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collaborators work is then the successful

indirect patterning of immunoglobulinG
(IgG). In this experiment, Protein A, which
has high affinity for the Fc domain of
immunoglobulins, was functionalized with
Q-peptide using a standard, nonspecific
bioconjugation technique (maleimide
thiol chemistry), and then photopatterned
into the hydrogel. Subsequent incubation
with a fluorescently tagged IgG resulted in
spatially controlled protein patterning as
observed with VEGF121, FN9-10 and PDGFBB. This demonstration exemplifies how
the method could be readily translated to
pattern commercially available Fc chimeric
proteins, which has important implications
for using dynamic protein patterning in

cell-biology studies. As this approach

would circumvent the need to engineer
proteins to present the Q-peptide domain, it
should make the chemistry more accessible
and thus facilitate its broader adoption.
Ultimately, Lutolf and colleagues method
should help shed light on fundamental
questions related to stem cell biology, tissue
morphogenesis and disease.

Daniel L.Alge and Kristi S.Anseth are at

the Department of Chemical and Biological
Engineering, the BioFrontiers Institute,
and the Howard Hughes Medical Institute,
University of Colorado at Boulder, Boulder,
Colorado 80303, USA.
e-mail: Kristi.Anseth@Colorado.EDU

References
Mosiewicz, K.A. etal. Nature Mater. 12, 10721078 (2013).
Tsien, R.Y. Angew. Chem. Int. Ed. 48, 56125626 (2009).
Losonczy, A. & Magee, J.C. Neuron 50, 291307 (2006).
Lee, S.H., Moon, J.J. & West, J.L. Biomaterials
29, 29622968 (2008).
5. DeForest, C.A., Polizzotti, B.D. & Anseth, K.S. Nature Mater.
8, 659664 (2009).
6. Alge, D.L., Azagarsamy, M.A., Donohue, D.F. & Anseth, K.S.
Biomacromolecules 14, 949953 (2013).
7. Culver, J.C. etal. Adv. Mater. 24, 23442348 (2012).
8. Kloxin, A.M., Kasko, A.M., Salinas, C.N. & Anseth, K.S. Science
324, 5963 (2009).
9. Wirkner, M. etal. Adv. Mater. 23, 39073910 (2011).
10. Griffin, D.R. etal. Biomacromolecules 14, 11991207 (2013).
11. DeForest, C.A. & Anseth, K.S. Angew. Chem. Int. Ed.
51, 18161819 (2012).
12. Guvendiren, M. & Burdick, J.A. Nature Commun. 3, 792 (2012).
13. Luo, Y. & Shoichet, M.S. Nature Mater. 3, 249253 (2004).
14. Wylie, R.G. etal. Nature Mater. 10, 799806 (2011).
15. Zisch, A.H., Schenk, U., Schense, J.C., Sakiyama-Elbert, S.E. &
Hubbell, J.A. J.Control. Release 72, 101113 (2001).
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4.

STRUCTURAL TRANSITIONS

Ferroelectricity in a metal

The discovery of a ferroelectric-like structural transition in metallic LiOsO3 identifies a new class of materials with
unconventional properties, providing an exotic playground for theorists and experimentalists.

Veerle Keppens

erroelectric materials exhibit an

intrinsic electric polarization that
can be changed or reversed by an
applied electric field. While initially
ferroelectrics were little more than an
academic curiosity, today they can be
found at the heart of many technological
devices that exploit their ferro-, piezoand pyroelectric properties, with the
most advanced application perhaps
being that of ferroelectric non-volatile
memories1. Although metallic behaviour
and ferroelectricity have long been thought
to be incompatible because conduction
electrons screen the internal electric
field, Anderson and Blount 2 nonetheless
suggested almost 50years ago that certain
structural transitions observed in metals
might be ferroelectric in nature. However,
a clear example of a ferroelectric metal
has so far remained elusive. Writing
in Nature Materials, a collaboration
led by Kazunari Yamaura and Andrew
Boothroyd now reports the discovery of a
structural ferroelectric-like transition in
LiOsO3, which might very well be the first
realization of a ferroelectric metal3.
Ferroelectric materials typically
undergo a phase transition at the Curie
temperature TC , from a high-temperature
non-polarized paraelectric state to a
low-temperature ferroelectric (polarized)
state4. The spontaneous polarization is a
952

a Piezoelectric material
++++++++

Applied
stress

b Pyroelectric material
++++++++

Temperature
change

c Ferroelectric material
++++++++

++++++++
Applied electric
field

Figure 1 | Piezoelectric, pyroelectric and

ferroelectric materials. a, In piezoelectric
materials, the coupling between mechanical and
electrical energy results in an electric polarization
when stress is applied. b, The polar axis of a
pyroelectric material allows a net polarization
when the temperature is changed. c, Ferroelectrics
are a special subset of pyroelectrics, in that their
polarization can be reversed on the application
of an electric field. All ferroelectrics are both
pyroelectric and piezoelectric.

