Gadonanotubes as a Dual Modal T1- and T2-weighted MRI Contrast Agent:

Magnetic Property Characterization by SQUID Magnetometry

Michael L. Matson and Lon J. Wilson
matson@rice.edu

Ultra-short, single-walled carbon nanotube capsules (US-tubes) internalized with aqueous gadolinium-ion clusters (Gadonanotubes) are a dual modal MRI contrast agent
capable of decreasing both T1 and T2.1,2 The magnetic properties of both the empty, US-tube nanocapsules and the Gadonanotubes were measured via SQUID
magnetometry. The results suggest the empty US-tube nanocapsules have a superparamagnetic domain, while the internalized aqueous Gd3+ -ion clusters of the
Gadonanotubes posses a separate paramagnetic domain. These two domains together allow for significant shortening of both T1 and T2.

Gadonanotube Efficacy M vs T M vs H
Magnetization normalized to catalyst wt%. Magnetization normalized to catalyst wt%.
T1-weighted phantom MRI images by a 1.5 T MRI scanner Field strength = 1000 Oe. ZFC (black) and FC (white). SWNTs (black), US-tubes (white), and Gadonanotubes (grey) .
([Gd3+ ] 0.04 mM) Measurements taken at 2K after cooling in zero field.
HiPCO Arc HiPCO

SWNTs
Water Magnevist TM
Gadonanotubes

r1 ~ 170 mM [Gd3+ ] -1 s -1
r2 ~ 305 mM [SWNT catalyst] -1 s -1

Gadonanotube Synthesis

> 2 μm Single-walled carbon nanotubes (SWNTs)

Two synthetic routes:
• High pressure CO process (HiPCO )1
Fe as catalyst | Diameter ~ 1.0 nm US-tubes
• Electric-arc discharge technique (Arc)2
Ni-Y alloy as catalyst | Diameter ~ 1.4 nm Arc
1% F2 in He 100 oC, 2 hr

Partially fluorinated SWNTs (f-SWNTs)3

> 2 μm • F-SWNT stoichiometry: CFx (x ≤ 0.2)
• F atoms add around tube’s circumference
• Dramatic banded structure:

Gadonanotubes

STM image of f-SWNT3

1) 1000 oC 2) HCl (conc.)

under Ar wash

Ultra-short SWNTs (US-tubes)4

20-80 nm • Pyrolysis removes fluorocarbons
• Both COF2 and CF4 Comparison of the magnetization vs. temperature curves shows a clear bifurcation between zero-field cooled (ZFC) and field cooled (FC) curves
• US-tubes average length < 50 nm for both SWNTs and US-tubes; the magnetic transition at ca. 75 K for arc-synthesized SWNTs is still under examination. These measurements
• 80 % of US-tubes < 60 nm in length were obtained using Quantum Design MPMS-XL magnetometer based on a superconducting quantum interference device (SQUID). This ZFC/FC
• Side-wall defects (holes) formed bifurcation coupled with no thermoremnant magnetization (irreversibility in the FC curve) is strongly indicative of superparamagnetism.6 The peak
• Loss in metal catalyst (see Table below) of the ZFC curve (the mean blocking temperature, TB) indicates the lowest temperature a material demonstrates superparamagnetic behavior. The
GdCl3 (aq) Bath sonication, lower TB becomes, the smaller the mean particle size; the smaller the temperature range between TB and the ZFC/FC bifurcation, the more
pH < 3 1 hr uniform the distribution of particle sizes. Unfortunately, the trend of decreasing both TB and the range of particle sizes upon decreasing catalyst
metal %, as shown between SWNTs and US-tubes, is masked by the ferromagnetic signature of GdCl3 below 3K (the sharp increase in
magnetization upon cooling). The hysteresis curve of the gadonanotubes fits the Brillouin function characteristic of a strongly paramagnetic
20-80 nm
material to be expected upon loading the US-tubes with GdCl3; hence, the loading of a superparamagnetic material (US-tubes) with a strongly
Gadolinium loaded US-tubes (Gadonanotubes)5 paramagnetic material (Gd3+ ions) renders a powerful, dual modal MRI contrast agent capable of enhancing both T1- and T2-weighted MRI.

References
Metal Concentration
HiPco Arc
1) C. Journet et. al. Nature, 1997, 388, 756.
Sample wt% Fe wt% Gd wt% Ni wt% Gd 2) P. Nikolaev et. al. Chem. Phys. Lett., 1999, 313, 91-7.
SWNTs 17.15 - 22.76 - 3) K. F. Kelly et. al. Chem. Phys. Lett., 2000, 313(3), 445-450.
4) Z. Gu et. al. Nano Lett. 2002, 2(9), 1009-13.
US-tubes 2.32 - 4.23 -
5) B. Sitharaman et al. Chem. Commun. 2005, 31, 3915-7.
Gadonanotubes 1.96 4.87 2.70 4.29 6) D. Kumar et. al. J. Magn. and Magn. Mater., 2001, 232, 161-7.

Depiction of Gadonanotube Metal concentrations determined using inductively coupled plasma

(To scale, green represents Gd3+ cation; mass spectroscopy (ICP-MS)
Cl- anion and H2O molecules not shown)