Molybdenum blue: binding to collagen fibres and microcrystal formation

Collagen fibres have been shown by transmission electron microscopy to progressively bind the polyoxomolybdate ring-complex, termed molybdenum blue. Nucleation of cuboidal molybdenum blue microcrystals occurs on the surface of the collagen fibres, leading eventually to extensive coating of the fibres with microcrystals.     

Parallel organization of contralateral and ipsilateral prefrontal cortical projections in the rhesus monkey

Background  

The neocortical commissures have a fundamental role in functional integration across the cerebral hemispheres. We investigated whether commissural projections in prefrontal cortices are organized according to the same or different rules as those within the same hemisphere, by quantitatively comparing density, topography, and laminar origin of contralateral and ipsilateral projections, labeled after unilateral injection of retrograde tracers in prefrontal areas.     

The structural and spectroscopic characterisation of three actinyl complexes with coordinated and uncoordinated perrhenate: [UO2(ReO4)2(TPPO)3], [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2 and [NpO2(TPPO)4][ReO4

The first structural characterization of an actinide complex with coordinated perrhenate is reported, [UO2(ReO4)2(TPPO)3] (1). In this [UO2]2+ complex two [ReO4]- anions and three TPPO (triphenylphosphine oxide) P=O donor ligands are coordinated in the equatorial plane in a cisoid arrangement. This bonding arrangement, and apparent strain observed in the equatorially bonded ligands, is attributed to the solid state packing in adjacent molecules in which hydrophobic TPPO ligands form an effective "shell" around a hydrophilic core of two UO2(ReO4)2 moieties. Solid state vibrational spectroscopy (infrared and Raman), 31P CP MAS NMR and elemental analysis are also consistent with the formula of 1. Solution state vibrational spectroscopy and 31P NMR measurements in EtOH indicate the lability of the TPPO and [ReO4]- groups. The photolytic generation of peroxide in EtOH solutions of 1 leads to the formation of trace quantities of [[(UO2)(TPPO)3]2(mu2-O2)][ReO4]2, 2, in which the coordinated [ReO4]- groups of 1 have been displaced by bridging O2(2-), derived from atmospheric O2. Finally, attempts to synthesise a [NpO2]+ analogue of have resulted only in the formation of [NpO2(TPPO)4][ReO4], 3, in which [ReO4]- acts solely as a counter anion. From these results it can be concluded that [ReO4]- will bond to [UO2]2+, but will be readily displaced by a more strongly coordinating ligand (e.g. peroxide) and will not coordinate to an actinyl cation with a lower charge, [NpO2]+, under the same reaction conditions.     

Chemical shift anisotropy amplification

A new NMR experiment which allows a measurement of the chemical shift anisotropy (CSA) tensor under magic angle spinning (MAS) is described. This correlates a fast MAS spectrum in the omega2 dimension with a sideband pattern in omega1 in which the intensities mimic those for a sample spinning at a fraction of the rate omega r/N, and these sidebands result from an amplification by a factor N of the modulation caused by the CSA. Standard methods can be used to extract the principal tensor components from the omega1 sideband patterns, and the nature of the experiment is such that the use of a large number of t1 increments can be avoided without compromising the resolution of different chemical sites. The new experiment is useful for accurately measuring narrow shift anisotropies.     

Growth Cone Pathfinding: a competition between deterministic and stochastic events

Background  

Growth cone migratory patterns show evidence of both deterministic and stochastic search modes.     

Synthesis, chiroptical properties, and solid-state structure determination of two new chiral dipyrrin difluoroboryl chelates

Two new types of optically active BODIPY fluorophores bearing chiral phenyl substituents either at the meso-position or at both external alpha-positions have been synthesized. Their chiroptical properties are strongly dependent both on the position of the chiral group and on the protonation of the chromophore. The solid-state structures of one of the difluoroboryl chelates bearing the chiral phenyl substituent at the meso-position (9a) as well as of the corresponding ligand (8a) and its perchlorate have been determined by X-ray diffraction analysis. These are, to the best of our knowledge, the first crystal structures of a dipyrrin free base and of a dipyrrin salt which have been obtained by X-ray diffraction analysis. Hence, for the first time, the helical structure of a protonated dipyrrin chromophore has been proved experimentally.     

Alkali-stable high-pI isoelectric membranes for isoelectric trapping separations

Alkali-stable, high-pI isoelectric membranes have been synthesized from quaternary ammonium derivatives of cyclodextrins and poly(vinyl alcohol), and bifunctional cross-linkers, such as glycerol-1,3-diglycidyl ether. The new, high-pI isoelectric membranes were successfully applied as cathodic membranes in isoelectric trapping separations in place of the hydrolytically more labile, polyacrylamide-based cathodic isoelectric membranes, and permitted the use of catholytes as alkaline as 1 M NaOH. The new high-pI isoelectric membranes have shown excellent mechanical stability, low electric resistance and long life times, even when subjected to electrophoresis with current densities as high as 80 mA/cm2.     

Generation of strong, homochiral bases by electrochemical reduction of phenazine derivatives

Electrochemical reduction of enantiomerically pure amino- and alkoxy-phenazine derivatives forms strongly basic radical anions which give asymmetric induction in the conversion of 3,4-epoxytetrahydrothiophene-1,1-dioxide into the allylic ester with facile regeneration of the phenazine.