Comparison of results from several AOGCMs for global and regional sea-level change 1900-2100

Sea-level rise is an important aspect of climate change because of its impact on society and ecosystems. Here we present an intercomparison of results from ten coupled atmosphere-ocean general circulation models (AOGCMs) for sea-level changes simulated for the twentieth century and projected to occur during the twenty first century in experiments following scenario IS92a for greenhouse gases and sulphate aerosols. The model results suggest that the rate of sea-level rise due to thermal expansion of sea water has increased during the twentieth century, but the small set of tide gauges with long records might not be adequate to detect this acceleration. The rate of sea-level rise due to thermal expansion continues to increase throughout the twenty first century, and the projected total is consequently larger than in the twentieth century; for 1990-2090 it amounts to 0.20-0.37 in. This wide range results from systematic uncertainty in modelling of climate change and of heat uptake by the ocean. The AOGCMs agree that sea-level rise is expected to be geographically non-uniform, with some regions experiencing as much as twice the global average, and others practically zero, but they do not agree about the geographical pattern. The lack of agreement indicates that we cannot currently have confidence in projections of local sea- level changes, and reveals a need for detailed analysis and intercomparison in order to understand and reduce the disagreements.

Intrinsic chess rating

This paper develops and tests formulas for representing playing strength at chess by the quality of moves played, rather than by the results of games. Intrinsic quality is estimated via evaluations given by computer chess programs run to high depth, ideally so that their playing strength is sufficiently far ahead of the best human players as to be a `relatively omniscient' guide. Several formulas, each having intrinsic skill parameters s for `sensitivity' and c for `consistency', are argued theoretically and tested by regression on large sets of tournament games played by humans of varying strength as measured by the internationally standard Elo rating system. This establishes a correspondence between Elo rating and the parameters. A smooth correspondence is shown between statistical results and the century points on the Elo scale, and ratings are shown to have stayed quite constant over time. That is, there has been little or no `rating inflation'. The theory and empirical results are transferable to other rational-choice settings in which the alternatives have well-defined utilities, but in which complexity and bounded information constrain the perception of the utility values.

Resolving the spatial variability of soil N using fractions of soil organic matter

The spatial variability of soil nitrogen (N) mineralisation has not been extensively studied, which limits our capacity to make N fertiliser recommendations. Even less attention has been paid to the scale-dependence of the variation. The objective of this research was to investigate the scale-dependence of variation of mineral N (MinN, N–NO3− plus N–NH4+) at within-field scales. The study was based on the spatial dependence of the labile fractions of SOM, the key fractions for N mineralisation. Soils were sampled in an unbalanced nested design in a 4-ha arable field to examine the distribution of the variation of SOM at 30, 10, 1, and 0.12 m. Organic matter in free and intra-aggregate light fractions (FLF and IALF) was extracted by physical fractionation. The variation occurred entirely within 0.12 m for FLF and at 10 m for IALF. A subsequent sampling on a 5-m grid was undertaken to link the status of the SOM fractions to MinN, which showed uncorrelated spatial dependence. A uniform application of N fertiliser would be suitable in this case. The failure of SOM fractions to identify any spatial dependence of MinN suggests that other soil variables, or crop indicators, should be tested to see if they can identify different N supply areas within the field for a more efficient and environmentally friendly N management.

Understanding distributions of chess performances

This paper presents evidence for several features of the population of chess players, and the distribution of their performances measured in terms of Elo ratings and by computer analysis of moves. Evidence that ratings have remained stable since the inception of the Elo system in the 1970’s is given in several forms: by showing that the population of strong players fits a simple logistic-curve model without inflation, by plotting players’ average error against the FIDE category of tournaments over time, and by skill parameters from a model that employs computer analysis keeping a nearly constant relation to Elo rating across that time. The distribution of the model’s Intrinsic Performance Ratings can hence be used to compare populations that have limited interaction, such as between players in a national chess federation and FIDE, and ascertain relative drift in their respective rating systems.

