meta‐ and para‐Phenylenediamine‐Fused Porphyrin Dimers: Synthesis and Magnetic Interactions of Their Dication Diradicals

meta‐ and para‐Phenylenediamine‐fused nickel(II) porphyrin dimers were synthesized by S_NAr reaction of meso,β,β‐trichloro nickel(II) porphyrin with meta‐ and para‐phenylenediamines and subsequent Pd‐catalyzed intramolecular C?H arylation. Their tetrachlorinated dication diradicals are very stable, allowing SQUID magnetometry and revealing clear open‐shell characters for both meta and para isomers with ferro‐ and anti‐ferromagnetic interactions, respectively. The nitrogen analogue of Thiele's hydrocarbon usually displays predominant closed‐shell nature but its hidden diradical characters increase either in a twisted conformation or upon insertion of an additional phenylene spacer. The observed distinct diradical nature of the para‐congener indicates that diradical properties can be enhanced also by efficient spin delocalization.     

Cation distribution of the cochlea wall (Stria vascularis)

Summary It was possible to maintain the differentiated structure of inner ear tissues by freezing in supercooled propane, freeze-drying under special conditions and embedding the tissue in a low viscosity resin. Using LAMMA we were able to measure intracellular ion concentration and concentration gradients in the soft tissues such as muscle and stria vascularis specimens. The preliminary results demonstrate that the distribution of cations in the lateral wall of the cochlear duct is not uniform. The K/Na ratio in the basal cells was significantly higher (121) than in the spiral ligament and middle part of the stria vascularis (71). Changes of such concentration ratios recorded after anoxia suggest that an energy dependent active transport mechanism must exist in the stria vascularis.

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Kationenverteilung in der Schneckengangwand des Ohres (Stria vascularis)