Tag Archives: Daniela Paunescu

How do you know that’s extra virgin olive oil?

Who guarantees that expensive olive oil isn’t counterfeit or adulterated? An invisible label, developed by ETH researchers, could perform this task. The tag consists of tiny magnetic DNA particles encapsulated in a silica casing and mixed with the oil.

So starts Barbara Vonarburg’s April 24, 2014 ETH Zurich (Swiss Federal Institute of Technology or Eidgenössische Technische Hochschule Zürich) news release (also on EurekAlert). She goes on to describe the scope of the situation regarding counterfeit foods,

The worldwide need for anti-counterfeiting labels for food is substantial. In a joint operation in December 2013 and January 2014, Interpol and Europol confiscated more than 1,200 tonnes of counterfeit or substandard food and almost 430,000 litres of counterfeit beverages. The illegal trade is run by organised criminal groups that generate millions in profits, say the authorities. The confiscated goods also included more than 131,000 litres of oil and vinegar.

Jon Henley’s Jan. 4, 2012 article for the UK’s Guardian provides more insight into the specifics of counterfeit olive oil (Note: A link has been removed),

Last month [December 2011], the Olive Oil Times reported that two Spanish businessmen had been sentenced to two years in prison in Cordoba for selling hundreds of thousands of litres of supposedly extra virgin olive oil that was, in fact, a mixture of 70-80% sunflower oil and 20-30% olive.

… So with a litre of supermarket extra virgin costing up to £4, and connoisseurs willing to pay 10 times that sum for a far smaller bottle of seasonal, first cold stone pressed, single estate, artisan-milled oil from Italy or Greece, can we be sure of getting what we’re paying for?

The answer, according to Tom Mueller in a book out this month [January 2012], is very often not. In Extra Virginity: the Sublime and Scandalous World of Olive Oil, Mueller, an American who lives in Italy, lays bare the workings of an industry prey, he argues, to hi-tech, industrial-scale fraud. The problem, he says, is that good olive oil is difficult, time-consuming and expensive to make, but easy, quick and cheap to doctor.

Most commonly, it seems, extra virgin oil is mixed with a lower grade olive oil, often not from the same country. Sometimes, another vegetable oil such as colza or canola is used. The resulting blend is then chemically coloured, flavoured and deodorised, and sold as extra-virgin to a producer. Almost any brand can, in theory, be susceptible: major names such as Bertolli (then owned by Unilever [see Henley’s article for details about the 2008 Italian olive oil scandal]) have found themselves in court having to argue, successfully in this instance, that they had themselves been defrauded by their supplier.

Meanwhile, the chemical tests that should by law be performed by exporters of extra virgin oil before it can be labelled and sold as such can often fail to detect adulterated oil, particularly when it has been mixed with products such as deodorised, lower-grade olive oil in a sophisticated modern refinery.

Given the benefits claimed for olive oil, I imagine lower grade olive oil which is more highly processed or, worse yet, a completely different kind of oil would diminish or, possibly, eliminate any potential health benefit.

Getting back to the ETH Zurich news release, here’s more about the anti-counterfeiting ‘label’,

Just a few grams of the new substance are enough to tag [label] the entire olive oil production of Italy. If counterfeiting were suspected, the particles added at the place of origin could be extracted from the oil and analysed, enabling a definitive identification of the producer. “The method is equivalent to a label that cannot be removed,” says Robert Grass, lecturer in the Department of Chemistry and Applied Biosciences at ETH Zurich.

A forgery-proof label should not only be invisible but also safe, robust, cheap and easy to detect. To fulfil these criteria ETH researchers used nanotechnology and nature’s information storehouse, DNA. A piece of artificial genetic material is the heart of the mini-label. “With DNA, there are millions of options that can be used as codes,” says Grass. Moreover, the material has an extremely low detection limit, so tiny amounts are sufficient for labelling purposes.

However, DNA also has some disadvantages. If the material is used as an information carrier outside a living organism, it cannot repair itself and is susceptible to light, temperature fluctuations and chemicals. Thus, the researchers used a silica coating to protect the DNA, creating a kind of synthetic fossil. The casing represents a physical barrier that protects the DNA against chemical attacks and completely isolates it from the external environment – a situation that mimics that of natural fossils, write the researchers in their paper, which has been published in the journal ACS Nano. To ensure that the particles can be fished out of the oil as quickly and simply as possible, Grass and his team employed another trick: they magnetised the tag by attaching iron oxide nanoparticles.

