NANO

LETTERS

Cooperative Assembly of Magnetic 2003

Vol. 3, No. 11
Nanoparticles and Block Copolypeptides 1489-1493
in Aqueous Media
Larken E. Euliss,†,‡,§ Stephanie G. Grancharov,†,‡,| Stephen O’Brien,|
Timothy J. Deming,§ Galen D. Stucky,§ C. B. Murray,‡ and G. A. Held*,‡

IBM TJ Watson Research Center, PO Box 218, Yorktown Heights, New York 10598,
Departments of Chemistry and Biochemistry and Materials, UniVersity of California,
Santa Barbara, California 93106, and Department of Applied Physics,
Columbia UniVersity, New York, New York 10027

Received July 3, 2003

ABSTRACT
We demonstrate that highly crystalline, monodisperse maghemite (γ-Fe2O3) nanoparticles, synthesized in organic solvents, can be effectively
transferred into an aqueous medium using an ammonium salt and stabilized at neutral pH. The nanoparticles remain monodisperse, as
characterized by TEM and XRD, as well as superparamagnetic, as determined by SQUID magnetometry. When the aqueous maghemite is
combined with the block copolypeptide poly(EG2-lys)100-b-poly(asp)30, the nanoparticles assemble into uniform clusters comprised of approximately
20 nanoparticles, resulting in a water soluble block copolypeptide−nanoparticle composite structure.

As methods of controlling the crystalline structure, magnetic
properties, and interparticle ordering of magnetic nano-
particles improve,1 so also does the interest in utilizing them
as building blocks for new devices2,3 and composite materi-
als.4 In particular, there has been much interest in utilizing
magnetic nanoparticles in biological applications such as
magnetic resonance imaging contrast enhancement5 and drug
delivery.6,7 In the case of drug delivery, magnetic fields can
be utilized to direct the particles (and thus the drug) to
specific locations within the body. However, before these
particles can act as drug delivery agents, they must be
stabilized in a physiological environment. Block copoly-
peptides provide one promising means of stabilizing drug
carriers.8 These block copolypeptides can self-assemble into
micelles that are capable of trapping drugs within a hydro-
phobic core, while their hydrophilic exteriors can be designed
so as to be stable within a wide range of physiological
environments.
In this paper we demonstrate the use of block copoly-
peptides to stabilize clusters of magnetic nanoparticles in
an aqueous environment. We first demonstrate that highly
monodisperse maghemite (γ-Fe2O3) nanoparticles, which are
* Corresponding author. e-mail: gaheld@us.ibm.com. phone: 914-945-
2609.
† L.E.E. and S.G.G. contributed equally to this work and should be
regarded as joint first authors.
‡ IBM TJ Watson Research Center.
§ University of California, Santa Barbara.
| Columbia University.
10.1021/nl034472y CCC: $25.00 © 2003 American Chemical Society
Published on Web 09/06/2003
synthesized in organic media, can be transferred to an
aqueous solution with no loss of structural or magnetic
properties. We then find that combining these particles
with the block copolypeptide poly(EG2-lys)100-b-poly(asp)309
results in the formation of magnetic nanoparticle clusters.
As both ends of this block copolypeptide are hydrophilic,
we believe that the aspartic acid residues bind electrostatically
with the surface of the nanoparticles, followed by the
formation of micelle-like assemblies, each containing ap-
proximately 20 nanoparticles in its core.10 The resulting
micellar assemblies will have a magnetic moment 20 times
that of a single nanoparticle, and have the high physiological
stability provided by a poly(EG2-lys) shell. Both of these
attributes increase the viability of using such particles for
effective drug delivery.
Experimental Section. Synthesis of Water Soluble
Maghemite Nanocrystals. In preparing monodisperse iron
nanocrystals, known methods11 were followed. Specifically,
28 mL of octyl ether was added to 3 mL of oleic acid. The
mixture was heated to 100 °C under an inert atmosphere for
30 min. To this mixture, 0.8 mL of Fe(CO)5 was added, the
temperature was then raised to 300 °C, and the solution
stirred for 1 h. The mixture was then allowed to cool to
room temperature. The solution was centrifuged and the
precipitate removed. The remaining supernatant solution
was then collected, and ethanol was added to produce
reversible flocculations of the nanocrystals. The solution
was centrifuged again, and the precipitate saved and subse-

