Sun-Pumped. The image of Richard J. Tarzaiski, an RCA physicist, is reflected in the parabolic mirror that collects the sun’s rays to power a sun-pumped laser. Such a device, which requires no other power, might be a communications link from a spaceship 50 million miles from the earth (UPI Photo).
To many people, thallium is synonymous with rat poison. It is more toxic to mammals than mercury, cadmium, and lead and has been responsible for many deliberate, accidental, occupational, and therapeutic poisonings of people since its discovery in 1861.
Public angst and concern were first drawn in the late 1960s to reports of widespread contamination of the Great Lakes’ ecosystems with toxic metals. At the time, I was a graduate student at the University of Toronto. Of the various groundbreaking studies on the hazards of heavy metals in the Great Lakes basin, I was captivated by reports that alluded to the fact that symptoms typical of thallium poisoning were being observed in many wildlife populations in the Great Lakes basin, and especially one report that claimed that nine out of the 34 bald eagles found sick or dying in 1971-72 in parts of the basin in the U.S. were poisoned by thallium.
Compared with many heavy metals, thallium has a short history and what appears to be a rosy future. Its traditional uses (in rodenticides and insecticides, pigments, wood preservatives, and ore separation; in mercury lamps to increase the intensity and spectrum of the light; as catalysts in chemical syntheses; and so forth) are being phased out in deference to its toxicity. At the same time, there is increasing demand for thallium in the high-technology and future-technology fields.
Among the growing uses for thallium are in the semiconductor and laser industry, in fiber (optical) glass, in scintillographic imaging, in superconductivity, and as a molecular probe to emulate the biological function of alkali-metal ions.
Alexander Litvinenko (top). The high-profile Russian defector was felled by polonium-210.
In yet another oft-told tale, the book recounts the 1910 murder in England of Belle Elmore, better known as the wife of the notorious Dr. Crippen. Mrs. Crippen was a minor but popular singer in Edwardian London. Dr. Crippen was, by most standards, a con artist with problems on both sides of the Atlantic. As many stories of the infamous crime tell, Mrs. Crippen had the money and Dr. Crippen had a mistress, ensuring that their marriage would come to an unpleasant end.
The murder happened when, after a small party, Dr. Crippen, who had earlier purchased hyoscine or scopolamine from a pharmacist, apparently gave his wife a drink containing it. Instead of dying neatly, she must have required a coup de grace that made the body impossible to pass off as a natural death. Crippen disposed of the body by removing the flesh, treating it with quicklime and burying it in the basement of his house.
After the murder was discovered and the body located, Crippen and his mistress—interestingly disguised as father and son—boarded a ship for Canada. The ship’s captain recognized Crippen and radioed the authorities in London, something unusual in 1910. A faster ship with a pursuing detective chased Crippen to Canada and he was arrested there. At his trial, he was convicted of murder, and he was subsequently hanged. The trial involved the well-known pathologist Sir Bernard Spilsbury (who appears again later in the book). This case strained the limits of the known sciences of the time, including an identification of the victim from soft tissue (a recently questioned identification), the chemist’s identification of the poison, and the use of the new “wireless” for communication to alert the police.
-Reviewed by Charles S. Tumosa
Murderous Molecules: Accounts of true crimes in which victims were polished off by poison
Bismuth is the heaviest nonradioactive element and is essentially a nontoxic neighbor of lead and thallium in the periodic table. It is mined as bismuth oxide (Bi2O3, also known as bismite) or bismuth sulfide (Bi2S3, bismuthinite), and the brittle, silvery elemental form is one of a few substances (water is another) for which the solid is less dense than the liquid. Although bismuth has been extensively used in alloys, pharmaceuticals, electronics, cosmetics, pigments, and organic, the chemistry of bismuth is perhaps the least well established of the group-15 elements (known as the pnictogens). Compounds of bismuth typically have low solubility in most solvents, so that definitive formula assignments are usually based on X-ray diffraction studies of crystalline samples that have been isolated in small or indefinite quantities. Most isolated compounds are unique rather than members of a series of related compounds illustrating fundamental chemical trends.
