Posts Tagged ‘chemistry’
reading matters 12: food mysteries
New Scientist 3292 July 25 2020
Jacinta: So this cover story reminds me of something I read or heard a few years back – that if you were to list the chemical ingredients of a hen’s egg, you’d never come to the end, or something like that.
Canto: Well you’re on the right track, the cover story is titled ‘the dark matter in your diet’, but instead of a hen’s egg it starts with garlic. Both of these commonly consumed edibles, like just about everything else we eat, contain ‘nutritional dark matter’ that scientists have only recently started to focus on, surprisingly considering that we are, to a fair degree, what we eat.
Jacinta: Yes, so we all know that food components or nutrients are usually divided into fats, carbohydrates and proteins, though these three can be subdivided to a near-infinite degree, but there are also vitamins, minerals and other biochemical elements in various quantities, and with variously vital effects. Currently the US Dept of Agriculture (USDA) has a database of 188 nutritional components of food, under which some info is provided on many thousands of chemical elements.
Canto: So garlic, the USDA reckons, is found in 58,055 foodstuffs, including, uhh, garlic. Raw garlic itself is described as containing 67 nutrients, both macro and micro, some of which can only be found in very minute quantities. And yet many components, such as allin, which helps to give garlic its particular odour and flavour, aren’t listed on the database.
Jacinta: Allin is converted into allicin, through the enzyme allinase, when you crush or chop garlic. That’s when that lovely/notorious stink hits you.
Canto: Right, and this is apparently a major problem across the whole database. They added a few dozen flavonoids – plant compounds that can lower the prevalence of cardiovascular disease – in 2003, but recent researchers have been frustrated by the many gaps, and are building their own more comprehensive database, based on their own chemical analyses. It’s called FooDB, which now lists almost 400 times the number of nutritional compounds as the USDA database. 2306 for garlic, for example, compared to the USDA’s 67. But there’s a lot of work still to be done, even on garlic. Only a tiny fraction of those compounds have been quantified – we don’t know the exact concentrations. And this is a problem for the whole of FooDB, with about 85% of compounds unquantified.
Jacinta: Sounds like we need an equivalent of the old human genome project – but for every single edible product? Nice, a few hundred lifetimes’ work, if you can get the funding.
Canto: Well, it suggests that we’ve massively overlooked the complexity of our food – and not only the foods themselves, but their interaction with the microbes and enzymes in our body. But here’s the thing – brace yourself – some nutritionists disagree!
Jacinta: OMG! Scientists are disagreeing?
Canto: The counter-argument is that ‘dark matter’ in nutritional terms is a beat-up. That, though much research is still needed in nutritional epidemiology, in relation to particular conditions and so forth, we know what the essential nutrients are, so the ‘dark matter’, which tends to exist in ultra-minute quantities, would make little difference. But the researcher who coined the term ‘nutritional dark matter’, Albert-Laszlo Barabasi, begs to differ – of course. He points out, for example, that vitamin E, or its absence, can have adverse effects at minuscule quantities, and it may be that all the flip-flopping advice we’re given about nutrition may have much to do with the gaps in our knowledge. Taking garlic again, it was found that of the 67 compounds listed for it on the USDA database, 37 had health effects one way or another, but of the 2306 on FooDB, some 574 had what they called ‘potential’ health effects. In any case, it seems to me that a more complete knowledge of what’s in our food can’t be a bad thing, and will very likely be of benefit in the long run.
Jacinta: That makes sense, but isn’t everything even more complicated, when you think of how all these nutrients interact with our individual microbiota, and the enzymes that break down our food more or less efficiently, depending on how numerous and healthy they are, which no doubt varies between individuals?
Canto: Yes, Barabasi and others working on all this ‘dark matter’ are well aware of these complex interactions, but they reckon that doesn’t detract from the need to know much more about this particular component of the food-nutrient-digestion-health cycle. And Barabasi does in fact compare the current state of knowledge with the days before the human genome project, when much DNA was considered ‘junk’. It’s just not a good idea to assume that such a large proportion of nutrients are barely worth knowing about. Let’s return to garlic again. It features quite a lot in the Mediterranean diet, which seems protective against cardiovascular disease. Steak, on the other hand, can be problematic. Our gut bacteria breaks down red meat, in the process producing a compound, trimethylamine, which our liver converts into trimethylamine-N-oxide (TMAO). High levels of TMAO in the bloodstream are linked to heart and vascular problems. But allicin, from garlic, which we’ve mentioned before, and which wasn’t on the USDA database, is known to inhibit the production of trimethylamine, so a diet containing red meat – not too much mind you – can be rendered a wee bit safer, and tastier, with a nice garlic dressing.
Jacinta: And allicin appears to be an anti-carcinogen too. And luteolin, another component of garlic not on the standard database, is also reported to protect against cardiovascular disease. We love garlic! But what about processed foods. Surely there are all sorts of ways of processing, that’s to say transforming, foods and their component nutrients that won’t show up on the list of ingredients. And how do we know if those ingredient lists are accurate in the first place?
Canto: Well, baby steps I suppose. Cooking, of course, has vital transformative effects upon many foods. And I recall that when you whisk an egg it becomes ‘denatured’ – how transformative does that sound! The more you think about the interaction of foods, with all their barely recognised components, with transformative processes occurring both outside and within our bodies, the more it makes your head spin, and the more you realise that dietary science has a long long way to go.
garlic cultivars from the Phillippines
about ozone, its production and depletion
People will remember the ‘hole in the ozone’ issue that came up in the eighties I think, and investigators found that it was all down to CFCs, which were quite quickly banned, and then everything was hunky dory….
Or that’s how I vaguely recall it. Time to take a much closer look.
I take my cue from ‘An ancient ozone catastrophe?’, chapter 4 of David Beerling’s The emerald planet, in which he looks at the evidence for a previous ozone disaster and its possible relation to the great Permian extinction of 252 millions years ago. I’ll probe into that matter in another post. In this post I’ll try to answer some more basic questions – what is ozone, where is the ozone layer and why does it have a hole in it?
