Nanoparticles – small things, big effects

Opportunities and risks

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Nanoparticles – small things, big effects
Opportunities and risks
FOrEwOrd

Foreword

Nanomaterials may be almost invisible, but it is

difficult to imagine our everyday lives without them:
Nanomaterials make our cars safer and more envi-
ronmentally friendly, our medicines more effective
and at the same time more gentle, and our mobile
phones or laptops smaller and more efficient. In
addition, nanotechnology offers great potential for
protecting both the climate and natural resources.
Thanks to nanotechnology, we now have a number
of effective environmental technologies and can
make more efficient use of regenerative sources of Dr. Annette Schavan, MdB
energy. Federal Minister of Education and Research
 1

Contents
Everything Nano, or what? 4

Infobox: Nanos in the summer meadow 5

Nanoparticle Zoo 7

How do nanoparticles come into the world? 8

Industrial production of nanoparticles 10

Unintentional creation of nanoparticles 12
Home-made nanoparticles 12
Material cycle 13
Nanoparticle technology of our ancestors 14

Nanoparticles in the technosphere 16

Palladium nanos on bacterium membranes for catalysis 17

Nanomaterials for new lithium ion accumulators 18
Use of nanoparticles: Silver as bacteria killer 20
Experience with the industrial manufacture of nanomaterials 22
Interview with Dr. Markus Pridöhl 22
Quantum dots 24
Exotic nanos: Graphenes 25

Nanoparticles in the biosphere 26

Nanotechnology for health and medical technology 26

Nanotechnology for food 28
2
CONtENts 3

Health effects of nanoparticles 32

Gateways for nanoparticles 32

Infobox: Asbestos – a story that must not be repeated 33
Nanoparticles – how dangerous? 34
Research on respirable aerosols 35
Risk to the heart and blood vessels 37
Effects of nanoparticles on the skin 38
Interview with Prof. Tilman Butz 38

Public awareness and social debate 40

Nano – the beginnings 40

Nano Hype 40
End of the Nanobots 41
Nano Fakes 42
Nano Myths 42
Nano Disputes 43

risk management in nanotechnology 46

Nanoanalysis as a basis for risk analysis 46

Nanotechnology activities of the Federal Government 47
Nano safety research of the BMBF: NanoCare 48
Interview with Prof. Dr. Harald Krug 48
Activities of industry 50

small particles, large effects – opportunities and risks

of nanoparticle technology 52

Glossary 54

Further Information 56

Index of abbreviations 57
4 EvErytHING NANO, Or wHAt?
Everything Nano, or what?
A nanometre is a millionth of a millimetre.
that is already very small; atoms, the building
blocks of matter, are only ten times smaller.
well over 10 to the power of 10 dots with a
diameter of a nanometre would fit in the dot
on this i. that is more than 10,000,000,000.
Nanotechnology is the art of the knowing utilisation
for our own purposes of structures possessing useful
functions in the size range between 1 and 100 nano-
metres. The word „knowing“ is important, otherwise
even butter making would be nanotechnology, as
milk contains countless nano-scale particles, but this
knowledge is not necessary for churning butter. The
cells of every living creature, every poppy flower, are
packed full of nano-nature.
Nanoparticle technology is restricted to synthetic
particles. This is the technology with the most eco-
nomic importance at present. Nano-scale particles
are already found in paints which break down odour
substances, on surgical instruments which keep
themselves sterile, in sun creams which do not make
one‘s nose white, in tablets which release their active
constituents instantly and so on. The word „nano“
has become so attractive for many marketing mana-
gers that they sometimes write „nano“ on the packet
even when there is none inside. As a rule, nanoparti-
cles possess other properties than the same material
in coarser form.
While the gold in a wedding ring shines yellow,
gold nanoparticles can colour a wine glass red. In
this case that is a consequence of the laws of quan-
tum mechanics, which have different rules for very
small things. Gold is also a very unreactive material
on a large scale, but in the form of nanoclusters it
can be catalytically active, like the platinum in the
automobile catalytic converter.
Nanoparticles are more reactive for geometrical
reasons, as the proportion of surface atoms increases
as the size of a particle decreases. Surface atoms are
strongly inclined to make use of their bonding pos-
sibilities. For this reason, some nanoparticles have
to be stored in inert gas, as they would immediately
burn up in the air. Dust explosions are also conceiva-
ble, but that is not a nano characteristic, as they can
also occur with flour dust. Expensive nano-dusts will
be contained securely for financial reasons alone,
but even more so for reasons of work safety.
The high proportion of surface atoms in nanoclu-
sters and their high proportion of unsaturated che-
mical bonds also make this material state especially
interesting for catalysis - the acceleration of a chemi-
cal reaction without consumption of the catalyst.
Because nanoparticles are so reactive, they also tend
to bond with each other. That must be prevented
with special coatings if the nano-scale advantage
is not to be lost. On the other hand, because of their
bonding affinity, escaping nanoparticles usually
neutralise each other by combining to form larger
units. Even so, wherever inorganic solid, ceramic or
metallic nanoparticles are concerned, there is a need
for scientific research into their safety for humans.
Lurking in the background is the horror word „asbe-
stos“, the carcinogenic effects of which were denied
for years, although clear evidence existed for its
danger (see box on page 33).
The Federal Ministry for Education and Research
is therefore supporting safety research for nanopar-
ticle technology in a number of projects. The risks of
this technology are explained in more detail below,
but also, in particular, the opportunities it offers.
These are, in fact, so great that they should at least in
part be able to neutralise the foreseeable risks of the
clearly unavoidable industrialisation of the whole
world in years to come. The possible risks should
therefore be weighed against the opportunities to be
missed by dispensing with the utilisation of nanopar-
ticles. Binding statements on the extent of possible
risks can naturally only be made after the conduct
of nano-safety research. Until then, research and
industry will make every effort to study and to avoid
any possible harmful effects.
Nanoparticles, by the way, are not confined to
technology - they are building blocks of nature and
are found in every flowering meadow.
EvErytHING NANO, Or wHAt?
Nanos in the summer meadow
Nature is full of nanotechnological subtleties.
Cicadas, for example, protect
themselves against both water
and dirt by means of a coating
containing innumerable „bro-
chosomes“, airy protein globules,
some of which are similar in form
to the famous C60 fullerene, also
known as buckyballs.
Immediately after moulting its
skin, a milky droplet is excreted
from its abdomen and it spreads
this with its legs over its whole
body, where it hardens into a
waxy protective coating.
With a diameter of one nanome-
tre, C60 buckminsterfullerene is
a hundred times smaller than
a brochosome. It also occurs in
nature, in the air after a forest fire,
for example, but filling it with a
foreign atom, such as a nitrogen
atom, has only succeeded in the
laboratory.
Exotic nanoparticles like this
might one day become the com-
puting elements for a quantum
computer.
5
If we zoom in close enough to a
snail‘s head, we see sub-micron
scale, finely formed rasping teeth
made of mineral components.
Also bacteria of course. Their
skins, like those of other cells, are
covered with large numbers of
nano-scale bumps, sensors for the
outside world, the triggering of
which initiates complex cascade
reactions inside the cell.
At the end of this journey stands
a hydrogen atom, the smallest
of all atoms, with a diameter of
a tenth of a nanometre. If it is
„excited“ by the input of energy,
its electron cloud can become
appreciably larger and assume
extremely complicated structural
forms. The hydrogen atom is
where all nanotechnology ends,
as we have no constructive access
to the underlying structures.
6 NANOPArtICLE ZOO
Nanoparticle Zoo
Nanoparticles come in many different vari-
eties, which is exactly what makes them so
technically attractive. And different proper-
ties can be combined in one particle, for exa-
mple hard mineral cores with water-repellent
chemical skins. this can be used to make a
non-scratch, water-repellent car finish.
Nanoparticles can be equipped with numerous
refinements. For example, nanoparticles with a
magnetic core can be given a first coating toxic for
cancer cells, followed by a second coating of antibo-
dies which only adhere to cancer cells. When that
has taken place in the body of a patient („drug tar-
geting“), alternating electromagnetic fields heat up
the magnetic cores, which are now located exactly
where required, and the heat releases the anti-can-
cer substance from the first coating. There are great
and justified hopes that such sophisticated concepts
will represent valuable therapeutic instruments in
the near future. In any case, the nanoparticle con-
cept opens up possibilities not possessed by classical
materials chemical (see chapter Medical Technology
on page 26). The immense number of variations in
which nanoparticles can occur, on the other hand,
makes life difficult for toxicologists. While, in the
case of a simple chemical like sodium chloride (com-
mon salt), the substance is defined by specifying the
chemical formula, NaCl, and the degree of purity, in
the case of a water-insoluble metal oxide nanopar-
ticle, at least the size, the shape and the crystal class
of the particles would have to be specified before
toxicological studies were comparable, for all these
properties can have an influence on the possible to-
Nanoparticles are widely used.
NANOPArtICLE ZOO 7

xicity. In fact, the manufacturing process should also This intellectual concept brought Zwicky many new
be specified, as this determines the impurities on the discoveries in his time, some of which could be profi-
surface of the particle. Characterisation, the reliable tably patented. The diagram below is a first attempt.
recording of properties, is usually immensely more
difficult than for classical chemicals. In fact, in order
to explore all the possibilities of the nanoparticle
concept, a multidimensional representation is nee-
ded, perhaps a „morphological box“ like that of the
deceased Swiss-American astrophysicist Fritz Zwicky.

Nanoparticles can be manufactured in countless variants.

8 HOw dO NANOPArtICLEs COME INtO tHE wOrLd?

How do nanoparticles come into the world?

Nanoparticles are not a human invention. be on the move in the air, invisibly, of course.The
they also occur naturally, although mostly Sahara dust also contains iron compounds which
actually fertilise the regions of the ocean they fall
in forms other than those useful for industry.
on. Fast growing algae then emit dimethyl sulphi-
the sand in Mark Brandenburg, for example,
originates from weathering of the so-called
Baltic shield, a mountain range with peaks
which once reached the cruising altitudes of
today‘s large passenger planes. Its destruc-
tion must have released millions of tonnes
of nanometre fine particles into the environ-
ment, for there is no law of nature which says
that weathering should stop at the nanome-
tre scale.

Actually, weathering products at nanometre scale

tend to combine together again to form larger parti-
cles. Technical nanoparticles are generally protected
against this by special coatings, so that the technical
advantages of the nano-scale are not lost. At the
same time, the dust storms of the Sahara, which blow
so much sand over the ocean that the clouds can be
seen from space, give an idea of the amount of nano-
The Sahara releases huge quantities of mineral dust annually, including
scale quartz, silicon dioxide (SiO2 ), which might nano-scale particles. Such dust usually consists of mixed oxides of the
elements silicon, aluminium, titanium, iron, potassium and calcium.

de, which forms microscopic crystals in the air - no

doubt also nanoparticles. When these reach high al-
titudes, water droplets condense on them and clouds
are formed: nanoparticles as rain makers.

This dust even lands on German car roofs, but the nano-scale fraction is
invisible.

Elements like silicon are synthesised in stars, are found as nanoparticles

in the stellar atmosphere and in interstellar space and fall continuously
on the earth.
HOw dO NANOPArtICLEs COME INtO tHE wOrLd?
The iron in seawater also combines to form nano-
particles, in magnetotactic bacteria. These form
chains of nanometre fine magnetite crystals. They
have a good reason, for the magnet chains act like
compass needles which can guide the bacteria into
different water layers according to the inclination
of the earth‘s magnetic field. In this way, they reach
Volcanic eruptions release huge quantities of nanoparticles.
9
Sand deposits are the remains of weathered mountains. The weathering
process also creates nanoparticles, mainly by wind erosion in the case of
exposed sand.
layers with particularly good living conditions. The
bacteria sink to the ocean bed in such masses that
they are regarded as candidates for the formation of
iron ore deposits. And when they sink to the seabed,
they lay themselves parallel to the earth‘s magnetic
field at the time, thus recording its orientation for
posterity. So nanoparticles have become witnesses
for so-called Sea Floor Spreading, the drifting apart
of sections of the earth‘s crust on the seabed. There
has never been a shortage of magnetite particles.
Bathers can swallow them, even in fresh water, for
magnetotactic bacteria are everywhere. Their nano-
particles of magnetite are so perfect, by the way, that
they are being researched for high-tech applications
in medical technology.
Magnetotactic bacterium.
10 HOw dO NANOPArtICLEs COME INtO tHE wOrLd?

Left: Networks of carbon atoms can assume many different forms,

including, starting at the top: C80 fullerene, cone, double-walled carbon
nanotube (DWNT), triple-walled carbon nanotube (MWNT).

Seemingly exotic particles are also created naturally.

Just a forest fire is enough to produce the full palette
of so-called fullerenes: Buckyballs, Buckytubes, Gra-
phenes – everything worthy of a name in the latest
carbon chemistry.

Industrial production of nanoparticles

There are two different principles for obtaining

nanoparticles. A large piece of material can be con-
tinually broken down until the fragments attain the
dimension of nanometres. An example is the widely
used industrial method of grinding mineral compo-
nents with ball mills. In order to attain nano dimen-
sions, powders with typical particle sizes of 50 µm
are placed, together with balls of hardened steel or
tungsten carbide, in a closed container which is then
violently agitated. With this method, particle sizes
from three to 25 nm can be achieved. Processes like
this come under the heading „top-down“, i.e. from
larger to smaller structures. This principle of minia-
turisation has been applied in information techno-
logy for decades to produce ever more powerful and
handier electronic devices such as notebooks, mobile

Plasma reactor at the

Nanotechnology Centre of
the University of Duisburg-
Essen. The yellowish glow
in the upper part of the
plasma flare is caused by
the hot particles. Many
nanoparticles are indus-
trially manufactured in a
similar way.
HOw dO NANOPArtICLEs COME INtO tHE wOrLd? 11

phones or MP3 players. The other method consists of reacts with this gas to form a compound; in the case
building up nano-scale particles from the smallest of a noble gas, nanoparticles of pure metal are for-
available building blocks, atoms or molecules. Such med. These particles bond so readily that they joint
methods are labelled „bottom-up“. That is nature‘s to form alloys at low temperatures; in this way, brass
preferred method. is formed from electro-exploded copper and zinc
An example of the „top down“ method: If nano- powders at only 200 °C.
particles are to be manufactured from a specific ma- A very popular „bottom-up“ method, the so-
terial, suitable input substances must be found. For called sol-gel technology, makes use of tricks
the production of iron nanoparticles, for instance, a reminiscent of kitchen practices like the making of
compound of chlorine and iron, FeCl3, can be finely mayonnaise. Mayonnaise consists of a mixture of ex-
ground with sodium in an inert atmosphere in a tremely fine vinegar droplets in oil, largely produced
ball mill. The two substances react together to form by vigorous stirring. Similar mixtures of substances
nano-scale iron and sodium chloride, common salt, are used in industry to create nanoparticles. When
which can be simply washed out with water. What these particles are formed by the reaction of two
remains are the iron nanoparticles.
One particularly spectacular „top down“ method
is the electro-explosion. Here, a very short, but very
powerful pulse of current flows through a thin metal
wire. The wire becomes so hot, 20,000 to 30,000 °C,
that it breaks down into its atomic constituents, only
continuing to exist as a glowing cloud of plasma,
held together by the strong magnetic field accom-
panying the current impulse. This all takes place in
a closed, gas-filled container. The metal cloud then

Fit for the finest particles: Sol/Gel particle reactor.

