Hot Chili Pepper Chemistry

The English word pepper is ambiguous. Botanically it could be refer to plants that produce black powdered pepper. The angiosperms (flowering plants) who serve as a source of that spice belong to the order Piperales and to the 3600-member family Piperaceae. (Kings play chess only for goodness’ sake is a mnemonic for remembering the order of biological classification: kingdom, a group of related phyla, which in turn, at least in singular form, phylum, is a group of related classes, and so on with orders, families, genera and species. ) Piperine is the compound mainly responsible for black pepper’s pungency, but as expected it does not appear in unrelated plants also dubbed as peppers.

1280px-Ripe_jalapeno_pepper
In jalapeños,  dihydrocapsaicin and capsaicin, are the two  amides mainly responsible for their hotness.

Pepper can also refer to Capsicum chinense, the Red Savino haanero chili, a member of the tomato family, Solanacea.  That fruit scores in the hundreds of thousands of units on the Scoville scale of “hotness”.  Other hot  peppers and milder ones are found among the many varieties of another Capsicum species, known as annum, which includes sweet peppers, jalapeños, and New Mexico chili.

 

There are four different amides (specifically, capsaicioids) found in hot peppers of the Capsicum genus. A Brazilian study revealed that in these fruits capsaicin makes up anywhere from 24% (in jalapeños) to 95% (pimenta preta) of capsaicioids present. These in turn combine to account anywhere from 0.2 mg to 7 mg per gram of fresh pepper, in other words, less than 1%. The percentage of course soars when the pepper is dried. Except in jalapeños and fatalis, the equally potent compound, dihydrocapsaicin, is the second most abundant amide. The greatest concentration (9.2%) of nordihydrocapsaicin, a substance about half as hot, was found in pimenta de mesa. Finally another related compound, homocapsaicin, the least potent of the quartet, is entirely absent from most spicy peppers, but it makes up 12% of dedo-de-moça pequena’s capsaicioids.

Nordihydrocapsaicin
nnordihydrocapsaicin 9 100 000
Dihydrocapsaicin
dihydrocapsaicin 16 000 000
Homocapsaicin
homocapsaicin 8 600 000
capsaicin
capsaicin 16 000 000
pimenta de mesa
The hot amides in pimenta de mesa consist of about 53% capsaicin, 37% dihydrocapsaicin, 1% homocapsaicin and about 9% nordihydrocapsaicin . The latter’s concentration is not surpassed in 20 other species of Capsicum.

From examining the above structural diagrams notice that in comparison to capsaicin,  homocapsaicin’s double bond is slightly further away from the tail end of the molecule. On the other hand, nordihydrocapsaicin’s strength is compromised by being one CH2 shorter than its hotter counterpart, dihydrocapsaicin.

How do these compounds exert such a powerful reaction in our mouths? In all mammals they cause tingling and burning sensations by activating  a non-selective cation channel, called VR1, on nerve endings. It’s not a coincidence that the same channel also interacts with compounds released by inflammation from actual intense heat sources or acidic protons. Birds, however, have a variant of VR1, which is still sensitive to heat and acid but which does not interact with capsaicin or its analogues.  It’s likely an example of co-evolution between Capsicum plants and animals who can eat their fruits without suffering deterring consequences. They then fly to other destinations to spread ingested seed.
We get more evidence of coevolution thanks to Jordi Altimiras of  Linköping University who made me aware of a study revealing that chilli seed germination is decreased in the gastrointestinal tract of mammals but not by the passage through the tract of birds.

Finally why are peppers producing capsaicioids in the first place? Any biosynthesis is catabolic and thus consumes energy. But making capsaicinoids in fruits is a worthwhile investment; it reduces fungal infection and seed mortality. From that narrow perspective we mammals have more in common with fungi than birds.

Sources:

  • Molecular basis for species-specific sensitivity to “hot” chili peppers.  2002 Feb 8;108(3):421-30.
  • Comparative Study of Capsaicinoid Composition in Capsicum Peppers Grown in Brazil
    http://www.tandfonline.com/doi/full/10.1080/10942912.2015.1072210
  • Directed deterrence by capsaicin in chillies. Nature 412: 403-404 and Tewksbury JJ, Reagan KM, Machnicki NJ, Carlo TA, Haak DC, et al. (2008)
  • Evolutionary ecology of pungency in wild chilies. ProcNatAcadSciUSA 105: 11808-11811 .
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From Playing Cards to Clover

If we keep looking at the same thing over a period of time with an uncritical, non-curious or distracted mind, attenuation sets in. And not only do our nervous systems tune out what’s commonplace, we also develop a false sense of history. We act as if things always were as they currently appear to be, and as if they will continue to be immune from flux.