Ozone is also known as trioxygen, which gives a handy clue to its structure. Oxygen can exist in different allotropes or molecular structures which are more or less stable. O3, ozone, is much less stable than O2 and has a very pungent chlorine-like odour and a pale blue colour. It’s present in minute quantities throughout the atmosphere but is most concentrated in the lower part of the stratosphere, 20 to 30 kilometres above the Earth’s surface. This region is called the ozone layer, or ozone shield, though it’s still not particularly dense with ozone, and that density varies geographically and seasonally. Ozone’s instability means that it doesn’t last long, and has to be replenished continually.
In 1928 chlorofluorocarbons (CFCs) were developed as a seemingly safe form of refrigerant, which, under patent as Freon, came to be used in air-conditioners, fridges, hair-sprays and a variety of other products. As it turned out, these CFCs aren’t so harmless when they reach the upper atmosphere, where the chlorine reacts with ozone to form chlorine monoxide (ClO), and regular O2. This reaction is activated by ultraviolet radiation, which then breaks up the unstable ClO, leaving the chlorine to react with more ozone in a continuing cycle.
By the eighties, it had become clear that something was going wrong with the ozone layer. Studies revealed that a gigantic hole in the layer had opened up over Antarctica, and without going into detail, CFCs were found to be largely responsible. There was the usual fight with vested business interests, but in 1987 the Montreal protocol against the use of ozone-depleting substances (ODS) was drawn up, a landmark agreement which has been successful in starting off the long and far from completed process of repair of the ozone shield.
As a very effective oxidant, ozone has many commercial applications, but the same oxidising property makes it a danger to plant and animal tissue. Much better for us to keep most of it up above the troposphere, where its ability to absorb UV radiation has made it virtually essential for maintaining healthy life on Earth’s surface.
So here are some questions. Why does ozone proliferate particularly at the top of the troposphere, in the lower stratosphere? If it’s so reactive, how does it maintain itself at a particular rate? Has the thinning or reduction of that layer seriously influenced life on Earth in the past? From my reading, mainly of Beerling, I think I can answer the first two questions. The third question, which Beerling explores in the above-mentioned chapter of his book, is more speculative, and more interesting.
Sidney Chapman, a brilliant geophysicist and mathematician of the early twentieth century, essentially answered the first question. He realised that ozone was both formed and destroyed by the action of sunlight, specifically UV radiation, on atmospheric oxygen. He calculated that this action would reduce and finally stop at a point approximately 15 km above sea level, because the reactions which had produced the ozone higher up had absorbed the UV radiation in the process. No activation energy to produce any more ozone. That explained the lower limit of ozone. The upper limit was explained by the lack of oxygen in the upper stratosphere to produce a stable layer – for production to exceed destruction. This was interesting confirmation of observations made earlier by the meteorologist and balloonist Léon-Phillippe Teisserenc de Bort, who noted that, contrary to his expectations, the air temperature didn’t fall gradually with altitude but reached a point of stabilisation where the air even seemed to become warmer. He named this upper layer of air the stratosphere, and the cooler more turbulent layer below he called the troposphere. It’s now known that this upper-air warming is caused by the absorption of UV radiation by ozone.
Our picture of ozone still had some holes in it, however, as it seemed there was a lot less of it around than the calculations of Chapman suggested. To quote from Beerling’s book:
… there had to be some as-yet unappreciated means by which ozone was being destroyed. The fundamental leap required to solve the problem was taken comparatively recently, in 1970, by a then young scientist called Paul Crutzen. Crutzen showed that, remarkably, the oxides of nitrogen, produced by soil microbes, catalysed the destruction of ozone many kilometres up in the stratosphere. Few people appreciate the marvellous fact that the cycling of nitrogen by the biosphere exerts an influence on the global ozone layer: life on Earth reaches out to the chemistry of the stratosphere.
Now to explain why the hole in the ozone shield occurred above the Antarctic. My understanding and explanation starts with reading Beerling and ends with this post from the USA’s National Oceanic and Atmospheric Administration’s Earth System Research Laboratory (NOAA/ESRL).
The ozone hole over Antarctica varies in size, and is largest in the months of winter and early spring. During these months, due to the large and mountainous land mass there, average minimum temperatures can reach as low as −90°C, which is on average 10°C lower than Arctic winter minimums (Arctic temperatures are generally more variable than in the Antarctic). When winter minimums fall below around −78°C at the poles, polar stratospheric clouds are formed, and this happens far more often in the Antarctic – for about five months in the year. Chemical reactions between halogen gases and these clouds produce the highly reactive gases chlorine monoxide (ClO) and bromine monoxide (BrO), which are destructive to ozone.
Most ozone is produced in the tropical stratosphere, in reactions driven by sunlight, but a slow movement of stratospheric air, known as the Brewer-Dobson circulation, transports it over time to the poles, so that ozone ends up being more sparse in the tropics. Interestingly, although most ozone-depleting substances – mainly halogen gases – are produced in the more humanly-populated northern hemisphere, complex tropospheric convection patterns distribute the gases more or less evenly throughout the lower atmosphere. Once in the stratosphere and distributed to the poles, the air carrying the halogen-gas products becomes isolated due to strong circumpolar winds, which are at their height during winter and early spring. This isolation preserves ozone depletion reactions for many weeks or months. The polar vortex at the Antarctic, being stronger than in the Arctic, is more effective in reducing the flow of ozone from tropical regions.
So – I’ve looked here briefly at what ozone is, where it is, and how it’s produced and destroyed, but I haven’t really touched on its importance for protecting life here on Earth. So that, and whether its depletion may have had catastrophic consequences 250 million years ago, will be the focus of my next post.
References
The Emerald Planet, by David Beerling, Oxford Landmark Science, 2009
a little about the chemistry of water and its presence on Earth
So I now know, following my previous post, a little more than I did about how water’s formed from molecular hydrogen and oxygen – you have to break the molecular bonds and create new ones for H2O, and that requires activation energy, I think. But I need to explore all of this further, and I want to do so in the context of a fascinating question, which I’m hoping is related – why is there so much water on Earth’s surface?
