NChem Research Highlights: Bryostatin, dendrimers and rowing microparticles

A busy week in the Nature Chemistry office: Anne has just returned from a tour of Japanese universities, Stu is about to head off to Bath for Catalysis and Sensing for our Environment 08, Gav’s already in Grenoble for ElecMol 08, Steve’s visiting Harvard tomorrow and I’m off to a symposium in honour of Professor the Lord Lewis of Newnham at the Royal Society on Thursday and Friday. Phew! But we’ve still time to bring you a dose of Research Highlights.

Total synthesis can be mind-bogglingly difficult, so why not just go and marvel at bryostatin 16?

Dendrimers, I imagine, are probably normally a big writhing mass of chemistry, but these pyrene dendrimers sound a lot more…staid. Thanks to the stiffness of the dendron units themselves, the whole thing is pretty rigid.

Another article that really needs a movie…swimming microparticles! Although rowing is quite a good way to get your head round it. A big particle (the boat) is linked to a smaller one (the oar). They’re magnetic, so a precessing magnetic field makes them rotate (errr, the rower? Bear with me!). In a bulk solvent, they’d just happily rotate, but when they’re close to a surface, the viscosity gradient means that the oar ‘grips’ the the gloopier liquid and the particle/boat moves.

And finally…some shameless slapping of our own backs. According to this post over at Nascent, we almost totally rule! Well, we’re in joint second place for the chemistry blog most linked from the blogs registered at nature.com blogs.

Thanks for linking,

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Twisting, diversity and order from disorder

Monday = Research Highlights.

What actually happens when molecules isomerise? How do the atoms really move? I’ve never really thought about how little I know about it, so it was interesting to read how stilbene (two benzene rings linked by double-bonded carbon atoms) twists as it changes from cis to trans. It’s just a shame there’s no movie with the article!

As I’m sure many of you know (and as more organic colleagues have told me), making complicated organic molecules can, apparently, be a rather time-consuming and tricky business. Removing tongue from cheek, being able to sample as large a portion of ‘chemical space’ as possible is crucially important in drug discovery. Now, using only 6 simple reactions (hence Steve’s ‘Six degrees of separation’ headline) a team at Leeds have been able to generate over 80 different scaffolds.

Molecules adsorbed on a surface are unlikely to align themselves in periodic, crystalline array. But using a molecule that can bond in defined ways resulted in a hexagonal ‘hole’ appearing no matter how the molecules themselves were arranged. This resulted in the holes forming an ordered array while the actual molecules had no order.

I’m afraid the chemistry blogosphere/world of news has run dry for the “And finally…” section this week, so you’ll have to put up with this shocking joke:

Why do white bears dissolve in water?

Because they’re polar.

I do apologise – any better ones gratefully received!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Metathesis, omniphobes and di-iron

Let’s be havin’ some Research Highlights.

Ring-closing metathesis lets you (well, organic chemists) make a lot of different sizes of rings, and is tolerant to different functional groups, but it still can’t quite do everything. It’s domination of the world has come a step closer, however, thanks to some fluxional ligands. The catalysts are stereogenic at the metal centre, meaning you (well, organic chemists) can do rapid enantioselective catalysis.

Papers about hydrophobic surfaces often contain great pictures and/or videos of the materials in action (which provides me with another excuse to link to the superhydrophobic desktop hockey video!), but materials that can repel organic species are much rarer. So creating a surface that is repellant to both “oil” and water is pretty impressive. It’s all about the shape of the surface features…

As people’s responses to Question 3 in Reactions interviews are telling us, it’s All About Energy. So understanding how enzymes work – for example oxidising hydrogen – could give us clues on how to produce energy more cleanly. Which is why studying how a model of hydrogen bonding to a di-iron model of an enzyme can reveal the role of electron-donating ligands on the spectator iron.

Did you enter the Dance your PhD thesis competition?? I hope so – you can enjoy the winning entries here.

