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.

Will bromine turn squirrels purple?

Most winters Punxatawney Phil is the furry face of Pennsylvania, but last year, he had competition: meet the purple squirrel of Jersey Shore (which should not be confused with either a television show or a town in New Jersey).

The news report offers a number of theories about the squirrel's unique coloration.  A dye job seems the likely culprit, whether from the squirrel's nesting material or an inadvertent bath in a violet solution.  Computer scientist Krish Pillai had a novel suggestion: "This is not good at all. That color looks very much like Tyrian purple. It is a natural organobromide compound seen in molluscs and rarely found in land animals. The squirrel (possibly) has too much bromide in its system."

Leaving aside that Tyrian purple (produced by a particular class of marine snail and to the best of my knowledge and research abilities by no mammal) is a much redder color, this assertion is roughly equivalent to saying that if I eat too much chloride, say from table salt, my body could start synthesizing Splenda, an organochloride.  No, just, no.

Pillai is apparently extrapolating from reports that bromide (bromine anion - Br^-) has been found contaminating wells near fracking sites.  Calcium bromide is used in drilling fluids to increase density, by some estimates 20% of the bromine used in the US ends up in "clear brine fluids" — mixtures of various bromides.  But it is a long way from bromine ions to 6,6′-dibromoindigo along very specific biochemical pathways.  Which squirrels don't have.  Or humans.  (What can and does happen is that the bromide reacts with various chlorine compounds used in water purification to form organohalides, which aren't healthy to ingest....)

It's worth noting that direct ingestion of dyes can have interesting effects on pigmentation.  Flamingos get their characteristic color from ingesting shrimp pigment, and you can change the color of a canary's feathers by feeding it paprika.  Humans who eat too many carrots can develop carotenemia — they turn orange.  These processes are reversible, stop eating the shrimp or carrots and feather or skin return to their normal coloration.  Unfortunately consuming silver or gold can produce a permanent change in skin coloration, as in argyria.

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An alternate definition of a purple squirrel via Urban Dictionary.

Red Dwarfs

A version of this was written as a guest post for an artist friend's blog.

If you see a colored compound in chemistry, you can almost bet that it will contain a transition metal. Though we think of metals as being a shiny grey hue (with a few exceptions, gold being one), metals are key elements in producing colors for artist. The visible frequencies of light are relatively low in energy, and conveniently correspond to the small gaps in energy that electrons can leap in metals (what chemists call d to d transitions). Cobalt blue, one of my favorite hues, is (as its name suggests) a cobalt salt: CoAl₂O₄. To get different colors, you have to use different metal salts. You can get a brilliant, though not long-lasting, yellow pigment using lead chromate, the same chrome yellow that Vincent Van Gogh made famous. Tweaking colors to get slightly different hues requires either mixing materials or finding a different salt altogether, the gaps that the electrons leap over when they absorb light aren't adjustable.

But there are other ways to capitalize on the properties of metals to create color. Red stained glass has been made for centuries by adding gold to molten glass and carefully controlling the temperature. The gold clusters together in small particles which then become evenly distributed and suspended in the glass.

These tiny clusters are called nanoparticles, because they are 100 nanometers or less in size. One nanometer is 1 billionth of a meter, the period in this sentence is about a million nanometers across, the little gold balls in red glass are about 25 nanometers in diameter. (The prefix nano, comes from the Greek word for "dwarf," hence the title of this post.)

The gold nanoparticles are not dissolved in the glass, but form a colloid. And one property of colloids is that they scatter light. Different frequencies of light scatter differently, which is why the sky is blue, though the scattering of light by a colloid is a slightly different process. (Scattering isn't the only process involved in the color, but unless you really want to fly off the math cliff with me, let's leave talk of quantum dots and wavefunctions to another day.)

The color of light that a colloid scatters depends on the size and shapes of the particles dispersed. It turns out just by varying the size and shape of the particles involved you can tune your gold nanoparticles to be red, red-violet or even green and many colors in between!

If you are interested in knowing more about the history and chemistry of color, Bright Earth: Art and the Invention of Color by Philip Ball is a terrific introduction. He has a recent blog post about color here. For a readable introduction to nanoparticles, quantum dots and color, try this article in the NY Times.

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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Bunsen and quantum mechanics

Today's Google doodle honors the 200th birthday of Robert Bunsen, the inventor (or not?)of the eponymous burner. The doodle is great, click on it and it bubbles and whirs.

