Coverage-dependent structural evolution in the interaction of NO2 with Au{111}

We have used low-temperature STM, together with DFT calculations incorporating the effects of dispersion forces, to study from a structural point of view the interaction of NO2 with Au{111} surfaces. NO2 adsorbs molecularly on Au{111} at 80 K, initially as small, disordered clusters at the elbows of the type-x reconstruction lines of the clean-surface herringbone reconstruction, and then as larger, ordered islands on the fcc regions. Within the islands, the NO2 molecules define a (√3 × 2)rect. superlattice, for which we evaluate structural models. By around 0.25 ML coverage, the herringbone reconstruction has been lifted, accompanied by the formation of Au nanoclusters, and the islands have coalesced. At this stage, essentially the whole surface is covered with an overlayer consisting predominantly of domains of the (√3 × 2)rect. structure, but also containing less wellordered regions. With further exposure, the degree of disorder in the overlayer increases; saturation occurs close to 0.43 ML.

Sensitivity of terrestrial precipitation trends to the structural evolution of sea surface temperatures

Pronounced intermodel differences in the projected response of land surface precipitation (LSP) to future anthropogenic forcing remain in the Coupled Model Intercomparison Project Phase 5 model integrations. A large fraction of the intermodel spread in projected LSP trends is demonstrated here to be associated with systematic differences in simulated sea surface temperature (SST) trends, especially the representation of changes in (i) the interhemispheric SST gradient and (ii) the tropical Pacific SSTs. By contrast, intermodel differences in global mean SST, representative of differing global climate sensitivities, exert limited systematic influence on LSP patterns. These results highlight the importance to regional terrestrial precipitation changes of properly simulating the spatial distribution of large-scale, remote changes as reflected in the SST response to increasing greenhouse gases. Moreover, they provide guidance regarding which region-specific precipitation projections may be potentially better constrained for use in climate change impact assessments.

The dynamics of a polar low assessed using potential vorticity inversion

The dynamics of a polar low are examined using a piecewise potential vorticity (PV) inversion method. In previous studies of this and other polar lows, structural evolution has been described in terms of regions of anomalous PV. In this study the relative importance of different PV anomalies and the interactions between them have been quantified using PV diagnostics. The intensification of the polar low occurred in three stages (in contrast to previous studies of polar lows that have only identified two stages). The dynamical characteristics of stages one and two are consistent with the proposed type C cyclogenesis mechanism. A diabatically-generated lower-tropospheric PV anomaly dominated intensification after initial triggering by a positive upper-level PV anomaly. A phase tilt between the upper and lower levels was maintained through retardation of the positive upper-level anomaly by the effects of latent heat release. Stage three was a period of growth dominated by wind-induced surface heat exchange (WISHE), which contributed at least 18% to the amplitude of the mature surface polar low.

Fullerene-like models for microporous carbon: a review

Microporous carbons are important in a wide variety of applications, ranging from pollution control to supercapacitors, yet their structure at the molecular level is poorly understood. Over the years, many structural models have been put forward, but none have been entirely satisfactory in explaining the properties of the carbons. The discovery of fullerenes and fullerene-related structures such as carbon nanotubes gave us a new perspective on the structure of solid carbon, and in 1997 it was suggested that microporous carbon may have a structure related to that of the fullerenes. Recently, evidence in support of such a structure has been obtained using aberration-corrected transmission electron microscopy, electron energy loss spectroscopy and other techniques. This article describes the development of ideas about the structure of microporous carbon, and reviews the experimental evidence for a fullerene-related structure. Theoretical models of the structural evolution of microporous carbon are summarised, and the use of fullerene-like models to predict the adsorptive properties of microporous carbons are reviewed.

Influence of the size distribution of particles on the viscous property of an electrorheological fluid

The influence of the size distribution of particles on the viscous property of an electrorheological fluid has been investigated by the molecular dynamic simulation method. The shear stress of the fluid is found to decrease with the increase of the variance sigma(2) of the Gaussian distribution of the particle size, and then reach a steady value when sigma is larger than 0.5. This phenomenon is attributed to the influence of the particle size distribution on the dynamic structural evolution in the fluid as well as the strength of the different chain-like structures formed by the particles.

Rational conversion of substrate and product specificity in a Salvia monoterpene synthase: structural insights into the evolution of terpene synthase function

Terpene synthases are responsible for the biosynthesis of the complex chemical defense arsenal of plants and microorganisms. How do these enzymes, which all appear to share a common terpene synthase fold, specify the many different products made almost entirely from one of only three substrates? Elucidation of the structure of 1,8-cineole synthase from Salvia fruticosa (Sf-CinS1) combined with analysis of functional and phylogenetic relationships of enzymes within Salvia species identified active-site residues responsible for product specificity. Thus, Sf-CinS1 was successfully converted to a sabinene synthase with a minimum number of rationally predicted substitutions, while identification of the Asn side chain essential for water activation introduced 1,8-cineole and alpha-terpineol activity to Salvia pomifera sabinene synthase. A major contribution to product specificity in Sf-CinS1 appears to come from a local deformation within one of the helices forming the active site. This deformation is observed in all other mono- or sesquiterpene structures available, pointing to a conserved mechanism. Moreover, a single amino acid substitution enlarged the active-site cavity enough to accommodate the larger farnesyl pyrophosphate substrate and led to the efficient synthesis of sesquiterpenes, while alternate single substitutions of this critical amino acid yielded five additional terpene synthases.