Homemade nanoparticles in mayonnaise. All you need is a powerful

mixer. Most of the fat/vinegar droplets are on a micrometer scale, other-
wise the mayonnaise would be clear.

components, one of which can only exist in droplets,

and the other is introduced through the carrier
substance, the two substances react together in the
limited reaction volumes of the droplets and the
reaction stops when the particles are nano-scale.
12 HOw dO NANOPArtICLEs COME INtO tHE wOrLd?

Unintentional production of nanoparticles

There are numerous methods of producing nano-

particles, and new ones are continually being found.
On the question of the toxicity of intentionally and
unintentionally produced nanoparticles, there
currently exists – even – more reason to worry about
unintentionally produced nanoparticles. A study by
the European Union, „Industrial application of nano-
materials – chances and risks“, states:

„Unintentionally released nanoparticles, created by

combustion processes in traffic or in energy conversion,
in mechanical wear processes or conventional industri-
al processes, currently contribute more to anthropoge-
nic nanoparticle emissions than industrial nanoparti-
cle production.“ The unfiltered exhaust gases from diesel engines contain large
quantities of potentially harmful nanoparticles from the incomplete
combustion of fuel.

Homemade nanoparticles

Organic nanoparticles can be easily made with kit-

Even in the fireplace at home, fullerenes like Buckyballs or Buckytubes
are formed when wood is burned.
chen utensils: just a powerful mixer, vinegar and oil.
If you are aiming at the stars of today‘s nanoparticle
scene, just pour some lead: the soot which condenses
on the bottom of the spoon contains buckyballs,
buckytubes, graphenes – and nanodiamonds.

Nanos when pouring lead: The soot of a candle flame contains hydrocar-
bon particles in countless forms, including fullerenes and diamonds.
HOw dO NANOPArtICLEs COME INtO tHE wOrLd?
Material cycle
Humans can come into contact with nanoparticles
at almost all points in the industrial material cycle.
The aim of the safety research is to eliminate any
risks which might accompany the many anticipated
positive consequences of nanoparticle technology.
What is more, by means of nanotechnology, many
13
proven harmful substances will be able to be re-
placed by common, non-toxic substances, which can
also be manufactured using less energy. Just one ex-
ample: the replacement of toxicologically objection-
able cobalt blue by a pigment made of clay particles
and indigo according to an old Mayan recipe
(see p. 14).
Nanoparticles in the material cycle.
14 HOw dO NANOPArtICLEs COME INtO tHE wOrLd?

the nanoparticle technology of our ancestors The blue of this old Mexican figure
is a highly stable nanocomposite
of a porous clay mineral and an
organic pigment. The nanopig-
Humans have been making technical use of the ment is now produced again as
properties of nanoparticles since prehistory, but Mayacrom® and replaces toxic
heavy metal compounds.
they did not know it. Perhaps the oldest examples
are objects made of clay. Clay largely consists of the
mineral kaolinite, which has a structure of very thin
platelets, only a few tens of nanometres thick. These
are white, soft and very malleable, but, most impor-
tantly, they slide readily over each other when the
mineral has absorbed water. That is why clay is so
smeary and easily formed.
Starting from the eighth century, the Mayas
were able to paint their clay figures with a high-tech
pigment which, once again, contained a clay mine-
ral, this time palygorskite. The translucent mineral
sometimes forms felt-like mats at its deposit sites, so
it is sometimes known as „mountain leather“. The
mineral is perfused with nanometre thin channels
which are filled with water. By heating the probably
pulverised material and adding blue organic indigo
pigment, the Mayas succeeded in synthesising an
inorganic-organic composite material, a pigment of
high stability which could resist the ravages of time.
In the USA, the firm MCI Mayan Pigments, Inc. is now
producing the old pigment once more.
Damascus blades enjoyed great renown in the
Middle Ages because of their filigree markings, their
sharpness and, above all, their fracture toughness.
For a long time, modern metallurgy was unable to
find a scientific explanation for these properties; at
the end of 2006, however, scientists of the Institute
for Structural Physics at the Technological University
of Dresden discovered the probable solution to the

Top: Kaolinite
particles under the Damascus blades owe their hardness and strength to embedded
electron micro- carbon nanotubes.
scope. The mineral
is an important
component of clay.

Left: Nanotechno-
logy from the stone
age, 3000 B.C.:
Mehrgarh clay figu-
rine, exhibited in the
Musée Guimet.
HOw dO NANOPArtICLEs COME INtO tHE wOrLd? 15

puzzle: Damascus blades contain carbon nanotubes, brilliant red in church windows is caused by a colloi-
so-called buckytubes, some of which are filled with dal, or in other words, an extremely fine, nano-scale
cementite, a compound of iron and carbon. It is dispersion of gold. This colour endures for centuries.
clearly this nanowire reinforcement which gives
the Damascus blades their legendary properties, or
at least explains their fracture toughness. The early
smiths could not have known about the nanoscopic
factor in their success, but researchers today believe
they were skilled in experimenting with additives of
wood and leaves and special iron ore from India.
The mediaeval makers of stained glass windows
also understood colouring with nanoparticles. The

Amiens Cathedral. The red in the mediaeval windows is due to colloidal

nano-scale gold.
16 NANOPArtICLEs IN tHE tECHNOsPHErE

Nanoparticles in the Technosphere

If all 800 million vehicles which now exist
were to be converted to an environmentally
friendly fuel cell technology requiring plati-
num as a catalyst, the earth‘s economically
useful platinum reserves would be exhausted
within 15 years, estimate scientists.

Indium, which, among other things, is indispensable

in the computer industry for the manufacture of flat
screens, says the U.S. Geological Survey, could be the
first high-tech element to run out, possibly in as soon
as ten years.
If not for all, for many of the high-tech elements
which are becoming scarce, nanoparticle technolo-
gy will be able to provide a complete replacement,
largely made of inexhaustible elements such as
In a crystal, the atoms are stacked like fruit in a bazaar. If the tomatoes
carbon and silicon. Before that, it can research and are to remain whole, only certain planes can be laid through the stack,
utilise the sophisticated laws of the nanocosmos for these being more or less stepped according to inclination.
improvements, increasing efficiencies and making
massive savings in material, including platinum.
Platinum is usually catalytically active (accelerating elementary building blocks, atoms or molecules, are
a chemical reaction without itself being consumed) stacked regularly, like tomatoes at the greengrocer.
in the form of submicroscopic crystals. In crystals the Arrays of spheres packed like this cannot be divided

Simulation of a gold cluster, including models of the crystal surfaces. In

the basic state on the left, smooth atomic surfaces are formed by prefe-
Computer simulation of a nanoparticle with a gold core and a silver skin. rence; the excited state on the right has rough atomic surfaces which, as
Preferred planes can also be recognised in the stacks of atoms. a rule, would be more active in a catalyst.
NANOPArtICLEs IN tHE tECHNOsPHErE
Perfect palladium nanocrystals grow in the pores of a bacterium
membrane.
by planes at all angles because, unlike tomatoes,
atoms cannot be cut through. Among the many
boundary planes of the crystal which are still possi-
ble, the atomically smooth are preferred by nature,
in which as many surface atoms as possible have
fixed bonding partners. Then, as a rule, however, the
catalytic activity, for which free bonds („dangling
bonds“) are mainly responsible, is not as high as that
which occurs on atomically rough interfaces. These
„exotic“ crystal surfaces can also be stabilised by
alloying with different elements.
Nano-scale particles also make it possible to
resort to less active substances for catalysis, for at the
nanometre scale even otherwise unreactive metals
like gold become active, semiconductors become
metals and metals become semiconductors.
A particularly refined nanoparticle variant has
now been synthesised by Peter Strasser at the Uni-
versity of Houston, Texas, USA. These particles have a
core of copper and cobalt and a skin of platinum and,
in a fuel cell, have from four to five times the catalytic
activity of pure platinum for the cleavage of oxygen
required.
17
Palladium nanos on bacteria membranes for
catalysis
Sometimes nanoparticle technologists discover
unexpected helpers, like Bacillus sphaericus JG-A12.
This bacterium was discovered in 1997 by a team
of biologists from the Research Centre Rossendorf
(FZR) on the uranium ore waste heap at Johanngeor-
genstadt in Saxony, where it had developed a very
robust protein shell as protection against the heavy
metal uranium. Large areas of the shell are cove-
red with a very regular pattern of nanometre fine
pores. When the FZR scientists placed the skin of the
bacterium in contact with a salt solution of the noble
metal palladium, using infrared spectroscopy, they
observed a close bonding of the salt complexes with
their substrate. Finally, when the palladium salt was
chemically transformed into the pure metal, minute
nanoclusters grew in the pores, small, regular collec-
tives of atoms with only from 50 to 80 members. The-
se nanoclusters display considerably higher catalytic
activity than conventionally dispersed palladium, for
example in the decontamination of vehicle exhaust
gases.
18
The FZR scientists want to extend their bacterial
clustering method to other noble metals such as
gold. As they have very precise knowledge of the
nature and location of the bond between the noble
metal and the skin of Bacillus sphaericus JG-A12, they
should be able to trim the shell of the bacterium for
the purpose by means of gene technology. Then, the
uranium heap dwellers could even be used to ma-
nufacture materials with new magnetic and optical
properties.
So surprises are possible at any time in the nano-
cosmos. The nanoparticle technology will play a very
crucial role in overcoming future material shortages.
Uranium ore waste heap, home of „Bacillus sphaericus JG-A12“, which
possesses a tough skin with regular arrays of pores.
Apart from this, the history of raw materials has
always been very changeable. The 17th century,
for example, was entirely untroubled by the lack of
platinum. In the Columbian region of Chocó, the
metal, which was recovered together with gold, was
regarded as an undesirable impurity which had to be
expensively sorted out by hand. In the end, howe-
ver, they did find a use for it, even if an illegal one:
A gold plated platinum bar could be sold as a gold
bar, because the density of platinum is similar to that
of gold. This made the deception hard to detect. In
order to put an end to this problem, the government
simply had large quantities of platinum collected
and sunk in the Bogotá River.
Nanomaterials for new rechargeable lithium
batteries
The vehicles of the future would not necessarily
have to be loaded with chemical fuels if accumula-
tors existed which could take up large quantities of
NANOPArtICLEs IN tHE tECHNOsPHErE
With nano-scale sintering agents, the foil can be burnt (sintered) at a re-
latively low temperature and thus inexpensively produced „roll to roll“.
electrical energy in a short time. These do not exist
yet, but their realisation appears likely if the develop-
ment to date of the lithium ion rechargeable battery
continues at the same pace. Optimism is justified by
the refinement of certain details, such as the „sepa-
rator“. Lithium ion accumulators require a separator
layer which, on the one hand electrically separates
two electrodes differently charged with lithium ions
and, on the other hand, allows lithium ion to pass
when required. A particularly attractive separator
comes from Germany, made by Evonik Industries AG,
formerly Degussa. The firm has developed a polymer
fleece with microfine layers of aluminium oxide
ceramic, made possible because nano-scale sintering
agents allow the baking and sintering of the alumini-
um oxide particles at relatively low temperatures. The
composite material, contrary to the suggestion of the
term „ceramic“, is so flexible that it can be manufac-
tured and wound in a rolling process, like paper. This
material, known as SEPARION®, promises to make
lithium ion accumulators even safer and to increase
dramatically the cycle stability (the number of charge
NANOPArtICLEs IN tHE tECHNOsPHErE
and discharge cycles possible without significant fall
in quality). Evonik Industries AG claims ten thousand
cycles for SEPARION® equipped accumulators, twen-
ty times more than can be expected from a current
notebook battery.
However, even in new accumulators, the energy
storage density leaves much to be desired. Here, with
the help of nanoparticles, which can be produced in
a plasma torch, there is hope of an improvement by a
factor of three or more - if a number of complications
can be sorted out. In the case of success, use for electri-
cal vehicles would be the next step, particularly since
inexpensive power electronics is now available for the
efficient control of electric motors. There are also new
magnetic materials for lightweight, high perfor-
mance motors - also made possible by nanoparticle
technology. The lithium ion accumulators would also
Lithium ion accumulators of the latest generation have a ceramic se-
parator foil which makes them very much more robust, both thermally
and mechanically.
19
be supported by very fast charging and discharging
supercapacitors (Supercaps) with nano-scale dielec-
trics, with which power generated, for example, by
braking of an electric vehicle could be immediately ta-
ken up and then, appropriately regulated, passed on
to the lithium ion accumulator. Conversely, supercaps
would contribute to power surges for acceleration.
The development of new lithium ion accumulators
and supercapacitors is supported by the BMBF with
considerable funds in the joint projects LiBaMobil and
NanoCap.
The high cycle stability of the new lithium ion
accumulators would also make them suitable as effi-
cient, mobile electricity storage for balancing power,
thus simplifying the expansion of renewable energies
such as wind and sun, with their natural fluctuations.
separator
Negative electrode
separator
Positive electrode
20 NANOPArtICLEs IN tHE tECHNOsPHErE

