37 research outputs found
Neuropsychological study of amyotrophic lateral sclerosis and parkinsonism-dementia complex in Kii peninsula, Japan
さまざまな認知症との出会い―Pick-like presenile dementia with ALS, Gerstmann-Sträussler-Scheinker 病, レビー小体病, パーキンソン・認知症複合など
Synthesis, structures and properties of benzoporphycenes and naphthoporphycenes
A series of benzoporphycenes and naphthoporphycenes and their zinc complexes were prepared from bicyclo[2.2.2]octadiene fused porphycenes by a retro-Diels-Alder reaction and their photophysical properties were studied. Free-base tetranaphthoporphycene was not soluble in common organic solvents, but zinc tetranaphthoporphycene was slightly soluble in pyridine and showed B- and Q-bands at 507 and 690 nm, respectively. Dinaphthoporphycene showed broad B- and Q-bands due to its lower symmetry. Tetrabenzo-, dibenzo-, and dinaphthoporphycenes showed fluorescence at 673, 654, and 670 nm with quantum yields of 0.32, 0.42, and 0.31, respectively, although their precursors were non-fluorescent. Zinc complexes of tetrabenzo-, dibenzo-, tetranaphtho-, dinaphthoporphycenes and their bicyclo[2.2.2]octadiene-fused precursors revealed moderate fluorescence with quantum yields of 0.15-0.37. The crystal structures of tetrabenzo- and dibenzoporphycenes showed herringbone structures, while the zinc tetrabenzoporphycene showed a hexagonal box-structure with six pyridine ligands inside
Cerebrospinal Fluid Biomarkers for Kii Amyotrophic Lateral Sclerosis/Parkinsonism-Dementia Complex
Objective. Amyotrophic lateral sclerosis/parkinsonism-dementia complex is classified as one of the tauopathies. Methods. The total tau, phosphorylated tau, and amyloid β42 levels were assayed in cerebrospinal fluid from patients with Kii amyotrophic lateral sclerosis/parkinsonism-dementia complex (), Alzheimer’s disease (), Parkinson’s disease (), amyotrophic lateral sclerosis (), and controls () using specific enzyme-linked immunosorbent assay methods. Results. Total tau and phosphorylated tau did not increase and amyloid β42 was relatively reduced in Kii amyotrophic lateral sclerosis/parkinsonism-dementia complex. Relatively reduced amyloid β42 might discriminate Kii amyotrophic lateral sclerosis/parkinsonism-dementia complex from amyotrophic lateral sclerosis and Parkinson’s disease, and the ratios of phosphorylated-tau to amyloid β42 could discriminate Kii amyotrophic lateral sclerosis/parkinsonism-dementia complex from Alzheimer’s disease. Conclusions. Cerebrospinal fluid analysis may be useful to differentiate amyotrophic lateral sclerosis/parkinsonism-dementia complex from Alzheimer’s disease, amyotrophic lateral sclerosis, and Parkinson’s disease
First Synthesis of Dodecasubstituted Porphycenes
The synthesis of dodecasubstituted porphycenes has not been reported, to date. Herein, the preparation of tetramethyloctaethylporphycene by a McMurry-type coupling of 3,3′,4,4′-tetraethyl-5,5′-diformyl-2,2′-bipyrrole was attempted at first, but dodecasubstituted porphycene was not successfully obtained and only pyrrolocyclophene was obtained. The structure of the pyrrolocyclophene was determined by 1H NMR spectroscopy, FAB MS, and X-ray crystal-structure analysis. The pyrrolocyclophene was not successfully oxidized to porphycene. Then, the McMurry-type coupling of bicyclo[2.2.2]octadiene (BCOD)-fused 5,5′-diacyl-2,2′-bipyrroles was performed and tetra-meso-octa-β-substituted (dodecasubstituted) porphycenes were successfully obtained for the first time. The structures were determined by 1H NMR spectroscopy and X-ray crystal-structure analysis. The crystal structures and NMR spectra were compared carefully with octasubstituted porphycenes, and there was a good correlation between the position of the substituents, the N1-N2 and N1?N4 distances of the porphycene inner nitrogen atoms, and NMR chemical shifts of the inner NH protons, which expressed the strength of N-H…N hydrogen bonding between N1 and N2. These results suggested that the BCOD structure was relatively compact compared with common alkyl groups and that was why the dodecasubstituted porphycenes were available this time. UV/Vis absorption and fluorescence properties are also discussed