Experiments in the lab showed that the tiny tags dispersed well in the oil and did not result in any visual changes. They also remained stable when heated and weathered an ageing trial unscathed. The magnetic iron oxide, meanwhile, made it easy to extract the particles from the oil. The DNA was recovered using a fluoride-based solution and analysed by PCR, a standard method that can be carried out today by any medical lab at minimal expense. “Unbelievably small quantities of particles down to a millionth of a gram per litre and a tiny volume of a thousandth of a litre were enough to carry out the authenticity tests for the oil products,” write the researchers. The method also made it possible to detect adulteration: if the concentration of nanoparticles does not match the original value, other oil – presumably substandard – must have been added. The cost of label manufacture should be approximately 0.02 cents per litre.

The researchers have plans for other products that could benefit from this technology and answers to questions about whether or not people would be willing to ingest a label/tag along with their olive oil,

Petrol could also be tagged using this method and the technology could be used in the cosmetics industry as well. In trials the researchers also successfully tagged expensive Bergamot essential oil, which is used as a raw material in perfumes. Nevertheless, Grass sees the greatest potential for the use of invisible labels in the food industry. But will consumers buy expensive ‘extra-virgin’ olive oil when synthetic DNA nanoparticles are floating around in it? “These are things that we already ingest today,” says Grass. Silica particles are present in ketchup and orange juice, among other products, and iron oxide is permitted as a food additive E172.

To promote acceptance, natural genetic material could be used in place of synthetic DNA; for instance, from exotic tomatoes or pineapples, of which there are a great variety – but also from any other fruit or vegetable that is a part of our diet. Of course, the new technology must yield benefits that far outweigh any risks, says Grass. He concedes that as the inventor of the method, he might not be entirely impartial. “But I need to know where food comes from and how pure it is.” In the case of adulterated goods, there is no way of knowing what’s inside. “So I prefer to know which particles have been intentionally added.”

Here’s a link to and a citation for the researchers’ paper,

Magnetically Recoverable, Thermostable, Hydrophobic DNA/Silica Encapsulates and Their Application as Invisible Oil Tags by Michela Puddu , Daniela Paunescu , Wendelin J. Stark , and Robert N. Grass. ACS Nano, 2014, 8 (3), pp 2677–2685 DOI: 10.1021/nn4063853 Publication Date (Web): February 25, 2014

Copyright © 2014 American Chemical Society

This article is behind a paywall.

The Swiss aren’t the only ones interested in tagging petrol (gas), they’re already tagging petrol with nanoparticles in Malaysia with as per my Oct. 7, 2011 posting on the topic.

ATMs (automated teller machines) fend off attackers with biomimicry and nanoparticles

Attack an ATM (automated teller machine) and you will be in peril one day soon, if Swiss researchers at ETH Zurich (Swiss Federal Institute of Technology in Zurich) have their way. An April 11, 2014 news item on Nanowerk describes the inspiration,

Hot foam may soon send criminals running if they damage [an] ATM. ETH researchers have developed a special film that triggers an intense reaction when destroyed. The idea originates from a beetle that uses a gas explosion to fend off attackers.

An April 11, 2014 ETH Zurich news release (also on EurekAlert), which originated the news, item, provides more details about the insect inspiring this new approach to protecting ATMs and information about the increase of ATM attacks,

Its head and pronotum are usually rusty red, and its abdomen blue or shiny green: the bombardier beetle is approximately one centimetre long and common to Central Europe. At first glance, it appears harmless, but it possesses what is surely the most aggressive chemical defence system in nature. When threatened, the bombardier beetle releases a caustic spray, accompanied by a popping sound. This spray can kill ants or scare off frogs. The beetle produces the explosive agent itself when needed. Two separately stored chemicals are mixed in a reaction chamber in the beetle’s abdomen. An explosion is triggered with the help of catalytic enzymes.

“When you see how elegantly nature solves problems, you realise how deadlocked the world of technology often is,” says Wendelin Jan Stark, a professor from the ETH Department of Chemistry and Applied Biosciences. He and his team therefore looked to the bombardier beetle for inspiration and developed a chemical defence mechanism designed to prevent vandalism – a self-defending surface composed of several sandwich-like layers of plastic. If the surface is damaged, hot foam is sprayed in the face of the attacker. This technology could be used to prevent vandalism or protect valuable goods. “This could be used anywhere you find things that shouldn’t be touched,” said Stark. In agriculture and forestry, for example, it could be used to keep animals from gnawing on trees.

