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Making the shortlistScience Communication Competition 2012

Chemistry worldsCienCe CommuniCation Competition 2012

Communication lies at the very heart of human culture, indeed life. It is the means by which we create and interact, enquire and understand. It shapes our identities, forming the bonds of families, cultures and nations. Science, of course, would die without communication. Robert Winston recently said ‘If you cannot communicate science, it may as well have not been carried out’. I could not agree more. What good is knowledge if it is not put to use, if it cannot be built upon? Its existence is philosophical, like the sound of a tree falling unobserved.

But this refers to more than communication between scientists. It refers to communication beyond our own, in-the-know communities to society at large, to show the relevance, prevalence and usefulness of science. Communicating science to the public is vital because science surrounds us. Science cannot be separated from society – each supports and improves the other.

Unfortunately, science journalism is often outside the mainstream, appearing further down the news agenda than we would otherwise like it to be. And not every scientist is an excellent communicator. The consequence of this is alienation. In the most recent Public Attitudes to Science survey, just over half of those who took part said they hear and see too little information about

Introduction

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science. The research also highlighted the challenge of public engagement with science. The majority of people surveyed said they did not feel informed about science, and scientific research and developments. This is the role that science communicators must fulfil.

The entries to the Chemistry World Science Communication Competition have been excellent, and a joy to read. The breadth of topics and the variety of styles reflect the diversity of science itself. Each tells its story in a different way, showing how science excites, intrigues and illuminates; how it asks and answers. Crucially, enthusiasm and passion are clear throughout, but never at the cost of the science.

My congratulations to the finalists – you are all talented writers and the pieces presented here are excellent examples of effective, engaging science communication.

Lesley YellowleesPresident of the Royal Society of Chemistry

in association with ChemCareers

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evident in an increasing demand for products due to a growing world population. If the use of solvent continues like this, even greater environmental impacts than we are seeing now will occur.

Restricting chemistry research to theoretical work for fear of harming the environment is not a feasible option. In computational chemistry an infinite amount of computer power is required to model real world systems, so assumptions are made as a result. These assumptions will lead to models that won’t fully describe the world around us and, with regards to theoretical methods, advances in our understanding of chemistry are often made by trying to rationalise experimental results. Since we can’t change our method of research, we will have to change our attitude to using solvents.

By seriously considering how we use solvents and,where possible, using no solvent we can limit the environmental impact that they will have. Currently there is the categorisation of solvents, with greener solvents being more favoured but, as highlighted previously, hazardous solvents cannot always be avoided. This means we have to look beyond our current methods and consider developing better ways to use solvents. It isn’t much of a stretch to consider solvent–capture as an option given the current focus on CO2 capture. We can also consider methods of recycling solvents that will ideally lead to no net solvent waste. Even if the cost of advancement inhibits us, we should take it upon ourselves to consider the effect that our research will have on our environment as a priority. Finding the answer to the world’s problems will mean nothing if there is no sustainable world to live in. We have to make the conservation of solvents an active decision, if not for our own sake, for the sake of others and the future of chemistry. Sandra Atkinson

Solvent use in chemistry is very important but the implications are frequently overlooked. Within the study of chemistry, the attempts made to understand and rationalise the world around us include research and investigation of relevant chemical reactions and systems. This often involves aqueous or non–aqueous conditions and solvents. The negative impact of solvents in these reactions can be potentially harmful to the environment and wildlife but reactions involving harmful solvents cannot always be avoided. For some reactions there are no alternative methods and the use of solvents can be a necessary stepping–stone toward ‘greener’ chemistry methods. Solvents have also played an important role in some of the great advances in the 20th century. These include their use in chromatography as an analytical technique (as used in the discovery of the structure of insulin), and in consumer items such as the disposable lithium battery.

In recent years there has been a greater focus on greener chemistry due to climate change and the energy crisis. The global cost of fuel has risen and governments have proposed reaching lower targets for CO2 emissions in response to climate change. However, whether you think climate change is due to human influences or not, there is a general consensus that we must conserve our diminishing natural resources. As these resources are depleted, alternatives will only become more important. Global political decisions have driven governments to invest more money and resources in science, in particular research, to find sustainable alternatives. The need for a solution means that chemistry will play an important role. This leads to a dichotomy: we will need to do chemistry in order to save the environment, but in doing so could hurt the environment further.

Scientific publications over recent years show an increased focus on more environmentally friendly chemistry. Often this involves reporting a synthesis of a compound with less harmful solvent (or more water) or a new method of synthesis with a greater atom economy, with less waste as unwanted by–products. Some of the research being conducted presently focuses on greener chemistry as possible solutions to the energy crisis. Examples include developments towards hydrogen storage for hydrogen–powered cars (with water as a by–product) and the development of electric powered cars as replacements for gasoline. On the other hand, there are experiments conducted by researchers with the main

focus on synthesis and structure to further their chemistry understanding. Often the results of these experiments hypothesise potential practical applications but, in most cases, won’t ever eventuate as they are not an advance or an improvement on current alternatives.

The solvent used in these types of experiments can be considered as doing more harm than good. Solvents are used and wasted by the bucketload in some syntheses with much of it being tipped down the drain. However solvent is necessary for these reactions to occur, especially in industrial manufacture of commercial products. The concerning part here is that the scale of solvent use around the world will only continue to grow. This will be

Solvent use (and abuse)

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Diagnostics on paper

Paper microfluidics Paper has been long used as a platform for chemical analysis. Traditionally, the acidity or alkalinity of an aqueous fluid can be measured using pH papers. The change of colour of these papers corresponds to a certain pH value. Comparing the colour of the paper after soaking in an aqueous solution with a reference colour scheme provided, the pH of the aqueous solution can be determined. Although it has limited accuracy when compared to benchtop pH meters, determination of pH through pH papers is simple, lightweight, disposable and electricity-free. What if we can incorporate all those ideal properties into an analytical device for diagnostics?

The concept of paper microfluidics was pioneered by George Whitesides at Harvard University, US. Paper is an ideal platform for diagnostics because it is inexpensive, abundant, lightweight, disposable and compatible with most biological assays. The ability of paper to draw up aqueous liquid (wicking)

In some parts of Africa, the healthcare situation is still dire. Diseases such as malaria and AIDS are major killers. The lack of cheap and accessible diagnostic tools impedes healthcare decisions that could potentially save lives. Early diagnosis of infectious diseases is critical in order for doctors to perform the proper course of action. However, modern clinical diagnostics are expensive. Moreover, they require trained personnel to operate and interpret the analyses. Aside from the medical viewpoint, the lack of reliable power supplies and infrastructure further complicate the healthcare problem. The World Health Organization (WHO) has set out important criteria for diagnostic technologies: affordable, sensitive, specific, accessible, high throughput and robust. Innovative technologies to miniaturise diagnostics, to make devices from low-cost materials and to do analysis using minimal sample with minimal footprint should make cheap diagnostics possible.

Microfluidic approachResearch efforts have been focused on developing diagnostic technologies that do not require electricity and trained personnel to operate. Microfluidics is an interesting platform in developing diagnostic technologies that has comparable performance characteristics to clinical-based diagnostics, while only using cheap materials. The concept of microfluidics is based on manipulating small volumes of fluid samples within a monolithic fluidic chip. Additional accessories such as pumps, valves and switches for increased fluid control and detectors for analysis can also be found in a typical analytical microfluidic device. For practical reasons (price, additional weight), implementation of this technology is still difficult.

provides a pump-free method to allow aqueous liquid to flow. Channels can be fabricated by placing hydrophobic barriers on the paper. The advent of inkjet printing allows the patterning of more complicated channels. Colourimetric detection is suitable for paper since it provides good contrast with its white background. This allows analysis using the naked eye, portable scanners or even cell phone cameras. Moreover, three-dimensional paper microfluidic devices can also be fabricated by patterning multiple layers of fluidic channels or by folding paper. Compared to monolithic paper microfluidic devices, three-dimensional paper microfluidics expands the number of analyses that can be done in a single paper. For examples, recent research described a breakthrough for three-dimensional paper microfluidics, in which a paper microfluidic device allows the detection of four cancer markers at a time using whole blood sample as input. No complex pre-separation of the red blood cells to collect the

serum is required prior to analysis, which makes their proposed method faster and simpler. Another group has demonstrated the feasibility of early detection of HIV using dried blood samples without the need for expensive equipment or trained personnel.

The challenges and futureMass production of paper microfluidic devices is feasible because its components are cheap. However, colourimetric detection through paper microfluidics has limitations. The number of demonstrated colourimetric analyses through paper microfluidics is only a few. Developing new colourimetric assays compatible with the microfluidic platform is important if paper microfluidics are to be widely implemented for detection of a wide variety of diseases. Nevertheless, simple, cheap, robust and lightweight medical diagnostics are possible with paper microfluidic devices. Hopefully, this technology would be implemented in the near future.James Earl Patrick Banal



Using radioactive isotopes to generate energy that can be used to power future space missions is an exciting area of science. Researchers at the UK’s National Nuclear Laboratory are developing a process that can be used to isolate 241- americium from plutonium for use in space batteries.

Traditionally, solar panels have been used on space missions to provide energy for spacecraft instruments and communication devices. A downside of solar panels is that they struggle to meet power demands once the distance from the sun is too great. This problem can be overcome by using a radioisotope as a power supply in a so-called ‘space battery’.