Germin and germin-like proteins: evolution, structure, and function

Germin and germin-like proteins (GLPs) are encoded by a family of genes found in all plants. They are part of the cupin superfamily of biochemically diverse proteins, a superfamily that has a conserved tertiary structure, though with limited similarity in primary sequence. The subgroups of GLPs have different enzyme functions that include the two hydrogen peroxide-generating enzymes, oxalate oxidase (OxO) and superoxide dismutase. This review summarizes the sequence and structural details of GLPs and also discusses their evolutionary progression, particularly their amplification in gene number during the evolution of the land plants. In terms of function, the GLPs are known to be differentially expressed during specific periods of plant growth and development, a pattern of evolutionary subfunctionalization. They are also implicated in the response of plants to biotic (viruses, bacteria, mycorrhizae, fungi, insects, nematodes, and parasitic plants) and abiotic (salt, heat/cold, drought, nutrient, and metal) stress. Most detailed data come from studies of fungal pathogenesis in cereals. This involvement with the protection of plants from environmental stress of various types has led to numerous plant breeding studies that have found links between GLPs and QTLs for disease and stress resistance. In addition the OxO enzyme has considerable commercial significance, based principally on its use in the medical diagnosis of oxalate concentration in plasma and urine. Finally, this review provides information on the nutritional importance of these proteins in the human diet, as several members are known to be allergenic, a feature related to their thermal stability and evolutionary connection to the seed storage proteins, also members of the cupin superfamily.

On the structural differences between markers and genomic AC microsatellites

AC microsatellites have proved particularly useful as genetic markers. For some purposes, such as in population biology, the inferences drawn depend on the quantitative values of their mutation rates. This, together with intrinsic biological interest, has led to widespread study of microsatellite mutational mechanisms. Now, however, inconsistencies are appearing in the results of marker-based versus non-marker-based studies of mutational mechanisms. The reasons for this have not been investigated, but one possibility, pursued here, is that the differences result from structural differences between markers and genomic microsatellites. Here we report a comparison between the CEPH AC marker microsatellites and the global population of AC microsatellites in the human genome. AC marker microsatellites are longer than the global average. Controlling for length, marker microsatellites contain on average fewer interruptions, and have longer segments, than their genomic counterparts. Related to this, marker microsatellites show a greater tendency to concentrate the majority of their repeats into one segment. These differences plausibly result from scientists selecting markers for their high polymorphism. In addition to the structural differences, there are differences in the base composition of flanking sequences, marker flanking regions being richer in C and G and poorer in A and T. Our results indicate that there are profound differences between marker and genomic microsatellites that almost certainly affect their mutation rates. There is a need for a unified model of mutational mechanisms that accounts for both marker-derived and genomic observations. A suggestion is made as to how this might be done.

The Ferritin-like superfamily: evolution of the biological iron storeman from a rubrerythrin-like ancestor

Background: The Ferritins are part of the extensive ‘Ferritin-like superfamily’ which have diverse functions but are linked by the presence of a common four-helical bundle domain. The role performed by Ferritins as the cellular repository of excess iron is unique. In many ways Ferritins act as tiny organelles in their ability to secrete iron away from the delicate machinery of the cell, and then to release it again in a controlled fashion avoiding toxicity. The Ferritins are ancient proteins, being common in all three domains of life. This ubiquity reflects the key contribution that Ferritins provide in achieving iron homeostasis. Scope of the review: This review compares the features of the different Ferritins and considers how they, and other members of the Ferritin-like superfamily, have evolved. It also considers relevant features of the eleven other known families within the Ferritin-like superfamily, particularly the highly diverse rubrerythrins. Major conclusions: The Ferritins have travelled a considerable evolutionary journey, being derived from far more simplistic rubrerythrin-like molecules which play roles in defence against toxic oxygen species. The forces of evolution have moulded such molecules into three distinct types of iron storing (or detoxifying) protein: the classical and universal 24-meric ferritins; the haem-containing 24-meric bacterioferritins of prokaryotes; and the prokaryotic 12-meric Dps proteins. These three Ferritin types are similar, but also possess unique properties that distinguish them and enable then to achieve their specific physiological purposes. General significance: A wide range of biological functions have evolved from a relatively simple structural unit.