The newly developed film may be particularly well suited to protecting ATMs or cash transports, write the researchers in their paper published in the Journal of Materials Chemistry A. In ATMs, banknotes are kept in cash boxes, which are exchanged regularly. The Edinburgh-based European ATM Security Team reports that the number of attacks on ATMs has increased in recent years. During the first half of 2013, more than 1,000 attacks on ATMs took place in Europe, resulting in losses of EUR 10 million.

While protective devices that can spray robbers and banknotes already exist, these are mechanical systems, explains Stark. “A small motor is set in motion when triggered by a signal from a sensor. This requires electricity, is prone to malfunctions and is expensive.” The objective of his research group is to replace complicated control systems with cleverly designed materials.

More technical information about the films and about an earlier project applying a similar technology to seeds is offered in the news release,

The researchers use plastic films with a honeycomb structure for their self-defending surface. The hollow spaces are filled with one of two chemicals: hydrogen peroxide or manganese dioxide. The two separate films are then stuck on top of each another. A layer of clear lacquer separates the two films filled with the different chemicals. When subjected to an impact, the interlayer is destroyed, causing the hydrogen peroxide and manganese dioxide to mix. This triggers a violent reaction that produces water vapour, oxygen and heat. Whereas enzymes act as catalysts in the bombardier beetle, manganese dioxide has proven to be a less expensive alternative for performing this function in the lab.

The researchers report that the product of the reaction in the film is more of a foam than a spray when compared to the beetle, as can be seen in slow motion video footage. Infrared images show that the temperature of the foam reaches 80 degrees. Just as in nature, very little mechanical energy is required in the laboratory to release a much greater amount of chemical energy – quite similar to a fuse or an electrically ignited combustion cycle in an engine.

To protect the cash boxes, the researchers prepare the film by adding manganese dioxide. They then add a dye along with DNA enveloped in nanoparticles. If the film is destroyed, both the foam and the dye are released, thereby rendering the cash useless. The DNA nanoparticles that are also released mark the banknotes so that their path can be traced. Laboratory experiments with 5 euro banknotes have shown that the method is effective. The researchers write that the costs are also reasonable and expect one square meter of film to cost approximately USD 40.

In a similar earlier project, ETH researchers developed a multi-layer protective envelope for seed that normally undergoes complex chemical treatment. Researchers emulated the protective mechanism of peaches and other fruit, which releases toxic hydrogen cyanide to keep the kernels from being eaten. Wheat seeds are coated with substances that also form hydrocyanic acid when they react. However, the base substances are separated from each other in different layers and react only when the seeds are bitten by a herbivore. Stark describes the successful research method as “imitating nature and realising simple ideas with high-tech methods.”

Here are links to and citations for both research papers (ATM & seeds),

Self-defending anti-vandalism surfaces based on mechanically triggered mixing of reactants in polymer foils by Jonas G. Halter, Nicholas H. Cohrs, Nora Hild, Daniela Paunescu, Robert N. Grass, and Wendelin Jan Stark. J. Mater. Chem. A, 2014, DOI: 10.1039/C3TA15326F First published online 07 Mar 2014

Induced cyanogenesis from hydroxynitrile lyase and mandelonitrile on wheat with polylactic acid multilayer-coating produces self-defending seeds by Jonas G. Halter, Weida D. Chen, Nora Hild, Carlos A. Mora, Philipp R. Stoessel, Fabian M. Koehler, Robert N. Grass, and Wendelin J. Stark. J. Mater. Chem. A, 2014,2, 853-858 DOI: 10.1039/C3TA14249C
First published online 03 Dec 2013

The ‘anti-vandalism’ paper is open access but the ‘cyanogenesis’ paper is not. As for the beetle who inspired this work, here’s an image of one courtesy of ETH,

The bombardier beetle inspired the researchers of ETH Zurich. (Photo: jayvee18 – Fotolia)

The bombardier beetle inspired the researchers of ETH Zurich. (Photo: jayvee18 – Fotolia)

It looks rather pretty with its hard green (iridescent?) back shell.