A third “hot” molecule that also fits this theory of molecular shape is zingerone (C11H14O), found in the underground stem of the ginger plant, Zingiber officinale. Although smaller than either piperine or capsaicin (and, most people would argue, not as hot), zingerone also has an aromatic ring with the same HO and H3C-O groups attached as in capsaicin, but with no nitrogen atom.
Why do we eat such pain-causing molecules? Perhaps for some good chemical reasons. Capsaicin, piperine, and zingerone increase the secretion of saliva in our mouths, aiding digestion. They are also thought to stimulate the movement of food through the bowel. Unlike taste buds that in mammals are mainly on the tongue, pain nerves, able to detect the chemical messages from these molecules, occur in other parts of the human body. Have you ever inadvertently rubbed your eyes while chopping up a chili pepper? Workers who harvest hot peppers need to wear rubber gloves and eye protection against the chili oil containing capsaicin molecules.
The heat we feel from peppercorns appears to be directly proportional to the amount of pepper in the food. Heat from a chili pepper, on the other hand, can be deceptive. Color, size, and region of origin all affect the “hotness” of a chili pepper. None of these guides are reliable; while small peppers are often associated with heat, large peppers are not always the mildest. Geography does not necessarily supply a clue, although the world’s hottest chili peppers are said to grow in parts of East Africa. Heat generally increases as a chili is dried.
We often experience a feeling of satisfaction or contentment after eating a fiery meal, and this feeling may be due to endorphins, opiate-like compounds that are produced in the brain as the body’s natural response to pain. This phenomenon may account for some people’s seeming addiction to hot spicy food. The hotter the chili, the more the pain, so the greater the trace amounts of endorphins produced and ultimately the greater the pleasure.
Apart from paprika, which became well established in Hungarian food like goulash, the chili pepper did not invade the food of Europe the way it did African and Asian cuisine. For Europeans, piperine from the peppercorn remained the hot molecule of choice. Portuguese domination of Calicut and thus control of the pepper trade continued for about 150 years, but by the early seventeenth century the Dutch and the English were taking over. Amsterdam and London became the major pepper trading ports in Europe.
The East India Company—or to give the formal name by which it was incorporated in 1600, the Governor and Company of Merchants of London Trading into the East Indies—was formed to gain a more active role for England in the East Indian spice trade. The risks associated with financing a voyage to India that would return with a shipload of pepper were high, so merchants initially bid for “shares” of a voyage, thus limiting the amount of potential loss for any one individual. Eventually this practice turned into buying shares of the company itself and thus could be considered responsible for the beginning of capitalism. It may be only a bit of a stretch to say that piperine, which surely nowadays must be considered a relatively insignificant chemical compound, was responsible for the beginnings of today’s complex economic structure of the world stock markets.
THE LURE OF SPICES
Historically, pepper was not the only spice of great value. Nutmeg and cloves were also precious and were a lot rarer than pepper. Both originated in the fabled Spice Islands or Moluccas, now the Indonesian province of Maluku. The nutmeg tree, Myristica fragrans, grew only on the Banda Islands, an isolated cluster of seven islands in the Banda Sea, about sixteen hundred miles east of Jakarta. These islands are tiny—the largest is less than ten kilometers long and the smallest barely a few kilometers. In the north of the Moluccas are the equally small neighboring islands of Ternate and Tidore, the only places in the world where Eugenia aromatica, the clove tree, could be found.
For centuries the people of both these island groups had harvested the fragrant product of their trees, selling spices to visiting Arab, Malay, and Chinese traders to be shipped to Asia and to Europe. Trade routes were well established, and whether they were transported via India, Arabia, Persia, or Egypt, spices would pass through as many as twelve hands before reaching consumers in western Europe. As every transaction could double the price, it was no wonder that the governor of Portuguese India, Afonso de Albuquerque, set his sights farther afield, landing first at Ceylon and later capturing Malacca, on the Malay Peninsula, then the center of the East Indian spice trade. By 1512 he reached the sources of nutmeg and cloves, established a Portuguese monopoly trading directly with the Moluccas, and soon surpassed the Venetian merchants.