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: graphene, the chemistrode and hypervalence

It’s a good week for Research Highlights

Firstly, it’s good to see chemists really getting in on the act with graphene. The original route to make it (using sticky tape) was a little bit comical, but “chemical” methods were hindered by the sheets of carbon atoms re-aggregating. It turns out that using the reducing agent, hydrazine, as a solvent as well stops the problem.

Next, electrodes have been used to investigate biological signalling for oooh ages. But most biological signals are chemical, not electrical. To investigate them, Rustem Ismagilov and colleagues have created a microfluidic ‘chemistrode’ – it can stimulate, record and analyse the released molecules. [Alternative headline for this piece that I wouldn’t let Gav get away with: Chemistrode to joy. Groan.]

Thirdly, sulfur can form bonds to itself very easily (hence its many allotropes), but it can also form ‘hypervalent’ bonds (in sulfuranes) – where its formal valence is above 8. Organic compounds like this are incredibly rare, and generally unstable, so its quite an achievement that a sulfur-substituted organosulfurane has been made and structurally characterised. Similar S–S bonds are found in proteins, so the ease with which they can be cleaved in this model has implications for redox processes in biology.

And finally, in an effort to even up the culinary War of the Roses, here is a link to a recipe for Lancashire Hotpot. It’s quite interesting to see that the page says “Keep in mind that this is cooking, not chemistry, so a few grams this way or that won’t matter.” What an excellent and accurate sentiment!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: BO, drag and knotty molecules

Put the kettle on, settle down and read our Research Highlights.

The Born-Oppenheimer approximation simplifies the Schrodinger equation into more manageable pieces (unlike physicists, some of us have to deal with more than one electron…) and is pretty crucial for quantum chemistry. It doesn’t always hold, however, but in some complicated physical chemistry we let Gav write about, it still holds up in reactions between hydrogen and chlorine.

Seeing as one day nanoscale people will be driving around in nanoscale cars, it’s worth making sure that they won’t be breaking the 2nd law of thermodynamics. Fortunately for everyone, it doesn’t look like they will: a classical mechanical ratchet on the molecular scale just slows down, rather than going in one direction.

Molecular knots are normally tricky beasts to make – as you might expect – but now a method to make some by simply allowing silver ions and organic ligands to diffuse together takes only one step. Different length ligands produce different knots.

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: layering liquids, double metallocenes and fixing fingerprints

Time for another dose of Research Highlights – we scour the literature so you don’t have to…

First up, would you expect ionic liquids to separate into layers of anions and cations on surfaces? At first glance, you’d probably think they’d mix it around to balance the charge – but not if the surface is charged, as is the case.

Next we have some ‘double metallocenes’ – rather than just one Cp (or indeed Cp*) ring above and below the metal, these have two fused Cp* rings sandwiching two metals. In the 250-word article, I didn’t have space to go into the full story of the magnetic, electronic and redox properties investigated, so you’ll have to go over to JACS for the details.

Serendipity…not just a good name for a cat or a posh word for luck. Where would chemistry be without it? In this case, without a method for ‘fixing’ fingerprints. While trying to make sulfur nitride polymers Paul Kelly and colleagues noticed that the precursor, disulfur dinitride, was so reactive that it was even reacting with the fingerprints on the glassware…and you can imagine the rest!

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Bimetallic nanoparticles, oxo complexes and those blue bananas

Greetings blogateers, welcome to another batch of Research Highlights.

Busy week for Gabor Somorjai: paper in Science, featured in C+E News editorial, now a Nature Chemistry Research Highlight! Gav covers the work, which used ambient-pressure XPS to discover that bimetallic nanoparticles essentially turn inside out in different conditions.

Someone else with a busy week was David Milstein, who had a paper in Big Nature, features in this week’s ChemPod (which itself features in C+E News) and now in a Research Highlight. Oxo complexes are believed to intermediates in lots of crucial catalytic processes, but isolating complexes has been extremeley difficult – find out how here.

Picking up almost as much attention is our final piece: did YOU know that bananas fluoresce blue under UV light – but only when they’re ripe?? It’s quite amazing to think that in all the years that humans have had UV lights no-one’s noticed this before!

