Self-assembly of a modified amyloid peptide fragment: pH-responsiveness and nematic phase formation

The self-assembly of peptide YYKLVFFC based on a fragment of the amyloid beta (A) peptide, A beta 16-20, KLVFF has been studied in aqueous solution. The peptide is designed with multiple functional residues to examine the interplay between aromatic interactions and charge on the self-assembly, as well as specific transformations such as the pH-induced phenol-phenolate transition of the tyrosine residue. Circular dichroism (CD) and Fourier-transform infrared (FTIR) spectroscopies are used to investigate the conditions for beta-sheet self-assembly and the role of aromatic interactions in the CD spectrum as a function of pH and concentration. The formation of well-defined fibrils at pH 4.7 is confirmed by cryo-TEM (transmission electron microscope) and negative stain TEM. The morphology changes at higher pH, and aggregates of short twisted fibrils are observed at pH 11. Polarized optical microscopy shows birefringence at a low concentration (1 wt.-%) of YYKLVFFC in aqueous solution, and small-angle X-ray scattering was used to probe nematic phase formation in more detail. A pH-induced transition from nematic to isotropic phases is observed on increasing pH that appears to be correlated to a reduction in aggregate anisotropy upon increasing pH.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Model predictive control using dynamic integrated system optimisation and parameter estimation (DISOPE)

DISOPE is a technique for solving optimal control problems where there are differences in structure and parameter values between reality and the model employed in the computations. The model reality differences can also allow for deliberate simplification of model characteristics and performance indices in order to facilitate the solution of the optimal control problem. The technique was developed originally in continuous time and later extended to discrete time. The main property of the procedure is that by iterating on appropriately modified model based problems the correct optimal solution is achieved in spite of the model-reality differences. Algorithms have been developed in both continuous and discrete time for a general nonlinear optimal control problem with terminal weighting, bounded controls and terminal constraints. The aim of this paper is to show how the DISOPE technique can aid receding horizon optimal control computation in nonlinear model predictive control.

Investigation of the faecal microbiota of kittens: monitoring bacterial succession and effect of diet

Weaning is a stressful process for kittens, and is often associated with diarrhoea and the onset of infectious diseases. The gastrointestinal microbiota plays an essential role in host well-being, including improving homeostasis. Composition of the gastrointestinal microbiota of young cats is poorly understood, and the impact of diet on the kitten microbiota unknown. The aims of this study were to monitor the faecal microbiota of kittens and determine the effect(s) of diet on its composition. Bacterial succession was monitored in two groups of kittens (at 4 and 6 weeks, and 4 and 9 months of age) fed different foods. Age-related microbial changes revealed significantly different counts of total bacteria, lactic acid bacteria, Desulfovibrionales, Clostridium cluster IX and Bacteroidetes between 4-week- and 9-month-old kittens. Diet-associated differences in the faecal microbiota of the two feeding groups were evident. In general, fluorescence in situ hybridization analysis demonstrated bifidobacteria, Atopobium group, Clostridium cluster XIV and lactic acid bacteria were dominant in kittens. Denaturing gradient gel electrophoresis profiling showed highly complex and diverse faecal microbiotas for kittens, with age- and/or food-related changes seen in relation to species richness and similarity indices. Four-week-old kittens harboured more diverse and variable profiles than those of weaned kittens.