Use of nanoparticles: silver as a bacterium killer

Of the metals quoted in connection with nanopar-

ticle technology, silver is currently the second most
frequently mentioned, both in praise and in war-
ning, by reputable and dubious sources. The metal
is an old acquaintance in the history of technology
and has been used for at least 8000 years. Alexander
the Great is already said to have valued the sterilising
effect of the metal and, therefore, to have favoured
water containers of silver. In recent times, the anti-
bacterial effects of silver, frequently used in the past,
have been rediscovered, as the growing resistance
of many organisms to standard antibiotics makes
alternatives desirable.
As in other metals, transformation of silver to its
nanoparticle state changes a number of properties.
In comparison with the tangible metal, for example,
silver nanoparticles, have a stronger effect per mass
on bacteria and viruses, merely because of the higher
proportion of surface atoms. While sections of alter-
native medicine ascribe to silver ions almost magical
effects on body and soul, environmental protection
organisations see a great danger in silver nanoparti-
cles and are therefore demanding a halt to the sale of
washing machines with built-in silver nanoparticle
generators.
The manufacturer points out that, while his PR
„refers to silver nanoparticles, these do not possess
Over the decades, through the fixation of black and white photographs
any altered properties, but, from a chemical point of alone, hundreds of tonnes of nano-scale silver have been released into
view, are still silver ions. However, these are ascribed the environment without detectable consequences.
the strongest anti-bacterial effect.“
The cacophony of disputing voices is a clear sign
of one thing: the need for research and education. silver loadings in Vienna‘s waste water were caused,
Without anticipating the results of the research con- as also in the waste waters of other municipalities, by
cerned, it must be said that the industrialised coun- the discarded wastes from photochemical processes
tries already have many years of experience with (fixing baths).
extremely finely dispersed silver in the environment, These amounted worldwide to 500 tonnes of
involuntarily and everywhere. In the year 2000, the silver per year. No disastrous consequences have yet
City of Vienna alone complained of a silver loading been reported. However, this figure represents an
of 1 tonne per year in its waste water, which passed enormous waste. In 2005, the much quoted material
into the sewage sludge, which was incinerated and scientist Armin Reller from the University of Augs-
the ashes of which were then spread over the fields burg estimated the reserves-to-production ratio
as fertiliser. As the content of the sludge ash threa- of silver, calculated from demand, production and
tened to exceed the permitted limit of 50 mg silver geological availability (all assumed as remaining
per kilogramme ash, abandonment of the process constant), at only twelve years.
was recommended. Elsewhere, including in Germa- If all the estimated 400,000 washing machines in
ny, the spreading of unincinerated sewage sludge Vienna were silver machines and if they emitted the
components as fertiliser is possible. These masses 0.05 gram silver per year specified by the manufac-
must inevitably contain finely dispersed silver. The turer, this would amount to 20 kilograms per year or
NANOPArtICLEs IN tHE tECHNOsPHErE 21

2 % of the silver annually tipped down the drain by

thoughtless photo amateurs - before the advent of
digital photography.
A whole series of small and medium sized enter-
prises are currently researching possibilities of using
the anti-bacterial effects of colloidal silver for wor-
thwhile products. One of these is Bio-Gate in Nurem-
berg, which, in collaboration with scientists from
the Fraunhofer Institute IFAM in Bremen, coats the
surfaces of medical instruments with anti-bacterial
silver. This can be very useful, since organisms can
get into the body by way of contaminated catheters

Raster electron microscopic image of silver nanoparticles, mean prima-

ry particle size 50-200 nm

and scalpels, leading in the worst case to a sepsis,

extremely dangerous blood poisoning. More people
die from inflammations caused by infected catheters
than in road accidents.
The potential risks of nanoparticle technology
must always be balanced against the risks they elimi-
nate.

Photo above: Transmission electron microscopic images of silver nano- Photo below: Prototype of a silver-coated catheter. The silver can also
particles, embedded in a silicon oxide plasma polymer film. destroy organisms which have become resistant to antibiotics.
22
Experience with the industrial manufacture of
nanomaterials
Industry has decades of experience in the handling
of nanomaterials, only they used not to be identified
as such. The production volumes for the nanostruc-
tured tyre filler carbon black, for example, amount
to millions of tonnes per year. This great expertise
naturally makes the standpoint of the industry parti-
cularly interesting.
„the law says, put simply, that we have a duty
to put products into circulation safely. And
that is all it says. It does not matter whether
the products are nano, micro or macro.“
dr. Markus Pridöhl, Coordinator of Nanotech-
nology at Evonik Industries AG
At the same time, one thing is very clearly in the
interest of industry. The economic significance of
the development is so great that any setbacks due,
for example, to a lack of safety awareness would be
very damaging – a warning example here is gene
technology.
NANOPArtICLEs IN tHE tECHNOsPHErE
Interview with dr. Markus
Pridöhl, Coordinator of
Nanotechnology at Evonik
Industries AG
How big is a nanoparticle?
The current definition of a nanoparticle proposed by
the International Standards Organisation, ISO, says:
between approx. 1 and 100 nm.
But „between 0.1 and 100 nm“ is also seen. The
lower limit there would be in the range of the atoms?
These definitions must be harmonised. If every
institute has its own definition, we shall continue to
talk at cross-purposes. That is why I am very much in
favour of the consistent use of internationally stan-
dardised terms in order to avoid misunderstandings
and to make progress in the field.
What does that mean for your products?
According to this definition, Evonik Industries AG,
formerly Degussa, does not make nanoparticles, but
nanostructured materials in the form of aggregates.
These aggregates are constructed of nano-sized buil-
ding blocks and therefore display the same specific
surface as nanoparticles, but they are much larger
than the individual building blocks.
Are there any other reasons for norms and stan-
dards?
ISO standards are also important for the preparation
of nanomaterials and nanoparticles for toxicological
tests. Very many references in the literature are of
little practical use because the materials, for an in-
halation or a cell culture test, for example, have not
been reproducibly prepared. If you do not know how
large these particles are or how they are dispersed,
you cannot retroactively derive any effects related
to particle size from these studies. It is therefore very
important to introduce much higher quality stan-
dards into scientific work of the subject of toxicolo-
gy with nanoparticles or nanomaterials, and here
standards in the field of sample preparation would
also be helpful.
„Nanoparticles“, „nanostructured materials“, is that
really more than just splitting hairs?
Absolutely. For instance, we manufacture our oxides
in flame reactors. In these reactors, the nanoparticles
just formed meet at such high temperatures in the
gas phase that they melt and form aggregates which
are really fused together. These aggregates possess a
surface chemistry that leads to a further very strong
NANOPArtICLEs IN tHE tECHNOsPHErE
mutual attraction and, as a result, they continue to
agglomerate, becoming even larger.
So, when you finally pack your powder into a sack
and put it on a train, it is agglomerates, or larger
particles?
Exactly.
What experience does Evonik have with the safe
handling of your nanostructured materials?
We have been producing the reinforcement fillers
silicon oxide and carbon black for 60 years, and
nanostructured titanium dioxide for more than 35
years. Today, we manufacture more than a million
tonnes of these materials. So we really have extraor-
dinarily wide and longstanding experience with our
products, including their safe handling. Years ago,
we founded a special department in which experts
work on techniques for the low-dust handling of
our products. With this knowledge, we first give our
customers support with correct and safe handling.
Secondly, however, it also contributes to reducing
dust at the workplaces in our firm. For the manuf-
acture of nanostructured products, we largely work
in closed facilities, often additionally with negative
pressure, which guarantees safety, even in the case
of leaks. Our employees have also been subject to
medical examinations for over 33 years.
Among other things, these include lung function
tests, resting ECG, blood pressure measurements
and a normal anamnesis interview in which the
employee is questioned about any health problems.
The studies have given no indication of anomalies in
comparison with the „normal“ population.
What is so special about the titanium dioxide
produced by Evonik?
The special feature of our nanostructured titanium
dioxide is that it is transparent for visible light, but
absorbs or reflects UV radiation. These properties are
used in cosmetic products, especially in sun creams.
The advantage is that the sun cream cannot be seen
on the skin, but the skin is particularly effectively
protected against UV rays.
Skin contact appears to be harmless!
In fact, the safe use of titanium dioxide in cosmetic
products has been documented by a large number of
independent studies.
How do you deal with open questions on safety?
We take part in worldwide activities for the respon-
sible handling of nanotechnology. Nationally, those
are the BMBF project NanoCare for safety research
and the corresponding VCI, DECHEMA and DIN wor-
king groups. Internationally, the ECETOC, OECD and
ISO should certainly be mentioned. In addition, we
23
conduct our own research projects as a complement
to these activities or to establish the specific connec-
tion with our products.
What does that mean in concrete terms?
For example, we investigated the question of
whether our nanostructured products can break
down in the lung into smaller nanoparticles. We
tested, both with experiments and with theoretical
calculations, using the example of titanium dioxide,
what energy is needed to break down the agglome-
rates. As a result, we could prove that the agglome-
rates are stable in lung fluid. The lipids in the fluid,
which enclose the agglomerates and could theoreti-
cally disperse them into smaller nanoparticles, sim-
ply cannot produce the energy input which would
be necessary to break the bonding energy between
the agglomerates, to say nothing of that between
the aggregates. And we have been able to verify this
in corresponding in-vitro experiments. But it has
also been confirmed by current experiments carried
out within the framework of NanoCare: The agglo-
merates of titanium dioxide are found in the lungs
of animals exactly as they were previously inhaled
with careful measurement of the particle size in the
gas phase. So there are a number of indications that
these agglomerates do not break down in the lungs.
For the macroscopic „mother substances“ of the
nanoparticles, there are regulations such health and
safety ordinances, toxicological classifications etc.
Can these regulations be applied to the correspon-
ding nanoparticles, to which new properties are
ascribed?
The law says, put simply, that we have a duty to put
products into circulation safely. And that is all it says.
It does not matter whether the products are nano,
micro or macro. That means, we are obliged to assess
products with regard to their safety, and that is what
we do. So there is no need for additional regulati-
on. There is a need, however, for the development
of additional, refined testing methods. And that is
the reason why we also participate very actively at
different levels, national and international, in the
development of corresponding refined methods.
24 NANOPArtICLEs IN tHE tECHNOsPHErE

Quantum dots close to the ancient hair-dying method quantum dot

high-tech can be.
The researchers dipped a thin glass tube, 75 mi-
Even the most modern of concepts, like the nano crons in diameter, in a solution of lead sulphide na-
quantum dot, were already used, unknowingly, in nodots (PbS) they had obtained by heating a mixture
ancient times. Two thousand year old Greek reci-
pes for the darkening of unwanted fair or grey hair At the Institute for Scienti-
fic Computation of the TU
specify a paste of lead oxide and calcium hydroxide
Dresden, within the fra-
which, when used repeatedly, still darkens hair mework of the EU project
today. Researchers at the Centre de recherche et de re- „MagDot“, the researchers
want to find out by mathe-
stauration des musées de France have now been able,
matical simulation how
with the help of an electron microscope, to show regular quantum dot struc-
why: the hair protein keratin obviously produces tures can be manufactured
- for tomorrow‘s terabyte
crystallisation pits (also see: Nanos on bacterium
memories.
membranes, p. 9), in which quantum dots of lead
sulphide form, nanocrystallites with a diameter of
about 5 nanometres. The sulphur comes from the
sulphurous amino acids in the keratin. Quantum
dots, crystallites like those in ancient hair-dye, owe of oleic acid (the main constituent of olive oil), lead
their special characteristics to the restraints presen- and sulphur compounds and then drying it all with
ted by their minute size for the motion possibilities of a hot air blower. A uniform PbS quantum dot layer
their electrons. was deposited on the inner surface of the tube and
While electrons can assume countless different the world‘s first liquid born infrared laser, in which
energy states in an extended piece of metal, in a the light spirals along the inner wall of the tube, thus
quantum dot, because of its size, only much more becoming coherent laser light.
limited ranges are possible. This can make grey ma-
terials brightly coloured, for example.
Naturally, much more is hoped of quantum dots.
They are seen as potential elements for a quantum
computer, which should be able to solve certain
classes of mathematical problems in a fraction of
the time taken by any conceivable conventional
computer. Self-organised quantum dots could be the
The micron-sized „Optical Resonator“ contains quantum dots of
memory elements of the terabyte hard discs of the nanometre size. With this structure, Karlsruhe scientists are studying
next generation. If an iron-platinum compound is light-material interactions.

