The Chemistry of Chocolate? Eggcellent.*

Part I

With Easter coming up, and so many people giving up their sweet tooth for Lent, it seems like chocolate is on everyone’s mind. So what better topic for my first blog post for Science Brainwaves than the science of chocolate…

The first record of chocolate dates back to around 1500 BC, when the Aztecs and Mayans began drinking a cold, bitter mixture of cocoa and water. They named this cacaoatl, which literally translates to “foamy water”. Delicious. Three thousand years later, chocolate reached the European mainland, and from then on, there was no stopping it. By 1831, John Cadbury was selling drinking chocolate, and in 1876, Nestle released the first bar of milk chocolate onto the market.

Despite the huge variety of chocolate on offer in the shops, the basic recipe is very simple – cocoa butter, sugar, cocoa solids and milk solids. The difference in taste comes mainly down to different amounts of each ingredient, although dark chocolate has no milk solids (which is why it tastes less “creamy”) and white chocolate has no cocoa solids, which explains the pale colour.

The way cocoa beans are processed are the key to how the end result will taste. After being picked, they’re fermented for about a week, dried for a fortnight and then transported to a factory. Fermenting the beans adds around 30 new chemicals to the mix, some useful and some not, so at the factory, the beans undergo a process known as the Maillard reaction. It has at least 9 steps, and converts the amino acids in the cocoa beans (which don’t taste of anything) to aldehydes (which generally taste great).  Depending on how hot the reaction is, how acidic you make it and how long you run it for, you can get over 1000 different tastes from the Maillard reaction, including coffee, caramel and roasting meat.

Next, cocoa solids (made from grinding the beans) are conched. This means warming them up, grinding them with sugar and blowing air over the top. The heat removes any volatile (easily evaporated) chemicals from the beans, and the air whisks them away. The main thing removed from the beans is acetic acid, which is more commonly known as household vinegar.

Conching the cocoa solids decides what quality the chocolate is. The smaller they get, the better the chocolate – anything greater than 0.03mm (0.003cm, or three hundred thousandths of a metre) wide and the chocolate will feel gritty in your mouth. European chocolatiers, like the Belgians and Swiss, prefer very, very fine particles, which makes it melt more slowly in your mouth, and explains why European chocolate is more expensive.

A useful tip is to never store chocolate anywhere too warm or too cold. If you leave it in a warm room, you get a “fat bloom” – the white powder you sometimes find when you keep an Easter egg for too long, or forget about the Dairy Milk in your handbag. The increased heat means the fat rises to the top where you can see it. You can get rid of the bloom by gently warming it, then letting it cool down slowly, but it’s tricky to get it right without ending up with a puddle of chocolate. If you keep your chocolate in the fridge, you’ll get a “sugar bloom”. Any water vapour inside the fridge or the packet will collect on the surface of the chocolate as it cools down, dissolving any sugar it can reach. This eventually crystallizes on the top, giving you a gritty layer of sugar on your chocolate. There’s no way to undo this, so store your KitKat at room temperature for the best taste and texture.

* Well done if you made it past the pun! The alternative was “The Easter Bun(ny)sen.” In part II, I’ll be looking at why chocolate makes you feel good, and how it can help you stay awake. Title suggestions gratefully received!

 

Doing chemistry in reverse

So, amides. If you’re any kind of a chemist, these are your bread and butter. Making a bond between an amine and a carboxylic acid to form an amide is one of the first reactions any chemistry student ever learns about. And even if you’re not a chemist, if I tell you that the amide bond is also called the peptide bond perhaps you might start to get interested; that’s right, the very amino acids that make up the life-giving proteins in out bodies are linked together by this vital type of bond.

Here’s how a traditional amide bond forming reaction might be written out:

In this reaction the amine has a lone pair of electrons which flow towards the positively charged carboxylic acid carbon. Water is eleimnated and the amide is formed.

This reaction is literally great, becasue no matter what groups are attached to the components (i.e. the groups I’ve called ‘R’) they can be stitched togethr with this neat condensation (so called because water is given out during the reaction).

Does it itself nanotechnology

In my first post  I mentioned that one of the key advantages to nanomaterials is that their properties depend directly upon the size and shape of the particles. This becomes important in developing new technologies as the material can be tailored to suit a specific task by changing the size and shape of the nanostructures.

Current manufacturing cuts and stamps things to order. We cut and etch silicon wafers for electronics and we mould plastics for casings. In some ways this is like trying to make a house out of a cave. To a large extent it works, you can drill and dig new chambers to make new rooms and put in plumbing for hot showers etc. However, you are always limited by the tools you have to cut and dig with, and the size of the cave. People have always found it easier to build houses from the ground up and changing the size and shape to fit the future occupants (two bedrooms and one bathroom for a one-child family, sixteen rooms for several generations under one roof).

In a very general sense, this is what nanotechnology promises, the means to put molecules together into larger structures or grow particles to specific sizes fit to our needs. The key to achieving this is to understand the processes of self-assembly. This is exactly what it sounds like, putting molecules together in the right conditions so that they may spontaneously arrange themselves into a larger structure or pattern that we can use for various purposes. A larger structure made when individual molecules are put together like building blocks is called a “supramolecular structure.”

