Computational cogitation of Cn@Al12 clusters.

A variety of novel Cn Al12 core-shell nanoclusters have been investigated using density functional calculations. A series of Cn cores (n=1-4) have been encapsulated by icosahedral Al12 , with characteristic physical properties (energetics and stabilities, ionisation energies, electron affinities) calculated for each cluster. Other isomers, with the Cn moiety bound externally to the Al12 shell, have also been studied. For both series, a peak in stability was found for n(C)=2, a characteristic that appears to be inextricably linked with the relaxation of the constituent parts upon dissociation. Analysis of trends for ionisation energies and electron affinities includes evaluation of contributions from the carbon and aluminium components, which highlights the effects of composition and morphology on cluster properties.

A copper(I)-arene complex with an unsupported η6 interaction.

Addition of PR3 (R=Ph or OPh) to [Cu(η(2)-Me6C6)2][PF6] results in the formation of [(η(6)-Me6C6)Cu(PR3)][PF6], the first copper-arene complexes to feature an unsupported η(6) arene interaction. A DFT analysis reveals that the preference for the η(6) binding mode is enforced by the steric clash between the methyl groups of the arene ligand and the phenyl rings of the phosphine co-ligand.

A computational study of 'Al-kanes' and 'Al-kenes'.

Two novel series of 'Al-kanes' (CnAl2n+2) and 'Al-kenes' (CnAl2n) have been studied theoretically in order to shed light on their structure, stability and properties. Density functional calculations suggest that the structures tend to be dictated by the constituent aluminium atoms, rather than the carbon backbone. This is the net effect of the aluminiums attempting to adopt preferred close-packed structures. Calculated energetics suggest a special stability of clusters with n(C) = 2 and 4 in both series and plausible interpretations are suggested.

Communication: a density functional investigation of structure-property evolution in the tetrakis hexahedral C4Al14 nanocluster.

Nanoclusters are prime objects of study in modern nanotechnology and offer a variety of applications promoted by their properties tunable by size, shape, and composition. DFT calculations are employed to analyze structure, stability, and selected electronic properties of a core-shell C4Al14 species. With insertion of the carbon core, the original low-symmetry aluminum cluster is predicted to undergo a considerable reshaping and acquire a striking D4h tetrakis-hexahedral geometry, with proportions controlled by a near-degenerate spin state or charge. The system also becomes more stable to dissociation. Surprisingly, other properties such as ionisation energy and electron affinity do not change significantly, although still exhibit some interesting features including opposite variations for vertical and adiabatic values. The stability and property evolutions are analyzed in terms of contributions from reshaping of the shell and its further interaction with the core. The system thus has potential applications as a symmetric building unit and a molecular device for nano-electronics/spintronics.

On the lubricity of transition metal dichalcogenides: an ab initio study.

Owing to specific characteristics engendered by their lamellar structures, transition metal dichalcogenides are posited as being some of the best dry lubricants available. Herein, we report a density functional investigation into the sliding properties and associated phenomena of these materials. Calculated potential energy and charge transfer profiles are used to highlight the dependence of shear strength on chemical composition and bilayer orientation (sliding direction). Furthermore, our calculations underscore the intrinsic relationship between incommensurate crystals and the oft-touted superlubric behaviour of molybdenum disulfide.

Computer assisted detection of abnormal airway variation in CT scans related to paediatric tuberculosis.

Airway deformation and stenosis can be key signs of pathology such as lymphadenopathy. This study presents a local airway point distribution model (LA-PDM) to automatically analyse regions of the airway tree in CT scans and identify abnormal airway deformation. In our method, the airway tree is segmented and the centreline identified from each chest CT scan. Thin-plate splines, along with a local mesh alignment method for tubular meshes, are used to register the airways and develop point distribution models (PDM). Each PDM is then used to analyse and classify local regions of the airway. This LA-PDM method was developed using 89 training cases and evaluated on a 90 CT test set, where each set includes paediatric tuberculosis (TB) cases (with airway involvement) and non-TB cases (without airway involvement). The LA-PDM was able to accurately distinguish cases with airway involvement with an AUC of the ROC classification (and 95% confidence interval) of 0.87 (0.77-0.94) for the Trachea-LMB-RMB region and 0.81 (0.68-0.90) for the RMB-RUL-BI region - outperforming a comparison method based on airway cross-sectional features. This has the potential to assist and improve airway analysis from CT scans by detecting involved airways and visualising affected airway regions.

Structure-activity relationship refinement and further assessment of indole-3-glyoxylamides as a lead series against prion disease.

Structure-activity relationships within the indole-3-glyoxylamide series of antiprion agents have been explored further, resulting in discovery of several new compounds demonstrating excellent activity in a cell line model of prion disease (EC50 <10 nM). After examining a range of substituents at the para-position of the N-phenylglyoxylamide moiety, five-membered heterocycles containing at least two heteroatoms were found to be optimal for the antiprion effect. A number of modifications were made to probe the importance of the glyoxylamide substructure, although none were well tolerated. The most potent compounds did, however, prove largely stable towards microsomal metabolism, and the most active library member cured scrapie-infected cells indefinitely on administration of a single treatment. The present results thereby confirm the indole-3-glyoxylamides as a promising lead series for continuing in vitro and in vivo evaluation against prion disease.