Butyric acid, a very smelly molecule

Did you know that you’re walking around with an incredibly sensitive chemical detector, capable of detecting and identifying substances at levels as low as 0.2 parts per billion (I’m talking about gases here, but if you think about this ratio in another way it’s about half a second in a century), and possibly even lower? Capable of distinguishing between millions and very probably trillions of different substances and mixtures of substances?

nose

Did you nose you were carrying around a very sensitive chemical detector?

Well you are. It’s your nose. Dogs, of course, can do even better than humans (bloodhounds can easily detect substances in the parts per trillion range) but our noses are still pretty impressive.

We are particularly good with nasty smells, for very sensible evolutionary reasons. If it smells bad it’s probably bad for you, stay away and definitely don’t eat it.

Which brings me to butyric acid, or butanoic acid (to give it its official IUPAC name, which literally no one uses outside of A-level chemistry). Butyric acid is a small molecule, early in the list of carboxylic acids, and you might imagine a chemistry student would meet it, well, if not frequently then at least once or twice during their studies. After all barely a week goes by when we don’t crack open the ethanoic acid (also known as acetic acid, the stuff that gives vinegar its pungent smell).

And yet I managed to go for years and years without ever knowingly coming across the stuff. I knew about its theoretical existence of course, and never really thought about it much beyond that. After all, you can’t use every chemical can you? I obediently followed my lab book instructions and then later specialised in physical chemistry, so the opportunity to fiddle around with cocktails of interesting organic molecules of my own choosing never really arose.

Butyric-acid

Butyric acid: it’s very stinky.

When I finally did get my hands on a bottle of butyric acid I quickly learned why it had never featured in an undergraduate practical task.

It stinks.

Of horrible things.

Everyone that smells it seems to identify it slightly differently, but descriptions fall out of the: ‘pooh, farts, sick, smelly feet, sweat, gone-off curry, sour milk’ general category of bad smells. Occasionally someone will generously suggest parmesan cheese, but really, it’s not that nice.

It’s not a smell that goes away, either. It’s a stench that just keeps on giving. One of my students managed to get a tiny drop of it on a lab bench and, despite trying to clean it up, the smell lingered for weeks. In fact it was quite interesting. Most people could smell it for about two weeks (as in, they walked into the room and immediately said “ugh, what’s that smell?!”) After that fewer and fewer people immediately reacted, but every now and then someone would walk in and complain of a horrible stink, which by then no one else was really noticing. I assume these were individuals with unfortunately (in this situation) sensitive noses, perhaps with great futures ahead of them as chefs, sommeliers and perfumers. Although some fairly recent research has suggested that ability to recognise smells has more to do with training than innate ability. Still, who nose? (Hehe)

So what is butyric acid and why is it so stinky? It’s name actually comes from the Latin word butyrum (or buturum) meaning butter, because it was first extracted from rancid butter by the French chemist Michel Eugène Chevreul (bet he loved his job). It’s a fatty acid, which means it’s one of the building blocks of fats. The fat molecule made from butyric acid makes up 3-4% of butter, and tied up in this form it’s completely innocuous. However once those fats start to break down, the evil butyric acid starts to be released.

italian-parmesan-cheese

Probably the least offensive thing associated with butyric acid. Probably.

It’s generally found in dairy products, and is a product of anaerobic fermentation (that is, fermentation that happens in the absence of oxygen), hence the links to butter and parmesan cheese. Anaerobic fermentation also happens in the colon. Hence, ahem, the pooh smell. Oh yes, and butyric acid is also what gives vomit that distinctive, smell-it-a-mile-off, odour.

And this, of course, is why we’re so good at detecting it. Humans can pick this stuff up at 10 parts per million (going back to those time analogies, that’s the equivalent of 32 seconds out of a year) which explains why the stench appeared to linger on and on – that single drop of pure butyric acid would have contained something like a thousand trillion molecules. Evolution has trained us to detect and avoid this stuff because it’s very probably a sign of disease and potential infection (gone-off food, vomit, faeces etc). This is stuff we need to steer well clear of to avoid getting ill, and so nature has given us a handy mechanism by which to detect and avoid it, of the “yuck! What is that smell?! I’m out of here!” variety.

pineapple

From nasty to really quite nice: you can make pineapple scents from butyric acid.

