Chemistry World Podcast - November 2011

01:22- World's longest carbon-carbon bond created

04:20- Pitcher plant inspires ultimate non-stick surface

07:54- NASA's John Grotzinger discusses the difficulties of getting the Curiosity rover to Mars with its massive payload of analytical instruments, and what it will do when it gets there

15:55- Conjuring up gram quantities of a stabilising anion

19:07- Bacteria: the ultimate secret agent

22:38- Ever felt you're facing the world alone? This year's chemistry Nobel laureate Dany Shechtman fought hard to establish the idea of quasicrystals in the face of criticism. Hans-Rainer Trebin from the University of Stuttgart explains a little about the story and what a quasicrystal is

29:37- Chameleon clothes to detect falling oxygen levels

32:23- Patching up patients with a heart of gold

36:14- Trivia - Why is 23 October an important day for chemists?

(Promo)

Brought to you by the Royal Society of Chemistry, this is the Chemistry World Podcast.

(End Promo)

Interviewer - Chris Smith

This month, we're off to Mars in a mini, well almost.

Interviewee - John Grotzinger

The thrusters will push against the gravitational pull of Mars until it hovers, maybe 20 meters or so above the surface and then it reels the rover out on a set of cables down to the surface of the planet.

Interviewer -- Chris Smith 

That's NASA's John Grotzinger, the chief scientist behind the curiosity Mars rover machine, which blasts off to the red planet later this month. We'll hear from him how you get a car-sized rover down in one piece and the chemistry it's destined to do later in the program. Hello I'm Chris Smith. Welcome to the November 2011 edition of the Chemistry World podcast. Also with me this month are Phillip Broadwith, Laura Howes and Patrick Walter and they'll be talking about the creation of the world's longest chemical bond and the world's slipperiest substance. Plus it's your chance to brush up on what a quasicrystal is when we take a look at this year's Nobel Prize for chemistry.

(Promo)

The Chemistry World Podcast is brought to you by the Royal Society of Chemistry. Look us up online at chemistryworld dot org.

(End Promo)

(01:22 - World's longest carbon-carbon bond created)

Interviewer - Chris Smith

And to kick us off in the world of chemical bonds, size and certainly length are definitely important. Phil.

Interviewee - Phillip Broadwith

Absolutely Chris and one of the things that lot of chemists are trying to do is to trying to make the longest bonds they possibly can to test out the limits of, you know, how strongly atoms are held together and how they can design molecules that have particular shapes or particularly strained and weak bonds that might be particularly reactive in different ways or things like that.

Interviewer - Chris Smith 

Indeed. So what have they done here? 

Interviewee - Phillip Broadwith 

This group led by Peter Schreiner at the Justus Liebig University in Germany has made what they're claiming as the longest carbon-carbon bond in an alkane. It's 1.7 angstroms long, which is a little bit longer than a normal, sort of a carbon-carbon bond, averaged at about 1.5 angstroms. So, it's a little bit longer.

Interviewer - Chris Smith

So, how they actually done this because my understanding is that when you actually bond something together covalently like a hydrocarbon, it's because the clouds of electrons from one atom interact with the clouds of electrons from the second atom and you bring about a bond. So, how can you manipulate the length of that?

Interviewee - Phillip Broadwith 

Okay Chris, well that interaction is the same but that's if you're just talking about those two atoms. What chemists generally do to try and elongate these bonds is to attach other stuff to those atoms of the covalent bond. So, if you attach great big, bulky groups to those two atoms, you get like a dumb-bell shaped molecule. So the carbon-carbon bond is the bar of the dumb-bell and you've got this other bulky stuff attached to the carbons on either end.

Interviewer - Chris Smith 

And those two big bulky things repel each other and that pushes the bond apart.

Interviewee - Phillip Broadwith 

Yeah. So, the bulky stuff on either end literally just pushes the bond apart and puts strain on that bonding interaction, which just holds the carbon atoms just a little bit further apart, far enough apart that they can still just about interact and make a bond, but that bond is much weaker. 

Interviewer -- Chris Smith 

Now you mention that there could be some use in understanding this kind of thing because you know that you could use this sort of chemistry to create bits of molecules that are bit more vulnerable to that bond breaking than in another region or something. Are there any ways where this could immediately be exploited or applied then?

Interviewee - Phillip Broadwith 

Probably not directly, but the interesting thing about this particular work is that basically to make these kind of long bonds stable, you need not just a repulsion but some kind of attractive force to balance that out just enough to keep the bond together and what Schreiner and his group have done is use a van der waals interaction. So the big bulky molecules that they've got on either end of their carbon-carbon bond have relatively flat faces that are covered in hydrogen, and they have just enough van der waals atraction between them to keep the bond together. And so using that principal, you could think about designing other molecules, or using it to stabilize different kinds of new molecules and materials.

