Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes.
A series of chelating amphiphiles and their gadolinium (Gd(III)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.
CSIRO Materials Science and Engineering, PO BOX 52, North Ryde, NSW, 1670, Australia. minoo.moghaddam@csiro.au
Minoo J
MJ
Moghaddam
Liliana
L
de Campo
Nigel
N
Kirby
Calum J
CJ
Drummond
D002614:Chelating Agents / Q000737:chemistry*; D003287:Contrast Media / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D003460:Crystallization; D005682:Gadolinium / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D008279:Magnetic Resonance Imaging; D049329:Nanostructures / Q000737:chemistry; D004369:Pentetic Acid / Q000737:chemistry*; D053838:Scattering, Small Angle; D014961:X-Ray Diffraction
D002614:Chelating Agents; D003287:Contrast Media; D056831:Coordination Complexes; D004369:Pentetic Acid; D005682:Gadolinium