A key element of such a structure is that the smaller molecules are NOT chemically bonded together. If you picture a jig-saw puzzle, the pieces all fit together to make your picture of (let’s say) the Houses of Parliament. You’ll notice it is not necessary to glue the pieces together but that the notches and bumps one the sides of each piece allows them to stay connected when fit correctly. In nature, molecules and atoms experience all sorts of interactions and attractions that make them want to stick together without the need for the more extreme process (the transfer of electrons) of forming a chemical bond.

One example of such a connection is the hydrogen “bond“. This is best explained if we take a look at a water molecule as in the image below (original source here).


Most of science can be described by the fact that Mother Nature is lazy. Atoms and molecules always want to be in the state or position of lowest energy. They don’t like to be bouncing off the walls or doing stuff, they don’t want to be promoted at work and have more stress and responsibilities, they want to be chilled out on the couch and doing as little as possible.  They will also do anything to try and get into this lowest energy state, which scientists often call the most stable state, maybe because the ‘couch potato state’ sounded bad. In general, atoms form chemical bonds because they find that together they have to do less i.e. have lower energy than on their own.

In the water molecule an oxygen atoms has determined its best chance for stability is to hook up with two hydrogen atoms (hence the chemical name H2O). When the bond is formed the hydrogen atoms share their electrons with the oxygen atoms and this combined pool of electrons are now buzzing about all three atoms like a cloud of bees. However, the negatively charged electrons are attracted to positively charged protons in each atom. The much larger oxygen atom has 8 protons and the hydrogens atoms only one each, in other words the oxygen atom has most of the honey and more bees (electrons) will swarms around the oxygen atoms than the hydrogen atoms. This effect makes the region surrounding the oxygen atom more negative due to the greater number of swarming electrons, and the end where the hydrogen atoms are more positive due to the lack of electrons. The difference is small, but enough to have effects on how the molecules behave, and is shown in the diagram where blue = negative and green = positively charged regions of the cloud.

Hydrogen bonding occurs when several of molecule with this subtle charge imbalance are put close together. Positive attracts negative and so the negatively charged ends of a molecules will be attracted to the positive ends of a neighbouring molecule. In some cases, depending on how fast the molecules are moving and how strong the charge difference is, this attraction may be enough to let the ends of molecules stick to each despite not actually forming a chemical bond the way that the atoms did in forming the molecule. For example the hydrogen ends of a water molecule can ‘stick’ to the oxygen end of another water molecule but not in the same way that the hydrogen atoms are attached to the oxygen atoms within each molecule. In fact, this is what happens when water becomes ice and it determines the shape of ice crystals such a snow flake.

Back the the nanotechnology, the image below is from the website of the nanoscience group at the University of Nottingham. This shows a Scanning Tunnelling Microscope image (another technique that allows scientists to take pictures of individual atoms) of a hexagonal network made from hydrogen-bonded self-assembly. The scientist, Dr Luis Perdigao, put a rod-shaped molecule (the grey ovals) and a triangular molecule onto a flat surface (just visible as darker edges to the grey molecules). He then heated the molecules to give them the energy to skim around the surface and mix themselves up then let it cool. As the molecules cooled they began to get slower and started to feel this hydrogen bonding effect start to stick the molecules together. The end of the rods were attracted to the edges of the triangle to make a joint that was similarly shaped to the letter Y. When lots of these joints stick together they make a pattern resembling a honeycomb (back to the bees again!) . You can try it yourself by drawing a Y and then drawing another one, the same size, next to it with the arms touching. Then draw a third Y, this time with the two arms touching the leg of each of the previous Ys. You should have a hexagonal space in the middle and if you keep going with that pattern, you’ll end up with a honeycomb.

This is a very simple example of self-assembly, which is still some way from being developed into a new technology. However, you can already see the next step which is to use the honeycomb pattern as a template or mould to arrange other molecules. In this case Dr Perdigao used the open spaces to arrange clusters of Buckminster Fullerene molecules (buckyballs, the white spheres in the image). It is possible that patterns of fullerenes like this could be sued to develop new computers. However, it demonstrates the potential for self-assembly. Self-assembled patterns like this can be seen as a foundation allowing us to put other molecules into precise arrangements suited for specific functions. These devices would built layer-by-layer from the ground up, using single molecules as building blocks much like the houses built to fit different families mentioned earlier. This vision of future manufacturing is called ‘bottom-up’ processing.

I hope that provides an adequate introduction to the concept of self-assembly. I hope to add some posts about other possible applications of self-assembled nanostructures, how they can be used in new technologies now and not in 20 years time and how biology got there first.

Nanofuses?

I thought this was kind of cool.

http://news.bbc.co.uk/1/hi/sci/tech/8556656.stm

Nanotubes, you say?

