see a real New Zealand Haka (well known to those who like to watch international rugby), a little before a ‘fire dance’ accompanied by fireworks on Waikiki beach…

The only thing is that I missed a few speakers that I really wanted to go and listen to – I may just have to come back in five years time!

Anne

Anne Pichon, Associate Editor (Nature Chemistry )

Pacifichem 2010: Variety is the spice of life

This past couple of days I have been attending more traditional, ‘core’ areas of chemistry at the inorganic, macromolecular and organic sessions. I first went to “the new age of advanced materials” symposium, and although I was fighting a little bit of jet lag and sleep deprivation (not a good combination) it made for a very interesting morning. Among exciting endeavours on helicity, supramolecular chirality, and controlled assembly and organization, Sam Stupp from Northwestern University showed interesting bioapplications with his supramolecular polymers, such as some neurotherapy studies that look promising against Parkinson’s disease.

In the inorganic sessions, I indulged in some metal–organic frameworks (MOFs) chemistry — these relatively young hybrid materials seem to be acquiring some maturity, rapidly moving to a new level of complexity and functionality. For example, Seth Cohen from University of California, San Diego, wishes that they could soon(ish) be used as scaffolds, in which just the right functional groups would be held in just the right place and orientation to mimic a metallo-protein active centre. Talking about bio-inspired applications, I particularly liked this comment from Ivan Huc that “mimicking isn’t copying”: scientist do get inspiration from nature – who controls activity, accessibility, or selectivity with remarkable precision – but rather than trying to reproduce the same functions they will then look to construct systems that do what nature cannot.

This morning I headed over to a ‘redox redux’ session on non-innocent ligands from an inorganic and an organometallic perspectives. Although as Cortlandt Pierpont reminded us they have been alluded to as far back as 1966, and described clearly in 1978, the role of these redox-active ligands had then not been mentioned much. They have recently been attracting attention, and I was happy to see elegant compounds and reactivities, including a combination of redox and acidic activities in Thomas Rauchfuss’ talk, or some unusual oxidation states [such as Pd and Pt(III), Ag(II), or Ni(III)] from Martin Schröder’s lab. Over on the organic side of things, a symposium dedicated to Bob Moss was also packed with intermediates and unusual molecules, and we saw in particular some pretty versatile reactivity from carbenes and nitrenes.

I’d like to borrow the (nearly) last thought for today from Eugenio Coronado at the University of Valencia, who showed some interesting studies in which monolayers – rather than molecules – serve as building blocks to prepare functional materials. He highlighted that this work requires a combination of inorganic, organic, coordination, supramolecular and surface chemistries, which fits nicely in the spirit of such a broad conference.

And finally… for those of you who haven’t finished their Christmas shopping, check out the Periodic Quest! Featuring two board games and about 4 or 5 card games – all centred about the elements, as the name suggests – this might just be the perfect present to keep busy with (chemistry-friendly) family and friends during those long winter nights (those what?)

Anne

Anne Pichon, Associate Editor (Nature Chemistry)