The bioutility of bismuth compounds has a 250-year history that includes numerous medicinal applications; however, the mechanisms of bioactivity are not understood. Moreover, as for most compounds of bismuth, the chemical characterization of biorelevant complexes remains incomplete. Although the “heavy metal” designation has impeded application of bismuth chemistry in medicine, two compounds have been extensively used for gastrointestinal medication for decades. Pepto-Bismol contains bismuth subsalicylate, and De-Nol contains colloidal bismuth subcitrate. The use of these compounds for the treatment of travelers’ diarrhea, non-ulcer dyspepsia, nonsteroidal anti-inflammatory drug damage, and various other digestive disorders extends from the previous use of bismuth compounds in the treatment of syphilis and tumors, in radioisotope therapies, and in the reduction of the renal toxicity of cisplatin.
Coherent light. Bell Telephone scientists W.S. Boyle (left) and R.J. Collins prepare to fire an optical maser—microwave amplification by simulated emission of radiation—from Holmdel, N.J., to Murray Hill, N.J., 25 miles away (top photo). Heart of the maser is a synthetic ruby rod silvered at the ends. When illuminated, the rod produces a beam of coherent (single phase) light. Red flashes from the maser are picked up on a phototube (lower photo) by scientists W.L. Bond (at tube) and D.F. Nelson in Murray Hill. Message comes through in a code based on repeated flashes.
Today in 1902, chemist Kurt Alder was born. With Otto Diels, Alder won the Nobel Prize in Chemistry in 1950 for “the development of the diene synthesis, or Diels-Alder reaction, which consists of the 1,4-addition of an ethylenic compound to a conjugated diene.” The reaction has been used by many a synthetic organic chemist in making all sorts of stuff from plastics to drugs. But the prize also led to bit of a scramble for the 1950 C&EN newsroom, as documented in the Newscripts below:
In our efforts to obtain timely cover pictures, we sometimes skim disconcertingly close to deadlines. Cover subjects are always available; in fact, we often have a choice. But pictures are something else again. This week’s cover is a case in point.
We knew before the Nobel prize in chemistry was announced that we would want the picture of the winner, or winners, for the Dec. 4 cover, the week following the cover picture of the two chemists, Kendall and Reichstein, who shared in the Nobel prize in medicine. The Kendall picture, of course, was easy. We already had a photo in our files, taken at the same time as the one we used on the June 19 cover. Our European editor, Richard L. Kenyon, then in London, got the other picture by phoning Reichstein, who sent it to us directly from Basel.
When the chemistry prize was announced Nov. 10, we again called on Kenyon, this time to get pictures of Diels and Alder from Germany. Unable to reach them by phone, Kenyon wired. Alder, in Cologne, responded promptly by sending a picture and biographical material. But Diels, in Kiel, still couldn’t be reached. Up to the time when the cover engraving is usually being made, we still had no satisfactory picture of Diels. Then began phone calls to historians of chemistry in this country and others whom we thought might possibly have a photo. Although several people were helpful in providing biographical information on Diels and evaluations of the diene synthesis for the cover story, no one had a picture. So another rush cable was sent to Kenyon who was by that time in Paris. Still no picture, he replied; but he did put us on the trail of a good, recent picture of Diels in this country. We got it the next day. Success at last.
To provide an ironical anticlimax, one of the Washington staff members saw pictures of Diels and Alder in the news-reel at a downtown movie that night. There they were, both men in their laboratories, receiving congratulations from their friends. Then the news-reel “voice” commented that the two chemists had won the prize for their “dean” synthesis, which was “responsible for the development of plastics.” (!) Wonderful how everything can be so simple, after all, isn’t it?
Underwater Record. Surgeon Lt. S. Davidson (left) of the British Royal Air Force records the reactions of pilot John Rawlins in underwater hand-eye coordination tests. Comdr. Rawlins sits in a device that simulates weightlessness. The tests, made at the Institute of Aviation Medicine, Farnborough, England, are part of a study of inefficiency in flight.
Happy Fourth from the Watch Glass! On this special Throwback Thursday, check out our 1981 feature on how fireworks moved from art to science. And remember to enjoy your chemistry responsibly this weekend!