When Earth was first formed, from planetesimals energetically colliding together, generating lots of heat (which may have helped with the creation of H2O, but not in liquid form??) there just doesn’t seem to have been a place for water, which would’ve evaporated into space, wouldn’t it? Presumably the still-forming, virtually molten Earth had no atmosphere.
The most common theory put out for Earth’s water is bombardment in the early days by meteors of a certain type, carbonaceous chondrites. These meteors were formed further out from the sun, where water would have frozen. Carbonaceous chondrites are known to contain the same ratio of heavy water to ‘normal’ water as we find on Earth. Heavy water is formed with deuterium, an isotope of hydrogen containing a neutron as well as the usual proton. Obviously there had to have been plenty of these collisions over a long period to create our oceans. Comets have been largely ruled out because, of the comets we’ve examined, the deuterium/hydrogen ratio is about double that of the chondrites, though some have argued that those comets may be atypical. Also there’s some evidence that the D/H ratio of terrestrial water has changed over time.
So there are still plenty of unknowns about the history of Earth’s water. Some argue that volcanism, along with other internal sources, was wholly or partly responsible – water vapour is one of the gases produced in eruptions, which then condensed and fell as rain. Investigation of moon rocks has revealed a D/H ratio similar to that of chondrites, and also that of Earth (yes, there’s H2O on the moon, in various forms). This suggests that, since it has become clear that the Moon and Earth are of a piece, water has been there on both from the earliest times. Water ice detected in the asteroid belt and elsewhere in the solar system provides further evidence of the abundance of this hardy little molecule, which enriches the hypotheses of researchers.
But I’m still mystified by how water is formed from molecular, or diatomic, hydrogen and oxygen. It occurs to me, thanks to Salman Khan, that having a look at the structural formulae of these molecules, as well as investigating ‘activation energy’, might help. I’ve filched the ‘Lewis structure’ of water from Wikipedia.
It shows that hydrogen atoms are joined to oxygen by a single bond, the sharing of a pair of electrons. They’re called polar covalent bonds, as described in my last post on the topic. H2 also binds the two hydrogen atoms with a single covalent bond, while O2 is bound in a double covalent bond. (If you’re looking for a really comprehensive breakdown of the electrochemical structure of water, I recommend this site).
So, to produce water, you need enough activation energy to break the bonds of H2 and O2 and create the bonds that form H2O. Interestingly, I’m currently reading The Emerald Planet, which gives an example of the kind of activation energy required. The Tunguska event, an asteroid visitation in the Siberian tundra in 1908, was energetic enough to rip apart the bonds of molecular nitrogen and oxygen in the surrounding atmosphere, leaving atomic nitrogen and oxygen to bond into nitric oxide. But let’s have a closer look at activation energy.
So, according to Wikipedia:
In chemistry and physics, activation energy is the energy which must be available to a chemical or nuclear system with potential reactants to result in: a chemical reaction, nuclear reaction, or various other physical phenomena.
This stuff gets complicated and mathematical very quickly, but activation energy (Ea) is measured in either joules (or kilojoules) per mole or kilocalories per mole. A mole, as I’ve learned from Khan, is the number of atoms there are in 12g of carbon-12. So what? Well, that’s just a way of translating atomic mass units (amu) to grams (one gram equals one mole of amu).
The point is though that we can measure the activation energy, which, in the case of molecular reactions, is going to be more than the measurable change between the initial and final conditions. Activation energy destabilises the molecules, bringing about a transition state in which usually stable bonds break down, freeing the molecules to create new bonds – something that is happening throughout our bodies at every moment. When molecular oxygen is combined with molecular hydrogen in a confined space, all that’s required is the heat from a lit match to start things off. This absorption of energy is called an endothermic reaction. Molecules near the fire break down into atoms, which recombine into water molecules, a reaction which releases a lot of energy, creating a chain of reactions until all the molecules are similarly recombined. From this you can imagine how water could have been created in abundance during the fiery early period of our solar system’s evolution.
I’ll end with more on the structure of water, for my education.
As a liquid, water has a structure in which the H-O-H angle is about 106°. It’s a polarised molecule, with the negative charge on the oxygen being around 70% of an electron’s negative charge, which is neutralised by a corresponding positive charge shared by the two hydrogen atoms. These values can change according to energy levels and environment. As opposite charges attract, different water molecules attract each other when their H atoms are oriented to other O atoms. The British Chemistry professor Martin Chaplin puts it better than I could:
This attraction is particularly strong when the O-H bond from one water molecule points directly at a nearby oxygen atom in another water molecule, that is, when the three atoms O-H O are in a straight line. This is called ‘hydrogen bonding’ as the hydrogen atoms appear to hold on to both O atoms. This attraction between neighboring water molecules, together with the high-density of molecules due to their small size, produces a great cohesive effect within liquid water that is responsible for water’s liquid nature at ambient temperatures.
We’re all very grateful for that nature.
exploring oxygen
I’ve been reading David Beerling’s fascinating but demanding book The Emerald Planet, essentially a history of plants, and their contribution to our current life-sustaining atmosphere, and it has inspired me to get a handle on atmospheric oxygen in general and the properties of this rather important diatomic molecule. Demanding because, as always, basic science doesn’t come naturally to me so I have to explain it to myself in great detail to really pin it down, and then I forget. For example, I don’t have any understanding of oxidation right now, though I’ve read about it, and probably written about it, and more or less understood it, many times. Things fall apart, and then we fall apart…
Okay, let me pull myself together. Oxygen is a highly reactive gas, combining with other elements readily in a number of ways. A bushfire is an example of oxidation, in which free oxygen is ‘consumed’ rapidly, reacting with carbon in the dry wood to produce carbon dioxide, among other gases. This is also called combustion. Rust is a slower form of oxidation, in which iron reacts with oxygen to form iron oxide. So I think that’s basically what oxidation is, the trapping of ‘free’ oxygen into other gases or compounds, think carbon monoxide, sulphur dioxide, hydrogen peroxide, etc etc. Not to mention its reaction with hydrogen to form water, that stuff that makes up more than half our bodily mass.
