Influence of the molecular architecture on the secondary relaxations of Poly(styrene-co-methylmethacrylate) copolymers

The processes of adsorption of grafted copolymers onto negatively charged surfaces were studied using a dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The control parameters in the study of the adsorption are the existence or absence on the molecular architecture of grafted polyethyleneglycol (PEG) chains with different lengths and the chemical nature of the main chain, poly(allylamine) (PAH) or poly(L-lysine) (PLL). It was found out that the adsorption kinetics of the polymers showed a complex behavior. The total adsorbed amount depends on the architecture of the polymer chains (length of the PEG chains), on the polymer concentration and on the chemical nature of the main chain. The comparison of the thicknesses of the adsorbed layers obtained from D-QCM and from ellipsometry allowed calculation of the water content of the layers that is intimately related to the grafting length. The analysis of D-QCM results also provides information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. It is shown that the adsorption of polymers with a charged backbone is not driven exclusively by the electrostatic interactions, but the entropic contributions as a result of the trapping of water in the layer structure are of fundamental importance.

The relationship between soil geochemistry and the bioaccessibility of trace elements in playground soil

A total of 32 samples of surficial soil were collected from 16 playground areas in Madrid (Spain), in order to investigate the importance of the geochemistry of the soil on subsequent bioaccessibility of trace elements. The in vitro bioaccessibility of As, Co, Cr, Cu, Ni, Pb and Zn was evaluated by means of two extraction processes that simulate the gastric environment and one that reproduces a gastric + intestinal digestion sequence. The results of the in vitro bioaccessibility were compared against aqua regia extractions (“total” concentration), and it was found that total concentrations of As, Cu, Pb and Zn were double those of bioaccessible values, whilst that of Cr was ten times higher. Whereas the results of the gastric + intestinal extraction were affected by a high uncertainty, both gastric methods offered very similar and consistent results, with bioaccessibilities following the order: As = Cu = Pb = Zn > Co > Ni > Cr, and ranging from 63 to 7 %. Selected soil properties including pH, organic matter, Fe and CaCO3 content were determined to assess their influence on trace element bioaccessibility, and it was found that Cu, Pb and Zn were predominantly bound to organic matter and, to a lesser extent, Fe oxides. The former fraction was readily accessible in the gastric solution, whereas Fe oxides seemed to recapture negatively charged chloride complexes of these elements in the gastric solution, lowering their bioaccessibility. The homogeneous pH of the playground soils included in the study does not influence trace element bioaccessibility to any significant extent except for Cr, where the very low gastric accessibility seems to be related to the strongly pH-dependent formation of complexes with organic matter. The results for As, which have been previously described and discussed in detail in Mingot et al. (Chemosphere 84: 1386–1391, 2011), indicate a high gastric bioaccessibility for this element as a consequence of its strong association with calcium carbonate and the ease with which these bonds are broken in the gastric solution. The calculation of risk assessments are therefore dependant on the methodology used and the specific environment they address. This has impacts on management strategies formulated to ensure that the most vulnerable of society, children, can live and play without adverse consequences to their health.

Functional, structural and phylogenetic analysis of domains underlying the Al sensitivity of the aluminum-activated malate/anion transporter, TaALMT1.

Triticum aestivum aluminum-activated malate transporter (TaALMT1) is the founding member of a unique gene family of anion transporters (ALMTs) that mediate the efflux of organic acids. A small sub-group of root-localized ALMTs, including TaALMT1, is physiologically associated with in planta aluminum (Al) resistance. TaALMT1 exhibits significant enhancement of transport activity in response to extracellular Al. In this study, we integrated structure–function analyses of structurally altered TaALMT1 proteins expressed in Xenopus oocytes with phylogenic analyses of the ALMT family. Our aim is to re-examine the role of protein domains in terms of their potential involvement in the Al-dependent enhancement (i.e. Al-responsiveness) of TaALMT1 transport activity, as well as the roles of all its 43 negatively charged amino acid residues. Our results indicate that the N-domain, which is predicted to form the conductive pathway, mediates ion transport even in the absence of the C-domain. However, segments in both domains are involved in Al3+ sensing. We identified two regions, one at the N-terminus and a hydrophobic region at the C-terminus, that jointly contribute to the Al-response phenotype. Interestingly, the characteristic motif at the N-terminus appears to be specific for Al-responsive ALMTs. Our study highlights the need to include a comprehensive phylogenetic analysis when drawing inferences from structure–function analyses, as a significant proportion of the functional changes observed for TaALMT1 are most likely the result of alterations in the overall structural integrity of ALMT family proteins rather than modifications of specific sites involved in Al3+ sensing.

Arsenosugar phospholipids and arsenic hydrocarbons in two species of brown macroalgae

Fourteen arsenolipids, including 11 new compounds, were identified and quantified in two species of brown algae, Wakame (Undaria pinnatifida) and Hijiki (Hizikia fusiformis), by high resolution mass spectrometry, high performance liquid chromatography–mass spectrometry and gas chromatography–mass spectrometry. Both algal species contained arsenosugar-phospholipids as the major type of arsenolipid, and arsenic-hydrocarbons were also significant components, particularly in Hijiki. The origin of the various arsenolipids, and the possible significance of their relative quantities, is briefly discussed.

