Bis[1,1 '-N,N '-(2-picolyl)aminomethyl]ferrocene as a redox sensor for transition metal ions

The compound bis[1,1'-N,N'-(2-picolyl) aminomethyl] ferrocene, L-1, was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ were determined in aqueous solution by potentiometric methods at 25degreesC and at ionic strength 0.10 mol dm(-3) in KNO3. The compound L-1 forms only 1:1 (M:L) complexes with Pb2+ and Cd2+ while with Ni2+ and Cu2+ species of 2:1 ratio were also found. The complexing behaviour of L-1 is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L-1 was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L1 bridges at a long distance of 8.781(10) Angstrom. The electrochemical behaviour of L-1 was studied in the presence of Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+, showing that upon complexation the ferrocene-ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift (DeltaE(1/2)) of 268 mV was found in the presence of Pb2+, followed by Cu2+ (218 mV), Ni2+ (152 mV), Zn2+ (111 mV) and Cd2+ (110 mV). Moreover, L-1 is able to electrochemically and selectively sense Cu2+ in the presence of a large excess of the other transition metal cations studied.

Gaps in second language sentence processing

Four groups of second language (L2) learners of English from different language backgrounds (Chinese, Japanese, German, and Greek) and a group of native speaker controls participated in an online reading time experiment with sentences involving long-distance whdependencies. Although the native speakers showed evidence of making use of intermediate syntactic gaps during processing, the L2 learners appeared to associate the fronted wh-phrase directly with its lexical subcategorizer, regardless of whether the subjacency constraint was operative in their native language. This finding is argued to support the hypothesis that nonnative comprehenders underuse syntactic information in L2 processing.

Collaborative tele-rehabilitation: A strategy for increasing engagement

This paper examines the influence of a collaborative rehabilitation environment that encourages a long-distance collaborative "play" using two robot-mediated environments. This study presents a strategy for increasing motivation on able-bodied persons, applicable to impaired persons, to engage, sustain play and relate during a shared task. The study consisted of a series of eighteen single case studies, each involved in two distinct phases and assessed using a multidimensional measurement intended to assess participant' subjective experience. The results showed a clear positive trend in favour of the robot-mediated game environment. Subjects found the collaborative environment more valuable and more interesting and enjoyable. As a consequence, it appears subjects were willing to spend more time at a task.

Sentence repetition in adolescents with specific language impairments and autism: an investigation of complex syntax

Background: Recent studies have indicated that many children with autism spectrum disorders present with language difficulties that are similar to those of children with specific language impairments, leading some to argue for similar structural deficits in these two disorders. Aims: Repetition of sentences involving long-distance dependencies was used to investigate complex syntax in these groups. Methods & Procedures: Adolescents with specific language impairments (mean age = 15;3, n = 14) and autism spectrum disorders plus language impairment (autism plus language impairment; mean age = 14;8, n = 16) were recruited alongside typically developing adolescents (mean age = 14;4, n = 17). They were required to repeat sentences containing relative clauses that varied in syntactic complexity. Outcomes & Results: The adolescents with specific language impairments presented with greater syntactic difficulties than the adolescents with autism plus language impairment, as manifested by higher error rates on the more complex object relative clauses, and a greater tendency to make syntactic changes during repetition. Conclusions & Implications: Adolescents with specific language impairments may have more severe syntactic difficulties than adolescents with autism plus language impairment, possibly due to their short-term memory limitations.

Provenance of chalk tesserae from Brading Roman Villa, Isle of Wight, UK

Thin section petrographical analysis of chalk tesserae at Brading Roman Villa, Isle of Wight, England, identifies a range of planktonic foraminifera and the calcareous algal cyst Pithonella that identify the Late Cenomanian Rotalipora cushmani Biozone (BGS Foraminiferal Biozones 4iii to 7). The local chalk crop to the north of the villa includes rocks of R. cushmani Biozone age, and indicates a likely local, rather than long distance, source for the tesserae. Microfossils provide a powerful tool for identifying the provenance of artefacts in Roman Britain.

Women, other "fresh” workers, and the new manufacturing workforce of interwar Britain

Structural, organizational, and technological changes in British industry during the interwar years led to a decline in skilled and physically demanding work, while there was a dramatic expansion in unskilled and semiskilled employment. Previous authors have noted that the new un/semiskilled jobs were generally filled by “fresh” workers recruited from outside the core manufacturing workforce, though there is considerable disagreement regarding the composition of this new workforce. This paper examines labour recruitment patterns and strategies using national data and case studies of eight rapidly expanding industrial centres. The new industrial workforce is shown to have been recruited from a “reserve army” of workers with the common features of relative cheapness, flexibility, and weak unionization. These included women, juveniles, local workers in poorly paid nonindustrial sectors, such as agriculture, and (where these other categories were in short supply) relatively young long-distance internal migrants from declining industrial areas.

Modern pollen samples from alpine vegetation on the Tibetan Plateau.

