The crucial importance of agostic interactions in intermediates formed in propylene polymerization using neutral salicyladiminato palladium(II) and nickel complexes as catalysts

The structures of intermediates formed in propylene polymerisation using neutral salicyladiminato palladium(II) and nickel(II) complexes as catalysts have been investigated using density functional theory. Calculations show that all low energy intermediates contain agostic interactions either between the metal and a hydrogen from the added propylene forming four- or five-membered chelate rings, or, when a phenyl ring is present, between the metal and an aromatic C-C bond. The agostic interactions with the metal are concomitant with changes in ligand dimensions and electronic properties. In particular when a metal to hydrogen bond is formed, there is a lengthening of the C-H bond. Significant differences are found for the agostic interactions with palladium and nickel in that for Pd there is a clear preference for specific intermediates but for Ni there are several different structures with similar energies which are likely to lead to a greater variety of products on further polymerisation. (c) 2007 Elsevier B.V. All rights reserved.

Variability of the accommodation response in early onset myopia

Purpose. Hyperopic retinal defocus (blur) is thought to be a cause of myopia. If the retinal image of an object is not clearly focused, the resulting blur is thought to cause the continuing lengthening of the eyeball during development causing a permanent refractive error. Both lag of accommodation, especially for near targets, and greater variability in the accommodative response, have been suggested as causes of increased hyperopic retinal blur. Previous studies of lag of accommodation show variable findings. In comparison, greater variability in the accommodative response has been demonstrated in adults with late onset myopia but has not been tested in children. This study looked at the lag and variability of accommodation in children with early onset myopia. Methods. Twenty-one myopic and 18 emmetropic children were tested. Dynamic measures of accommodation and pupil size were made using eccentric photorefraction (Power Refractor) while children viewed targets set at three different accommodative demands (0.25, 2, and 4 D). Results. We found no difference in accommodative lag between groups. However, the accommodative response was more variable in the myopes than emmetropes when viewing both the near (4 D) and far (0.25 D) targets. Since pupil size and variability also varied, we analyzed the data to determine whether this could account for the inter-group differences in accommodation variability. Variation in these factors was not found to be sufficient to explain these differences. Changes in the accommodative response variability with target distance were similar to patterns reported previously in adult emmetropes and late onset myopes. Conclusions. Children with early onset myopia demonstrate greater accommodative variability than emmetropic children, and have similar patterns of response to adult late onset myopes. This increased variability could result in an increase in retinal blur for both near and far targets. The role of accommodative variability in the etiology of myopia is discussed.

The Structure of the chiral Pt{531} surface: a combined LEED and DFT study

The structure of the chiral kinked Pt{531} surface has been determined by low-energy electron diffraction intensity-versus-energy (LEED-IV) analysis and density functional theory (DFT). Large contractions and expansions of the vertical interlayer distances with respect to the bulk-terminated surface geometry were found for the first six layers (LEED: d(12) = 0.44 angstrom, d(23) = 0.69 angstrom, d(34) = 0.49 angstrom, d(45) = 0.95 angstrom, d(56) = 0.56 angstrom; DFT: d(12) = 0.51 angstrom, d(23) = 0.55 angstrom, d(34) = 0.74 angstrom, d(45) = 0.78 angstrom, d(56) = 0.63 angstrom; d(bulk) = 0.66 angstrom). Energy-dependent cancellations of LEED spots over unusually large energy ranges, up to 100 eV, can be explained by surface roughness and reproduced by applying a model involving 0.25 ML of vacancies and adatoms in the scattering calculations. The agreement between the results from LEED and DFT is not as good as in other cases, which could be due to this roughness of the real surface.

