Technical note: Organics-induced fluorescence in Raman studies of sulfuric acid aerosols

Fluorescence is a troublesome side effect in laboratory Raman studies on sulfuric acid solutions and aerosol particles. We performed experiments showing that organic matter induces fluorescence in H2SO4/H2O solutions. The intensity of the fluorescence signal appears to be almost independent of the concentration of the organic substances, but depends strongly on the sulfuric acid concentration. The ubiquity of organic substances in the atmosphere, their relatively high abundance, and the insensitivity of the fluorescence with respect to their concentrations will render most acidic natural aerosols subject to absorption and fluorescence, possibly influencing climate forcing. We show that, while fluorescence may in the future become a valuable tool of aerosol diagnostics, the concurrent absorption is too small to significantly affect the atmosphere's radiative balance.

The dependent variable problem in quantitative studies of Active Labour Market Programmes: uncovering hidden dynamics?

The question of what explains variation in expenditures on Active Labour Market Programs (ALMPs) has attracted significant scholarship in recent years. Significant insights have been gained with respect to the role of employers, unions and dual labour markets, openness, and partisanship. However, there remain significant disagreements with respects to key explanatory variables such the role of unions or the impact of partisanship. Qualitative studies have shown that there are both good conceptual reasons as well as historical evidence that different ALMPs are driven by different dynamics. There is little reason to believe that vastly different programs such as training and employment subsidies are driven by similar structural, interest group or indeed partisan dynamics. The question is therefore whether different ALMPs have the same correlation with different key explanatory variables identified in the literature? Using regression analysis, this paper shows that the explanatory variables identified by the literature have different relation to distinct ALMPs. This refinement adds significant analytical value and shows that disagreements are at least partly due to a dependent variable problem of ‘over-aggregation’.

Early modern Oxford bindings in twenty-first century markup

Purpose – The Bodleian Binders Book contains nearly 150 pages of seventeenth century library records, revealing information about the binders used by the library and the thousands of bindings they produced. The purpose of this paper is to explore a pilot project to survey and record bindings information contained in the Binders Book. Design/methodology/approach – A sample size of seven pages (91 works, 65 identifiable bindings) to develop a methodology for surveying and recording bindings listed in the manuscript. To create a successful product that would be useful to bindings researchers, it addressed questions of bindings terminology and the role of the library in the knowledge creation process within the context that text encoding is changing the landscape of library functions. Text encoding formats were examined, and a basic TEI (Text Encoding Initiative) transcription was produced. This facilitates tagging of names and titles and the display of transcriptions with text images. Findings – Encoding was found not only to make the manuscript content more accessible, but to allow for the construction of new knowledge: characteristic Oxford binding traits were revealed and bindings were matched to binders. Plans for added functionality were formed. Originality/value – This research presents a “big picture” analysis of Oxford bindings as a result of text encoding and the foundation for qualitative and statistical analysis. It exemplifies the benefits of interdisciplinary methods – in this case from Digital Humanities – to enhance access to and interpretation of specialist materials and the library's provenance record.

Creating and implementing a biodiversity recording app for teaching and research in environmental studies

This case study reports on the development of a bespoke mobile recording app for collating records of biodiversity sightings on a University campus. This innovative project was achieved through a multi-disciplinary partnership of staff and students. It is hoped that the app itself will benefit lecturers by streamlining data collection during teaching and learning activities, whilst engaging students and highlighting the wealth of diversity available on campus

A cautionary note on the use of Ornstein Uhlenbeck models in macroevolutionary studies

Phylogenetic comparative methods are increasingly used to give new insights into the dynamics of trait evolution in deep time. For continuous traits the core of these methods is a suite of models that attempt to capture evolutionary patterns by extending the Brownian constant variance model. However, the properties of these models are often poorly understood, which can lead to the misinterpretation of results. Here we focus on one of these models – the Ornstein Uhlenbeck (OU) model. We show that the OU model is frequently incorrectly favoured over simpler models when using Likelihood ratio tests, and that many studies fitting this model use datasets that are small and prone to this problem. We also show that very small amounts of error in datasets can have profound effects on the inferences derived from OU models. Our results suggest that simulating fitted models and comparing with empirical results is critical when fitting OU and other extensions of the Brownian model. We conclude by making recommendations for best practice in fitting OU models in phylogenetic comparative analyses, and for interpreting the parameters of the OU model.

