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3.

Metal-guzzling plants harvested to


make nanomaterials
Vegetation that cleanses contaminated soil adds to its virtues

Source: iStock
Brassica juncea, a type of mustard plant, absorbs heavy metals through its
roots

Plants partial to a diet of heavy metals are an ideal raw material for
nanomaterials once they have cleaned up contaminated soil. So says a team of
Chinese scientists behind a method that turns this vegetation into
nanoparticles and nanotubes.

Heavy metals are naturally occurring elements with important industrial,


agricultural and technological uses. Many human activities such as mining
and industry lead to the local build-up of toxic heavy metals in soil and
groundwater. Typically toxic and carcinogenic, their release into the
environment is a major concern as they can accumulate in the food chain,
damaging the health of wildlife and humans alike.

Certain plant species known as hyperaccumulators can grow in soil


contaminated with heavy metals. They absorb the metals through their roots
and concentrate them in their own tissues a genetic trait designed to make
themselves toxic to hungry herbivores. These plants have been used in the
past to clean up contaminated areas; a technique called phytoremediation.
Once the plants have extracted the metals, they themselves need to be
removed, as if left to complete their natural lifecycle they would simply return
the metals to the soil. The metal-containing plant waste is often incinerated.

Now, Jiao Qu and his team at Northeast Normal University in China have
used this biomass as a raw material to make useful nanomaterials. They
collected a hyperaccumulating species from the site of a copperzinc mine and
digested the plant material in acid. Then by subjecting it to a series of simple
heating, cooling and purification steps, they made multi-walled carbon
nanotubes (MWCNTs), Cu/ZnO nanoparticles and MWCNTs Cu/ZnO
nanoparticle composites. Significantly, the process produced a large yield of
pure materials and was cost effective compared to other methods. The profit
margin of making 1kg of multi-walled carbon nanotubes using our process is
not less than 80%, but the environmental benefit is also significant,
comments Haiyang Liu, part of the team behind the research.

Plant species have tremendous capabilities and this study really highlights an
effort at vegetative multi-tasking, observes Jason White, a nanomaterial
accumulation and toxicity expert at the Connecticut Agricultural Experiment
Station, US. The concept of growing a hyperaccumulator species on a
contaminated site to both facilitate soil remediation and then subsequently
generate engineered nanomaterials in a reproducible and cost-effective
fashion is quite appealing.

Next, Qus group want to expand the repertoire of materials they can make
from these plants.
References

This article is free to access until 22 February 2017

H Liu et al, Environ. Sci.: Nano, 2017, DOI: 10.1039/c6en00287k

1.Biological fuel cell could power cleaner ammonia production

Harnessing nitrogenase enzyme makes key fertiliser material while generating


electricity

Ammonia-producing proteins from humble nitrogen-fixing soil bacteria could


help flip humanitys fertiliser consumption from a massive energy drain into a
power generator, thanks to a biofuel cell that reacts atmospheric nitrogen with
hydrogen.

Todays dominant and energy-intensive Haber-Bosch process also uses


nitrogen and hydrogen to make ammonia. But its conditions, at around 500C
and 200 times atmospheric pressure, mean it contributes up to 3% of global
carbon dioxide emissions. We could do it at room temperature and ambient
pressure while simultaneously producing small quantities of electrical energy,
says Shelley Minteer from the University of Utah, US, whose team developed
the fuel cell.

Most biological fuel cells focus on increasing electricity generation from


oxygen and hydrogen or glucose. By contrast, Minteers team realised that
they could use the nitrogenase enzyme to replace the oxygen with nitrogen.
Nitrogenase hasnt been exploited before partly because it degrades in oxygen.
Source: Wiley-VCH

The ammonia-producing fuel cell exploits the hydrogenase enzyme to make


protons, which nitrogenase uses to reduce nitrogen to ammonia

Having isolated the enzyme and kept it away from air, the researchers also
faced the problem that electrons usually move slowly between enzymes and
fuel cell electrodes. They therefore used methyl viologen to shuttle electrons in
both compartments of their cell. In one compartment they put nitrogenase,
nitrogen and a carbon paper electrode. The other, separated from the first by a
membrane that allows only protons through, contained hydrogen, the enzyme
hydrogenase that converts hydrogen to protons, and another electrode. The
cell produced around five milligrams of ammonia for each milligram of
nitrogenase, and passed 60 milliCoulombs of electrical charge between
compartments.

Ammonia and power output can be continuous if the cell is kept supplied with
its chemical fuels, which are hydrogen and the biological energy molecule
ATP. Eliminating ATP is an important hurdle to overcome, Minteer admits,
which the group is working on.

