SAXS observation of RCM1 under cyclical shear

A cylinder forming poly(styrene-b-butadiene-b-styrene) triblock copolymer melt is cyclically processed through a capillary at a high shear rate in the Cambridge Multipass Rheometer (MPR). In situ X-ray diffraction experiments enable observation of the effect of the shear on the block copolymer (BCP) nanophase orientation, both during and after processing. Temporal resolution of the X-ray exposures is increased, whilst retaining intensity, by exploiting the cyclical nature of the shear and the material's response to it; short exposures from many cycles, individually having few counts, are added together to produce well resolved X-ray patterns. Orientation of the cylinders reduces during processing, then increases during pauses between processing. The loss of orientation is attributed to the high shear rate deforming the melt faster than the structure can respond, whilst it is believed that melt relaxation, linked to the compressibility of the material, produces much lower shear rates after mechanical processing has ceased, which induces strong orientation of the nanostructure.

Terrestrial ecosystems from space: a review of earth observation products for macroecology applications

Aim Earth observation (EO) products are a valuable alternative to spectral vegetation indices. We discuss the availability of EO products for analysing patterns in macroecology, particularly related to vegetation, on a range of spatial and temporal scales. Location Global. Methods We discuss four groups of EO products: land cover/cover change, vegetation structure and ecosystem productivity, fire detection, and digital elevation models. We address important practical issues arising from their use, such as assumptions underlying product generation, product accuracy and product transferability between spatial scales. We investigate the potential of EO products for analysing terrestrial ecosystems. Results Land cover, productivity and fire products are generated from long-term data using standardized algorithms to improve reliability in detecting change of land surfaces. Their global coverage renders them useful for macroecology. Their spatial resolution (e.g. GLOBCOVER vegetation, 300 m; MODIS vegetation and fire, ≥ 500 m; ASTER digital elevation, 30 m) can be a limiting factor. Canopy structure and productivity products are based on physical approaches and thus are independent of biome-specific calibrations. Active fire locations are provided in near-real time, while burnt area products show actual area burnt by fire. EO products can be assimilated into ecosystem models, and their validation information can be employed to calculate uncertainties during subsequent modelling. Main conclusions Owing to their global coverage and long-term continuity, EO end products can significantly advance the field of macroecology. EO products allow analyses of spatial biodiversity, seasonal dynamics of biomass and productivity, and consequences of disturbances on regional to global scales. Remaining drawbacks include inter-operability between products from different sensors and accuracy issues due to differences between assumptions and models underlying the generation of different EO products. Our review explains the nature of EO products and how they relate to particular ecological variables across scales to encourage their wider use in ecological applications.

Observation impact in data assimilation: the effect of non-Gaussian observation error.

Data assimilation methods which avoid the assumption of Gaussian error statistics are being developed for geoscience applications. We investigate how the relaxation of the Gaussian assumption affects the impact observations have within the assimilation process. The effect of non-Gaussian observation error (described by the likelihood) is compared to previously published work studying the effect of a non-Gaussian prior. The observation impact is measured in three ways: the sensitivity of the analysis to the observations, the mutual information, and the relative entropy. These three measures have all been studied in the case of Gaussian data assimilation and, in this case, have a known analytical form. It is shown that the analysis sensitivity can also be derived analytically when at least one of the prior or likelihood is Gaussian. This derivation shows an interesting asymmetry in the relationship between analysis sensitivity and analysis error covariance when the two different sources of non-Gaussian structure are considered (likelihood vs. prior). This is illustrated for a simple scalar case and used to infer the effect of the non-Gaussian structure on mutual information and relative entropy, which are more natural choices of metric in non-Gaussian data assimilation. It is concluded that approximating non-Gaussian error distributions as Gaussian can give significantly erroneous estimates of observation impact. The degree of the error depends not only on the nature of the non-Gaussian structure, but also on the metric used to measure the observation impact and the source of the non-Gaussian structure.

Poetry on Pre-Raphaelite principles: science, nature and knowledge in William Michael Rossetti’s 'Fancies at Leisure' and 'Mrs. Holmes Grey'

This article demonstrates how early Pre-Raphaelite poetry worked according to the principle that art should be modelled on science theorised by the Pre-Raphaelites in their early essays. As the main theorists (rather than practitioners) of Pre-Raphaelite art, F. G. Stephens and William Michael Rossetti defined the Pre-Raphaelite project in terms of observation, investigation, experiment, the “adherence to fact” and the “search after truth”. In the hands of the early Pre-Raphaelite poets, and particularly Rossetti himself, poetry too becomes a mode of scientific enquiry into the natural world, the nature of observation, human psychology and medical practice.

Gaussian anamorphosis in the analysis step of the EnKF: a joint state-variable/observation approach

The analysis step of the (ensemble) Kalman filter is optimal when (1) the distribution of the background is Gaussian, (2) state variables and observations are related via a linear operator, and (3) the observational error is of additive nature and has Gaussian distribution. When these conditions are largely violated, a pre-processing step known as Gaussian anamorphosis (GA) can be applied. The objective of this procedure is to obtain state variables and observations that better fulfil the Gaussianity conditions in some sense. In this work we analyse GA from a joint perspective, paying attention to the effects of transformations in the joint state variable/observation space. First, we study transformations for state variables and observations that are independent from each other. Then, we introduce a targeted joint transformation with the objective to obtain joint Gaussianity in the transformed space. We focus primarily in the univariate case, and briefly comment on the multivariate one. A key point of this paper is that, when (1)-(3) are violated, using the analysis step of the EnKF will not recover the exact posterior density in spite of any transformations one may perform. These transformations, however, provide approximations of different quality to the Bayesian solution of the problem. Using an example in which the Bayesian posterior can be analytically computed, we assess the quality of the analysis distributions generated after applying the EnKF analysis step in conjunction with different GA options. The value of the targeted joint transformation is particularly clear for the case when the prior is Gaussian, the marginal density for the observations is close to Gaussian, and the likelihood is a Gaussian mixture.

Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.