Because Mg(II) and Ca(II) are difficult to detect in biological systems, techniques substituting the lanthanide(III) ions as replacement probes for these alkaline earth ions have been developed. We would like to continue to build upon our twenty years experience with the chemistry of the lanthanide ions in order to further understand their properties and to compare them to both the radioactive actinides which are present in our environment and the d-type transition elements which are important in many enzymes. The fundamental studies to be undertaken include: the determination of whether species bound to the lanthanides are inner or outer sphere complexes; the effect of an ion charge on complexation and coordination number changes; the characterization of a complex lanthanide salt to determine the effect of water using FT-IR, NMR and other techniques; low temperature coordination studies to detect loss of solvent upon the addition of water; NMR solvation studies; the use of ultramicroelectrodes and chemiluminescence to model biological transport across membranes; and to determine similarities with actinide compounds. We also intend to utilize the ultrasonic relaxation technique to investigate some Zn-containing enzymes to determine if a coordination number change can be detected by this technique. Among the new techniques to be used by our group are FT-NMR, electrochemistry, chemiluminescence and cryostatic FT-IR, and these will allow us to carry out future studies of biochemical importance.
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