Lanthanide shift reagents

The focus of this thesis is to develop lanthanide (Ln) luminescent materials through the exploration of coordination polymers and nanomaterials. Herein, dimethyl-3,4- furanedicarboxylate acid undergoes hydrolysis under hydrothermal conditions to form coordination polymers with lanthanide ions. The resulting coordination polymers exhibited luminescent properties, with quantum yields and lifetimes for the Eu-and Tb-CP of 1.14+-0.32% and 0.387=-0.0001 mx, and 3.33=-0.82% and 0.769=-0.006 ms, respectively. While the incorporation of lanthanides was not achieved in this work, progress toward the production of pure phase InP in the nanoregime has been made, using a low-cost, hydrothermal method. Through SEM and PXRD conflict, it is believed that pure INP particles with a size range of 58-81 nm were successfully synthesized.

Within solid-state chemistry, coordination polymers have gained interest for use in various applications such as sensing, catalysis, display technology, hydrogen storage, etc. The use of lanthanide ions in these materials provides a mean of exploring how structure may affect luminescence efficiency. In this study, the photophysics of several lanthanide benzenecarboxylates was studied. This data combined with data from other coordination polymers created in our lab indicate that the established guidelines for producing highly efficient materials may not correlate directly from solution to the solid state and that structure may also play a role.

Commercial longline fishing results in large amounts of incidental bycatch of elasmobranch fishes (sharks, skates, and rays). Teleost species lack electrosensory systems and development of technologies which target the ampullary organs of sharks provides an avenue to selectively deter elasmobranchs without affecting the catch rate of target teleosts. Electric field measurements and a controlled scientific longline study were conducted testing whether the lanthanide metal neodymium or zinc/graphite might reduce elasmobranch catch per unit effort (CPUE). Baited longline hooks were treated with neodymium and zinc/graphite and catch rates were compared to that of controls. Shark CPUE decreased by 60% on neodymium treated hooks and 80% on zinc/graphite treated hooks. The effectiveness of both treatments varied among species with significant reductions shown for Atlantic sharpnose sharks (Rhizoprionodon terranovae) but less dramatic differences for others. Zinc/graphite is potentially a viable tool for reduction of shark bycatch in a commercial longline fishery.

Sharks comprise a large portion of bycatch in pelagic longline fisheries worldwide. Lanthanide metals have been proposed as shark repellents. This study quantified the normalized voltage of lanthanide metals in seawater and found that there was no difference in normalized voltage among the six tested metals. Temperature and salinity had a significant effect on lanthanide normalized voltage. The output at 18ºC was significantly greater than at both 12 and 24ºC. The normalized voltage was significantly greater in freshwater than brackish or seawater. The dissolution rate for the lanthanides varied from -1.6 to -0.2g/h. As the metals dissolved the voltage remained constant. In a behavioral assay, neodymium was ineffective at repelling bonnethead sharks (Sphyrna tiburo) tested individually and in groups, and lemon sharks (Negaprion brevirostris) in groups. Due to high cost, fast dissolution rates, and lack of deterrent effects, lanthanide metals are not recommended for use in mitigating shark bycatch.