The statistical properties of tropical ice clouds generated by the West-African and Australian monsoons from ground-based radar-lidar observations

In the present paper we characterize the statistical properties of non-precipitating tropical ice clouds (deep ice anvils resulting from deep convection and cirrus clouds) over Niamey, Niger, West Africa, and Darwin, northern Australia, using ground-based radar–lidar observations from the Atmospheric Radiation Measurement (ARM) programme. The ice cloud properties analysed in this paper are the frequency of ice cloud occurrence, cloud fraction, the morphological properties (cloud-top height, base height, and thickness), the microphysical and radiative properties (ice water content, visible extinction, effective radius, terminal fall speed, and concentration), and the internal cloud dynamics (in-cloud vertical air velocity). The main highlight of the paper is that it characterizes for the first time the probability density functions of the tropical ice cloud properties, their vertical variability and their diurnal variability at the same time. This is particularly important over West Africa, since the ARM deployment in Niamey provides the first vertically resolved observations of non-precipitating ice clouds in this crucial area in terms of redistribution of water and energy in the troposphere. The comparison between the two sites also provides an additional observational basis for the evaluation of the parametrization of clouds in large-scale models, which should be able to reproduce both the statistical properties at each site and the differences between the two sites. The frequency of ice cloud occurrence is found to be much larger over Darwin when compared to Niamey, and with a much larger diurnal variability, which is well correlated with the diurnal cycle of deep convective activity. The diurnal cycle of the ice cloud occurrence over Niamey is also much less correlated with that of deep convective activity than over Darwin, probably owing to the fact that Niamey is further away from the deep convective sources of the region. The frequency distributions of cloud fraction are strongly bimodal and broadly similar over the two sites, with a predominance of clouds characterized either by a very small cloud fraction (less than 0.3) or a very large cloud fraction (larger than 0.9). The ice clouds over Darwin are also much thicker (by 1 km or more statistically) and are characterized by a much larger diurnal variability than ice clouds over Niamey. Ice clouds over Niamey are also characterized by smaller particle sizes and fall speeds but in much larger concentrations, thereby carrying more ice water and producing more visible extinction than the ice clouds over Darwin. It is also found that there is a much larger occurrence of downward in-cloud air motions less than 1 m s−1 over Darwin, which together with the larger fall speeds retrieved over Darwin indicates that the life cycle of ice clouds is probably shorter over Darwin than over Niamey.

The core-periphery model with three regions and more

We determine the properties of the core-periphery model with three regions and compare our results with those of the standard 2-region model. The conditions for the stability of dispersion and concentration are established. As in the 2-region model, dispersion and concentration can be simultaneously stable. We show that the 3-region (2-region) model favours the concentration (dispersion) of economic activity. Furthermore, we provide some results for the n-region model. We show that the stability of concentration of the 2-region model implies that of any model with an even number of regions.

Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone),on the gelation of aqueous micellar solutions of Pluronic copolymer F127

The micellization of F127 (E98P67E98) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (rh,app) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G0 max) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.

Effects of organic and conventional fertiliser treatments on host selection by the aphid parasitoid Diaeretiella rapae

The type and quantity of fertilizer supplied to a crop will differ between organic and conventional farming practices. Altering the type of fertilizer a plant is provided with can influence a plant’s foliar nitrogen levels, as well as the composition and concentration of defence compounds, such as glucosinolates. Many natural enemies of insect herbivores can respond to headspace volatiles emitted by the herbivores’ host plant in response to herbivory. We propose that manipulating fertilizer type may also influence the headspace volatile profiles of plants, and as a result, the tritrophic interactions that occur between plants, their insect pests and those pests’ natural enemies. Here, we investigate a tritrophic system consisting of cabbage plants, Brassica oleracea, a parasitoid, Diaeretiella rapae, and one of its hosts, the specialist cabbage aphid Brevicoryne brassicae. Brassica oleracea plants were provided with either no additional fertilization or one of three types of fertilizer: Nitram (ammonium nitrate), John Innes base or organic chicken manure. We investigated whether these changes would alter the rate of parasitism of aphids on those plants and whether any differences in parasitism could be explained by differences in attractivity of the plants to D. rapae or attack rate of aphids by D. rapae. In free-choice experiments, there were significant differences in the percentage of B. brassicae parasitized by D. rapae between B. oleracea plants grown in different fertilizer treatments. In a series of dual-choice Y-tube olfactometry experiments, D. rapae females discriminated between B. brassicae-infested and undamaged plants, but parasitoids did not discriminate between similarly infested plants grown in different fertilizer treatments. Correspondingly, in attack rate experiments, there were no differences in the rate that D. rapae attacked B. brassicae on B. oleracea plants grown in different fertilizer treatments. These findings are of direct relevance to sustainable and conventional farming practices.