"It is known that several substances have the property of producing certain bright lines when brought into the flame. A method of qualitative analysis can be based on these lines, whereby the field of chemical reactions is greatly widened and hitherto inaccessible problems are solved. We limit ourselves here to developing the method for alkali and earth-alkali metals and demonstrating its value by some examples.

The lines show up the more distinctly the higher the temperature and the lower the luminescence of the flame itself. The gas burner described by one of us (Bunsen, these Ann. 100, p. 85) has a flame of very high temperature and little luminescence and is, therefore, particularly suitable for experiments on the bright lines that are characteristic for these substances." Opening to Gustav Kirchhoff and Robert Bunsen, Annalen der Physik und der Chemie 110 (1860), 161-189.

Bunsen is not a name typically associated with the development of quantum mechanics, yet I might argue he is one of the key figures. The observation of line spectra and the realization that the lines are characteristic of particular elements is a significant step toward the development of quantum mechanics. It's one of the observations that Bohr was trying to explain in his model of the atom. General chemistry texts boast figures of line spectra to demonstrate the point - I showed several in my lecture last week. This apparatus developed by Kirchoff and Bunsen made possible the routine observation of such lines. I have a beautiful brass example in my office.

This paper goes on to note that sodium, even at very low concentrations produces quite bright lines. It reminds me of the many happy hours I spent playing with my mom's gas stove and making flame tests on anything I could scrounge up (most of which contained sodium). Is this the formative experience that impelled me toward quantum mechanics? Who knows! I do still think of sodium and line spectra every time the pasta boils over and the flame on my stove flares that characteristic sodium yellow-orange.

Happy birthday, Bunsen, I might not have a job without you!

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There is more on Bunsen beyond the burner at The Sceptical Chymist.

Fiat Lux 1: On Fire for Quantum Mechanics

My sailboat's name is the Fiat Lux — "let there be light" in Latin — drawing from both my theological and scientific personae. I sail a Laser, an Olympic class racing dingy, which is an apt boat for a quantum mechanic. The ability to amplify light by stimulating an existing emission process was first predicted by quantum mechanics, then the apparatus to actually do it was built. Laser is really an acronym: Light Amplification by Stimulated Emission of Radiation. The radiation is electromagnetic radiation, not the radioactive radiation.

There's been a smattering of conversation about light production around my house this weekend between sailing the Laser, setting off fireworks and observing fireflies. One of my teen guests wondered how the fire in fire flies was different from the fire in fireworks. All light is not created in quite the same way....though there are some fundamental similarities.

There are really two fires in fireworks, the thermal explosives that send them skyward, and the "rockets red glare" — the glittering burst of color in the sky. The heat from the thermal explosion (usually blackpowder or a similar substance) is what trigger the colors.

If you ever done a flame test, putting a solid substance or a concentrated solution on a wire loop and placing it in a flame to see what color is produced, you've done the same chemistry. The extreme heat excites electrons in an atom or molecule, and as they fall back down to their lowest energy, or ground state, emitting a photon (a bit of light) that just exactly matches the difference in energy between the excited state and the ground state. An orange flame meant you had sodium on the wire, while a violet flame suggested potassium. More properly this technique is called atomic emission spectroscopy.

For atoms the picture you usually see in a high school text of this process is of a ladder, where electrons are shown moving from rung to rung. The larger the distance between the two rungs (or states) the higher the energy of the photon emitted. If the distance corresponds to photons in the visible region, you see a color, otherwise you have to use something fancier to figure out the energy of the photons being released.

Different atoms have different spacings between states and so the colors they emit when heated to high temperatures are likewise different. There are in fact many states, and so many types of photons can be emitted, but few are in the visible region.

If you click here, you can see a simulation of the photons you'd expect to see when an excited sodium atom returns to the ground state. Are you surprised that sodium can be used for yellow-orange in fireworks? Some urban legends suggest that lead (or radioactive barium) are used in fireworks, but if you look at the line spectrum of lead you can see why it can't be true -- there is no rung to rung jump in lead that corresponds to a visible photon. So a lead firework would be invisible! (Lead used to be used to make the fireworks "crackle"...)

(And it's true that barium salts are used in fireworks, but they are not radioactive. There are no naturally occurring radioactive isotopes of barium.)

