Synthesis of 3,7-anhydro-D-glycero-D-ido-octitol 1,5,6-trisphosphate as an IP(3) receptor ligand using a radical cyclization reaction with a vinylsilyl tether as the key step. Conformational restriction strategy using steric repulsion between adjacent bulky protecting groups on a pyranose ring

3,7-Anhydro-D-glycero-D-ido-octitol 1,5,6-trisphosphate (5) was designed as a novel IP(3)-receptor ligand having a C-glycosidic structure and was synthesized via a radical cyclization reaction with a temporary connecting vinylsilyl tether as the key step. The phenyl 2-O-dimethylvinylsilyl-3,4, 6-tri-O-benzyl-1-seleno-beta-D-glucopyranoside (7), in the usual (4)C(1)-conformation, was successively treated with Bu(3)SnH/AIBN and under Tamao oxidation conditions to give a mixture of five C-glycosidic products. On the other hand, similar successive treatment of the corresponding 3,4-di-O-TBS-protected substrates 13 and 24, which were in an unusual (1)C(4)-conformaion due to the steric repulsion between the bulky silyl protecting groups, gave the desired 1alpha-C-glycosides 18 and 25, respectively, as the major products. Thus, the course of the radical cyclization was effectively controlled by a change in the conformation of the pyranose ring into a (1)C(4)-form due to steric repulsion between the adjacent bulky TBS-protecting groups at the 3- and 4-hydroxyl groups. From 25, the target 5 was synthesized via phosphorylation of the hydroxyls by the phosphoramidite method. The C-glycoside trisphosphate 5 has significant binding affinity for IP(3) receptor of calf cerebella.

Endovascular therapy for massive haemothorax caused by ruptured extracranial vertebral artery aneurysm with neurofibromatosis Type 1.

Extracranial vertebral artery aneurysm is uncommon, and the common cause is penetrating trauma. Rupture of extracranial vertebral artery aneurysm into the thoracic cavity is extremely rare and fatal due to haemorrhagic shock by massive haemothorax. We report an intrathoracic rupture of the extracranial vertebral artery aneurysm with neurofibromatosis Type 1, successfully treated by coil and liquid embolisation.

Crystallographic orientation contrast associated with Ga+ ion channelling for Fe and Cu in focused ion beam method.

In this study, Cu and Fe single crystals are used to examine the change in secondary electron intensity associated with Ga(+) ion channelling in a focused ion beam (FIB) system. The single crystals having three different orientations are tilted with respect to the beam incidence and the resulting variation in the secondary electron intensity is measured through the variation in brightness of the crystals. It is shown that intensity minima appear at the beam directions normal to the lower indices of the crystal orientations. The appearance of the intensity minima including the magnitude of the minima is consistent with the prediction based on the event of ion channelling in the crystal and is affected by the crystal structure. The effect of background on the intensity minima is discussed in this study. It is suggested that the presence of the intensity minima may be used to identify a crystal orientation including a crystal structure.