Funnily enough though, it does have its uses. There are molecules called esters which can be made from butyric acid (that’s why we were experimenting with it in the first place) which actually smell rather nice. In particular there’s one that has a lovely apple-pineapple smell, and another that smells of apricots and pears. As a result, these much nicer-smelling substances are used as food and perfume additives.

The salts of butyric acid (butyrates, or butanoates) have interesting effects on the cells that might be in your colon. Butyrate actually slows down the growth of cancer cells in this area, while at the same time somehow managing to promote healthy, normal cells. Exactly how this works isn’t well understood, but it seems to be linked to dietary fibre. Yes, I’m afraid to say you can’t swap cheese for bran flakes and vegetables. You still need to eat your fibre.

Butyric acid also helps to prevent salmonella bacteria from taking hold in poultry, and as result it’s used as a chicken feed additive (lucky chickens). It’s also been used as a fishing bait additive, particularly for carp bait. And perhaps not surprisingly it’s been used, along with a cocktail of other stinky stuff, in stink bombs.

So even the stinkiest of molecules has it’s uses, and maybe it’s not so bad after all. Makes you wonder how anyone ever developed a taste for parmesan cheese though, doesn’t it?
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Tales of asking for evidence: are chia seeds all they’re cracked up to be?

I’ve mentioned it before, but this summer I got involved with Sense About Science’s Ask for Evidence Campaign. This is a brilliant campaign in which Sense About Science (for some reason they never abbreviate their name to initials) encourages people to ask organisations about dubious ‘scientific’ claims. Ever wondered what on earth Boswelox actually is and whether it can really counteract ‘skin microcontractions’? Ask the company for evidence. See what they say. (In that particular case the UK Advertising Watchdog has already weighed in, but you get the idea.)

chia-seeds-photo

Are chia seeds all they’re cracked up to be?

I picked up on a few different claims, the first of which had to do with chia seeds. They are the latest health food craze (well, you know, one of latest – this is an area that moves fast, another health food craze could have gone from magical weight-loss aid to dangerous cancer risk in the time it’s taken me to type this), and come with all manner of interesting claims from stabilising blood sugar levels to having “8 times more Omega 3 than salmon“. The trail led back to AZChia, a company set up by Dr Wayne Coates of the University of Arizona. Although, in Dr Coates defence, many of the more hyperbolic media claims don’t appear to have actually started with him, and his work seems to be rigorous.

There are lots of claims out there in the press, but they most seem to boil down to omega-3 fatty acids. Now, there’s a whole other essay to be written on that topic, but essentially (wait for it) these are essential (boom) fatty acids. That means we need them to maintain good health and although there’s some controversy over exactly what they do and don’t affect, there’s no question they’re vital for a healthy metabolism. However they can’t be made in the body (not from scratch, anyway) so we have to eat them. This is potentially tricky for vegetarians because the main source of omega-3 fatty acids is fish oils. But they do turn up in certain plant foodstuffs, and one such foodstuff is chia seeds. In fact, chia seeds biggest claim is that they are the “richest natural plant source of omega-3 fatty acids“.

But before we go any further with this it’s important to realise that there’s more than one type of omega-3 fatty acid. There is a group of molecules that fall into this category, and some of them are tricker to obtain from certain food sources than others. In particular, there’s something called ALA (α-Linolenic acid), another called EPA (eicosapentaenoic acid) and finally DHA (docosahexaenoic acid – these names just get better and better don’t they?).

The main source of these last two, DHA and EPA, is cold-water oceanic fish, like cod and salmon. Both EPA and DHA are converted into prostaglandins which regulate cell activity. DHA is a structural component of such minor essentials as your brain, retina and skin. Make no mistake, you need these molecules.

ALA is slightly different. ALA is available from plants such as, guess what, chia. And also kiwifruit seeds (bizarrely, these have nearly as much as chia seeds), perilla and flax, otherwise known as linseed. Humans cannot make ALA; we have to eat it. However our bodies can make DHA and EPA from ALA.  So, eat your ALA-packed plants and, in theory, you get the complete set.

But it’s not quite that simple (it never is, is it?)  Yes we can synthesise DHA and EPA from ALA, but only poorly. For adults, it might be less than 1% for DHA, and probably less than 5% for EPA (the numbers are slightly higher, although not much, for babies).