All glasses contain

cadmium disele-
nide nanoparticles,
only the varying
particle sizes
producing the dif-
ferent fluorescence
colours.

vaporised on to a silicon wafer, it naturally forms tiny

islands which can be influenced magnetically, so can
carry one bit of information. In order to make tech-
nical use of this effect, it must be possible to control
the growth of these islands precisely, if possible with
computer simulations. A team of scientists from To-
ronto University, Canada, demonstrated in 2006 how
NANOPArtICLEs IN tHE tECHNOsPHErE
Exotic Nanos: Graphenes
In the course of the voyage of the natural sciences into
the nanocosmos, real surprises continually come to
light, things no one had expected. This includes the
art, using only a soft pencil, of putting oneself in con-
ditions similar to those at the edge of a neutron star,
and that happens as follows:
Graphite is pure carbon in a special crystalline
form, consisting of stacks of carbon networks. Within
a network, the carbon atoms are firmly fixed together,
but the individual networks or layers are very loosely
connected, so that they can easily slide over one ano-
ther. That is how a pencil with a lead mainly consisting
Graphenes are 0.15 nm thin networks of carbon atoms only. With their
physics, phenomena at the edge of a neutron star in a galaxy can also be
described.
of graphite can be „soft“. In writing, layer after layer is
detached from the graphite crystals in the pencil lead.
Naturally, scientists were not slow to think of isolating
such a single-atom layer for study purposes. However,
the theory predicted its immediate collapse. Without
a supporting substrate, a single graphite layer known
as a „graphene“ could not be made. Until 2004, that
is, when such layers were discovered experimentally.
In March 2007, experimenters, from the Max Planck
Institute among others, were able to report free gra-
phene flakelets with an area of a square micron and
containing 30 million atoms. Such areas are tiny, but
they could serve as networks for electron microscopes
which do not cast a shadow in the electron beam and
could possibly hold a single molecule for examinati-
on. The graphene layers owe their stability to the fact
25
that they are slightly crumpled, like paper which has
been wrinkled and then flattened again.
These crumpled graphite networks are currently
regarded as really hot stuff in the physics world, not
just because of their suitability for electron microsco-
py, of course. The electrical properties of the monoa-
tomic layers are even more amazing. They display the
so-called quantum echo effect, for which Klaus von
Klitzing still had to reach temperatures near absolu-
te zero, at room temperature, along with a series of
related effects. Then the constraint of conductivity
to a layer only one atom thick imposes a bizarre kind
of collective behaviour on the electrons. They form
quasi-particles which appear as light speed electrons -
the idea of superfast switches has already appeared in
the literature. What is more, the electrical properties
of the graphite flakelets are described using mathe-
matics also applied to extreme conditions like those
prevailing at the edge of a neutron star. Anyone wri-
ting with a pencil produces large numbers of graphite
flakelets, so pencils lead directly into highly stressed
regions of the cosmos.
The methods used for manufacturing free mo-
noatomic graphite layers are at present not the kind
to arouse the enthusiasm of the chip industry – one
method is actually to apply adhesive tape to graphite
layers and to peel them off until only one layer is left.
But if larger, reliably reproducible, mass producible
graphenes were available, they would certainly find
numerous applications. The carbon networks should
really be able to be structured photolithographically,
so that any desired pattern could be applied. In this
way, quantum mechanical model systems might be
created for the most intricate of tasks, like the mathe-
matical simulation of a neutron star.
Not untypical for nano: From something as insi-
gnificant as a pencil mark, through knowledge (and a
relatively modest budget), the potential is created for
something very big.
26 NANOPArtICLEs IN tHE BIOsPHErE

Nanoparticles in the biosphere

Particularly great hopes are held for medi-
cal applications of nanoparticle technology.
Nanoparticles can be made multilayered
or in the form of hollow spheres, so a large
number of functions can be accommodated
in the small particles. Here, their ability to
move through the body without apparent ob-
structions is both an advantage and a disad-
vantage.

Nanotechnology for health and medicine

A major problem of conventionally packed drugs is

that they mostly act not only at the point intended,
but throughout the body. So most highly potent can-
cer drugs also affect healthy tissue. Packed in nano-
particles coated with antibodies, they could in future
be released directly on the tumour. Another compli-
cation: If drugs are not water soluble, they cannot be
taken up (unpacked) by the blood and transported to
their point of action.
These and other problems can be tackled with
new, highly variable encapsulation techniques
which, for example, solve the problem of water
insoluble active constituents as follows: First, the
Capsulution has also begun to develop drug delivery systems for the
selected active constituents are reduced to nano- transport of active constituents into human cells, a matter of great
particles, which are suspended in a solution and importance for gene therapy, for example. In comparison with other
products, in particular, greater precision in application and less side
coated with polyelectrolytes. A polyelectrolyte is a
effects are claimed for these highly complex systems.
polymer whose individual building blocks carry an
electrolyte which sheds ions in water. The remaining
polyelectrolyte coating of the nanoparticle is then
electrically charged and the shell, with its contents,
can move freely in the water, so, as a unit, it is now
Nano-scale highlighters, an innovative diagnostics system for the highly
sensitive and precise early detection of disorders. water soluble. There is no need to stop at one shell.
The addition of a polyelectrolyte solution with oppo-
site charge leads to the growth of a second coating,
repetition of the procedure to a third and so on, layer
by layer. Typical capsule walls have 4 to 20 layers and
thicknesses between 8 and 50 nm. The technology,
developed with support from the BMBF in a joint
project, among others, at the Max Planck Institute
for Colloidal and Interface Research in Potsdam and
commercialised and patented by the spin-off firm
Capsulution, permits the manufacture of nanocap-
sules of different sizes with almost any pharmaceu-
NANOPArtICLEs IN tHE BIOsPHErE
Precise planning in 3D: The physician can decide the quantity of nano-
particles to be applied before the treatment.
tical, biochemical, electrical, optical and magnetic
properties. Interest is correspondingly great.
Ambivalence with MagForce Nanotechnologies
Nanoparticles are so small that, in watery tissue
(and humans consist of 70 % water), they can move
much more freely than larger particles. This much is
known, but there is a lack of detailed studies of the
mobility of nanoparticles in tissue. What is more, in
the few studies available, unrealistically high parti-
cle concentrations have been used, so that it is not
clear for most nanoparticle types whether and how
they are absorbed by the body, how they disperse in
the body and how they change, congregate or are
excreted.
As far as the penetration and deposition of nano-
particles are concerned, the lungs are regarded, for
obvious reasons, as the organ most at risk. They pos-
sess a very large internal surface for the exchange of
gases which can be penetrated by any nanoparticles
27
in the air, so that the particles can then be distributed
throughout the body by the circulation of the blood.
Certain nanoparticles can pass through lipid double
membranes, so they can penetrate cell organelles
such as mitochondria or enter the nucleus of the
cell. Negative consequences include inflammatory
reactions, blood clotting irregularities, deposits such
as plaques, heart rhythm disturbances and disorders
of the respiratory tract.
On the other hand, medicine has recently been
attempting to make use of the absorbency of the
lungs for nanoparticles for better medication,
against lung cancer, for example. In this case, special
organic nanocapsules introduce the enzyme telo-
merase into the nuclei of lung cancer cells, stopping
their division and the spread of the cancer.
This dual character of nanoparticle technology,
risk and opportunity, is not an isolated case. Particles
containing iron, for example, regarded as toxicolo-
gically questionable, are now also being tested, in
special casing, for cancer therapy. At the Berlin firm
MagForce Nanotechnologies, special iron com-
pounds are so coated that cancer cells near which
they are injected absorb them permanently. An
externally applied alternating magnetic field then
heats up the particle cores, and thus the tumour,
28 NANOPArtICLEs IN tHE BIOsPHErE

destroying it or rendering it more receptive for che-

motherapies. This method, hope the developers, who
are supported by the BMBF, will one day rank equally
with radiological methods, but without their side
effects. The technique should be especially helpful
in the treatment of insidious brain tumours like the
glioblastoma.
Nanoparticles, which contain magnetic cores,
like those synthesised by magnetotactic bacteria (see
page 9), can even be dragged to their action site with
special high-powered magnets which generate a
particularly inhomogeneous field. Their shells would
be loaded with active constituents. Application of
a powerful ultrasonic field, which does not dama-
ge healthy tissue, would then burst the shells and
release the drug.
There are many ideas like this. The umbrella
term is drug targeting, the administration of drugs
targeted at diseased tissue. Until now, it has been
necessary and normal to expose the whole body to
a drug for the treatment of a small inflammation,
for example. With efficient drug targeting, the dose
could be raised for this inflammation alone, with no
fear of increased side effects. Nanoparticles in tumour tissue: Left, the healthy cells, right the cancer
cells which have been loaded with nanoparticles.

Nanotechnology for food

Nanotechnology is already used today in food tech-

High gradient magnet for the control of magnetic particles in the body.
The magnet, developed within the framework of the BMBF project
„Nanomagnetomedicine“, is light enough, at 47 kg, to be swivelled over
the patient‘s bed. The previous magnet weighed 1.5 tonnes.
nology, even in unexpected sectors like the manufac-
ture of luxury chocolates. Nanotechnology also has
great potential in the food sector. Nanosensors, for
example, will in future provide information on the
age and condition of foodstuffs (see „Nanosensors
for the food industry“, page 31). In industrialised
countries, according to calculations by the BBC, 40 %
of the food produced is thrown away. Reliable infor-
mation on freshness and suitability for consumption
can reduce such waste, for foods are today thrown
away not because of their actual condition, but on
the basis of the best by date alone. Great expectations
are also associated with the use of nanomembranes
in the field of sterilisation at low temperatures. In
view of the potential risks of such a use, this deve-
lopment is being closely watched by the Ministry for
Consumer Protection and the Federal Institute for
Risk Assessment.
„Nanotechnology for food“ covers a wide variety
of different areas of technology, some of which can
be classified as naturally harmless.
NANOPArtICLEs IN tHE BIOsPHErE
A glass of wheat beer. The large bubbles grow at the expense of the
small, a phenomenon widespread in nature.
Sieves, Filters, Membranes
Sieves, filters and membranes have long been a part
of food technology; nanotechnology merely repre-
sents a refinement in this sector. Filters with pore
sizes of less than a micron can stop bacteria and finer
ones can even stop viruses. This makes them suitable
for the cold sterilisation of juices, milk and other
liquids, while conserving important constituents
like vitamins. Today, where particular reliability is
required, even filters made of silicon wafers, like
those for the manufacture of semiconductors, are
used. Using photolithographic methods, submicro-
scopic holes with very precisely defined dimensions
are etched in these filters. Filters like this allow the
exact mechanical type sorting of substance mixtures.
As a rule, the membrane thicknesses are smaller than
the diameters of the holes, resulting in substance
throughputs two or three times greater than those
with conventional filters.
Conversely, filters like this can be used as nozzles
for the production of stable mixtures of substances
like fats and water which, in nature, tend to separate.
29
Such a mixture is found in ice-cream, for example,
together with air, and if this remains for a long time
in the freezer, it usually gets a coating of ice needles:
the air, fat and water have partially separated. With
nano-nozzles, however, ultrafine, uniform droplet
mixtures can be made which break down much
more slowly, so manufactured ice-cream would
remain stable for longer.
The reason for this is two rules which apply to fine
substance mixtures, dispersed in droplets or foams:
„The large swallow up the small“ and „If something
very small wants to grow, it needs help“. Both rules
can be studied in a glass of wheat beer. The initial-
ly fairly homogeneous head of foam breaks down
into bubbles of different sizes, the large ones visibly
growing at the expense of the small ones. The main
origins of the beer bubbles, when the great distur-
bance of the pouring has settled down, are specific
points on the glass wall, small faults, lint or corrosion
pits, at which the so-called nucleation work for the
formation of gas bubbles is reduced, for the energy
balance for bubble growth only becomes positive at
a specific minimum size. The faults reduce this mini-
mum size, then it bubbles. So, in substance mixtures
which should remain stable (like mayonnaise), care
must be taken to ensure that the bubbles/droplets
are very uniform and, if possible, remain below the
critical size which allows them to grow.
Micelle, my Belle
Many healthy substances like omega-3 fatty acids
do not taste good and fats and oils, the solvents and
carriers of important vitamins, do not mix with
water. Both problems could be solved with nano-en-
capsulations with an outer skin which bonds readily
with water and which only opens when it reaches
the stomach, which is not sensitive to unpleasant fla-
vours. Nano-capsules also have the great advantage
that they cannot be seen with the naked eye, so they
do not spoil the appearance.
The manufacture of nano-encapsulations is now
possible with a whole series of processes, including
those using tensides. These have longish molecules,
one end of which likes water and the other, fat. So
the fat loving ends of the tenside molecules settle on
the fat and the water loving ends on the water. The
result is the formation of countless small fat globules,
covered with tenside molecules like a hedgehog‘s
prickles and suspended in the water like a mist - fat
and water are mixed, which is not possible without
30
tensides. According to this principle, refined formu-
lae have been developed, protected by many patents,
for enclosing various active constituents in capsules
with a diameter of 30 nm.
Another possible application of nano-encapsulation:
Invisible, encapsulated vitamin C, technically known
as ascorbic acid, as an anti-oxidant for edible oils.
Nano-encapsulated, ascorbic acid can even protect
milk and yoghurt products, so that they no longer go
sour. This process is now subject to a trial under food
legislation. The objections which have increasingly
been heard recently in connection with nanopar-
ticles in food may perhaps be worthy of discussion
for mineral substances, but cannot apply to groups
of substances like fats. The body itself works here
with nanoparticles. Anyone who drinks milk or eats
an egg swallows huge quantities of micelles and,
furthermore, the ability to be broken down into the
smallest particles is actually a precondition for the
body‘s utilisation of nutrients.
NANOPArtICLEs IN tHE BIOsPHErE
Controversial visions: Protein nutrition of the
future
Three quarters of the available fresh water, a third of
the agricultural land and a fifth of the energy used
are currently utilised for food production. In the year
2050, 9 billion humans are expected, for whom, by
the standards of the industrialised countries, 450
billion tonnes of meat must be provided per year - a
meat cube with sides 700 m long. Meat production
is very inefficient for inherent reasons. To produce
one kilogramme of animal protein, it takes three to
ten kilograms of vegetable protein. Some experts
are therefore demanding a protein transition, which
would not mean dispensing entirely with naturally
grown meat, but its replacement with high quality
vegetable protein in various foods. Acceptance will
largely depend on the structure of the Novel Protein
Foods (NPF). The advantages of such a technology for
humans and the environment are not particularly
convincing, but are being intensively researched by
the food industry. The Netherlands hold the lead in
this field (particularly the University of Wagenin-
gen), for one very good reason, among others: Becau-
se of its intensive animal husbandry, the country has
a severe slurry problem.
NANOPArtICLEs IN tHE BIOsPHErE 31

Nano-wire sensors would have the great advan-

tage that they only consume very little energy, in the
order of a picowatt, about a millionth of a millionth
of the power of a torch. Energy levels like this can ea-
sily be provided by transmission to RFID radio labels.
With a combination of radio label, plastic display
and nano-wire sensor, justice could at last be done
to every single cheese on the supermarket shelf.
The immature and over-ripe cheese would signal
its condition with a lower price and the one which
is just right with a higher price, and no more would
be thrown away. True, in the corner shop, the grocer
would have managed that with the help of his nose,
but the grocer is no longer there.

The growing world population will have to place new, environmentally

sounder forms of food production alongside the traditional methods.
Corresponding technologies which include nanotechnology are being
researched particularly intensively in the Netherlands, where the soil is
unacceptably polluted with slurry.