Alkenyl derivatives of the metals. Oxidative addition to intermediate tin(II) alkenyls; isolation, and crystal and molecular structure of n-butyltris(triphenylethenyl)tin(IV)

Reaction of tin(II) chloride with Li(CPhCPh2) at –78 °C in diethyl ether–hexane–tetrahydrofuran affords a deep red solution whose colour fades on warming, and which we believe contains the (unstable) first dialkenyltin(II) species. The latter survives long enough at low temperatures to undergo intermolecular oxidative addition, and one such adduct leads ultimately to the formation of Sn(CPhCPh2)3Bun, which has been fully characterised including a crystal and molecular structure study. The mechanism of formation of the final product has been examined and results are reported.

Unsaturated σ-hydrocarbyl transition-metal complexes. Part 4. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)-(phenylethynyl)platinum(II) and comments on the relative trans influence of various carbon ligands

The molecular structure of trans-[PtCl(CCPh)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are monoclinic, space group P21, with a= 12.359(3), b= 13.015(3), c= 9.031(2)Å, β= 101.65(2)°, and Z= 2. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.046 for 1 877 diffractometric intensity data. The crystals contain discrete molecules in which the platinum coordination is square planar. The phenylethynyl group is non-linear, with a Pt–CC angle of 163(2)°. Selected bond lengths are Pt–Cl 2.407(5) and Pt–C 1.98(2)Å. The structural trans influences of CCPh, CHCH2, and CH2SiMe3 ligands in platinum(II) complexes are compared; there is only a small dependence on hybridization at the ligating carbon atom.

Unsaturated σ-hydrocarbyl transition-metal complexes. Part 3. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)(vinyl)platinum(II)

The molecular structure of trans-[PtCl(CHCH2)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are orthorhombic, space group Pbcn, with a= 10.686(2), b= 13.832(4), c= 16.129(4)Å, and Z= 4. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.044 for 1 420 diffractometric intensity data. The crystals contain discrete molecules in which the platinum co-ordination is square planar. The Pt–Cl bond vector coincides with a crystallographic diad axis about which the atoms of the vinyl group are disordered. Selected bond lengths (Å) are Pt–Cl 2.398(4), Pt–P 2.295(3), and Pt–C 2.03(2). The Pt–CC angle is 127(2)°. From a survey of the available structural data it is concluded that there is little, if any, back donation from platinum to carbon in platinum–alkenyl linkages.

Therapeutic and cytotoxic effects of the novel antipsoriasis codrug, naproxyl-dithranol, on HaCaT cells

A novel topical codrug, naproxyl–dithranol (Nap-DTH), in which dithranol and naproxen are linked via an ester in a 1:1 ratio to form a single chemical entity, was synthesized. The antiproliferative, anti-inflammatory and toxic effects of Nap-DTH were assessed, at the cellular level, using various in vitro methods. Cultured HaCaT keratinocytes were treated with Nap-DTH, and the cellular effects were compared with those of the parent compounds, individually and as a 1:1 mixture of naproxen:dithranol to mimic 1:1 in situ liberation from Nap-DTH. The results demonstrate that Nap-DTH did not modify proliferation and only exhibited slight toxic effects after 24 h at concentrations >21 μM. At a lower concentration (3.4 μM), Nap-DTH did not alter cell proliferation or inflammation, which suggests that the codrug is therapeutically inert. Relating to this, the 1:1 mixture of naproxen:dithranol exhibited the lowest toxic effect and the highest antiproliferative effect on HaCaT keratinocytes compared to dithranol at the same concentration. Moreover, the 1:1 mixture exhibited a reduced inflammatory effect compared to dithranol alone, as reflected by the upregulation of cyclooxygenase-2 by 45% and 136%, respectively. In spite of the 1:1 mixture showing a greater downregulation of Ki-67 and a 2-fold reduction of proliferating cell nuclear antigen (both cellular markers of proliferation) than dithranol, dithranol showed a much greater induction of cleaved caspase-3 protein expression (upregulated by 287%, compared to 85% for the 1:1 mixture). This suggests that when dithranol was administered with naproxen, inhibition of cell growth plays a more important role in the antiproliferation effects than the induction of apoptotic cell death. These results confirm that the codrug would lead to a better therapeutic profile and fewer adverse effects compared to its parent compounds.