Surface viscoelasticity in model polymer multilayers: From planar interfaces to rising bubbles

International audienceIn the present work a polymeric transient viscoelastic network is used as a model system to investigate several fundamentals of interfacial viscoelasticity and non-linear behavior, in simple shear, compression and for simple mixed deformations. A supramolecular polymer bilayer, characterized by long but finite relaxation times, is created at the water-air interface using a layer-by-layer assembly method. The possibility of studying the individual layers starting from an unstrained reference state enabled the independent quantification of the equilibrium ther-modynamic properties, and the viscoelastic response of the bilayer could be studied separately for shear and compressional deformations. Time-and frequency-dependent material functions of the layer were determined in simple shear and uniform compression. Moreover, a quasi linear neo-Hookean model for elastic interfaces was adapted to describe step strain experiments on a viscoelastic system by allowing the material properties to be time-dependent. The use of this model made it possible to calculate the response of the system to step deformations. Within the linear response regime, both stress-strain proportionality and the superposition principle were investigated. Furthermore, the onset of non-linear behavior of the extra stresses was characterized in shear and for the first time in pure compression. We conclude by investigating the multilayer system in a rising bubble setup and show that the neo-Hookean model is able to predict the extra and deviatoric surface stresses well, up to moderate deformations

Dark Matter Halo Environment for Primordial Star Formation

We study the statistical properties (such as shape and spin) of high-z halos likely hosting the first (PopIII) stars with cosmological simulations including detailed gas physics. In the redshift range considered ($11 < z < 16$) the average sphericity is $= 0.3 \pm 0.1$, and for more than 90% of halos the triaxiality parameter is $T \lesssim 0.4$, showing a clear preference for oblateness over prolateness. Larger halos in the simulation tend to be both more spherical and prolate: we find $s \propto M_h^{\alpha_s}$ and $T \propto M_h^{\alpha_T}$, with $\alpha_s \approx 0.128$ and $\alpha_T= 0.276$ at z = 11. The spin distributions of dark matter and gas are considerably different at $z=16$, with the baryons rotating slower than the dark matter. At lower redshift, instead, the spin distributions of dark matter and gas track each other almost perfectly, as a consequence of a longer time interval available for momentum redistribution between the two components. The spin of both the gas and dark matter follows a lognormal distribution, with a mean value at z=16 of $=0.0184$, virtually independent of halo mass. This is in good agreement with previous studies. Using the results of two feedback models (MT1 and MT2) by McKee & Tan (2008) and mapping our halo spin distribution into a PopIII IMF, we find that at high-$z$ the IMF closely tracks the spin lognormal distribution. Depending on the feedback model, though, the distribution can be centered at $\approx 65 M_\odot$ (MT1) or $\approx 140 M_\odot$ (MT2). At later times, model MT1 evolves into a bimodal distribution with a second prominent peak located at $35-40 M_\odot$ as a result of the non-linear relation between rotation and halo mass. We conclude that the dark matter halo properties might be a key factor shaping the IMF of the first stars.Comment: 10 pages, 6 figures, accepted for publication in MNRA

Financial Satisfaction and (in)formal Sector in a Transition Country

This paper examines the relationship between working in the formal or informal sector and self-reported individual financial satisfaction in a country in transition. It does so by allowing for individual heterogeneity in terms of perceived financial insecurity and tax morale. The empirical analysis uses a dataset for Albania, a country in transition. The method applied is the ‘self-administered questionnaire’, which combines personal contacts with written questionnaire. The results indicate that, for most individuals, working in the informal sector has negative effects on their self reported financial satisfaction. For some individuals, however, this effect is positive. The characteristic defining these two groups of individuals is their attitude towards the perceived financial insecurity related to not paying taxes. These findings have important implications, in particular for transition countries with large informal sectors. Given the involuntary participation in the informal sector in these countries, the majority of individuals working in this sector will remain financially dissatisfied as long as they have no other social safety net

Multidimensional screening in a monopolistic insurance market

Support from the Government of Catalonia project 2005SGR00836 and the Barcelona GSE Research Network, as well as from the Ministerio de Educación y Ciencia, project ECO2009-07616 and CONSOLIDER-INGENIO 2010(CSD2006-0016)We consider a population of individuals who differ in two dimensions, their risk type (expected loss) and their risk aversion, and solve for the profit-maximising menu of contracts that a monopolistic insurer puts out on the market. Our findings are threefold. First, it is never optimal to fully separate all the types. Second, if heterogeneity in risk aversion is sufficiently high, then some high-risk individuals (the risk-tolerant ones) will obtain lower coverage than some low-risk individuals (the risk-averse ones). Third, because women tend to be more risk averse than men (in that the risk aversion distribution for women first-order stochastically dominates that for men), gender discrimination may lead to a Pareto improvement

Perspectives for biocatalytic lignin utilization: cleaving 4-O-5 and C??-C?? bonds in dimeric lignin model compounds catalyzed by a promiscuous activity of tyrosinase

Background: In the biorefinery utilizing lignocellulosic biomasses, lignin decomposition to value-added phenolic derivatives is a key issue, and recently biocatalytic delignification is emerging owing to its superior selectivity, low energy consumption, and unparalleled sustainability. However, besides heme-containing peroxidases and laccases, information about lignolytic biocatalysts is still limited till date. Results: Herein, we report a promiscuous activity of tyrosinase which is closely associated with delignification requiring high redox potentials (&gt;1.4 V vs. normal hydrogen electrode [NHE]). The promiscuous activity of tyrosinase not only oxidizes veratryl alcohol, a commonly used nonphenolic substrate for assaying ligninolytic activity, to veratraldehyde but also cleaves the 4-O-5 and C??-C?? bonds in 4-phenoxyphenol and guaiacyl glycerol-??-guaiacyl ether (GGE) that are dimeric lignin model compounds. Cyclic voltammograms additionally verified that the promiscuous activity oxidizes lignin-related high redox potential substrates. Conclusion These results might be applicable for extending the versatility of tyrosinase toward biocatalytic delignification as well as suggesting a new perspective for sustainable lignin utilization. Furthermore, the results provide insight for exploring the previously unknown promiscuous activities of biocatalysts much more diverse than ever thought before, thereby innovatively expanding the applicable area of biocatalysis