Well, maybe I should add some context to this

Elemental materials are substance completely composed of one type (element) of atom. Despite this, there are a couple of elemental materials that come in different forms, with very different structures and properties. This phenomenon is called allotropy and the best example are materials made of carbon. You will have come across two most common allotropes of carbon: graphite and diamond. Graphite is the materials in pencils often mistaken for ‘lead’ i.e. the part that makes the marks. Diamonds, well diamonds are those sparkly things you put on rings when you want someone to marry you. Thinking about those examples should be enough to illustrate, just how different things made from the same atoms can be.

The carbon atoms in graphite are joined together in six-sided rings which are all then joined together to make large, flat sheets of carbon. Graphite, in its purest form, is made up of millions upon millions of these sheets stacked on top each other like the pages in a book. However, they are interesting in nanotechnology because of what happens when you start to play with one of these pages (a single sheet is called graphene and is attracting a lot of interest of it own).

The products of this “carbon sheet origami” are called fullerenes. These molecules are the third allotrope of carbon and they are fast becoming the workhorses of nanotechnology.

With the right conditions and adding a bit of energy, usually in the form of a large electric spark, it is possible to make these sheets roll themselves into balls. The result is a hollow sphere made out of interlocking carbon rings. It’s easy to get the idea if you to try to picture the way hexagonal patches are glued together on the outside of a football (soccerball). This is a fullerene.  The first discovered and most common variety is ‘Buckminster fullerene’ a.k.a the ‘buckyball‘. Coming in at around 1 nm wide, buckyballs are large as molecules go but small for nanomaterials.

It is also possible to roll the sheet up into a cylinder like a paper straw, and this is called a carbon nanotube. These materials have been found to have some amazing properties such as being able to conduct heat and electricity in interesting new ways, and they are far stronger than steel when pulled, in fact they have the highest tensile strength of any material discovered so far.

So there we go, dipping our toes into the world of carbon nanomaterials. Trust me these little things are important and I believe they’ll be making a huge impact in future technologies.

Oh and graphite is one of the easier materials to do fancy microscopy on. When I say fancy, I mean seeing the ACTUAL ATOMS of the carbon rings. It easy to see such images if you google for ‘graphite’ and either ‘scanning tunnelling microscope’ or ‘atomic force microscope’. This one is from the Institut fur Physik, the University of Augsburg, Germany.

 

  

There are days when I am still gobsmacked by the fact that we humans, the hairless, fart-joke obsessed apes we are, have managed to find a way to take photographs of ACTUAL ATOMs. Even after four years of being the one taking those pictures I stil feel that way and hope I never stop.

 

What is Nano?

 

Nanotechnology is quickly becoming one of the hottest buzzwords in science. Nanopods, nanoparticles, nanotubes, even the iPod Nano. The last one is a major pet peeve as it has nothing to do with the growing field of nanoscience. The aim of this blog is to try and sort the facts about nanotechnology from the sc ience fiction plotlines, ‘grey-goo’ apocalypse scenarios and wild fantasies of tiny robots.  By exploring the latest research findings, cutting through the hype of the newspapers and letting the science speak for itself the true wonder of the ‘nanoworld’ becomes apparent.

So what is ‘Nano’?

Well, if you’re familiar with how much Coke is in a 330 millilitre can compared to a two litre bottle, or how heavy a kilogram of sugar is compared to a 5 gram sugar pack, then nano will be no problem. Like those examples, nano is a prefix used to describe very small fraction of (one billionth) of some quantity. The work of scientists often requires them to switch between the tiny scale of atoms and molecules to the vast sizes of galaxies.  Scientists are also somewhat lazy, and it gets very tedious having to say one millionth of a gram or ten billion metres all of thye time. So we use prefixes, like nano, milli and kilo, to be able to avoid such mouthfuls.

The most fundamental quantity in nanoscience is the nanometre (nm), which is one billionth of a metre.  To put that in perspective, it takes hundreds of thousands of nanometres to equal the width of one human hair. Also, whilst you read that sentence your fingernails grew by about one nanometre. Now compare those few seconds with often you usually cut your nails (which I would assume is best measured in weeks, assuming you’re not a nervous nail-biter). We’re talking a tiny tiny distance.

The flash applet linked below (from the University of Utah) is an excellent resource for putting this into more context. Use the slider at the bottom to explore the length scales. There is also more info on the prefixes scientists use for different length scales below the applet.

Nanotechnology involves the use and development of devices and materials whose properties originate in structures ranging from 1 nm to a couple of hundred nanometres. On the applet, that’s the size of the measles virus down to the phospholipid, that are both dwarfed even by bacteria.

http://learn.genetics.utah.edu/content/begin/cells/scale/

A good next question would be: Why are scientists so interested in things of this size? After all, atoms and molecules are smaller still. I’ll try to answer that issue in more detail in my next post. However, the simple answer, for now, is that things act differently in the nanoworld. For example, at the sizes we’re used to gold glitters. A clear liquid, when filled with small gold nanoparticles turns blood red. If you use slightly larger particles, the liquid is yellow. This doesn’t sound all that remarkable but scientists are now studying how these gold nanoparticles can be used to treat breast cancer, all because of the science behind this colour change.

I’m getting this ominous sense that I’ll be using the words ‘Size matters’ a great deal in this blog. The truth is, in nanotechnology it really does. However, here all the excitement is in the small things.