They envision getting hydrogen from the same source as the current Haber-
Bosch process, energy-intensive steam-reforming of methane. Minteer
highlights that the energy their cell generates during the final step would
reduce emissions during ammonia production. But she adds that her
coauthors from CSIC, in Madrid, Spain, recently produced hydrogen using a
photosynthesis protein and light. That could potentially erase ammonias
carbon footprint altogether.

Producing the cell shows the teams deep understanding of the enzyme
behaviour, comments Katherine Holt from University College London. The
next question will be to improve enzyme stability and longevity for long-term
use and to develop large surface area electrodes to allow for scale up.

References

R D Milton et al, Angew. Chem. Int. Ed., 2017, DOI: 10.1002/anie.201612500

2.Gecko-inspired adhesive unsticks with a flash of light

UV-responsive sticky surface can be switched on and off in a matter of


seconds

Researchers have developed a gecko-inspired dry adhesive system that uses


UV light to switch and control its level of stickiness within seconds. The
approach is faster and simpler than other photo-controlled adhesives, and
could find uses in light-driven robotic systems.

Light responsive materials such as liquid crystal elastomers (LCEs) have been
used to make switchable adhesives before. But they are often slow and
complicated, needing high temperatures or additional stimuli to activate or
return them to their original state.

Source: Emre Kizilkan

The surface has adhesive microstructures which mimic the fibres on a geckos
toes

Now, scientists from Kiel University and the University of Bremen in Germany
have developed a much simpler and quicker LCE-based adhesive. Their
system requires only UV light to switch between sticky and non-sticky states
in a matter of seconds, and to control the amount of adhesion. It can also pick
up and drop objects; a first for light responsive adhesives according to the
team.

Of course, other gecko-inspired adhesives have been developed in recent


years, some which perform well enough to enable a person to climb a wall like
Spider-Man. But to replicate the speed and grace of a superhero, an adhesive
needs to dynamically attach and detach. This was the starting point; we
wanted a quick detachment with a reversible adhesive character, says Emre
Kizilkan, one of the researchers involved.

The material works using a LCE layer sandwiched between two


Polydimethylsiloxane (PDMS) layers. One of these layers is covered with tiny
mushroom-shaped microstructures that mimic the array of fibres on geckos
feet that enable them to stick to surfaces via intermolecular van der Waals
forces.

To control adhesion, the team used azobenzene in the LCE as the light
responsive molecule, which isomerises quickly from one state to another and
changes size under UV light. This effect flexes the material enough to cause
the microstructures to peel away from a surface and unstick, akin to how a
gecko loses adhesion by moving its feet. When the light is removed, the
material quickly recovers to its flat, sticky state.

Source: Emre Kizilkan & Jan Strueben

The azobenzene changes shape in response to UV light, causing the


adhesive to bend and peel away from a surface

The material can also stick to and transport objects much bigger than the
adhesive surface after an initial preload force of 6mN is applied, including
glass spheres, microscope slides and plastic Eppendorf tubes. Applying UV
light releases the objects. We would like to use this material in a locomoting
robot driven by light. Therefore, we plan to optimize the layers thicknesses
and control the light-induced deformation, says Kizilkan.

This is an intersting innovation, comments Elliot Hawkes from Stanford


University in the US, who developed gecko-inspired adhesive gloves 2014.
However, I wonder about what the limits on speed are. In many robotic
applications, speed of grasp is important, he says. A second question is
whether adhesion can be achieved without such a large preload. For grasping
delicate objects, large preloads can be problematic.

References

E. Kizilkan, et al., Sci. Robot., 2017, DOI: 10.1126/scirobotics.aak9454


4.

Informatics tool helps researchers visualise complex toxicity datasets

To help predict and avoid designing toxic nanomaterials, researchers have


created an informatics tool that can pull out and visualise key information
from a large collection of complex nanomaterials research.

Nanomaterials are now common in commercial products such as clothing and


cleaning agents, and the amount of research into potential adverse
environmental and health effects has increased exponentially. However, there
is no comprehensive way to compare, or visualise, this information that could
help researchers find correlations between nanomaterial properties and their
toxicity. As well as the sheer volume of information, different studies also
often consider different experimental conditions and biological material,
making it very difficult to compare data directly.

Now, Sandra Karcher at Carnegie Mellon University, US, and her team have
designed N4mics, a tool that can visualise nanoparticle toxicity research on
zebrafish stored in the Nanomaterial-Biological Interactions Knowledgebase.
Karcher says: We developed the tool as a testbed to demonstrate how data
that are standardised and shared can be mined to create visual comparisons
between nanomaterial types. These visualisations are then used to generate
novel hypotheses about how the properties of those materials affect their
toxicity potential.

The team shows N4mics, which is available for public use, can mine data from
151 zebrafish studies; users can select data subsets such as nanomaterials with
specific core structures, and then visualise the results by biological response
or a combination of nanomaterial characteristics they are interested in.
Karchers data mining indicated that toxicity most strongly correlates with
nanomaterials shell components, rather than other properties such as size.

