July 2008



Behind every beautiful van Gogh masterpiece lies… another beautiful van Gogh masterpiece. It is known that the artist often painted over his earlier work, but the first use of a technique based on synchrotron radiation induced x-ray fluorescence spectroscopy has revealed a previously hidden painting in unparalleled detail and, even better, in colour.

 

The van Gogh painting Patch of Grass hangs in the Kroller-Muller Museum, Otterlo, the Netherlands. It was completed in 1887, but a vague shadow of a face lurking under the surface had been seen with the help of x-ray radiation transmission radiography and infrared relectography. Now, a detailed colour reconstruction of this hidden painting has been put together by materials expert Joris Dik at Delft University of Technology together with experts at the Deutsches Elektronen-Synchrotron in Hamburg, Germany.

 

‘This is an extremely exciting new piece of work with major significance both for the scientific and the art historical community,’ says Catherine Higgitt, head of science at the British Museum’s department of conservation and scientific research. ‘It has produced a stunning and totally unique view of the hidden painting using non-invasive analytical methods and has yielded an image far superior to that which can be obtained with more conventional imaging techniques.’

 

Painting all over a van Gogh original would be an inestimable crime these days, but the great man did it himself on numerous occasions. About a third of his paintings are thought to lie on top of earlier paintings. To date, researchers have used conventional x-ray radiography to look at these hidden works of art. But the major advantage of the synchrotron radiation-based technique is that the measured fluorescence is specific to each chemical element. Different atoms and different paint pigments can be charted individually. And it’s a speedy process, so relatively large areas can be scanned.

 

 

Analysing van Gogh’s Patch of Grass revealed this tritonal colour reconstruction of a woman’s face (above). The flesh colour of the hidden face is attributed to antimony (yellowish white) and mercury (red).

 

The painting was scanned at the synchrotron radiation source DORIS at Deutsches Elektronen-Synchrotron DESY in Hamburg. Over the course of two days, the area covering the image of a woman’s head was scanned, measuring 17.5 x 17.5 cm.

 

‘This approach greatly extends the more familiar imaging techniques available in the field,’ Higgitt told Chemistry World. ‘Sadly, this is not an approach that may be able to be widely adopted, either because of the intrinsic difficulties of taking fragile and sensitive museum objects or paintings to a synchrotron or because other works may not show such a marked change in the artists palette, which was a crucial factor in the success of this project. Nevertheless this is a hugely exciting development.’

 

The researchers have high hopes for the technique. ‘Our approach literally opens up new vistas in the nondestructive study of hidden paint layers, which applies to the oeuvre of van Gogh in particular and to old master paintings in general,’ they conclude in their paper published in Analytical Chemistry.

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Wild animals with a daily alcohol intake that would intoxicate most humans have been discovered living a life of sobriety in a West Malaysian rainforest. The surprising discovery of mammals that survive, nay, thrive, on this chronic alcohol intake, has much to teach those investigating the genetically inheritable traits of human alcohol use and abuse, say researchers.

shrew1

Seven species of mammal, including the pentailed treeshrew (believed to be similar to the last common ancestor of all primates), pollinate the Bertam palm in return for a daily (or, more likely, nightly) drink of alcoholic plant nectar. The nectar can be as strong as 3.8% alcohol by volume – exactly the strength of the real-ale favourite, Deuchars IPA. Indeed, the researchers say the plant smells like a brewery when it’s in flower.

Plants produce psychoactive substances for two possible reasons: first, to attract pollinators; second, to deter herbivores. In this case, alcohol in nectar certainly seems to increase the attractiveness of flower buds to pollinators such as the pentailed treeshrew. And the alcohol does not cause typical drunken behaviour expected in people; the shrews move as efficiently over the spiny Bertam palm as over any other plant or structure.

The researchers, led by Frank Wiens at Bayreuth University in Germany, estimated the amount of alcohol ingested over the period that the mammals fed on the Bertam palm (12 hours) that would cause blood alcohol concentrations to exceed 0.05% (wt/vol). Humans with higher concentrations than this are considered legally intoxicated in most countries (though not in the UK, where the legal limit is 0.08%).

