Paramagnetic lanthanide(III) complexes that contain hyperfine-shifted exchangeable protons offer considerable advantages over diamagnetic molecules as chemical exchange saturation transfer (CEST) agents for MRI. As part of a program to investigate avenues to improve the sensitivity of such agents, the CEST characteristics of europium(III) macrocyclic complexes having appended hydroxyethyl groups were investigated. The CEST spectrum of the asymmetrical complex, EuCNPHC 3+ , shows five distinct peaks for each magnetically nonequivalent exchangeable proton in the molecule. The CEST spectra of this complex were fitted to NMR Bloch theory to yield exchange rates between each of six exchanging proton pools (five on the agent plus bulk water). Exchange between the Eu 3+ -bound hydroxyl protons and bulk water protons was slow in dry acetonitrile but accelerated incrementally upon stepwise addition of water. In pure water, exchange was too fast to observe a CEST effect. The utility of this class of europium(III) complex for CEST imaging applications is ultimately limited by the small chemical shifts induced by the hydroxyl-appended ligands of this type and the resulting small Δω values for the exchangeable hydroxyl protons.
Dank effizienter Präorganisation der Reaktanten gelang erstmals die 1,6‐Polymerisation eines Triacetylens: Der Komplex aus einer Triacetylendicarbonsäure und einem vinylogen Amid bietet ideale strukturelle Voraussetzungen für die durch γ‐Bestrahlung ausgelöste Polymerisation zu einer basenlöslichen Polytriacetylenpolycarbonsäure (siehe Bild). Diese Arbeit demonstriert die Leistungsfähigkeit der supramolekularen Synthese als präparatives Werkzeug.
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