!"#$%$&"'$(($%%)
!"#$%&'()*+,*-$./-0")1()1-
five years on
BY NANCY MILLS
The fruits of five years of user operations
at the Australian Synchrotron include
some fine examples of scientific research
and collaboration.
J
uly marked five years of user
operations for the Australian
Synchrotron (AS). More than
3000 researchers, many of them
chemists, from 186 organisations
and 27 countries, have made a
combined total of 10 000 visits to
use the synchrotron’s cutting-edge
techniques.
To date, more than 1000 refereed
journal publications have resulted
from activities funded through
the AS, with over half of these a
26!|
Chemistry in Australia
direct result of research conducted
at AS beamlines. These include
developments in areas of strong
national interest such as agriculture,
medical and biosciences, materials
science, minerals, energy and the
environment.
What have users done?
Ask the synchrotron’s principal scientists
to nominate the most significant
research projects or groups that
have used their beamlines, and their
August 2012
synchrotron milestone
unanimous response is ‘that’s a very
tough question’. The following examples
illustrate but do not fully capture the
diversity and outstanding quality of the
research groups that use the AS.
Concrete – largely gravel, sand,
water and a binder such as Portland
cement – has been a popular
construction material for centuries.
The key is the cement, a mixture of
various minerals, including tricalcium
silicate (3CaO.SiO2) and aluminate
(3CaO.Al2O3), which hydrates when
mixed with water and then hardens
to bind the aggregate particles.
Unfortunately, however, the
manufacture of cement for concrete
produces 5–8% of the world’s carbon
dioxide. Geopolymer alternatives
replace the high-calcium binder
with industrial wastes such as fly ash,
simultaneously cutting CO2 emissions
by 80% and solving a major wastemanagement problem.
Melbourne company Zeobond
produces ‘green’ cement on a
commercial scale for use in footpaths
and major road construction projects.
Researcher John Provis, until recently
August 2012
at the University of Melbourne, has
used synchrotron infrared and X-ray
techniques to investigate the basic
chemistry of geopolymer formation. His
results are improving our understanding
of these materials, and aiding Zeobond
in utilising other waste materials and
designing green cements for specific
applications.
Visiting the synchrotron in May 2012,
Zeobond’s chief operating officer Peter
Duxson said there was huge potential
for geopolymer cements to replace
conventional alternatives in major
construction projects in China and India.
This could have a significant impact on
global carbon emissions.
Another project with industrial
and environmental impacts is Nathan
Webster’s powder diffraction studies of
the Bayer process for extracting alumina
(Al2O3) from bauxite. Nathan and
colleagues from CSIRO Process Science
and Engineering developed and used
a new powder diffraction flow cell to
replicate Bayer process temperature
and pH conditions. Their focus was the
mechanism of formation of gibbsite
(Al(OH)3) and other troublesome and
expensive scale deposits on mild steel
process equipment.
Xuebin Yu (formerly from
Wollongong University) from Fudan
University in Shanghai has been
using powder diffraction since 2009,
in collaboration with Wollongong
University researchers and Qinfen
Gu from the AS. The collaborators are
synthesising and solving the crystal
structures of promising new hydrogen
storage materials with storage
capacities up to 18% by weight – well
above the design target of 6.3% set by
the US Department of Energy. Several of
these structures can release hydrogen
at relatively low temperatures.
The molecular shape
of things to come
Stuart Batten and his Monash University
research group are using smallmolecule X-ray crystallography to
investigate supramolecular ‘nanoball’
cages (~ 3 nanometres across)
synthesised using self-assembly of
divalent octahedral metal cations and
a scorpionate ligand. Functionality is
determined by the cation. Nanoballs
Chemistry in Australia
| 27
have potential applications in gas
storage or as magnetic switches for
electronic switching devices, data
storage and molecular sensing.
Void space and crystal size make
synchrotron microcrystallography
essential.
International collaborators Sota Sato
and Makoto Fujita from the University
of Tokyo and Kari Rissanen from the
University of Jyväskyla in Finland,
with assistance from Christine Gee
at the AS, recently demonstrated the
successful prediction and controlled
self-assembly of huge M24L48 spheres
formed from palladium ions and
pyrrole ligands. The work is inspired
by spherical virus capsids and other
huge, well-defined, naturally occurring,
self-assembled structures.
Two other scientists achieving
notable results from small-molecule
X-ray crystallography are Michael
Gardiner from the University of
Tasmania and Kei Saito from Monash
University.
Michael and his colleagues
are deriving the structures of
organometallic complexes involved in
C–C bond-forming reactions, as part of
their research into industrial palladium
and platinum catalysts. Ligand binding
in organometallic complexes is highly
variable, so single-crystal structure
determinations are important for
unambiguous identification. However,
the collaborators’ Pt(III) and Pd(I)
complexes only form single crystals
of 10–40 microns. Using the AS, the
researchers obtained publishable
quality structures, helping them attract
an ARC Discovery Project grant for
further work.
Green chemist Kei Saito is using
microcrystallography to assist the
development of a novel polymer
recycling system based on thyminefunctionalised monomers that
undergo solvent-free, photo-reversible
polymerisation in the solid state.