Figure 1. Molecular structure of block copolypeptide poly(EG2-
lys)100-b-poly(asp)30 ) poly(Ne-2[2-(2-methoxyethoxy)ethoxy]acetyl-
L-lysine)100-b-poly(L-aspartic acid, sodium salt)30.
quently suspended in hexanes to produce a suspension of
6 nm iron particles. Exposing this suspension to air for
1 week resulted in the complete oxidation of the iron
nanoparticles, the result being a dispersion of highly crystal-
line 6 nm maghemite (γ-Fe2O3) nanoparticles. The concen-
tration of oleic acid stabilized maghemite particles in this
suspension was approximately 12 mg/mL. The precipitation
of the nanoparticles present in a 5 mL aliquot of this
suspension was accomplished by the addition of ethanol,
followed by centrifugation. The supernatant was then dis-
carded, and the precipitate was resuspended in 15 mL of
1.0 M tetramethylammonium hydroxide (TMAOH).12,13
Deionized water was added to bring the total volume to 100
mL. The addition of 0.2 gm sodium citrate followed, and
adding 0.1 M HCl dropwise to the solution brought the
resulting mixture to a pH of 6.5. During this reduction in
pH, a precipitate appeared and was removed by filtration
(Pall Acrodisc 0.8 µm Versapor filter no. 4459).
Synthesis of Block Copolypeptide Poly(EG2-lys)100-b-poly-
(asp)30 ) poly(Ne-2[2-(2-methoxyethoxy)ethoxy]acetyl-L-
lysine)100-b-poly(L-aspartic acid, sodium salt)30. The synthesis
of this block copolypeptide was accomplished using previ-
ously reported methods.14,15 Stepwise polymerization of the
monomer (Ne-2[2-(2-methoxyethoxy)ethoxy]acetyl-L-lysine)-
N-carboxyanhydride, followed by the monomer b-benzyl-
(L-aspartic acid)-N-carboxyanhydride using 2,2′-bipyridyl-
Ni-1,5-cyclooctadiene initiator gave the protected polymer,
which was then deprotected using equimolar amounts of
trifluoroacetic acid and 33% HBr in acetic acid. The structure
of the resulting polymer is shown in Figure 1. Impurities
and byproducts were removed by dialysis against water. The
protected block copolypeptide was analyzed using gel
permeation chromatography in 0.1 M LiBr/dimethylforma-
mide (DMF) at 60 °C to determine the molecular mass.
Polymer block composition was analyzed by 1H NMR of
the deprotected copolypeptide in trifluoroacetic acid (TFA)-d
and found to be within 10% of the predicted ratios. The
polymer was then dissolved in water to produce a 2-mg/mL
solution (pH 7).
Preparation of Poly(EG2-lys)100-b-poly(asp)30/Maghemite
Nanocrystal Composite. Deionized water (1 mL) was added
to 1 mL of the aqueous suspension of maghemite nanocrys-
tals described above (pH 6.5) and stirred. To this mixture,
50 µL of the 2-mg/mL solution of poly(EG2-lys)100-b-poly-
(asp)30 was added. The mixture was allowed to stand
1490
overnight and then filtered (Pall Acrodisc 0.8 µm Versapor
filter no. 4459).
Sample Preparation and Characterization. Samples stud-
ied with transmission electron microscopy (TEM) were
prepared by placing one drop of a nanoparticle dispersion
(hexanes or aqueous based) onto the amorphous carbon
substrate of a TEM grid and then drying the grid under
vacuum at 100 °C for several hours. TEM images were taken
with a Philips CM-12 120 keV TEM.
Samples studied with X-ray diffraction (XRD) were
prepared by drying the nanoparticle dispersion onto a glass
substrate under vacuum at 100 °C. Those substrates onto
which an aqueous dispersion had been dried were then lightly
washed with water; this had the effect of dissolving excess
TMAOH salt, while the nanoparticles remained bound to the
substrate. XRD data were collected using Co KR radiation
(λ ) 1.78892 Å) with a Seimens D-500 diffractometer.
Magnetometry measurements were taken with a Quantum
Design MPMS SQUID magnetometer. Samples were pre-
pared by drying the nanoparticle dispersion in a glass sample
tube under vacuum at 100 °C.
Results and Discussion. Water Soluble 6 nm Maghemite
Nanocrystals. Previous studies have shown that the decom-
position of Fe(CO)5 in hydrocarbon solvents provides a
simple and effective method to prepare highly monodisperse
nanocrystals of magnetic iron.11 We find that simple exposure
of these particles dispersed in hexanes to the atmosphere
results in their complete oxidation into monodisperse, highly
crystalline 6 nm maghemite nanoparticles. Further, we have
demonstrated that nanoparticles prepared by this method can
be transferred into an aqueous medium with the objective
of biocompatibility. TEM and X-ray diffraction (XRD) were
used to obtain information about the maghemite nanoparticles
dispersed in both water and hexanes, as well as about their
interaction with poly(EG2-lys)100-b-poly(asp)30. TEM images
show that the maghemite nanoparticles are crystalline and
monodisperse. In addition, these images indicate that no
degradation takes place upon transfer from organic to
aqueous solution (Figure 2a,b). Figure 2a shows maghemite
particles taken from a dispersion in hexanes in which they
were stabilized against aggregation with a layer of oleic acid.
The subsequent change of ligand from oleic acid in hexanes
to TMAOH in water results in continued stabilization of the
particles in solution; there continues to be very little
aggregation (Figure 2b). Figure 3 shows XRD data taken
from the maghemite nanoparticles following removal from
both aqueous and organic solutions. The locations of
expected, indexed Bragg reflections of the maghemite
structure are also shown. It is clear from this figure that
particles dispersed in both hexanes and water exhibit a
maghemite crystal structure. Further, XRD confirms the high
degree of crystallinity of the particles; Debye-Scherrer
calculations16 predict a diameter of 5.6 nm for particles taken
from both the hexanes and water dispersions, in good
agreement with the average diameter of 5.7 nm obtained from
TEM (again, the same value for particles from both disper-
sions). Thus, both XRD and TEM characterizations indicate
that neither particle crystallinity nor monodispersity was
Nano Lett., Vol. 3, No. 11, 2003