Well, I’m wrong. Oxidation doesn’t have to involve oxygen at all. Which I think is criminally confusing. Yes, fire and rust are examples of oxidation reactions, but so is a reaction between hydrogen and fluorine gas to produce hydrofluoric acid (it’s actually a redox reaction – hydrogen is being oxidised and fluorine is being reduced). According to this presumably reliable definition, ‘oxidation is the loss of electrons during a reaction by a molecule, atom or ion’. Reduction is the opposite. The reason it’s called oxidation is historical – oxygen, the gas that Priestley and Lavoisier famously argued over, was the first gas known to engage in this sort of behaviour. Basically, oxygen oxidises other elements, getting them to hand over their electrons – it’s an electron thief.
Oxygen has six valence electrons, so needs another two to feel ‘complete’. It’s diatomic in nature, existing around us as O2. I’m not sure how that works – if each individual atom wants two electrons, to make eight electrons in its outer shell for stability, why would it join with another oxygen to complete this outer shell, and then some? That makes for another four electrons. Are they now valence electrons? Apparently not, in this stable diatomic form. Here’s an expert’s attempt to explain this, from Quora
For oxygen to have a full outer shell it must have 8 electrons in it. But it only has 6 electrons in its valence shell. Each oxygen atom is actively seeking to get more electrons to complete its valence shell. If no other atoms except oxygen atoms are available, each oxygen atom will try to wrestle extra valence electrons from another oxygen atom. So if one oxygen atom merges with another, they “share” electrons, giving both a full outer shell and ultimately being virtually unreactive.
For a while this didn’t make sense to me, mathematically. Atomic oxygen has eight electrons around one nucleus. Six in the outer, ‘valence’ shell. Molecular oxygen has 16 electrons around two nuclei. What’s the configuration to make it stable? Presumably both nuclei still have 2 electrons configured in their first shells, that makes 12 electrons to make for a stable configuration, which doesn’t seem to work out. Did it have something to do with ‘sharing’? Are the shells configured now around both nuclei instead of separately around each nucleus? What was I missing here? Another expert on the same website writes this:
[The two oxygen atoms combine to] create dioxygen, a molecule (O2) in which both oxygen atoms have 8 valence electrons, so they are happy (the molecule is stable).
But what about the extra electrons? It seems I’d have to give up on understanding and take the experts’ word, and I hate that. However, the Khan academy has come to the rescue. In video 14 of his chemistry series, Khan explains that the two atoms share two pairs of electrons, so yes, sharing was the key. So each atom can ‘kind of pretend’, in Khan’s words, that they have eight valence electrons. And this is a covalent bond, unlike an ionic bond which combines metals with non-metals, such as sodium and chloride.
Anyway, moving on. One of the most important features of oxygen, as mentioned, is its role in water – which is about 89% oxygen by weight. But how do these two elements – diatomic molecules as we find them in our environment – actually come together to form such a very different substance?
Well. According to this video, when H2 and O2, and presumably other molecules, are formed
electrons lose energy to form the new orbitals, the energy gets away as a photon, and then the new orbitals are stuck that way, they can’t undo themselves until the missing energy comes back.
This set me on my heels when I heard it, I’d never heard anything like it before, possibly because photon stuff tends to belong to physics rather than chemistry, though photosynthesis rather undoes that argument…
So, sticking with this video (from Brigham Young University Physics Department), to create water from H2 and O2 you need to give them back some of that lost energy, in the form of ‘activation energy’, e.g by ‘striking a match’. The video turns out to be kind of funny/scary, and it again involves photons. After the explosion, water vapour was found condensing on the inside of the glass through which hydrogen was pumped and ignited…
Certainly the demonstration was memorable (and there are a few of these explosive vids online), but I think I need more theory. Hopefully I’ll get back to it, but it seems to have much to do with the strong covalent bonds that form, for example, molecular hydrogen. It requires a lot of energy to break them.
Once formed, water is very stable because the oxygen’s six valence electrons get two extras, one from each of the hydrogens, while the hydrogens get an extra electron each. The atoms are stuck together in a type of bonding called polar covalent. Oxygen is more electronegative than hydrogen, meaning it attracts electrons more strongly – the negative charge is polarised at the oxygen, giving that part of the molecule a partial negative charge, with a proportional positive charge at the hydrogens. I might explore the effects of this polarity in another post.
The percentage of oxygen in our atmosphere seems stable at 21% – that’s to say, it appears to be the same now as when I was born, but that’s not a lot of time, geologically. The issue of oxygen levels in our atmosphere over geological time is complex and contested, but the usual story is that something happened with the prokaryotic life forms that had evolved in the oceans billions of years ago, some kind of mutation which enabled a bacterial species to capture and harness solar energy. This green mutation, cyanobacteria, gave off gaseous oxygen as a waste product – a disaster for other life forms due to its highly reactive nature. The photosynthesising cyanobacteria, however, multiplied rapidly, oxygenising the ocean. Oxygen reacted with the ocean’s iron, creating layers of rust (iron oxide) on the ocean floor, later visible on land through tectonic forces over the eons. Gradually over time, other organisms evolved that were adapted to the new oxygen-rich atmosphere. It became an energy source, which in turn produced its own waste product, carbon dioxide. This created a near-perfect cycle, as cyanobacteria required CO2 as well as water and sunlight to produce oxygen (and sugar). Other photosynthesising water-based and land-based life forms, plants in particular, emerged. In fact, these life forms had harnessed cyanobacteria as chloroplasts, a process known as endosymbiosis.
I’ll end this bitsy post with the apparent fact, according to this Inverse article, that our oxygen levels are actually falling, and have been for near a million years, and that’s leaving aside the far greater effects due to human activity (fossil fuel burning consumes oxygen and releases CO2). Of course oxygen is very vastly more abundant in the atmosphere than CO2, and the change is minuscule on the overall scale of things (unlike the change we’re making to CO2 levels). It will make much more of a difference in the oceans however, where the lack of dissolved oxygen is creating dead zones. The article explains:
The primary contributor to these apocalyptic scenes is fertilizer runoff from agriculture, which causes algal blooms, providing a great feast for bacteria that consume oxygen. The abundance of these bacteria cause O2 levels to plummet, and if they go low enough, organisms that need it to survive swim away or die.