Vicki Grassian, an expert in nanoscience and its implications on health and


the environment at the University of California San Diego, US, says: This
visualisation tool is a step forward in shedding some light on our
understanding of structure-property-hazard relationships but not on the
underlying mechanisms that are needed for understanding causes of the
hazard.

Karchers team is now working on identifying the best format for data
collection so that they can design other tools that can answer more of these
questions.
References

This article is free to access until 21 November 2016

S Karcher et al, Environ. Sci.: Nano, 2016, DOI: 10.1039/C6EN00273K

How LSD Could Change The


5.

World
Behind the tie-dyed wave of rebellion that swirled across the US in the 1960s were a test
tube, a Bunsen burner, and a periodic table. In the hands of two talented and idealistic
chemists, the tools of the scientific establishment were repurposed to manufacture the
fuel of cultural change: lysergic acid diethylamide, or LSD.

One particular strain of the drug, known as Orange Sunshine, became synonymous with
the psychedelic revolution, and was famous for being the purest acid ever made. Yet the
drugs co-creator Tim Scully tells IFLScience that the chemical ultimately didnt manage
to save the world, in part because its users turned their back on science.

However, with the number of scientific research papers about LSD reaching their highest
level for 50 years in 2016, mainstream science may now have a chance of bringing
about its own psychedelic revolution.

The Chemistry of Rebellion

A new documentary called The Sunshine Makers tells the story of the rise and fall of
Orange Sunshine, and how Scully, along with his friend Nick Sand, attempted to
manufacture 750 million doses of the drug, in an audacious attempt to turn on the world
and usher in an era of peace and love.

As rebellious as this project may sound, you dont create such a vast quantity of
impeccably pure acid without discipline and scientific rigor not to mention an expert
grasp of chemistry. Lab technique is everything when youre making acid, because
lysergic compounds are very fragile and easy to mishandle, explains Scully.

Working in a Breaking Bad-style makeshift lab in Point Richmond, California, the pair had
to block out all outside light, because daylight is death to LSD. In the presence of water,
UV light turns LSD into lumi-LSD, which has a water molecule attached. Then theres the
problem of burning off solvents without heating the solution to above room temperature.
The solution? We were getting through about a tonne of dry ice a week.

But just as the finished product helped to warp the values and beliefs of its users, the
cultural and scientific remit of LSD itself was largely defined by the prevailing wisdom of
the world outside the lab.

Nick Sand, Tim Scully and co making LSD. The Sunshine Makers

How The World Changed LSD

Back in the 1960s, neuroscientists believed that psychedelic drugs were


psychotomimetic, meaning they induce psychosis, and began to experiment with these
substances in an attempt to study the psychotic mind. This model was later abandoned
when it became clear that the effects of LSD are in fact far removed from psychosis.
Interestingly, a study published last year found that the acute effects of LSD do share
some similarities with psychosis, but that these quickly give way to longer-lasting
therapeutic effects, like elevated mood and decreased anxiety.

Like the neuroscientists of today, Scully disagreed with the psychotomimetic paradigm,
and though he didnt envision the drug being used as a treatment for mental and
emotional disorders, he certainly hoped it would be used to generate sanity rather than
madness. I was more interested in what healthy people could do with LSD like
becoming more gentle and responsible towards each other rather than for therapy.

Yet there is a protocol that must be followed when taking acid, defined by a combination
of what researchers call set and setting. When this procedure is not followed, the drug
can easily become a psychedelic spanner that unhinges the mind which is, to some
extent, what the world turned LSD into.

Giving it out at acid tests and rock concerts was not the right setting, and there were
some bad side effects, says Scully. Too many people ended up believing in magical
thinking rather than logic or science. It created a lot of conspiracy theorists, like the anti-
vaxxers.

Ultimately, we didnt manage to save the world just look at the results of the last
election. Clearly people still have an interest in doing nasty things to each other.

Yet ironically, the inauguration of Donald Trump comes at a time when the scientific
community finds itself on the cusp of its own psychedelic awakening. How his
administration positions itself in relation to this type of research will be critical in
determining whether or not drugs like LSD are given another shot at bringing about a
positive change in the world.

The Future of LSD

Not all LSD users strayed from the path of good science in the 1960s. One of Nick
Sands old friends, named Amanda Feilding, told IFLScience that she developed an
interest in trying to discover the mechanisms underlying the changes in consciousness
brought about by LSD in 1966. Later, as the founder and director of the Beckley
Foundation, she coordinated the first ever brain imaging study on LSD, which
revealed how the drug generates feelings of oneness and positivity by loosening
connectivity in a brain region called the default mode network.

