Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

The synthesis and co-ordination chemistry of a new ‘bulky yet flexible’ N-heterocyclic carbene (“IPaul”) is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*OMe complexes

Scanning Electron Microscopy Methodology for Study of the Pathophysiology of Calcification in Bioprosthetic Heart Valves

Scanning electron microscope (SEM) morphologic analysis combined with energy dispersive characteristic X-ray (EDX) microprobe analysis provides insight into the mechanisms associated with disease-related crystal formation in biological materials. SEM and EDX were employed in analyzing specimens which were embedded in standard fashion in glycolmethacrylate (JB-4). The specimen surfaces under electron microscope investigation resulted from microtomy used in the preparation of reference light microscope histological sections; thus histology served as a direct reference for the SEM and EDX analyses. The particular application of these methods was in the study of bioprosthetic heart valve calcification, largely responsible for clinical failure of these heart valve substitutes. To simulate the clinically observed mineralization processes, glutaraldehyde-pretreated porcine heart valve leaflets were implanted subcutaneously in rats and subsequently removed at various time intervals from 1 to 56 days. Also, to address the hypothesis that the calcification process generates crystalline materials analogous to those in bone, EDX data obtained from pure hydroxyapatite were compared with the embedded tissue results. Further, EDX results were compared with data obtained by chemical analysis of the bulk specimens to assess the validity of the electron microscope technique

Instrumental vetoes for transient gravitational-wave triggers using noise-coupling models: The bilinear-coupling veto

LIGO and Virgo recently completed searches for gravitational waves at their initial target sensitivities, and soon Advanced LIGO and Advanced Virgo will commence observations with even better capabilities. In the search for short duration signals, such as coalescing compact binary inspirals or "burst" events, noise transients can be problematic. Interferometric gravitational-wave detectors are highly complex instruments, and, based on the experience from the past, the data often contain a large number of noise transients that are not easily distinguishable from possible gravitational-wave signals. In order to perform a sensitive search for short-duration gravitational-wave signals it is important to identify these noise artifacts, and to "veto" them. Here we describe such a veto, the bilinear-coupling veto, that makes use of an empirical model of the coupling of instrumental noise to the output strain channel of the interferometric gravitational-wave detector. In this method, we check whether the data from the output strain channel at the time of an apparent signal is consistent with the data from a bilinear combination of auxiliary channels. We discuss the results of the application of this veto on recent LIGO data, and its possible utility when used with data from Advanced LIGO and Advanced Virgo.Comment: Minor changes; To appear in Phys. Rev.

Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

Two new nickel catalysts have been prepared using a convenient procedure where nickelocene, the NHC.HBF4 salts, and [Et4N]Cl were heated in THF using microwave irradiation. The resulting [NiCl(Cp)(NHC)] complexes are air- and moisture stable in the solid state, and represent two new members of this valuable and practical class of nickel catalyst. The new species were fully characterised using methods including NMR spectroscopy and X-ray crystallography. When tested in model Suzuki-Miyaura cross-coupling reactions, these complexes were found to be active for the cross-coupling of aryl bromides and aryl chlorides

The electrophilic fluorination of enol esters using SelectFluor : a polar two-electron process

The reaction of enol esters with SelectFluor is facile and leads to the corresponding α-fluoroketones under mild conditions and, as a result, this route is commonly employed for the synthesis of medicinally important compounds such as fluorinated steroids. However, despite the use of this methodology in synthesis, the mechanism of this reaction and the influence of structure on reactivity are unclear. We present a rigorous mechanistic study of the fluorination of these substrates, informed primarily by detailed and robust kinetic experiments. The results of this study implicate a polar two-electron process via an oxygen-stabilised carbenium species, rather than a single-electron process involving radical intermediates. The structure/reactivity relationships revealed here will assist synthetic chemists in deploying this type of methodology in the syntheses of α-fluoroketone

Carrier generation and transport in bulk heterojunction films processed with 1,8-octanedithiol as a processing additive

Improved performance of polymer-based solar cells based on poly[2,6-(4,4-bis-(2-ethylhexyl)- 4H -cyclopenta[2,1-b;3,4- b???] dithiophene)-alt-4,7-(2,1,3-benzo-thiadiazole)] PCPDTBT has been obtained by using 1,8-octanedithiol (ODT) as a processing additive in the polymer solution used to spin cast the bulk heterojunction films. Although ultrafast spectroscopy studies indicate that the carrier losses are reduced in the films processed with ODT [similar to the reduced carrier losses after thermal annealing of bulk heterojunction (BHJ) materials made from P3HT:PCBM], the magnitude of the reduction is not sufficient to explain the observed factor of 2 increase in the power conversion efficiency. From the analysis of carrier transport in field effect transistors, we find increased electron mobility in the PCPDTBT: PC70 BM composites when fabricated with ODT, which is indicative of enhanced connectivity of PC70 BM networks. The improved electron mobility appears to be the primary origin of the improved power conversion efficiency in BHJ films.open453

Effect of androgen treatment during foetal and/or neonatal life on ovarian function in prepubertal and adult rats

We investigated the effects of different windows of testosterone propionate (TP) treatment during foetal and neonatal life in female rats to determine whether and when excess androgen exposure would cause disruption of adult reproductive function. Animals were killed prepubertally at d25 and as adults at d90. Plasma samples were taken for hormone analysis and ovaries serial sectioned for morphometric analyses. In prepubertal animals, only foetal+postnatal and late postnatal TP resulted in increased body weights, and an increase in transitory, but reduced antral follicle numbers without affecting total follicle populations. Treatment with TP during both foetal+postnatal life resulted in the development of streak ovaries with activated follicles containing oocytes that only progressed to a small antral (smA) stage and inactive uteri. TP exposure during foetal or late postnatal life had no effect upon adult reproductive function or the total follicle population, although there was a reduction in the primordial follicle pool. In contrast, TP treatment during full postnatal life (d1-25) resulted in anovulation in adults (d90). These animals were heavier, had a greater ovarian stromal compartment, no differences in follicle thecal cell area, but reduced numbers of anti-Mullerian hormone-positive smA follicles when compared with controls. Significantly reduced uterine weights lead reduced follicle oestradiol production. These results support the concept that androgen programming of adult female reproductive function occurs only during specific time windows in foetal and neonatal life with implications for the development of polycystic ovary syndrome in women