Macroclimate and viticultural zoning in Europe: observed trends and atmospheric forcing

Temperature and precipitation are major forcing factors influencing grapevine phenology and yield, as well as wine quality. Bioclimatic indices describing the suitability of a particular region for wine production are a commonly used tool for viticultural zoning. For this research these indices were computed for Europe by using the E-OBS gridded daily temperature and precipitation data set for the period from 1950 to 2009. Results showed strong regional contrasts based on the different index patterns and reproduced the wide diversity of local conditions that largely explain the quality and diversity of grapevines being grown across Europe. Owing to the strong inter-annual variability in the indices, a trend analysis and a principal component analysis were applied together with an assessment of their mean patterns. Significant trends were identified in the Winkler and Huglin indices, particularly for southwestern Europe. Four statistically significant orthogonal modes of variability were isolated for the Huglin index (HI), jointly representing 82% of the total variance in Europe. The leading mode was largely dominant (48% of variance) and mainly reflected the observed historical long-term changes. The other 3 modes corresponded to regional dipoles within Europe. Despite the relevance of local and regional climatic characteristics to grapevines, it was demonstrated via canonical correlation analysis that the observed inter-annual variability of the HI was strongly controlled by the large-scale atmospheric circulation during the growing season (April to September).

The variable link between PNA and NAO in observations and in multi-century CGCM simulations

The link between the Pacific/North American pattern (PNA) and the North Atlantic Oscillation (NAO) is investigated in reanalysis data (NCEP, ERA40) and multi-century CGCM runs for present day climate using three versions of the ECHAM model. PNA and NAO patterns and indices are determined via rotated principal component analysis on monthly mean 500 hPa geopotential height fields using the varimax criteria. On average, the multi-century CGCM simulations show a significant anti-correlation between PNA and NAO. Further, multi-decadal periods with significantly enhanced (high anti-correlation, active phase) or weakened (low correlations, inactive phase) coupling are found in all CGCMs. In the simulated active phases, the storm track activity near Newfoundland has a stronger link with the PNA variability than during the inactive phases. On average, the reanalysis datasets show no significant anti-correlation between PNA and NAO indices, but during the sub-period 1973–1994 a significant anti-correlation is detected, suggesting that the present climate could correspond to an inactive period as detected in the CGCMs. An analysis of possible physical mechanisms suggests that the link between the patterns is established by the baroclinic waves forming the North Atlantic storm track. The geopotential height anomalies associated with negative PNA phases induce an increased advection of warm and moist air from the Gulf of Mexico and cold air from Canada. Both types of advection contribute to increase baroclinicity over eastern North America and also to increase the low level latent heat content of the warm air masses. Thus, growth conditions for eddies at the entrance of the North Atlantic storm track are enhanced. Considering the average temporal development during winter for the CGCM, results show an enhanced Newfoundland storm track maximum in the early winter for negative PNA, followed by a downstream enhancement of the Atlantic storm track in the subsequent months. In active (passive) phases, this seasonal development is enhanced (suppressed). As the storm track over the central and eastern Atlantic is closely related to the NAO variability, this development can be explained by the shift of the NAO index to more positive values.

EOF analysis of three records of sea-ice concentration spanning the last 30 years

Several continuous observational datasets of Artic sea-ice concentration are currently available that cover the period since the advent of routine satellite observations. We report on a comparison of three sea-ice concentration datasets. These are the National Ice Center charts, and two passive microwave radiometer datasets derived using different approaches: the NASA team and Bootstrap algorithms. Empirical orthogonal function (EOF) analyses were employed to compare modes of variability and their consistency between the datasets. The analysis was motivated by the need for a reliable, realistic sea ice climatology for use in climate model simulations, for which both the variability and absolute values of extent and concentration are important. We found that, while there are significant discrepancies in absolute concentrations, the major modes of variability derived from all records were essentially the same.