The surface geometries of the medium and high coverage carbon monoxide structures c(2 × 4)–(2CO) and p(root7- x root7)R19°–(4CO) structure

The surface geometries of the p (root7- x root7)R19degrees-(4CO) and c(2 x 4)-(2CO) layers on Ni {111} and the clean Ni {111} surface were determined by low energy electron diffraction structure analysis. For the clean surface small but significant contractions of d(12) and d(23) (both 2.02 Angstrom) were found with respect to the bulk interlayer distance (2.03 Angstrom). In the c(2 x 4)-(2CO) structure these distances are expanded, with values of d(12) = 2.08 Angstrom and d(23) = 2.06 Angstrom and buckling of 0.08 and 0.02 Angstrom, respectively, in the first and second layer. CO resides near hcp and fcc hollow sites with relatively large lateral shifts away from the ideal positions leading to unequal C-Ni bond lengths between 1.76 and 1.99 Angstrom. For the p(root7- x root7-)R19'-(4CO) layer two best fit geometries were found, which agree in most of their atomic positions, except for one out of four CO molecules, which is either near atop or between bridge and atop. The remaining three molecules reside near hcp and fcc sites, again with large lateral deviations from their ideal positions. The average C Ni bond length for these molecules is, however, the same as for CO on hollow sites at low coverage. The average CNi bond length at hollow sites, the interlayer distances, and buckling in the first Ni layer are similar to the c(2 x 4)(2CO) geometry, only the buckling in the second layer (0.08 Angstrom) is significantly larger. Lateral and vertical shifts of the Ni atoms in the first layer lead to unsymmetric environments for the CO molecules, which can be regarded as an imprint of the chiral p(root7- x root7-)R19degrees lattice geometry onto the substrate.

The effect of the spacer length on the nature of coupling in side chain liquid crystals polymers and elastomers

Side chain liquid crystal polymers and elastomers exhibit a rich phase behaviour which arises from the antagonistic influences of the entropically disordered polymer chain configuration and the long range orientational ordering of the mesogenic units. This competition arises since the natural macroscopic phase separation is inhibited by the inherent chemical connectivity of the system. At the heart of this connectivity is the spacer link and we consider here its influence on the phase behaviour. In particular we consider a series of elastomers in which the number of alkyl units in the spacer is systematically varied from 2 to 6. The lengthening of the coupling spacer is accompanied by an alternation of the sign of coupling between the polymer chain and the mesogenic unit. These results demonstrate the dominating influence of the so-called hinge effect in determining the phase behaviour. In addition to the alternation of the sign there is some decrease in the magnitude of the coupling with increasing spacer length.

Stratospheric variability and tropospheric annular‐mode timescales

Climate models tend to exhibit much too persistent Southern Annular Mode (SAM) circulation anomalies in summer, compared to observations. Theoretical arguments suggest this bias may lead to an overly strong model response to anthropogenic forcing during this season, which is of interest since the largest observed changes in Southern Hemisphere high‐latitude climate over the last few decades have occurred in summer, and are congruent with the SAM. The origin of this model bias is examined here in the case of the Canadian Middle Atmosphere Model, using a novel technique to quantify the influence of stratospheric variability on tropospheric annular‐mode timescales. Part of the model bias is shown to be attributable to the too‐late breakdown of the stratospheric polar vortex, which allows the tropospheric influence of stratospheric variability to extend into early summer. However, the analysis also reveals an enhanced summertime persistence of the model’s SAM that is unrelated to either stratospheric variability or the bias in model stratospheric climatology, and is thus of tropospheric origin. No such feature is evident in the Northern Hemisphere. The effect of stratospheric variability in lengthening tropospheric annular‐mode timescales is evident in both hemispheres. While in the Southern Hemisphere the effect is restricted to late‐spring/early summer, in the Northern Hemisphere it can occur throughout the winter‐spring season, with the seasonality of peak timescales exhibiting considerable variability between different 50 year sections of the same simulation.

