Electron paramagnetic resonance structure investigation of copper complexation in a hemicarcerand.

The double-bridged hemicarcerand [A,B-(CH2OH)2-cavitand]-(CH2NHCH2)2-[A,B-(CH2OH)2-cavitand] 23 (and several other related compounds) was synthesized by the condensation of the two complementary precursors A,B-(CH2NH2)2(CH2OH)2-cavitand and A,B-(CH2Br)2(CH2OAc)2-cavitand followed by hydrolysis of the acetate groups. This hemicarcerand has nitrogen and oxygen donor atoms located on the interior of the spherical cavity and thus allows endohedral coordination of metal ions. The cavity has a volume of approximately 0.12 nm3, a value obtained by calculating a Connolly-type contact surface and the molecular electrostatic potential. The Cu2+ complex of hemicarcerand 23 was studied in detail by EPR and DFT calculations at the UB3LYP/6-31G level to verify the anticipated endohedral nature of the metal complex. It could be shown that the copper ion is coordinated to four oxygen donor atoms and no deviation from axial symmetry at the copper site could be detected. No direct coordination to nitrogen atoms of the hemicarcerand could be observed; however, complexation with DMF solvent molecules was detected by ESEEM and HYSCORE experiments. The closed structure of the hemicarcerand was also confirmed by an evaluation of proton-copper distances. Results from DFT calculations are in accord with the EPR results, and further support suggested coordination of the Cu(II) within the hemicarcerand cavity by four oxygen donor atoms.

Hidrocystoma and adenoma of apocrine anal glands.

Five cases of apocrine hidrocystoma of the anal glands are described, two of which are dealt with in detail, as they were a primary cause of the patients' complaints. The three additional cases were found incidentally during histologic examination of hemorrhoidectomy specimens. All five patients were women between 32 and 65 years of age. The similarities with the better known cutanous hidrocystomas of other sites harbouring apocrine sweat glands are emphasized and the morphogenesis of these lesions is considered. In addition, a rare adenoma of the apocrine anal glands in a 46 year old woman is described and the problems of diagnostic classification in examples lacking predominantly papillary structures are discussed.