Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Early warning with calibrated and sharper probabilistic forecasts

Given a nonlinear model, a probabilistic forecast may be obtained by Monte Carlo simulations. At a given forecast horizon, Monte Carlo simulations yield sets of discrete forecasts, which can be converted to density forecasts. The resulting density forecasts will inevitably be downgraded by model mis-specification. In order to enhance the quality of the density forecasts, one can mix them with the unconditional density. This paper examines the value of combining conditional density forecasts with the unconditional density. The findings have positive implications for issuing early warnings in different disciplines including economics and meteorology, but UK inflation forecasts are considered as an example.

Initial distribution spread: A density forecasting approach

Ensemble forecasting of nonlinear systems involves the use of a model to run forward a discrete ensemble (or set) of initial states. Data assimilation techniques tend to focus on estimating the true state of the system, even though model error limits the value of such efforts. This paper argues for choosing the initial ensemble in order to optimise forecasting performance rather than estimate the true state of the system. Density forecasting and choosing the initial ensemble are treated as one problem. Forecasting performance can be quantified by some scoring rule. In the case of the logarithmic scoring rule, theoretical arguments and empirical results are presented. It turns out that, if the underlying noise dominates model error, we can diagnose the noise spread.

Flavor-protein binding: disulfide interchange reactions between ovalbumin and volatile disulfides

The irreversible binding of selected sulfur-containing flavor compounds to proteins was investigated in aqueous solutions containing ovalbumin and a mixture of disulfides (diethyl, dipropyl, dibutyl, diallyl, and 2-furfuryl methyl) using solid-phase micro-extraction (SPME). In systems which had not been heated, the recovery of disulfides from the headspace above the protein at the native pH (6.7) was similar to that from an aqueous blank. However, significant losses were observed when the pH of the solution was increased to 8.0. When the protein was denatured by heating, much greater losses were observed and some free thiols were produced. In similar heat-denatured systems at pH 2.0, no losses of disulfides were observed. Disulfides containing allyl or furfuryl groups were more reactive than saturated alkyl disulfides. Interchange reactions between protein sulfhydryl groups and the disulfides are believed to be responsible for the loss of the disulfides.

Sbiancare un etiope. La pelle cangiante di un topos antico

The book is part of a multi-year investigation on the historical construction and representation of ethnic otherness through the use of language, and focuses on the history of the tópos expressed by the proverb Lavare/sbiancare un etiope (‘to wash an Ethiop white’), a tópos which is traceable in different languages across many centuries (and since II c. A.D.), which stays for either ‘to attempt the impossible’ or ‘to do something useless’. The research also tries to shine a light upon the cultural and social contexts in which ‘Ethiopian’ otherness have generated. Its final goal is to find out how the washing-the-Ethiopian tópos (in its verbal and iconographical forms) has become long-lasting, ductile and semantically productive key expression whose heterogeneous use not only document but also produce and fix otherness in time.

Protein structure prediction servers at University College London

A number of state-of-the-art protein structure prediction servers have been developed by researchers working in the Bioinformatics Unit at University College London. The popular PSIPRED server allows users to perform secondary structure prediction, transmembrane topology prediction and protein fold recognition. More recent servers include DISOPRED for the prediction of protein dynamic disorder and DomPred for domain boundary prediction.

Rapid protein domain assignment from amino acid sequence using predicted secondary structure

The elucidation of the domain content of a given protein sequence in the absence of determined structure or significant sequence homology to known domains is an important problem in structural biology. Here we address how successfully the delineation of continuous domains can be accomplished in the absence of sequence homology using simple baseline methods, an existing prediction algorithm (Domain Guess by Size), and a newly developed method (DomSSEA). The study was undertaken with a view to measuring the usefulness of these prediction methods in terms of their application to fully automatic domain assignment. Thus, the sensitivity of each domain assignment method was measured by calculating the number of correctly assigned top scoring predictions. We have implemented a new continuous domain identification method using the alignment of predicted secondary structures of target sequences against observed secondary structures of chains with known domain boundaries as assigned by Class Architecture Topology Homology (CATH). Taking top predictions only, the success rate of the method in correctly assigning domain number to the representative chain set is 73.3%. The top prediction for domain number and location of domain boundaries was correct for 24% of the multidomain set (±20 residues). These results have been put into context in relation to the results obtained from the other prediction methods assessed