Codon and mRNA sequence optimization of microdystrophin transgenes improves expression and physiological outcome in dystrophic mdx mice following AAV2/8 gene transfer

Duchenne muscular dystrophy is a fatal muscle-wasting disorder. Lack of dystrophin compromises the integrity of the sarcolemma and results in myofibers that are highly prone to contraction-induced injury. Recombinant adenoassociated virus (rAAV)-mediated dystrophin gene transfer strategies to muscle for the treatment of Duchenne muscular dystrophy (DMD) have been limited by the small cloning capacity of rAAV vectors and high titers necessary to achieve efficient systemic gene transfer. In this study, we assess the impact of codon optimization on microdystrophin (ΔAB/R3-R18/ΔCT) expression and function in the mdx mouse and compare the function of two different configurations of codon-optimized microdystrophin genes (ΔAB/R3-R18/ΔCT and ΔR4-R23/ΔCT) under the control of a muscle-restrictive promoter (Spc5-12). Codon optimization of microdystrophin significantly increases levels of microdystrophin mRNA and protein after intramuscular and systemic administration of plasmid DNA or rAAV2/8. Physiological assessment demonstrates that codon optimization of ΔAB/R3-R18/ΔCT results in significant improvement in specific force, but does not improve resistance to eccentric contractions compared with noncodon-optimized ΔAB/ R3-R18/ΔCT. However, codon-optimized microdystrophin ΔR4-R23/ΔCT completely restored specific force generation and provided substantial protection from contraction-induced injury. These results demonstrate that codon optimization of microdystrophin under the control of a muscle-specific promoter can significantly improve expression levels such that reduced titers of rAAV vectors will be required for efficient systemic administration.

Delivery of AAV2/9-microdystrophin genes incorporating helix 1 of the coiled-coil motif in the C-terminal domain of dystrophin improves muscle pathology and restores the level of α1-syntrophin and α-dystrobrevin in skeletal muscles of mdx mice. Level of α1-Syntrophin and α-Dystrobrevin in Skeletal Muscles of mdx Mice

Duchenne muscular dystrophy is a severe X-linked inherited muscle wasting disorder caused by mutations in the dystrophin gene. Adeno-associated virus (AAV) vectors have been extensively used to deliver genes efficiently for dystrophin expression in skeletal muscles. To overcome limited packaging capacity of AAV vectors (<5 kb), truncated recombinant microdystrophin genes with deletions of most of rod and carboxyl-terminal (CT) domains of dystrophin have been developed. We have previously shown the efficiency of mRNA sequence–optimized microdystrophin (ΔR4-23/ΔCT, called MD1) with deletion of spectrin-like repeat domain 4 to 23 and CT domain in ameliorating the pathology of dystrophic mdx mice. However, the CT domain of dystrophin is thought to recruit part of the dystrophin-associated protein complex, which acts as a mediator of signalling between extracellular matrix and cytoskeleton in muscle fibers. In this study, we extended the ΔR4-23/ΔCT microdystrophin by incorporating helix 1 of the coiled-coil motif in the CT domain of dystrophin (MD2), which contains the α1-syntrophin and α-dystrobrevin binding sites. Intramuscular injection of AAV2/9 expressing CT domain–extended microdystrophin showed efficient dystrophin expression in tibialis anterior muscles of mdx mice. The presence of the CT domain of dystrophin in MD2 increased the recruitment of α1-syntrophin and α-dystrobrevin at the sarcolemma and significantly improved the muscle resistance to lengthening contraction–induced muscle damage in the mdx mice compared with MD1. These results suggest that the incorporation of helix 1 of the coiled-coil motif in the CT domain of dystrophin to the microdystrophins will substantially improve their efficiency in restoring muscle function in patients with Duchenne muscular dystrophy.

