Podcasting

Audio or video podcasts can be a useful tool to supplement practical exercises such as business simulations. In our case study we have used different types of podcast to support the delivery of various courses at the Business School at Leeds Metropolitan University. These podcasts were used as reusable learning resources as they were utilised for three student cohorts with approximately 700 students in total. It was possible to offer the podcasts to students studying at a range of different levels since the podcasts' main focus was to support the learner using a computer-based business simulation

Anomalous thermal expansion in 1D transition-metal cyanides: what makes the novel trimetallic cyanide Cu1/3Ag1/3Au1/3CN behave differently?

The structural dynamics of a quasi-one-dimensional (1D) mixed-metal cyanide, Cu1/3Ag1/3Au1/3CN, with intriguing thermal properties is explored. All the current known related compounds with straight-chain structures, such as group 11 cyanides CuCN, AgCN, AuCN and bimetallic cyanides MxM’1-xCN (M, M’ = Cu, Ag, Au), exhibit 1D negative thermal expansion (NTE) along the chains and positive thermal expansion (PTE) perpendicular to them. Cu1/3Ag1/3Au1/3CN exhibits similar PTE perpendicular to the chains, however PTE, rather than NTE, is also observed along the chains. In order to understand the origin of this unexpected behavior, inelastic neutron scattering (INS) measurements were carried out, underpinned by lattice-dynamical density-functional-theory (DFT) calculations. Synchrotron-based pair-distribution-function (PDF) analysis and 13C solid-state nuclear-magnetic-resonance (SSNMR) measurements were also performed to build an input structural model for the lattice dynamical study. The results indicate that transverse motions of the metal ions are responsible for the PTE perpendicular to the chains, as is the case for the related group 11 cyanides. However NTE along the chain due to the tension effect of these transverse motions is not observed. As there are different metal-to-cyanide bond lengths in Cu1/3Ag1/3Au1/3CN, the metals in neighboring chains cannot all be truly co-planar in a straight-chain model. For this system, DFT-based phonon calculations predict small PTE along the chain due to low-energy chain-slipping modes induced by a bond-rotation effect on the weak metallophilic bonds. However the observed PTE is greater than that predicted with the straight-chain model. Small bends in the chain to accommodate truly co-planar metals provide an alternative explanation for thermal behavior. These would mitigate the tension effect induced by the transverse motions of the metals and, as temperature increases and the chains move further apart, a straightening could occur resulting in the observed PTE. This hypothesis is further supported by unusual evolution in the phonon spectra, which suggest small changes in local symmetry with temperature

A crystallographic and theoretical study of an (E)-2-Hydroxyiminoethanone derivative: prediction of cyclooxygenase inhibition selectivity of stilbenoids by MM-PBSA and the role of atomic charge

We recently reported that a hydroxyiminoethanone derivative behaves as a highly selective COX-1 inhibitor (COX-1 SI= 833), and also an interesting scaffold with unique characteristics. In the current study, a comprehensive crystallographic and computational study was performed to elucidate its conformational stability and pharmacological activity. Its conformational energy was studied at the B3LYP/6-311G** level of theory and compared to the single-crystal X-ray data. In addition, computational studies of three structurally different stilbenoid derivatives used as selective COX-1 or COX-2 inhibitors were performed to predict their COX selectivity potentials. Flexible docking was performed for all compounds at the active site of both COX-1 and COX-2 enzymes by considering some of the key residues as flexible during the docking operation. In the next step, molecular dynamic simulation and binding free energy calculations were performed by MM-PBSA. Final results were found to be highly dependent on the atomic charges of the inhibitors and the choice of force field used to calculate the atomic charges. The binding conformation of the hydroxyiminoethanone derivative is highly correlated with the type of COX isoform inhibited. Our predictive approach can truly predict the cyclooxygenase inhibition selectivity of stilbenoid inhibitors

Group 6 metal complexes as electrocatalysts of CO2 reduction: strong substituent control of the reduction path of [Mo(η3-allyl)(CO)2(x,x′-dimethyl-2,2′-bipyridine)(NCS)] (x = 4–6)

