High-resolution crystal structure of the intramolecular d(TpA) thymine-adenine photoadduct and its mechanistic implications.

A high-resolution crystal structure is reported for d(TpA)*, the intramolecular thymine–adenine photoadduct that is produced by direct ultraviolet excitation of the dinucleoside monophosphate d(TpA). It confirms the presence of a central 1,3-diazacyclooctatriene ring linking the remnants of the T and A bases, as previously deduced from heteronuclear NMR measurements by Zhao et al. (The structure of d(TpA)*, the major photoproduct of thymidylyl-(3'-5')-deoxyadenosine. Nucleic Acids Res., 1996, 24, 1554–1560). Within the crystal, the d(TpA)* molecules exist as zwitterions with a protonated amidine fragment of the eight-membered ring neutralizing the charge of the internucleotide phosphate monoanion. The absolute configuration at the original thymine C5 and C6 atoms is determined as 5S,6R. This is consistent with d(TpA)* arising by valence isomerization of a precursor cyclobutane photoproduct with cis–syn stereochemistry that is generated by [2 + 2] photoaddition of the thymine 5,6-double bond across the C6 and C5 positions of adenine. This mode of photoaddition should be favoured by the stacked conformation of adjacent T and A bases in B-form DNA. It is probable that the primary photoreaction is mechanistically analogous to pyrimidine dimerization despite having a much lower quantum yield.

Base free dynamic kinetic resolution of secondary alcohols using ‘piano stool’ complexes of N-heterocyclic carbenes

Piano stool complexes of rhodium and iridium activated by fluorinated and non-fluorinated N-heterocyclic carbene (NHC) ligands were shown to be catalysts for racemization in the one-pot chemoenzymic dynamic kinetic resolution (DKR) of secondary alcohols. Excellent conversions and good enantioselectivities were observed for alkyl aryl and dialkyl secondary alcohols.

A Blueprint for Democratic Policing Anywhere in the World? Police Reform, Political Transition and Conflict Resolution in Northern Ireland

This article provides an overview of the police reform process undertaken in Northern Ireland since 1999 as part of a broader program of conflict resolution. It considers the recommendations of the Independent Commission on Policing (ICP), which proposed a number of changes to policing structures and arrangements in Northern Ireland, and it assesses the degree to which these have been operationalized in the 8 years since the ICP published its report. It suggests that although the police reform process in Northern Ireland has been moderately successful and provides a number of international best practice lessons, the overall pace of change has been hindered by difficulties of implementation and, more fundamentally, by developments in the political sphere and civil society.

Far-Field Optical Microscopy with a Nanometer-Scale Resolution Based on the In-Plane Image Magnification by Surface Plasmon Polaritons

A new far-field optical microscopy capable of reaching nanometer-scale resolution is developed using the in-plane image magnification by surface plasmon polaritons. This approach is based on the optical properties of a metal-dielectric interface that may provide extremely large values of the effective refractive index neff up to 103 as seen by surface polaritons, and thus the diffraction limited resolution can reach nanometer-scale values of lambda/2neff. The experimental realization of the microscope has demonstrated the optical resolution better than 60 nm at 515 nm illumination wavelength.

High-resolution optical spectroscopy of the sharp-lined B-type star HD83206

Very-high-resolution (R~160000) spectroscopic observations are presented for the early B-type star, HD83206. Because it has very sharp metal lines, this star affords an opportunity to test theories of model atmospheres and line formation. Non-LTE model atmosphere calculations have been used to estimate the atmospheric parameters and absolute metal abundances (C, N, O, Mg and Si); an LTE analysis was also undertaken to investigate the validity of this simpler approach and to estimate an iron abundance. For the non-LTE calculations, there is excellent agreement with observations of the Balmer lines Ha and Hd and the lines of Siii and Siiii for atmospheric parameters of Teff~=21700+/-600K and logg~=4.00+/-0.15dex. The agreement is less convincing for the LTE calculations, and a higher gravity is deduced. Careful comparison of the metal line profiles with non-LTE calculations implies that the projected rotational and microturbulent velocities have maximum values of ~=5 and ~=2kms-1, respectively. The latter value is smaller than has often been adopted in LTE model atmosphere analyses of main-sequence stars. Non-LTE absolute metal abundances are estimated, and a comparison with those for normal B-type stars (deduced using similar non-LTE techniques) shows no significant differences. A comparison of the abundances deduced using non-LTE and LTE calculations implies systematic differences of 0.1-0.2dex, showing the importance of using a non-LTE approach when accurate absolute abundances are required. Its location in the Hertzsprung-Russell diagram and normal metal abundance lead us to conclude that HD83206 is probably a main-sequence B-type star. As such, it is among the sharpest-lined young B-type star discovered to date.

Dynamics of North Patagonian rainforests from fine-resolution pollen, charcoal and tree-ring analysis, Chonos Archipelago, Southern Chile

Fine-resolution palaeoecological and dendrochronological methods were used to investigate the impacts of climate change, and natural and anthropogenic disturbances on vegetation in the North Patagonian rainforest of southern Chile at decadal to century timescales during the late Holocene. A lake sediment mud–water interface core was collected from the northern Chonos Archipelago and analysed for pollen and charcoal. Dendrochronological analysis of tree cores collected from stands of Pilgerodendron uviferum close to the lake site was incorporated into the study. The combined analysis showed that the present mosaic of vegetation types in this region is a function of environmental changes across a range of timescales: millennial climate change, more recent natural and anthropogenic disturbances, and possibly short-term climatic variations. Of particular interest is the spatiotemporal distribution of Pilgerodendron uviferum dieback/burning in the Chonos Archipelago region.

High-resolution organellar genome analysis of Triticum and Aegilops sheds new light on cytoplasm evolution in wheat

We have utilised polymorphic chloroplast microsatellites to analyse cytoplasmic relationships between accessions in the genera Triticum and Aegilops. Sequencing of PCR products revealed point mutations and insertions/deletions in addition to the standard repeat length expansion/contraction which most likely represent ancient synapomorphies. Phylogenetic analyses revealed three distinct groups of accessions. One of these contained all the non-Aegilops speltoides S-type cytoplasm species, another comprised almost exclusively A, C, D, M, N, T and U cytoplasm-type accessions and the third contained the polyploid Triticum species and all the Ae. speltoides accessions, further confirming that Ae. speltoides or a closely related but now extinct species was the original B-genome donor of cultivated polyploid wheat. Successive decreases in levels of genetic diversity due to domestication were also observed. Finally, we highlight the importance of elucidating longer-term evolutionary processes operating at microsatellite repeat loci.

Resolution of an ancient surface science anomaly: Work function change induced by N adsorption on W{100}

For many decades it has been assumed that an adsorbate centered above a metal surface and with a net negative charge should increase the work function of the surface. However, despite their electronegativity, N adatoms on W{100} cause a significant work function decrease. Here we present a resolution of this anomaly. Using density functional theory, we demonstrate that while the N atom carries a negative charge, of overriding importance is a reduction in the surface overspill electron density into the vacuum, when that charge is engaged in bonding to the adatom. This novel interpretation is fundamentally important in the general understanding of work function changes induced by atomic adsorbates.