Figure 2. TEM micrographs of maghemite nanoparticles deposited
from dispersions in (a) hexanes and (b) water. Inset in (a) is a
selected area electron diffraction pattern.
Figure 3. X-ray diffraction patterns of maghemite nanoparticles
deposited onto glass substrates from dispersions in hexanes (blue)
and water (red). Intensity is plotted as a function of wavevector
((4π/λ)sinθ). Background has been subtracted from the red spectrum
and the intensity of the blue spectrum has been offset by 200.
Expected positions of Bragg peaks corresponding to the maghemite
structure are shown as black lines and labeled.
compromised by the exchange of ligand, transfer to water,
and subsequent neutralization of the nanoparticle dispersion
with HCl.
The use of TMAOH to stabilize magnetite nanoparticles
synthesized under aqueous conditions is well known.12,17
However, the synthesis of metallic nanoparticles under
organic conditions followed by transfer into aqueous solu-
tions has thus far been limited to nonmagnetic particles.18
Nano Lett., Vol. 3, No. 11, 2003
Figure 4. Low-field susceptibility as a function of temperature
measured after zero-field cooling (0) and cooling in a 10 Oe field
(9) measured for 6 nm maghemite nanoparticles deposited from
dispersions in (a) hexanes and (b) water. The field-cooled and zero-
field-cooled scans for a given sample overlap at temperatures where
the sample is in thermal equilibrium and diverge at the blocking
temperature.
As magnetic nanoparticles synthesized in an organic envi-
ronment often have better crystallinity and monodispersity
than those synthesized in an aqueous environment,11,18 a
method of transferring organically synthesized particles to
aqueous conditions is clearly desirable. After precipitating
maghemite nanoparticles out of a hexanes solution (by the
addition of ethanol followed by centrifugation), we find that
these particles readily dissolve in a 1:6 1.0 M TMAOH/
deionized water mixture. As these particles are insoluble in
water alone, we believe that the oleic acid ligands are
displaced by the ammonium salt, TMAOH. Specifically,
when placed in water with TMAOH, the positively charged
surface of the each maghemite nanocrystal associates elec-
trostatically with the negative hydroxide ions, which are
surrounded, in turn, by positive tetramethylammonium
cations, the result being an electrostatic double layer of ions
that stabilizes the particles in aqueous solution.12,19,20 We find
that the nanoparticles precipitated from hexanes will not
dissolve in NaOH (aq) or tetramethylammonium bromide
(aq), confirming the need for both tetramethylammonium
cations and hydroxide anions in producing an aqueous
maghemite nanoparticle dispersion. Neutralization of this
dispersion by the addition of HCl removes some of the
hydroxide ions from the maghemite surface, resulting in a
small amount of precipitation. This is consistent with earlier
reports on colloidal nickel ferrite spheres.20 However, we
find that the addition of sodium citrate ensures that the
nanoparticles remain suspended in solution, presumably
because the citrate anions are able to associate with the
nanoparticle surface and, thus, replace the neutralized
hydroxide anions.
SQUID magnetrometry measurements demonstrate that the
magnetic properties of the maghemite nanoparticles are not
significantly affected by the change from an organic to an
aqueous solvent. In Figures 4a and b are shown field-cooled/
zero-field-cooled measurements of the magnetic susceptibility
of nanoparticles that had been dispersed in organic and
aqueous media, respectively. The superparamagnetic block-
ing temperature is identified as the temperature below which
the field-cooled and zero-field-cooled susceptibilities di-
verge.21 From Figure 4, we conclude that the blocking
temperatures of the nanoparticles dispersed in hexanes and
1491
Figure 5. Magnetic moment as a function of applied magnetic
field measured for 6 nm maghemite nanoparticles deposited from
dispersions in (a) hexanes and (b) water. Data were collected at
300 K and (inset to a) 10 K. Solid lines are best fits of the data to
the Langevin paramagnetic function (see text).
water are 75 and 60 K, respectively. This relatively small
shift in blocking temperature suggests a modest reduction
in the magnetic volume of the nanoparticles as a result of
their transfer to an aqueous environment.
In addition, we find that measurements of magnetic
moment as a function of applied field taken at 300 K show
little change between nanoparticles taken from hexanes and
aqueous dispersions (Figures 5a and b). Neither measure-
ment shows evidence of hysteresis, and thus both may be
modeled by the Langevin paramagnetic function, which is