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Read more:

An article at C&E News on the chemistry of fireworks

Related posts:

Jello lasers
Romancing the stone (lasers in the plot line of a romance novel)

Image from Wikimedia.

All that glitters...may be tin

While medieval alchemists were searching for the secrets of turning base metals, such as lead and tin, into gold, medieval artists had already figured out how to do this. Gold was often applied to manuscripts in medieval Europe and the Middle East to “illuminate” them, an illuminated page would have the functional equivalent of little mirrors scattered across it, making the most of dim interior lighting. In addition to being reflective, gold does not corrode or oxidize, so gold will not discolor with time. There is a fine collection of medieval illuminated manuscripts at a library near me, and as you turn the pages of Book of Hours that is half a millenia old (wearing gloves, of course), the golden decorations wink at you as brightly as the day they were applied.

Gold is expensive, and hard to handle, particularly in the thin sheets necessitated by the cost. One alternative is to use a tin base, then brush on a saffron oil glaze. Polish it up and you might not notice. The glaze blocks out the oxygen and moisture in the air, preventing many of the chemical reactions which can cause the metal to discolor. The resulting preparation is called auripetrum - Peter’s gold. Peter had a good idea - whoever he was.

Does anyone know more about the source of this name? I'd love to know.

Weird Words of Science 8: Ligands, the ties that bind

Many transition metals react with bases (such as ammonia) to produce beautifully colored transition metal-ligand complexes. The word ligand comes from the Latin ligare which means to tie or bind. The same root leads to ligaments, which tie your bones together.

The photo shows green Ni(H₂O)₆²⁺ and blue green Ni(NH₃)₆²⁺. The ligands are water and ammonia respectively, "tied" to the Ni(II) center. The ligands form an octahedron around the metal center.

van Gogh's Palette

In an attempt to brighten a dreary Philadelphia day, I pulled out a coffee mug that glows with Vincent van Gogh's sunflowers. Among the most vivid of his favorite pigments is chrome yellow. Chrome yellow was first isolated from a natural source (the mineral crocoite) in the late 18th century by Parisienne chemist Vauquelin. By the late 19th century, when van Gogh's sunflowers took form, the vibrant yellow was one of a series of new and exceptionally vivid colors. Chrome yellow is actually a lead salt, lead chromate (PbCrO₄. The pigment isstill used today but it has been replaced in many cases by similarly colored, less toxic organic pigments. Unfortunately chrome yellow degrades over time, so that the once brilliantly glowing sunflowers now appear to be dry, drab ocher shadows of van Gogh's vision.

Perhaps influenced by the mug, this week's webcast general chemistry example problem is based on a simple inorganic synthesis of the chrome yellow pigment. One of my colleague's uses another synthesis. in her course on "The Stuff of Art"

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Read more about the history and chemistry of color in Bright Earth: Art and the Invention of Color by Philip Ball.

What do flamingos, Cheetos and Quantum Chemistry have in common?

The vibrant colors of flamingos and Cheetos Cheez Whiz™ are both the result of related carotenoid dyes. Carotenoids (named for the vegetable in which they were first found!) are based on a linear conjugated diene skeleton, and provide nature with many colorful accents. Canthaxanthin, for example, is fed to captive flamingos to produce their characteristic pink color (a similar pigment found in brine shrimp does the same favor for wild flamingos). Astaxanthin is responsible for the characterstic color of lobsters. Canaries, whose signature color is a greenish yellow, can be turned red if they are fed paprika during their molt. The new feathers will grow in orange-red.

If you're tired of only changing the color of your hair, you can try for a pumpkin look for fall. The compound that gives this class of vegetable pigments its name - β-carotene - when consumed in large quantities by humans, will turn them orange. [Really, but don't try this at home! It was observed clinically in Britain during WW II when food shortages led some people to include large amounts of carrots in their diets.]

If you thought the bright color of Cheez-Whiz and Cheetos was artificial -- it's not. Bixin or annatto, a natural pigment used for centuries, is the source of that unforgettable orange. Researchers have recently elucidated the biochemical pathway for the synthesis of bixin and are pursuing genetic engineering approaches to its bulk synthesis in tomatoes [Florence Bouvier in Science, 300:2089-2091, June 27, 2003].

What does this all have to do with quantum chemistry? A very simple quantum mechanical model, the particle in a one-dimensional box, can be used to predict the color of conjugated dyes.

UPDATE: Bixin isn't used to color Cheetos, but is used in Cheez Whiz.