Monomer crystal structures are vital for
determining reactant topochemistry and
structure–function relationships. Kei’s
28!|
Chemistry in Australia
aim is to identify naturally occurring
mechanisms that can be exploited
in synthetic systems using polymer,
supramolecular, catalyst and nano
chemistry.
*++,("-,(%./"0(12$&)1%."
34"5,)6,(1,"
Joint research
Many human joints exploit lubrication
mechanisms familiar to us from
mechanical systems. Boundary
lubrication, in which adsorbed
molecules form a thin lubricating layer
between two surfaces that are rubbing
together, is thought to be important as
the last line of defence to prevent wear
of joint surfaces. David Beattie and his
University of South Australia team are
using infrared microspectroscopy to
study the molecular basis of boundary
lubrication in polymer multilayer
systems that combine chitosan with
hyaluronic acid or fucoidan, a sulfated
polysaccharide from seaweed. The
work will aid the development of novel
lubricants for bio-implants.
Image matters
X-ray fluorescence microscopy (XFM)
maps the presence, location and
chemical speciation of trace metals
in biological and other environmental
samples. Enzo Lombi, from the
University of South Australia, and his
collaborators have undertaken many
XFM studies, such as looking at rice
varieties enriched with iron and zinc
for nutritional purposes. Environmental
pollution and remediation projects
include mapping arsenic in plant roots,
selenium in rice, mercury in hair and
toenails, contaminant metals in biochar
and soil organic matter, lead exposure
in animal models, lead scale and
oxidation in drinking water pipes, and
copper and zinc in sewage waste.
More recently, Enzo has begun
looking at the ecotoxicology of
manufactured silver nanomaterials,
which are used in some consumer
products for their antimicrobial
properties. The environmental fate of
nanoparticles is thought to be linked to
surface chemistry and functionality.
.1+,2$'(*(#$'()&0(&)#$13$4,-&0+#*)$5(67778$019:+#;$
<5(=>#?@864,:/8=A7$,'1+*(#2$*'$*-$
,-(#)9#2,*(#$,-$1;,2*(,B#$*22,(,1-$(1$5(6778C
David Thurrowgood from the
National Gallery of Victoria and
Deborah Lau from CSIRO Materials
Science and Engineering are
working with Daryl Howard from
the AS to develop XFM techniques
for mapping different elements in
paintings. Knowing which elements are
present and where provides valuable
information on pigment usage, assisting
scholars, curators and restorers – and
potentially helps to answer questions of
provenance and authenticity.
David, Deborah and Daryl have
captured the world’s highest-definition
elemental maps of the surfaces of
historic paintings and conducted an
in-depth study of a self-portrait of Arthur
Streeton subsequently painted over by
the artist. They are continuing to refine
their methods.
August 2012
synchrotron milestone
D#3($(1$),E"(F$%)("&)$.()##(1-$'#+3G:1)()*,($,-$B,',4+#$+,E"(H$I,-0$9*:H$I,-0$9*:$01))#0(#2$31)$+#*2$:*,-($1B#)+*/C$
More for users
In April 2012, the synchrotron opened its
onsite guesthouse for users, offering 50
self-contained rooms, a large communal
kitchen, laundry facilities and reception
areas with fast wireless internet
access. The new National Centre for
Synchrotron Science provides improved
user office facilities, a 320-seat
auditorium, a purpose-built education
laboratory and a cafeteria.
In May 2012, the AS began using
‘top-up’ injections for stored beam
operations, improving long-term photon
beam stability and consistency for
user experiments. In top-up mode,
the electron beam current in the
storage ring is maintained to within
a few per cent by delivering single
shots every few minutes. This replaces
scheduled 12-hourly injections. Top-up
implementation has involved 12 months
of effort by AS accelerator physicists,
operators, engineers, technicians and
others led by Greg LeBlanc.
August 2012
The upgraded and extended
imaging and medical beamline will be
made available to expert users later this
year in preparation for general usage
in 2013. While the beamline will mainly
be used for biomedical purposes, it will
also be of keen interest to chemists and
others engaged in materials science or
studying specimens such as fossils that
cannot be sectioned.
An eye to the future
In March 2012, after months of media
speculation, the federal and state
governments jointly announced funding
totalling $100 million for the next four
years of AS operations. More than half
this total has been secured from the
ARC’s Special Research Initiative, with
NHMRC and university support. The
remainder will come mainly from the
Victorian Government, ANSTO and
the New Zealand Government, and by
application to the Science and Industry
7,&.+"839,&:/"*;)%&,+1,("<.(=>&3%&3("
Endowment Fund, which was recently
rejuvenated with monies from CSIRO’s
wireless LAN licensing fees
‘We’re indebted to the university
and CSIRO communities for their
continued support for our efforts to
secure operational funding,’ AS director
Keith Nugent said. ‘We also plan to
apply for additional funding from
competitive grant sources to upgrade
our equipment and further expand
our capabilities.’
AS staff are working with the facility’s
Science Advisory Committee and
synchrotron researchers from Australia
and New Zealand to ensure that work
on new equipment and upgrades can
begin as soon as this additional funding
becomes available. Beamline scoping
groups are developing design concepts
for several proposed new beamlines.
Nancy Mills <[email protected]>
is the Australian Synchrotron’s science writer.
Chemistry in Australia
| 29