(04:20 - Pitcher plant inspires ultimate non-stick surface)

Interviewer -- Chris Smith 

Thank you Phil, new flies on him. Talking of flies, tell us about this pitcher plant inspired slippery stuff, Patrick, apparently the most slippery substance known to man apart from Tony Blair has been invented.

Interviewee - Patrick Walter

(laughs)Okay. So Joanna Aizenberg's group at Harvard University were looking at new ways to develop omniphobic material. So these are materials that repel both liquids like water, and also organic liquids like oil.

Interviewer - Chris Smith

Have we not already got super-slippery substances and what's Teflon then?

Interviewee - Patrick Walter

Yeah, Teflon is a super-slippery substance, but it's kind of different to the other kind of nano-engineered approaches they've been looking at. So people have been looking at super-hydrophobic slippery surfaces based on the lotus leaf. So the lotus effect is based on miniature papillae that sit on top of the lotus leaf and when something like water rests on the lotus leaf, the small pockets of air trapped beneath the water droplets, this creates nice round droplets to just roll straight off. But this doesn't work for oils because oils do not have the surface tension that water does. So they just collapse. So they wet the leaf.

Interviewer -- Chris Smith 

So they're just going to get underneath the air.

Interviewee - Patrick Walter

Exactly.

Interviewer - Chris Smith 

And displace the air around.

Interviewee - Patrick Walter

So, what Joanna Aizenberg has done is she's tried to copy the pitcher plant. So pitcher plants are plants that grow throughout Southeast Asia. These plants have a bulb which is filled with a digestive fluid and when insects land on the top of this opening of this bulb, they just simply slip off and fall in. So they started looking into why this happens and they wanted to copy it. 

Interviewer -- Chris Smith 

Why does it?

Interviewee - Patrick Walter

So, what's special about the pitcher plant is around the top of this bulb, where the insects tend to meet their rather unpleasant end, is there's this small, nano-sized pillars kind of sticking out from the plant's surface and this is coated in a kind of nectar. So this means that when the flies land on it, the oils don't grip, they just slip straight off in. 

Interviewer -- Chris Smith

Oh! Because the fly's foot is oily, you got this watery layer on the surface of the plant. Oil and water when mixed, so you got fluid on fluid and it's slippery

Interviewee - Patrick Walter

So oil and water are immiscible, they're not going to mix and this creates a slipperiness.

Interviewer - Chris Smith 

Now obviously they're not going to reinvent the oil making another pitcher plant. So what did this Harvard group do?

Interviewee - Patrick Walter

They had two different approaches. One approach was to create small nano-pillars a bit like many of these super-hydrophobic materials that have gone in the past and then a completely unstructured Teflon surface made with just a complete mixture of Teflon fibres and then what they did, copying the pitcher plant with its nectar liquid. They used a fluorinated compound. So, they just soaked this structure with it and this created a slippery surface. So, things like oils can't interact with this fluorinated compound and neither can water, it's immiscible with both. So anything that lands on it, they tested things like jam, ants.

Interviewer -- Chris Smith 

It's a liquid, it's not a gas. With the lotus leaf, you've got air, this gas is compressible and displaceable, whereas if you have a liquid there, it won't get compressed, will it so?

Interviewee - Patrick Walter

Exactly. So what's very important is.

Interviewer - Chris Smith

It will work under very interesting condition

Interviewee - Patrick Walter

Yeah. This is very useful because it can work under high pressures, things like oil pipelines perhaps. It's self-healing, so it just keeps recovering if it gets knocked.

Interviewer -- Chris Smith 

Something I think we wish we could all do. Thank you Patrick. 

(07:54 - NASA's John Grotzinger discusses the difficulties of getting the Curiosity rover to Mars with its massive payload of analytical instruments, and what it will do when it gets there)

Interviewer - Chris Smith

Mars is the focus of the space science fraternities' attention this month, when Curiosity, a new rover machine blasts off on November the 25th. NASA's John Grotzinger is the chief scientist on the project.

Interviewee - John Grotzinger

The Curiosity rover differs from that of previous machines. In that it has a very involved set of instruments that are most complex that's ever been flown to the surface of another planet and between those instruments we should be able to make a variety of measurements and integrate the measurements that are made to create a new insight into the habitability of ancient environments on Mars as well as get a sense for the current surface environments of Mars.

Interviewer -- Chris Smith 

First of all, how big is Curiosity?