Space batteries provide energy regardless of the distance from the sun, allowing ventures into deeper space. An example is the Voyager 1 satellite, which was launched in 1977 and is now more than 18 billion miles from the earth. Communication with the satellite is still possible, despite it being about to leave our solar system.

Space batteries use thermocouples to convert radioactive alpha decay energy into electricity. Significant engineering challenges need to be overcome to ensure that there is no risk of accidental radioisotope release. Maintaining structural integrity at all times is vital and the fuel pellet is contained within several different layers of protection and casing.

During previous space missions, 238-plutonium has been used as a radioisotope power source. Within Europe, there are no facilities for 238-plutonium production and therefore an alternative is needed. 241-Americium has been identified as a possible option. This isotope is formed from the radioactive decay of plutonium dioxide, which itself is a product of reprocessing spent nuclear fuel at Sellafield, UK. The challenge is to separate americium from the plutonium dioxide

in which it formed. Work has begun to demonstrate a process for this using solvent extraction chemistry.

The fundamentals of solvent extraction chemistry centre on the solubilities of species in a two-phase solvent system. Aqueous acid is generally used to bring all of the ions into solution. When vigorously mixed with a solvent phase containing receptor molecules, the selective extraction of target ions (out of the aqueous phase) takes place. The ions that are not extracted by the receptor remain in the aqueous phase and thus the first step towards separation is complete. Backwashing occurs when extracted ions are washed back into the aqueous phase. Generally it is preferable to end up with the separated ions in the aqueous phase as this allows for subsequent ease of handling and processing.

The successful extraction of target ions relies entirely on the behaviour of the receptor and several criteria need to be met: the receptor needs to be selective for the target ion(s)

to enable its separation; the resultant receptor–ion complex that forms needs to be soluble in the other solvent; the complex formed should not be too strong as subsequent decomplexation (backwashing) and release of the target ions is necessary; and the receptor needs to be radiation resistant, acid resistant and synthetically accessible.

Solvent extraction is already a well established technology within the nuclear industry. The purex process (plutonium uranium extraction) uses a tributylphosphate (TBP) receptor and a nitric acid–odourless kerosene (OK) two-phase solvent system. Spent nuclear fuel is dissolved in nitric acid then mixed with TBP–OK. This enables the selective extraction of U(vi) and Pu(iv) from a mixture of fission products that are present in dissolved spent fuel. The uranium and plutonium are then separated and undergo further purification processes to produce a product that is suitable for safe, long term storage.

To use 241-americium in a space battery requires its separation

from stored plutonium dioxide. The first step is to dissolve the plutonium dioxide in nitric acid. Silver is used as a catalyst to aid dissolution and therefore silver then needs to be separated from the dissolved plutonium and americium. A two-stage solvent extraction process has been conceived. The first solvent extraction separates plutonium from a mixture of plutonium, americium and silver, and the second separates americium from the remaining americium–silver mixture. Using receptor molecules that are selective for each element facilitates separation and three product streams are produced – one for each of plutonium, americium and silver.

For future European space missions, 241-americium is a promising option as a radioisotope power source. As the isotope is already present in stored plutonium dioxide, its use is sustainable. Furthermore, it is an example of how established solvent extraction technology can be extended and developed for new applications. Katie Bell

Space batteries



Chemistry, like every other walk of life, has its ‘stars’. Often, however, the greatest progress does not come from the greatest names. Sometimes it is a chemist from more humble origins who, after years of hard work and dedication, finds the answer to the big problem that no one else could resolve.

George Olah was such a chemist. In the early 1950s, he began his doctoral studies in the field of carbohydrate chemistry at the Technical University of Budapest, Hungary. He became interested in developing a method of selective α or β glycoside synthesis from acetofluoroglucose. To do this he would require acyl fluorides, which he would also have to make himself. His supervisor, Gera Zemplen, was not terribly impressed. According to Olah, Zemplen ‘thought attempts to study fluorine compounds, which necessitated “outrageous” reagents … to be extremely foolish’.

Nevertheless, Olah was permitted to convert an open balcony on the top floor of chemistry building into a small laboratory. In this poorly equipped environment, and with the help of some rather brave co-workers, Olah successfully synthesised the highly toxic gases hydrogen fluoride and boron trifluoride and, from these, the acyl fluorides required for his studies.

His ‘folly’ presumably now accepted by his supervisor, he extended his interest to alkyl fluorides and mechanistic studies of their reactions, particularly the carbocationic intermediates thought to be formed therein. While various pieces of evidence had been gathered over the first part of the 20th century pointing to their existence, no one had yet managed to isolate a carbocation

to be able to study them in any real depth. Olah was intrigued, and began trying to find ways to stabilise them.

His stroke of genius was to use an excess of a strong, but non-nucleophilic, Lewis acid fluoride to ionise an alkyl fluoride. This would be powerful enough to dissociate the C–F bond and form a carbocation but lacked the nucleophilicity required to cause any further reactions, giving a long enough lifetime for characterisation. However, due to the limited nature of the analytical tools at hand – Olah was at the time monitoring carbocation formation using only conductivity measurements – progress was slow.

In 1956, the Hungarian Revolution intervened. Olah left the country, ending up in Ontario, Canada at the Dow Chemical Company. Now working in a somewhat better equipped

laboratory, he embarked on a comprehensive search for an appropriate Lewis acid fluoride, eventually finding that SbF5 was particularly suited to the task. Using this he isolated the tert-butyl and isopropyl cations and, with techniques such as IR and NMR spectroscopy now available to him (though the use of the latter involved hopping in the car with his samples and driving 100 miles across the American border to another Dow laboratory!), he was able to characterise their structures. Olah had finally managed to pin down the elusive carbocation.

In the summer of 1962 he presented his findings at the Brookhaven Organic Reaction Mechanism Conference. The norbornyl cation debate was in full swing. This had been triggered in 1949 when Saul Winstein had postulated a structure for the aforementioned

cation which contained a pentacoordinate carbon atom. This was forbidden by classical chemistry, the prevailing view being that carbon could only ever form four bonds. Herbert Brown, later to win a Nobel prize, was foremost among those who opposed Winstein’s idea, arguing instead that the norbornyl cation contained only tetravalent carbons in a rapidly fluctuating structure. Without a method to stabilise the cation long enough to characterise it and settle the argument, there seemed little chance the occasionally heated discussion would end.

It was against this backdrop that George Olah presented his work on the tert-butyl and isopropyl cations. As he put it: ‘It must have come to them [Winstein and Brown] and others in the audience as quite a surprise that a young chemist from an unknown industrial laboratory was invited to give a major lecture’, and in which he presented such a simple way to solve their very difficult problem. In 1969 Olah finally resolved the norbornyl cation controversy by using his method to obtain its structure and confirm that Winstein had indeed been right. A young Hungarian immigrant of whom the scientific establishment had barely heard had succeeded where some of the greatest minds in chemistry had failed.

George Olah was awarded the 1994 Nobel prize in chemistry. He had risen from obscurity to become one of the leading lights in his field. His story is a perfect illustration that sometimes the most profound of insights originate from the most unheralded of sources. Perhaps as we search for the solutions to the chemistry conundrums of our day, we would do well to heed this lesson.Paul Brack

From humble beginnings come great things…



Uranium – the mere mention of this element may conjure feelings of distrust, fear and anger. But is this truly justified? Uranium has had much negative press over the last few decades, being intrinsically linked in the minds of many with the destructive power of the nuclear bomb. More recently it has been blamed for the devastation caused by its unmeasured use as a military weapon, including links to Gulf War Syndrome (though unproven), and reported increased incidences in cancer and birth defects in some war-torn areas.

The depleted uranium (DU) used in weapons is actually slightly different to natural uranium in terms of the proportion of isotopes present. DU has a diminished proportion of the fissile 235U isotope compared to 238U, and is used in weapons because of its high density (19g/cm3) and its pyrophorocity (above 600°C).

DU is actually a waste product of the uranium enrichment process used to create fuel suitable for nuclear reactors (where the proportion of the 235U isotope is increased), making it cheap and readily available.

Interestingly, the human body itself contains, on average, 90μg of uranium. This fact may surprise most of us, but small amounts are present in our daily intake of food, water and air, passing through the body and eventually being excreted.

Uranium has found a diverse range of uses throughout history. For example, due to its high density it has been used in x-ray shielding and as counterweights in aircraft and the keels of yachts. Many people fear the radioactive properties of this element, when in fact its isotopes have radioactive half lives of hundreds of millions (235U) to over 4 billion (238U) years, considerably diminishing the threat of radioactivity concerns in normal circumstances.

Prior to the radioactive properties of uranium being discovered, it was commonly used as a colourant in the glass and ceramic industries, producing beautiful yellow/green tints. Its ability to fluoresce also led to its use as a photographic intensifier. It was even used to improve the cosmetic appearance of dentures! The radioactivity of uranium was discovered in 1896, over a century after the discovery of the element in 1789. At the end of the 19th century, pitchblende – a predominately uranium-containing ore – was painstakingly chemically separated by Marie Curie and her husband Pierre in order to isolate a previously unknown source of radiation. This was radium, and it took three tonnes of uranium ore to yield just one gram of this precious commodity. The use of radium to create such novelties as glow in the dark clocks and aircraft dials sparked the worldwide industry in uranium mining.