Working out how much nectar, on average, the shrews were consuming in 12 hours suggested that the animals would have been intoxicated every third day. Since watching the shrews each night suggested that that wasn’t the case, the researchers conclude that the pentailed treeshrew and some of its fellow mammalian pollinators have a modified metabolic mechanism to eliminate alcohol.

Ingested alcohol is distributed in the body and either broken down or conjugated to other molecules by several different pathways. Enzymes that conjugate alcohol to other molecules include UDP-glucuronosyltransferases (UGTs), which produce ethyl glucuronide (EtG) – a biomarker that enters the hair shafts and stays there for a long time, even after an animal has died. Measurements of EtG in the treeshrews’ hair suggest that they were indulging in what would be considered risky alcohol consumption in humans.

The researchers suggest that treeshrews keep concentrations of alcohol in their blood and brain low by improving the effectiveness of the glucuronidation pathway of alcohol detoxification.

‘Some of the mechanisms involved in maintaining a positive evolutionary fitness balance of alcohol consumption may eventually help combat human pathologies related to alcohol abuse,’ conclude Wiens and colleagues.

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The UK, US, Canada, Australia, China, Norway, Denmark, Holland, Germany and many other countries are all looking carefully at the prospects of capturing carbon dioxide from coal or gas power plants and storing it deep underground. Barely a day goes by without some new pronouncement – whether it’s politicians saying they are advancing the technology; think tanks, scientists and environmental groups saying they’re not moving fast enough; or industry trumpeting joint agreements for carbon capture projects.

In case you’re feeling slightly bewildered about where and when any serious commercial-scale plants will be built (we haven’t seen one yet, by the way), the Scottish Centre for Carbon Storage has developed a brilliant interactive map of projects (large and small) announced so far. Highly recommended. Since each individual large scale plant (say, 400MW or above) will cost at least $1 billion, the first movers in this field are going to require deep pockets, or substantial state support.

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In this week’s Chemistry World business news round-up, we cover Roche’s spending spree, a meeting of generic giants, and the bioethanol bonanza.

Chemical Industry

Evonik boosts peroxide sales:
Korea’s SKC has started up the world’s first commercial-scale plant making propylene oxide (PPO) using hydrogen peroxide. The technology is licensed from German firm Evonik, who developed a new catalyst to make PPO from propylene and hydrogen peroxide. Evonik, the world’s second largest producer of hydrogen peroxide, say the new technology could boost the hydrogen peroxide market by 200,000 tonnes per year over the next decade.

Air sells healthcare arm:
US-based Air Products has announced it will sell its underperforming US healthcare business. From the fourth financial quarter of 2008, the company will report the business as a discontinued operation – and take a $315 million (£158 million) charge – but will continue to operate the healthcare arm until a buyer can be found.

Reach bulk registration comes online:
The European Chemicals Agency has overcome the computer glitch that prevented companies from bulk pre-registering all the substances they produce or use that fall under the new Reach regulation. The bug had meant companies had had to pre-register all their substances one by one. Companies have until 1 December to pre-register their entire inventory of substances.

Sabic streamlining:
The European arm of Saudi petrochemicals firm Sabic is to restructure its aromatics production on Teesside, UK. To ensure long-term economic viability of the site, the Aromatics 2 unit will be closed, but the remaining Aromatics 1 unit may be upgraded.

Pharmaceuticals

Roche stops HIV drug research:
Swiss pharmaceutical company Roche has suspended its HIV drug research programme, after deciding that none of the candidates in its current pipeline are significantly better than existing drugs. The company had several candidates in preclinical trials.
Meanwhile, Roche has also announced it plans to buy out minority shareholders in Genentech, which the Swiss firm already majority owns buy currently runs largely independently. Roche plans to pay $43 billion for the outstanding stake, and plans to tighten its cooperation with the US biotech arm.
Roche has also agreed to buy US RNAi therapeutics firm Mirus, who have developed a proprietary method to deliver RNA into cells. The company will also acquire Arius for approximately $191 million. The Toronto, Canada-based firm have developed a screening technology to rapidly identify antibodies that are promising drug leads.

