Gas-phase Fragmentation of Deprotonated p-Hydroxyphenacyl Derivatives

Electrospray ionization of methanolic solutions of p-hydroxyphenacyl derivatives HO-C6H4-C(O)-CH2-X (X = leaving group) provides abundant signals for the deprotonated species which are assigned to the corresponding phenolate anions −O-C6H4-C(O)-CH2-X. Upon collisional activation in the gas phase, these anions inter alia undergo loss of a neutral “C8H6O2” species concomitant with formation of the corresponding anions X−. The energies required for the loss of neutral roughly correlate with the gas phase acidities of the conjugate acids (HX). Extensive theoretical studies performed for X = CF3COO in order to reveal the energetically most favorable pathway for the formation of neutral “C8H6O2” suggest three different routes of similar energy demands, involving a spirocyclopropanone, epoxide formation, and a diradical, respectively

The roles of temperature, nest predators and information parasites for geographical variation in egg covering behaviour of tits (Paridae)

This is the final version. Available from Wiley via the DOI in this record. Abstract Aim Nest building is widespread among animals. Nests may provide receptacles for eggs, developing offspring and the parents, and protect them from adverse environmental conditions. Nests may also indicate the quality of the territory and its owner and can be considered as an extended phenotype of its builder(s). Nests may, thus, function as a sexual and social signal. Here, we examined ecological and abiotic factors—temperature, nest predation and interspecific information utilization—shaping geographical variation in a specific nest structure—hair and feather cover of eggs—and its function as an extended phenotype before incubation in great (Parus major) and blue tits (Cyanistes caeruleus) across Europe. We also tested whether egg covering is associated with reproductive success of great tits. Location Fourteen different study sites and 28 populations across Europe. Taxon Parus major, Cyanistes caeruleus. Methods We recorded clutch coverage estimates and collected egg covering nest material from the tit nests. We also measured nest specific breeding parameters and phenotypic measurements on adults. We tested whether mean spring temperatures, nest predation rates and flycatcher (Ficedula spp) densities in the study areas explain the large‐scale geographical variation of clutch coverage and reproductive success of tits. Results The degree of egg coverage of great tits increased with lower mean spring temperature, higher nest predation rate and higher flycatcher density. We did not find egg covering of blue tits to be associated with any of the ecological or abiotic factors. Moreover, egg covering of great tits was not associated with reproductive success in our cross‐sectional data, yet a rigorous assessment of fitness effects would require long‐term data. Main conclusions Our findings suggest that, in great tits, egg covering may simultaneously provide thermal insulation against cold temperatures during egg‐laying in spring and also represent a counter‐adaptation to reduce information parasitism by flycatchers and nest predation. Hence, geographical variation in interspecific interactions, and consequently in co‐evolutionary processes, may affect the evolution of nest characteristics besides environmental conditions.Biotieteiden ja Ympäristön Tutkimuksen ToimikuntaAgencia Estatal de Investigación, Ministry of Economy, Industry and Competitiveness, Spanish Research Council

Use of anthropogenic material affects bird nest arthropod community structure: influence of urbanisation, and consequences for ectoparasites and fledging success

Nests are a critically important factor in determining the breeding success of many species of birds. Nevertheless, we have surprisingly little understanding of how local environment helps shape materials used in construction, how this differs among related species using similar nest sites, or if materials used directly or indirectly influence the numbers of offspring successfully reared. We also have little understanding of any potential links between nest construction and the assemblage of invertebrates which inhabit the nest and in particular, with ectoparasites. We addressed these questions by monitoring the success rates of nest-box using Blue Tits Cyanistes caeruleus and Great Tits Parus major, from rural, urban greenspace and urban garden settings. We collected used nests, identified arthropods present, and measured the proportions of highly processed anthropogenic materials used in their construction. Some 25% of Great Tit nest materials were of an anthropogenic source and this was consistent across habitats, while Blue Tits used little (1-2%) except in gardens (~16%), suggesting that Great Tits preferentially sought out these materials. In fledged nests, increasing use of anthropogenic material was associated with lower general arthropod diversity and ectoparasite predator abundance (Blue Tits only) but higher levels of Siphonapterans (fleas). Higher arthropod diversity was associated with lower flea numbers, suggesting that increased diversity played a role in limiting flea numbers. No direct link was found between breeding success and either anthropogenic material usage, or arthropod diversity and abundance. However, breeding success declined with increasing urbanisation in both species and increased with nest weight in Blue Tits. The interplay between urbanisation and bird ecology is complex; our work shows that subtle anthropogenic influences may have indirect and unexpected consequences for urban birds

Synthesis, structure, and opto-electronic properties of organic-based nanoscale heterojunctions

Enormous research effort has been put into optimizing organic-based opto-electronic systems for efficient generation of free charge carriers. This optimization is mainly due to typically high dissociation energy (0.1-1 eV) and short diffusion length (10 nm) of excitons in organic materials. Inherently, interplay of microscopic structural, chemical, and opto-electronic properties plays crucial role. We show that employing and combining advanced scanning probe techniques can provide us significant insight into the correlation of these properties. By adjusting parameters of contact- and tapping-mode atomic force microscopy (AFM), we perform morphologic and mechanical characterizations (nanoshaving) of organic layers, measure their electrical conductivity by current-sensing AFM, and deduce work functions and surface photovoltage (SPV) effects by Kelvin force microscopy using high spatial resolution. These data are further correlated with local material composition detected using micro-Raman spectroscopy and with other electronic transport data. We demonstrate benefits of this multi-dimensional characterizations on (i) bulk heterojunction of fully organic composite films, indicating differences in blend quality and component segregation leading to local shunts of photovoltaic cell, and (ii) thin-film heterojunction of polypyrrole (PPy) electropolymerized on hydrogen-terminated diamond, indicating covalent bonding and transfer of charge carriers from PPy to diamond

AVONET: morphological, ecological and geographical data for all birds

Functional traits offer a rich quantitative framework for developing and testing theories in evolutionary biology, ecology and ecosystem science. However, the potential of functional traits to drive theoretical advances and refine models of global change can only be fully realised when species‐level information is complete. Here we present the AVONET dataset containing comprehensive functional trait data for all birds, including six ecological variables, 11 continuous morphological traits, and information on range size and location. Raw morphological measurements are presented from 90,020 individuals of 11,009 extant bird species sampled from 181 countries. These data are also summarised as species averages in three taxonomic formats, allowing integration with a global phylogeny, geographical range maps, IUCN Red List data and the eBird citizen science database. The AVONET dataset provides the most detailed picture of continuous trait variation for any major radiation of organisms, offering a global template for testing hypotheses and exploring the evolutionary origins, structure and functioning of biodiversity