Thousands of tonnes of uranium are now mined annually. Kazakhstan lays claim

to the largest amount of uranium procured from the terrestrial environment – in 2011, nearly 18,000 tonnes were mined here, 35% of the global haul of over 64,000 tonnes. Large quantities can also be found in Canada, Australia, Russia and parts of Africa. Prices for yellowcake (a mix of uranium oxides) are slowly rising – from $10/lb in 2003 to around $50/lb in 2012. This has led to ever-increasing resources being used in exploration. The amount of uranium that is considered to be easily accessible from the Earth is 5 million tonnes. However, this pales in comparison to the estimated 4.5 billion tonnes available in seawater globally. Extracting it is currently prohibitive in terms of difficulty and cost, but much research is occurring in this area.

The mining of uranium remains important in order to fuel the nuclear energy industry. Nuclear fission using uranium is a much more efficient way of generating energy than traditional coal-burning power stations. Despite some widely

reported scares from the process going awry, uranium-fuelled nuclear energy remains a valid and tested way of producing reliable clean energy at a level that renewable energy has not matched. In the UK in 2011, 72.8% of power generated by major producers used fossil fuels, 23.1% used nuclear energy, with only 4.1% from renewables. It is obvious from these figures that significant advances in renewable power must be made in order to move to an environmentally friendly future for power generation. Replacing the aging nuclear infrastructure is a controversial issue, and as yet no firm plans have been made by the UK government.

So, take a look around and marvel at the array of electrical gadgetry we use in everyday life. Now, remember that uranium is partly responsible for our ability to keep up with the population’s increasing reliance on luxuries such as computers, mobile phones and tablet computers. Perhaps it should not get such a bad press after all.Susan Brittain

Elemental illuminations: uranium



One may be mistaken in thinking that these are superheroes. In fact, they are. Well, maybe just for chemists. To the rest of the world, they would appear no different than common table salt. They only get interesting when you look very closely.

Metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), zeolitic imidazolate frameworks (ZIFs) and metal–organic polyhedra (MOPs) – names given by one of their discoverers, Omar Yaghi (a true acronymist) – belong to a new generation of porous materials. These crystalline compounds, which are assembled from metal ions and organic molecules (or purely organic molecules in the case of COFs), are being tested in applications as diverse as gas storage, catalysis, chemical sensing and drug delivery.

Porous materials, as the name suggests, contain pores and holes. MOFs – and their cousins, COFs, ZIFs and MOPs – are full of nanopores. So many in fact, that these materials are practically just empty space. For example, their densities can be as low as 0.13 g/cm3. Compare that with the density of beach sand, 2.65 g/cm3. The size of these nanopores can range from 0.5–10nm, and are perfect for storing molecules. So now you can trap all kinds of things in there: fuels, greenhouse gases, metal nanoparticles – anything that can fit.

Now this is where the superhero part comes in. Arguably the biggest problem facing humans on the planet today, apart from social issues, is climate change. And CO2 is the main culprit. Humans release around 30 gigatonnes of the stuff into the atmosphere every year. As the atmospheric concentration of CO2 continues to increase, so does the global temperature. June 2012 was the fourth warmest

June since temperature records began in 1880. So what do we do? Well, the best solution would be to produce less. But while we continue to depend on fossil fuels, our CO2 emissions won’t fall much. The next option is to store it: carbon capture. MOFs and ZIFs are currently some of the top candidates for this job. For example, one litre of ZIF-69 can store 82.6 litres of CO2.

These materials are not just limited to CO2: they can also store fuels, such as hydrogen and methane. One of the main challenges preventing the use of CH4 as a transport fuel is its storage. While our oil supplies may be dwindling, there are still vast amounts of methane in the Earth. Methane is already used as a fuel for vehicles in the form of compressed natural gas. However, squeezing and freezing

methane is a costly and energy-intensive process, not to mention the increased space required for the gas cylinders. This has hindered the development of natural gas vehicles. Enter COFs. These crystalline materials are assembled from purely organic components (a major accomplishment in its own right). The best of these can store 187mg of CH4 per gram of COF at 35 bar and 25°C, roughly four times the density of methane at the same temperature and pressure. If your tank contains some of these COFs, you can travel further in your methane-fuelled car before having to refuel. BASF are now making MOFs on an industrial scale with the aim to use them for methane storage on board vehicles.

But MOFs are not only for storage. The pores of a MOF can

be lined with metal complexes or nanoparticles. The MOF is now a catalyst, a nano-sized reaction flask. Molecules can diffuse through the channels and react inside the MOF. Unique combinations of catalytic sites are brought into close proximity, almost like an enzyme, with various functional groups interacting together.

And this brings us to the next step for MOFs: complexity. In our world, a pure compound typically contains just one or two components. Take, for instance, nylon-6, which is made from just one ingredient: ε-caprolactam. Ternary systems are rarer, and any more components generally result in a mixture of materials. Most multi-component materials are physical mixtures. Nature, however, has learnt to synthesise ordered materials containing many components. DNA, for example, contains four different nucleobases. Proteins contain even more parts and form incredibly complex structures, such as enzymes, muscles or membranes. One of the major developments within the field of MOFs has been the realisation of multivariate MOFs (MTV-MOFs, another wonderful acronym). These materials contain numerous functionalities within one material – up to nine so far.

And this is the true power of MOFs: the ability to incorporate many components into a single, crystalline material. Multiple metals, mixed molecules, diverse functionalities and tandem properties. Such control within materials synthesis will undoubtedly lead to the production of readily tuneable, multifunctional devices – something that chemists dream of. While these materials are not quite saving the world yet, they are certainly on the way.Fabian Carson

MOFs, COFs, ZIFs and MOPs: can they save the world?



It’s all too easy to believe that every scientific discovery – the release of a new drug, the synthesis of a new material or the invention of a new technology – has been carefully considered, rationalised and researched until being released on the market as the latest scientific wonder. But this is not always true. Chemistry, like any other science, has had its fair share of accidental discoveries, which have often led to significant advances in their respective areas.

It is seemingly acceptable that, historically, when scientific understanding was not as advanced as it is considered to be today, accidental discoveries were more likely to occur and would have had a far greater impact on society than they would today where new discoveries are continuously being made, even if they go unreported. This is not necessarily the case; as advanced as we are there still remains a vast amount of inventions, concepts and theories to be identified and understood and commercial products yet to be produced.

Many of these accidental

findings have occurred where the scientist was looking for a new medical marvel. In 1856, this was exactly how William Henry Perkin began his journey on the road to discovering the first chemical dye. His aim was to synthesise an artificial quinine as a cure for malaria, but instead made what appeared to be a horrible mess and the sign of a failed synthesis. Upon closer inspection, a strong purple colour within the reaction caught his attention and it was here where the first chemical dye, mauveine, a multi-aromatic compound, was synthesised. Perkin went on to open his own dyeworks, leading to the mass production of mauveine.

This was the start of chemistry being seen as a profitable science, where new inventions were seen to have the potential to change how people lived. In this case, what started as a search for a medicine reverted back to its origins through the German chemist Paul Ehrlich who took these dyes and used them to pioneer immunology and chemotherapy.

Later, in 1886, one of the

world’s largest commercial soft drinks was, unknowingly, formulated by pharmacist John Pemberton who was in fact looking for a cure for headaches. Having made a concoction of ingredients that still remain a secret today, the potion was sold in a drug store for eight years before it became sufficiently well-liked to warrant selling it in bottles. By the late 1890s, it was one of America’s most popular fountain drinks and today Coca-Cola is one of the biggest international soft drink brands in the world.

The most famous of the accidental discoveries in chemical science remains the fortunate discovery of penicillin in 1928, one of the most widely used antibiotics in the world. Sir Alexander Fleming was a doctor studying influenza at St. Mary’s Hospital, London, UK, when he noticed mould had begun to grow on the culture dishes he used to grow the staphylococci germ. The mould had prevented the bacteria from growing within a radius around it. After further investigation, Fleming named

the active ingredient penicillin and determined it would be of great benefit provided it could be isolated and mass produced. This did not occur until some years later, when Howard Florey and Ernst Chain isolated penicillin and in the 1940s it was mass produced in the US.

Back in 2012, science has come a long way since the days of poor equipment, a lack of funding and minimal theoretical understanding. Does this make accidental discoveries a thing of the past? It would appear not.

The latest accidental discovery by chemists, described as exactly that in a news report, is once again from the pharmaceutical industry. This time, a drug being trialled for cancer treatment has given indications for being a contraceptive pill for men. American scientists at the Dana-Farber Cancer Institute in Boston, US, have found that a compound, JQ1, when tested on rodents for its effect against the cancer gene BRD4 inhibits sperm production in a rapid and reversible way. By penetrating the blood–testis boundary it prevents spermatogenesis, which decreases the amount and quality of sperm produced. Further investigations need to be undertaken to determine the efficacy and viability of the drug, but the potential for a male contraceptive pill could have a major impact on contraception worldwide, and all because of a series of fortunate events.

Although most scientific discoveries, including those from the pharmaceutical industry, are derived from carefully considered synthetic routes and based on sound biological understanding, some scientific innovations are serendipitous, pure and simple. But that does not take anything away from the impact they have on people’s lives.Laura Daubney

Scientific discoveries...a series of fortunate events?