Take playing cards as an example. If one was raised in North America and was not in contact with recent Spanish, Moroccan or Italian immigrants, it’s likely that the person has a fixed image of playing cards: 52 cards, 13 in each of four suits: clubs (clover), hearts, spades and diamonds with three of the cards being a king, queen and a jack.

Cards
The four suits of Neapolitan playing cards like those of other Spanish and Italian cards differ from French ones.  The former’s suits are far more similar to those of the first cards imported into Europe from Egypt in the 14th century. Pic by the author.

But these familiar cards are just one version, one that originated under the rule of  King Charles VI of France between 1380 and 1422. They continued to evolve a little later in the 15th century into their current forms which are neither unique nor static.  Take a tour of  cafes in Italy and you will see people playing with variations upon the theme of Italian-Spanish cards:  the king is still present, but there is a cavalier and a servant instead of the queen and jack, respectively. And there are only 40 cards with suits of clubs (large sticks), cups, swords and coins. These strike more of a resemblance to the first cards that were imported into Europe by Italian merchants around 1360. They discovered them while trading with Mamluks in Egypt. The cards had the same suits like those of contemporary Spanish and Italian cards, except that they featured a wand instead of a club.  Regional cards in Northeastern Italy still include a wand as a suit.

I often wondered why the word “club” is used for the clover leaf, one of the four suits of French cards. One hypothesis is that the suit was associated with commoners who grew clover alternately with their crops for fodder and in order to enrich the soil. But wooden clubs were also commoners’ weapon of choice, so the name “clubs” stuck to clover.

Clover is a legume whose roots include a mutualistic relationship between bacteria and plant cells.

cloverroots
The arrows point to white clover’s root- nodules, the site of nitrogen fixation by mutualistic bacteria. (The scale is in inches. 1 inch = 2.54 cm) Picture from NC State Extension Publications – NC State University

Thanks to bacterial enzymatic action, valuable nitrogen compounds are made from otherwise unusable nitrogen air molecules. In exchange, the bacteria receive shelter and sugars. Before many people developed the bad habit of adding herbicide to lawn grass, white clover seed  was often mixed with grass seed. Clover, when coexistent, helps grass by adding nitrogen compounds to the soil.

Like playing cards, not all clovers are alike. White clover is adapted to moist conditions. It should not be the only companion of lawn grass. Especially where grass grows on slopes where water drains easily, it makes more sense to grow bird’s foot trefoil. Scientifically known as Lotus corniculatus , it is another leguminous plant which does better in arid conditions and which will help abate dandelions. These unpopular relatives of the lettuce in turn out-compete grass when less water is available. A smaller legume with smaller yellow flowers, black medic, can do well in both moist and more arid soils. And of course there is a common origin to the genera of the bird’s foot (Lotus), to medic (Medicago) and to that of at least 238 Trifolium species, including red and white clover—-we see it in the similarity of leaflet shape, small pea-like flowers and to the all-important and welcome infection in their productive roots.

clover
Clover and clover-like plants belonging to 3 different genera of the legume family: from left to right, Trifolium repens (white clover), Lotus corniculatus (bird foot’s trefoil) and Medicago lupulina (black medic). Just about all Trifolium species are bee-pollinated. All pics from wikipedia commons.

Their family Leguminosae evolved about 56 million years ago, 9 million years after large dinosaurs went extinct. A few million years later, their most important clades separated. From genetic analyses, it’s been determined that their evolution occurred quickly, reminiscent of  the way playing cards quickly branched out in Europe. And like the latter,  the 18000 species of legumes are now spread all over the planet. They are being used for food, oil, lumber, fiber, medicines, aesthetic purposes and not least of all, for a vital role in the Earth’s nitrogen cycle.

SOURCES:

Lavin, et al. 2004. Evolutionary Rates Analysis of Leguminosae Implicates a Rapid Diversification of Lineages during the Tertiary. Systematic Biology 54 (4): 530-549 http://sysbio.oxfordjournals.org/content/54/4/575.full

The Botanical Garden. Phillips and Rix

The Mediterranean and Mediterranean World. Francois Braudel

The four suits of a pack of cards www.theguardian.com/books/booksblog/2013/dec/04/books-advent-calendar-4-four-card-suits

Have you ever wondered why the symbols on playing cards are called…. http://www.brierfieldbridgeclub.org.uk/themes/Have%20you%20ever%20wondered.htm

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