Scientists are now using this information to develop proper protocols including the
appropriate set and setting in order to harness the drugs therapeutic potential. For
instance, a recent study showed that LSD can bring about lasting reductions in
anxiety among people with terminal illnesses.
The number of scientific research papers published about LSD. The Beckley Foundation

Of course, the chemists and neuroscientists working on these research projects have
come a long way from the dingy basement lab that Scully and Sand converted into their
psychedelic arsenal. The Beckley/Imperial research program, for example, is bringing
this type of research into the scientific open, with rigorously controlled studies into the
therapeutic potential of psychedelics taking place at Imperial College London.

Yet with psychedelic research constantly hovering over a political precipice, the Trump
administration could pose a major threat to the advancement of this field of scientific
investigation, potentially forcing LSD back underground.

Disclosure: Ben Taub is an employee of the Beckley Foundation, a UK-based


think-tank and UN-accredited NGO that focuses on global drug policy reform
and scientific research into psychoactive substances.

Like the neuroscientists of today, Scully disagreed with the psychotomimetic paradigm,
and though he didnt envision the drug being used as a treatment for mental and
emotional disorders, he certainly hoped it would be used to generate sanity rather than
madness. I was more interested in what healthy people could do with LSD like
becoming more gentle and responsible towards each other rather than for therapy.

Yet there is a protocol that must be followed when taking acid, defined by a combination
of what researchers call set and setting. When this procedure is not followed, the drug
can easily become a psychedelic spanner that unhinges the mind which is, to some
extent, what the world turned LSD into.
Giving it out at acid tests and rock concerts was not the right setting, and there were
some bad side effects, says Scully. Too many people ended up believing in magical
thinking rather than logic or science. It created a lot of conspiracy theorists, like the anti-
vaxxers.

Ultimately, we didnt manage to save the world just look at the results of the last
election. Clearly people still have an interest in doing nasty things to each other.

Yet ironically, the inauguration of Donald Trump comes at a time when the scientific
community finds itself on the cusp of its own psychedelic awakening. How his
administration positions itself in relation to this type of research will be critical in
determining whether or not drugs like LSD are given another shot at bringing about a
positive change in the world.

The Future of LSD

Not all LSD users strayed from the path of good science in the 1960s. One of Nick
Sands old friends, named Amanda Feilding, told IFLScience that she developed an
interest in trying to discover the mechanisms underlying the changes in consciousness
brought about by LSD in 1966. Later, as the founder and director of the Beckley
Foundation, she coordinated the first ever brain imaging study on LSD, which
revealed how the drug generates feelings of oneness and positivity by loosening
connectivity in a brain region called the default mode network.

Scientists are now using this information to develop proper protocols including the
appropriate set and setting in order to harness the drugs therapeutic potential. For
instance, a recent study showed that LSD can bring about lasting reductions in
anxiety among people with terminal illnesses.

Incredible New Project


6.

Converts Carbon Dioxide Into


Stone
Like a modern-day version of Medusa, an Icelandic project turns enemies to
stone. The modern enemy is carbon dioxide, and success relies on the basaltic
rocks on which the island sits.

Carbon capture and sequestration (CCS) has been promoted as fossil fuels'
savior in a warming world. The idea is to collect carbon dioxide from coal- and
gas-fired power stations and pump it into the Earth rather than into the
atmosphere.

Special circumstances aside, however, CCS has been an expensive failure.


Among the many reasons is the fear the carbon dioxide won't stay down. Any
large-scale release would be catastrophic for local populations. Even a slower
leakage at rates of more than 0.1 percent per year would destroy the value of
the operation.
In 2012, the Hellisheidi power plant in Hengill, southwest Iceland, pumped 230
tonnes (254 tons) of carbon dioxide mixed with water and 18 tonnes (20
tons) of hydrogen sulphide into wells drilled 150 to 3,000 meters (500 to
10,000 feet) through basaltic lavas. The carbon dioxide was spiked with extra
carbon-14 so that it could be distinguished from naturally occurring gas.
Injection has now since increased to 4,500 tonnes (5,000 tons) a year.

Hellisheidi is the largest geothermal plant in the world, and far cleaner than coal or gas, but it is
aiming to do even better. Kevin Krajick/Lamont-Doherty Earth Observatory

A study published in Science found that more than 95 percent of the original
trial's carbon was converted to rocky carbonate within two years. This
astonishingly rapid transformation, the paper notes, contrasts with the
common view that the immobilization of CO2 as carbonate minerals within
geologic reservoirs takes several hundreds to thousands of years.
The process was found to work even when the carbon dioxide was mixed with
a high concentration of hydrogen sulphide, which was thought might interfere
with the carbonization process.

