Jaws up close

Posted on behalf of Leonie Mueck, Associate Editor, Nature.

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In Jaws up close, I highlighted an article from a group of researchers led by Zhongchang Wang at Tohoku University on a new electron microscopy technique that achieved atomic resolution of the fluoroapatite structure in shark teeth without damaging the sample. A technical comment has now been published, which refutes the proposed bonding situation in fluoroapatite. On the basis of density functional theory calculations, Wang et al. had claimed that the Ca-F bond in fluoroapatite is covalent, which could be crucial in understanding why shark teeth are so healthy.

Based on further calculations and bonding analysis, Antti Karttunen from Aalto University, Finland, and Florian Kraus, from Technische Universitaet Muenchen, Germany, now show in their comment that this conclusion is unsubstantiated. Rather, the Ca-F bond should be seen as ionic which rules out its strengthening function in shark teeth.

NChem Research Highlights: Nanotube electrocatalysts, pentagonal prisms and corroding platinum

Did you know you can get an RSS feed of our Research Highlights?

Carbon nanotubes can do anything, it seems. And now vertical arrays of nitrogen-doped CNTs have been found to be effective oxygen reduction electrodes, for use in fuel cells. Another cheaper alternative to platinum, which is the usual material used.

According to valence shell electron pair repulsion rules (VSEPR – remember learning those in long-ago undergrad days?), what structure would you expect a compound with 10 Ge atoms around 1 Co? Distribute all those bonds equally and you’d get a bicapped square antiprism. But instead you get a nearly geometrically perfect pentagonal prism — even the Ge–Ge distances BETWEEN the pentagonal faces are nearly the same as those WITHIN the faces.

Platinum and corrosion are two words I don’t normally associate with each other — especially because during my PhD we had a (terrifyingly expensive) Pt crucible that could withstand anything, at any temperature. But it looks like chlorine can do it, and exposing certain Pt surfaces to chlorine gas results in PtCl4 clusters forming as part of a highly ordered Cl-PtCl4 layer.

And finally…watch this space for more from Stu later today!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Catalysis, catenanes and qubits

Let’s dive straight in: Catalysts’ performances can be tuned by including other metals – for example, a CuPt alloy. You might expect that, for an effective catalyst, the surface would feature more of the reactive metal – in this case, Pt. But no! The less reactive Cu atoms migrate to the surface, where they create islands of Pt atoms to do the biz with the CO molecules.

Catenanes are molecules of interlocked rings and are normally made by interlocking rings containing either pi-donor or -acceptor groups. What Jeremy Sanders and colleagues have done is put pi-donors AND -acceptors into both rings. The building blocks link together with a donor-acceptor-donor-acceptor pi-section.

One day, we’ll all be using quantum computers. But to get to that exciting future, we need quantum binary digits – or qubits as they are handily abbreviated to – and to control their entanglement. Now, two Cr7Ni rings have been linked together through a Cu-containing ligand system. This provides three qubits, and their entanglement could be controlled by microwave pulses.

And finally…Gav caught physical chemistry textbook guru Peter Atkins on TV yesterday morning. You may be able to watch on the BBC’s iPlayer here. Not a vast amount of chemistry, admittedly, but most definitely a chemist!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Polymers, magnets and suprabowls

With most of the UK enduring or enjoying a couple of inches of snow, normal Research Highlight service is resumed.

As we’ve known since The Graduate, polymers are the future – especially ones that conduct. But the way that electrons (or excitons to be a bit more accurate) move along polymer chains has always been assumed to be by ‘hopping’ between excited areas. It turns out that they might move more smoothly [the Perspective even says ‘surfing’] and even retain some ‘coherence’.

Metals from the d- and f-blocks are generally pretty different: directional bonding vs diffuse, a range of oxidation states vs stick-in-the-mud 3+, and so on. Compounds that have a metal from both families, therefore, can be pretty interesting – especially magnetically. And that’s just the case for some copper-lanthanide complexes that are (sort of) a trimer of dimers.

Apparently, there was some sort of big sports game thing on Sunday, and it meant Steve could get away with using the word ‘suprabowl’ in his headline. Topical. Anyway, back to the science. The bowls in question are tris(spiroborate)s that form supramolecular polymers with iridium complexes – at room temperature.

And finally…two links that could help improve the way publishing works. One is hosted by the RSC on behalf of a UK funding body (JISC) to understand how you communicate and use information. The other one is to help categorize the comments on PLoS ONE papers. Do your bit for Science 2.0!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: π interactions, field-effect transistors and ion recognition

Tuesday already! How time flies… Wait no longer, here are this week’s Research Highlights.