Interviewee - John Grotzinger

Curiosity weighs 899.2 kilograms. It's about the size of a Mini Cooper. 

Interviewer - Chris Smith

Wow! That's pretty big, is that not what an order of magnitude, larger than the ones that are down there at the moment?

 

Interviewee - John Grotzinger

It's about half an order magnitude. Spirit and Opportunity each weighed about 180 kilograms and with Curiosity weighing at 900, it's a very significant increase in the mass of the rover.

Interviewer - Chris Smith

And size too, so what are you going to pack into this Mini Cooper sized frame? What will go in there and why are we scaling up to this ginormous size?

Interviewee - John Grotzinger

The reason for the increase in the size is because we have two instruments that function within the internal environment of the rover, so they're sort of in the belly of the beast, if you will, and when we collect samples, we do it by drilling and we need a kind of a drill that's able to penetrate into rocks up to depths of about 5 centimetres, drill bits about a centimetre and a half a diameter and then it feeds these powders through a very complex labyrinth of processing elements, so that it comes out, the sample is sieved down to about a 150 microns and then it goes inside the rover and in there, we have these two very specialized instruments. So that's what results really in the increase of the mass.

Interviewer - Chris Smith

What sorts of rocks are you going to be drilling into? What are you looking for?

Interviewee - John Grotzinger

Well, we've chosen a landing site that sits quite near the equator of Mars, but near a feature called the dichotomy boundary, where Mars basically gets cleft into two different hemispheres of different topographic elevation and at that break in elevation, there's a spot called Gale Crater which is a topographic depression that's a 150 kilometres in diameter and within that depression is a great mound of layered strata and what we can see on the strata is evidence for what was formerly aqueous environments and we should be able to study effectively a series of time records within their earliest history of Mars and begin to understand its evolution from a very wet planet and possibly habitable to microorganisms to the dry planet that it is today.

Interviewer - Chris Smith

So this has got a small drill though, so you can only really metaphorically speaking, scratch the surface of the planet. So how far back in time do you think you'll be able to go?

Interviewee - John Grotzinger

Well, we know that the crater that contains this thick pile of strata is probably over 4 billion years old and then using some other evidence that we have available we suspect that the strata themselves are probably not much younger than 3 billion years. So somewhere between 4 billion and 3 billion years ago, we've got 5 kilometres of sediment that has been piled up to form these layers. To look at and that really represents the principal target debris after.

Interviewer - Chris Smith

What sorts of questions will you be able to answer? How Mars started off, how it evolved, got wet, got dry, and then possibly life?

Interviewee - John Grotzinger

What we're able to do is take advantage of the fact that these strata have been quite deeply eroded and so what was once buried is now exposed, we're able to tap right into what would originally have been the sort of the internal part of this mountain of strata and when you go from the lower to the upper layers, you're basically going from the oldest records of time to the youngest records of time and where there are sediments there are records of the environment and so by drilling and sampling our way up through this pile of strata, we're effectively given the chance to reconstruct not just the state of the environment early on in Mars, but also the way it might have evolved.

Interviewer - Chris Smith

But looking at the practicality from in it, how do you get almost a ton of rover out there? How long is it going to take to get there and then how do you get it down onto the surface of Mars once you arrive?

Interviewee - John Grotzinger

To begin with, we launch and then on the cruise from Earth to Mars, everything is pretty much the same, there is a solar array which keeps the rover charged; takes about eight months and then we begin to feel the pull of the gravitational field as we enter the planet's atmosphere and begin to descend, but this time, in contrast to previous Mars landed missions, the aeroshell which is the bit that you see in these videos, that sort of screaming along with flame shooting out beneath it, it's actually able to steer a little bit because we have an ejectable mass, and it offsets the centre of mass from the centre of symmetry and it allows it to fly a bit like an airplane wing and then there are thrusters that are activated to allow it to correct the trajectory and so instead of, sort of, plunging vertically through the atmosphere, it's actually coming down at quite a low angle and then when it decelerates to about Mach 2, it deploys a parachute, and that slows it down even further and then when we get down to may be a kilometre above the surface, the heat shield falls away and from that now, everything gets very different from previous missions. We now have a forced spacecraft called the power descent vehicle. And the power descent vehicle has eight rocket thrusters and beneath it is attached the rover pretty much ready to go with the wheels hanging down. The descent stage then will drop down the thrusters, while pushing against the gravitational pull of Mars until it hovers may be 20 meters or so above the surface and then it reels the rover out on a set of cables down to the surface of the planet and then there, the descent vehicle detects the change in mass because now the planet is partially supporting the weight of the rover. The cables are cut and the descent stage goes off and crash lands and the rover, unlike previous rovers, this one requires very little effort to actually get going. It's pretty much it lands ready to go, as a result of that process.