Generics giants to merge:
Israel-based generic drug giant Teva is to buy US rival Barr, in a deal worth $7.46 billion. Teva says that buying Barr – the world’s fourth largest generic drug firm – will strengthen its position in the US, but also in key European markets. The company’s combined 2007 revenues would have totalled $11.9 billion.

Vytorin further failure:
US pharmaceutical firms Merck and Schering-Plough have had more negative news over cholesterol drug Vytorin, after a clinical trial showed the drug failed to meet the main goal of a heart study looking at thickening of the main valve to the aorta. Vytorin sales have slipped since a study showed the drug was no better at cutting arterial plaque than a cheap statin. The latest study also suggested the drug could increase the risk of cancer – although the study’s authors dismiss the finding as an anomaly.

GSK settles over Relenza:
GSK has agreed to pay Aus$20 million (£9.6 million) to settle claims by Biota, the Australian biotech firm that originally developed GSK’s flu drug Relenza, that the UK pharma company had failed to make sufficient efforts to market the drug. Biota had originally sought Aus$430 million in damages. Sales of Relenza, which has to be inhaled, have lagged far behind those of Tamiflu, which governments have stockpiled in case of a global flu pandemic – although a recent study highlighted the danger of only stockpiling a single drug.

Energy

British Energy takeover:
British Energy, the UK’s nuclear operator, is expected to announce that it will be bought by French energy firm EDF, in a deal that values the company at £12.4 billion. EDF is reportedly looking to agree a deal with UK firm Centrica – who owns British Gas – to take a minority stake in British Energy, ensuring the nuclear energy firm remains partially UK-owned.

Bioethanol bonanza:
UK petrochemicals firm Ineos says it plans to start making bioethanol from municipal waste, using a patented biocatalytic process, within two years. Ineos has piloted the use of bacteria to make the ethanol from syngas, a mixture of carbon monoxide and hydrogen produced by superheating waste.
Meanwhile, Dow and the US National Renewable Energy Laboratory are to jointly develop a similar process, using a catalyst to turn the syngas into a mixture of alcohols including ethanol. The feedstock for the process is non-food biomass such as corn plant leaves and wood waste.
And DuPont and Danisco, who in May formed a joint venture to produce cellulose from ethanol, are collaborating with the University of Tenessee to build a pilot-scale biorefinery. The plant will convert the high cellulose content of switchgrass fuel crops into bioethanol.

Agrochemicals

Carbofuran ban:
The US Environmental Protection Agency (EPA) has moved to ban carbofuran residues in food and drinking water – effectively banning the pesticide’s use. While carbofuran is not widely used in the US, the residue ban also applies to imported foods, and the compound is used more widely in the developing world. FMC is the sole manufacturer of carbofuran in the US, and is already battling the EPA in the courts as the regulator bids to cancel the pesticide’s registration.

BASF Amflora legal challenge:
Germany’s BASF has filed an action with the European Court against the EU Commission for failing to act in the approval process for the company’s genetically modified starch potato, Amflora. The crop was deemed safe by the European Food Standards Authority in 2006, but the EU Commissioner has since failed to authorise the potato for cultivation.

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Gents, you might want to stop sipping that soy latte.

A US study has found that eating soy products such as tofu and tempeh, or soy-based meat-free alternatives to mince, sausages and burgers, can have quite a dramatic effect on sperm count. Eating a portion of soy every other day – for example, 115g of tofu, a soy burger or a 240ml glass of soy milk – lowered the sperm count by an average 41 million sperm per millilitre. That’s quite a drop, considering the healthy male produces 80-120 million per ml.

Still hungry?