Nitrates occur naturally within the environment. However, their levels have greatly increased as a result of anthropogenic sources such as synthetic nitrate fertilisers. These increased loads cause various environmental and health risks, and have made nitrate a contaminant of concern. To date, the focus has been on measuring nitrate concentrations. However, there is a recent shift towards environmental forensics, which focuses on identifying sources, rather than levels, of contamination. Such a viewpoint paves the way for applying the ‘polluter pays’ principle and achieving more effective site-remediation. This shift is largely attributed to the environmental liability directive within the EU and corresponding legislation worldwide, such as the US natural resource damage assessment regulations. For example, the UK environmental forensics market is expected to have a value of around £10–15 million per annum by 2015 from a minimal current valuation.

Environmental forensics studies have been particularly investigated for nitrate. To date, nitrate stable isotope compositions have mainly been used. However, since humans are essentially animals, these do not successfully distinguish between two major sources of nitrate: sewage (human faecal matter) and manure (animal faecal matter), because their transformation processes are similar. Therefore, their stable isotope compositions overlap. However, the risk to humans is higher from sewage than from manure. This is because viruses, which are a major source of illness resulting from faecal exposure, are highly source specific. Therefore, separating sewage and manure sources is key.

In identifying sewage and manure sources, various approaches have been attempted. The use of faecal indicator bacteria (FIB) was one of the earliest approaches. However, while they are useful for detecting faecal contamination, they do not discriminate between human and animal faecal matter sources. Studies on the ratios of different classes of FIBs, such as faecal coliforms and faecal streptococci, followed. However, due to variable survival rates of bacterial classes and the variety of ratios within different animals, these ratios are no longer considered suitable.

For this reason, other approaches must be used to achieve this differentiation. Molecular techniques, such as antibiotic resistance, DNA fingerprinting and genetic markers, have recently been investigated. These provide highly specific information on the host source of faecal matter. However, a number of studies carried out by the US Geological Survey to assess

available techniques concluded that none of the investigated methods was ready for field application. This is because of a number of challenges, such as host specificity, marker stability and costs.

An alternative approach is to use chemical markers. Ideal chemical markers should meet a number of criteria. Of critical importance is that they are ubiquitous in the source and derive only from the particular source. Furthermore, they should be present at detectable concentrations in contaminated environmental samples but not in clean water. These can fall into several classes:

Chemicals that are produced by the body, such as faecal sterols

Chemicals that are ingested, such as pharmaceuticals and food additives

Chemicals that are associated with sewage, for example detergents

Chemicals such as pharmaceuticals and food additives are considered to be more desirable than others, such as detergents. This is because they are ingested and would be excreted from the consumer (human or animal) indicating a direct relationship. Furthermore, they are generally synthetic chemicals leading to low natural background levels and are commonly persistent.

Through the careful selection of chemicals that are used in human-only or animal-only treatment, it is possible to distinguish between sewage and manure contamination.

Current research is focusing on using various chemical markers to differentiate sewage and manure. Through an understanding of pharmaceuticals’ fate during environmental transport, it is possible to achieve additional characterisation. For example, the presence of sewage markers that are easily removed within wastewater treatment plants, such as paracetamol, and others that are persistent within wastewater treatment plants, such as carbamazepine, indicate the presence of a raw sewage source.

The studies carried out to date have shown the suitability of the specific chemical markers selected for characterising point and diffuse inputs of sewage and manure into surface waters. Nevertheless, it is likely that multiple approaches are required to achieve full characterisation of nitrate inputs into water bodies, allowing for source corroboration between analytical techniques. In fact, work is also focussing on the development of decision tools that may be applied in order to identify the most suitable approach to adopt in a particular scenario of nitrate contamination.Cecilia Fenech

From environmental monitoring to environmental forensics



Perhaps unsurprisingly, given its biological origin, a number of uses have emerged involving animals. Treating bird seed is an effective deterrent for mammals, and growing chillies as a barrier crop helps stop elephants foraging in rural farms in Africa. Capsaicin is also a banned substance in equestrian sports, as it acts as a hypersensitiser and analgesic for horses – the Beijing Olympics in 2008 saw four competitors disqualified for its use. It’s also been patented for use in some types of anti-fouling and animal repellent paints and coatings, and research and commercialisation is ongoing. Perhaps the most exciting use of capsaicin is as a ‘get out of jail free’ card: 18 prisoners held in a Sumatran jail in 2006 escaped by steeping chillies in water and spraying it at the guards, incapacitating them. However, while it might get you out of jail, it will also get you straight back in – the escapees were all quickly caught and re-incarcerated.

So, next curry night, spare a thought for this fascinating chemical before digging in.Vishal Gulati

The dishes are served up from your favourite Friday night curry haunt, the air laden with spice. They make the tantalising journey from plate, to fork, to taste buds, culminating in the unique phenomenon of pain mixed with pleasure – delicious flavour wrapped around the fiery heat of the chilli pepper. You may not realise it, but you are sharing this experience with ancestral humans going back several thousand years, though there is little evidence of any prehistoric chicken vindaloo with a side of rhaita.

Thought to have originated in Central America, chilli peppers belong to the genus Capsicum, and there is evidence for their consumption as far back as 7000 BC. On their journey into modernity, chillies owe much to Christopher Columbus, who named them chilli ‘peppers’ due to their similarity in flavour to the black peppercorns with which he was familiar. Diego Àlvarez Chanca, Columbus’ physician, is credited with introducing chillies to Spain in 1494 and, by the 17th century, the whole world had gained an appetite for the fiery fruits.

The ‘heat’ in chillies is measured in Scoville heat units (SHU), and arises from capsaicinoids, a family of vanillylamine branched chain fatty acid alkaloids synthesised as secondary metabolites within the placental tissue. Capsaicin (8-methyl-N-vanillyl-6-nonenamide; 16,000,000 SHU) is the primary compound, typically forming approximately 70% of the capsaicinoid content.

Capsaicin binds to the vanilloid receptor TrpV1, a cation channel found in neuronal membranes normally opened by heat or abrasion, allowing calcium ions to flood into neurons and resulting in the feeling of pain. Binding causes the channel to open at lower temperatures, which is why the result is often described as a burning sensation. The alkyl ‘tail’

of the molecule means it is also sufficiently soluble to have this effect across skin and mucosal membranes – something that anyone who has rubbed their eyes after handling hot chillies can attest to. Such mild toxicological effects of capsaicin are well known but more extreme cases can cause gastrointestinal discomfort, and very severe exposure can even result in death, with an LD50 in mice of 47.2mg/kg. Interestingly, birds do not respond in the same way, and chilli seeds can survive in their gastrointestinal tract – this is the predominant method of dispersion in the wild.

Crude capsaicin was isolated in 1816 by Christian Bucholz, in the first report of several chemists attempting to obtain the pure essence of the chilli pepper. He used solvent extraction to produce a thick amber oil he called ‘capsicin’, half a grain (about 32mg) of which would apparently ’cause all who respire the air of the room to cough and sneeze’ when volatised in a large room – an experiment which we would not recommend you try at home. The name ‘capsaicin’ was provided by John Thresh in 1876, though Karl

Micko was the first to fully purify the isolated extract in 1898. The chemists Ernst Späth and Stephen Darling synthesised capsaicin in 1930, coupling isobutylzinc iodide with an acid chloride to form the branched chain as a 1,6-keto acid. The ketone was then reduced, brominated and eliminated to place the E-alkene in the correct position, before the vanillylamine component was added to the acid to form the amide and complete the synthesis.

The most well known use of capsaicin is probably in hot sauces, which often use oil extracted from chillies, as do pepper sprays. In medicine, creams containing around 0.05% capsaicin are rather paradoxically used as topical analgesics, effectively lowering sensitivity to pain by temporarily depleting a neurotransmitter known as substance P. A controversial hypothetical use is within abusable drugs with a time release coating, such as oxycodone. Anyone crushing and insufflating such tablets would experience considerable pain, while those consuming them as directed would not notice the additive.

A few words on capsaicin



when carried out in solution often give only a single product in high stereochemical purity. Hundreds of unit reactions have been carried out in these conditions and all that now remains is their application to industrially significant processes at the appropriate scale. When this does happen, the purported environmental and economic savings that result will lead to further exploration and implementation of this technique in as many processes and reactions as possible – a revolution in the chemical industry.

Besides these alternatives, there are a host of other interesting alternatives being explored. Supercritical carbon dioxide is a promising new solvent where the simple manipulation of pressure can effect separation, returning practically pure solvent. Ionic liquids are another option that is being researched. These have several advantages as, having essentially no vapour pressure, they can be used at significantly higher temperatures than many commercial solvents and they can be customised to exhibit different properties.

The absence of a solvent altogether or using a clean, ‘green’ one is becoming a reality in modern chemistry but these should stop being exotic possibilities and become the standard. The future of chemistry is green and necessarily needs to be so. The human race as a whole is beginning to take responsibility for the indiscriminate use and abuse of our planet’s natural resources. At the same time, society cannot do without the advancements afforded by our industrialisation. The middle path is before us and it only remains for us to make a conscious decision to take it. We ought to now begin to reflect more on solvents – why we use them, when we use them and how we use them. The options are numerous but the final choice is our own. Nivedh Jayanth

We live in the age of the atom, of polymers and of catalysts – in short, the age of chemistry. But this ubiquitous field is a double-edged sword. It gave us nylon but also CFCs and ozone depletion; it gave us aspirin but also gave us DDT. Chemistry has irreversibly altered our lives but also led to its own fair share of problems.

