Trying to explain earthing with atoms

My ungrounded feet in rubber boots.

This week the Washington Post has an article headlined "Could walking barefoot on grass improve your health? Some science suggests it can."  The link itself is subtitled: The science behind grounding.

The article gets a lot of things right about atoms (they make up everthing!), but it confuses "free-radicals" with positive ions. (Free radicals don't have to be charged.) Then it tries to explain why negative ions can help. And while it is true that a positive ion and a negative ion can react in some circumstance to produce a neutral compound (think of hydroxide and hydrogen ions reacting to make water in an acid base reaction), random negative ions won't necessarily disarm a free radical.  You need an antioxidant for that, a molecule that can participate in a reaction that can soak up extra electrons.  You still need to eat your vegetable and wear sunscreen.

Negative ions and positive ions co-exist quite nicely in your body. You need those positively charged potassium ions, in fact, to keep your heart beating rhythmically. So on its face, the "science behind grounding" given in the article is bunk. If all those negative ions in the ground started neutralizing all the positive ions in our bodies, we'd be dead.

While I get this is a not a science news piece, but a perspective piece (a "[d]iscussion of news topics with a point of view, including narratives by individuals regarding their own experiences"), I wish someone at the Post had fact-checked the science.  Yes, it feels nice to walk barefoot on the grass, or to be outside.  I'm pretty certain the negative ions aren't the reason why.

Formaldehyde: not just for dead things

Next spring I'm teaching a course on the physical chemistry of food while a colleague is teaching a course on the analytical chemistry of foodstuffs.  Among other science texts we'll be using John Coupland's Introduction to the Physical Chemistry of Food, but I'm also collecting short pieces to put some of the work into a historical and social context.

These aren't actual biological specimens preserved
in formaldehyde, but Halloween decorations.  

Though these days we tend to think of chemists as the untrustworthy creators of toxic, artificial everything, the systematic training of chemists was driven in part by the desire for the public to know what was in their food and water.  In 19th century Britain, hundreds of chemists made their living testing the purity of everything from butter to well water.  So when the Food Babe tells you there is something "yucky" in your food, the reason we know it is there is some chemist developed a careful protocol for its analysis, and other chemists tested the material.

Molecular structure
of formaldehyde

I've been thinking about formaldehyde, one of the simplest organic molecules (to a chemist, organic means made up mostly of carbon and hydrogen atoms, and has nothing to do with whether the molecule is synthetic or natural or...). Last year, formaldehyde, which is a preservative, was in the news because Johnson & Johnson had agreed to remove it from baby shampoo, though as Matt Hartings and Tara Haelle clearly pointed out in a piece at Slate, it was in such low concentrations that it posed no risk to babies (who, they point out, themselves contain substantial amounts of formaldehyde.)

Pepsi is reformulating Diet Pepsi to take out the artificial sweetener aspartame. The Food Babe is crowing that she and her army have forced Kraft to remove the so-called coal tar dyes (e.g. tartrazine/FD&C Yellow 5), to be replaced by natural colorings from spices.  What does all this have do do with formaldehyde?

From the Food Babe's 'campaign' literature.

To start with those natural colorings - at least one of them used in the UK version of mac and cheese, beta-carotene, isn't extracted from natural sources but synthesized from petroleum feedstocks (just like those coal-tar dyes).  One of the starting materials:  formaldehyde. The other natural colorings on the table — annatto, turmeric and paprika — are not quite what you might think either.  While you might imagine shaking in some spices from a quaint bottle, the spices themselves are not used as colorants, the colorants are extracted using organic (not that kind of organic, the chemist's kind of organic) solvents, such as ethyl acetate.  It's unclear to me why these colorants, particularly beta-carotene pass muster with the Food Babe.


Aspartame is sometimes vilified because it is metabolized into methanol and formaldehyde in the body.  Which it is.  You already contain a lot of formaldehyde, about 12 milligrams per liter of fluid in your cells.  One source is metabolism of the amino acids, particularly, serine and glycine (in naturally occurring proteins), from which your body scavenges methyl groups (CH₃) to pop on to various structures.  Aspartame is a very tiny protein, so the same pathways that produce methanol and formaldehyde from natural sources, dismantle aspartame to yield methanol and formaldehyde, though the amounts produced are tens of times lower than what comes from eating apples and fish.

Because formaldehyde occurs naturally in foods (about 5 mg per serving in some fruits, fish is also high, pectin containing fruits such as apples add significantly to the amount of formaldehyde ingested), our bodies have a mechanism for dealing with it, we process about 60 to 100 grams of formaldehyde a day and do so quickly.  Formaldehyde has a half-life of about 1 to 2 minutes in the body.

