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Source: Karen
Wooley's Web page (314) 935-7136
Related: Article
on Wooley in Wasington Magazine,Spring
2001
Related: Record
article on Wooley's receipt of
the Cope award

New
nanoparticle coating mimics dolphin
skin Prevents 'biofouling' of
ship hulls

[St. Louis, MO.,
10-27-02]

By Carolyn Jones Otten
Dolphins, long considered the
second-smartest species on the
planet, recognize one another
by name, possess a distinct concept
of "self' and, it turns out, have
some surprisingly good ideas about
techniques for keeping the hulls
of maritime ships clean.
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Karen Wooley |
Karen
L. Wooley, Ph.D., professor of
chemistry at Washington University
in St. Louis, has noted the shape
and texture of dolphin skin and
how it naturally prevents marine
creatures from clinging to dolphin
skin. The observation fits into
her study of finding ways to mediate
interactions between biological
systems and synthetic materials,
designing chemical "functionalities,"
or groups of atoms, that either
promote or discourage binding
between them.
In one recent example, Wooley
and collaborator John-Stephen
A. Taylor, Ph.D., Washington University
professor of chemistry, hope to
employ nanoparticles that will
take advantage of naturally occurring
chemical interactions to deliver
therapeutic drugs directly to
diseased cells. At the same time,
Wooley currently is developing
a group of nontoxic "antifouling"
coatings that may one day inhibit
marine organisms such as barnacles,
tube worms and zoo spores from
attaching to, say, the hulls of
ships.
"Basically if we understand how
these various materials interact
at the molecular level, then we
can turn the interactions on or
turn them off," said Wooley. "With
the nanoparticles we want to turn
them on; with the antifouling
coatings materials we want to
turn them off."
Fouling is a huge problem for
the U.S. Navy as well as the commercial
shipping industry. Marine organisms
secrete a type of gluey adhesive
protein and, over time, cause
physical damage by promoting corrosion
of the metal. However, the more
pressing problem is their effect
on a ship's performance -- the
extra growth on the hull increases
friction and drag, leading to
increased energy consumption.
And fouling is more than just
an economic issue; a less fuel-efficient
ship emits greater amounts of
the greenhouse gas carbon dioxide
in addition to sulfur and nitrogen
oxides, which promote acid rain.
Wooley presented her research
to an international group of science
writers, Oct. 27, 2002, at the
Council for the Advancement of
Science Writing's New Horizons
in Science 40th Annual Briefing.
New Horizons was held Oct. 27-30
at Washington University in St.
Louis, which sponsored the event.
Wooley's research is supported
in part by research grants from
the National Science foundation
and the Office of Naval Research.
Do like the dolphins
do

The key to Wooley's antifouling
agents is, perhaps counter-intuitively,
their three-dimensional topography,
which mimics such naturally occurring
hydrodynamic surfaces as the skin
of a dolphin. Using high-powered
electron microscopy, researchers
have found that dolphin skin,
for all its seeming smoothness,
is slightly rippled on the nanometer
scale. Still, these ripples are
not large enough to hinder movement
through the water but are small
enough that they leave few "niches"
for marine creatures to grip.
"For a long time antifouling work
was geared toward making super-smooth
surfaces," explained Wooley. "It
was thought that if the surfaces
were super-smooth and had less
surface energy then the organisms
couldn't attach.
"In fact, that's completely false,"
she continued. Her current antifouling
project "completely goes against
the grain of what was being done.
I think that I generally like
to do that -- just try the completely
opposite approach and see what
happens."
Of course, marine fouling isn't
new, and for years the problem
has been combated by applying
tin or copper-based coatings,
which reduce aquatic attachment
but come at a price: copper and
tin leach into the surrounding
water, polluting the environment.
In fact, the International Maritime
Organization, an agency of the
United Nations, has called for
a worldwide ban on the use of
the tin-based paint by 2003 and
aims to completely remove it from
all ships by 2008 -- a timetable
that has increased demand for
a non-toxic replacement.
Wooley, an organic polymer chemist
by trade, became aware of the
problem, through the Office of
Naval Research (ONR) which for
years supported research into
fluoropolymers (for instance,
Teflon and other non-stick polymers)
and other minimally adhesive surfaces.
Wooley formulated the idea of
mixing two normally incompatible
polymers -- a hyperbranched fluoropolymer
and a linear polyethylene glycol
-- and allowing them to phase-separate
into distinct domains, one interspersed
in the other. A chemical process
called crosslinking then solidifies
the mixture, thus creating a heterogeneous
coating that, upon close examination,
reveals treacherous nano-sized
terrain composed of mountains
and valleys, ranging from hard
to soft, hydrophilic to hydrophobic.
Getting a feel
for the terrain

So how does such a coating minimize
macroscopic fouling? The key is
the complex surface, which makes
it difficult for marine organisms
to establish a toehold. Wooley's
hypothesis is that, if the coating's
surface features are in the same
size-regime as the secreted protein,
then the protein will be unable
to bind sufficiently to maintain
attachment.
"When the polymer surface is first
prepared, it looks like a bunch
of sub-microscopic mountains but
when it's placed under artificial
sea water, the entire surface
swells and gives us this inverted
structure," Wooley explained.
"I think this is really exciting
because what it means is that
we can 'tune' the size of the
surface features and determine
whether our hypothesis is really
correct -- do surface feature
sizes influence the attachment
of marine organisms?"
If she's right, the implications
could be straight out of science
fiction: man-made ships protected
by layers of synthetic dolphin
skin. Mother Nature, it seems,
may have some competition.
Questions

Contact: Gerry Everding, Office
of Public Affairs, Washington
University in St. Louis, (314)
935-6375; gerry_everding@aismail.wustl.edu
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