Recent climatic trends and linkages to river discharge in Central Vietnam

In this study, change in rainfall, temperature and river discharge are analysed over the last three decades in Central Vietnam. Trends and rainfall indices are evaluated using non-parametric tests at different temporal levels. To overcome the sparse locally available network, the high resolution APHRODITE gridded dataset is used in addition to the existing rain gauges. Finally, existing linkages between discharge changes and trends in rainfall and temperature are explored. Results are indicative of an intensification of rainfall (+15%/decade), with more extreme and longer events. A significant increase in winter rainfall and a decrease in consecutive dry days provides strong evidence for a lengthening wet season in Central Vietnam. In addition, trends based on APHRODITE suggest a strong orographic signal in winter and annual trends. These results underline the local variability in the impacts of climatic change at the global scale. Consequently, it is important that change detection investigations are conducted at the local scale. A very weak signal is detected in the trend of minimum temperature (+0.2°C/decade). River discharge trends show an increase in mean discharge (31 to 35%/decade) over the last decades. Between 54 and 74% of this increase is explained by the increase in precipitation. The maximum discharge also responds significantly to precipitation changes leading to a lengthened wet season and an increase in extreme rainfall events. Such trends can be linked with a likely increase in floods in Central Vietnam, which is important for future adaptation planning and management and flood preparedness in the region. Copyright © 2012 John Wiley & Sons, Ltd.

Business cycle asymmetries: characterisation and testing based on Markov-switching autoregressions

Tests for business cycle asymmetries are developed for Markov-switching autoregressive models. The tests of deepness, steepness, and sharpness are Wald statistics, which have standard asymptotics. For the standard two-regime model of expansions and contractions, deepness is shown to imply sharpness (and vice versa), whereas the process is always nonsteep. Two and three-state models of U.S. GNP growth are used to illustrate the approach, along with models of U.S. investment and consumption growth. The robustness of the tests to model misspecification, and the effects of regime-dependent heteroscedasticity, are investigated.

A continuum anisotropic model of sea-ice dynamics

We develop the essential ingredients of a new, continuum and anisotropic model of sea-ice dynamics designed for eventual use in climate simulation. These ingredients are a constitutive law for sea-ice stress, relating stress to the material properties of sea ice and to internal variables describing the sea-ice state, and equations describing the evolution of these variables. The sea-ice cover is treated as a densely flawed two-dimensional continuum consisting of a uniform field of thick ice that is uniformly permeated with narrow linear regions of thinner ice called leads. Lead orientation, thickness and width distributions are described by second-rank tensor internal variables: the structure, thickness and width tensors, whose dynamics are governed by corresponding evolution equations accounting for processes such as new lead generation and rotation as the ice cover deforms. These evolution equations contain contractions of higher-order tensor expressions that require closures. We develop a sea-ice stress constitutive law that relates sea-ice stress to the structure tensor, thickness tensor and strain rate. For the special case of empty leads (containing no ice), linear closures are adopted and we present calculations for simple shear, convergence and divergence.

Aircraft-based observations of air–sea turbulent fluxes around the British Isles

Observations of turbulent fluxes of momentum, heat and moisture from low-level aircraft data are presented. Fluxes are calculated using the eddy covariance technique from flight legs typically ∼40 m above the sea surface. Over 400 runs of 2 min (∼12 km) from 26 flights are evaluated. Flight legs are mainly from around the British Isles although a small number are from around Iceland and Norway. Sea-surface temperature (SST) observations from two on-board sensors (the ARIES interferometer and a Heimann radiometer) and a satellite-based analysis (OSTIA) are used to determine an improved SST estimate. Most of the observations are from moderate to strong wind speed conditions, the latter being a regime short of validation data for the bulk flux algorithms that are necessary for numerical weather prediction and climate models. Observations from both statically stable and unstable atmospheric boundary-layer conditions are presented. There is a particular focus on several flights made as part of the DIAMET (Diabatic influence on mesoscale structures in extratropical storms) project. Observed neutral exchange coefficients are in the same range as previous studies, although higher for the momentum coefficient, and are broadly consistent with the COARE 3.0 bulk flux algorithm, as well as the surface exchange schemes used in the ECMWF and Met Office models. Examining the results as a function of aircraft heading shows higher fluxes and exchange coefficients in the across-wind direction, compared to along-wind (although this comparison is limited by the relatively small number of along-wind legs). A multi-resolution spectral decomposition technique demonstrates a lengthening of spatial scales in along-wind variances in along-wind legs, implying the boundary-layer eddies are elongated in the along-wind direction. The along-wind runs may not be able to adequately capture the full range of turbulent exchange that is occurring because elongation places the largest eddies outside of the run length.