Just another of the threats to sea-life caused by humans.
Always chemical: how to reflect upon naturopathic remedies
most efficacious in every case
So here’s an interesting story. When I was laid up with a bronchial virus (RSV) a few weeks ago, coughing my lungs up and having difficulty breathing, with a distinct, audible wheeze, I was offered advice, as you do, by a very well-meaning person about a really effective treatment – oregano oil. This person explained that, on two occasions, he’d come down with a bad cough and oregano oil had done the trick perfectly where nothing else worked.
I didn’t try the oregano oil. I followed my doctor’s recommendation and used the symptom-relieving medications described in a previous post, and I’m much better now. What I did do was look up what the science-based medicine site had to say about the treatment (I’d never heard of oregano oil, though I’ve had many other plant-based cures suggested to me, such as echinacea, marshmallow root and slippery elm – well ok I lied, I found the last two on a herbal medicine website).
I highly recommend the science-based medicine website, which has been run by the impressively-credentialed Drs David Gorski and Steve Novella and their collaborators for years now, and which thusly has a vast database of debunked or questionable treatments to explore. It’s the best port of call when you’re offered anecdotal advice about any treatment whatsoever by well-wishers. Not that they’re the only people performing this service to the public. Quackwatch, SkepDoc, and Neurologica are just some of the websites doing great work, but they’re outnumbered vastly by sites spreading misinformation and bogus cures, unfortunately. It’s almost a catch-22 of the internet that you have to be informed enough to use it to get the best information out of it.
As to oregano oil specifically, Scott Gavura at science-based medicine proves a detailed account. I will summarise here, while also providing my own take. Firstly people need to know that when a substance, any substance – a herb or a plant, an oil extracted therefrom, or a tablet, capsule or mixture,something injectable or applied to the skin, whatever – is suggested as a treatment for a condition, they should consider this simple mantra – always chemical. That’s to say, a treatment will only work because it has the right chemistry to act against the treated condition. In other words you need to know something (or rather a lot) about the chemistry of the treating substance and the chemistry of the condition being treated. It’s no good saying ‘x is great for getting rid of coughs – it got rid of mine,’ because your cough may not have the same chemical cause as mine, and your cough in February 2007 may not have the same chemical cause as your cough in August 2017. My recent cough was caused by a virus (and perhaps I should change the mantra – always biochemical – but still it’s the chemistry of the bug that’s causing the problem), but no questions were asked about the cause before the advice was given. And you’ll notice when you look at naturopathic websites that chemistry is very rarely mentioned. And I’m not talking about toxins.
Gavura gives this five-point test for an effective treatment:
When we contemplate administering a chemical to deliver a medicinal effect, we need to ask the following:
- Is it absorbed into the body at all?
- Does enough reach the right part of the body to have an effect?
- Does it actually work for the condition?
- Does it have any hazardous, unwanted effects?
- Can it be safely eliminated from the body?
The answer to Q1 is that oregano oil contains a wide variety of chemical compounds, particularly phenolic compounds (71%). It’s these phenolic compounds that are touted as having the principal beneficial effects. However, though we know that there’s some absorption, we don’t have a chemical breakdown. We just don’t know which phenolic compounds are being absorbed or how much.
Q2 – No research on this, or on absorption generally. Topical effects (ie effects on the skin) are more likely to be beneficial than ingested effects, as the oil can maintain high concentration. This would have no effect on a cough.
Q3 – According to one manufacturer the oil has ‘scientifically proven results against almost every virus, bacteria, parasite, and fungi…’ (etc, etc, but shouldn’t that be bacterium and fungus?). In fact, no serious scientific research has ever been conducted on oregano oil and its effectiveness for any condition whatsoever. So the answer to this question is – no evidence, beyond anecdote.
Q4 – There have been reports of allergic reactions and gastro-intestinal upsets, but the naturopathy industry is more or less completely unregulated so you can never be sure what you’re getting with any bottle of pills or ‘essential oils’. As Gavura points out, the lack of research on possible adverse effects, for this and other ‘natural’ treatments, is of concern for vulnerable consumers, such as pregnant women, young or unborn children, and those with pre-existing conditions.
Q5 – At low doses, there’s surely no concern, but nobody has done any research about dosing up on carvacrol, the most prominent component of oregano oil, which gives the plant its characteristic odour. Other organic components are thymol and cymene.
So there’s no solid evidence about oregano oil, or about the mechanism for its supposed efficacy. But what if my well-wisher was correct, and something in the oregano oil cleared up his cough – twice? And did so really really well? Better than several other treatments he tried?
Well, then we might be onto something. Surely a potential billion-dollar gold-mine, considering how debilitating your common-or-garden cough can be. And how, if not cleared up, it can leading to something way more serious.
So how would a person who is sure that oregano oil has fantastic curative properties (because it sure worked for him) go about capitalising on this potential gold-mine? Well, first he would need evidence. His own circle of friends would not be enough – perhaps he could harness social media to see if there were sufficient people willing to testify to oregano oil curing their cough, where other treatments failed. Then , if he had sufficient numbers, he might try to find out the causes of these coughs. Bacterial, viral, something else, cause unknown? It’s likely he wouldn’t make much headway there (most people with common-or-garden coughs don’t go to the doctor or submit to biochemical testing, they just try to ride it out), but no matter, that might just be evidence that the manufacturer was right – it’s effective against a multitude of conditions. And yet, it seems that oregano oil is a well-kept secret, only known to naturopathic companies and health food store owners. Doctors don’t seem to be prescribing it. Why not?
Clearly it’s because Big Pharma doesn’t support the stuff. Doctors are in cahoots with Big Pharma to sell attractive pills with long pharmacological names and precise dosages and complex directions for use. Together they like to own the narrative, and a multi-billion dollar industry is unlikely to be had from an oil you can extract from a backyard plant.