The authors attribute the rapid mineralization to calcium, iron, and


magnesium ions released by the basalt and the alkaline waters into which the
carbon dioxide was injected.

Storing the carbon as a solid, rather than a gas, removes the danger
associated with conventional reservoirs such as earthquakes, removal of the
holding rock or gas leakage through small pores.

Hellisheidi is a surprising place for such a trial. It is geothermal, running on


the heat generated by the volcanic conditions. The carbon dioxide and
hydrogen sulphide are volcanic gasses released with the steam that drives the
station's turbines. The 36,000 tonnes (40,000 tons) of CO 2 released annually
are 5 percent of what an equivalently-sized coal-fired power plant would emit,
but Iceland is aiming for complete carbon neutrality.

In the future, we could think of using this for power plants in places where
there's a lot of basalt and there are many such places," said Professor Martin
Stute of Columbia University in a statement. Indeed, one-tenth of continental
rock is. Virtually the entirety of the ocean floor is also basalt, although
pumping carbon dioxide far out to sea is expensive.

Where basalt and ample water are conveniently available to the point of
capture, the authors calculate that a fully developed version of the system
might produce a price for CCS that may be as low as $30 per ton, compared
to $130 for scaled-up versions of other methods. Yet even this may struggle to
compete with renewables in producing cheap, pollution-free electricity.

Engineers Create Gold


7.

Aerogel That's Almost As Light


As Air
Gold is a genuinely fascinating material. Its incredibly rare, created only
during the most powerful stellar explosions in the universe. Its relatively easy
to shape, conducts electricity and heat pretty well, and looks rather beautiful,
so we assign a high economic value to it. Its also quite dense, however, so it
may strike you as unusual that researchers at ETH Zurich have revealed that
theyve created a gold aerogel so light it can float on the frothy surface of a
well-made cappuccino. Their study is published in the journal Advanced
Materials.

This new form of gold is one thousand times lighter than its conventional
form, despite the fact that it looks identical to a lump of gold. Its lighter than
water and even has a density approaching that of just air. Its so soft that it
can be molded into shapes by hand. Even its value compared to conventional
gold has barely slipped a piece the size of a dime is still 20 carats, meaning
that this aerogel is made of 83 percent pure gold. The rest of it is composed of
nothing but porous spaces filled with air, and a little milk.

To make it, milk proteins were heated until they formed nanometer-sized
fibers called amyloid fibrils, before they were placed into a solution containing
positively-charged gold ions. As the solution was allowed to evaporate, the
fibers arranged themselves automatically into a 3D lattice-like network, along
which the gold began to crystallize thus producing a golden grid full of
spaces. As air drying could damage the gold, the team chose a slow, delicate
drying process using carbon dioxide to remove the liquid solution.

Image credit: The gold is so light that it can rest on the top of a small flower. Nystrom and Mezzenga/ETH Zurich

Often dubbed frozen smoke, aerogels such as this are synthetically


manufactured, highly porous solids. But instead of a liquid component, theres
gas mixed in; as a result, the material has an incredibly low density.
Somewhat misleadingly, they arent actually gels; theyre merely made from
gels, which are more jelly-like solid-liquid mixtures.

Most aerogels are made by causing chemical constituents to crystallize on a


pre-existing grid network; in this instance, the grid formed in synchronization
with the precious metal. Not only does this quickly produce a pure gold
aerogel with no traceable contaminants, but it means that its optical
properties can be customized.

The optical properties of gold depend strongly on the size and shape of the
gold particles, said Gustav Nystrm, postdoc at ETH Zurich and first author of
the study, in a statement. Therefore we can even change the color of the
material. When we change the reaction conditions in order that the gold
doesn't crystallize into microparticles but rather smaller nanoparticles, it
results in a dark-red gold.

Apart from its use in creating easy-to-shape, valuable jewelry, the aerogel
has multiple engineering applications as well. Gold is a chemical catalyst,
meaning that it can speed up the reactions of huge industrial processes,
including during the combustion of hydrocarbons. The huge surface area of
the gold aerogel would improve its catalytic abilities to a perhaps
unprecedented degree.

In addition to this, it can also be used as a pressure-sensitive conductor of


electrical currents. Normally, the gold particles within the aerogel do not
touch, so it acts as an insulator. If put under significant pressure, however,
they connect, and a circuit is formed.

8. What Makes Popcorn Pop? The Chemistry of Popcorn


Today (19th January) is apparently National Popcorn Day, so what better time to
look at the chemistry behind it? This graphic takes a brief look at some of the
compounds that give popcorn its flavour and aroma, as well as what makes it
pop!
There havent been a great number of studies on the chemicals that make up the
aroma and flavour of popcorn. The first of these, way back in 1970, identified a
range of compounds, and made some general suggestions as to which ones
were important for flavour. Compounds called pyrazines contribute nutty flavours,
with 2-acetylpyrazine, whose aroma is itself described as popcorn-like, cited as
a key odorant.