Spain, too, coveted the spice trade. In 1518 the Portuguese mariner Ferdinand Magellan, whose plans for an expedition had been rejected by his own country, convinced the Spanish crown that it would not only be possible to approach the Spice Islands by traveling westward but that the route would be shorter. Spain had good reasons for supporting such an expedition. A new route to the East Indies would allow their ships to avoid Portuguese ports and shipping on the eastern passage via Africa and India. As well, a previous decree by Pope Alexander VI had awarded Portugal all non-Christian lands east of an imaginary north-south line one hundred leagues (about three hundred miles) west of the Cape Verde Islands. Spain was allowed all non-Christian lands to the west of this line. That the world was round—a fact accepted by many scholars and mariners of the time—had been overlooked or ignored by the Vatican. So approaching by traveling west could give Spain a legitimate claim to the Spice Islands.
Magellan convinced the Spanish crown that he had knowledge of a pass through the American continent, and he had also convinced himself. He left Spain in September 1519, sailing southwest to cross the Atlantic and then down the coasts of what are now Brazil, Uruguay, and Argentina. When the 140-mile-wide mouth of the estuary of the Río de la Plata, leading to the present-day city of Buenos Aires, turned out to be just that—an estuary—his disbelief and disappointment must have been enormous. But he continued southward, confident that a passage from the Atlantic Ocean to the Pacific was always just around the next headland. The journey for his five small ships with 265 crewmen was only to get worse. The farther south Magellan sailed, the shorter the days became and the more constant the gales. A dangerous coastline with surging tides, deteriorating weather, huge waves, steady hail, sleet and ice, and the very real threat of a slip from frozen rigging added to the misery of the voyage. At 50 degrees south with no obvious passageway in sight and having already subdued one mutiny, Magellan decided to wait out the remainder of the southern winter before sailing on to eventually discover and navigate the treacherous waters that now bear his name.
By October 1520, four of his ships had made it through the Strait of Magellan. With supplies running low, Magellan’s officers argued that they should turn back. But the lure of cloves and nutmeg, and the glory and wealth that would result from wresting the East Indies spice trade from the Portuguese, kept Magellan sailing west with three ships. The nearly thirteen-thousand-mile journey across the vast Pacific, a far wider ocean than anyone had imagined, with no maps, only rudimentary navigational instruments, little food, and almost depleted water stores, was worse than the passage around the tip of South America. The expedition’s landfall on March 6, 1521, at Guam in the Marianas, offered the crew a reprieve from certain death by starvation or scurvy.
Ten days later Magellan made his last landfall, on the small Philip-pine island of Mactan. Killed in a skirmish with the natives, he never did reach the Moluccas, although his ships and remaining crew sailed on to Ternate, the home of cloves. Three years after leaving Spain, a depleted crew of eighteen survivors sailed upriver to Seville with twenty-six tons of spices in the battered hull of the Victoria, the last remaining ship of Magellan’s small armada.
THE AROMATIC MOLECULES OF CLOVES AND NUTMEG
Although cloves and nutmeg come from different plant families and from remote island groups separated by hundreds of miles of mainly open sea, their distinctively different odors are due t
o extremely similar molecules. The main component of oil of cloves is eugenol; the fragrant compound in oil of nutmeg is isoeugenol. These two aromatic molecules—aromatic in both smell and chemical structure—differ only in the position of a double bond:
The sole difference in these two compounds—the double bond position—is arrowed.
The similarities between the structures of these two compounds and of zingerone (from ginger) are also obvious. Again the smell of ginger is quite distinctive from that of either cloves or nutmeg.
Zingerone
Plants do not produce these highly scented molecules for our benefit. As they cannot retreat from grazing animals, from sap-sucking and leaf-eating insects, or from fungal infestations, plants protect themselves with chemical warfare involving molecules such as eugenol and isoeugenol, as well as piperine, capsaicin, and zingerone. These are natural pesticides—very potent molecules. Humans can consume such compounds in small amounts since the detoxification process that occurs in our livers is very efficient. While a massive dose of a particular compound could theoretically overpower one of the liver’s many metabolic pathways, it’s reassuring to know that ingesting enough pepper or cloves to do this would be quite difficult.