Unless…
Our hero’s investment of time and energy has convinced him there’s heaps of money to be made from oregano oil’s miraculous properties, but that same investment has also convinced him that it’s the chemical properties that are key, and that if the correct chemical formula can be isolated, refined and commercialised, not only will he be able to spend the rest of his life in luxury hotels around the globe, but he will have actually saved lives and contributed handsomely to the betterment of society. So he will join Big Pharma rather than trying to beat it. Yes, there would have to be a massive upfront outlay to perform tests, presumably on rats or mice at first, to find out which chemical components or combinations thereof do the best job of curing the animals, who would have to be artificially infected with various bugs affecting the respiratory system, or any other bodily system, since there are claims that the oil, like Lily the Pink’s Medicinal Compound™, is ‘most efficacious in every case’.
But of course it would be difficult for any average bloke like our hero to scratch up the funds to build or hire labs testing and purifying a cure-all chemical extract of oregano oil. Crowdsourcing maybe, considering all the testimonials? Or just find an ambitious and forward-thinking wealthy entrepreneur?
Is that the only problem with the lack of acceptance, by the medical community, of all the much-touted naturopathic cures out there? Lack of funds to go through the painstaking process of getting a purefied product to pass through a system which ends with double-blind, randomised, placebo-controlled human studies with large sample sizes?
Permit me to be sceptical. It’s not as if the chemical components of most herbal remedies are unknown. It’s highly unlikely that pharmacologists, who are in the business of examining the chemistry of substances and their effects for good or ill on the human body, haven’t considered the claimed cornucopia of naturopathic treatments and the possibility of bringing them into the mainstream of science-based medicine to the benefit of all. Yes, it’s possible that they’ve missed something, but it’s also possible, indeed more likely, that people underestimate the capacity of our fabulous immune system, the product of millions of years of evolution, to bring us back to health when we’re struck down by the odd harmful bug. When we’re struck down like this, we either recover or we die, and if we don’t die, we tend to attribute our recovery to any treatment applied. Sometimes we might be right, but it pays to be skeptical and to do research into a treatment, and into what ails us, before making such attributions. And to do so with the help of a good science-based medical practitioner. And remember again that motto: always chemical.
an intro to chemistry for dummies by dummies
orbitals – one day we may understand
Jacinta: Well, in ‘researching’ – I have to put it in quotes cause what I do is so shallow it barely counts as research – the last piece, I came across a reference to Philip Ball’s choice of the top ten unsolved mysteries in science, at least chemical science.
Canto: Philip Ball, author of Curiosity…
Jacinta: Among other things. His list was published in Scientific American in 2011, the official ‘Year of Chemistry’ – which passed unnoticed by supposedly scientific moi. The actual article is largely unavailable to the impoverished, but at least I’ve been able to access the list here. So I thought we might have fun discussing it in our quest to self-educate autant que possible before we die.
Canto: Yes I don’t know enough about chemistry to say whether this is a bog-standard list or an eccentric one, but there are no quibbles about the first mystery – the origin of life. But have we already covered that?
Jacinta: Not really. Ball’s mystery number 1, to be exact, is ‘How did life begin?’ – by which he presumably means life as we know it. And, as Jack Szostak puts it, the answer lies with ‘chemistry plus details’. Putting the right chemistry together in the right order under the right conditions, which they’ve managed to do in a ‘small way’ in the lab, synthesising a pyrimidine nucleotide, as noted in our last post.
Canto: Yes it seems to me we’re never going to solve this mystery by somehow stumbling upon the first life on Earth, or even a trace of it. How will we ever know it’s the first? Then again creating different kinds of conditions – gases and pressures and molecular bits and pieces – and mixing and shaking and cooking, that may not solve the mystery either, because we’ll never know if it happened like that, but it might show how life can begin, and that would be pretty awesome, if I may use that word correctly for once.
Jacinta: Usage changes mate, live with it. So what’s Ball’s second mystery?
Canto: ‘How do molecules form?’ Now we’re really getting into basic chemistry.
Jacinta: But isn’t that a known known? Bonding isn’t it? Like O² is an oxygen atom bonding with another to create a more stable configuration… I don’t know.
Canto: Well let’s look into it. What exactly is a chemical bond and why do they form? Molecular oxygen is common and stable, but what about ozone, isn’t that just oxygen in a different molecular form, O³? Yet in different molecular form, oxygen has different qualities. Ozone’s a pungent-smelling gas, whereas standard oxygen’s odourless. So why does it have different molecular forms? Why does it have any molecular form, why doesn’t it just exist as single atoms?
Jacinta: But then you could ask why do atoms exist, and why in different configurations of protons and neutrons, etc? Best to stick to how questions.
Canto: Okay, I’d like to know how, under what conditions, oxygen exists as O³ rather than O².
Jacinta: So we have to go to bonding. This occurs between electrons in the ‘outer shell’ of atoms. In molecular oxygen, O2, the two oxygen atoms form a covalent bond, sharing four electrons, two from each atom. The water and carbon dioxide molecules are also covalently bonded. Covalently bonded molecules are usually in liquid or gas form.
Canto: What causes the atoms to form these bonds though?
Jacinta: There are two other types of bonds, ionic and metallic. As to causes, there are simple and increasingly complex explanations. I’m sure Ball was after the most complex and comprehensive explanation possible, which I believe involves quantum mechanics. For a very introductory explanation to the types of bonds, this website is useful, but this much more complex, albeit brief, explanation of the O2 bond in particular will leave you scratching your head. So I think we should do a sort of explication de texte of this response, which comes from organic chemist David Shobe:
If you mean the molecule O2, that is actually a complicated question. It is a double bond, but not a typical double bond such as in ethylene, CH2=CH2. In ethylene, each carbon atom has a sigma orbital and a pi orbital for bonding, and there are 4 electrons available (after forming the C-H bonds), so each bonding orbital (sigma and pi) has 2 electrons, which is optimal for bonding. Also, since each orbital has a pair of electrons, one gets a singlet ground state: all electrons are in pairs.