X-ray diffraction study of the influence of temperature on the structural correlations of poly(2-hydroxypropyl ether of bisphenol A)

The X-ray diffraction pattern of glassy poly(2-hydroxypropyl ether of bisphenol A) is studied at room temperature on oriented samples in order to associate its different peaks to different structural correlations. On the other hand, X-ray diffraction patterns have been obtained at different temperatures from Tg − 50 K up to Tg + 50 K for the above-mentioned polymer. Attention has been paid to the evolution with temperature of the position of the wide diffraction maximum corresponding to interchain correlations in the polymer. The temperature evolution of this parameter shows a marked discontinuity just at the glass transition temperature.

The shape and tempo of language evolution

There are approximately 7000 languages spoken in the world today. This diversity reflects the legacy of thousands of years of cultural evolution. How far back we can trace this history depends largely on the rate at which the different components of language evolve. Rates of lexical evolution are widely thought to impose an upper limit of 6000-10,000 years on reliably identifying language relationships. In contrast, it has been argued that certain structural elements of language are much more stable. Just as biologists use highly conserved genes to uncover the deepest branches in the tree of life, highly stable linguistic features hold the promise of identifying deep relationships between the world's languages. Here, we present the first global network of languages based on this typological information. We evaluate the relative evolutionary rates of both typological and lexical features in the Austronesian and Indo-European language families. The first indications are that typological features evolve at similar rates to basic vocabulary but their evolution is substantially less tree-like. Our results suggest that, while rates of vocabulary change are correlated between the two language families, the rates of evolution of typological features and structural subtypes show no consistent relationship across families.

Structural spoilers or structural supports? Unionism and the strategic integration of HR functions

The strategic integration of the human resource (HR) function is regarded as crucial in the literature on (strategic) human resource management ((S)HRM). Evidence on the contextual or structural influences on this integration is, however, limited. The structural implications of unionism are particularly intriguing given the evolution of study of the employment relationship. Pluralism is typically seen as antithetical to SHRM, and unions as an impediment to the strategic integration of HR functions, but there are also suggestions in the literature that unionism might facilitate the strategic integration of HR. This paper deploys large-scale international survey evidence to examine the organization-level influence of unionism on this strategic integration, allowing for other established and plausible influences. The analysis reveals that exceptionally, where the organization-level role of unions is particularly contested, unionism does impede the strategic integration of HR. However, it is the predominance of the facilitation of the strategic integration of HR by unionism which is most remarkable.

Structural spoilers or structural supports? Unions and the strategic integration of HR functions

The strategic integration of the human resource (HR) function is regarded as crucial in the literature on (strategic) human resource management ((S)HRM). Evidence on the contextual or structural influences on this integration is, however, limited. The structural implications of unionism are particularly intriguing given the evolution of study of the employment relationship. Pluralism is typically seen as antithetical to SHRM, and unions as an impediment to the strategic integration of HR functions, but there are also suggestions in the literature that unionism might facilitate the strategic integration of HR. This paper deploys large-scale international survey evidence to examine the organization-level influence of unionism on this strategic integration, allowing for other established and plausible influences. The analysis reveals that exceptionally, where the organization-level role of unions is particularly contested, unionism does impede the strategic integration of HR. However, it is the predominance of the facilitation of the strategic integration of HR by unionism which is most remarkable.

Molecular archaeology of Flaviviridae untranslated regions: duplicated RNA structures in the replication enhancer of flaviviruses and pestiviruses emerged via convergent evolution.

RNA secondary structures in the 3'untranslated regions (3'UTR) of the viruses of the family Flaviviridae, previously identified as essential (promoters) or beneficial (enhancers) for replication, have been analysed. Duplicated enhancer elements are revealed as a global feature in the evolution of the 3'UTR of distantly related viruses within the genera Flavivirus and Pestivirus. For the flaviviruses, duplicated structures occur in the 3'UTR of all four distantly related ecological virus subgroups (tick-borne, mosquito-borne, no known vector and insect-specific flaviviruses (ISFV). RNA structural differences distinguish tick-borne flaviviruses with discrete pathogenetic characteristics. For Aedes- and Culex-associated ISFV, secondary RNA structures with different conformations display numerous short ssRNA direct repeats, exposed as loops and bulges. Long quadruplicate regions comprise almost the entire 3'UTR of Culex-associated ISFV. Extended duplicated sequence and associated RNA structures were also discovered in the 3'UTR of pestiviruses. In both the Flavivirus and Pestivirus genera, duplicated RNA structures were localized to the enhancer regions of the 3'UTR suggesting an adaptive role predominantly in wild-type viruses. We propose sequence reiteration might act as a scaffold for dimerization of proteins involved in assembly of viral replicase complexes. Numerous nucleotide repeats exposed as loops/bulges might also interfere with host immune responses acting as a molecular sponge to sequester key host proteins or microRNAs.