Metal fluorides, metal chlorides and halogenated metal oxides as Lewis acidic heterogeneous catalysts. Providing some context for nanostructured metal fluorides

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials

Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

The interaction of CO with an attapulgite-supported Cu(II)Cl2 catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by a catalyst pre-treatment where the supported Cu(II)Cl2 sample is exposed to a diluted stream of chlorine. Subsequent CO exposure at ~ 370°C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of x-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu+ and a small amount of Cu2+. Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu+/Cu2+ catalyst is required to support CO chemisorption

Harvest-induced disruptive selection increases variance in fitness-related traits

The form of Darwinian selection has important ecological and management implications. Negative effects of harvesting are often ascribed to size truncation (i.e. strictly directional selection against large individuals) and resultant decrease in trait variability, which depresses capacity to buffer environmental change, hinders evolutionary rebound and ultimately impairs population recovery. However, the exact form of harvest-induced selection is generally unknown and the effects of harvest on trait variability remain unexplored. Here we use unique data from the Windermere (UK) long-term ecological experiment to show in a top predator (pike, Esox lucius) that the fishery does not induce size truncation but disruptive (diversifying) selection, and does not decrease but rather increases variability in pike somatic growth rate and size at age. This result is supported by complementary modelling approaches removing the effects of catch selectivity, selection prior to the catch and environmental variation. Therefore, fishing most likely increased genetic variability for somatic growth in pike and presumably favoured an observed rapid evolutionary rebound after fishery relaxation. Inference about the mechanisms through which harvesting negatively affects population numbers and recovery should systematically be based on a measure of the exact form of selection. From a management perspective, disruptive harvesting necessitates combining a preservation of large individuals with moderate exploitation rates, and thus provides a comprehensive tool for sustainable exploitation of natural resources

Soft-decision minimum-distance sequential decoding algorithm for convolutional codes

The maximum-likelihood decoding of convolutional codes has generally been considered impractical for other than relatively short constraint length codes, because of the exponential growth in complexity with increasing constraint length. The soft-decision minimum-distance decoding algorithm proposed in the paper approaches the performance of a maximum-likelihood decoder, and uses a sequential decoding approach to avoid an exponential growth in complexity. The algorithm also utilises the distance and structural properties of convolutional codes to considerably reduce the amount of searching needed to find the minimum soft-decision distance paths when a back-up search is required. This is done in two main ways. First, a small set of paths called permissible paths are utilised to search the whole of the subtree for the better path, instead of using all the paths within a given subtree. Secondly, the decoder identifies which subset of permissible paths should be utilised in a given search and which may be ignored. In this way many unnecessary path searches are completely eliminated. Because the decoding effort required by the algorithm is low, and the decoding processes are simple, the algorithm opens the possibility of building high-speed long constraint length convolutional decoders whose performance approaches that of the optimum maximum-likelihood decoder. The paper describes the algorithm and its theoretical basis, and gives examples of its operation. Also, results obtained from practical implementations of the algorithm using a high-speed microcomputer are presented

Long-term changes in the diet of pike (Esox lucius), the top aquatic predator in a changing Windermere

1. Pike (Esox lucius) is a key and flexible piscivore in many fresh waters of the northern temperate zone, but no previous studies have provided a continuous long-term perspective on its diet in response to changing environmental conditions. Here, we describe its winter diet from 1976 to 2009 in the North and South Basins of the lake of Windermere, U.K., where climate change, eutrophication and species introductions have combined to induce fundamental changes in the fish community. 2. A total of 6637 adult pike (fork length 390 to 1090 mm) was examined and found to have consumed a total of 4436 fish prey of which 98% of individuals identifiable to species comprised native Arctic charr (Salvelinus alpinus), brown trout (Salmo trutta), perch (Perca fluviatilis) and pike and non-native roach (Rutilus rutilus). Over the 34-year study period, the dietary importance of the salmonids Arctic charr and brown trout decreased, while that of the percid perch, the esocid pike and particularly the cyprinid roach increased. These changes were particularly marked in the more eutrophicated South Basin of the lake. 3. The above chronological trends in species-specific contributions to the diet composition of pike had considerable overall impacts. In the 1970s, pike diet composition was dominated by Arctic charr and brown trout which together comprised 94% of the diet. In contrast, in the 2000s, these two species accounted for just 55% of the diet, with perch and roach now comprising 41%. 4. Recent changes observed in the Windermere fish community of a decrease in native salmonids and an increase in cyprinids are consistent with the generally expected effects of climate change in the northern temperature zone. Here, we have shown that they have led to corresponding changes in the diet composition of pike. In turn, this may have implications for lake’s food web structure through shortening food chain length from the primary producers to the top aquatic predator

Neutrality of narrative discussion in annual reports of UK listed companies

This paper reports the results of an investigation into the neutrality of the narrative discussion of financial performance and position, as evidenced in 179 annual reports of UK listed companies. Neutrality of narrative discussion was determined by comparing the average proportions of good and bad news contained in the narrative and statutory accounts sections of the annual reports. The results of a comparison of the proportion of good news in the two sections of the annual reports suggest that the narrative sections contained a significantly higher proportion of good news than the statutory accounts sections. Comparison of proportions of bad news, however, indicates that the narrative sections contained a significantly lower proportion of bad news compared to the statutory accounts sections. Finally, the results also suggest that the proportion of good news as compared to bad news in the narrative sections is significantly higher than the proportion of good news compared to bad news in the statutory accounts section. The results are consistent with the suggestion that company management highlights good news in narrative discussions. The implications of the findings for company management, users, auditors and regulators are discussed