Amalgamation of complex iron(III) ions and iron nanoclusters with MWCNTs as a route to potential T2 MRI contrast agents

Abstract

Nikodem Kuźnik,1 Mateusz M Tomczyk,1 Marzena Wyskocka,1 Łukasz Przypis,1 Artur P Herman,1 Rafał Jędrysiak,1 Krzysztof K Koziol,2 Slawomir Boncel11Department of Organic Chemistry, Bioorganic Chemistry and Biotechnology, Faculty of Chemistry, Silesian University of Technology, Gliwice, Poland; 2Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UKAbstract: Iron-filled multiwall carbon nanotubes (Fe@MWCNTs) were functionalized toward a variety of potential magnetic resonance imaging contrast agents. Oxidized Fe@MWNCTs were covered with PEG5000 via direct esterification or using acyl chloride derivatives. Alternatively, the latter were functionalized with an aminophenol ligand (Fe@O-MWCNT-L). Moreover, pristine Fe@MWCNTs were functionalized with N-phenylaziridine groups (Fe@f-MWCNT) via [2+1] cycloaddition of nitrene. All of these chemically modified nanotubes served as a vehicle for anchoring Fe3+ ions. The new hybrids – Fe(III)/Fe@(f-/O-)MWCNTs – containing 6%–14% of the “tethered” Fe3+ ions were studied in terms of the acceleration of relaxation of water protons in nuclear magnetic resonance. The highest transverse relaxivity r2=63.9±0.9 mL mg-1 s-1 was recorded for Fe(III)/Fe@O-MWCNT-L, while for Fe(III)/Fe@f-MWCNT, with r2=57.9±2.9 mL mg-1 s-1, the highest impact of the anchored Fe(III) ions was observed. The T1/T2 ratio of 30–100 found for all of the nanotube hybrids presented in this work is a very important factor for their potential application as T2 contrast agents. Increased stability of the hybrids was confirmed by ultraviolet–visible spectrophotometry.Keywords: multiwall carbon nanotubes, Fe3+, transverse relaxation time T2, MRI contrast agent