Engineering lanthanide complexes with controlled water exchange rates for magnetic resonance imaging
The control of the rate of water exchange in lanthanide complexes is critical to their future development as contrast agents in magnetic resonance imaging. In traditional T/sub 1/ shortening agents an optimal water residence lifetime (/spl tau//sub M/) of around 25 ns is required if the highest relaxivities are to be achieved. In contrast the newer PARACEST agents require that water exchange is much slower with /spl tau//sub M/ on the order of microseconds. It is now possible to rationally design complexes that exhibit water exchange rates that are ideal for their intended use. The selection of appropriate ligating groups allow a broad control mechanism. Anionic ligating groups such as carboxylates favour faster exchange whereas neutral ligands such as amides favour slower exchange. By altering the steric hindrance around the water coordination site water exchange rates can be fine tuned. The steric hindrance can be altered by controlling the coordination environment of the lanthanide ion and optimal water exchanges rates so achieved.
Toward the Design of MR Agents for Imaging β-Cell Function.
The chemistry of Gd(3+)-based MRI agents has advanced considerably during the past decade toward agents with higher relaxivity and agents that respond to physiology and/or metabolism. This review describes various approaches that have been taken toward the development of responsive contrast agents and discusses the importance of fast water exchange for advancement of targeted Gd(3+)-based agents with higher sensitivity. The recent discovery of Eu(3+) complexes having extraordinarily slow water exchange has opened a new avenue in contrast agent design based upon the chemical exchange saturation transfer (CEST) mechanism. These new paramagnetic complexes called PARACEST agents offer new possibilities of imaging biological functions such as tissue pH and metabolite levels. The lower detection limits that may apply to each class of contrast agent (Gd(3+)-based versus PARACEST) are discussed and the extent to which they may be applied to the imaging of β-cells is considered.
Luminescence Phenomena Involving Metal Enolates
1 
Introduction 
 
2 
Metal Enolates 
 
3 
Luminescence of Rare-Earth Enolates 
 
4 
Luminescence Involving s, p and d Metal Block Enolates 
 
5 
Applications 
 
6 
Acknowledgments 
 
 
 
Keywords: 
 
luminescence phenomena involving metal enolates; 
chemistry of metal β-diketonate complexes; 
luminescence of rare-earth enolates; 
photoluminescence of rare-earth β-diketonates; 
diketonate ligand–rare-earth ion energy transfer rates; 
luminescence involving s, p and d metal block enolates; 
photoluminescence of d-transition metal enolates; 
applications - time-resolved detection of luminescence for bioassays