Interviewer - Chris Smith

And assuming it does go according to plan how long will Curiosity be able to drive around on the surface of the planet?

Interviewee - John Grotzinger

It's one Mars year, which is a bit longer than two Earth years, but if you compare it to MER, those were built to go three months, so with two years, who knows how long we'll be able to go?

Interviewer - Chris Smith

NASA's John Grotzinger and if you'd like to find out a bit more about Curiosity there is a terrific feature in this month's edition of Chemistry World magazine, which is well worth a read.

(15:55 - Conjuring up gram quantities of a stabilising anion)

Interviewer - Chris Smith

You're listening to Chemistry World with me Chris Smith. Still to come, sending messages by bacteria, and clothes that change colour according to how much oxygen there is around, but first we were talking about Teflon earlier, now we're back for more and this time to hear how you can stick it to boron, Laura.

 

Interviewee -- Laura Howes

A group led by Helge Willner from the Bergische University in Wuppertal were looking at trying to make large weakly coordinating anions. So these are very large spherical, symmetrical anions that their charge is ready to spread out, it's not really polarized, so it doesn't interact very much, but it can help stabilize these cations that are quite weak. One of the anions that people have been thinking about for a long time is boron, surrounded by Teflon group, so CF3.

Interviewer -- Chris Smith 

Why would that be good?

Interviewee -- Laura Howes

Well, it would have all the properties that you'd want. I mean, the CF3 would mean that around it, it's not very polarized but because it's so large and like big, big ball. So it's sort of, you know, you've got your boron in the middle surrounded by these huge great big molecules and there's not really anywhere for the electrons to sort of go.

Interviewer - Chris Smith

I sense a but coming?

Interviewee -- Laura Howes

But, yes, they just couldn't make it. They tried various different ways of doing it, but they often found that it just wasn't going to work because of boron's lowest acid capabilities, they couldn't. Usually when you make an anion like this, you do look in substitutions. You put something on it; you take something off and put a different bit on it.

Interviewer - Chris Smith

Very laborious, very inefficient, so.

Interviewee -- Laura Howes

But boron, it just wasn't working

Interviewer - Chris Smith

So what have they done instead?

Interviewee -- Laura Howes

Instead, they've used these great interhalogen compound especially chloride trifluoride, so ClF3, which it will set fire if it interacts with just about anything. If you mix it with sand, it will set fire, if you mix it with asbestos, it will set fire, if you mix it with yourself, it will set fire. So there's not a lot of labs in the world that want to do anything with this stuff.

Interviewer -- Chris Smith 

I'm not surprised. So what did they do with it?

Interviewee -- Laura Howes

You have to keep it under very cold conditions, keep it under a very inert atmosphere and just be very, very, very careful with it.

Interviewer -- Chris Smith 

What do you keep it in?

 

Interviewee -- Laura Howes

I think, they keep it in stainless steel, but I wouldn't like to say for certain, it's been a while.

Interviewer - Chris Smith

Or try even.

Interviewee -- Laura Howes

No. (laughs) 

Interviewer - Chris Smith

So they've managed to make this material safely.

Interviewee -- Laura Howes

They have managed to make it. They have now got up to sort of 62 grams of the stuff they got.

Interviewer - Chris Smith

So you have boron, you react it with this chlorine trifluoride.

Interviewee -- Laura Howes

So, actually what you work on is a boron with cyanide groups around it, and instead of substituting onto the boron, what you do instead is you add the fluorine to the carbon and break the C-N bonds of your cyanide and replace those with fluorines.

Interviewer -- Chris Smith 

What could they do with it?

Interviewee -- Laura Howes

Well, at the moment, they've got to see whether it's actually got all the properties that they hope it has. At the moment, it's all just you know, it's a theoretical target they've got at and this is amazing. They think it's going to be pretty good. What they'd like to use it for ionic liquids, but obviously you need to have a good pairing and so this can help with that.

Interviewer -- Chris Smith 

Why are ionic liquids important and what can we do with them?

Interviewee -- Laura Howes

Basically they're made by, you know, two ions, cation and an anion. There are ways of doing chemistry often without other solvents, so it can make thing without all the nasty sort of organic solvents often we try and avoid.

(19:07 - Bacteria: the ultimate secret agent)

Interviewer - Chris Smith

Well, from the nastiest chemical known to man to perhaps becoming one of the most useful onto something else, potentially nefarious but also with good intentions to bacteria that could send secret messages.