Nanosensors for the food industry

Much food is thrown away merely because its best by With chips from the Fraunhofer Institute for Silicon Technology, ISIT,
fast DNA sensors for the detection of pathogenic bacteria and other
date has expired. The best by date, however, is only
biogenic substances are being developed.
a minimum estimate of keeping quality. If the food
package had a cheap analytical device on board, that
could signal the edibility instead of the best by date,
permitting much more economical householding.
On the other hand, rotten food is also sold. Nano-
sensors could help with both problems, perhaps
those with nano-wires of different materials, only a
few millionths of a millimetre thick. When a foreign
substance docks on such thin wires, their electrical
characteristics change so dramatically that, in princi-
ple, not just bacteria, but tiny viruses and even single
molecules can be detected.
What is measured depends on the coating of the
nano-wire. If ammonia is to be detected, the coat
should absorb ammonium molecules by preference,
highly selectively if possible. Use can naturally also
be made of antibodies which only bond with mat-
ching antigens, thus making them quickly detecta-
ble.
32 HEALtH EFFECts OF NANOPArtICLEs

Health effects of nanoparticles

T

The lungs have an internal area about the size of a tennis court, so they
offer potentially dangerous particles the most important entry surface.
The probability of entry also depends on the type of breathing; sport is
unfavourable for particle exposure.

Gateways for nanoparticles

One large potential gateway, with an area of 2 m2, is

the skin. However, studies have shown that healthy,
unbroken skin presents a reliable barrier. It is ano-
ther matter with skin that is broken or already da-
maged, perhaps as a result of sunburn. Here, experts
advise against avoidable exposure (see interview
with Prof. Tilman Butz on page 38).
HEALtH EFFECts OF NANOPArtICLEs
Asbestos – a story that must not be repeated
Asbestos has a glorious history. The ancient Greeks
used the variant known as „Carpathian stone flax“,
plaited, as an indestructible wick for oil lamps. Kaiser
Karl V. is said to have had a tablecloth woven of asbe-
stos, which he liked to have thrown into the fire after
a meal, only then to be retrieved undamaged to the
astonishment of his guests.
In the technology of the new age, asbestos was
also regarded as a wonder material. With some justi-
fication, as the substance possesses high strength, is
an excellent thermal insulator, is heat and acid resi-
stant and, depending on modification, is so mechani-
cally hard that it could even be used in brake linings.
Asbestos is a naturally occurring mineral, main-
ly consisting of silicon and oxygen, with varying
proportions of embedded calcium, magnesium, iron
and nickel. So asbestos exists in many variants. As
„simple asbestos“, Klockmann‘s Text Book of Mine-
ralogy names chrysotile asbestos, „parallel fibrous
masses of shimmering silky lustre, pale yellow,
The Cologne tower block formerly used by Deutsche Welle is a case for
asbestos remediation.
33
brownish yellow or pale green.“ What was to make
asbestos undesirable as a material in the industriali-
sed societies was its „fibrous“ nature. When asbestos
is mechanically stressed, fragments of this fibre are
released into the air and if these are inhaled, they can
have disastrous consequences, such as lung cancer.
And asbestos was used in large quantities in the
industrial societies. As early as 1820, the fibres were
woven to produce fireproof clothing for firemen.
In 1900, an Austrian patent was issued for so-called
Eternite, a building material containing asbestos, out
of which, from this date on, large quantities of roof
tiles, corrugated roofing, pipes etc. were produced.
The Eternite was not, as the name suggested, eternal,
but weathered and released asbestos fibres. By 1900,
asbestosis was recognised as a sickness, an inflamm-
atory reaction of the lung tissue which damages
them severely and, after a long period of latency, can
finally lead to lung cancer.
Among other things, buildings were lavishly
coated with sprayed asbestos as fireproofing, like
the Palace of the Republic in Berlin or the Deutsche
Welle tower in Cologne in more recent times.
In 1979, sprayed asbestos was prohibited in Germany,
followed in 1993 by asbestos in general and, since
2005, there has also been an EU prohibition.
The long latency period between exposure and
onset of the disorder has ensured that asbestos will
remain a topic for many years to come. In 2003,
the health insurance bodies registered 3500 new
occupationally caused disorders, with a rising trend.
The annual costs of these disorders are now over €314
million. Such a story, everyone agrees, must never be
repeated.
The asbestos experience is an essential back-
ground to the safety debate accompanying nano-
particle technology. Important in this connection:
Bonded asbestos, which lies in the earth or has been
fixed with concrete, is harmless. Bonded synthetic
nanoparticles may also be regarded as completely
harmless. The following risk assessment relates
exclusively to unbonded nanoparticles which could
enter the human body through breathing, eating or
other means.
34 HEALtH EFFECts OF NANOPArtICLEs

Nanoparticles – how dangerous? toxic. In some of the literature, it is even assumed

that potential nanoparticle toxicity rises constantly
as the size decreases.
At present, the vast majority of nanoparticles with This relationship, however, cannot be strictly
which people come into contact are unintentio- true, for molecules and atoms, the smallest compo-
nally caused by industrial activities, in road traffic nents in material chemistry, would then have to be
and through normal technological civilisation. naturally toxic. But this is the matter of which we are
Increasingly, however, attention is also turning to made.
industrially produced nanoparticles: For 2007, the
production of fullerenes, for example, was estimated
at several thousand tonnes. What began as a labora-
tory curiosity has now reached industrial scale, also
making it interesting for the toxicology, the science
of the tolerance to substances and, of course, for the
protection of workers and consumers (see page 50).
Nanoparticles are unique insofar as the physical
models applicable to the particles begin to change at
the transition into the nanometre dimension: While
classical physics applies above 100 nm, quantum Particle analysis with the ATOFMS aerosol mass spectrometer. Individual
physics applies below this size, with quite different particles are detected in the air and sorted according to size by light
laws. The transition is blurred. As a result, magic can sensors. After subsequent vaporisation and ionisation, the composition
of the particles can be determined in seconds, practically in real time.
be performed with nanoparticles: merely by altering
their size (depending on the material the particle is
made of), properties such as solubility, transparency,
colour, conductivity and melting point can be modi-
fied.
Furthermore, a large proportion of the atoms in
nanoparticles are surface atoms. Thus, a spherical
iron particle with a diameter of 5 nm would have
about 27 % surface atoms, while a particle with a
diameter of a micron would only have 0.15 %. But
surface atoms are not bonded with neighbouring
atoms around them, so they have free bonds and
these are very reactive. Therefore they do not remain
unbonded for long, attaching themselves to each
other or to available free molecules or surfaces. This,
as long-term air measurements in the town of Erfurt
have shown, has the curious effect that a reduction of
fine dust can increase the number of nanoparticles
in the air and, thus, the concentration of ultrafine
dust, for with less larger particles in the air, the finest
particles lack possibilities for attaching themselves.
The high number of surface atoms also increases the
catalytic activity of these particles, that is the ability
to accelerate chemical reactions without themselves
being consumed, which makes them interesting for
industry. Naturally, if the active surfaces cannot be
shielded, the particles rapidly agglomerate to form
larger, less active units and the interesting properties
are lost.
A large number of readily bonding, catalytical-
ly active surface atoms may, of course, also have
undesirable consequences and render nanoparticles
R 35
The most important source of information on the
toxicity of nanoparticles is currently the literature
gathered from aerosol research on the effects of
fine dust PM10, which, however, cannot be equated
with industrially manufactured nanoparticles. PM10
stands for particles with a diameter less than 10µm
(1 micrometer = 1,000 nanometres). The body‘s own
mechanisms for the neutralisation of particles of this
size range in the respiratory tract - like embedding
them in mucus, which is subsequently disposed of
- fail in the case of nano-scale particles; one reason
why the entry of such particles into the lungs is cur-
rently receiving the greatest attention. The lung has
an internal surface the size of a tennis court (approx.
140 square metres) and because it is designed for a
rapid exchange of gas, the barriers to the blood cir-
culation in the pulmonary alveoli are extraordinarily
thin, so they may also be passable for nanoparticles.
In fact, the aerosol research, which is mainly
conducted in Germany by the GSF Research Centre
for the Environment and Health in the Helmholtz
community, has been able to prove that nanoparti-
cles penetrate the lung epithelium and can get into
the blood. It may therefore be assumed that nano-
particles can, in themselves, represent a health risk,
which would have consequences for the evaluation
Two-dimensional gas chromatography: In order to determine their
chemical composition, aerosol samples are sorted according to two
different principles: 1. Volatility, (x axis), 2. Polarity (y axis). Each peak of
the xy chromatogram on the screen represents a chemical compound
present in the aerosol. The height of the peak represents its relative
frequency.
of air quality. Then, in addition to the mass of the
particles in the air, their number would also have
to be measured, in order to determine how many
portions, including nanoportions, a pollutant is
divided into. The difference is important: with the
mass of particles in the air as the criterion, the respi-
ratory tracts of townspeople have three times the
exposure of the population in the countryside, but if
the number of particles is taken as the criterion, the
Soot particles under the electron microscope.
urban population comes off very much worse, with
19 times the exposure of those in rural areas. As sour-
ces of manmade dust particles < 10 µm, the aerosol
research identified industrial processes with 45 %, the
trans-shipment of dry bulk goods with 21 % and dust
particles emitted in road traffic with 17 % of total dust
emissions. If abrasion from tyres, road surfaces and
brakes are also counted, road traffic rises to 33 %. A
good proportion of these particles are nanoparticles.
If the inhalation of nanoparticles is dangerous
and nanoparticles also occur frequently in nature
without human intervention, then evolution must
have given breathing organisms the ability to deal
with nanoparticles. That is in fact the case, but the
protection is imperfect. In humans, the nose repre-
sents the first barrier. The curvature of the airways
presents no obstacle to the free flow of the air, but,
because of their momentum, particles larger than
2.5 µm go off course and land on the mucous memb-
rane of the nose. Admittedly, this filter is absent in
the case of breathing through the mouth, when
airborne particles arrive practically unimpeded into
the pharynx and bronchia. Particles larger than 5 µm
and smaller than 10 nm largely settle here, while the
rest flow further. Part is deposited in the bronchioles
36
and part in the alveoli. Strangely, particles with a
diameter of about 500 nm are hardly deposited, but
are mostly breathed out again. As their size decreases
to 20 nm, the proportion of particles deposited in the
periphery of the lungs rises sharply.
Whether and how particles are deposited in the
lungs also depends on the kind of breathing. Slow,
deep breathing transports the most dust into the
lungs.
Once they are deposited, particles need not ne-
cessarily remain permanently in the body. In heal-
thy bronchia, for example, the epithelial cells are
equipped with cilia under the mucus which, through
synchronised waving, transport foreign bodies to the
larynx, from where they pass into the gastro-intesti-
nal tract and are digested or excreted.
Another of the body‘s protective mechanisms:
Macrophages move around in the respiratory tract,
scavenger cells which not only attack particles they
recognise as foreign, but also bacteria and viruses. Of
course, tiny nanoparticles are often overlooked.
Scientists from the Institute for Inhalation Bio-
logy of the GSF have established that inhaled nano-
scale particles - ultrafine particles in the jargon of
HEALtH EFFECts OF NANOPArtICLEs
With a gamma camera, it is possible to observe over a number of days
where marked particles settle in the lung and how long they stay there.
the aerosol researchers - can land in the livers, in the
hearts and even in the brains of rats. The mechanis-
ms by which the particles get into the blood circulati-
on and internal organs are still strongly disputed, as
is the extent to which the results from experimental
laboratory and animal models can also be applied to
humans.
In discussion as possible transport paths, for
example, are absorption through the nervous sy-
stem (e.g. along the olfactory nerve into the brain),
through the lymphatic system or into the blood-
stream through the thin 0.5 µm barrier in the lungs
between the alveoli and the capillaries. Already
damaged lung tissue is considered more susceptible
to the passage of nanoparticles into the organism. Its
physicochemical nature has a great influence here
on the behaviour of the particle in the organism.
Ultrafine dusts do not behave in the same way as
industrially manufactured nanomaterials - the exact
facts will have to be clarified by future research.
R 37
It is known from fine dust research that when nano-
particles get into the blood circulation, they would
normally be arrested and made harmless by macro-
phages, scavenger cells, the police of the immune
system. Because of their minute size, however, that
often does not happen. Then they can even have an
effect on the heart. GSF scientists and veterinarians
at the Ludwig-Maximilians University in München-
Großhadern have investigated some unique relati-
onships in this connection. Thus, epidemiological
studies have shown a relationship between the fre-
quency of heart attacks or sudden fatal cardiac arrest
and unusually high particle concentrations in the air,
such as those occurring on days of high traffic and
atmospheric inversion conditions. A plausible cause
and effect chain for this phenomenon cannot be sci-
entifically formulated, but it is conjectured that fine
and ultrafine dusts may play a role here. One possi-
ble explanation: When, in an animal experiment,
specific nanoparticles were injected in high con-
centrations directly into the bloodstream, the blood
Nanoparticles can cause inflammatory reactions in the human vascu-
lar system.
platelets reacted by clotting the blood faster, incre-
asing the risk of thrombosis and making infarctions
more likely. When, for the purposes of the fine dust
investigation, typical nanoparticles acted directly on
the cells of the heart‘s musculature and conduction
system, a change occurred in the calcium balance, so
that the heart muscle was no longer able to contract
as strongly. As the bioelectrical activities which make
the heart beat are also partly determined by the cal-
cium ion concentration, nanoparticles could in prin-
ciple contribute to heart rhythm disturbances. The
extent to which these experiments can be applied
to the real situation, however, is still fully unclear.
The corresponding studies are controversial in the
specialist scientific scene.
But nanoparticles which do not leave the lung‘s
alveoli can also have an effect on the heart by acting
on receptors on the surface of the alveoli which influ-
ence the vegetative nervous system and thus also the
heart‘s rhythm. This may then become less variable,
so that the heart can no longer react appropriately to
changing performance requirements.
As a third action chain for high nanoparticle
concentrations, such as those which occur in unfa-
vourable traffic conditions or forest fires, the scien-
tists have identified inflammatory processes which
are triggered by the particles in lung tissue and lead
to the release of messengers. These increase the clot-
ting capacity of the blood and the body mobilises its
defences - processes which tend to speed up sclerosis
of the arteries.
It is therefore undisputed that certain dust
particles which come into contact with the human
organism over prolonged periods and in high con-
centrations can have a harmful effect on health. This
also applies for certain industrially manufactured
nanoparticles, so the exposure of employees, consu-
mers and the environment should, as far as possible,
be avoided (see Risk Management p. 46 ff.)
38
Effects of nanoparticles on the skin
Nanoparticles are turning up in more and more pro-
ducts, the express purpose of which is to come into
close contact with the human body, like toothpaste
or sun cream. NANODERM is an international project
financed by the EU with the participation of twelve
institutes and dedicated to research on possible risks
in this connection.
Healthy skin is a reliable barrier against na-
noparticle penetration. what we are not sure
about is what really happens in skin badly
damaged by sunburn and already peeling off,
if you smear it on then. I cannot imagine that
there is no contact with vital tissue, so I would
strongly advise against doing anything of the
kind.
Prof. dr. tilman Butz, Coordinator of the EU
project NANOdErM
Titanium dioxide particles in sun cream. The substance effectively
filters out harmful UV light, without being visible. In European cosmetic
products, the photocatalytic properties of the titanium dioxide desired
elsewhere are suppressed by coating of the particles, with silicon for
example.
HEALtH EFFECts OF NANOPArtICLEs
Interview with Prof. dr.
tilman Butz, director of
the Institute for Nuclear
solid state Physics, Uni-
versity of Leipzig, Coor-
dinator of the EU project
NANOdErM
How can nanoparticles be detected in the skin?
One very powerful method is high resolution trans-
mission electron microscopy. For this purpose, you
need skin cross-sections, so you have to take skin
samples, biopsies, skin punch plugs, and slice these
into very thin layers of skin. Very thin means about a
thousandth of the width of a hair. With high resolu-
tion transmission electron microscopy, you can then
see individual nanoparticles. The nanoparticles in
sun creams are typically about 20 nm in size, and,
with the right equipment, you can also find out what
these particles are made of. That is certainly not a
routine method, as heavy equipment is required.
Preparation of the samples is also very elaborate and
there is a danger that preparation artefacts will then
be visible. What is more, only very small details can
be seen and you have no overview of the skin cross-
sections; only one small, deep section.
The next method I would mention is ion microscopy,
better known by the name Particle Induced X-Ray
Emission, PIXE. Here, ions, preferably protons, are
fired at skin cross-sections, this time not quite as
thin, but in the range of a few microns. Here it is no
longer possible to detect individual particles, but the
advantage is that large areas can be scanned and you
can zoom in on areas of interest.
Do protons have a greater penetration depth?
Yes, the penetration of protons is much greater
than that of electrons, so thicker samples can also
be studied. A combination of these two microscopic
techniques is already very good in my opinion. Then
there is another method, so-called laser scanning
microscopy, which requires you to have particles
tagged with fluorescent markers to make them visi-
ble. This is not unproblematic, because the fluores-
cent markers must each be bonded stably to parti-
cles, otherwise they would give false results. But, this
apart, it is a very efficient method, which can also
produce three-dimensional images with a certain
degree of depth resolution. So these are the three
techniques I consider most interesting. Another is
the use of radioactive marked particles and autora-
HEALtH EFFECts OF NANOPArtICLEs
diography. Naturally, that is only possible for skin
explants. Little use has been made of this method up
to now.
What can be done if such elaborate techniques
are not available?
Very widespread is so-called tape stripping: you take
some adhesive tape, like Tesa-Film, and can pull off
the surface of the skin layer by layer and analyse
what you have removed. Very simple and cheap, but
in fact it gives little depth information because it
also measures wrinkles, hair follicles and so on at the
same time and it appears to show a deeper penetra-
tion than is usually the case. The last technique uses
so-called Franz diffusion cells. You take a skin explant
and mount it in a cell. On one side, the material you
want to apply to the skin is added and, on the other
side, what passes through the skin is collected in a
buffer medium. This procedure is standard but also
very prone to errors. If you do not know the path by
which the material penetrates the skin, the result
is not very informative. Let us assume, you have cut
into a hair follicle. Then, you have made a small
channel through which the material can pass. Or you
may have damaged the skin while mounting it, so
it passes through the tear. So those are the relevant
techniques.
Others require you to take skin samples. That is
not something you can do in vivo without damaging
the skin. There is no technique as yet for doing this.
Is healthy skin a reliable barrier?
Yes, it is a reliable barrier against nanoparticle
penetration. Everything we know indicates that the
penetration into the epidermis is a mechanical pro-
cess. The particles are rubbed in mechanically. The
upper layer of the epidermis is similar to puff pastry,
with loose layers of corneocytes, and the material is
rubbed between them. The lower part of the epider-
mis, the compactum, is more similar to the pages of
a book which have not yet become wet. And we have
not detected emigration into the compactum. So
healthy skin is a reliable barrier. However, there are
two or three publications which give cause for con-
cern. In the case of severe mechanical stress, when
the skin has been stretched a few thousand times at
45 ° in one direction and then at 45 ° in the other,
deeper penetrations have been detected.
And how does sick skin behave?
Unfortunately, there is not much information about
this yet. In the case of psoriasis, as may be imagined,
the proliferation, that is the renewal of the skin, is
drastically accelerated. As a result, instead of 15 µm
of epidermis, you have over 100 µm, so it is much
39
thicker and contains dead cells alongside living ones.
And when that is mechanically stressed, it is like
spreading a cut French croissant, a flaky pastry, with
cold butter from the freezer: it breaks into pieces. So
you then have contact with living cells. Then lesions,
microlesions, an open wound you yourself are not
aware of because it is so small, is clearly a path where
you can have nanoparticles in contact with vital tis-
sue and also with vital cells. So, application on open
wounds is certainly very unadvisable. What we are
not sure about is what really happens in skin badly
damaged by sunburn and already peeling off, if you
smear it on then. I cannot imagine that there is no
contact with vital tissue, so I would strongly advise
against doing anything of the kind.
There are naturally other paths under discussion,
particularly the hair follicles. We have found na-
noparticles in hair follicles, at a depth of about half
a millimetre. But not in the vital tissue around the
follicle. It seems that the cladding of the hair follicle
is also a good barrier. The final possibility would be
through the sweat glands or sebaceous glands. We
have occasionally seen cross-sections of sweat and
sebaceous glands, but not with particles in them. In
the case of sweat glands, the milieu is certainly not
suitable.
The formulations of sun screen creams are hy-
drophobic, more fatty, so it is almost inconceivable
that anything could be rubbed into the sweat glands
which would not immediately be flushed out again.
In the sebaceous glands it would be more likely, but
we have not seen it. In any case, I would say it has
little relevance.
40 PUBLIC AwArENEss ANd sOCIAL dEBAtE