Later studies looked in more detail at the contributing compounds. They found
that although 2-acetylpyrazine is present, it isnt one of the more significant
contributors to aroma. Though many compounds make a degree of contribution,
the three key compounds identified were: 2-acetyl-1-pyrroline, with a roasty,
popcorn-like aroma; (E,E)-2,4-decadienal, with a fatty, fried aroma; and 2-
furfurylthiol, which in isolation has a roasted coffee-like aroma. A number of other
pyrazine, pyridine, phenol, and aldehyde compounds make more minor
contributions.

Flavourings can also add their compounds to the mix. 2,3-butanedione


(commonly known as diacetyl) is one such compound, which was used in butter
flavourings. Its use in these flavourings has declined due to concern regarding
workers preparing the flavourings inhaling the compound. Inhalation of diacetyl
can cause inflammation of the bronchioles in the lungs, a condition sometimes
referred to as popcorn lung.

Popcorn lung is not a significant concern for consumers, as they are unlikely to
be inhaling large amounts of the compound, though there have been isolated
cases of people preparing popcorn in large quantities on a regular basis showing
symptoms. Diacetyl is less frequently used as a flavouring now, though its
substitute, 2,3-pentanedione, has also been linked with the condition in workers.

Theres also some chemistry behind the cooking process of popcorn. Popcorn
kernels contain around 14% water by mass. As they are heated, this water
vaporises; however, it remains trapped inside the kernel, and so the continued
heating raises the pressure inside the kernels shell. Eventually, usually at around
180C, the kernels shell will crack, and the corn will pop.

The popping noise that accompanies this is not, as might be expected, the sound
of the kernels shell cracking, but rather a consequence of the release of the
pressurised water vapour. As its released, the cavity inside the kernel acts as an
acoustic resonator, which is what amplifies the sound of the pop and makes it
audible. During heating, the starch inside the kernel becomes molten, and when
the kernel pops it quickly escapes, rapidly cooling and forming popcorns
characteristic fluffy shape as it solidifies.
9. A Brief Guide to Doping in Sports

The Rio Olympics are underway, and after a build-up thats already been marred
by the Russian doping scandal, officials will be on the look-out for athletes trying
to gain an edge by using performance-enhancing drugs. What types of drugs will
they be looking for, and why might athletes be tempted to use them in the first
place? This graphic takes a look at some of the major classes of banned
substances and the reasons that they are banned.

Anabolic Agents

Anabolic agents are the biggest class of prohibited drugs at the Olympics, and
theyre also the most frequently detected. In 2014, the World Anti-Doping Agency
found that 48% of positive tests were due to the use of anabolic agents. Their list
of prohibited substances names around 74 different agents, but also includes any
substances with similar chemical structures.

Anabolic steroids are the major group of drugs included in this class. They are
structurally similar to the natural human hormone, testosterone, and when taken
mimic its effects. As such, they are used by athletes to help them increase their
muscle mass and physical strength. Commonly, theyre taken in the run-up to
competitions, rather than during the competition itself. This would make them
harder to detect with testing at the Olympics alone, which is why out-of-
competition testing also takes place. With that said, recent research has found
that steroid metabolites persist in the bodies of those using them for several
months, making them easier to detect.
Anabolic steroids were at the centre of the recent Russian doping scandal,
detailed in a previous post with C&EN magazine. Their cocktail used a
combination of three different steroids; one of these was changed as detection
methods for it improved. Metanedienone, developed in the 1960s, was regularly
used by body-builders, weight-lifters, and shot-putters before anabolic steroids
were banned from Olympic competitions in 1975.

Steroid use doesnt come without risks. Their side effects include high blood
pressure, which can lead to heart disease, and also kidney damage. In both men
and women, they can also have aesthetic effects. For men, they can shrink the
testicles and enlarge breasts, as well as reducing sperm count. In women, they
increase body hair, decrease breast size, and deepen the voice.

This category of drugs also includes some non-steroidal agents, and notably
clenbuterol. Clenbuterol is used to treat breathing disorders, as it widens the
airways and also acts as a decongestant. For athletes, it has modest muscle-
building effects, but can also be taken to help increase the metabolism and help
burn fat. A number of athletes in a variety of sports have been banned for using
this drug.

Stimulants

The second most frequently detected class of doping drugs are stimulants. In
2014, they accounted for 15% of the positive tests recorded by the World Anti-
Doping Association, and the stimulant methylhexanamine was reportedly found in
45.9% of positive athletics urine samples worldwide in 2012.