Interviewee - Phillip Broadwith 

Well yes Chris. Next time, you get a spam message, maybe you should read it, at least that's if it's the kind of spam that David Walt at Tufts University of Massachusetts is talking about?

Interviewer -- Chris Smith 

What Viagra offers mortgages and chair of a dead dictator in Nigeria's fortune?

Interviewee - Phillip Broadwith 

Not quite Chris. It's a steganography by printed arrays of microbes. Steganography being the encoding of secret messages.

Interviewer - Chris Smith

Or spam for short, hence the acronym, okay. So what have they actually done?

Interviewee - Phillip Broadwith 

The idea is that you take engineered strains of E. coli that are made to be fluorescent. They have taken seven different strains, which fluoresce in seven different colours and if you combine two of those together to make a sort of bit of information that gives you 49 different combinations, which is plenty to do all of the letters of the alphabet and numbers, bit of punctuation in bits and bulbs. You can then kind of put strings of those past together to make a message. So if for example, you put an orange strain with the green one, that's an 'i' and a yellow one with the red one that's an 'r' and what this team did was put enough of those together to spell out the message. This is a bio-encoded message from the Walt Lab @ Tufts University, 2011.

Interviewer -- Chris Smith

How do you read it?

Interviewee - Phillip Broadwith 

Well the idea of transmitting the message is that the person you want to send the message grows up the bacteria in a little multi-well plate or something like that. You can then get a sheet of paper or nitrocellulose or something like that, press it onto the surface which transfers some of the bacteria, shift that in the post, the other person at the other end gets the sheet of cellulose, puts that into some growth medium, grows up the colonies of bacteria, and they start fluorescing and you can then read out the pairs of colours and get your message.

 

Interviewer -- Chris Smith

So what's the security side to this though?

Interviewee - Phillip Broadwith 

Okay, well first of all you need to know that there's a message on the paper, it's pretty much invisible until you start growing the bacteria, but if you know that then you can add a second layer of cipher by using antibiotics. So, instead of in each well of just having one form of bacteria, you can have two different strains that different colours and are resistant to different antibiotics. So you then need to treat the whole thing with the right antibiotic to get the message and the group did that and so they encoded a message that if you treat it with Ampicillin, you get the same message that I said before about being a bioencoded message from the Walt Lab @ Tufts, but if you use kanamycin, which is a different antibiotic, you get the message that says you have used the wrong cipher and this message is gibberish and if you use a non-selective antibiotic, then you just get a complete load of guff anyway.

 

Interviewer -- Chris Smith

What do they say it could be used for though?

Interviewee -- PhillipBroadwith 

Well, for the first then you got to rely on some kind of postal service which introduces a bit of a weak link especially if you're talking about a royal mail. It's kind of an experiment in a concept of sending messages, but there are ways that you can improve it even further. David Walt's talking about having bacteria that change the way they fluoresce over time, so you have a message that would automatically self-destruct. So, if your message is not particularly urgent, but you really need it to be secure, perhaps that's a possible application.

 

(22:38 - Ever felt you're facing the world alone? This year's chemistry Nobel laureate Dany Shechtman fought hard to establish the idea of quasicrystals in the face of criticism. Hans-Rainer Trebin from the University of Stuttgart explains a little about the story and what a quasicrystal is)

Interviewer -- Chris Smith 

Puts a whole new spin on the idea of a message going viral. Thank you Phil. Last month was Nobel time again and the chemistry prize this year went to the Israeli scientist, Dany Shechtman for his discovery of the concept of quasicrystals. But it was no plain sailing for Shechtman beforehand. He endured a very rough ride, when he first announced his findings in the 1980s including a scathing put down from the chemist, Linus Pauling. He described the work as nonsense remarking there is no such thing as quasicrystals, only quasi scientists. Well that got proved wrong, but if like me, you only have a quasi understanding of what a quasicrystal is then may be physicist Hans-Rainer Trebin from Stuttgart University can help

Interviewee -- Hans-Rainer Trebin

Crystalsare composed of atoms in such a way that the structure repeats periodically. This is like a wall paper where you have certain decoration and this repeats to left and right up and down. In a crystal, you have this periodic pattern in three directions. So if you know what the basic pattern is, you know, what the crystal is looking at infinite distances. Now there is a certain restriction on the symmetry of periodic systems. You can rotate a square crystal for example by 90 degrees. This is called a four field rotation; because 90 degrees is 360 degrees over four. You can rotate the periodic crystal also by 60 degrees. So one has certain rotation symmetries, which means, you rotate them and they look like after the rotation and for periodic systems, this rotation is twofold, three fold, four fold, six