Metal-templated synthesis of rigid and conformationally restricted cyclic bisporphyrins: specific retention times on a cyanopropyl-modified silica gel column.

A series of rigid and conformationally restricted cyclic bis(zinc porphyrin)s connected via 2,2'-bipyridine and phthalamide, isophthalamide, or terephthalamide moieties were prepared by metal-templated synthesis. The yields were significantly improved when compared with those obtained under metal-free conditions. In particular, phthalamide and terephthalamide derivatives were obtained only by metal-templated synthesis. Structural analyses and dynamics of the exchange between the conformers in each cyclic porphyrin were examined by NMR spectroscopy. Although the distances between the two zinc porphyrins were extended in the order of phthalamide, isophthalamide, and terephthalamide derivatives, the order of the specific retention of the cyclic porphyrins on cyanopropyl-modified silica gel (CN-MS) chromatography columns varied. Thus, this order was reversed in the isophthalamide and terephthalamide derivatives. Based on the rigid structure of the terephthalamide derivative, the origin of the specific retention on the CN-MS chromatography column was attributed to both the distance and rigidity of the cyclic porphyrins.

Effects of Diluents on the Separation of Minor Actinides from Lanthanides with Tetradodecyl-1,10-phenanthroline-2,9-diamide from Nitric Acid Medium.

To investigate the effective separation of actinides (Ans) from lanthanides (Lns), single-stage batch extraction experiments were performed with a novel extractant, tetradodecyl-1,10-phenanthroline-2,9-diamide (TDdPTDA) with various diluents such as 3-nitrobenzotrifluoride (F-3), nitrobenzene, and n-dodecane for Am, Cm, and Lns. The extraction kinetics with TDdPTDA was rapid enough to perform continuous extraction experiments using mixer-settler extractors. The slopes of the distribution ratio versus the TDdPTDA concentration and the distribution ratio versus the nitric acid concentration were similar for F-3 and nitrobenzene systems, but different from the n-dodecane system. These differences were attributed to the characteristics of the diluents. This study revealed high distribution ratios of Am (DAm) and Cm (DCm) for TDdPTDA, with the high separation factors (SFs) of Am from Lns enough for their separation.