A series of complexes [Mo(η3-allyl)(CO)2)(x,x′-dmbipy)(NCS)] (dmbipy = dimethyl-2,2′-bipyridine; x = 4–6) have been synthesized and their electrochemical reduction investigated using combined cyclic voltammetry (CV) and variable-temperature spectroelectrochemistry (IR/UV-vis SEC) in tetrahydrofuran (THF) and butyronitrile (PrCN), at gold and platinum electrodes. The experimental results, strongly supported by density functional theory (DFT) calculations, indicate that the general cathodic path of these Group 6 organometallic complexes is closely related to that of the intensively studied class of Mn tricarbonyl α-diimine complexes, which, themselves, have recently been identified as important smart materials for catalytic CO2 reduction. The dimethyl substitution on the 2,2′-bipyridine ligand backbone has presented new insights into this emerging class of catalysts. For the first time, the 2e– reduced 5-coordinate anions [Mo(η3-allyl)(CO)2)(x,x′-dmbipy)]− were directly observed with infrared spectroelectrochemistry (IR SEC). The role of steric and electronic effects in determining the reduction-induced reactivity was also investigated. For the 6,6′-dmbipy, the primary 1e– reduced radical anions exert unusual stability, radically changing the follow-up cathodic path. The 5-coordinate anion [Mo(η3-allyl)(CO)2)(6,6′-dmbipy)]− remains stable at low temperature in strongly coordinating butyronitrile and does not undergo dimerization at elevated temperature, in sharp contrast to reactive [Mo(η3-allyl)(CO)2)(4,4′-dmbipy)]− that tends to dimerize in a reaction with the parent complex. The complex with the 5,5′-dmbipy ligand combines both types of reactivity. Under aprotic conditions, the different properties of [Mo(η3-allyl)(CO)2)(x,x′-dmbipy)]− are also reflected in their reactivity toward CO2. Preliminary CV and IR SEC results reveal differences in the strength of CO2 coordination at the free axial position. Catalytic waves attributed to the generation of the 5-coordinate anions were observed using CV, but only a modest catalytic performance toward the production of formate was demonstrated by IR SEC. For 6,6′-dmbipy, a stronger catalytic effect was observed for the Au cathode, compared to Pt

Chemistry and structure by design: ordered CuNi(CN)4 sheets with copper(II) in a square-planar environment

Layered copper–nickel cyanide, CuNi(CN)4, a 2-D negative thermal expansion material, is one of a series of copper(II)-containing cyanides derived from Ni(CN)2. In CuNi(CN)4, unlike in Ni(CN)2, the cyanide groups are ordered generating square-planar Ni(CN)4 and Cu(NC)4 units. The adoption of square-planar geometry by Cu(II) in an extended solid is very unusual

Postcopulatory sexual selection

The female reproductive tract is where competition between the sperm of different males takes place, aided and abetted by the female herself. Intense postcopulatory sexual selection fosters inter-sexual conflict and drives rapid evolutionary change to generate a startling diversity of morphological, behavioural and physiological adaptations. We identify three main issues that should be resolved to advance our understanding of postcopulatory sexual selection. We need to determine the genetic basis of different male fertility traits and female traits that mediate sperm selection; identify the genes or genomic regions that control these traits; and establish the coevolutionary trajectory of sexes

Divergent artificial selection for female reproductive investment has a sexually concordant effect on male reproductive success

This is the final version of the article. Available from Wiley via the DOI in this record.Depending on the genetic architecture of male and female fitness, sex-specific selection can have negative, positive, or neutral consequences for the opposite sex. Theory predicts that conflict between male and female function may drive the breakdown of intrasexual genetic correlations, allowing sexual dimorphism in sexually antagonistic traits. Reproductive traits are the epitome of this, showing highly differentiated proximate functions between the sexes. Here we use divergent artificial selection lines for female reproductive investment to test how female-specific selection on a sex-limited trait affects male reproductive success in a precocial bird, the Japanese quail (Coturnix japonica). We demonstrate that selection for increased egg investment in females positively affects male reproductive success both in competitive and non-competitive mating situations. This increased reproductive success was linked to a relatively larger left testis in males originating from lines selected for high female reproductive investment. Given that female quail have functional gonads only on their left side, this correlated response indicates that selection has acted on the shared developmental basis of male and female gonads. Our study thereby provides evidence for a positive genetic correlation between key reproductive traits in males and females despite a high degree of sexual dimorphism, and suggests that, in this system, selection on reproductive function is sexually concordant.The study was financially supported by the Swiss National Science Foundation (PP00P3_128386 and PP00P3_157455 to BT and P2ZHP3_164962 to JLP)

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)(3)N)]Sb4S7

The chromium(II) antimony(III) sulphicle, [Cr((NH2CH2CH2)(3)N)]Sb4S7, was synthesised under solvothermal conditions from the reaction of Sb2S3. Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction. elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2(1)/n with a = 7.9756(7), b = 10.5191(9), c = 25.880(2) angstrom and beta = 90.864(5)degrees. Alternating SbS33- trigonal pyramids and Sb36 semi-cubes generate Sb4S72- chains which are directly bonded to Cr(tren pendant units. The effective magnetic moment of 4.94(6)mu(B) shows a negligible orbital contribution, in agreement with expectations for Cr(II):d(4) in a (5)A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides. (C) 2007 Elsevier Ltd. All rights reserved