Credit: Pascal Blachier via Wiki commons

When humanity’s predilection for perfume meddles with the sense of smell of insects and animals, it can sometimes be fortuitous. Case in point: the discovery that Calvin Klein’s Obsession perfume lures jaguars, tigers, and other big cats to expectant nature photographers and videographers. But meddling with odor receptors of other creatures can prove problematic. For example, the cosmetic and food fragrance 1-methylbutyl 3-methylbutanoate elicits aggressive defense behaviour in hornets. Sometimes people meddle with an insect’s ability to smell sexual pheromones as a means to combat invasive species. In 2007, California’s agricultural industry tried spraying an overwhelming amount of invasive moth species pheromone onto fruit crops because they hoped the signal overload would confuse the male moths and disrupt the species’ mating cycle–a solution that led to serious controversy.

The question that Richard Bolek, a PhD student, and his adviser, Klaus Kümmerer, at the University of Freiburg Medical Center, in Germany, want answered is whether some of the fragrances we use—in perfumes, personal care products, and cleaning agents, which get released into the air or down the drain–are inadvertently interrupting some of the chemical communication networks that benign or beneficial insects and animals rely on.

Is our obsession with smelling nice disrupting networks, such as, say, the fascinating ménage à trois network reported in last month’s Science? In that study, moth larvae (Manduca sexta) feeding on tobacco plants leave behind spit chemicals that isomerize some of the plant volatiles floating out of the munched-up leaf. These isomerized plant volatiles then attract predators (Geocoris), which find the larvae delectable.

Some people’s perfumes, and the fragrance of some bathroom cleaners, certainly drive me to near aggression. Bolek is trying to find out if insects and animals feel the same way. As he pointed out at the EUCHEMS conference this week in Nuremberg, Germany, not all fragrances are biodegradable, and there are three times more fragrances used in laundry and other cleaning products now in Germany than just a few decades ago–fragrances that inevitably end up down the drain or in the air. The project is just getting started: Bolek is currently analyzing levels of fragrance molecules he sampled from hospital waste streams, an experimental setting chosen because hospital administrations keeps track of how much and which brands of cleaning products are used. It’s the beginning of something worth keeping an eye (nose?) on.

Credit: Shutterstock

The Washington Post‘s continued coverage of the massive Kellogg’s 28 million cereal box recall in June, when 2-methylnaphthalene from the packaging percolated into the cereal, and yesterday’s news that Congress is now investigating that recall are good reminders that for any food you consume, a small part of the wrapping inevitably ends up in your body, too. Ditto for pharmaceutical drugs.

Last summer I wrote about how food and pharma companies are starting to deal with these packaging leachables, and so a couple of people at C&EN asked me to speculate on how the 2-methylnaphthalene had ended up in America’s Froot Loops.

According to the Kellogg’s press release, the voluntary recall occured due to an “uncharacteristic off-flavor and smell coming from the liner in the package.” The CDC’s website notes that naphthalene is often found in moth balls and deoderant, but it can also be found in resin (presumably how Kellogg’s thinks the 2-methylnaphthalene ended up in the cereal box liner) and printing dye ingredients. Substituted naphthalenes have high vapor pressure, which means they can migrate through all sorts of packaging, including cardboard and polyolefins.

I have no reason to debate Kellogg’s conclusion that the 2-methylnaphthalene did in fact come from the cereal box liner. But I wonder if the company also checked into the possibility that the  2-methylnaphthalene came from printing dyes on the cardboard box, since dye ingredients have a particular penchant for slipping through food and pharma packaging of all kinds.
For example, last year Europe also had a cerealgate, when 4-methylbenzophenone was found in chocolate muesli–which is a granola-like breakfast cereal eaten with near religious fervor on the continent. In the European cereal recall, the 4-methylbenzophenone was a component of the printing ink typically found on the outside of the box that had migrated to the inside.

Another way for printing ink chemicals to enter food from cardboard containers is when the packaging is recycled from paper products that possess dyes containing the chemical. A quick web search brought up this, albeit 0ld, 1994 reference to rice and pasta contaminated by six diisopropylnaphthalenes which probably came from the recycled paper used to make the cardboard packaging.

When packaging printing dyes end up in food or drugs, it doesn’t always mean they’ve percolated through the packaging. Sometimes food and drugs can be contaminated by the way packaging is stored prior to use. For example, packaging is often rolled up or packed in such a way that the printed exterior is touching the non-printed interior, creating opportunities for printing ingredients to taint the side of the packaging which contacts or is closer to the product. This led to a major recall in 2005 of baby formula stored in Tetrapak packaging that had been rolled up in this way.