On flow reversal boundaries and transpolar voltage in average models of high-latitude convection

The implications of polar cap expansions, contractions and movements for empirical models of high-latitude plasma convection are examined. Some of these models have been generated by directly averaging flow measurements from large numbers of satellite passes or radar scans; others have employed more complex means to combine data taken at different times into large-scale patterns of flow. In all cases, the models have implicitly adopted the assumption that the polar cap is in steady state: they have all characterized the ionospheric flow in terms of the prevailing conditions (e.g. the interplanetary magnetic field and/or some index of terrestrial magnetic activity) without allowance for their history. On long enough time scales, the polar cap is indeed in steady state but on time scales shorter than a few hours it is not and can oscillate in size and position. As a result, the method used to combine the data can influence the nature of the convection reversal boundary and the transpolar voltage in the derived model. This paper discusses a variety of effects due to time-dependence in relation to some ionospheric convection models which are widely applied. The effects are shown to be varied and to depend upon the procedure adopted to compile the model.

Interhemispheric dynamics of the African rainbelt during the late Quaternary

The spatial pattern of precipitation variability in tropical and subtropical Africa over the late Quaternary has long been debated. Prevailing hypotheses variously infer (1) insolation-controlled asymmetry of wet phases between hemispheres, (2) symmetric contraction and expansion of the tropical rainbelt, and (3) independent control on moisture available in Southern Africa via sea surface temperatures in the Indian Ocean. In this study we use climate-model simulations covering the last glacial cycle (120 kyr) with HadCM3 and the multi-model ensembles from PMIP3 (the Palaeoclimate Model Intercomparison Project) to investigate the long-term behaviour of the African rainbelt, and test these simulations against existing empirical palaeohydrological records. Through regional model-data comparisons we find evidence for the validity of several hypotheses, with various proposed processes occurring concurrently but with different regional emphasis (e.g. asymmetric shifts at the seasonal extremes and symmetric expansions/ contractions towards West equatorial regions). Crucially, variations in rainfall are associated with multiple forcing mechanisms that vary in their dominance both spatially and temporally over the glacial cycle; an important consideration when interpreting and extrapolating from often relatively short palaeoenvironmental records.

Transatlantic flight times and climate change

Aircraft do not fly through a vacuum, but through an atmosphere whose meteorological characteristics are changing because of global warming. The impacts of aviation on climate change have long been recognised, but the impacts of climate change on aviation have only recently begun to emerge. These impacts include intensified turbulence and increased take-off weight restrictions. Here we investigate the influence of climate change on flight routes and journey times. We feed synthetic atmospheric wind fields generated from climate model simulations into a routing algorithm of the type used operationally by flight planners. We focus on transatlantic flights between London and New York, and how they change when the atmospheric concentration of carbon dioxide is doubled. We find that a strengthening of the prevailing jet-stream winds causes eastbound flights to significantly shorten and westbound flights to significantly lengthen in all seasons. Eastbound and westbound crossings in winter become approximately twice as likely to take under 5 h 20 min and over 7 h 00 min, respectively. For reasons that are explained using a conceptual model, the eastbound shortening and westbound lengthening do not cancel out, causing round-trip journey times to increase. Even assuming no future growth in aviation, the extrapolation of our results to all transatlantic traffic suggests that aircraft will collectively be airborne for an extra 2000 h each year, burning an extra 7.2 million gallons of jet fuel at a cost of US$ 22 million, and emitting an extra 70 million kg of carbon dioxide, which is equivalent to the annual emissions of 7100 average British homes. Our results provide further evidence of the two-way interaction between aviation and climate change.