consequence of the structural transition

that takes place at TC , and involves a
(usually small) symmetry-breaking
distortion. The structure of the lowtemperature ferroelectric material is always
non-centrosymmetric, and therefore
does not display inversion symmetry,
as this prevents the charge separation
inherent to the electric polarization5. The
compound BaTiO3 is often regarded as
the prototypical ferroelectric, belonging
to a family of ferroelectrics known as
perovskite oxides. Below 393K, the cubic
BaTiO3 structure distorts to a ferroelectric
tetragonal structure, a transition that is
dominated by small displacements of Ti
atoms with respect to the oxygen network.
Another celebrated ferroelectric found
in many technological applications is
LiNbO3. Although it bears some similarities
to the cubic perovskites, the hightemperature structure is rhombohedral.
The low-temperature ferroelectric phase is
obtained from small symmetry-breaking
displacements of the Li atoms, with the loss
of the inversion symmetry resulting in a
spontaneous polarization at 1,483K.
The compound discovered by
Yamaura, Boothroyd and colleagues3 is
closely related to LiNbO3. It displays the
same rhombohedral structure at high
temperatures and undergoes a structural
phase transition at 140K, involving a

NATURE MATERIALS | VOL 12 | NOVEMBER 2013 | www.nature.com/naturematerials

2013 Macmillan Publishers Limited. All rights reserved

news & views

shift in the position of the Li atoms.
Given the metallic nature of LiOsO3, the
similarity of its structural behaviour with
LiNbO3 is quite surprising: free electrons
typically screen the Coulomb interactions
that favour the off-centre displacements,
preventing ferroelectricity.
To be considered a ferroelectric metal
according to the definition of Anderson
and Blount2, several criteria have to be met.
First, the structural transition has to be
continuous (which is to say that it cannot
show discontinuous jumps in physical
properties that are first derivatives of the
free energy, such as the heat capacity);
second, the low temperature structure has
to be non-centrosymmetric; and third, the
low-temperature structure needs to support
a unique polar axis (which is a rotational
axis of symmetry without a mirror plane
perpendicular to it). Whether or not a
material has such a polar axis is determined
solely by its crystal structure and

establishes the subtle difference between

piezo- and pyroelectrics, illustrated in
Fig.1. Almost a decade ago, the pyrochlore
system Cd2Re2O7 was tentatively identified
as a potential ferroelectric metal6, but it
falls short: although the material displays a
continuous phase transition to a structure
that lacks inversion symmetry, it does
not support a unique polar axis and is
therefore considered piezoelectric, but
not ferroelectric. The compound LiOsO3
does possess the essential polar axis, and
combined with the structural transition
involving Li-ion displacements, it satisfies
the Anderson and Blount criteria to
be considered a ferroelectric metal.
Some caution, however, is warranted
as the metallic nature of the compound
prevents an actual polarization from
being observed.
The findings reported by Yamaura
and Boothroyd3 point to the very first
realization of ferroelectric behaviour in

NATURE MATERIALS | VOL 12 | NOVEMBER 2013 | www.nature.com/naturematerials

2013 Macmillan Publishers Limited. All rights reserved

a metallic compound, and more unusual

behaviour is likely to be discovered in this
material. Although practical applications
are at this stage hard to envisage, the
ferroelectric-like transition found in
LiOsO3 is quite unique, and its further
study may help elucidate ferroelectric
transitions in related technologically
relevant materials.

Veerle Keppens is at the Department of Materials

Science and Engineering, the University of
Tennessee, Knoxville, Tennessee 37996-2100, USA.
e-mail: vkeppens@utk.edu
References
Scott, J.F. & Paz de Araujo, C.A. Science 246, 14001405 (1989).
Anderson, P.W. & Blount, E.I. Phys. Rev. Lett. 7, 217219 (1965).
Shi, Y. etal. Nature Mater. 12, 10241027 (2013).
Rabe, K. etal. Topics in Appl. Phys. 105, 130 (2007).
Halasyamani, P.S. & Poeppelmeier, K. Chem. Mater.
10, 27532769 (1998).
6. Sergienko, I. etal. Phys. Rev. Lett. 92, 065501 (2004).
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5.

Published online: 22 September 2013

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