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The synthesis of ligand L(P)H(8), based on a 2,6-bispyrazolyl-pyridine scaffold functionalized by iminobismethylenephosphonate functions, is described and its pK values were determined by a combination of pH-spectrophotometric titrations and potentiometry. The interaction of L(P) with Tb(3+) was investigated in water (0.01 M TRIS/HCl pH = 7.0) by means of UV-vis and fluorescence titration experiments and evidenced the formation of at least three species with 1:1; 1:2, and 2:1 M-L ratios, the 1:1 complex appearing as particularly stable under these conditions (log K(cond)8). Na(4)[LnL(P)H] complexes (Ln = Eu and Tb) were prepared and characterized by elemental analysis, IR spectroscopy, and electrospray mass spectrometry. Their photophysical properties were investigated in aqueous solutions, revealing an excellent shielding of the Ln cations from the solvent environment (no water molecules in the first coordination sphere), very long luminescence lifetimes (τ(H(2)(O)) = 1.50 and 3.28 ms, respectively, for Eu and Tb) and reasonable luminescent quantum yields (ϕ(H(2)(O)) = 2.4 and 37%, respectively, for Eu and Tb). Using fetal bovine serum as a model for biological media showed the Tb complex to remain luminescent in these conditions. The structure of the europium complex was studied by means of density functional theory (DFT) modeling, confirming the wrapping of the ligand around the cation, and the very good shielding of the coordinated Ln cation. The conditional stability constant for the formation of the Tb complex with L(P) was determined by competition experiments with EDTA and monitored by fluorescence spectroscopy (log K(TbL(P)cond) = 14.1 ± 0.3, 0.01 M TRIS/HCl, pH = 7.4) and was used to determine the thermodynamic constant (log K(TbL(P)) = 20.4 ± 0.4). A systematic comparison with ligand L(C), in which phosphonate functions are replaced by carboxylate ones, is made throughout the study, highlighting the large interest of the introduction of phosphonate moieties to obtain biologically stable luminescent lanthanide complexes.

Large volumes of unconventional fossil resource are untapped because of the capillary forces, which kept the oil stranded underground. Furthermore, with the increasing demand for sustainable energy and the rising attention geared towards environment protection, there is a vital need to develop materials that bridge the gap between the fossil and renewable resources effectively. An intensive attention has been given to nanomaterials, which from their native features could increase either the energy storage or improve the recovery of fossil energy. The present chapter, therefore, presents the recent advancements of nanotechnology towards the production of unconventional resources and renewable energy. The chapter focuses primarily on nanomaterials applications for both fossils and renewable energies. The chapter is not intended to be an exhaustive representation of nanomaterials, rather it aims at broadening the knowledge on functional nanomaterials for possible engineering applications.