A concise asymmetric route to the bridged bicyclic tropane alkaloid ferruginine using enyne ring-closing metathesis

[reaction: see text] Enyne metathesis has been used to prepare bridged azabicycles and applied in a short asymmetric synthesis of the tropane ferruginine. A Grubbs first generation catalyst proved to be superior to the second generation catalyst in the enyne metathesis reaction.     

The first three anisotropy constants of nickel

The technique of ferromagnetic resonance at 23 GHz has been used to determine the first three anisotropy constants of pure Ni down to 4.2K. A temperature and orientation dependent linewidth has also been observed.     

Evaluation of matrix effects in analysis of estrogen using liquid chromatography–tandem mass spectrometry

Matrix effects of different biological samples, including phosphate‐buffered saline–bovine serum albumin (PBS‐BSA), gelded horse serum, mouse serum, and mouse brain, were investigated for the determination of 17α‐ and β‐estradiol using derivatization with dansyl chloride prior to LC‐MS/MS. Matrix effects were evaluated based on the slopes of regression lines plotted from results obtained in biological matrices versus pure standard solutions. Such plots indicate the enhancement or suppression of signal based on the presence of a particular biological fluid for a particular method. The matrix effects from PBS‐BSA were similar to those of mouse serum. In contrast, analyses performed from horse serum and mouse brain yielded significant ion suppression, especially for 17β‐estradiol. Precipitation during derivatization was observed when pre‐concentrated samples were processed with ethyl acetate as an extraction solvent. This was overcome with the use of methyl tert‐butyl ether; however, matrix effects from this preparation were still present, evidenced by signal suppression and poor linearity in the standard curve. This work affirms that caution should be taken in the transfer of methods for use with different biological matrices, especially in the case where surrogate matrices are necessary for calibration purposes.     

The structures of ordered defects in thiocyanate analogues of Prussian Blue

We report the structures of six new divalent transition metal hexathiocyanatobismuthate frameworks with the generic formula , M = Mn, Co, Ni and Zn. These frameworks are defective analogues of the perovskite-derived trivalent transition metal hexathiocyanatobismuthates M^III[Bi(SCN)₆]. The defects in these new thiocyanate frameworks order and produce complex superstructures due to the low symmetry of the parent structure, in contrast to the related and more well-studied cyanide Prussian Blue analogues. Despite the close similarities in the chemistries of these four transition metal cations, we find that each framework contains a different mechanism for accommodating the lowered transition metal charge, making use of some combination of Bi(SCN)₆³⁻ vacancies, M_Bi antisite defects, water substitution for thiocyanate, adventitious extra-framework cations and reduced metal coordination number. These materials provide an unusually clear view of defects in molecular framework materials and their variety suggests that similar richness may be waiting to be uncovered in other hybrid perovskite frameworks.

We report the structures of six new divalent transition metal hexathiocyanatobismuthate Prussian Blue analogues frameworks, which contain complex ordered defect structures.