There are so many routes for packaging materials to enter food and drugs it’s a bit mindblowing: At a conference last spring in Barcelona for people in industry and regulatory agencies whose job it is to worry about possible sources of packaging leachables in pharmaceutical drugs, we heard ample examples. For instance, an FDA participant told us that a set of injectible protein drugs in disposable syringes were spoiled because a tungsten filament used to poke a hole through the tip of the syringe needle had left behind a tungsten oxide salt residue that later percolated into the liquid-drug formulation causing protein aggregation.

In the case of the Kellogg’s cereal, 2-methylnaphthalene caused some nausea and vomiting. What might it be next time? Here’s an extentive analysis by the Environmental Working Group that argues the FDA should do much more about chemicals that leach from packaging.

The university announced the board of inquiry’s results in September 2009 but it was prevented from releasing the full report publically by a court order from the graduate student involved. According to a post today on the ETH website: “The Court has now ruled, in an initial decision taken at the end of December 2009, that ETH Zurich may in principle publish the export report but only in such an anonymised form “that no conclusions can be drawn about the dissertation or the identity of the complainant”.”

You have to go to the university’s German site to access the report. The blacked out lines are actually multicolor and here is the legend: Blue = PhD Student, green = molecule 1, yellow = molecule 2, black = miscellaneous, red and grey = additional members of the research group.

The basic conclusion from the board of inquiry: “The only credible explanation is manipulation of the data.” They finger the graduate student and vindicate Chen.

Some parts of the 22-page document are dry, but in general it is well-written and shows a measured and comprehensive analysis by the scientific board of inquiry. It also gives insight into how such investigations proceed…

Yeah yeah. I know I’m not the first to grin, groan, or comment about the puns, pop references, and general goofiness ACIE puts into its online abstracts. Many a blogger (Derek Lowe, Excimer, “Phil,” and Chiral Jones ) have also, um, “admired” ACIE’s ability to bring Shakespeare (“Double, double, no toil and trouble”), Star Trek (“Beam me up,” twice), the X-files (“The truth is out there“), and the disembodied voice from the London Underground (“Mind the gap”) into the world of chemistry. The journal has even gotten pretty risqué of late with “Metal ménage à trois” and “Balls galore!”

But Mannich Monday followed soon on the heels of the caption “The Write Stuff,” which permitted the New Kids On The Block hit–(oh yes, here’s the video)–to breach my consciousness for the first time in 20 years—a particularly traumatic reminder of the boy band phenomenon.

So much so, that I had to meet the evil mastermind behind it all.

So I contacted the friendly folks at ACIE, asking whether I could interview (and then, um, perhaps, hound) the person responsible for all the journal’s quirky little abstract captions.

You can imagine my palpable disappointment when Guy Richardson, one of ACIE’s senior associate editors broke the news that the journal’s doozies, like most of science, aren’t the work of a lone genius, but the output of many minds. According to Richardson, “The majority of these texts are indeed the handiwork of the editors (there are about a dozen Ph.D. chemists who work for ACIE, all of whom are native English speakers), but some very good texts do, in fact, come from the authors, and we are always very grateful to authors who join in the fun.”

Yet someone had come up with the Mannich Monday gem, and that someone, I found, is an ACIE editor named Andrew Kelly. He’s only been on staff for a few months “but clearly has a knack for this kind of thing,” Richardson notes. So kudos to you, Dr. Kelly. And here’s a challenge: Try slipping Walk Like An Egyptian into an ACIE caption, given its (remote) chemical connection. (The guy who wrote the pop hit is brother to the chemist who did alot of the early bench work for Visudyne, a macular degeneration drug.)

While we’re on the topic of the humor hot spot of Weinheim, Germany, where ACIE’s headquarters is located, I’ve received a few inquiries about whether the German version of the journal has abstracts that are just as punny. The answer, I fear, is no.

Many of the German abstract titles have a nice alliterative ring to them, and there are definitely a few puns (one about ruthenium employs the element’s symbol: “Ru-ndum erneuert,” which means “completely refurbished” and is possibly droll if you read the article), but there are no thigh-slapping groaners–that I could find.

It would be unfair to expect a snappy German translation of “Just another Mannich Monday” because it’s in reference to an English pop tune. But the risqué “Metal ménage a trois,” which needs no translation, was skipped in favor of “Die Kraft dreier Metalle,” meaning “the power of three metals.” Ah well.