Chemists are targeting military pyrotechnics, such as the deployed decoy flares shown here, for more eco-friendly formulations.
Typical pyrotechnics function by burning, so their basic chemical components consist of an oxidant and a fuel. Black powder, the original pyrotechnic, blends potassium nitrate oxidizer with charcoal and sulfur fuel. Set this witch’s brew alight, and in a flash the nitrate oxidizes the charcoal and sulfur, producing glowing solids and a vast volume of hot gases. Other components, such as colorants, binders, and propellants, can be added to the mix, depending on the task the pyrotechnic has to perform.
Over the years, perchlorate has become the oxidizer of choice for most pyrotechnic applications, supplanting less stable chlorate oxidants that were the cause of numerous deadly explosions. “Potassium perchlorate is the ideal oxygen donor to use in pyrotechnics in terms of safety, cost, and reproducibility,” says John A. Conkling, a pyrotechnics expert and adjunct professor of chemistry at Washington College, in Chestertown, Md.
Unfortunately, perchlorate has also been identified as a potential human health hazard. Studies suggest that it inhibits the thyroid’s ability to take up iodine from the bloodstream and can reduce the production of thyroid hormone. And because the anion is highly water soluble, it readily slips into groundwater. “The major effort in most areas of environmentally friendly pyrotechnics research is to find perchlorate replacement materials,” Conkling says.
Pyrotechnics for the Planet: Chemists seek environmentally friendlier compounds and formulations for fireworks and flares
The February issue of Grace Digest, published by W. R. Grace & Co., reports a little of the history of soccer, which today is the world’s most popular spectator sport. Soccer appears to have started with a Greek game, Harpaston, which the Romans called Harpastum and took to England when they invaded that country. The game caught on quickly, but later the British kings began to suspect that their troops were goofing off in order to play. In consequence, the Digest says, they outlawed the game in 1314, 1349, 1389, 1401, 1504, and 1581 before finally giving up. The Scottish clergy opposed the playing of the game on Sunday—the only day that most people had time to play it—so it was banned by the Scottish Kings James I and II, who ruled, respectively, in 1603-25 and 1685-88. Soccer (football) finally won out, and the first formal rules were drawn up in 1862. Soccer is played today in more than 150 countries before crowds of up to 150,000.
Compounds found in the shell of cashew nuts, which hang from the bottom of the cashew fruit, are sources of chemical raw materials (top).
When chemists think of basic raw materials, ethylene, propylene, benzene, or even vegetable oil usually comes to mind. Cashew nutshell liquid (CNSL), not so much. But for a couple of companies, this material is seeing strong growth as a coating additive.
CNSL is a by-product of processing cashew nuts in places like Brazil, India, and Vietnam, as well as in Africa. The liquid is mostly anacardic acid, which is used as an antiseptic. When heated, it undergoes decarboxylation to yield cardanol.
It is cardanol—a phenol with an unsaturated carbon chain attached—that is of interest to chemists. “You can use the unsaturation of the C15 side chain to do chemistry like you do on linseed or soybean oils, or you can do traditional phenolic chemistry,” says Doug Rhubright, technical director at Palmer International. Skippack, Pa.-based Palmer is the smaller of the two U.S. producers of CNSL derivatives.
-Alexander H. Tullo
A Nutty Chemical: Naturally occurring phenol compounds in cashew shells are becoming increasingly useful to industry
At World Cup soccer championship first-round match in Washington, D.C., Saudi Arabia’s Khalid Al Muwallid (left) vies with the Netherlands’ Frank Rijkaard for control of the ball—a new, improved plastic ball developed jointly by German sports equipment maker Adidas and German chemical company Bayer. Named Questra, the ball incorporates three bonded layers of proprietary polyurethane products made by Bayer. A foamed plastic layer below the synthetic outer skin ensures rapid ball deformation during shots on goal, and this layer’s shock-absorbing qualities help prevent headaches in players who “head” the ball. A layer of nonwoven fibers provides reinforcement to help Questra keeps its shape. In contrast to leather balls used previously, this ball is made by a special process that prevents moisture from seeping through the seams. “This special design gives the ball better dimensional stability, speed, and accuracy, and makes its behavior more predictable,” says Otto Dobrounig, an Adidas technician who worked two years with Bayer engineers to create the ball.