Every year, several thousand tonnes of waste are generated by various chemical industries. A large part of this waste (up to 80–90% by mass) is solvents. The pharmaceutical industry, for example, is indispensable but is terrible in terms of waste generation – for every kilogram of desired product, there is between 25–100kg of waste produced. When you consider the scale of production per annum, the magnitude of the waste generated is mind boggling! And most of this waste is solvent.

The solvents that are commonly used in industries around the world range from benign ones like ethanol to toxic ones like dichloromethane. Solvents once used can be recovered

but recovery rates are only about 50%. The remaining contaminated solvent can only be incinerated, leading to solid and gaseous wastes. Considering the nature of many solvents, their sustained use is not in the best interest of human health or the environment. Most solvents are respiratory irritants, benzene and related solvents are carcinogenic and chlorinated hydrocarbons cause severe liver and kidney damage, just to name a few.

But worry not, chemists these days have come up with alternatives. Humanity is in no danger of drowning in a sea of contaminated acetone just yet. The new paradigm of green chemistry, launched in the early nineties by Paul Anastas and John Warner, provides a fresh perspective to redesign chemical reactions to be more environmentally friendly. Over the last decade, there has been a conscious shift away from the more toxic solvents of petrochemical origin to safer, more sustainable ones like alcohols or even water. For

example, the pharmaceutical giant Pfizer has heavily invested in green synthetic methodologies over the last few years, leading to astounding solvent reduction. They redesigned several synthetic procedures including their synthesis of atorvastatin (Lipitor, their most widely selling drug) to use microorganisms and enzymes to biocatalyse this reaction in an aqueous environment. Thus they managed to reduce total organic waste by 65%, which translates to about 3.5 million litres of solvent per year in the production of just one drug.

The most drastic reduction in solvent use however comes with the total elimination of solvents. Over the last few years, the scope of solvent-free reactions and solid-state organic reactions has exploded, with chemists identifying several that can be done in the complete absence of solvents. These come with an added bonus – far greater control on the stereochemistry of the products. In fact, reactions that give mixtures of products

A solution to solvents



development of languages over the ages, it could be argued that English is the new Latin; obvious parallels between the Roman and British empires exist, and if Rome had made it to America, Latin may very well have remained the dominant language of science. Nowadays, I suspect it is academic tradition that sustains the use of phrases such as de novo synthesis, in vitro models and stannous chloride.

The ancient Oracle at Delphi reminds us to ‘know thyself’. I am a chemist fascinated by classics, and for this reason I’ll admit to occasionally delving into the classical roots of certain chemical facts mid-lecture. If nothing else, it gives my students brief respite from quantum mechanics, and who knows, it may even help them win a pub quiz or two in the student’s union – that alone surely makes it worthwhile! Peter McPherson

How many times have you evaporated a solvent in vacuo, read of ab initio quantum chemistry methods or considered visiting a purveyor of aqua vitae when your synthesis didn’t go to plan? Yes, English may be the official language of science, but its classical origins are clear to see for those in the know.

There was a time when chants of amo, amas, amat could be heard echoing across school playgrounds with a gusto equal to that of recitations of the first 36 elements. Alas, the former has disappeared from our schools. Even so, it is heartening to know that a student taking GCSE chemistry can name (one hopes) organic compounds using a system of prefixes based on Greek nouns, or recognise that Roman numerals are used to denote the oxidation number of an element in a compound. However, what is it about ancient languages being used in scientific contexts?

An obvious answer is that many English words have Greek or Latin roots and the practice has been continued into the scientific vocabulary. I suppose there is also an element of tradition similar to that in the legal and medical professions. Personally, I like to think that we are paying homage to our forefathers who established the foundations of our art. Indeed, the word ‘chemistry’ has Arabic roots in recognition of the contribution of the early Islamic chemists. This raises an interesting historical point – why is Latin so extensively used in deference to Greek or Arabic? The answer lies with the history of Roman civilisation.

According to myth, Rome was founded in 753 BC by Romulus and Remus, descendents of the Latin-speaking kings of Latium. As Roman civilisation flourished and moved across Europe, Latin became the lingua franca of the day. As new discoveries were made, they were recorded in Latin and carried across Europe, either by monks or invading Romans. Of course, the Romans gave us

more than language. Roman ‘chemists’ made considerable advances in metallurgy and materials chemistry (concrete is a Roman invention), and the Naturalis Historia, written by Pliny the Elder, is a meticulous catalogue of the physical properties of various natural substances. Indeed, Pliny predicted the ultimate hardness of diamond long before the Mohs scale.

With the decline of the Roman Empire (curiously attributed by some to plumbism), scientific curiosity was lost in what became known as the Dark Ages. Our eventual emergence from this period was marked by an explosion of scientific endeavour, communicated across the lands by so-called ‘new Latin’ (neo-Latin for the purists).

The major works of this time include Newton’s Principia (1687) and Linnaeus’ Systema Naturae (1735). Oddly, Robert Boyle’s

Sceptical Chymist (1661) was first published in English and it wasn’t until several years later that a Latin edition (Chymista Scepticus) appeared in Rotterdam. Aside from this, a great many chemistry textbooks were published in Latin: Baumer’s Fundamenta Chemiae Theoretico-Practicae (1783) and Vogel’s Institutiones Chemiae (1762) were required reading for students of medicine and natural sciences.

Thankfully the literature of chemistry is now available to everyone. That said, I sometimes think that deciphering chemical names can be as demanding as translating Catullus. The compound name bis(η5–cyclopentadienyl) iron is virtually a classical portmanteau – we have ‘bis’ (Latin word; ‘two’); η (Greek letter, denoting hepticity); and ‘cyclopenta’ (Greek; five-membered ring).

I suppose, considering the

Classical chemistry



At present, the textile industry relies heavily upon oil byproducts, or withering natural resources to meet its over-the-brim demand – an immense 1800 litres of water is needed to make a single cotton t-shirt. Now, Qmilch (aptly named after Q for quality and the German word for milk) presents itself as a novel answer to the industry’s dilemmas. It is a fabric created from milk that is allowed to ferment, reducing a milk protein called casein into a powder. It is then heated and mixed with a few natural additives like beeswax into strands that can be woven into a fabric.

Now if there were any qualms about just how ecological the manufacture of a new textile is, the biochemist/fashion-designer/mastermind behind Qmilch, Anke Domaske, affirms that, ‘Water consumption during the process is minimized to a maximum of two litres. There is no waste in the whole process; all ingredients are used in the fibre.’

Qmilch even provides a useful output for the abundance of expired dairy we chuck out on a daily basis. ‘We also take a waste product from the dairy industry, as we use the 20% of cow’s milk unfit for human consumption,’ Domaske says. Although she told Reuters ‘it feels like silk and it doesn’t smell’, whether we would jump at the chance to buy a £1700 designer jacket made from Bill-down-the-road’s rancid butter, is a different matter completely.

Qmilch is the offshoot of milk fibre production that has been looming around (no pun intended) since the 1930s, albeit abandoning the chemicals previously used in the 60-hour manufacturing process.

So it may be a rehash of an older concept, but Domaske’s search for such a versatile fabric was inspired by her cancer-stricken father who suffered

substantial to the claims, as it appears to assemble into a naturally-occurring fibrous protein, called amyloid fibrils, when in blood vessels.

It is said Domaske’s use of body-indigenous design dips its toes in the waters of biomimicry. By examining the makeup of matter found in nature and how those structures relate to the functions they carry out, the purpose of biomimicry is to implement these ideas into the

creation and improvement of synthetic items, like Qmilch.

At the moment, the clothes are biodegradable, reducing landfill space. But it is thought the fibres can be used again, depending on the finishing. The casein fibres are considered thermoplastic, meaning the fibres turn to a homogenised liquid when heated but they can also harden when cooled. Frozen thermoplastics become brittle and fracture. These qualities are reversible, so they can be heated, reshaped and frozen forevermore, which makes thermoplastics recyclable.

The head of the Textile Research Association, Klaus Jansen says: ‘We know that everything that is based on oil has a limit, that materials like cotton that take up a lot of land, water and chemicals are limited, so we need to think about how we produce fabrics and textiles in the future.’

If alternative textiles such as Qmilch are an indication of where an industry vexed by anti-fur activism, rampant globalisation and a carbon footprint the size of Wales is going, should we concern ourselves with the imminent?

‘Fashion feeds a growing industry and ranks textile and clothing as the world’s second-biggest economic activity for intensity of trade. However, stiff competition forces down costs while working conditions, more often than not in developing countries, are far from ideal,’ Lakshmi Challa, head of Apparel Technology at Bangalore University tells us. ‘But the environment pays a heavy price too. To improve conditions for workers and stem pollution, textile manufacturers are launching the first initiatives built around sustainable development.’ It may just be that green is the new black.Razzan Nakhlawi

Got milk? Biopolymers get revamped

skin problems from irritating and non-organic fabrics whilst going through treatment. ‘There are so many people who really suffer just by wearing normal clothing,’ Domaske told the Associated Press. ‘I wanted to find a way to help them.’

On top of its non-allergenic qualities, it is even claimed that the proteins that make up the textile retain antibacterial and anti-ageing amino acids. Casein’s biochemistry is



Euro 2012, the largest international football competition behind the world cup, is drawing to a close. The fans clamour for fast, free-flowing and attacking football. That is until they concede a goal. Then suddenly the manager got it all wrong: the tactics, the strategy and the squad. Game over and the once mighty team is defeated – it’s all about staying one step ahead. And the pharmaceutical industry is no different.