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Why are those spices colored?  What does it have to do with quantum mechanics, flamingos and canaries?  Read this post, the very first one written for the blog,  to find out.

References
EFSA report on endogenous versus exogenous sources of formaldehyde.
EFSA review of curcurmin, a component of turmeric, which had been suspected of being genotoxic.

St. Ignatius' Beans: Strychnine and herbal remedies

Before chemists became adept at synthesizing and purifying single molecules, materia medica relied heavily on plant based materials.  The chemicals in plants are not uniformly innocuous, or safe at any dose, a point I tried to make in this article at Slate a couple of weeks ago.  A case in point:  St. Ignatius' beans.

Last fall, I was digging through a 1903 organic chemistry text (looking for examples of eponyms for this article), when a familiar name caught my eye. What was St. Ignatius doing in a chemistry textbook, an organic one at that?  Jesuits, I could understand (quinine is extracted from cinchona, also called Jesuits' bark), but Ignatius (the founder of the Jesuits) himself?

"Strychnine, C₂₁H₂₂O₂N₂, is found in St. Ignatius' bean..."  What is a violent poison doing in a bean named for Ignatius?  Despite the fact that I was up against an impending writing deadline and had a couple of dozen exams to grade, I had to know.

Faba Sancti Ignatii were first described by an Austrian Jesuit living in the Philippines in the 17th century, George Kamel, S.J. (his description was published in the Philosophical Transactions in 1699 - and yes, I looked up the Latin version).  Later authors speculated the plant was named for Ignatius because of its many medicinal virtues (which they do not list).  At the turn of the last century strychnine was part of the US Pharmacopoeia, prescribed as a stimulant — it was implicated in a early Olympic doping scandal — and for gastric upset; in the Phillipines it was often (more sensibly) the bean was worn on a string around the neck for protection against various diseases. These days it forms the basis for a homeopathic nostrum prescribed for grief and melancholia, particularly when associated with an abundance of tears.

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A version of this post appeared at Quantum Theology.

Chemophobia: The Boy with a Thorn in His Joints

I'm at ScienceOnline2013 where Carmen Drahl and Dr. Rubidium just finished running a terrific session on chemophobia: how can we bridge the gap between "better living through chemistry" and ads for "chemical-free sleep aids." The thrust of the session was not how to convince people chemistry and chemicals are good, but more about how to inject nuance into the public conversation. Chemicals have risks and benefits — and of course, are unavoidable. But we current view chemical as synonymous with toxic, hazardous, unnatural or just plain bad.

What are the roots of this cultural shift? Can understanding these help scientists and writers communicate more clearly and in the end help people not only understand what is in their "stuff" — chemicals, it's all chemicals — but give them tools to work with and make decisions about the materials that make up the world — chemicals. As @docfreeride (ethicist Janet Stemmwedel) noted at another session yesterday, we can agree on facts, and still make different decisions based on them.

Today's New York Times has a perfect example of the various ways chemophobia presents in the Magazine: The Boy with a Thorn in His Joints. The piece chronicles Susannah Meadow's search for an effective treatment for her son's rheumatoid arthritis. She agonizes about the decision to give him methotrexate (which in high doses is used in anticancer treatment) and turns to alternative treatments, in particular four-marvels powder. There are intense arguments with the pediatricians and with her husband over the issue. I was struck by two things in this piece. First, the language Meadows uses to limn the controversy, and second her ignorance, not so much of the chemistry that is in your face (methotrexate), but of the ways in which chemistry is couched in alternative cultural schemes(four-marvels powder).

It makes me wonder how chemophobia is linked to the language we use to talk about it. It can be nearly impossible for an non-chemist to figure out what methotrexate is (beyond "a chemical"). The very name sounds harsh. Four-marvels powder is easy to parse: a powder with four effects. Its name rings with hope.

I also wonder if we worry more about stuff we are familiar with, we've heard more talk on the street about their risks. So we obsess about vaccines, because we hear and read about the side-effects of vaccines, but how many people know anyone who has died of measles? (One of my sister's friends died of measles when I was a child, before there was a vaccine.) So we get in the Times' piece "I was desperate to find a way...without the drugs." pushed up against "[My husband] has always been more comfortable with pharmaceuticals, more trusting in general."

Of course, four-marvel powder is a pharmaceutical, it's just from a different pharmacopoeia — the traditional Chinese — than the one Meadows or her husband is familiar with. Meadows can read the package insert with information on the side-effects of methotrexate, she may be unaware of the routine advice given in Chinese medicine programs (and yes, there are formal academic programs in Chinese medicine, e.g. at Nanyang Technical University) about four-marvels powder (it should never be given to pregnant women, for example, which might make you hesitate before giving it long term to infants or young children).