Back to that claim that chia seeds have 8 times more omega-3 than salmon (not, I should stress, a claim actually made by Dr Coates). It is true? Well, 100 g of salmon contains roughly 0.4 g of ALA, whereas 100 g of chia seeds contains more like 18 g. So that’s actually a lot more than 8 times. On the other hand, chia seeds contain no DHA or EPA (fish sources, remember) whereas salmon will give you about 1.4 g and 0.4 g respectively. Chia seeds may contain more omega-3 in total than salmon, but it’s not the good stuff. There’s none of the DHA that’s so important for healthy brain, skin and eyes. You might be able to convert a little bit from the ALA that is there, probably enough to get by (particularly if you’re a vegetarian or a vegan and willing to eat a lot of seeds), but oily fish really is the best source.

What about the claim that chia seeds are the richest plant source of omega-3 fatty acids? I pressed Dr Coates for evidence of this, since it’s a statement he makes on his website, and his response was as follows:

“No one paper is going to say that. You are wanting something that does not exist to my knowledge. You would need to compare hundreds of analyses and papers, determine good analyses from bad, etc. Different harvest cycles, growing locations, varieties, all affect the numbers so impossible to really do it. The statement is based on years of work and knowledge.”

So tricky to prove, but probably true. Possibly.

There is a little more to this story. Chia seeds are often promoted as a whole food, packed full of many nutrients over and above omega-3s. A ‘super-food‘, if you will. They do indeed contain a whole range of nutrients. But Dr Loren Cordain, author of the book The Paleo Dietcontends that chia seeds also contain high levels of phytate.  Phytate is the salt of phytic acid, and is a substance that binds minerals such as calcium, iron, zinc, magnesium and copper, making them unavailable for absorption by the body. As a result, chia seeds are actually quite a poor source of these minerals. And, as with all plants, it’s a similar situation with vitamin B6 – it’s something we absorb far more effectively from animal sources. In short, just because something’s in a plant, doesn’t mean we can make use of it.

oily_fish_box

If you’re not a vegetarian, stick to your oily fish.

So, in summary, should you be sprinkling chia on your breakfast cereal? Well, it probably won’t do any harm. If you’re a strict vegetarian or vegan they may be worth considering, although they’re probably not worth paying a lot of money for. If you’re a meat eater, you’re almost certainly better off sticking with oily fish – it’s a much better source of the really essential fatty acids.

….

I also investigated some other claims for Ask for Evidence, one of which was the statement made by Health Journalist Hazel Courteney on national radio that “the average person absorbs into their bloodstream alone about 14 kg of toxins annually through their skin.” There is more to follow on this particular story, and it should appear on the Ask for Evidence page shortly.

There was also something on anti-bac pens which I’ll discuss next time. Watch this space!

The chemistry of chocolate

A lot of people believe there’s a deep religious significance to the holiday we’re enjoying right now.  Others argue it’s older than that: an ancient spring festival, celebrating the spring equinox, fertility and new growth.

funny-chocolate-Periodic-Table-chemistryBut every child knows what Easter is really all about.  Yes.  Chocolate.  Yummy, delicious chocolate.

So with that in mind, let’s talk a little about the chemistry of chocolate.  For it is very interesting stuff.  What’s in the lovely, creamy, sweet brown stuff?  And how do they get it to melt so perfectly in your mouth?  And does it really give you a happy high?

How do they get chocolate to melt so perfectly at body temperature?  There is more to this than you might imagine.  First of all you have to know something about crystals.  Most people, upon hearing the word crystals, think about clear, shiny things twinkling from from Katie Price’s latest wedding dress.  But in fact lots of substances form crystals, because a crystal is just a piece of any solid material that has regular shapes arranged symmetrically.  Crystals don’t have to be transparent.  Metals are crystalline.  Pure iodine forms rather pretty grey-silver crystals.  And, crucially, fat also crystallises.