There are so many companies, and so many illnesses to treat, and currently it takes a decade or more to get a drug through to market, each company knowing their opposition may be doing the same thing. That means they need to invest, they need to be fast and attacking, cornering the market and impressing their shareholders. However this style of business can lead to them being left open for the opposition to score that killer goal

to give no hope of equalising and ultimately being knocked out of the competition. Shareholders demand results and they demand results quickly, cue the accusations of the wrong manager and the wrong tactics once again. If the tactics are changed then the chance of winning the biggest prizes are increased and the shareholders woes are eased if the risk pays off.

On the same day that Germany nigh on guaranteed their progression to the quarter finals, a blog on the NASDAQ community website reported the change of tactics shown by GlaxoSmithKline (GSK) in their £61 million takeover of Cellzome and increased interest in Theravance and Human Genome Sciences (HGS).

Proteomics is the study of proteins and in particular their structures on a large scale. Errors in protein structure are known to cause diseases, their function follows their form so to speak and

as such these need to be tackled. However, the R&D of many

of the leading pharmaceutical manufacturers still use the old fashioned methods of finding effective target molecules and modifying them. Making small incremental progress, they eventually develop the desired compound to interact correctly with the enzyme or protein. But with the use of proteomic screening techniques comes a greater understanding of the proteins, their interactions and the role they truly play in causing diseases. With this information, the drugs that can be developed can be designed to be ‘magic bullets’ – selectively targeting illnesses through specific protein–drug interactions with few or no side-effects. And it is this understanding that GSK are ploughing money into with the hope that it will be profitable to them in the future. As was stated in GSK’s press release: ‘Cellzome

adds significantly to our scientific capabilities and capacity to characterise drug targets and provides the opportunity to further enhance GSK’s ability to bring medicines to patients in a more effective manner.’

The new screening processes offered to GSK through this deal meant that they can more effectively target interactions of drugs with proteins. And it is those proteins that ultimately run the show in nature. Any way to inhibit or promote the behaviour of a protein will have significant effects on the organism. The utility of this approach means that GSK have strongly bolstered their squad, bringing a new and exciting line up to the competition. By investing in the early stages of drug development there is the potential to cut down the length of development programmes, to get the most effective drugs to market and to cure previously incurable illnesses – the technology of HGS is currently branching into immunology and oncology and with the financial weight of GSK behind programmes such as those, the company could be ready to tackle the heavyweights of the viral world.

However, this significant investment will not show through immediately, there will always be a teething period and it is a very open move on display to all the other major competitors. Proteomics is not new but it is underused, therefore of the major companies in the field, GSK has the headstart but as has been seen before the gap can shrink dramatically quickly with AstraZeneca already having numerous small collaborations with proteomics companies as well.

It looks promising but in the game of pharmaceuticals we could be heading for extra time once more. Duncan Parker

Proteomics – champion of the pharmaceuticals



and problem solving. The UK needs to move away from traditional textbook learning and look towards a more vocational, ‘apprenticeship’ system. The National HE STEM Programme, which, amongst other activities, has brought the likes of spectroscopy to those in the classroom, is a step in the right direction to introduce young people to the practical needs of modern science. This approach to higher education needs to be carried through to universities and beyond to ensure we support our young scientists throughout whichever career path they choose. Science policy needs to reflect this – ‘training’ scientists during their degrees, rather than simply educating them.

We need to ensure that these industry skills are intertwined with science learning, not only for perhaps the duration of one year of the degree but throughout its course. This way, the education and employment gap is closed, allowing both new graduates and employers to reap the benefits of employing young scientists.Sarah Pattison

What becomes of the thousands of students graduating from science degrees this summer? Evidence suggests that science is one of the best degree choices for young people to make, with the average salary for science, technology, engineering and mathematics (STEM) graduates higher than other, non-STEM graduates. But is the science career path as straightforward as it seems – train as a scientist and become a scientist? Delving into figures published from the Higher Education Statistics Agency and the Department for Business Innovation and Skills, it seems the career path of a scientist is somewhat more challenging.

For new science graduates, there are two clear pathways for career progression: further study or employment. Of the 24,000 first-degree leavers in biological sciences in 2010–2011, 21% went on to further study. Compare this to other STEM subjects (26%, 29% and 16% for maths, physical sciences and engineering, respectively) and it seems the norm for STEM graduates to continue studying. Compare this, then, to non-STEM subjects (11%, 11% and 16% for business, architecture and social studies, respectively) and the polarity between STEM and non-STEM graduates becomes clear.

Why then, such a discrepancy? A recent House of Lords report highlighted that universities are failing to provide enough ‘high calibre STEM graduates’, so you’d be forgiven for thinking STEM graduates feel the need to develop their technical skills before entering employment. This may be the case. In fact, a report by BIS suggests that STEM specialists (employers whose core business surrounds STEM subjects) have ‘perceived deficiencies in STEM graduate skills’. Here we see the shortfall in the education system in science – there is a gap between a university education and employer needs, resulting in thousands of scientists straining

to Find related employment. Alongside this, companies are struggling to find graduates with ‘adequate’ skills. Surely undertaking a degree in science should, after at least three years training and around £27,000 spent, produce at the very least an employable scientist?

In the past, scientists who chose to move away from education after their first degree are found in ‘no man’s land’ – unable to enter commercial science due to a lack of experience, technical ability or ‘soft skills’. They find that their only option is to pursue alternative career choices, such as academia or other employment in non-STEM areas.

In real terms, it is not feasible to expect companies to invest in training new graduates up to speed, when they may have postdoc students’ applications to choose from. In reality, climbing the career ladder in science has been somewhat more difficult for those without a PhD, with the general consensus being that postgraduate study displays an array of sought-after skills: experimental design, problem

solving and communication, to name a few. The importance of a PhD should not be ignored. It gives robust evidence showing the capabilities of a scientist. However, those opting out of further study and choosing learning in a commercial environment find it difficult to prove such skills, even though they are likely to be exhibiting them. What science policy needs is a step towards the recognition of these skills and nurturing them for further employment in STEM subjects. The RSC’s new registers, for both technicians and scientists, are a great leap forward in this – both provide the chance to be commended for skills that had previously only been deemed recognisable via attaining a PhD.

The reality persists that the UK produces thousands of well-equipped science graduates but loses many of them to alternative sectors simply because of the mismatch between science education and employment. What, then, is the alternative to the current system? Modern science is heavily reliant on technical ability, practicality

STEMming the skills gap



With action films bombarding us with a torrent of explosions and fire balls, it can be easy to forget that some of the greatest security threats facing us today are in fact silent. Unlike conventional weapons, chemical warfare does not rely on explosive destruction, but rather depends on the effects of a particular chemical in the body. Miniscule amounts of these chemicals are capable of tremendous damage, and they are certainly much simpler to produce, not to mention cheaper, than nuclear weapons. But what exactly are they? And what makes them so dangerous?

Chemical weapons are nothing new. Their history extends through both world wars, with the wind wafting clouds of chlorine gas in 1915, the deployment of mustard gas in the trenches in both 1917 and the late 1930s, and of course the barbaric use of lethal Zyklon-B inside concentration camps. More recently, nerve agents such as sarin have been used in various attempted terrorist attacks across the globe; for example, in the Tokyo subway in 1995. There are now a whole range of different chemical weapons, all with varying effects, but many of them capable of fatal damage. These include nerve, choking and blister agents.

Nerve agents are perhaps the most toxic chemical weapons threatening us today. They are derived from organophosphorus compounds, and can be divided into V and G varieties. V nerve agents are described as persistent because they are less volatile, and so take much longer to disperse, whereas G agents are more volatile and their effects short-lived – not that you’d survive long enough to appreciate this. Typical nerve agents include VX gas, tabun and sarin, which when pure are often colourless, odourless liquids, so the release of any of these would come as a most

unpleasant surprise. Nerve agents are either

absorbed through the skin as a liquid or inhaled as a gas, depending on their volatility. Once inside the body, they bind to acetylcholinesterase, the enzyme needed to break down acetylcholine. Acetylcholine is a transmitter in the nervous system, produced by neurons to help electrical impulses cross a synapse, and is usually hydrolysed by the enzyme after

use. If this enzyme is inhibited by a nerve agent, however, acetylcholine can accumulate at nerve endings, isolating nerves so that they become uncontrollable. Muscles throughout the body are continuously stimulated, and death usually occurs by asphyxiation, due to continuous contraction of the diaphragm. Certainly an unpleasant end.

What makes nerve agents so particularly toxic is the tiny dosage required to have an effect.

Possibly the most dangerous is therefore VX: absorbing one drop is enough to kill an adult, one litre is enough to kill a million people, and the fact that it is a good adhesive and persistent means that an airfield or enemy base would still be lethal for several weeks after exposure. Absorbed as a liquid it causes death within a couple of hours, whereas if inhaled, its effects are almost immediate and the swift end that ensues would come as a relief. Fortunately there is one other small saving grace: the anti-nerve agent atropine, although a toxin itself, can be used to remove VX from the enzyme. This antidote is administered as an injection, which – if you were unlucky enough to have inhaled VX – would have to be delivered straight into the heart.