And in this week’s prize for Press Releases with Staggeringly Tenous Links to Chemistry, the RSC win again! To add to the annals of cringe (Sherlock Holmes, ‘on-screen chemistry’, football managers chewing gum, Carol Vorderman in mauve…), there’s a competition that manages to shoehorn chemistry into the Italian Job. You can win a trip to Turin, so it’s almost worth gritting your teeth and having a go. Do remember that submissions must “be based upon the principles of serious scientific rigour” (whatever that means), helicopters aren’t allowed, and you can’t use what Michael Caine has revealed would have been the real ending. And they got the quote wrong – spotter’s badge to film-boy Ed.

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Bidentate ligands, squares and chirality

Monday morning usually means a big jug of coffee, discussions about points accrued over the weekend in the Nature fantasy football league and of course… Nature Chemistry Research Highlights.

First up, Steve discusses studies on the unexpected reactivity of bidentate ligands, carried out in my beautiful hometown of Durham.

Neil writes about a technique for creating nanoscale square patterns using the supramolecular assembly and controlled phase separation of diblock copolymers.

And Anne describes research that shows the transmission of chirality from a monomer to a solid mesoporous material during its polymeric synthesis.

And finally, since the closest I get to doing experiments these days is playing around in my kitchen (and as announced on the last ChemPod, I honestly do wear my Nature Chemistry lab coat when cooking) an interesting “”https://www.wired.com/techbiz/startups/magazine/16-10/pl_create">taster" for a book called “The Hungry Scientist Handbook” caught my eye in Wired magazine.

Using kitchen equipment for science seems to be the order of the day. Over at Chemical Technology (once edited by our very own Dr. Withers) they’ve just published a story called “Lab-on-an-egg-beater”.

Gav

Gavin Armstrong (Associate Editor, Nature Chemistry)

NChem Research Highlights: Strain, MOF tags and a certain prize

Hammer Research Highlight time.

Chemists love stressed and strained molecules – this must be true because Roald Hoffman and Philip Ball say so. Karl Irikura from NIST predicts that adamantane (imagine 4 fused cyclohexanes, or just look at the picture in the article!) can be stable with one of the hydrogen atoms pointing into the cage. He doesn’t predict how to make it though, so over to the synthesis guys…

Our new editor, Anne – the final piece in the NChem team jigsaw – writes about ‘tagging’ metal–organic framework materials so their volume can be fine tuned.

Our third one this week covers a certain prize you might have noticed being awarded last week. Well done to Stu for writing the piece in record time! On quite a sobering note, read about what Douglas Prasher is up to now – he isolated the gene behind GFP.

And finally…Martyn Poliakoff talks about the Nobel Prize on the Periodic Table of Videos. Want to be a science video star yourself? Why not enter the Science Dance Contest – all you have to do is interpret your PhD through the medium of dance! I can’t wait to see what chemistry looks like in dance format…

Neil

Neil Withers (Associate Editor, Nature Chemistry)

NChem Research Highlights: Oxonium, feedstocks and enzymes

It’s the weekly pick of the chemistry pops that we call Research Highlights

It’s not a ring of fire, but a ring of stability for our first piece. Oxonium ions (positively charged, triply bonded oxygen) are normally pretty unstable, but putting it at the core of a fused tricyclic compound makes a stable one – enough to be refluxed for 72 hours!

There’s a lot of carbon locked up in wood that could be used as a chemical feedstock instead of fossil fuels, but how do you get at it? Use a solid acid catalyst, that’s how. This hydrolyses the bulky cellulose into more smaller and more useful sugars.

The reason enzymes are such great catalysts is because they’re very specialised – so much so that it’s hard to get them to react with other substrates. Using a carrot and stick method to feed or kill bacteria depending on whether the enzymes they produce are effective or not, enzymes that act on the un-natural enantiomer were produced.

And finally…hooray for the Ig Nobel Prizes for research that ‘first makes people laugh, then makes them think’. The chemistry prize was split between two groups: one that showed cola can act as a spermicide and one that showed that it didn’t. Gav deserves a prize for asking whether they used Virgin Cola

Neil

Neil Withers (Associate Editor, Nature Chemistry)