Transforming lanthanide and actinide chemistry with nanoparticles.

Lanthanides and actinides are used in a wide variety of applications, from energy production to life sciences. To address toxicity issues due to the chemical, and often radiological, properties of these elements, methods to quantify and recover them from industrial waste are necessary. When used in biomedicine, lanthanides and actinides are incorporated in compounds that show promising therapeutic and/or bioimaging properties, but lack robust strategies to target cancer and other pathologies. Furthermore, current decorporation protocols to respond to accidental actinide exposure rely on intravenous injections of soluble chelating agents, which are inefficient for treatment of inhaled radionuclides trapped in lungs. In recent years, nanoparticles have emerged as powerful tools in both industry and clinical settings. Because some inorganic nanoparticles are sensitive to external stimuli, such as light and magnetic fields, they can be used as building blocks for sensitive bioassays and separation techniques. In addition, nanoparticles can be functionalized with multiple ligands and act as carriers for selective delivery of therapeutic and contrast agents. This review summarizes and discusses recent progress on the use of nanoparticles in lanthanide and actinide chemistry. We examine different types of nanoparticles based on composition, functionalization, and properties, and we critically analyze their performance in a comparative mode. Our focus is two-pronged, including the nanoparticles free of lanthanides and actinides that are used for the detection, separation, or decorporation of f-block elements, as well as the nanoparticles that enhance the inherent properties of lanthanides and actinides for therapeutics, imaging and catalysis.

Lauriston S. Taylor Lecture: the quest for therapeutic actinide chelators.

All of the actinides are radioactive. Taken into the body, they damage and induce cancer in bone and liver, and in the lungs if inhaled, and U(VI) is a chemical kidney poison. Containment of radionuclides is fundamental to radiation protection, but if it is breached accidentally or deliberately, decontamination of exposed persons is needed to reduce the consequences of radionuclide intake. The only known way to reduce the health risks of internally deposited actinides is to accelerate their excretion with chelating agents. Ethylendiaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) were introduced in the 1950's. DTPA is now clinically accepted, but its oral activity is low, it must be injected as a Ca(II) or Zn(II) chelate to avoid toxicity, and it is structurally unsuitable for chelating U(VI) or Np(V). Actinide penetration into the mammalian iron transport and storage systems suggested that actinide ions would form stable complexes with the Fe(III)-binding units found in potent selective natural iron chelators (siderophores). Testing of that biomimetic approach began in the late 1970's with the design, production, and assessment for in vivo Pu(IV) chelation of synthetic multidentate ligands based on the backbone structures and Fe(III)-binding groups of siderophores. New efficacious actinide chelators have emerged from that program, in particular, octadentate 3,4,3-LI(1,2-HOPO) and tetradentate 5-LIO(Me-3,2-HOPO) have potential for clinical acceptance. Both are much more effective than CaNa3-DTPA for decorporation of Pu(IV), Am(III), U(VI), and Np(IV,V), they are orally active, and toxicity is acceptably low at effective dosage.