With all this in mind, it should come as no surprise that a treaty advocating a worldwide ban of chemical weapons has been signed by all but a few countries. Unfortunately, even if we could achieve global eradication, this does not prevent independent terrorist groups from harnessing their devastating power. Not only can chemical weapons be deployed as a stealthy killer, but they can also be used tactically, for example to make agricultural land inaccessible. Even non-lethal varieties can still hinder soldiers’ fighting abilities, either by influencing the mind to effectively incapacitate them, by forcing them to wear restrictive protective clothing, or through injury. All of these can have catastrophic consequences.

So it just goes to show that danger is not only loud bangs and detonators! Although, combined with explosives, the potential destruction that could be caused by chemical weapons becomes even more terrifying. But we’ll try not to dwell on that one.Heather Powell

Silence is deadly – the threat of chemical assassins



All our livesdependent on years of research.

There is our daughter, her head turned to the side and she stares out, helpless and uncomprehending. We stand by the incubator listening to the beep of her monitor confirming each beat of her heart. You wait in anticipation for the next beat, anxious when it takes a little longer to arrive. Four pounds of fragile life lies upon the blanket. Her skin flushes with changing waves of colour. My wife reaches through the porthole in the side and strokes the tiny hand for the first time.

The ‘cares’ are explained to us and over the coming days we start a new routine. A few millilitres of her mother’s milk are ready to be loaded in to a syringe to be gently released down the tube disappearing up her nose. A chemical formula of minerals, lactose and antibodies that has been refined by evolution’s laboratory over thousands of years to give a baby the best chance of life. Simon Rees

‘I think my waters have broken,’ she said as she rushed in to the room, the anxiety in her voice and expression plain to see. ‘But she isn’t due for another couple of months.’

We rush to hospital as the contractions begin. The chemical messengers taking over as oxytocin is released from the posterior pituitary gland. The positive feedback cycle begins that ultimately results in a baby girl rushing into the world a few hours later. But there is no time for mother to hold child. The doctors check her breathing and then take her away.

The next time we see her, the nurse on duty takes us in to the special care baby room. We are instructed on the hygiene protocols and assiduously wash our hands with the alcohol-based steriliser. We enter the room and are greeted by a rhythmic symphony of beeps and clicks. Eight tiny babies in the room each one cocooned in plastic with silicone tubes and wires providing life support, their life chances

oxytocin

lactose

polydimethylsiloxane

Oxytocin is polypepetide hormone made up of nine amino acids. Note the sulfur bridge connecting the cysteine molecules. Oxytocin and another hormone, vasopressin,

were the first polypeptides to be sequenced and synthesised by Vincent du Vigneaud in 1953. He received the Nobel prize for chemistry in 1955 for this work.

Lactose (C12H22O11) is a disaccharide sugar found in milk that is formed from the condensation of galactose and glucose. Infant mammals secrete the enzyme lactase from the intestinal villi. The lactose molecule is hydrolysed and the glucose and galactose absorbed in to the body. In

most mammals the production of lactase reduces with maturity and milk is no longer consumed. In human populations where dairy products are a substantial part of the diet, however, genes for lifelong lactase production have evolved.

Silicone plastics are made from polymer chains containing an inorganic backbone of silicon and oxygen with organic side groups attached to the silicon atoms. By varying the Si–O chain lengths, side groups and crosslinking, silicones can

be synthesised with a wide variety of properties and compositions.Silicone based polymers have a diverse range of applications such as: aquarium sealant, automotive grease, cooking utensils, electronics and breast implants.

Silicon

Carbon

OxygenHydrogenMethyl

(CH3)

Oxytocin is made up of nine amino acids with a single disulfide bridge

Lactose in milk is hydrolysed to galactose and glucose

The building block of silicone based polymers



Solar powered team GB

a rain shower. When you see the respect that Britain’s heritage in science and engineering has on others around the world, it fills you with a realisation of great optimism and how grateful we should be for this.

Considering these events, I realise that the legacy for producing great chemists and chemical engineers should be cherished. Imagine life without this heritage. We should look firmly to the future in the knowledge of how the world sees us, and all try and show that as chemists we are worthy of our ancestors’ achievements. We have a reputation to keep up! More importantly, we need to harness the skills Britain presently has and use the interest shown in our chemists and our great universities from both home and abroad. Britain has a sought-after product, we just need the foresight to use this resource properly as we have done before with other resources in our famous past.Andrew Rollinson

‘What aspects of their nation are British people most proud of?’ The results of this survey were reported in the national press in early 2012. Coming top of the list was the general answer ‘British history’. The survey did not elaborate further, but undoubtedly famous chemists such as John Dalton, Robert Boyle, Michael Faraday and HumphryDavy would have helped create this perception of pride. I considered whether I would have also chosen this response if I had been asked, and I discussed the results of this survey with colleagues in a university chemistry department. Many were born abroad, yet all agreed that they too felt pride about coming to Britain because of its ‘history’.

Three months later, and I was working in the Middle East, now as a chemical engineer. I found myself again considering Britain for a number of different reasons. With junior colleagues from India and Pakistan, we were watching the Queen’s Jubilee celebrations and then the London Olympic games; both significant events for Britain, but this time under scrutiny from people across the world and not just in a national survey.

I was working in Qatar, in a small research group designing reactors to split methane into hydrogen and carbon using solar energy. Its products (H2 and C) are high-value commodities: hydrogen due to its potential for silent and non-polluting electricity generation in fuel cells, and carbon for materials such as pigments, fibres and lubricants. Using methane in this way is more efficient for energy purposes as no process heat is required, and it mitigates greenhouse gas emissions released via combustion.

Interestingly, it was the abundance of natural gas and not solar irradiation that was behind the project’s funding to bring chemical engineers like me to Qatar. Despite regular daytime temperatures of 45°C, there is

a dust haze in the sky for much of the time; fine sand particles are ubiquitous, and often full sandstorms occur. Furthermore, methane will not split by direct sunlight anyway. Carbon catalysts are employed as surface sites, and also because carbon re-radiates solar energy at just the right wavelength to crack the methane molecule.

I found that ‘history’ (just like in the survey) had preceded me in Qatar. As a British-educated researcher, I was held in high regard. This time the perceptions were from those who had never visited Britain. They spoke about the British as natural scientists: how engineers had built railways through mountains and opened up their country to the common citizen; how their structures still remain as good as ever and unchanged by time. To my surprise, Britain had a far greater image than I imagined and shamefully far greater than my own patriotism. It was based on history. Some even told me about the chemists behind these

stories such as Robert Hadfield who developed silicon steel, which advanced the industrial revolution by its use in hardened railway wheels and tracks.

Just as it was that the resources of the British Isles helped increase its wealth and shape its history (wool exports in the middle ages; the ash and yew of the long bow; coal, iron and now possibly even wind energy), so Qatar is shaping its own history through its natural gas. And as resources need scientists and engineers to exploit them, countries look to Britain.

Nine months on, I wonder how many people who participated in the national survey now feel extra pride about their heritage because of the achievements of Team GB in the Olympics? I suspect it will be a large number. How much larger would this be if they had also lived abroad and seen how highly valued British scientists are. Truly it takes you to miss something before you realise its worth, and it is not just being in 45°C temperatures that makes one long for a grey day and to be caught in



At 10:20am on 6 December 1907, more than 400 lives were instantly snuffed out. An explosion ripped through the Monongah coal mine in West Virginia, US, killing hundreds of Italian immigrant workers in the deadliest mining disaster ever known. The cause? A build up of flammable methane gas that ignited coal dust in the mine with catastrophic consequences. More than 100 years later, this clear, odourless gas is still one of the greatest threats to safety in the world’s mining industry.

Robert Hall and his colleagues probably weren’t thinking about mining when they were examining the properties of semiconductor chips in the early 1960s. Hall was trying to get the chips to emit bright coherent light – in other words, to act like a laser. At the General Electric research labs in 1962, Hall’s team achieved their goal by injecting the chips with huge densities of electrical current, producing the world’s first semiconductor diode laser.

In the 50 years since their invention, diode lasers have become a huge success story. They are manufactured in industrial quantities to emit light of many different colours and you’re probably not far from one now. They can be found in every DVD, Blu-ray and CD player in the world, offering a cheap and reliable source of laser light from a chip only a few millimetres across. But the applications are not just commercial – laser diodes have found a number of important scientific applications. The laser diode has acquired a significant role in analytical chemistry, not least in tackling the tricky problem of sniffing out methane.

To make a gas detector that is easy to use in challenging environments such as an underground mine it must be small and portable and return results quickly and reliably. A

number of techniques such as gas chromatography or mass spectroscopy have previously been used to measure methane gas concentration. Although these methods are very sensitive, the need for accurate calibration and bulky equipment can limit their usability in difficult environments. In addition, there are strict regulations on the use of electrical equipment in mines in order to avoid potentially lethal sparks. However, properties of the simple tetrahedral methane molecule (CH4) also make it amenable to detection by optical absorption spectroscopy.

There are four fundamental vibrational modes of methane. Its rotational and vibrational absorption lines exist in a range of wavelengths from 1000–3000nm and can overlap significantly with other gases such as carbon dioxide, carbon monoxide, ammonia and atmospheric water. However, at about 1650nm, in the infra-red region of the spectrum, CH4 has a cluster of transitions that are isolated from nearby contaminants, offering the perfect region to probe optically. Conveniently, laser

diodes fabricated from gallium arsenide semiconductor wafers are inexpensive to produce at this wavelength.

