Two-colour pulsed Raman studies of the lowest excited singlet state of tetraphenylporphyrin: band assignments and electronic structure

The resonance Raman spectra of the lowest lying singlet (S-1) state of free-base tetraphenylporphyrin and seven of its isotopomers were recorded under pump-and-probe conditions with a time delay of -2 ns between pump and probe laser pulses, In the S-1 spectra of the isotopomers, as in the ground state, there are dramatic splittings of what appear to be single bands in the natural isotopic abundance spectrum. The most structurally significant bands of the S-1 state were assigned on the basis of the isotope data, In some cases it was necessary to curve fit unresolved bands in the excited-state spectra in order to account for observed intensity ratios and to rationalize isotope shifts, The changes in band positions on excitation to the S-1 state were compared with those from earlier studies on the T-1 state. The changes in band positions were found to be similar For both excited states. Most notable was the similar shift in nu(2), the most widely used marker band for orbital character. The data are interpreted as implying that the lowest lying singlet state is a configuration interaction admixture of b(1u)b(2g) + a(u)b(3g) configurations with the coefficients weighted heavily in favour of b(1n)b(2g), which Is the configuration of the T-1 state. Copyright (C) 2000 John Wiley & Sons, Ltd.

Down with MNE-centric theories! Market entry and expansion as the bundling of MNE and local assets

Both Anderson and Gatignon and the Uppsala internationalization model see the initial mode of foreign market entry and subsequent modes of operation as unilaterally determined by multinational enterprises (MNEs) arbitraging control and risk and increasing their commitment as they gain experience in the target market. OLI and internalization models do recognize that foreign market entry requires the bundling of MNE and complementary local assets, which they call location or country-specific advantages, but implicitly assume that those assets are freely accessible to MNEs. In contrast to both of these MNE-centric views, I explicitly consider the transactional characteristics of complementary local assets and model foreign market entry as the optimal assignment of equity between their owners and MNEs. By looking at the relative efficiency of the different markets in which MNE and complementary local assets are traded, and at how these two categories of assets match, I am able to predict whether equity will be held by MNEs or by local firms, or shared between them, and whether MNEs will enter through greenfields, brownfields, or acquisitions. The bundling model I propose has interesting implications for the evolution of the MNE footprint in host countries, and for the reasons behind the emergence of Dragon MNEs.

Rao-Blackwellised particle filter for colour-based tracking

Colour-based particle filters have been used exhaustively in the literature given rise to multiple applications However tracking coloured objects through time has an important drawback since the way in which the camera perceives the colour of the object can change Simple updates are often used to address this problem which imply a risk of distorting the model and losing the target In this paper a joint image characteristic-space tracking is proposed which updates the model simultaneously to the object location In order to avoid the curse of dimensionality a Rao-Blackwellised particle filter has been used Using this technique the hypotheses are evaluated depending on the difference between the model and the current target appearance during the updating stage Convincing results have been obtained in sequences under both sudden and gradual illumination condition changes Crown Copyright (C) 2010 Published by Elsevier B V All rights reserved

Environmental indifference? A critique of environmentally deterministic theories of peatland archaeological site construction in Ireland

Climate change, whether gradual or sudden, has frequently been invoked as a causal factor to explain many aspects of cultural change during the prehistoric and early historic periods. Critiquing such theories has often proven difficult, not least because of the imprecise dating of many aspects of the palaeoclimate or archaeological records and the difficulties of merging the two strands of research. Here we consider one example of the archaeological record – peatland site construction in Ireland – which has previously been interpreted in terms of social response to climate change and examine whether close scrutiny of the archaeological and palaeoenvironmental records uphold the climatically deterministic hypotheses. We evaluate evidence for phasing in the temporal distribution of trackways and related sites in Irish peatlands, of which more than 3,500 examples have been recorded, through the examination of ~350 dendrochronological and 14C dates from these structures. The role of climate change in influencing when such sites were constructed is assessed by comparing visually and statistically the frequency of sites over the last 4,500 years with well-dated, multi-proxy climate reconstructions from Irish peatlands. We demonstrate that national patterns of “peatland activity” exist that indicate that the construction of sites in bogs was neither a constant nor random phenomenon. Phases of activity (i.e. periods in which the number of structures increased), as well as the ‘lulls’ that separate them, show no consistent correlation with periods of wetter or drier conditions on the bogs, suggesting that the impetus for the start or cessation of such activity was not climatically-determined. We propose that trigger(s) for peatland site construction in Ireland must instead also be sought within the wider, contemporary social background. Perhaps not surprisingly, a comparison with archaeological and palynological evidence shows that peatland activity tends to occur at times of more expansive settlement and land-use, suggesting that the bogs were used when the landscape was being more widely occupied. Interestingly, the lulls in peatland site construction coincide with transitional points between nominal archaeological phases, typically defined on the basis of their material culture, implying that there may indeed have been a cultural discontinuity at these times. © 2012 Elsevier Ltd. All rights reserved.

Equidiscrimination contours around an achromatic colour are convex but not balanced

A model based on the postreceptor channels followed by a Minkowski norm (Minkowski model) is widely used to fit experimental data on colour discrimination. This model predicts that contours of equal discrimination in colour space are convex and balanced (symmetrical). We have tested these predictions in an experiment. Two new statistical tests have been developed to analyse convexity and balancedness of experimental curves. Using these tests we have found that while they are in line with the convexity prediction, our experimental contours strongly testify against balancedness. It follows that the Minkowski model is, generally, inappropriate to model colour discrimination data. © 2002 Elsevier Science (USA).

Changing Paradigms in Space Theories:Recapturing 20th Century Architectural History

The concept of space entered architectural history as late as 1893. Studies in art opened up the discussion, and it has been studied in various ways in architecture ever since. This article aims to instigate an additional reading to architectural history, one that is not supported by "isms" but based on space theories in the 20th century. Objectives of the article are to bring the concept of space and its changing paradigms to the attention of architectural researchers, to introduce a conceptual framework to classify and clarify theories of space, and to enrich the discussions on the 20th century architecture through theories that are beyond styles. The introduction of space in architecture will revolve around subject-object relationships, three-dimensionality and senses. Modern space will be discussed through concepts such as empathy, perception, abstraction, and geometry. A scientific approach will follow to study the concept of place through environment, event, behavior, and design methods. Finally, the research will look at contemporary approaches related to digitally supported space via concepts like reality-virtuality, mediated experience, and relationship with machines.

Dual-colour HER2/chromosome 17 chromogenic in situ hybridisation enables accurate assessment of HER2 genomic status in ovarian tumours

Ovarian cancer is a leading cause of gynaecological cancer-related morbidity and mortality. There has been increasing interest in the potential utility of anti-human epidermal growth factor receptor 2 (anti-HER2) agents in the treatment of this disease, with the attendant need to identify suitable predictive biomarkers of response to treatment.

Dual-colour HER2/chromosome 17 chromogenic in situ hybridisation assay enables accurate assessment of HER2 genomic status in gastric cancer and has potential utility in HER2 testing of biopsy samples

Determination of HER2 protein expression by immunohistochemistry (IHC) and genomic status by fluorescent in situ hybridisation (FISH) are important in identifying a subset of high HER2-expressing gastric cancers that might respond to trastuzumab. Although FISH is considered the standard for determination of HER2 genomic status, brightfield ISH is being increasingly recognised as a viable alternative. Also, the impact of HER2 protein expression/genomic heterogeneity on the accuracy of HER2 testing has not been well studied in the context of gastric biopsy samples.