Recent climatic trends and linkages to river discharge in Central Vietnam

In this study, change in rainfall, temperature and river discharge are analysed over the last three decades in Central Vietnam. Trends and rainfall indices are evaluated using non-parametric tests at different temporal levels. To overcome the sparse locally available network, the high resolution APHRODITE gridded dataset is used in addition to the existing rain gauges. Finally, existing linkages between discharge changes and trends in rainfall and temperature are explored. Results are indicative of an intensification of rainfall (+15%/decade), with more extreme and longer events. A significant increase in winter rainfall and a decrease in consecutive dry days provides strong evidence for a lengthening wet season in Central Vietnam. In addition, trends based on APHRODITE suggest a strong orographic signal in winter and annual trends. These results underline the local variability in the impacts of climatic change at the global scale. Consequently, it is important that change detection investigations are conducted at the local scale. A very weak signal is detected in the trend of minimum temperature (+0.2°C/decade). River discharge trends show an increase in mean discharge (31 to 35%/decade) over the last decades. Between 54 and 74% of this increase is explained by the increase in precipitation. The maximum discharge also responds significantly to precipitation changes leading to a lengthened wet season and an increase in extreme rainfall events. Such trends can be linked with a likely increase in floods in Central Vietnam, which is important for future adaptation planning and management and flood preparedness in the region. Copyright © 2012 John Wiley & Sons, Ltd.

Globalization, economic freedom, and human rights

Using the KOF Index of Globalization and two indices of economic freedom, the authors empirically analyze whether globalization and economic liberalization affect governments’ respect for human rights in a panel of 106 countries over the 1981–2004 period. According to their results, physical integrity rights significantly and robustly increase with globalization and economic freedom, while empowerment rights are not robustly affected. Due to the lack of consensus about the appropriate level of empowerment rights as compared to the outright rejection of any violation of physical integrity rights, the global community is presumably less effective in promoting empowerment rights.

Reconstruction of geomagnetic activity and near-Earth interplanetary conditions over the past 167 yr - Part 3: improved representation of solar cycle 11

Svalgaard (2014) has recently pointed out that the calibration of the Helsinki magnetic observatory’s H component variometer was probably in error in published data for the years 1866–1874.5 and that this makes the interdiurnal variation index based on daily means, IDV(1d), (Lockwood et al., 2013a), and the interplanetary magnetic field strength derived from it (Lockwood et al., 2013b), too low around the peak of solar cycle 11. We use data from the modern Nurmijarvi station, relatively close to the site of the original Helsinki Observatory, to confirm a 30% underestimation in this interval and hence our results are fully consistent with the correction derived by Svalgaard. We show that the best method for recalibration uses the Helsinki Ak(H) and aa indices and is accurate to ±10 %. This makes it preferable to recalibration using either the sunspot number or the diurnal range of geomagnetic activity which we find to be accurate to ±20 %. In the case of Helsinki data during cycle 11, the two recalibration methods produce very similar corrections which are here confirmed using newly digitised data from the nearby St Petersburg observatory and also using declination data from Helsinki. However, we show that the IDV index is, compared to later years, too similar to sunspot number before 1872, revealing independence of the two data series has been lost; either because the geomagnetic data used to compile IDV has been corrected using sunspot numbers, or vice versa, or both. We present corrected data sequences for both the IDV(1d) index and the reconstructed IMF (interplanetary magnetic field).We also analyse the relationship between the derived near-Earth IMF and the sunspot number and point out the relevance of the prior history of solar activity, in addition to the contemporaneous value, to estimating any “floor” value of the near-Earth interplanetary field.