Stimulants are substances that help increase alertness, energy, and attention. A
number of them behave similarly to the human hormones adrenaline and
noradrenaline, commonly referred to as being involved in the bodys fight or
flight response. A very well-known example of a stimulant is caffeine, which isnt
banned in Olympic competition. Banned stimulants include amphetamines and
cocaine.

As with anabolic agents, there are health issues associated with stimulant use.
Many of them are addictive, and their use can also increase the risk of heart
failure. They can also lead to exhaustion. Modafinil, a stimulant that was added to
the list of prohibited substances for Olympic athletes in 2004, reportedly prolongs
exercise time for athletes, and several athletes have been banned for its use.

Hormones and Modulators

This class of prohibited substances is large and varied. Generally, they tend to be
substances that interfere either with human hormones or metabolism to give
athletes an edge. They can also be used in conjunction with anabolic steroids, as
they can act to reduce some of the undesirable physical effects of these drugs.

Some of the drugs in this class are those that effect the hormone oestrogen. This
can be beneficial for men using anabolic steroids, as steroid use leads to
gynecomastia, or enlarged breasts. Oestrogen-inhibiting drugs can help minimise
these effects. They are usually taken for this purpose, rather than having any
effect on athlete performance.
This class of drugs also include meldonium, which shot to prominence recently
when tennis player Maria Sharapova was banned for using it. Meldonium is a
drug that can be used to treat some heart problems, particularly coronary artery
disease. It helps widen the arteries, which can be useful for athletes as it helps
increase the flow of oxygen to the muscles in the body.

Meldonium was banned at the start of 2016 after evidence showed that athletes
in 15 out of 21 sports at the Baku 2015 European Games were using it to help
enhance their performance. Since being banned, 124 positive samples have
been taken from athletes in various sports, a large number of them Russian.
Meldoniums ability to enhance performance has, however, been
debated, particularly by the Latvian manufacturer of the drug.

Diuretics and Masking Agents

The drugs in this class are used for two purposes. Diuretics are substances that
promote the excretion of water in urine, and can be used by athletes to regulate
their body mass, particularly in events where competitors must be at or near a
certain weight such as boxing. They can also be used to mask the use of other
banned substances, as by diluting the urine they can help reduce the
concentration of banned agents and their metabolites. Masking agents are
substances that impair the detection of substances in the urine, either by
concealing or interfering with detection of metabolites of banned substances.

Diuretics and masking agents can lead to a range of side effects, including
dehydration and affecting salt balance. One of the most commonly used diuretics
is furosemide, which can increase urinary excretion by a factor of 30. Their
continued use can lead to gastrointestinal problems and kidney damage.

Narcotics

Narcotics are used primarily to manage pain. This can be to help athletes
overcoming minor injuries, or to simply increase their pain tolerance during
events. They also help reduce anxiety, which can be a benefit in the high
pressure environment of the Olympics.

This class of drugs includes well-known substances such as morphine and


codeine, collectively known as opioids. While these drugs were commonly used
in the first half of the 20th century in combination with anabolic steroids, their use
has drastically decreased due to the ease with which they can be identified in
urine. The use of painkillers which are not on the prohibited list of substances,
such as aspirin, has also reduced their use.

The side effects of narcotic use can also be severe. They are particularly
addictive, and the body can also build up tolerance to them, meaning that the
dose has to be routinely increased to see the same effects. Over-use can also
lead to adverse psychological effects.

Other banned substances

Though the main groups of abused substances have been discussed so far, there
are a number of other substances whose use is prohibited. Some are banned
outright; these include cannabis, cannabinoids, and glucocorticosteroids. Others,
such as alcohol, are only banned in-competition in particular sports such as
archery. Further substances are banned only above certain thresholds; for
example, beta-2 agonists, primarily used in the treatment of asthma in inhalers,
are largely banned, but the used by asthma sufferers are permitted to certain
levels.

Another banned agent worth a more extended mention is erythropoietin (EPO).


This is an agent used in what is sometimes termed as blood doping, the practice
of taking substances to increase the number of red blood cells in the blood. EPO
is a hormone that stimulates red blood cell production. Red blood cells help carry
oxygen to the bodys muscles, so increasing their number should help increase
athlete performance. Gene doping can also be used to achieve similar effects, as
C&EN detailed recently.

Its clear that doping in athletics is a constant game of cat and mouse, as the
recent issues with meldonium illustrate. Though some athletes risk the use of
banned substances to gain an edge, its clear that a number of others attempt to
do so using substances that the World Anti-Doping Agency has yet to explicitly
ban. Retroactive testing on samples taken at previous Olympics make it much
more likely that those using doping to get ahead will be caught out, if not
immediately, then eventually.
10. The Chemistry of Moisturisers

Its the middle of summer, and hopefully, if youre heading out in the sun, youre
taking the precaution of applying sun cream beforehand. Sometimes, however,
you can end up with sunburn despite your best efforts to prevent it. After sun and
moisturisers can help to soothe the burn here, we take a look at the chemicals
that allow them to do their jobs.