Even at a distance from a clove tree, the wonderful smell of eugenol is apparent. The compound is found in many parts of the plant, in addition to the dried flower buds that we’re familiar with. As long ago as 200 B.C., in the time of the Han dynasty, cloves were used as breath sweeteners for courtiers in the Chinese imperial court. Oil of clove was valued as a powerful antiseptic and a remedy for toothache. It is still sometimes used as a topical anesthetic in dentistry.
Drying cloves on the street in Northern Sulawesi, Indonesia. (Photo by Penny Le Couteur)
The nutmeg spice is one of two produced by the nutmeg tree, the other being mace. Nutmeg is ground from the shiny brown seed, or nut, of the apricotlike fruit, whereas mace comes from the red-colored covering layer, or aril, surrounding the nut. Nutmeg has long been used medicinally, in China to treat rheumatism and stomach pains, and in Southeast Asia for dysentery or colic. In Europe, as well as being considered an aphrodisiac and a soporific, nutmeg was worn in a small bag around the neck to protect against the Black Death, which swept Europe with regularity after its first recorded occurrence in 1347. While epidemics of other diseases (typhus, smallpox) periodically visited parts of Europe, the plague was the most feared. It occurred in three forms. The bubonic form manifested in painful buboes or swellings in the groin and armpits; internal hemorrhaging and neurological decay was fatal in 50 to 60 percent of cases. Less frequent but more virulent was the pneumonic form. Septicemic plague, where overwhelming amounts of bacilli invade the blood, was always fatal, often in less than a day.
It’s entirely possible that the molecules of isoeugenol in fresh nutmeg did act as a deterrent to the fleas that carry bubonic plague bacteria. And other molecules in nutmeg may also have insecticidal properties. Quantities of two other fragrant molecules, myristicin and elemicin, occur in both nutmeg and mace. The structures of these two compounds are very similar to each other and to those molecules we have already seen in nutmeg, cloves, and peppers.
Besides being a talisman against the plague, nutmeg was considered to be the “spice of madness.” Its hallucinogenic properties—likely from the molecules myristicin and elemicin—were known for centuries. A 1576 report told of “a pregnant English lady, having eaten ten or twelve nutmegs, became deliriously inebriated.” The accuracy of this tale is doubtful, especially the number of nutmegs consumed, as present-day accounts of ingestion of only one nutmeg describe nausea, profuse sweating, heart palpitations, and vastly elevated blood pressure, along with days of hallucinations. This is somewhat more than a delirious inebriation; death has been attributed to consumption of far fewer than twelve nutmegs. Myristicin in large quantities can also cause liver damage.
In addition to nutmeg and mace, carrots, celery, dill, parsley, and black pepper all contain trace amounts of myristicin and elemicin. We don’t generally consume the huge quantities of these substances necessary for their psychedelic effects to be felt. And there is no evidence that myristicin and elemicin are psychoactive in themselves. It is possible that they are converted, by some as-yet-unknown metabolic pathway in our body, to traces of compounds that would be analogs of amphetamines.
The chemical rationale for this scenario depends on the fact that another molecule, safrole, with a structure that differs from myristicin only by a missing OCH3, is the starting material for the illicit manufacture of the compound with the full chemical name of 3,4-methylenedioxy-N-METHYLAMPHETAMINE, abbreviated to MDMA and also called Ecstasy.
The transformation of safrole to Ecstasy can be shown as:
Safrole comes from the sassafras tree. Traces can also be found in cocoa, black pepper, mace, nutmeg, and wild ginger. Oil of sassafras, extracted from the root of the tree, is about 85 percent safrole and was once used as the main flavoring agent in root beer. Safrole is now deemed a carcinogen and, along with oil of sassafras, has been banned as a food additive.
NUTMEG AND NEW YORK
The clove trade was dominated by the Portuguese during most of the sixteenth century, but they never achieved a complete monopoly. They reached agreements on trading and building forts with the sultans of the islands of Ternate and Tidore, but these alliances proved temporary. The Moluccans continued to sell cloves to their traditional Javanese and Malayan trading partners.