1  A set of 316 modern surface pollen samples, sampling all the alpine vegetation types that occur on the Tibetan Plateau, has been compiled and analysed. Between 82 and 92% of the pollen present in these samples is derived from only 28 major taxa. These 28 taxa include examples of both tree (AP) and herb (NAP) pollen types. 2  Most of the modern surface pollen samples accurately reflect the composition of the modern vegetation in the sampling region. However, airborne dust-trap pollen samples do not provide a reliable assessment of the modern vegetation. Dust-trap samples contain much higher percentages of tree pollen than non-dust-trap samples, and many of the taxa present are exotic. In the extremely windy environments of the Tibetan Plateau, contamination of dust-trap samples by long-distance transport of exotic pollen is a serious problem. 3  The most characteristic vegetation types present on the Tibetan Plateau are alpine meadows, steppe and desert. Non-arboreal pollen (NAP) therefore dominates the pollen samples in most regions. Percentages of arboreal pollen (AP) are high in samples from the southern and eastern Tibetan Plateau, where alpine forests are an important component of the vegetation. The relative importance of forest and non-forest vegetation across the Plateau clearly follows climatic gradients: forests occur on the southern and eastern margins of the Plateau, supported by the penetration of moisture-bearing airmasses associated with the Indian and Pacific summer monsoons; open, treeless vegetation is dominant in the interior and northern margins of the Plateau, far from these moisture sources. 4  The different types of non-forest vegetation are characterized by different modern pollen assemblages. Thus, alpine deserts are characterized by high percentages of Chenopodiaceae and Artemisia, with Ephedra and Nitraria. Alpine meadows are characterized by high percentages of Cyperaceae and Artemisia, with Ranunculaceae and Polygonaceae. Alpine steppe is characterized by high abundances of Artemisia, with Compositae, Cruciferae and Chenopodiaceae. Although Artemisia is a common component of all non-forest vegetation types on the Tibetan Plateau, the presence of other taxa makes it possible to discriminate between the different vegetation types. 5  The good agreement between modern vegetation and modern surface pollen samples across the Tibetan Plateau provides a measure of the reliability of using pollen data to reconstruct past vegetation patterns in non-forested areas.

How do atmospheric rivers form?

Identifying the source of atmospheric rivers: Are they rivers of moisture exported from the subtropics or footprints left behind by poleward travelling storms? The term atmospheric river is used to describe corridors of strong water vapor transport in the troposphere. Filaments of enhanced water vapor, commonly observed in satellite imagery extending from the subtropics to the extratropics, are routinely used as a proxy for identifying these regions of strong water vapor transport. The precipitation associated with these filaments of enhanced water vapor can lead to high impact flooding events. However, there remains some debate as to how these filaments form. In this paper we analyse the transport of water vapor within a climatology of wintertime North Atlantic extratropical cyclones. Results show that atmospheric rivers are formed by the cold front which sweeps up water vapor in the warm sector as it catches up with the warm front. This causes a narrow band of high water vapor content to form ahead of the cold front at the base of the warm conveyor belt airflow. Thus, water vapor in the cyclone's warm sector, and not long-distance transport of water vapor from the subtropics, is responsible for the generation of filaments of high water vapor content. A continuous cycle of evaporation and moisture convergence within the cyclone replenishes water vapor lost via precipitation. Thus, rather than representing a direct and continuous feed of moist air from the subtropics into the centre of a cyclone (as suggested by the term atmospheric river), these filaments are, in-fact, the result of water vapor exported from the cyclone and thus they represent the footprints left behind as cyclones travel polewards from subtropics.

Agricultural innovations at a Late Iron Age oppidum: archaeobotanical evidence for flax, food and fodder from Calleva Atrebatum, UK

The development of oppida in the late first millennium BC across north-western Europe represents a major change in settlement form and social organisation. The construction of extensive earthwork systems, the presence of nucleated settlement areas, long-distance trade links and the development of hierarchical societies have been evidenced. These imply that changes in the style and organisation of agriculture would have been required to support these proto-urban population centres. Hypotheses of the subsistence bases of these settlements, ranging from a reliance on surplus arable production from local rural settlements, to an emphasis on pastoral activities, are here reviewed and grounded against a wider understanding of the expansion of agriculture in the Late Iron Age. These agricultural models have not been previously evaluated. This paper presents archaeobotanical data from six well fills from large-scale excavations at Late Iron Age and Early Roman Silchester, a Late Iron Age territorial oppidum and subsequent Roman civitas capital located in central-southern Britain. This is the first large-scale study of waterlogged plant macrofossils from within a settlement area of an oppidum. Waterlogged plant macrofossils were studied from a series of wells within the settlement. An assessment of taphonomy, considering stratigraphic and contextual information, is reported, followed by an analysis of the diverse assemblages of the plant remains through univariate analysis. Key results evidence animal stabling, flax cultivation, hay meadow management and the use of heathland resources. The staple crops cultivated and consumed at Late Iron Age and Early Roman Silchester are consistent with those cultivated in the wider region, whilst a range of imported fruits and flavourings were also present. The adoption of new oil crops and new grassland management shows that agricultural innovations were associated with foddering for animals rather than providing food for the proto-urban population. The evidence from Silchester is compared with other archaeobotanical datasets from oppida in Europe in order to identify key trends in agricultural change.