Incomplete Electrocyclization of a Sterically Hindered 1,4-Diphosphabutadiene.

Butadiene is the simplest neutral acyclic closed-shell π-conjugated system and is typically sufficiently stable enough to avoid electrocyclization to cyclobutene. In contrast, most congeners of butadiene containing heavier elements are easily converted into the corresponding 4-membered cyclobutene system. Herein, we demonstrate that the gauche 1,4-diphosphabutadiene (P=C-C=P) skeleton in a sterically encumbered 2,3-bis(phosphanylidene)-1,4-disilinane can be remarkably perturbed due to "incomplete electrocyclization" where P=C-C=P partially form the corresponding 1,2-dihydrodiphosphete (3,4-diphosphacyclobutene) by [2+2] electrocyclization. 31 P NMR data obtained in solution indicated that the coexistence of a closed ring substantially reduces the open-ring characteristics of the P=C-C=P moiety. However, the 31 P CP-MAS spectrum of 2,3-bis(phosphanylidene)-1,4-disilinane showed that the P=C-C=P structure is predominant in the solid-state. Single-crystal X-ray analysis revealed that decreasing the temperature promoted the generation of small amounts of incomplete 1,2-dihydrodiphosphete system in the crystalline state. Furthermore, the 1,2-dihydrodiphosphete units disappeared upon warming the single crystal, and this unique solid-state electrocyclization reaction was reversible.

Dynamic Chirality Control of tropos DPCB-digold Skeleton by Chiral Binaphthyldicarboxylate.

The planar 3,4-diphosphinidenecyclobutene (DPCB) can be remarkably twisted into a C2 -type helical structure by dual coordination of a AuCl moiety. A prompt chirality control of the twisted DPCB skeleton ligated by the digold units affords the enantiopure structure by exchanging the chloride ligands for chiral [1,1'-binaphthalene]-2,2'-dicarboxylate. The chirality of the diaurated 2,2'-bis(diphenylphosphanyl)-1,1'-biphenyl (BIPHEP) system can be controlled prior to that of DPCB. Mixing of a DPCB-bis(chlorogold) complex with the chiral silver salt dynamically leads to a single diastereomer, which was characterized by the (31) P NMR spectrum and the CD couplet patterns in the visible (DPCB) area. The absolute configuration of the singly induced helical structure was assigned by the theoretical CD spectra determined by TD-DFT calculations. Intramolecular alkoxycyclization of hexa-4,5-dien-1-ol catalyzed by the asymmetric DPCB-digold structure were also attempted.

Fluvoxamine inhibits weight gain and food intake in food restricted hyperphagic Wistar rats.

The effects of fluvoxamine, a selective serotonin reuptake inhibitor (SSRI), were studied in normophagic and food-restriction-induced hyperphagic middle-aged Wistar rats. Normophagic intact Wistar rats were given fluvoxamine (100 mg/kg/d, per os (p.o.)) or vehicle for 10 d. Hyperphagic middle-aged Wistar rats were subjected to 10 d of food restriction; they were allowed to refeed for 10 d, with ad libitum food access and administered fluvoxamine (100 mg/kg/d, p.o.) or vehicle during the 10-d refeeding period. Fluvoxamine administration to normophagic middle-aged Wistar rats affected neither their weight nor food intake. However, administration to food-restricted rats showed inhibitory effects of weight gain and food intake during 10 d of refeeding. Fluvoxamine-treated rats showed significantly lower neuropeptide Y (NPY) immunostaining levels in the paraventricular nucleus (PVN) and dorsomedial hypothalamic nucleus (DMH) than untreated controls. Hypophagic and weight-inhibiting effects of fluvoxamine might be mediated via decreased NPY in PVN and DMH. These results suggest that the appetite-controlling effect of fluvoxamine might be responsive to the rats' appetite condition.

Adiponectin is regulated differently by chronic exercise than by weight-matched food restriction in hyperphagic and obese OLETF rats.

This study was intended to investigate the effects of chronic exercise on blood adiponectin level. Male Otsuka Long Evans Tokushima Fatty (OLETF) rats (26 weeks old) were divided to undergo either regular 12-week wheel running exercise (EX) or to have food restriction (FR) that resulted in body weight reduction similar to that in EX. Both EX and FR induced similar reductions in body weight, abdominal fat volume and plasma leptin concentration compared with ad libitum control. At the end of the study, although plasma adiponectin level was increased in FR, the adiponectin level did not change in EX. Plasma testosterone level was higher in EX than in either of the other two groups. A significant inverse relationship existed between plasma levels of adiponectin and testosterone for all groups. Our results suggested that 12-week voluntary wheel running exercise induces different effects on plasma adiponectin level than does food restriction, despite similar reduction in body weight, fat tissue mass and plasma leptin concentration. We speculate that the elevated plasma testosterone concentration might offset any hyperadiponectinemic effect of body weight and fat volume reduction in exercising rats.