Still Hungry?

The results come out of the largest human study to date into the effect of phytoestrogens – plant-derived compounds that mimic oestrogen in the body – on semen quality. The key compounds found in soy are isoflavones, which the Harvard School of Public Health researchers suggest could be adversely affecting sperm production by interfering with the body’s hormone signals.

The Harvard team also found a link suggesting that soy’s effect was strongest in overweight or obese men – possibly because men with more body fat produce more oestrogen. This could be the reason why the men studied seem to be strongly affected by dietary soy, despite consuming 5-10 times fewer phytoestrogens than the average Asian diet. However, regardless of weight, the drop in sperm count seemed to be most pronounced in men with higher natural sperm concentrations. The team urge further randomised trials to determine the true clinical significance of their results.

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Rats that have been force-fed white wine (a 2004 Soave, to be precise) for 30 days suffer less damage to cardiac tissue following a heart attack. Yes, really, according to a paper in the American Chemical Society’s Journal of Agricultural and Food Chemistry.

 

Researchers in the US and Italy modelled heart attacks in the Soave-drinking rats and in rats who’d been drinking the same amount of alcohol (a 13 per cent solution) but not wine. The wine drinkers’ hearts had significantly smaller infarcts (areas where the cells had died off in oxygen-starved conditions) following a heart attack.

 

The team put the findings down to a survival pathway called the Akt/FOXO3a/eNOS, which is known to repair ‘infarcted’ heart muscle. Consequently, the researchers make the case for white wine-based therapy as ‘an effective treatment for human cardiac disease.’ Cheers.

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In a bizarre and very broad-scope experiment, a body called Yorkshire Chemical Focus challenged 150 students from Harrogate Ladies’ College in North Yorkshire, to spend 24 hours without using chemicals. Predictably, they found it quite difficult. The test even inspired some poetry: ‘Life without chemicals – O what the hell! I could not wash so now I smell!’

Short but to the point.

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In this week’s Chemistry World business news round-up, we cover Roche’s suspension, new obligations for nanotechnology firms and power from manure.

Chemical industry

New leader for ACC

Former Democratic congressman Calvin Dooley will succeed Jack Gerard as president and chief executive officer of the American Chemistry Council. Dooley is currently president of the Grocery Manufacturers Association (GMA), a trade group representing food manufacturers. He will take over on 8 September. Gerard will move on to the top job at the American Petroleum Institute.

New man at the ACC, Calvin Dooley

Ashland’s Herculean deal

Leading US speciality chemicals firm Ashland has confirmed that it has entered into a merger with Hercules, a leading supplier of speciality chemicals to the pulp and paper industry. Ashland will pay approximately $3.3 billion to acquire Hercules. The transaction, which would create a major, global specialty chemicals company, is expected to close by the end of 2008. According to James O’Brien, Ashland’s chief executive, the merger will combine the paper and water businesses of each company to create a global business with annual revenue of $2 billion.

Pharmaceuticals

GSK bids high for sleep drug

GlaxoSmithKline (GSK) is set to pay £1.6 billion to Switzerland-based biopharmaceutical firm Actelion for Almorexant, Actelion’s insomnia drug currently in phase III development. Both companies say the drug has ‘first-in-class potential’, but critics are suggesting that GSK may have paid over the odds for a late-stage addition to its pipeline. GSK will receive exclusive worldwide rights to co-develop and co-commercialise almorexant, and will contribute 40 per cent of the costs of the development programme and potential registration. The drug blocks orexin receptors in the brain which play an important role in the ‘sleep-wake cycle’.

Roche suspended

Roche has been suspended from the Association of the British Pharmaceutical Industry (ABPI) because of what the association has described as ‘serious breaches of the ABPI code’ and ‘actions likely to bring discredit on, or reduce confidence in the pharmaceutical industry’. According to the ABPI, a complaint was made by a former Roche employee who referred to an article in the Financial Times (12 February 2008). The article alleged that Roche sold large quantities of Xenical (a prescription only medicine for the treatment of obesity) to the operator of private diet clinics, and that Roche had agreed to provide £55 000 for the operator to purchase another clinic.