In fact the fat in chocolate, cocoa butter, can crystallise in many different forms.  Only one of these is the lovely, hard, shiny one that is so nice and snappy at room temperature.  If you’ve ever cooked with chocolate, or indeed just left it in the car on a hot day by accident, you probably know that if you melt it and then just let it solidify again the result is dull-looking and crumbly.  Getting the right form of chocolate crystals to form is called tempering, and it’s a complicated business.  First the chocolate has to be melted at a high enough temperature to melt all the crystals.  Then it needs to be cooled to just the right temperature for the best crystals to grow, then agitated, then warmed up a tiny bit (but not too much), then cooled again.  There are other methods, but this is the one that’s used in the big chocolate factories.  Just ask the Oompa Loompas.

This ideal fat crystal form not only looks good and snaps nicely, it also melts at 34 oC.  Normal body temperature is actually around 36 oC, with the oft-quoted 37 oC actually being a tad on the high side.  Skin temperature, on the other hand (geddit?), is somewhere between 32-35 oC depending on how warm the environment is.  This means that chocolate will just about stay solid in your fingers if you don’t hold it too long, but put it in your mouth and the temperature is just right to melt it perfectly, releasing delicious sweetness, creamy fats and other chemicals that stimulate your tastebuds and give chocolate its flavour (craving your easter eggs yet?)

What about the other question: does chocolate really give you a ‘happy high’?  Well, it turns out there’s a whole cocktail of naturally-occurring bioactive chemicals (some people see ‘natural chemicals’ as a bit of an oxymoron and that’s ironic in a way, since the very brain that learned big words like oxymoron is actually stuffed full of natural chemicals that make it work) in chocolate.  Firstly, caffeine, otherwise known its less tongue-tripping name of 1,3,7-trimethylxanthine, but we’ll stick to caffeine.

We’re all familiar with caffeine from tea and coffee, and that drink that’s falsely advertised as giving you wings, but its presence in chocolate is sometimes forgotten.  It is of course a stimulant, exciting the central nervous system (it’s very excitable), boosting heart rate and contracting muscles.  It also acts on receptors in the brain and causes them to release pleasure-producing chemicals.  There isn’t a lot in chocolate though: it varies by type but even in the darkest of dark chocolate, there’s generally less caffeine than you’d get from even a single cup of tea.  Milk chocolate has even less and white chocolate has none at all.

But there’s more of another chemical, also a stimulant: theobromine.  This is interesting stuff.  It’s a heart stimulant and, like caffeine, a diuretic (it makes you wee).  More recently it’s use as a potential treatment for cancer tumours has been investigated.  There is roughly eight times more theobromine in chocolate than caffeine, but we metabolise it quickly so it doesn’t hang around in our bodies for long.  It’s less safe for animals: as any responsible dog owner will tell you, chocolate is very bad for dogs.  This is mostly due to the theobromine (the caffeine isn’t great either, but there’s not so much of that).  If your pooch gets into your Easter eggs, they could suffer nausea and vomiting, diarrhea, muscle tremors and, potentially, heart failure.  So keep your eggs out of reach.

It’s not just stimulants.  Chocolate also contains fatty acids called cannabinoids.  Guess what they’re similar to?  The clue is in the name… yes, their cousin is called tetrahydrocannabinol, and it’s found in the cannabis plant.  When cannabinoids hit the brain they make you feel relaxed and intoxicated.  And that’s not all, chocolate also contains phenethylamine, sometimes dubbed ‘the love drug’ because levels increase in the body when you’re feeling romantic.  Although there isn’t much and it’s metabolised too quickly to  have a significant effect.

So with this delicious swirly mixture of stimulants and suppressants, surely chocolate ought to be on some sort of controlled drug list?  Well, no.  All of these chemicals are present in relatively small amounts, and have a limited effect on the body (human bodies anyway).  People who suffer chocolate cravings aren’t satisfied by just swallowing capsules that contain the relevant chemical compounds, but eating white chocolate – which contains no cocoa solids and therefore none of the psychoactive ingredients – does the trick.  This suggests that the real reason we like chocolate is simply the same reason we like cream cakes: lots of sugar and fat – yummy!

So now you’ve stuffed your brain full of sciencey-stuff, go ahead and stuff your mouth with lots of yummy chocolate.  Happy Easter!

P.S. have you noticed that it’s kem-is-try but cho-ko-late?  This alliteration spoiling bit of linguistics is because the word chemistry derives from the word alchemy, which (probably, people argue over these things) comes from the ancient Egyptian name for Egypt – khem or khame, or khmi.  Hence al-khmi, ‘the Egyptian art’.