The session at SciOnline2013 brainstormed about effective ways to help people develop a better sense of nuance around what is a chemical and what are the risks of this particular chemical? What strategies do you think would be most effective?

Cordial Chemistry: Syrup of Violets

Today's talk at the Chemical Heritage Foundation was by one of my fellow Fellows, Rebecca Laroche, on syrup of violets and Robert Boyle. It had long been known that adding an acidic material, such as lemon juice, to syrup of violets turned it a rose color. (More creepily, kids apparently used to hold pansies, also a member of the viola family, over ant hills to watch them change color, presumably from the formic acid produced by the ants.) Boyle is credited with the discovery that this botanical extract also changed color when exposed to alkalis, turning green (see his report here). This led to the development of a panel of pH sensitive indicators, helpful in chemical analysis in Boyle's time and now.

The color changes are due to the anthocyanins in the violets (the same thing that makes red cabbage change color with pH). Syrup of violets is not hard to make, you can find a modern recipe here, not much changed from the older recipes (see an assortment here), and you can buy it.

After Rebecca's talk a group of us went to lunch and, quite serendipitously, on the menu were drinks made with syrup of violets. Since some of us had writing to do this afternoon, we eschewed the vodka versions, but gave the club soda tonics a whirl. I wanted to see what happened when you added acid, would I get a pale rose drink? Alas, it seems not.

Turns out that commercial syrup of violets has citric acid added to it, which turns the pure syrup red, or it would if artificial colors were not added to make it violet again. Since it's already in the red form, adding more acid doesn't change the color.

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Pain relief in a cup of tea

I took a fall skiing last week¹, my skis went in one direction, my knees in the other. The audible pop sounded and felt much like what happens when I break the cartilage in the joint of a chicken. Argh.

Not surprisingly my knee hurts (though it's not all that swollen compared to the time I tore the ligament in my ankle, where the swelling was quite spectacular). I'm taking ibuprofen for the pain. NSAIDs, such as aspirin, naproxen, and ibuprofen are effective antinociceptives² - painkillers. But I'm also adding a dollop of caffeine to each dose. It turns out that caffeine is an effective adjuvant for NSAID (non-steroidal anti-inflammatory drugs).

NSAIDs work by blocking the activity of prostaglandins, molecules that are used by the body in many signaling roles, including the signaling of pain. If the signal from my knee to the brain that says "pain" doesn't get through, it doesn't hurt (though it may still be hurt).

Adding around 100 mg of caffeine (roughly what's in my big mug of FTGFOP³ Assam tea) to 400 mg of ibuprofen makes it 2 to 3 times more effective in relieving acute pain. [Forbes et al. Clin Pharmacol Ther. 1991 49(6):674-84.] Onset of pain relief is faster and the duration is markedly increased as well. Caffeine appears to increase the availability of the NSAID at the signaling site.

So sitting by the fire with a cup of tea (and an ice pack on my knee) is soothing in more ways than one...

1. Full disclosure: I fell in the lift line, my skis got entangled when I tried to retrieve the pole that got stuck in the snow. I'd love to say I did this catching an edge on a glorious powder run.
2. The word nociceptive was coined in 1904 by Charles Scott Sherrington to try to disentangle the psychological perception of pain from the physiological response. Noci- comes from the Latin nocere - to harm (think noxious and innocuous)
3. FTGFOP, Finest Tippy Golden Flowery Orange Pekoe, a description of the leaves, Orange Pekoe has nothing to do with any particular flavor of tea, including orange!
4. Food Research International Vol 29, Nos 3-4, pp. 325-330.

Calm amino acids

It's the time of the year when I covet both energy and calm. A young friend sent me the link to these mints, which promise both in a single package. The secret ingredient is L-theanine (structure shown at left), a naturally occurring amino acid found in Camelia sinensis. Interestingly, the dried, fermented leaves of Camelia sinensis are what I use to brew my preferred pharmacological concoction to decrease stress and increase alertness: tea.

Some amino acids (roughly 20) are used by biological systems to build proteins (the working machinery of cells). The basic structural motif of any amino acid has a carboxylic acid group (COOH, which occurs in molecules like acetic acid, aka vinegar) along with an amine group (NH₂ — certain amines are responsible for the characteristic odor of fish) as shown here:


Theanine is not one of the twenty plus amino acids used to construct proteins. There is some evidence that it works synergistically with caffeine to enhance cognitve performance, while moderating some of caffeine's less desirable effects.