The role of aromatic π-π interactions mustn’t be underestimated — they contribute to many biological functions, including pretty crucial ones like the stability of DNA, or drug binding. In previous studies benzene rings had received most of the attention, but you can now find out how heteroatoms affect these interactions.

How about a high-performance, photosensitive, nanoscale field-effect transistor? It is all possible thanks to the self-assembly of organic molecules into columns within the nanogaps of a carbon nanotube…

When it comes to ion recognition, selective binding to chloride (essential to human health) versus, say, cyanide (notably harmful) is essential. Steve tells us about a receptor that captures chloride and determines its concentration even in the presence of significant amounts of water, like in sports drinks.

And finally… although no metric can really quantify the value of scientific research, how can we estimate the importance of a particular paper? The number of citations? The Impact Factor of the journal? It looks like Google’s PageRank algorithm might be able to help

Anne

Anne Pichon (Associate Editor, Nature Chemistry)

NChem Research Highlights: Straight iron, protein binding and H-graphene

Like a cricket pitch with autumnal goal-posts, here’s a small sign of time passing: Research Highlights are now going to be more like 200 words than 250. Why? Because the print version of Nature Chemistry will require shorter stories, so we need to get in the habit now! I hope you’ve enjoyed the bonus 50 or so words per article – you’ll never have it so good again!

So anyway, onto the science. Of the few two-coordinate iron complexes known, most aren’t straight because the sneaky iron atom tries to increase its coordination by latching onto the other bits of the ligands. The tertiary-butyl amide complex recently made, however, IS linear. This gives rise to some slightly odd magnetic properties.

How proteins fold up into their beta-sheets is pretty important, especially because misfolding is implicated in some diseases/disorders. Some aminopyrazole derivatives could prevent misfolding, and now how they interact with peptides has been investigated in the gas phase. This led to all sorts of information about the conformation and H-bonding.

Graphene is the two-dimensional nanocarbon poster-child that lots of people are getting excited about – it’s even on the BBC website. But what if you could add hydrogen atoms to the sheets, and create ‘graphane’? Well…Andre ‘Mr Graphene’ Geim and Kostya Novoselov have hydrogenated graphene and found that it not only buckles up, but also changes into an insulator. Graphene for hydrogen storage, anyone??

And finally…while some things change (JACS has got cover “artwork” [mmm, nice spectra]), other things don’t (the RSC has got a press release with no discernable science)!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Cheap fuel cells, biopolymer threading and biosensors

Happy New Year! Here are the first batch of Research Highlights of 2009. (Although I should confess that we wrote them last year…)

So, we all know fuel cells are going to rule the energy world soon…but not if they’re stuffed full with platinum and similarly expensive metals. Which is why replacing such precious metals with cheaper ones, like silver, at the cathode is so important. [FYI: I checked out the market and silver is about 100 times cheaper than platinum]

The biological world is full of long chain molecules, like DNA or proteins. How exactly these chains manage to thread through pores – either in enzymes or membranes – is pretty challenging. We’re getting closer to understanding thanks to some clever chemistry: threading a fluorescent polymer through a macrocycle until it reaches a certain point, at which it stops fluorescing. The kinetics of threading can therefore by studied by the fluorescence quenching.

Hyperpolarised xenon has been investigated as an alternative to using gadolinium compounds as contrast agents in MRI – it can be probed directly instead of protons. And now Ivan Dmochowski and colleagues have used 129-Xe as a biosensor that can determine the difference between two isozymes of carbonic anhydrase.

So, apart from the honour of being featured on In the Pipeline, what else have we been checking out in the new year? Steve’s been looking at some pretty pictures, thanks to his former home Lab on a Chip and their Art in Science feature. I’ve been learning how to make your home-brew nice and cloud-free – it’s all down to Stokes Law and a galactose polymer (carrageenan)…

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Biosensing dyes, strong biomimics and levitating beads

So here it isResearch Highlights, everybody’s having fun. But before we all disappear for Christmas, here are the final RHs of the year.

I covered a pretty smart idea for a class of biosensors. Reducing cynanine dyes means they don’t fluoresce, until they come into contact with the nasty reactive oxygen species that mess around with cells. Even cleverer, the reduced forms can slip in and out cells willy-nilly, whereas the fluorescing ones are trapped inside the cells, showing you where the problem is.

You might well have seen this one elsewhere, but now you can read Tim’s take on the biomimetic material that’s thin and strong – it’s all about the ice templating, you know.

Last, but by no means whatsoever least, it’s a nifty idea for what could become ‘TLC for solid-supported synthesis’. And it involves magnetically levitating beads!

And finally…unlike the BMJ we haven’t got a load of spurious research to make it into the news-light festive season newspapers – watch out for next year though – and we’re a week before the RSC releases the same story about hangover cures for the 3rd or 4th year running, so I’ll leave you with some mathematical clues to help you wrap presents better!