In O2, there are 1 sigma orbital and 2 pi orbitals for bonding, but 12 valence electrons. Four electrons, 2 on each oxygen atom, are in lone pairs, away from the bonding area. This leaves 8 electrons for 3 bonding orbitals. Since each orbital can only hold 2 electrons, there are 2 electrons forced into antibonding orbitals. This is just what it sounds like: these electrons count negatively in determining the type of bond (technical term is bond order), so 2 sigma bonding electrons + 4 pi bonding electrons – 2 pi antibonding electrons, divided by 2 since an orbital holds 2 electrons, equals a bond order of 2: a double bond.
However, there are *two* pi antibonding orbitals with the same energy. As a result, one electron goes into each pi antibonding orbital. This results in a triplet ground state: one in which there are two unpaired electrons.
That may be more answer than you wanted, but it’s what chemists believe.
Canto: Wow, a tough but interesting task. So a very good place to start is the beginning. By double bond, does he mean covalent bond?
Jacinta: Well according to this clearly reliable site, ethylene, aka ethene (C2H4) is the simplest alkene, that is an unsaturated (??) hydrocarbon with double bonds – covalent bonds – between the carbons. So I think the answer to your question is yes… or no, there are triple covalent bonds too.
Canto: Okay so I’d like to know more about what a covalent bond is, and what valence electrons are, and then we need to know more about orbitals – pi and sigma and maybe others.
Jacinta: Well guess what, the more you dive into molecular bonding, the murkier stuff gets – until you familiarise yourself I suppose. There are different types of orbitals which lead to different types of covalent bonds, single, double and triple. The term ‘covalent’ means joint ownership, sharing, partnering, as we know, of valence. So how to describe valence? With great difficulty.
Canto: Just watched a video that tells me that covalent compounds or molecular compounds only exist between non-metallic elements, whereas ionic compounds are made up of non-metallic and metallic elements, and ionic bonds are quite different from covalent bonds. And presumably metallic bonds join only metallic elements. Don’t know if that helps any.
Jacinta: Well yes it does in that it tells us we really need to start from scratch with basic chemistry before we can get a handle on the molecule problem.
Canto: Okay, time to go back to the Khan academy.
Jacinta: Yes and we’ll do so always bearing in mind that fundamental question about the formation of molecules. So our chemistry lesson begins with elements made up of atoms so tiny that, for example, the width of a human hair, which is essentially carbon, can fit a million of them.
Canto: And the elements are distinguished from each other by their atomic numbers, which is the number of protons in their nuclei. They can have different numbers of neutrons, but for example, carbon must always have six protons.
Jacinta: And neutral-charge carbon will have six electrons buzzing about the nucleus, sort of. They keep close to the nucleus because they’re negatively charged, we don’t know why (or at least I don’t), and so they’re attracted to the positively charged protons in the nucleus.
Canto: More fundamental questions. Why are electrons negatively charged? Why are positively charged particles attracted to negatively charged ones? And if they’re so attracted why don’t electrons just fall into the nucleus and kiss their attractive protons, and live in wedded bliss with them?
Jacinta: Let’s stick to how questions for now. Electrons don’t fall into the nucleus but they can be lost to other atoms, in which case the atom will have a positive charge, having more protons than electrons. So with the losing and the stealing and the sharing of electrons between atoms, elements will have changed properties. Remember oxygen and ozone.
Canto: So it’s interesting that, right from the get-go, we’re looking at that ancient philosophical question of the constituents of matter. And though we now know that atoms aren’t indivisible, they do represent the smallest constituents of any particular element.
Jacinta: But as you know, that smallest constituent gets weird and mathematical and quantum mechanical, with electrons being waves or particles or probability distributions, with the probability of finding them or ‘fixing’ them being higher the closer you get to the nucleus. So this mathematical probability function of an electron is what we call its orbital. Remember that word?
Canto: Right, that’s a beginning, and it gives me an inkling into types of orbitals, such as antibonding orbitals. Continue.
Jacinta: We’ll continue next time. We’ve only just entered the darkness before the dawn.
http://solarfuel.clas.asu.edu/10-unsolved-mysteries-chemistry
https://www.factmonster.com/dk/encyclopedia/science/molecules
https://www.quora.com/What-type-of-bond-do-2-oxygen-atoms-have
Abiogenesis – LUCA, gradients, amino acids, chemical evolution, ATP and the RNA world
Jacinta: So now we’re thinking of the Earth 4 billion years BP, with an atmosphere we’re not quite sure of, and we want to explore the what and when of the first life forms. Haven’t we talked about this before?
Canto: Yeah we talked about the RNA world and viroids and abiogenesis, the gap between chemistry and biology, inter alia. This time we’re going to look more closely at the hunt for the earliest living things, and the environments they might’ve lived in.
Jacinta: And it started with one, it must have. LUA, or LUCA, the last universal common ancestor. Or the first, after a number of not-quite LUCAs, failed or only partially successful attempts. And finding LUCA would be much tougher than finding a viroid in a haystack, because you’re searching through an immensity of space and time.
Canto: But we’re much closer to finding it than in the past because we know so much more about what is common to all life forms.
Jacinta: Yes so are we looking definitely at the first DNA-based life form or are we probing the RNA world again?
Canto: I think we’ll set aside the world of viroids and viruses for now, because we want to look at the ancestor of all independently-existing life forms, and they’re all DNA-based. And we also know that LUCA used ATP. So now I’m going to quote from an essay by Michael Le Page in the volume of the New Scientist Collection called ‘Origin, Evolution, Extinction’:
How did LUCA make its ATP? Anyone designing life from scratch would probably make ATP using chemical reactions inside the cell. But that’s not how it is done. Instead energy from food or sunlight is used to power a protein ‘pump’ that shunts hydrogen ions – protons – out of the cell. This creates a difference in proton concentration, or a gradient, across the cell membrane. Protons then flow back into the cell through another protein embedded in the membrane, which uses the energy to produce ATP.
Jacinta: You understand that?
Canto: Sort of.
Jacinta: ‘Energy from food or sunlight is used..’ that’s a bit of a leap. What food? The food we eat is organic, made from living or formerly living stuff, but LUCA is the first living thing, its food must be purely chemical, not biological.