known to describe the magnetization of superparamagnetic
particles:22 M(x) ) Nµ(coth x - (1/x)), where x ) µH/kBT,
N is the number of nanoparticles, µ is the magnetic moment
of an individual nanoparticle, H is the applied field, kB is
Boltzmann’s constant, and T is the absolute temperature. Fits
of the data in Figure 5a and b to this function (shown as
solid lines in the figures) yield values of µ equal to 2.57 ×
10-17 emu and 1.56 × 10-17 emu, respectively. Assuming a
saturation magnetization of 363 G for the maghemite
nanoparticles,23 these results correspond to magnetic particles
with diameters of 6.3 and 5.3 nm for particles taken from
hexanes and aqueous solution, respectively. Again, the data
are consistent with a modest reduction in the effective
magnetic radius as a result of the transfer to an aqueous
environment. Note that at 10 K (inset, Figure 5a) the
nanoparticles exhibit the hysteretic behavior expected for
particles below their blocking temperature.
Block Copolypeptide-Maghemite Nanoparticle Assembly.
When either the block copolypeptide poly(EG2-lys)100-b-poly-
(asp)30 or the homopolymer poly(asp)30 is added to an
aqueous dispersion of 6 nm maghemite nanoparticles, the
nanoparticles assemble into soluble clusters. Transmission
electron micrographs of these clusters, taken following their
removal by drying from aqueous dispersions of nanoparticle/
poly(EG2-lys)100-b-poly(asp)30 (Figures 6a and 6b) and nano-
particle/ homopolymer poly(asp)30 (Figure 6c) illustrate the
structure of these assemblies. We note that no similar
clustering phenomenon is observed in the presence of the
homopolymer poly(EG2-lys)100. This suggests that the as-
sembly of the nanoparticles is facilitated by favorable
electrostatic interactions between the negatively charged
carboxylic acid side groups of the poly(asp)30 and the
positively charged surfaces of the maghemite nanocrystals.
1492
Figure 6. TEM micrographs of clusters of maghemite nanoparticles
deposited from dispersions in water to which (a), (b) poly(EG2-
lys)100-b-poly(asp)30, and (c) poly(asp)30 have been added. Note that
the homopolymer-nanoparticle mixture was not filtered prior to
preparation of the TEM grid.
Each nanoparticle may associate with more than one strand
of the polyaspartic acid and, likewise, each strand of
polyaspartic acid may bind to more than one nanoparticle,
the result being a bridging aggregation leading to controlled
organization.
For the case of the nanoparticle/homopolymer poly(asp)30
mixture, these clusters typically have dimensions of order
100 nm and, as such, are only observed if the nanoparticle-
homopolymer mixture is not filtered. Many, but not all of
these clusters, appear to be comprised of an aggregation of
smaller nanoparticle clusters (as in the upper cluster shown
in Figure 6c). The fact that these clusters are soluble suggests
that they may be stabilized by portions of the poly(asp)30
not directly attached to nanoparticles.
When the block copolypeptide poly(EG2-lys)100-b-poly-
(asp)30 is introduced to an aqueous dispersion of maghemite
nanoparticles, the nanoparticles cooperatively assemble into
clusters that are significantly more uniform than those
observed when the homopolymer poly(asp)30 is added to the
dispersion (Figure 6). Again, we assume that favorable
electrostatic interactions between the aspartic acid residues
and the nanoparticles occur. However, in the block co-
polypeptide case, the aggregates that form are limited in size
by the poly(EG2-lys)100 block. As both ends of poly(EG2-
lys)100-b-poly(asp)30 are hydrophilic, one would expect the
block copolypeptide to be soluble in water at physiological
pH. However, it is entirely plausible that the association of
the polyaspartic acid segment of the copolypeptide with a
maghemite nanoparticle would shift the critical point of
micellar formation,24 the result being micelles with cores
comprised of clusters of maghemite nanopartcles electrostati-
cally bound to polyaspartic acid and outer shells comprised
of the highly hydrophilic poly(EG2-lys) segments of the block
copolypeptide. A schematic illustration of such a micellar
assembly is shown in Figure 7.
In summary, we have investigated the transfer of magnetic
nanoparticles synthesized in organic media into an aqueous
Nano Lett., Vol. 3, No. 11, 2003
 manuscript, and Peter Allen for the artful rendering of Figure
7. L.E.E. and S.G.G. acknowledge financial support from a
NSF IGERT Fellowship and a NSF GK-12 Teaching
Fellowship, respectively. Part of this work was carried out
at the UCSB-MRL Central Facilities, supported by the NSF
under Award No. DMR-0080034. This work was also
supported in part by the MRSEC Program of the NSF at
Columbia University under award number DMR-0213574.