Fearing that my German skills aren’t good enough to catch subtle hilarity, I recruited several German chemists whose sense of humor I hold in high regard to help me scan the German abstracts. The humor task force agreed with my general consensus… but we are happy to be challenged by someone who wants to dig deeper into the archives. Time to ante-up, German speakers.

Fuchs is a physical chemist who leads a molecular simulation group at Chimie Paris Tech, and is also the university’s director. Chimie Paris Tech is part of a distinguished and influential group of higher learning institutions in France called “écoles nationales supérieures.” According to Le Monde, a mathematician named Antoine Petit and a cryptologist named Jacques Stern were also considered for the CNRS position.

Whoever gets the job will be responsible for 26,000 permanent CNRS staff and a budget of 3 billion Euros ($4.3 billion). That person will also be at the helm of an organization in transition: The French government is splitting the CNRS into 10 institutes by subject. For example the institute of chemistry will be separate from the institutes of physics and biological sciences.

The new CNRS director general-president will be kept busy: The relationship between President Nicholas Sarkozy’s government and French scientists (including those from CNRS) has been rocky. Some of the government’s proposed reforms to the CNRS and to universities have brought thousands of scientists out of their labs and into the streets in protest.

A counterfeit drug manufacturing lab in Colombia

As I was doing interviews for an article on fake pharmaceuticals, Paul Newton told me a story that I am unlikely to forget. Newton is a doctor in Laos who is involved in several projects to track down counterfeit malaria drugs in Southeast Asia and Africa; he’s also a doctor at a Wellcome Trust-funded hospital that is associated with tropical medicine at the University of Oxford.

We were talking about the fact that nobody knows exactly how many fake drugs are consumed around the world, but it’s pretty clear that the problem is greater in developing countries where there is less funding for regulation and/or policing. (The WHO estimates that markets in industrialized countries such as the U.S. and many parts of the E.U. have no more than about 1% counterfeits. In developing nations, some 10-50% of pills are guesstimated to be bogus.)

“Counterfeiters have killed with impunity,” Newton said. He went on to tell me that people sometimes spend what little money they have to unwittingly buy fakes, and then have succumbed to otherwise curable diseases because the medicines have not worked. “A Burmese patient died a few years ago of malaria having clearly taken fake artesunate,” a malaria drug, Newton said. “When he was admitted with malaria all the signs were that he should recover rapidly but then he deteriorated and died of cerebral malaria very tragically,” Newton added. The man’s community was so upset that people in “the village where the patient came from took all the medicine he had been taking from the shop. They burned it in a bonfire in the village in a spontaneous protest,” Newton told me.

It’s stories like these that have motivated the WHO to team up with INTERPOL to form an international anticounterfeiting task force called IMPACT (International Medical Products Anti-Counterfeiting Taskforce). Drug counterfeiters pull in a–guesstimated again–$75 billion per year. According to many who follow pharmaceutical counterfeiting, hard drug traffickers are now turning to the business of making bogus medicines because the profit margin is better and the penalties are softer… than for say, cocaine or heroin. The IMPACT taskforce has just a couple of full-time staff members, which seems rather small for the challenge of coordinating the international fight against fake medicines. Yet IMPACT has brought down counterfeiting operations in Southeast Asia, Tanzania, Uganda and in Nigeria. Here’s a catch of bogus drugs, courtesy of IMPACT:

Fake meds in nabbed in Tanzania and Uganda

Here is an example of the storage conditions for fake medicines found in Kenya, also courtesy of IMPACT:

Storage of counterfeit drugs in Mombasa

And last but not least, here’s a shot of manufacturing facilities for a counterfeit ring tracked down in China. Photo courtesy of Pfizer’s David Shore:

Fake drugs, made in China

Even though it may seem like counterfeiting is on the rise, Newton pointed out to me that the business of making fake medicines is as old as remedies themselves. Around 1500 BC, an Egyptian queen called Hatshepsut got so fed up with the quality of herbal medicines she was exposed to, that she led an expedition herself to get good quality medicines in the land of Punt, near current day Somalia. More recently, in the 1600s, quinine-containing Cinchona bark imported to Europe from South America as treatment for malaria was adulterated “at such an enormous scale that the public gave up on the medicine because it seems not to work,” Newton adds.

