Design and Synthesis of

Magnetic Nanoparticles with

Gold Shells for Single Particle
Optical Tracking
JitKang Lim, Robert D. Tilton, Frederick
Lanni, Caitlin Lanni, and
Sara A. Majetich
Carnegie Mellon University
Pittsburgh, PA 15213
sara@cmu.edu

Magnetically Guided
Sensors
Gold
Shell

Adsorbed
Biomolecule

Magnetic
core

Goal:GuideindividualFeoxide/Au
nanoparticlestomapthelocal
environmentswithinlivingcells

Magnetic force

Challenges:
Dualfunctionalityinsingleparticles
Stabilizinginabiologicalenvironment
Overcomingviscousdragforces

Target
protein
Magnetic
Force

Synthesis Overview
Synthesize magnetite nanoparticles in organic solvent and
transfer to water by using 10wt% tetramethylammonium
hydroxide.
Modify magnetite particle surfaces with
mercaptoundecanoic acid as adhesion layer.
Coat with gold nanoparticle seeds (~1.5nm).
Complete the gold shell by reduction of added HAuCl4.

Lim, J.K. et al., JMMM 2007, 311, 78 - 83

Transfer into water

Premade magnetite nanoparticles in organic solvent are
transferred to water using 10wt% tetramethylammonium
hydroxide.
10wt%
TMAOH
OA/OY

OH
OH

10wt%
TMAOH

OH
OH
OH
OH
OH

Ethanol
Get rid of excessive TMAOH
- Screening Agents

50 nm

OA Oleic Acid
OY - Oleylamine

50 nm

Stabilized in DI water with pH ~6-7

with zeta potential of -41.9mV
Veronica S.M., et al., Langmuir, Vol. 2004, 20, 6946-6950

Gold Particle Attachment and

Shell Formation
Iron
Oxide
particle

a)

b)

c)

d)

Gold particle

O
C

SH

Make small gold seeds by Duffs method 1

Particles remain stable after
mercaptoundecanoic acid (MUA)
attachment.

Seeding processes a) to b)
follow by adding in extra
gold precursor to form
complete shell c) to d)
Duff D.G., et al., Langmuir 1993, 9, 2310-2317

Dynamic Light Scattering

(DLS)

DLS gives the tatistical distribution

of nanoparticle sizes in solution.
About 70 80% of particles
formed are singlets.
Roughly 20% of particles are
doublets or triplets.

Plasmonic Response
(a)

(b)

(c)

(a) Iron oxide

(b) Iron oxide cores seeded
with gold nanoparticles

(c) Completed
nanoshell

UV-Vis spectra confirm core-shell

structure
Iron Oxide
seeded with
gold

Full Shell

Partially
completed
gold shell

Iron Oxide Only

Mathematical prediction
of resonance frequency
matches well with the
experimental data.
18 nm spherical
magnetite core
4.5 nm gold shell
Lim, J.K. et al., Adv. Mater. 2008, 20, 1721

Dark Field Optical

Microscopy

Before Introducing
the sample.
http://micro.magnet.fsu.edu/primer/
java/darkfield/cardioid/index.html

After Introducing
the sample.

Monitortherealtimemotionandspectraofmagnetically
guidednanoparticlesbytheirplasmonicresponse

Dark Field Optical Microscopy

Resolution limit of optical

microscope: 100x (NA 1.4)
objective ~ 200nm.
We can monitor the real time
motion nanoparticles with
~20nm core iron oxide
particles and ~5nm thick gold
shell by their plasmonic
response

#17
#6

#12

20um

20m

r 2 4 Dt
kT
D
6R

2D diffusion Eq.
Stokes-Einstein Eq.

Core-shell particle formation

~35
nm
Fe3O4
cores

Magnetophoresis of Individual
Particles
N
S

35 nm iron oxide core particles

Trajectories of tracked
particles

Particles diffusing from mu-metal

surface

Side of Tip on left

J. K. Lim, C. Lanni, E. Evarts, F. Lanni, R. D.

Tilton, and S. A. Majetich, ACS Nano 5, 217-226
(2011); J. K. Lim and S. A. Majetich, Nano
Today, 8, 98-113 (2013)