PubMed · 14405573
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P HURWITZ. 1960. Ophthalmic otrivin solution.. https://doi.org/10.1016/0002-9394(60)90686-3
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The lithium solvation in (1 -x)(EMI-TFSI), xLiTFSI ionic liquids where EMI(+) is the 1-ethyl-3-methylimidazolium cation and TFSI(-) the bis(trifluoromethanesulfonyl)imide anion, is shown by Raman spectroscopy to involve essentially [Li(TFSI)(2)](-) anionic clusters for 0 < x < 0.4, but addition of stoichiometric amounts of solvents S such as oligoethers changes the lithium solvation into [Li(S)(m)](+) cationic clusters; the lithium transference number in TFSI-based ionic liquid electrolytes for lithium batteries should thus be strongly improved.
Imidazole-substituted metalloporphyrins are valuable for studies of self-assembly and for applications where water solubility is required. Rational syntheses of porphyrins bearing one or two imidazol-2-yl or imidazol-4-yl groups at the meso positions have been developed. The syntheses employ dipyrromethanes, 1-acyldipyrromethanes, and 1,9-diacyldipyrromethanes bearing an imidazole group at the 5-position. The polar, reactive imidazole unit was successfully masked by use of (1) the 2-(trimethylsilyl)ethoxymethyl (SEM) group at the imidazole pyrrolic nitrogen, and (2) a dialkylboron motif bound to the pyrrole of the dipyrromethane and coordinated to the imidazole imino nitrogen. The nonpolar nature of such doubly masked imidazolyl-dipyrromethanes facilitated handling. Selected masked dipyrromethanes were characterized by 11B and 15N NMR spectroscopy. Five distinct methods were examined to obtain trans-A2B2-, trans-AB2C-, and trans-AB-porphyrins. Each porphyrin contained one or two SEM-protected imidazole units. The SEM group could be removed with TBAF or HCl. Two zinc(II) porphyrins and a palladium(II) porphyrin bearing a single imidazole moiety were prepared and subjected to alkylation (with ethyl iodide, 1,3-propane sultone, or 1,4-butane sultone) to give water-soluble imidazolium- porphyrins. This work establishes the foundation for the rational synthesis of a variety of porphyrins containing imidazole units.
A new polypyridyl ligand MPPIP {MPPIP=2-(3'-phenoxyphenyl)imidazo[4,5-f]-[1,10]phenanthroline} and its ruthenium(II) complexes, [Ru(bpy)(2)MPPIP](2+) (1) (bpy=2,2'-bipyridine) and [Ru(phen)(2)MPPIP](2+) (2) (phen=1,10-phenanthroline) have been synthesized and characterized. The binding of the two complexes to calf thymus DNA (CT-DNA) has been investigated with spectrophotometric methods, viscosity measurements, as well as equilibrium dialysis and circular dichroism spectroscopy. The results suggest that both complexes bind to CT-DNA through intercalation, and enantioselectively interact with CT-DNA in a way. However, complex 2 is a much better candidate as an enantioselective binder to CT-DNA than complex 1. When irradiated at 365nm, both complexes have also been found to promote the photocleavage of plasmid pBR322 DNA.