So…do the mints work as advertised? I've no idea, but browsing the literature suggests that my students might reap some benefit from the multiple cups of tea I drink while grading their exams. A calm, but alert grader can't be all bad!

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Related posts:

Where does the name amine, and hence amino acid come from?
How old are whales and what does this have to do with right and left handed amino acids

Warning, Dr. Smith! Warning!

An SF fan from the moment I discovered Heinlein's Have Spacesuit -Will Travel in the minuscule public library in the small (population 2500) Midwest town I grew up in, it's probably not a surprise that I would have been an avid watcher of SF on TV. When I get various 'urgent warnings' in my inbox, I often hear the Lost in Space robot's voice in my head, "Warning, Dr. Smith! Warning!"

A few days ago, this warning about the dangers of taking business cards from strangers appeared. Take one of these drug laden cards in your bare hands and soon you will be easy prey for swindlers and worse. Is such a thing possible? Can you be drugged against your will by briefly touching a drug?

In principle, yes. Unbroken skin, though a good way of keeping your insides in, is not an absolute barrier to molecules entering the body. Some molecules — such as DMSO — are better at getting in than others.

When I teach mathematical modeling, one topic we look at is ways to model diffusion. An application that many of my students find interesting are passive drug delivery systems that capitalize on diffusion. In other words - patches. To me this warning sounds like a folkloric riff on drug patches. In fact, delivery through a patch is a pretty complex system, it's not just a matter of soaking the equivalent of a gauze pad in a drug and taping it to your arm.

The drug cocktail purported to be on the business cards is burundanga - a mixture of two plant alkaloids, atropine and scopolamine. Both can be administered through the skin, when I had surgery a couple of years ago, the anesthesiologist use a scopolamine patch to manage my post-op nausea. But he didn't hand me a "don't throw up" card to hang onto for a few minutes in pre-op - that patch he applied behind my ear was a marvel of pharmaceutical engineering!

Burundanga has been used criminally but by slipping into a victim's food or drink. Incidental contact with atropine or scopolamine won't incapacitate you — though the prescribing information for the scopolamine patch points out that you should avoid touching the patch and then your eyes - resulting in dilated pupils and blurry vision.

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Scopolamine was used as an amnesia inducing agent during labor and delivery in the 60's. I suspect Betty Draper's halucinations during labor and delivery on Mad Men (The Fog, Season 3, episode 5).

Image is of belladona, from which atropine and scopolamine can be extracted.

Blue Color Workers

The title of this post was inspired by a student blooper in a sociology paper where the writer surely did not mean to say "blue color workers". Spell checkers have their limits. In the right context, however, blue color workers is not a candidate for Richard Lederer's next collection.

Exposure to silver can cause argyria, in which the skin turns a grey-blue color as a result of deposits in the dermis of metallic silver and silver compounds. Unlike the orange coloration that eating too many carrots can cause, the dark grey cast of argyria is permanent. The condition can be striking if the entire body is affected. Barnum & Bailey's Blue Man was found at autopsy to have argyria, perhaps from exposure while working as a silver miner: a real blue color worker.

Argyria in this century is more likely a result of exposure to quantities of silver in non-industrial settings. Silver preparations were used pharmaceutically in the early 20th century, and much of the literature about silver and skin discoloration dates to that time. There are reports of cases of argyria arising from use of colloidal silver compounds. Externally applied, salts of silver are effective antiseptics, hence the marketing of these silver solutions as nutritional supplements "to support the immune systems" and as "all-natural antibiotics". There is no evidence that these compounds are effective in these ways when taken internally - and the risk of being permanently blue is not one to be taken lightly! The FDA has ruled that products containing silver or colloidal silver are "not safe and effective" and may not be sold as having any medicinal benefits. Despite this, colloidal silver is readily available.

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The photo is of Rosemary Jacobs, who suffers from argyria, and is used with her permission. In 2006, Stan Jones, ran as the Libertarian candidate for U.S. Senate in Montana. He took a colloidal silver compound in 1999 and now has argyria as a result.

Dandelion Wine

At a party Saturday night someone mentioned a rumor about extracting illegal drugs from dandelions. This was news to me, I hadn't thought that dandelions had all that much to offer pharmacologically. Google didn't produce any hits, nor did my students know anything (though they did tell me that on MythBusters they'd made nitrous oxide from ingredients you could obtain at home). There is some evidence from rat models that dandelion extracts can interfere with antibiotic absorption (particulary those in the same class as ciprofloxacin), and it has potential for control of blood sugar, but I can't find anything in PubMed more interesting than that.