Ranbaxy challenged on generics

The US House Energy and Commerce Committee plans to investigate the US Food and Drug Administration’s (FDA) handling of allegations that the Indian generic drug firm Ranbaxy sold potentially adulterated meds, according to US reports. The move comes after the Department of Justice filed papers alleging employees at Ranbaxy’s plant in northern India used raw chemicals from unapproved sources. Meanwhile, Japanese pharmaceutical firm Daiichi Sankyo has confirmed that its plan to buy Ranbaxy is final.

MRI contrast agent approved

The FDA has granted Bayer Schering Pharma marketing approval for its magnetic resonance imaging (MRI) contrast agent, gadoxetate disodium, for the detection and characterisation of liver lesions. The agent is specifically taken up by liver cells (hepatocytes), enhancing the appearance of healthy liver tissue and allowing it to be distinguished from cancerous tissue which is not enhanced. Gadoxetate disodium now becomes the first organ-specific MRI contrast agent to gain US approval for over a decade. It will be marketed as Eovist in the US, with launch planned for the summer of 2008.

MRI scan of a human body

Agrochemicals

Insecticide collaboration

Syngenta has signed a crop-protection technology agreement with US specialty chemicals maker DuPont. Under the deal’s terms, the companies will share the costs to prepare regulatory studies for DuPont Cyazypyr, a new insecticide aimed to control moths and sucking insects such as leafhoppers and aphids. Syngenta will also give DuPont access to other chemicals, which DuPont said it plans to use in herbicide mixtures for use on corn and sugarcane. DuPont said the product is complementary to the DuPont Rynaxypyr insect control that Syngenta is developing through mixtures with its own insecticides.

Cyazypyr tackles leafhoppers (pictured) and aphids

Nanotechnology

Nanotechnology groups urge stewardship

Industry trade groups that represent nanotechnology companies are urging their members to join the US Environmental Protection Agency’s (EPA’s) voluntary Nanoscale Materials Stewardship Program (NMSP). In a joint statement, the American Chemistry Council’s Nanotechnology Panel, the NanoBusiness Alliance, and the Synthetic Organic Chemical Manufacturers Association’s Nanotechnology Small & Medium Enterprise Coalition highlighted the importance of the programme in helping the EPA make informed regulatory decisions about nanomaterials.

Energy

UK biogas boost

The UK Department for Environment, Food and Rural Affairs (Defra) met with agriculture, industry and NGO representatives on 17 July to discuss multi-million pound plans to make greater use of anaerobic digestion – the technology which produces energy from organic material like food waste and manure. The meeting heard that the process could produce enough electricity to power two million homes. Ministers also gave details of how a £10 million programme of ‘demonstrator’ projects – which was announced by Defra in February – could help to encourage investment.

producing power from waste materia

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Despite efforts to encourage more women to enter science, Chemistry World has reported that there are still too few women progressing to senior positions in academia.

Reasons why include a lack of encouragement, an unconscious bias towards men and a ‘macho’ scientific culture.

We want to know your views on the topic. Does chemistry favour men over women? And if so what can we do to change it?

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Scientists in Argentina have found a new way to tackle global warming – by capturing cows’ burps.

Cows have had a bad press in the fight against climate change, being accused of producing large amounts of methane when digesting food. But the scientists in Argentina have found a new, yet low-tech, way of analysing the cows’ emissions.

They’re collecting cows’ burps, by connecting the cow’s stomach to a bright red tank strapped to its back.

Apparently they’ve studied at least ten cows and, according to Guillermo Berra, a researcher at the National Institute of Agricultural Technology, their research shows that, ‘thirty percent of Argentina’s (total greenhouse) emissions could be generated by cows.’

Scientists are now thinking of putting cows on diets of alfalfa and clover to make them more environmentally friendly.

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