Canto: Of course, not a problem. I believe the microbes at hydrothermal vents live largely on hydrogen sulphide, and of course sunlight is energy for photosynthesising oganisms such as cyanobacteria.
Jacinta: Okay, so your simplest living organisms, or the simplest ones we know, get their energy by chemosynthesis, or photosynthesis. Its energy, or fuel, not food.
Canto: Semantics.
Jacinta: But there are other problems with this quote re abiogenesis. For example, it’s talking about pre-existent cells and cell membranes. So assuming that cells had to precede ATP.
Canto: No, he’s telling us how cells make ATP today. So we have to find, or synthesise, all the essential ingredients that make up the most basic life forms that we know – cell membranes, proteins, ATP and the like. And people are working towards this.
Jacinta: Yes and first of all they created these ‘building blocks of life’, as they always like to call them, amino acids, in the Miller-Urey experiments, since replicated many times over, but what exactly are nucleic acids? Are they the same things as nucleic acids?
Canto: Amino acids are about the simplest forms of organic compounds. It’s probably better to call them the building blocks of proteins. There are many different kinds, but generally each contain amine and carboxyl groups, that’s -NH2 and -COOH, together with a side chain, called an R group, which determines the type of amino acid. There’s a whole complicated lot of them and you could easily spend a whole lifetime fruitfully studying them. They’re important in cell structure and transport, all sorts of things. We’ve not only been able to create amino acids, but to combine them together into longer peptide chains. And we’ve also found large quantities of amino acids in meteorites such as the Murchison – as well as simple sugars and nitrogenous bases. In fact I think we’re gradually firming up the life-came from-space hypothesis.
Jacinta: But amino acids and proteins aren’t living entities, no matter how significant they are to living entities. We’ve never found living entities in space or beyond Earth. Your quote above suggests some of what we need. A boundary between outside and inside, a lipid or phospho-lipid boundary as I’ve heard it called, which must be semi-permeable to allow chemicals in on a very selective basis, as food or fuel.
Canto: I believe fatty acids formed the first membranes, not phospho-lipids. That’s important because we’ve found that fatty acids, which are made up of carbon, hydrogen and oxygen atoms joined together in a regular way, aren’t just built inside cells. There’s a very interesting video called What is Chemical Evolution?, produced by the Center for Chemical Evolution in the USA, that tells about this. Experimenters have heated up carbon monoxide and hydrogen along with many minerals common in the Earth’s crust and produced various carbon compounds including fatty acids. Obviously this could have and can still happen naturally on Earth, for example in the hot regions maybe below or certainly within the crust. It’s been found that large concentrations of fatty acids aggregate in warm water, creating a stable, ball-like configuration. This has to do with the attraction between the oxygen-carrying heads of fatty acids and the water molecules, and the repulsion of the carbon-carrying tails. The tails are forced together into a ball due to this repulsion, as the video shows.
fatty acids, with hydrophobic and hydrophilic ends, aggregating in solution
Jacinta: Yes it’s an intriguing video, and I’m almost feeling converted, especially as it goes further than aggregation due to these essentially electrical forces, but tries to find ways in which chemical structures evolve, so it tries to create a bridge between one type of evolution and another – the natural-selection type of evolution that operates upon reproducing organisms via mutation and selection, and the type of evolution that builds more complex and varied chemical structures from simpler compounds.
Canto: Yes but it’s not just the video that’s doing it, it’s the whole discipline or sub-branch of science called chemical evolution.
Jacinta: That’s right, it’s opening a window into that grey area between life and non-life and showing there’s a kind of space in our knowledge there that it would be exciting to try and fill, through observation and experimentation and testable hypotheses and the like. So the video, or the discipline, suggests that in chemical evolution, the highly complex process of reproduction through mitosis in eukaryotic cells or binary fission in prokaryotes is replaced by repetitive production, a simpler process that only takes place under certain limited conditions.
Canto: So under the right conditions the balls of fatty acids grow in number and themselves accumulate to form skins, and further forces – I think they’re hydrostatic forces – can cause the edges of these skins to fuse together to create ‘containers’, like vesicles inside cells.
Jacinta: So we’re talking about the creation of membranes, impermeable or semi-permeable, that can provide a safe haven for, whatever…
Canto: Yes, and at the end of the video, other self-assembling systems, such as proto-RNA, are intriguingly mentioned, so we might want to find out what’s known about that.
Jacinta: I think we’ll be doing a lot of reading and posting on this subject. I find it really fascinating. These limited conditions I mentioned – limited on today’s Earth surface, but not so much four billion years ago, include a reducing atmosphere lacking in free oxygen, and high temperatures, as well as a gradient – both a temperature gradient and a sort of molecular or chemical gradient, from more reducing to more oxidising you might say. These conditions exist today at hydrothermal vents, where archaebacteria are found, so researchers are naturally very interested in such environments, and in trying to replicate or simulate them.
Canto: And they’re interested in the boundary between chemical and biological evolution, and reproduction. There are so many interesting lines of inquiry, with RNA, with cell membranes….
Jacinta: Researchers are particularly interested in alkaline thermal vents, where alkaline fluids well up from beneath the sea floor at high temperatures. When this fluid hits the ocean water, minerals precipitate out and gradually create porous chimneys up to 60 metres high. They would’ve been rich in iron and sulphide, good for catalysing complex organic reactions, according to Le Page. The temperature gradients created would’ve favoured organic compounds and would’ve likely encouraged the building of complexity, so they may have been the sites in which the RNA world began, if it ever did.
a hydrothermal vent off the coast of New Zealand. Image from NOAA
Canto: So I think we should pursue this further. There are a lot of researchers homing in on this area, so I suspect further progress will be made soon.
Jacinta: Yes, we need to explore the exploitation of proton gradients, the development of proton pumps and the production of ATP, leaky membranes and a whole lot of other fun stuff.
Canto: I think we need to get our heads around ATP and its production too, because that looks pretty damn complex.
Jacinta: Next time maybe.