Arabidopsis thaliana DOF6 negatively affects germination in non-after ripened seeds and interacts with TCP14

Seed dormancy prevents seeds from germinating under environmental conditions unfavourable for plant growth and development and constitutes an evolutionary advantage. Dry storage, also known as after-ripening, gradually decreases seed dormancy by mechanisms not well understood. An Arabidopsis thaliana DOF transcription factor gene (DOF6) affecting seed germination has been characterized. The transcript levels of this gene accumulate in dry seeds and decay gradually during after-ripening and also upon seed imbibition. While constitutive over-expression of DOF6 produced aberrant growth and sterility in the plant, its over-expression induced upon seed imbibition triggered delayed germination, abscisic acid (ABA)-hypersensitive phenotypes and increased expression of the ABA biosynthetic gene ABA1 and ABA-related stress genes. Wild-type germination and gene expression were gradually restored during seed after-ripening, despite of DOF6-induced over-expression. DOF6 was found to interact in a yeast two-hybrid system andin planta with TCP14, a previously described positive regulator of seed germination. The expression of ABA1 and ABA-related stress genes was also enhanced in tcp14 knock-out mutants. Taken together, these results indicate that DOF6 negatively affects seed germination and opposes TCP14 function in the regulation of a specific set of ABA-related genes

Far wake structure in rarefied plasma flows past charged bodies

The asymptotic structure of the far-wake behind a charged body in a rarefied plasma flow is investigated under the assumption of small ion-to-electron temperature ratio and of flow speed hypersonic with respect to the ions but not with respect to the electrons. It is found that waves are excited even if the flow is subacoustic (flow velocity less than the ion-acoustic speed). For both superacoustic and subacoustic velocities a steep wave front develops separating the weakly perturbed, quasineutral plasma ahead, from the region behind where ion waves appear. Near the axis a trailing front develops;the region between this and the axis is quasineutral for superacoustic speeds. The decay laws in all of these regions, the self-similar structure of the fronts and the general character of the waves are determined.The damping of the waves and special flow detail for bodies large and small compared with the Debye length are discussed. A nonlinear analysis of the leading wave front in superacoustic flow is carried out. A hyperacoustic equivalence principle is presented.

On the charged particle drag acting on LAGEOS

A recent study by the authors points to Charged Particle Drag (CPD) as a contributor to revisit in the LAGEOS non-gravitational perturbations problem. Such perturbations must account for dynamical contributions in the order of pms−2 . The simulated effect takes into account: (i) spatial and temporal variations of the plasmatic parameters (temperature and concentration of the species), (ii) spacecraft potential variations caused by both the eclipse passages and variations in the parameters mentioned above, and (iii) solar and geomagnetic conditions. Furthermore, recent theoretical improvements concerning scattering drag overcome previous limitations allowing for a complete formulation of this effect. For each satellite the lifetime CPD instantaneous acceleration is computed. The plasmatic parameters have been obtained fromthe Sheffield Coupled Thermosphere-Ionosphere-Plasmasphere (SCTIP) semi-empirical model (up to the polar region), as well as alytical/empirical approximations based on spacecraft measurements for the auroral and polar regions. Results show that maximum amplitudes for LAGEOSI are larger than those for LAGEOS-II: −85 pms−2 and −70 pms−2 respectively. This is due to the almost (magnetically) polar orbit configuration of the first, producing larger combinations of plasmatic parameter values. High solar activity has a huge impact in the resulting LAGEOS accelerations: it yields a perfect modulation of the resulting acceleration with maximum amplitudes up to a factor of 10 when comparing low and high activity periods. On the other hand, the impact of the geomagnetic activity results into a reduction of the effect itself, probably due to a decrease in the hydrogen concentration for high energy input periods. The acceleration results will be used in a refined orbit computation in a subsequent investigation.

The determination of ionospheric charged particle temperatures from in situ measurements

The recently noticed disagreement between ionospheric charged-particle temperature values obtained from ground-based (incoherent backscatter) and in situ (Langmuir probe type) measurements is considered; it is suggested that a main cause of disagreement lies in the poor theoretical basis of present in situ measurements. It is pointed out that the usually neglected geomagnetic field influence may result in too high an electron temperature. It is also shown that the theory used at present to interpret data from ion retarding potential analyzers has serious pitfalls, and that these devices greatly disturb the surrounding plasma when measuring ion temperature. Finally, it is shown how the ion temperature can be accurately obtained from the characteristic of a cylindrical Langmuir probe in a rarefied plasma flow.

Determination of the hoop fracture properties of unirradiated hydrogen-charged nuclear fuel cladding from ring compression tests

In this work, a new methodology is devised to obtain the fracture properties of nuclear fuel cladding in the hoop direction. The proposed method combines ring compression tests and a finite element method that includes a damage model based on cohesive crack theory, applied to unirradiated hydrogen-charged ZIRLOTM nuclear fuel cladding. Samples with hydrogen concentrations from 0 to 2000 ppm were tested at 20 �C. Agreement between the finite element simulations and the experimental results is excellent in all cases. The parameters of the cohesive crack model are obtained from the simulations, with the fracture energy and fracture toughness being calculated in turn. The evolution of fracture toughness in the hoop direction with the hydrogen concentration (up to 2000 ppm) is reported for the first time for ZIRLOTM cladding. Additionally, the fracture micromechanisms are examined as a function of the hydrogen concentration. In the as-received samples, the micromechanism is the nucleation, growth and coalescence of voids, whereas in the samples with 2000 ppm, a combination of cuasicleavage and plastic deformation, along with secondary microcracking is observed.