See you all in the New Year – thanks for all the comments in 2008!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

Top 10 Research Highlights of 2008

So, with 2008 drawing to a close, we thought we’d select our favourites from the chemistry we’ve covered this year. The five of us editors had two picks each, so here’s our top 10 (in no particular order):

Gav

Ion transport: Testing the water

Eigen complexes, Zundel complexes, Grotthuss mechanism: there’s some great terminology related to water structure but we still don’t fully understand it! This paper was a good example of how fancy spectroscopic techniques can be used to understand just what is going on with the seriously speedy diffusion of hydroxide ions in water.

Catalytic hydrogenation: Guided by theory

The importance of heterogeneous catalysis to the chemical industry really can’t be overstated, so one of my favourites this year was this theoretical paper by Jens Nørskov and friends. They use computational methods to seek out the best (and economically viable) alternatives to expensive industry-standard hydrogenation catalysts. Watch out for a review in this area next year!

Stu

Nobel Prize 2008: Green fluorescent protein

Over the past few years GFP has been a favourite pick in the numerous ‘what will win the Nobel Prize in Chemistry this year’ lists. And now it has — and deservingly so. The question is, what will be the consensus pick for the next few years?

Coordination polymers: Ringing the changes

A research highlight that combines two of my favourite things — beer and football…no wait, I mean coordination polymers and Borromean rings.

Steve

Organocatalysis: Making light work of it

Most organocatalytic reactions involve typical polar reactions between one nucleophilic and one electrophilic partner. Not only is this approach radical, solving a long-standing problem in asymmetric synthesis, it was also the easiest headline I wrote all year.

Enzyme catalysis: Enantioselectivity evolved

Everyone knows that enzymes are good catalysts, but the search for the right enzyme can be a long one. I love the idea of training an enzyme to do what you want – and biasing evolution by using a clever reaction design is probably the ultimate way of achieving this.

Anne

Chirality: Handed over

Chirality can be a somewhat tricky property to introduce in materials. Here, the chirality of organic linkers is preserved and passed on to the bulk of an organosilicate material directly during the synthesis — a very elegant chirality transfer.

Molecular network: Random order

Check out these molecules that, when adsorbed onto a surface, form hexagonal ‘holes’ in a regular array regardless of how they arrange themselves. This leads to an ordered — yet aperiodic — molecular network.

Neil

Protein chemistry: Handy crystallization

The combination of painstaking chemical synthesis of both forms of the protein, followed by the conceptual leap to crystallise both of them in order to get the X-ray structure, made these two papers extremely impressive. And when you add the cool application – antifreeze proteins to help preserve donated organs — it adds up to work that made me say ‘I wish we’d published it!’

Superconductivity: The good samarium

It’s solid state inorganic chemistry, it’s superconductivity — I love it. This is just a sample of the ‘gold rush’ of work that was triggered by the pnictide superconductors.

And slightly less seriously, here are our top 10 Research Highlight headlines of the year:

Come on silene

The magnificent seven

Cage closed

The good samarium

Heterogeneous chemistry on Mars

All features great and small

Knot your usual molecules

Supersize sandwich

The 39 steps

Caught in a trap

And many thanks to Jane for copy-editing and Dipti for publishing everything for us all year!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Chiral alcohols, entrapment and nanotube motors

I’m dreaming ofResearch Highlights.

Making tertiary alcohols (ones without any hydrogen atoms attached to the carbon) with controlled chirality is a lot trickier than making other chiral species like secondary alcohols — those methods often rely on the difference in size between hydrogen and the other substituent. But now, using a simple method allows the choice of two achiral reagents to control which enantiomer is formed. And don’t forget to check out the News and Views article that Andy sold his soul so you can read it for FREE (for a week).

Germanium is an element in the no-man’s land of semi-metals between metallic and non-metallic elements, but it’s still not really a metal. And non-metals have rarely been observed as dications without a lot of accompanying ligands. But now dicationic germanium has been trapped inside a cryptand cage and caught with no clothes on. Which is a great amount of effort to go to in order to let Gav use the headline Caught in a trap.

And my prayers have been answered: a paper with supplementary info movies that show what’s going on. So, go and read Tim’s highlight about nanocapsules shuttling up and down inside carbon nanotubes, then watch the videos.

And finally…even though we haven’t published any issues yet, and won’t have an impact factor until about 2011, when we’re out and about we still get asked what we think Nature Chemistry’s magic number will be. Who knows?? Perhaps by then Thompson ISI will be using the corrected impact factor, as suggested by our heroes over at PHD comics.

Neil

Neil Withers (Associate Editor, Nature Chemistry)