Public awareness and social debate

Nanotechnology is often described as the art

of purposefully using structures between one
and 100 nanometres, which are indispensable
for a specific function. From this perspective,
physicists and chemists have been conduc-
ting nanotechnology for a long time without
giving it a name.

But regardless of exact definitions, such as those

currently being formulated in standardisation
committees, public perception of nanotechnology
will be crucial for its further development. The term
nanotechnology has developed through an interplay
of new concepts and visions dealing with the utilisa-
tion of the nanocosmos, accompanied by ever more
efficient equipment and analytical technology.

Cryo-electron tomography of the interior of a magnetotactic bacterium

Nano – the beginnings with a chain of magnetosomes. These are nanocrystals of magnetite in a
„mould“ of proteins.

The first to suspect the existence of real treasures in

the nanocosmos was Richard Feynman, a legendary
American physicist and Nobel Prize Winner. In his
1959 lecture, „There is Plenty of Room at the Bottom“,
he sketched for a wondering public the outlines of a
new cosmos, the nanocosmos:

„What would the properties of materials be if we could

really arrange the atoms the way we want them? They
would be very interesting to investigate theoretical-
ly. I can‘t see exactly what would happen, but I can
hardly doubt that when we have some control of the
arrangement of things on a small scale we will get an
enormously greater range of possible properties that
substances can have, and of different things that we can
do.“

Like making high-tech articles such as laser

diodes from materials long considered to be undesi-
rable impurities. The list of possibilities is very, very
long.
PUBLIC AwArENEss ANd sOCIAL dEBAtE 41

Nano Hype we run a grave risk - the risk that we might destroy the
biosphere on which all life depends.“

While it was Drexler‘s writings which were fol- The nanotechnology scene still believed at this time
lowed by the outburst of enthusiasm, the Polish in the concept of self-replicating nanobots and that
engineering philosopher Stanislav Lem had already was precisely the point that had disturbed Bill Joy –
predicted nanobots in his book „The Scene of the which relativises the criticism. In any case, it can be
Crime“ (also published as „Local Inspection“) in countered that the technologies adopted from the
1982. He called them „grippers“. In „ The Scene of 20th century are mostly unsuitable for the future and
the Crime“, at least the grippers only wanted to do urgently need modernisation, according to the state
good, and they were present everywhere, even in of the art, also using nanotechnology. As Lem said,
shirts. And if the possessor of one of these wanted to
do an evil deed, to stab another human for example, „The only answer for a bad technology is a good techno-
the nanotechnological shirt stiffened so powerfully, logy.“
thanks to masses of grippers locking together, that
the evil intent was thwarted. The wittiest and most But Bill Joys and other critics also had their good
intelligent version of the nanotechnology preview side: They started a serious, broad debate on the
was simultaneously the least widespread. Lem had opportunities and risks of nanotechnology. And as
not offered the prospect of a paradise. experience has shown, all technologies depend on a
critical accompaniment. Nanotechnology will be no
exception. However, especially in the case of nano-
End of the Nanobots technology, attention must be paid to which of its
branches the criticism refers. A pair of glasses made
scratch resistant with nano-coatings is hardly likely
Drexler‘s movement received a severe damper in to represent a danger to mankind. And the responsi-
2001, when Richard Smalley, Chemistry Nobel Laure- bility for the consequences of nanoelectronics does
ate in 1996, made public his gripping parable of the not belong to toxicology, but to cultural criticism.
fat and sticky fingers, as those of the atomic grippers
must appear in the nanocosmos. If, at nano-scale, the
Tunnel microscopic image of self-organised, nanometre-sized molecule
grippers were as clumsy as the things to be gripped,
complexes on a copper surface (Background: Simulation).
there was no future for the nanobots, any more than Nanotechnologists have great hopes for self-organisation processes like
shrimps could be peeled wearing oven gloves. Today these, but this technology is far removed from the „assembler“ visions
of Drexler.
(2007), Drexler agrees. The danger of mankind dissol-
ving into grey goo has been banished for the time
being.
In 2002, the bestseller author Michael Crichton
excited people‘s fantasy once more with his book
„Prey“, in which swarms of nanobots turned on their
creators with severe consequences. Stanislaw Lem
had already described something similar in 1964 in
his novel „The Invincible“, micro/nano as villain. The
public remained undisturbed.
Meanwhile, in 2000, powerful criticism came
from an unexpected source. Bill Joy, Chief Scientist
of Sun Microsystems, had published an extremely
pessimistic article, „Why the future doesn‘t need us“,
in the magazine „Wired“, on the consequences of
modern technology, including nanotechnology:

„An immediate consequence of the Faustian bargain

in obtaining the great power of nanotechnology is that
42
Meanwhile, for obvious reasons, one branch of
nanotechnology deserves special attention: nano-
particle technology. So this was also the main subject
of the report „Nanotechnology: Small particles, great
future?“, published in 2004 by the Swiss reinsurance
company Swiss Re, attracting great interest:
„The mere presence of the particles, even if they should
be present everywhere, does not, in itself, represent a
danger to humans and the environment. Only if specific
properties of the particles should turn out to be dan-
gerous, would one have to speak of a danger. As there
are no corresponding studies, however, it is hardly pos-
sible today to say whether and to what extent nanopar-
ticles or products manufactured using them represent a
concrete risk.“
This was followed in June 2005 by an equally weigh-
ty study by the Allianz Versicherungs-AG. The real
risk of nanotechnology, Allianz found, was the gap
which exists between its dynamic development and
the knowledge of possible dangers and necessary
safety standards for avoidance of negative effects.
Nano Fakes
Meanwhile, exaggerated expectations continued
to be directed at nanotechnology, so that, together
with the discussion of risks, public interest was
aroused and made audible in media reports. So, in
March 2006, the story of Magic Nano, a glass and
ceramic care product which caused serious health
disorders after inhalation of the spray, found an in-
ternational media echo because it was called Magic
Nano. However, the product contained no nanopar-
ticles, as was confirmed by the Federal Institute for
Risk Assessment after the questioning of experts and
suppliers. The manufacturer said he had only wanted
to point out that, after the spraying of his product,
a very fine film was formed on glass and ceramic
surfaces, so it was Nano. Magic Marketing would be a
more accurate interpretation. Even the film was not
nano, but micro.
This case nurtured the fear, felt even by declared
nanotechnology supporters, of the unregulated use
of nanoparticles, for: What happens if an unthinking
producer of cosmetics, for example, stirs nanopar-
ticles into his formulae without any testing, just so
he can advertise with Nano? Particles which subse-
quently turn out to be harmful? The whole branch
PUBLIC AwArENEss ANd sOCIAL dEBAtE
would fall into disrepute and the attractive effect of
the label Nano would turn into the opposite.
But the critics should also be wary - of skating on
thin ice and falling for nano-myths.
Nano Myths
Nanotechnology is so new, the nanotechnological
personnel coverage – including critics – so thin, the
safety debate so new, that a fruitful soil has been laid
for myths. One example: In October 2004, in the Pro-
ceedings of the Ninth Asia Pacific Physics Conference
(9th APPC), Hanoi, Vietnam, 25-31, a publication
appeared, according to which about 1200 rice grains
of the variety Thai purple had been shot with low
energy nitrogen ions - a routine procedure. Then the
grains were germinated and the seedlings allowed
to grow in the soil until they were ripe. Two of the
plants had changed their genetic make-up. While
the variety is usually purple, the leaves and stalks of
the mutants were green.
Now nanotechnology - completely innocent by
all the rules of logic - received the killer punch. An
author from the nanotechnology-critical Canadian
organisation ETC wrote:
„The research project includes the boring of a nanome-
tre-sized hole [...] through the wall and membrane of
a rice cell in order to inject a nitrogen atom. The hole
is bored with a beam of fast moving particles, then the
nitrogen atom is shot through to alter the genetic sub-
stance of the rice cell.“
This action, nothing to be ashamed of, but which had
not taken place in this way, was taken by critics as
an indication of the recklessness of nanotechnology
research and, with this interpretation, even found
its way into the risk assessments of major, reputable
organisations.
In fact, the radiation of seed in order to create
mutations, which also frequently occurs in nature,
but not in such close sequence, is routine. The Bava-
rian State Agriculture Agency quoted in 2006, „To
date, over 1800 new varieties have been put on the
market with the help of mutation breeding. In Italy,
durum wheat mutants (for pasta) cover about 70 %
of the area used for durum cultivation.“ This may be
criticised, although plant cultivators have always
used mutants, but it cannot be blamed on nanotech-
nology.
PUBLIC AwArENEss ANd sOCIAL dEBAtE
Nano disputes
Environmental protection organisations
Naturally, the environmental protection organi-
sations have also taken up the theme. Germany‘s
largest, the Bund für Umwelt and Naturschutz
Deutschland, BUND, calls - like others - for detailed
studies on the safety of nanoparticles, but also sees
extremely positive possibilities for nanotechnology
and points out...
„ ... that (superficial) effects for the relief of raw materials
and the environment by means of new technologies have
frequently only led to the masking of the changes in be-
haviour actually necessary. An example is the introduc-
tion of the catalyst since the mid-80s. In order to obtain
similarly clean air, 80 % fewer cars would have had to be
driven today. The superficial focus on technical solutions,
which are sold as future technologies, diverts attenti-
on from sustainable developments which must offer
solutions based on the real causes, like the unsustainable
lifestyles of the highly developed industrialised nations.“
The first hybrid Smart. In the USA, a pure electric version with Li-ion
batteries is also supplied by hybrid technologies.
So, little would actually be gained if, thanks to cold
sterilisation using nano-sieves (now allowing trans-
port over longer distances), milk were no longer only
to be carried from the German Alpenvorland to Bran-
denburg, which has its own cows, but over the Alps,
as now happens with supposedly premium quality
mineral water. For cost reasons, North Sea shrimps
make a detour by way of Morocco for peeling before
43
they land on the shelves of German supermarkets.
Nanotechnology will not change such capers as long
as there is money to be made out of them.
Consumer Vote
A consumer conference held in the Federal Institute
for Risk Assessment (BfR) on the application of nano-
technology in the fields of foodstuffs, cosmetics and
textiles arrives at the following statements, among
others, in its closing document, the Consumer Vote:
„It is considered a cause for concern that hardly any
measurement techniques exist. We find that, to date,
there are no limits for the risk assessment of nanopar-
ticles. In order to be able to carry out an exact control
of nanoparticles, we call for the development of new
analytical and measurement techniques and their stan-
dardisation by independent institutions. In this way,
standards can be set for occupational safety and end
products, and risks can be avoided for the consumer. In
the risk assessment, the whole life cycle of the product
(manufacture, use and disposal) must be considered.“
Here too, the positive potential of nanotechnology is
clearly seen.
Another demand from the consumers:
„We are of the opinion that research must be conducted
on really important topics in nanotechnology in the
The elements in an aerosol sample can be determined using „proton
induced x-ray emission“ (PIXE).
44
field of foodstuffs (for example, improved drinking
water treatment, quality monitoring and assurance,
intelligent (smart) packaging and durability) and that
products should be developed accordingly.“
Some demands would result in considerably higher
costs for the industry involved:
„We demand a compulsory „Nano“ marking, firstly so
that the consumer has a right of choice and, secondly,
so that deception can be avoided for the consumer. We
consider compulsory marking to be especially impor-
tant in the food sector, since the substances here are in-
troduced into the body directly. ... We need an approval
procedure for nano-scale substances in foodstuffs and
in their packaging. In this connection, we demand that
substances already approved (silicon dioxide, titanium
dioxide, aluminium silicates ...) be tested again if they
are used in the nano-scale range (supplementary test).“
PUBLIC AwArENEss ANd sOCIAL dEBAtE
The earth‘s atmosphere has proven to be very vulnerable. For this
reason alone, a modernisation of industrial society is urgently called for,
including the use of nanotechnology.
Association of the Chemical Industry, VCI
The Association of the Chemical Industry lists in its
„Positions and recommendations for the handling
of nanoparticles and nano-scale substances from
a legal perspective“, among other things, (also see
interview with Markus Pridöhl, p. 22):
„In the transition to sizes in the nanometre range, the
properties of substances - both the physicochemical
properties and the biological effects - change. This can
be explained by the increase in the surface/volume ratio
in comparison with coarser material, the higher surface
energy and the smaller particle size. This change in the
material characteristics in nanomaterials is currently
leading all over the world to questioning whether the
applicable legal regulations in materials law and other
legal areas are also adequate for substances with di-
mensions in the nano range or whether supplementary
regulations are required. [...] We consider that existing
PUBLIC AwArENEss ANd sOCIAL dEBAtE 45

law is sufficient to ensure the protection of humans of new nanomaterials and introduce a transparent
and the environment; amendments or supplements are global evaluation procedure for the consequences of
unnecessary. [...] since the basis of applicable law is not this technology on the social economy, health and the
the physical properties of specific substances, but the environment.“
hazardous properties of substances and the exposure of
humans and the environment. The resulting risk must In practice, this would mean an end to the develop-
be minimised by appropriate measures. These duties ment of nanoparticle technology, which would not
incorporated in the applicable law are not so narrowly be practicable.
formulated that they can only be applied to „conven-
tional“ chemicals. In fact, they also cover the special
features existing in nanoparticles and nano-scale
substances.“

So, all in all, the reactions of those involved tend to

moderation. Only the Canadian etc group (the Ac-
tion Group on Erosion, Technology and Concentrati-
on) demanded an immediate halt to the commercial
production of new nanomaterials in 2003:

„In view of the concerns about the possible contami-

nation of living organisms with nanoparticles, the
etc Group proposes that the governments impose an
immediate moratorium on the commercial production
In nanotechnology, formerly separate disciplines, such as mechanics,
electronics and biology, come together at the atomic level, making
possible very many more elegant technical solutions.
46
Risk management in nanotechnology
Nanotechnology is based on different scien-
tific disciplines, which means, among other
things, that its statements are proven or
rejected on the basis of reliable and objective
measurements. the instrumentation needed
for this purpose is growing from year to year.
Left: Computer reconstruction in seven million times magnifica-
tion: a nanoparticle with a platinum shell and an iron core (green), a
catalytically active nanomagnet. Modern high performance electron
microscopes permit examination of objects well below one nanometre.
Right: The original electron microscopic images.
Nanoanalysis as a basis for risk analysis
Many aspects of nanotechnology were already
known when Gerd Binnig and Heinrich Rohrer
presented their raster tunnel microscope in 1981. The
atomic model, for example, with a size of a tenth of a
nanometre, was already long established in physics
and chemistry, but with the scanning tunnelling
microscope, individual atoms could now be mapped
and even shifted around. The atomic force micro-
scope subsequently developed by Binnig can now
resolve subatomic details and map the oriented che-
mical bonds which, for example, hold a silicon cry-
stal together. These microscopes and their numerous
offshoots represented a conceptual breakthrough
which set an avalanche of ideas in motion and which,
under the term „nanotechnology“ had a common
denominator.
Today, even classical electron microscopes are
able to map individual atoms, to say nothing of the
Ri
much larger nanoparticles. Microscopes which work
with potentially ionising beams also have the great
advantage that not only the position of atoms can
be determined, but also the elements of which they
consist.
For when, after ionisation, the atoms return to
an electrically neutral state, they emit characteristic
radiation or electrons with an energy which betrays
their identity and their bonding status, if any.
So there is a large number of instruments ready
for nanoanalysis, but the scope for improvement is
equally great. For electron microscopes and related
instruments are large and expensive and, like the lar-
ge number of scanning probe microscopes, they too
can only examine tiny areas, which, on the one hand,
is their purpose, but which makes the characterisati-
on of a larger number of particles very time consu-
ming. Time is admittedly short in industrial produc-
tion, but any changes in the quality of nanoparticles
produced must be immediately detected, and the
risk assessment also wants quick results.
So the exposure to fine dusts and nanoparticles at
the workplace is measured with so-called SMPS de-
vices (Scanning Mobility Particle Sizers), which allow
determination of the number and size of particles
in a specific volume of air. The elemental composi-
tion of the particles and their shape, however, are
determined from filtered out samples, using electron
microscopes. Naturally, a cheap and handy device to
supply all the information quickly and at once would
be highly desirable.
In some chemical processes, like heterogeneous
catalysis, even the finest details on the surfaces of the
nanoparticles used play a role, which is also impor-
tant for the toxicity. Nanoanalysis can answer such
questions; its improvement is regarded as a key ele-
ment in nanotechnological development. In cataly-
sis, to remain with the example, small enhancements
can result in the saving of millions of Euros, in large
quantities of avoided pollutants or even in a Nobel
Prize for Chemistry, like that for Gerhard Ertl in 2007.
rIsk MANAGEMENt IN NANOtECHNOLOGy
Nanotechnology activities of the Federal
Government
The High-Tech Strategy for Germany of the Federal
Government has identified nanotechnology as one of
the most promising fields of technology, from which,
by 2015 at the latest, the large majority of all signi-
ficant innovations will originate. With the „Nano
Initiative – Action Plan 2010“, initiated in 2006, a
uniform and multidisciplinary action framework
was established, which also emphasises the responsi-
ble and safe use of nanomaterials. A series of relevant
initiatives and programmes was started with the aim
of making the undoubted toxic potential of nano-
materials measurable and thus controllable. A core
element of the initiative is the cluster of projects,
NanoCare, INOS and TRACER, in which science and
industry work together with public participation;
funding until 2009: approx. €8 million.
In cooperation with other ministries and the
federal authorities, the BMU has initiated a nano dia-
logue in which industry, scientists and participating
social interest groups can identify the opportunities
and risks in the handling of nanomaterials and esta-
blish the open questions still requiring research and
action. The Federal Institute for Risk Assessment, es-
tablished in the business area of the German Federal
Ministry of Food, Agriculture and Consumer Protec-
tion (BMELV), has conducted expert surveys to study
possible risks of nanotechnological applications
in the everyday areas of foodstuffs, cosmetics and
The nanoTruck brings nano information to the people and attracts
many visitors.
47
consumer products and the attitude of consumers to
the handling of nano products. In the business area
of the Federal Health Ministry, the risks of nano-scale
particles in drugs and medical products are being
evaluated, also for clinical trials and approvals.
In addition, the Federal Government is develo-
ping an interdisciplinary research strategy, under
the coordination of the Federal Agency for Safety
and Health At Work, within the framework of which,
in particular, the health and environmental risks of
insoluble nanoparticles are addressed. The strategy
includes, among other things, the development of
standardised measurement techniques for nanopar-
ticles, the collection of information on possible expo-
sures, with their toxicological and eco-toxicological
effects and the development of a risk related testing
and evaluation strategy. The Federal Government
attaches the greatest importance to a dialogue with
a well informed public and, to this end, is supporting
conferences, issuing newsletters, establishing Inter-
net portals and publishing analyses and press articles
containing information on the latest research results
and risk debates.
One instrument of information that is already
becoming popular is the nanoTruck, which travels
around Germany under the motto „nanoTruck:
High tech from the nanocosmos“ and reaches more
than 100,000 visitors per year. Also on board: the
BMBF brochure „Nanotechnology – Innovations for
the world of tomorrow“, already almost a standard
work, translated by the European Union into all the
languages of its member states and also into Arabic,
Chinese and Russian. A good thing, for, in view of
the complexity and far-reaching consequences of
nanotechnology, international consultation is of
particular importance. The Federal Government is
therefore participating intensively in international
activities connected with the responsible handling of
nanomaterials, for example in the framework of the
European Commission‘s action plan, the OECD „Wor-
king Party on Manufactured Nanomaterials“ and the
„International dialogue on responsible research and
development of nanotechnology“. Its aim is to coor-
dinate activities on the safety evaluation of nanoma-
terials, which are meanwhile very extensive, and to
establish internationally harmonised processes and
standards.
48
Nano-safety research by the BMBF: NanoCare
In order to ensure the compatibility of nanomateri-
als, the Federal Ministry for Education and Research,
together with the industry, has established the re-
search programme NanoCare. The BMBF will provide
NanoCare with about €5 million over the next three
years, while the industry will take part itself with a
further €2.6 million. NanoCare will bring to light
new scientific knowledge of the effects of nanoparti-
cles on health and the environment and will commu-
nicate this to the general public.
„If we are talking about health risks, then
all of those taking part in the corresponding
research projects see the problems with the
particles. As far as the need for research is con-
cerned, we must carry out studies for all impor-
tant materials to clarify possible exposures and
their biological effects.“
Prof. dr. Harald krug, NanoCare Coordinator.
rIsk MANAGEMENt IN NANOtECHNOLOGy
Interview with NanoCa-
re coordinator Prof. dr.
Harald krug from the
Institute for toxicology
and Genetics at the re-
search Centre karlsruhe.
What is special about the research project Nano-
Care, and what is its objective?
The objectives of NanoCare are special insofar as we
have a very large, integrated research programme,
essentially consisting of three parts. The first is the
generation of knowledge. In other words, we are
establishing relevant and evaluated testing systems
to test nanoparticles which are already in use today
and those currently in development for a possible
biological risk. We standardise these tests within
our consortium, which consist of nearly 10 partners
which also work in the biological sector. That means
that 10 different laboratories spread over Germany
have to apply the same methods. So we have a large
knowledge production section, in which we gene-
rate completely new data on the possible risk and
on possible exposure, including nanoparticles at the
workplace. The second pillar is knowledge manage-
ment, i.e. the knowledge gained is collected, com-
piled, internally processed, and stored in an internal
database, and then this processed information is
transferred to the third pillar. That means that, at
various events, also using publications and our own
large database, we shall distribute the information in
an appropriately presented form.
In what areas of nanotechnology - and it is a large
field - do you see a need for research as far as potenti-
al risks are concerned?
If we are talking about health risks, then all of those
taking part in the corresponding research projects
see the problems with the particles. As far as the
need for research is concerned, we must carry out
studies for all important materials to clarify possible
exposures and their biological effects. In the case of
nanotechnology and nanomaterials, we have the
great difficulty that we have to assess each material
individually and independently of others. Because,
among the materials, there are just as many different
variations, sizes and also surfaces which could be
active. So the results cannot be generalised, but this
already applies for many chemicals.
 49

50 rIsk MANAGEMENt IN NANOtECHNOLOGy

Activities of industry substances or technical processes harmful to health

Among the practical recommendations and proce-
dural instructions in the industrial nanoparticle sec-
tor is the „Guideline for activities with nanomaterials
at the workplace“, jointly prepared by the Federal
Agency for Health and Safety At Work (BAuA) and
the Association of the Chemical Industry (VCI). The
guideline clearly states:
„As a rule, in order to produce nanomaterials in the
form of isolated nanoparticles, extremely elaborate
chemical and physical processes are required. In most
cases, however, in the products currently produced
commercially at a larger scale, nanoparticles are not
present as individual particles, but aggregated and ag-
glomerated [see Glossary] as a group of several particles.
Aggregates and agglomerates are not nanoparticles in
the sense of the definition (see above), but nanostruc-
tured materials in which the nanoparticles are joined
together. The release of nanoparticles from these aggre-
gates and agglomerates is often impossible without a
major input of energy.
Some nanomaterials are already processed by the ma-
nufacturer to form granulates, formulations, dispersi-
ons or composites. In many cases, in the course of their
subsequent use, a release of isolated nanoparticles is
extremely unlikely.“
can be replaced by less hazardous substances or less
hazardous processes; production in closed systems,
if possible with the capture, limitation and removal
of dangerous gases, vapours and dusts at the point of
origin; provision of suitable washing facilities, pro-
tected storage of clothing not used at work, timing
of working procedures, training and briefing, access
and storage rules etc.; the use of personal protection
equipment, such as breathing masks, protective gog-
gles, gloves etc., in addition to technical and organi-
sational measures.
The potential risks of nanoparticle technology
are not in question; in the nature of things, they
are also to be expected. Particles which can initiate
useful chemical reactions can reveal their potency
just as well in unwanted reactions. In fact, there is a
string of evidence, mainly from in vitro „test-tube“
experiments, whose transferability to living orga-
The particles embedded in plastic granulates ensure long-lasting
effectiveness against bacteria and other microorganisms.