Taking place in a renovated water pumping station in the middle of the former so-called death strip, the no-mans land that abutted the Berlin Wall, a variety of top researchers from the sciences and humanities described the “walls” which were falling or which needed to fall in their area of research. The organizers had also managed to book German Chancellor Angela Merkel, who is a scientist-turned-politician from the former GDR (more below). Although no late-breaking new discoveries were announced, the conference provided a fascinating overview of research in a real potpourri of great topics: vaccines for neglected diseases like malaria and TB, three-dimensional televisions, how to make concrete less polluting, and how researchers are cracking the secrets of ancient civilizations , the origin of Homo sapiens. We also heard from Rolf-Dieter Heuer, the director general of CERN, about the Large Hadron Collider (which will hopefully start pumping out data one of these days) and from Norbert Holtkamp, who heads Iter, the fusion energy transnational research organization that originated during a 1985 conversation between Gorbachev and Reagan.

But the conference’s special guest was Angela Merkel, the German Chancellor, who knows a lot about falling walls. She’s Germany’s first female head of state, and also the first from the former Communist GDR, where she had worked at a physical chemistry research institute before the Berlin Wall came down. She said that the collapse of the Berlin Wall, “changed my life completely but it did not put a damper on my love of science.”

Merkel talked about the chasm many GDR scientists used to feel between their daily work–which required an open, inquisitive and challenging mind–and their daily lives–in which an unquestioning loyalty to the Communist Party was expected. But “you can’t tell people to start thinking in the morning and then to stop [after work],” she said.

Scientists could also “be a role model for politicians,” Merkel said. She explained that every day scientists aim for the seemingly impossible–and sometimes achieve it with breakthrough discoveries. This in itself should serve as inspiration for those faced by enormous challenges such as peace in the Middle East, or the fall of the Berlin Wall, that the impossible can sometimes be made possible, she added.

Then Merkel was whisked off by her handlers to walk across Berlin’s Bornholmer bridge, where she had joined the crowds 20 years ago that pushed border guards to allow passage to West Berlin, part of the sequence of events that led to the Berlin Wall’s collapse (Check out the footage I posted here). The rest of us learned about other new walls that need to come down…

A remaining section of the Berlin Wall

C&EN Berlin’s office is about a block-and-a-half from where the Berlin Wall used to stand, on the former Communist, East side (known as the German Democratic Republic, or GDR). When I get out the wrong subway stop exit, I have to retrace my steps across the infamous death strip–a no-man’s land just before the wall to the West–where people were shot dead trying to escape. Just down the road, one of the few remaining stretches the Wall has been left standing. Where the Wall has been torn down, a double brick strip in the pavement demarcates its former path. Even after two years in the neighborhood, I am amazed and sobered by how easy it is for me to pop over to the West, to buy some printer toner or to pick up lunch supplies at a nearby supermarket.

In this week’s issue, I’ve got an article about what it was like for GDR chemists who worked behind the wall. I talk to researchers who describe what it was like to be surveilled by the Stasi, the East German spy service, or what life was like after their supervisor escaped to the West. One chemist I spoke to named Christoph Naumann escaped by foot from Hungary to the former Yugoslavia and then to West Germany.

On Monday’s 20th anniversary, the city of Berlin will be buzzing with political dignitaries (such Hilary Clinton, Mikhail Gorbachev and Nicolas Sarkozy) who will congregate near the Brandenburg Gate where Jon Bon Jovi will sing (yes, exceptionally weird, I know) before Berlin’s mayor knocks over a sequence of large, painted dominoes that look like chunks of the former Wall.

When the Wall finally came down, it was due to a bureaucratic mistake–kind of. After months of civil unrest, and many East Germans escaping like Naumann did, the GDR was planning to loosen travel restrictions. But, while most Communist Party officials were in the throes of a conference, a poorly-briefed East German bureaucrat mistakenly announced, at an evening televised press conference, that travel restrictions were immediately removed. Shocked but excited Germans slowly began to congregate on both sides of the Berlin Wall, much to the dismay of border guards who had no idea what to do…

Here’s some awesome raw footage from that night, with some decent subtitles, from the East side, at the Bornholmer checkpoint. The video culminates in a wonderful rush of people through the wall at about minute six.

West Germans also gathered on their side of the wall near Berlin’s Brandenburg gate. See some raw footage from that night here:

A more detailed history of why the wall fell and other good historical stuff can be found at der Spiegel’s English website and elsewhere.

As I was working on the article, many of the chemists I spoke emphasized that a common misconception about the former GDR is that people had no idea what was going on in West Germany. In fact, most parts of the GDR could receive West German television. “We were informed about the most up-to-date politics, cars–everything that was broadcast on Western TV,” Ruediger Beckhaus told me. He says that after the Wall came down, he was surprised that West Germans could not name all the West German state governors, because he and many others from the GDR could. California aside, I’m willing to wager that most Americans need Google to name the governors of less populated US states, say Nebraska, Vermont and Montana. (Mea culpa, at least.) But East Germans used to watch so much Western TV, that another chemist told me that on his family’s first jaunt to the West side, his young daughter already knew what toy she wanted to buy–from having seen it advertized on West German TV.