In the next century the Dutch, who had more ships, more men, better guns, and a much harsher colonization policy, became masters of the spice trade, mainly through the auspices of the all-powerful Dutch East India Company—the Vereenigde Oostindische Compagnie, or VOC—established in 1602. The monopoly was not easily accomplished or sustained. It took until 1667 for the VOC to obtain complete control over the Moluccas, evicting the Spanish and Portuguese from their few remaining outposts and ruthlessly crushing opposition from the local people.
To fully consolidate their position, the Dutch needed to dominate the nutmeg trade in the Banda Islands. A 1602 treaty was supposed to have given the VOC sole rights to purchase all the nutmeg produced on the islands, but though the treaty was signed by the village chiefs, the concept of exclusivity was either not accepted or (maybe) not understood by the Bandanese, who continued selling their nutmeg to other traders at the highest offered price—a concept they did understand.
The response by the Dutch was ruthless. A fleet of ships, hundreds of men, and the first of a number of large forts appeared in the Bandas, all designed to control the trade in nutmeg. After a series of attacks, counterattacks, massacres, renewed contracts, and further broken treaties, the Dutch acted even more decisively. Groves of nutmeg trees were destroyed except around where the Dutch forts had been built. Bandanese villages were burned to the ground, the headmen were executed, and the remaining population was enslaved under Dutch settlers brought in to oversee nutmeg production.
The lone remaining threat to the VOC’s complete monopoly was the continued presence of the English on Run, the most remote of the Banda Islands, where years before the headmen had signed a trade treaty with the English. This small atoll, where nutmeg trees were so numerous that they clung to the cliffs, became the scene of much bloody fighting. After a brutal siege, a Dutch invasion, and more destruction of nutmeg groves, with the 1667 Treaty of Breda the English surrendered all claims to the island of Run in exchange for a formal declaration renouncing Dutch rights to the island of Manhattan. New Amsterdam became New York, and the Dutch got nutmeg.
In spite of all their efforts, the Dutch monopoly in the trade in nutmeg and cloves did not last. In 1770 a French diplomat smuggled clove seedlings from the Moluccas to the French colony of Mauritius. From Mauritius they spread all along the East African coast and especially to Zanzibar, where cloves quickly became the major export.
Nutmeg, on the other hand, proved notoriously difficult to cultivate outside its original home on the
Banda Islands. The tree requires rich, moist, well-drained soil and hot, humid conditions away from the sun and strong winds. Despite the difficulty competitors had in establishing nutmeg growth elsewhere, the Dutch took the precaution of dipping whole nutmegs in lime (calcium hydroxide or slaked lime) before export, to prevent any possibility of sprouting. Eventually the British managed to introduce nutmeg trees into Singapore and the West Indies. The Caribbean island of Grenada became known as “the Nutmeg Isle” and is now the major producer of the spice.
The great worldwide trade in spices would doubtless have continued were it not for the advent of refrigeration. With pepper, cloves, and nutmeg no longer needed as preservatives, the huge demand for piperine, eugenol, isoeugenol, and the other fragrant molecules of these once exotic spices has gone. Today pepper and other spices still grow in India, but they are not major exports. The islands of Ternate and Tidore and the Banda group, now part of Indonesia, are more remote than ever. No longer frequented by great sailing ships seeking to load their hulls with cloves and nutmeg, these small islands slumber in the hot sun, visited only by occasional tourists who explore the crumbling old Dutch forts or dive the pristine coral reefs.
The lure of spices is in the past. We still enjoy them for the rich, warm flavor their molecules impart to our food, but we rarely think of the fortunes they built, the conflicts they provoked, and the amazing feats of exploration they inspired.
2. ASCORBIC ACID
THE EAGE OF DISCOVERY was fueled by molecules of the spice trade, but it was the lack of another, quite different molecule that almost ended it. Over 90 percent of his crew didn’t survive Magellan’s 1519-1522 circumnavigation of the world—in large part due to scurvy, a devastating disease caused by a deficiency of the ascorbic acid molecule, dietary vitamin C.
Penny le Couteur & Jay Burreson Page 3