However, where risks cannot be ruled out, recom-

mendations are made which are largely identical
with those for other substances classified as po-
tentially hazardous, such as: Ascertain whether

Silver nanoparticles are directly precipitated into liquid carriers in an

integrated process. This process provides stable suspensions of isolated
particles with a large specific surface area and characterised by high
purity. Mean primary particle size 5 ... 50 nm
rIsk MANAGEMENt IN NANOtECHNOLOGy 51

Approximate estimate of the risk potential of different nanoparticles.

nisms is disputed, however. Thus, functions of the The expression refers to the clay mineral kaolinite, in
cell nucleus are apparently disturbed by nanoparti- use since the stone age, with which good pots can be
cles of silicon dioxide. C60 molecules and nano-scale baked. Under the electron microscope it can be seen
titanium dioxide have a lethal effect on water fleas, that the mineral consists of stacks of flat nanocry-
even in relatively low doses. The British Royal Society stals, similar to a roll of notes. When the nanocrystals
and the Royal Academy of Engineering see a need for are isolated by means of physicochemical tricks, the
research on zinc oxide for use in sunscreen agents. result is nanoclay, a versatile filler substance which,
The table enumerates a series of nanoparticles used for example, makes PET bottles more impermeable
in large numbers either now or in the near future to gas.
and gives a rough assessment.
A more solidly based classification is obvious-
ly hindered by the lack of comparability of many
studies due to insufficiently uniform methodologies.
The correction of this and other deficiencies is the
goal of a research strategy at present being worked
out by the Federal Agency for Health and Safety At
Work, the Federal Institute for Risk Assessment and
the Federal Department for the Environment. How
close together the old and the new can sometimes be
is shown in the table by the example „Nanoclay“.
52 sMALL PArtICLEs, LArGE EFFECts – OPPOrtUNItIEs ANd rIsks OF NANOPArtICLE tECHNOLOGy

Small particles, large effects – opportunities and

risks of nanoparticle technology
W

The waste heaps of nature, deposits of sunken living creatures once pro-
tected by chalky shells, become sightseeing destinations when geologi-
cal forces raise them above the surface – like the white cliffs of Dover.
 sMALL PArtICLEs, LArGE EFFECts – OPPOrtUNItIEs ANd rIsks OF NANOPArtICLE tECHNOLOGy 53

where. There is no alternative to efficient electric

motors. Very possibly, they will also contain nano-
scale magnetic materials.
Insofar as nanoparticles are toxic, ways and
means will be found to bind them in or to make them
safe in other ways. It all depends on the compound,
as chemists have always known. The elements sodi-
um and chlorine, for example, are both extremely
unappetising, but together they give sodium chlori-
de, common salt, which is indispensable for human
life.
With nanoparticles, the realisation of new ma-
terials for everyday life will also be possible, which,
at the end of their product life, will decompose
non-toxically like any leaf from a tree, or will at least
break down non-toxically in water. The urgency of
this problem is shown by reports of the „Pacific gyre“,
a whirlpool in the Pacific carrying plastic waste over
an area as large as Central Europe, an estimated
3,000,000 tonnes and growing - bottles, toys, six-
pack rings closely packed - a deadly danger for many
marine creatures. An extinction of species has now
started in the seas, comparable to that on land - a ca-
tastrophe of geohistoric proportions. So scientists are
urgently calling for the long overdue modernisation
of the industrial societies. Nanotechnology can help
here.
Warnings of this kind, of course, have long ema-
nated from reputedly sectarian circles, but they are
now also found on the websites of the aerospace and
armaments industry, wherever scientists are active.

A lime leaf, a disposable

item in nature, masters the
process of photosynthe-
sis: How are energy-rich
chemicals made from light,
water, carbon dioxide and
trace elements? Science is
no longer very far from its
complete decoding, which
will open a gigantic field of
work for nanotechnology -
and will undoubtedly earn
Nobel Prizes.
54
Glossary
Aerosols: Mixtures of solid or liquid particles with
air. Because of potential damage to the human
respiratory tract, aerosols are the subject of intensive
research. Air can carry particles in the size range of
particles, of which air itself consists, up to over 100
microns. Of primary importance for human health
are particles <10 µm.
Agglomerates, Aggregates: These terms have long
been used in powder technology to describe agglo-
merations of particles, but not always uniformly,
which sometimes leads to confusion. In German
industry, the term „aggregate“, when applied to
nanoparticles, means a group of a few particles ad-
hering to each other through strong chemical bonds.
„Agglomerates“, on the other hand, are collections
of aggregates, mainly held together by the weaker
Van-der-Waals bonding. There are smooth transi-
tions between aggregates and agglomerates.
Nanoparticles Aggregates Agglomerates
Bulk: In connection with nanoparticles, usually a
designation for the coarsely structured mother sub-
stance from which the nanoparticles are produced.
CdS: Cadmium sulphide, usually a synthetic com-
pound, but also occurring as a natural mineral. Used
among other things as a light fast pigment for paints
and plastic parts, now out of favour because of its
cadmium content.
CNT: Carbon NanoTubes for a large number of ap-
plications. Added to plastic material, CNTs improve
the mechanical properties of tennis racquets, for
example, make the material electrically conductive,
so prevent electrical charges (important for tank
GLOssAry
facilities) and increase thermal conductivity. Also see
SWNT and MWNT.
Computer tomography: The conversion of data
from a specific volume (a rib cage, a cell) into plastic
images. Best known are medical applications like x-
ray computer tomography, while the most spectacu-
lar technique is cryo-electron microscopy, which also
permits the display of molecular nanomachines.
Dendrimers: New class of substances, polymers of
supermolecular chemistry, „hyperbranched“ like a
tree or bush, with ever more astonishing properties.
On the numerous arms of such a molecule, a wide va-
riety of tools can be coupled. Between the branches
there is room for guest molecules, such as drugs for
cancer therapy.
Dendrimer space-filling model.
Between the branches of the
molecule, other substances can
be accommodated and functional
groups can be attached to the ends
of the branches.
Epidemiology: Research of causes, consequences
and spread of factors harmful to health for large
population groups using statistical methods, among
others.
Fine dust, ultrafine dust: Dust is ubiquitous and, in
principle, unavoidable. However, technical activities,
particularly combustion engines, have greatly incre-
ased pollution of the air. According to the size of the
particles, it is referred to as airborne dust, fine dust or
ultrafine dust. Airborne dust has a size of more than
10 microns (1 micron – µm – is 1 millionth of a metre).
Fine dust refers to a particle size between 0.1 µm (100
nanometres) and 10µm. Ultrafine dust has a particle
size of less than 100 nanometres.
• Fine dust up to a size of 10 µm reaches the upper
region of the lung;
• Fine dust with particles <2.5 µm reach the central
region of the lung.
GLOssAry
• Ultrafine dust is smaller than 100 nanometres and
can even penetrate into the lung‘s alveoli and circu
late further in the bloodstream.
Fullerenes: Group of molecules which owe their
name to their similarity with the architectural ele-
ments of Buckminster Fuller (1895 – 1983). The fulle-
renes include the „football molecule“ C60, also know
as a buckyball and hollow tubes of carbon atom
networks, buckytubes. Fullerenes now represent a
large group of substances; it is also known that balls,
networks and tubes can also be constructed using
atoms other than carbon.
Hollow fullerene
sphere, loaded with a
guest atom (model).
MWNT: Multiple Wall NanoTube – carbon nanotube
(CNT) with a multilayer wall.
Triple walled carbon nanotube
NanoClay: Filler substance, mainly consisting of
nano-scale platelets of the mineral montmorillo-
nite, which occurs in clay. With small additions, the
properties of plastics, for cables, PE foam, interior
and exterior parts for automobiles etc., can be much
improved. Used in PET bottles, it increases their
impermeability to gas, carbonised drinks remain
sparkling for longer and protection against atmos-
pheric oxygen is increased many times. Is also used
in foils for food packaging.
55
Plasma torch: Hot, highly ionised space in a gas
discharge reactor, in which, through the injection of
selected substances, many different kinds of nano-
particles can be synthesised.
Plasma torch
SWNT: Single Wall NanoTube – carbon nanotube
(CNT) with a single layer wall.
Single walled carbon
nanotubes.
TiO2: Titanium dioxide, among other things a white
filler for wall paints and heavy paper, may have a
starring career before it as a nano-scale component
of solar cells (Graetzel cell). Nanoparticles of TiO2
convert components of the air into reactive sub-
stances with a cleaning and sterilising effect when
exposed to light (photocatalysis). Nano-scale TiO2
is a subject of nano-safety research, but is already
used in large quantities in Japan as a photocatalyst.
Normal TiO2 white pigment is completely non-toxic,
is contained in toothpaste and gives white salami
skin its desired floury feel, without being susceptible
to microbic contamination.
ZnO : Zinc oxide, compound of zinc and oxygen. Its
traditional designation „zinc white“ refers to its use
in paint pigments. Because of its antiseptic effect, it is
also used in ointments. Nanoparticles of ZnO serve as
a UV screen in sun creams.
56 FUrtHEr INFOrMAtION

Further information
Internet addresses • European Nanotechnology Portal:
www.nanoforum.org
• Nanotechnology support from the EU:
Nanotechnology activities of the federal authori- www.cordis.lu/nanotechnology
ties
• www.bmbf.de/de/nanotechnologie.php
• www.baua.de/nanotechnologie Brochures
• www.bmu.de/nanotechnologie
• www.bfr.bund.de/cd/3862?index=78&indexid=7585
• www.umweltbundesamt.de/gesundheit/stoffe/ • Nano Initiative – Action Plan 2010, BMBF 2006
nanopartikel.htm • Hochschulangebote im Bereich Nanotechnolo-
• http://www.bmelv.de/cln_044/nn_749972/DE/02- gie, VDI TZ GmbH 2006
Verbraucherschutz/FAQNanotech.html • Nanotechnology – Innovations for tomorrow’s
world, BMBF 2006, 3. revised edition
Nanotechnology risk research and communica- • Dual training in innovative fields of technology,
tion BMBF 2005
• Nanotechnology conquers markets, BMBF 2004
• BMBF Project NanoCare:
www.nanopartikel.info
• BMBF Project INOS:
www.nanotox.de
• BMBF Project Tracer:
www.nano-tracer.de
• Info portal zu Nano regulation:
www.nano-regulation.ch
• Nanotechnology Standardisation ISO TC 229:
www.iso.org
• Information and data bases on the risk assess
ment of nanomaterials:
www.icon.rice.edu
• Info portal Nano safety research:
www.safenano.org

Other Internet portals

• High-Tech Strategy for Germany:

www.ideen-zuenden.de
• Nanotechnology portal of VDI TZ GmbH:
www.nanonet.de
• German Nanotechnology Competence Atlas:
www.nano-map.de
• Scientific communication on nanotechnology:
www.nanotruck.de
• Virtual voyage into the nanocosmos:
www.nanoreisen.de
• Educational opportunities in nanotechnology:
http://nanobildung.tech-map.de
INdEx OF ABBrEvIAtIONs 57

Index of Abbreviations
BAuA: Bundesanstalt für Arbeitsschutz und Arbeits- VCI: Verband der Chemischen Industrie (Associaton
medizin (Federal Institute for Occupational Safety of the German Chemical Industry)
and Health)
VDI: Verein Deutscher Ingenieure (Association of
BfR: Bundesinstitut für Risikobewertung (Federal Engineers)
Institute for Risk Assessment)
UV: Ultraviolet
BMBF: Bundesministerium für Bildung und For-
schung (German Federal Ministry for Research)

BMELV: Bundesministerium für Ernährung, Land-

wirtschaft und Verbraucherschutz (German Federal
Ministry for Consumer Protection)

BMU: Bundesumweltministerium (Federal Ministry

for Environment)

CNT: Carbon Nanotubes

DECHEMA: Gesellschaft für Chemische Technik und

Biotechnologie

DIN: Deutsches Institut für Normung (German Insti-

tute for Standardisation)

DNA: Deoxyribonucleic Acid

ECETOC: European Centre for Ecotoxicology and

Toxicology of Chemicals

EKG: Electrocardiogram

GSF: Deutsches Zentrum für Gesundheit und Umwelt

ISO: International Standardisation Organisation

OECD: Organisation for Economic Cooperation and

Development

PM: Particulate Matter (dust)

PE: Polyethylene

PET: Polyethylene terephthalate

RFID: Radio Frequency Identification

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