In order to build a detection system, the laser light must pass through the gas. This can be achieved by confining a sample of the gas in a glass cell at high density or by having the laser beam travel through the gas with a very long path length by using an arrangement of reflectors. The wavelength of the laser light can then be scanned through the molecular absorption lines by making small adjustments to the amount of electrical current flowing through the laser diode. Sensors then detect the attenuated light and a combination of electronics and computer software infers the concentration of gas.

It’s possible to detect methane concentrations of a few parts per million with optical equipment that is only a few tens of centimeters across. However, the real advantage of using optical techniques lies in the fact that the light can be transmitted along fibre optic cables over distances of hundreds of metres, keeping

the electronics – and the operator – well away from the potential danger area.

The challenge in further increasing the sensitivity and speed of methane detection is to improve the software and algorithms that recognise the molecular spectrum. Researchers at the University of Queensand in Australia have recently conducted tests in underground coalmines to assess how additional measurements of the ambient temperature and pressure can further improve the sophistication of the detection system.

In 2012, as scientists mark the 50th anniversary of the invention of the laser diode, it seems clear that beyond the many familiar applications of this revolutionary device in the home and workplace, this technology also has an important role to play in analytical chemistry. As systems for remote methane detection with optical absorption continue to improve, there is increasing hope that catastrophes on the scale of the Monongah mining disaster will remain a thing of the past. Chris Sinclair

Diodes to avoid a spectrum of disasters



Gene doping: when competitors aren’t as good as goldAs the 2012 Olympics draw to a close, a dark cloud is left hanging over the sporting world and it’s not the remnants of the closing ceremony’s spectacular firework display. With news of Belarusian shot putter Nadzeya Ostapchuk being stripped of her gold medal, doping once again taints the fantastic achievements and sportsmanship that hundreds of competitors have displayed during the Olympics.

Although doping scandals many have been on the downturn, with ever more effective means of scientific testing for illicit substances, new developments in the medical industry threaten to worsen, not ameliorate, the problem giving results almost impossible to test for. Welcome to the world of gene doping.

Many of the methods exploited in gene doping (where genes, other genetic elements or whole cells are used to improve a competitor’s performance) were originally developed for use in medicinal gene therapy. This is a fantastic technique, which could provide hope for sufferers of genetic diseases such as cystic fibrosis. However, its results could also be used to enhance the performance of able-bodied athletes.

While researching ways to restore muscle growth in patients with muscular dystrophy, scientists managed to create mice that had enormous muscles and increased strength, even into old age when muscle wasting usually occurs. These ‘Schwarzenegger mice’ were developed by injecting normal mice with a virus containing the gene for insulin growth factor 1 (IGF-1), which is a protein that promotes muscle fibre development. In this way, the extra genes allowed increased expression of the IGF-1 protein and hence improved muscle growth. Similar effects can be achieved by reducing levels of the protein myostatin which usually

inhibits muscle differentiation and growth. In this case the target gene expression could be reduced using siRNA where short double stranded regions of RNA, complimentary to the target gene’s DNA, are introduced to the body. This results in degradation of the endogenous RNA, thus reducing expression of its corresponding gene.

Another key target is erythropoietin (EPO) which promotes red blood cell production and enables increased endurance. In the past, athletes have administered this hormone by injection, which gives similar results to altitude training. However, there are now efficient tests to detect artificial EPO in the blood or urine. On the other hand, with the use of genetic doping, endogenous production is increased and it is almost impossible to tell if the EPO is of natural or doping origin, which makes detection difficult.

In fact some successful sportsmen and women have mutations in the aforementioned or other target genes that have aided their success. For example, Eero Mäntyranta, a double

Olympic gold medallist in 1964, had a mutation in the gene for EPO. This improved his body’s capacity to carry oxygen and consequently his endurance – no doubt beneficial for his sport of cross country skiing. The renowned cyclist Lance Armstrong has a genetic abnormality that means he produces around half as much lactic acid as most people. With recent news of Armstrong giving up his legal battle against the US Anti-Doping Agency and losing his seven Tour de France titles, we are once again reminded of the drug problems that already plague the world of sport. While his charges relate to the use of EPO, testosterone and corticosteroids – none of which reduce lactic acid build up – this case highlights the difficulties of testing for any drug use, let alone gene doping.

Aside from its detrimental effect on fair competition, gene doping could have disastrous consequences on the athletes themselves. Monkeys that underwent EPO injections did initially develop twice as many red blood cells. However, this made their blood incredibly thick and it

required regular thinning in order to flow. What’s more, their EPO levels suddenly fell dramatically resulting in severe anaemia and the monkeys had to be put down.

Whilst these risks would never be taken with patients undergoing gene therapy, the case is very different for athletes attempting illegal gene doping. A study in the 1980s by the US National Academy of Sports Medicine asked elite athletes whether they would be prepared to take an enhancement which guaranteed them gold but would also kill them within five years. More than half said yes. With sportsmen and women prepared to do whatever it takes to be the best, the market is open for gene doping to thrive.

No one wants to dampen the recent achievements of our incredible Olympians or any other deserving sportsmen and women. However, if we don’t face up to this problem the future of sporting success may be more dependent on genetic enhancement than the fantastic dedication to training displayed by so many competitors during these Olympic Games. Emily Stephens



studies based on the wrong isomer may need repeating. One thing that does seem certain is that the compound being tested in clinical trials is the real thing – Pfizer makes it and tests it in house, and they insist that no isomeric material has ever been administered to humans.

How deep does the rabbit hole go?The only reasonable explanation for the production of the isomeric material seems to be if the wrong aniline precursor was used in the synthesis. This could be the result of an incorrect synthesis of the anilinic isomer, purchasing of the wrong isomer, or purchasing the correct isomer but receiving the wrong compound. The latter case is probably most worrisome and, indeed, PKC has found that at least one incorrect compound is being sold as the required aniline. They are currently testing samples of 2,4-dichloro-5-aniline obtained from 28 worldwide vendors in order to locate a possible company that may be selling the wrong aniline to bosutinib producers.

Overall, instances of incorrect isomers being sold in the marketplace are very rare – bosutinib may be only the second example. Yet the implication that the problem goes back to an incorrect precursor is troubling, not just because many more bosutinib analogues are being generated by the medicinal chemistry community and may be propagating further structural errors. Other groups may have purchased the incorrect aniline for their own syntheses, leading to structural errors in molecules of a completely different class. And, unfortunately, there is no simple mechanism to alert the wider scientific community of this problem. In the end, the whole saga serves as a warning to researchers never to take the identity of purchased reagents for granted.Joanna Wojnar

The publication of a paper by Nicholas Levinson and Steven Boxer in PLoS ONE in April 2012 hit the biochemistry world like a bombshell. Its deceptively innocuous title, ‘Structural and spectroscopic analysis of the kinase inhibitor bosutinib and an isomer of bosutinib binding to the Abl tyrosine kinase domain’, hid a very worrisome discovery: two distinct chemical compounds were being sold by chemical suppliers as ‘bosutinib’. In one fell swoop, dozens of research papers and experimental results were cast into doubt.

Bosutinib (developed by Pfizer) is a selective kinase inhibitor, currently in clinical trials as a chemotherapeutic agent. Levinson, from Stanford University, US, was working on a crystal structure of bosutinib bound to a tyrosine kinase called Abl. He noticed a problem with the electron density around the area of the aniline ring – the expected chlorine at the 2 position seemed to be missing from his electron density map, and instead seemed to present at the 3 position. Somewhat worried about this, Levinson checked the crystal structure of bosutinib bound to serine threonine kinase 10, recently deposited in the Protein DataBank by Stefan Knapp and coworkers from England’s University of Oxford. Upon closer inspection, their electron density data showed that the 2-chloro atom on the aniline ring was missing, and a chlorine atom was instead located in the meta position. The authors had noted in their title that the compound was ‘radiation damaged’, but Levinson was now convinced they were afflicted by the same problem he was seeing.

What is bosutinib?Levinson and his supervisor Boxer immediately subjected their ‘bosutinib’ sample to a battery of tests. Multi-dimensional NMR experiments quickly revealed that not only was the

chlorine atom at the 3 position, instead of the 2 position, but the other chloro and methoxy group seemed to be switched as well. What they had been working on was not bosutinib, but in fact a bosutinib isomer. The difference is subtle – the isomer has the same mass and would give the same elemental analysis results. It also has some kinase inhibitory activity, so even biological activity assays could be fooled. The key to distinguishing the isomers is either x-ray or detailed NMR analysis, which would reveal the symmetry present in the aniline ring in the bosutinib isomer, but neither analysis is routinely performed on reagents purchased commercially.

Levinson and Boxer notified the company who supplied the wrong isomer – LC

Laboratories, a subsidiary of PKC Pharmaceuticals – who immediately launched a comprehensive investigation. What they uncovered was a widespread – indeed, worldwide – problem that probably went back as far as 2006. PKC Pharmaceuticals gathered unequivocal physical, HPLC, TLC and spectroscopic evidence that at least two different compounds have been, and possibly still are, being offered for sale under the name bosutinib by at least 18 different biochemical suppliers. What is worse, PKC found some other spectroscopic discrepancies that may indicate the existence of yet a third isomer. ‘What is bosutinib?’ is now a real and pressing question, as it impacts on many researchers whose results from

On the trail of bosutinib isomers

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