References
Figure 7. Schematic illustration of the proposed structure of the
micellar assemblies formed following the addition of the block
copolypeptide poly(EG2-lys)100-b-poly(asp)30 to an aqueous disper-
sion of 6 nm maghemite nanoparticles. The shell of the micelle is
comprised of poly(EG2-lys)100, which is known to form a stable
R-helical conformation in water,15 while the core is comprised of
maghemite nanoparticles electrostatically bound to the poly(asp)30
segments of the block copolypeptide.
environment, finding that this transfer can be accomplished
with no loss in the crystallinity, monodispersity, or magnetic
properties of the particles. In addition, we have studied the
cooperative assembly of magnetic nanoparticles in the
presence of amino acid based polymers, demonstrating that
electrostatic interactions between block copolypeptides and
nanoparticles can control the organization of these compo-
nents. The addition of polyaspartic acid initiates the ag-
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copolypeptide poly(EG2-lys)100-b-poly(asp)30 initiates a more
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By altering the composition of the block copolypeptide, it
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the resulting dispersed nanoparticle clusters, thereby greatly
expanding the potential applications and usefulness of these
cooperatively assembled nanocomposites.
Acknowledgment. The authors thank Franz X. Redl,
Jacek C. Ostrowski, and Jennifer N. Cha for helpful dis-
cussions, Geoffrey Grinstein for his critical reading of the
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NL034472Y

Nano Lett., Vol. 3, No. 11, 2003 1493