13C-2H correlation NMR spectroscopy studies of the in vivo transformations of natural products from Artemisia annua

13C-2H correlation NMR spectroscopy (13C-2H COSY) permits the identification of 13C and 2H nuclei which are connected to one another by a single chemical bond via the sizeable 1JCD coupling constant. The practical development of this technique is described using a 13C-2H COSY pulse sequence which is derived from the classical 13C-1H correlation experiment. An example is given of the application of 13C-2H COSY to the study of the biogenesis of natural products from the anti-malarial plant Artemisia annua, using a doubly-labelled precursor molecule. Although the biogenesis of artemisinin, the anti-malarial principle from this species, has been extensively studied over the past twenty years there is still no consensus as to the true biosynthetic route to this important natural product – indeed, some published experimental results are directly contradictory. One possible reason for this confusion may be the ease with which some of the metabolites from A. annua undergo spontaneous autoxidation, as exemplified by our recent in vitro studies of the spontaneous autoxidation of dihydroartemisinic acid, and the application of 13C-2H COSY to this biosynthetic problem has been important in helping to mitigate against such processes. In this in vivo application of 13C-2H COSY, [15-13C2H3]-dihydroartemisinic acid (the doubly-labelled analogue of the natural product from this species which was obtained through synthesis) was fed to A. annua plants and was shown to be converted into several natural products which have been described previously, including artemisinin. It is proposed that all of these transformations occurred via a tertiary hydroperoxide intermediate, which is derived from dihyroartemisinic acid. This intermediate was observed directly in this feeding experiment by the 13C-2H COSY technique; its observation by more traditional procedures (e.g., chromatographic separation, followed by spectroscopic analysis of the purified product) would have been difficult owing to the instability of the hydroperoxide group (as had been established previously by our in vitro studies of the spontaneous autoxidation of dihydroartemisinic acid). This same hydroperoxide has been reported as the initial product of the spontaneous autoxidation of dihydroartemisinic acid in our previous in vitro studies. Its observation in this feeding experiment by the 13C-2H COSY technique, a procedure which requires the minimum of sample manipulation in order to achieve a reliable identification of metabolites (based on both 13C and 2H chemical shifts at the 15-position), provides the best possible evidence for its status as a genuine biosynthetic intermediate, rather than merely as an artifact of the experimental procedure.

Winckelmann and the invention of antiquity: history and aesthetics in the age of Altertumswissenschaft

This volume provides a new perspective on the emergence of the modern study of antiquity, Altertumswissenschaft, in eighteenth-century Germany through an exploration of debates that arose over the work of the art historian Johann Joachim Winckelmann between his death in 1768 and the end of the century. This period has long been recognised as particularly formative for the development of modern classical studies, and over the past few decades has received increased attention from historians of scholarship and of ideas. Winckelmann's eloquent articulation of the cultural and aesthetic value of studying the ancient Greeks, his adumbration of a new method for studying ancient artworks, and his provision of a model of cultural-historical development in terms of a succession of period styles, influenced both the public and intra-disciplinary self-image of classics long into the twentieth century. Yet this area of Winckelmann's Nachleben has received relatively little attention compared with the proliferation of studies concerning his importance for late eighteenth-century German art and literature, for historians of sexuality, and his traditional status as a 'founder figure' within the academic disciplines of classical archaeology and the history of art. Harloe restores the figure of Winckelmann to classicists' understanding of the history of their own discipline and uses debates between important figures, such as Christian Gottlob Heyne, Friedrich August Wolf, and Johann Gottfried Herder, to cast fresh light upon the emergence of the modern paradigm of classics as Altertumswissenschaft: the multi-disciplinary, comprehensive, and historicizing study of the ancient world.