Before discussing moisturisers themselves, lets look at your skin. Skin is


composed of three main layers: the epidermis, the dermis, and the hypodermis
(also known as subcutaneous tissue). The hypodermis anchors skin to muscles,
and also contains fat, but its slightly less important to our discussion. The dermis,
on the other hand, is very important for water storage in fact much of the water
in our bodies is stored here. It has plenty of other roles too: it contains blood
capillaries, sweat glands, nerve endings, and hair follicles. In the context of the
skin its responsible for providing water, nutrients and energy to the epidermis.

The epidermis is the outermost layer of skin the layer we can see from the
outside. It itself can be subdivided into 5 different layers, the uppermost of which
is called the stratum corneum. This outer layer is composed of dead cells called
corneocytes, which are filled with the protein keratin. These form protein-based
bricks. In between these are a mixture of compounds, primarily lipids, that act as
the mortar, holding the bricks together.

These lipids (mainly a mixture of ceramides, cholesterol, and fatty acids) play an
important role in allowing the skin to retain water, as they form a semi-permeable
barrier to water. There are also substances in the skin called natural moisturising
factors (NMFs) which aids the retention of water in the epidermis. Some is lost,
however the process of its loss is known as transepidermal water loss (TEWL).
This water loss occurs as a result of diffusion and evaporation of the water. Its
not something we can control, so in cases of dry skin or sunburn, we have to take
steps to temper it.

Damage to the skin, as in the case of sunburn, boosts TEWL; so do high


temperatures, wounds, or even just very dry conditions. Moisturisers can assist
and help us fight back against this increased TEWL. In order to do that, they
contain a wide range of ingredients, but in terms of those that actually help the
moisturising process, we can split them into three key groups.

The first of these groups is the occlusive agents. These are essentially the most
primitive method of preventing TWEL; they are usually hydrophobic (water-
repelling) ingredients which form a non-permeable barrier over the skin to prevent
water from escaping. The most common example youve probably come across is
Vaseline, or petroleum jelly, which is a mix of hydrocarbons containing 25 or more
carbon atoms.

Whilst occlusive agents are effective at preventing water loss, they can leave the
skin with a greasy, oily feel, and as such their use on their own in moisturisers is
usually avoided. The layer they form can also trap the heat given off by sunburn,
exacerbating skin damage so dont go smearing vaseline on it!

Humectants are the second key group of compounds. These agents function
differently, as unlike the occlusive agents they are hydrophilic, and attract water.
Some of the natural moisturising factors in the skin, such as hyaluronic acid, are
also used in moisturisers as humectants. They draw water up from the dermis to
the epidermis to keep it hydrated. Other common humectants include glycerin,
sorbitol, and urea.

Whilst humectants can help to moisturise the skin, theyre also a bit of a double-
edged sword. By drawing water up to the top layer of the epidermis, they can also
lead to increased evaporation of water from the skin surface and actually
worsen any dryness, rather than improving it. As such, like the occlusive agents
theyre commonly used in combination with compounds from the other two
groups, rather than individually, particularly as at high levels they can cause
irritation.

The final main group of compounds used in moisturisers are the emollients. In
fact, some compounds that act as occlusive agents can also act as emollients in
moisturisers. When applied heavily, emollients can provide a similar layer on top
of the skin that prevents TEWL. However they can also help prevent water loss
by plugging gaps between dead skin cells in the upper layer of the epidermis.
Additionally they help smoothen rough skin.

Emollients can often be compounds naturally found in the skins epidermis for
example ceramides, cholesterol, or fatty acids. Mineral oil and squalene can also
be used. Compared to the other two groups, emollients have no real issues,
though like occlusive agents they can sometimes be a little greasy.

Not all of the ingredients in moisturisers are there to moisturise. Another


necessary additive is some form of fragrance, to mask the smells of the
moisturising ingredients used. Additionally, preservatives must be used to prevent
the moisturiser from turning rancid. Water-based moisturisers completely free of
preservatives are very hard to come by, because, unless theyre sold in very
small quantities, they run an almost inevitable risk of bacterial contamination
not good news!

Now we know all about the compounds that moisturisers are composed of, just
one question remains: do they actually work? Reviews seem to suggest some
evidence of benefit, but the lack of good quality clinical trials for a large number of
moisturisers has been criticised. As such, whilst they seem to be effective, theres
no evidence to categorically prove that one combination of ingredients is better
than another.

11. Periodic graphics: Why Li-ion batteries catch fire

Chemical educator and Compound Interest blogger Andy Brunning reveals


reasons why the compact components sometimes burst into flame

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