Strigolactone analogues induce suicidal seed germination of Striga spp. in soil

Striga hermonthica and Striga asiatica are obligate root parasites that cause serious problems in the production of staple cereal crops in Africa. Because of the high levels of infestation, there is an urgent need to control these weeds. A potentially useful control option is depletion of the soil seed bank by suicidal germination, which involves germination of the seeds in the absence of host plants. Suicidal germination is often mentioned in the literature, but not considered realistic, because of the alleged untimely decomposition of the stimulants in the soil, despite the fact that some encouraging results were reported around 1980. The alleged instability has prevented active research in this direction for the past 20–25 years. Five newly designed synthetic germination stimulants were investigated as candidates for suicidal germination. An important issue is the persistence of these stimulants in soil. Packets with Striga spp. seeds were put in pots with soil and then treated with aqueous solutions of the stimulants. All five compounds induced germination under these conditions, with percentages varying between 18% and 98% depending on stimulant and species. There were no noticeable signs of decomposition of the stimulants. The best performing stimulant is derived from 1-tetralone. We conclude that synthetic strigolactones analogues have excellent prospects for use in combating parasitic weeds. Further testing will be needed to evaluate whether such prospects can be realised in the field.

Coupled atmosphere-biophysics-hydrology models for environmental modeling

The formulation and implementation of LEAF-2, the Land Ecosystem–Atmosphere Feedback model, which comprises the representation of land–surface processes in the Regional Atmospheric Modeling System (RAMS), is described. LEAF-2 is a prognostic model for the temperature and water content of soil, snow cover, vegetation, and canopy air, and includes turbulent and radiative exchanges between these components and with the atmosphere. Subdivision of a RAMS surface grid cell into multiple areas of distinct land-use types is allowed, with each subgrid area, or patch, containing its own LEAF-2 model, and each patch interacts with the overlying atmospheric column with a weight proportional to its fractional area in the grid cell. A description is also given of TOPMODEL, a land hydrology model that represents surface and subsurface downslope lateral transport of groundwater. Details of the incorporation of a modified form of TOPMODEL into LEAF-2 are presented. Sensitivity tests of the coupled system are presented that demonstrate the potential importance of the patch representation and of lateral water transport in idealized model simulations. Independent studies that have applied LEAF-2 and verified its performance against observational data are cited. Linkage of RAMS and TOPMODEL through LEAF-2 creates a modeling system that can be used to explore the coupled atmosphere–biophysical–hydrologic response to altered climate forcing at local watershed and regional basin scales.

What GPs need to know about palliative-care drugs: ketamine

This is the first in a short series of articles that focus on what GPs should consider when monitoring and prescribing specialist-initiated palliative-care drugs. This first article summarises the key issues for patients receiving ketamine.

Probabilistic forecasting: why model imperfection is a poison pill

This volume is a serious attempt to open up the subject of European philosophy of science to real thought, and provide the structural basis for the interdisciplinary development of its specialist fields, but also to provoke reflection on the idea of ‘European philosophy of science’. This efforts should foster a contemporaneous reflection on what might be meant by philosophy of science in Europe and European philosophy of science, and how in fact awareness of it could assist philosophers interpret and motivate their research through a stronger collective identity. The overarching aim is to set the background for a collaborative project organising, systematising, and ultimately forging an identity for, European philosophy of science by creating research structures and developing research networks across Europe to promote its development.

Timing and climatic imprint of Greenland interstadials recorded in stalagmites from Northern Turkey

A 50 kyr-long exceptionally well-dated and highly resolved stalagmite oxygen (δ 18O) and carbon (δ 13C) isotope record from Sofular Cave in northwestern Turkey helps to further improve the dating of Greenland Interstadials (GI) 1, and 3–12. Timing of most GI in the Sofular record is consistent within ±10 to 300 years with the “iconic” Hulu Cave record. Larger divergences (>500 years) between Sofular and Hulu are only observed for GI 4 and 7. The Sofular record differs from the most recent NGRIP chronology by up to several centuries, whereas age offsets do not increase systematically with depth. The Sofular record also reveals a rapid and sensitive climate and ecosystem response in the eastern Mediterranean to GI, whereas a phase lag of ∼100 years between climate and full ecosystem response is evident. Finally, results of spectral analyses of the Sofular isotope records do not support a 1,470-year pacing of GI.

Timing and structure of the 8.2 kyr B.P. event inferred from δ18O records of stalagmites from China, Oman, and Brazil

Oxygen isotope records of stalagmites from China and Oman reveal a weak summer monsoon event, with a double-plunging structure, that started 8.21 ± 0.02 kyr B.P. An identical but antiphased pattern is also evident in two stalagmite records from eastern Brazil, indicating that the South American Summer Monsoon was intensified during the 8.2 kyr B.P. event. These records demonstrate that the event was of global extent and synchronous within dating errors of <50 years. In comparison with recent model simulations, it is plausible that the 8.2 kyr B.P. event can be tied in changes of the Atlantic Meridional Overturning Circulation triggered by a glacial lake draining event. This, in turn, affected North Atlantic climate and latitudinal position of the Intertropical Convergence Zone, resulting in the observed low-latitude monsoonal precipitation patterns.