In fact some journalists who lived in the GDR before the Wall fell, such as Timothy Garton Ash, argue that East Germans pushed so hard to get through the Wall on November 9th, because they had heard the Wall was open on West German TV, which they trusted more than GDR state TV news. (Incidentally, Timothy Garton Ash wrote a great book called The File, about his search for his Stasi informants.)

Also during the course of my research on science in the former GDR, I came across some great archival photos of scientific space in the former GDR and how it’s been revamped now (see the photo gallery below).

During the GDR era, especially the latter years, science was stymied by poor access to equipment, but as Ernst Schmitz, an organic chemist told me, scientists were forced to spend their times supporting the chemical industry, following research plans and agendas, such as the development of new routes to make synthetic fibres. During his academic career, Schmitz says he really missed having the freedom to follow research in new directions when data pointed to something exciting. He says that in 1961, the year the Wall was built, he went to a conference in Leningrad (St. Petersburg), Russia, where he met the famous chemist, Robert Burns Woodward. Schmitz says something Woodward said to him always popped into his mind when he was receiving new official research plans from on-high. Schmitz says Woodward had quipped to him, “A chemist who makes plans and keeps to them will be dead in two years.” When Schmitz heard the news that the Berlin Wall had come down Schmitz, then in his sixties, said the tears ran down.

Germany’s academic community is being rocked by investigations by the city of Cologne’s public prosecutor into a now insolvent consulting firm that connected students with professors at fees of up to €20,000. Professors taking in the students would receive €4,000 for their open door policy–a double payment for supervisory services already being compensated for by their academic salaries.

Now the public prosecutor is investigating over a hundred lecturers, instructors and professors from all over Germany, and from a wide spectrum of disciplines, under suspicions that they received bribes to accept and then graduate possibly undeserving students. According to der Spiegel, it’s the latest investigation in to the consulting firm, (Institut für Wissenschaftsberatung or Institute for Academic Consultancy), whose managing director was sentenced last year to three and a half years in prison for bribing a University of Hannover law professor.

Annette Schavan, Germany’s minister of education, said publically on Sunday that if the accusations are verified to be true, Germany’s academic credibility could be damaged. Um, yeah.

Der Spiegel has got a good piece on the whole bribing backstory here…

Hat tip: Chemistry World

Since 2006, the Chinese government has dispatched some 379 mini-lab vans to the Chinese countryside to test for counterfeit drugs and herbal medicine at rural pharmacies and hospitals. The country has apparently spent $70 million to equip the mini vans with TLC, near-infrared instruments and technicians for counterfeit hunting. So far the mobile labs have tracked down about 14,000 fake drugs being sold throughout China, and have helped to put a few counterfeiters behind bars. All this according to Jin Shaohong, of the Chinese National Institute for the Control of Pharmaceutical and Biological Products, the body charged with doing the testing. “When the mobile labs show up, some people say, ‘Come, come into my store,’ others close the door and try to leave,” he said.

The rest of the session was pretty interesting too: an Indian scientist talked about his country’s attempts control fake Ayurvedics medicines—which also sometimes include Viagra or heavy metals. A UK drug regulator mentioned Tamiflu counterfeits that lack the active ingredient, but feature Vitamin C and acetaminophen—not an entirely off-base remedy for cold sufferers, but well, not Tamiflu. A GSK scientist told us about a potpourri of analytical techniques, including isotopic analysis coupled to mass spec, that the company has used to identify 15 Chinese counterfeit sources for its Heptodin hepatitis B drug.

Besides fake drugs, the week-long conference will feature a potpourri of topics close to many chemically-minded hearts: astrochemistry, art heritage and conservation science, natural products synthesis, new weird and wonderful materials.

But the quirkiest conference offerings will be the food chemistry and health poster session on Thursday. Here’s what to expect from that buffet: The fatty acid composition of Serbian Sremska and Cajna sausages (yum!); the chemical profile of Jar cheese from West Azarbaijan, Iran (hmmm, I’d like to see how the data compares to cheese from a can); how extracts from an avocado pit may stop the characteristic browning of guacamole (preview the results below thanks to abstract figures!); and my favorite… an expose of how “toothbrushing affects salivary oxidative stress in young adults.” Don’t miss the fun, folks.