The scientist whose discovery stops speeding bullets was inducted into the National Women’s Hall of Fame in Seneca Falls, N.Y., on Oct. 4, 2003. Stephanie L. Kwolek, a retired research chemist from DuPont, was honored for research that led to the development of Kevlar, an aramid fiber five times stronger than steel. DuPont credits bullet- and knife-resistant body armor made of Kevlar with saving the lives of nearly 3,000 law enforcement officers.
Kwolek, 80, started work for DuPont in 1946 as a laboratory chemist in Buffalo, N.Y. She planned to stay with the company just long enough to save up for medical school. But the freedom and creativity she experienced in the DuPont environment led her to stay with the company for 40 years.
Sixty years ago, a 21-year-old English chemist named Diane Leather became the first woman to break a five-minute mile. She’s featured in the 2007 Newscripts below. Now Diane Charles, she was recently interviewed by The Guardian on the 60th anniversary of her record run. They write: “Staggeringly, Leather’s run was not recognised as a world record, only a world’s best, because the IAAF did not keep records above 800 m for women. And that is a story in itself.” Thanks for the tip to Newscripts reader Bryn Jones, who wrote in with a memory of Leather breaking the record while he was a chemistry student at Birmingham University.
The American Chemical Society’s photo archive, gently referred to as “The Morgue,” is a large assemblage of rotating shelves set into a wall in the ACS headquarters library in Washington, D.C. It’s chock full of photographs, some of which look like they date back to the invention of the camera itself. It’s good to sit and look through these old pictures sometimes.
While recently browsing through antiquated folders looking for a photo of Gilbert N. Lewis for an article on chemical bonding, I was stopped by a black-and-white photo of a serious-looking young woman in a lab. The back of the photo indicated that this was Diane Leather, a “microanalyst determining the nitrogen content of a sample.” There was no mention of where she worked or when the photo was taken. A few photos later, I came across the same serious- looking young woman crossing the finish line to win a track race. The back of this photo noted that Leather had just broken the women’s world record for 880 yards in a time of two minutes and nine seconds. I had to find out more.
It turns out Leather’s record run was in June 1954, when she was 21 and working in the chemistry department at the University of Birmingham, in England. A month earlier, she had become the first woman to break five minutes for the mile, which she accomplished just three weeks after her fellow countryman Roger G. Bannister ran the first sub-four-minute mile. Leather went on to break a number of other track records, and she was a four-time British national cross-country champion.
Forty-two years ago this month, the U.S. Environmental Protection Agency banned the use of DDT as a pesticide. Here’s a look back at the compound’s intriguing history, with links to notable moments in our archives.
Top photo, caption from C&EN, July 25, 1944: DDT, a new insecticide material, proved by extensive entomological tests to be toxic to a large number of insects, including the body louse, and by pharmacological tests to be noninjurious to human beings when applied to their skin, protects our fighting forces against the typhus-carrying cootie. By using a shaker-top can, specially designed for the purpose, soldiers have their clothing louseproofed without undressing. Bottom, structure of p,p’-dichlorodiphenyltrichloroethane (Leyo/Wikimedia Commons).
Most readers may know DDT by one of its many names: dichlorodiphenyltrichloroethane, “the miracle chemical,” “the killer of eagles,” the “poster child” of modern synthetic organic chemicals. But few people know the full and complex story of DDT, and fewer still know the story of DDT within the context of our modern history.
In “DDT and the American Century: Global Health, Environmental Politics, and the Pesticide That Changed the World,” David Kinkela, a historian at SUNY Fredonia, tells the biography of this important player and its role in the transition of the U.S. and the world from World War II to the present day. This rich and interesting story emphasizes the role of DDT in postwar U.S. military and foreign policy; the subsequent development of environmental policy; and DDT’s role in the multidimensional intersection of public health, modern agriculture, and global security. He makes a compelling case for how this one chemical influenced the U.S. and the world in numerous ways and at critical points in time over the past 60 years.
DDT’s Changing Face: Pesticide introduced in the 1940s has played a significant role in U.S. history