Adhesion and non-linear rheology of adhesives with supramolecular crosslinking points

Soft supramolecular materials are promising for the design of innovative and highly tunable adhesives. These materials are composed of polymer chains functionalized by strongly interacting moieties, sometimes called "stickers". In order to systematically investigate the effect of the presence of associative groups on the debonding properties of a supramolecular adhesive, a series of supramolecular model systems has been characterized by probe-tack tests. These model materials, composed of linear and low dispersity poly(butylacrylate) chains functionalized in the middle by a single tri-urea sticker, are able to self-associate by six hydrogen bonds and range in molecular weight (M n) between 5 and 85 kg/mol. The linear rheology and the nanostructure of the same materials (called "PnBA3U") was the object of a previous study 1,2. At room temperature, the association of polymers via hydrogen bonds induces the formation of rod-like aggregates structured into bundles for M n \textless{} 40kg/mol and the behavior of a soft elastic material was observed (G'\textgreater{}\textgreater{}G "and G'~$\omega$ 0). For higher M n , the filaments were randomly oriented and polymers displayed a crossover towards viscous behavior although terminal relaxation was not reached in the experimental frequency window. All these materials show however similar adhesive properties characterized by a cohesive mode of failure and low debonding energies (W adh \textless{}40J/m 2 for a debonding speed of 100$\mu$m/s). The debonding mechanisms observed during the adhesion tests have been investigated in detail with an Image tools analysis developed by our group 3. The measure of the projected area covered by cavities growing in the adhesive layer during debonding can be used to estimate the true stress in the walls of the cavities and thus, to characterize the in-situ large strain deformation of the thin layer during the adhesion test itself. This analysis revealed in particular that the PnBA3U materials with M n \textless{} 40 kg/mol soften very markedly at large deformation like yield stress fluids, explaining the low adhesion energies measured for these viscoelastic gels.

Ballot Box Zoning: Initiative, Referendum and the Law

This Article examines several of the more prominent legal and institutional issues which bear upon the use of initiative and referendum for rezoning land

Applications of sesquiterpene lactones : a review of some potential success cases

Sesquiterpene lactones, a vast range of terpenoids isolated from Asteraceae species, exhibit a broad spectrum of biological effects and several of them are already commercially available, such as artemisinin. Here the most recent and impactful results of in vivo, preclinical and clinical studies involving a selection of ten sesquiterpene lactones (alantolactone, arglabin, costunolide, cynaropicrin, helenalin, inuviscolide, lactucin, parthenolide, thapsigargin and tomentosin) are presented and discussed, along with some of their derivatives. In the authors’ opinion, these compounds have been neglected compared to others, although they could be of great use in developing important new pharmaceutical products. The selected sesquiterpenes show promising anticancer and anti-inflammatory effects, acting on various targets. Moreover, they exhibit antifungal, anxiolytic, analgesic, and antitrypanosomal activities. Several studies discussed here clearly show the potential that some of them have in combination therapy, as sensitizing agents to facilitate and enhance the action of drugs in clinical use. The derivatives show greater pharmacological value since they have better pharmacokinetics, stability, potency, and/or selectivity. All these natural terpenoids and their derivatives exhibit properties that invite further research by the scientific community.Portuguese Foundation for Science and Technology; European Commission; QREN; European Commission; COMPETE; cE3c centre (UIDB/00329/2020); LAQV-REQUIMTE (UIDB/50006/2020); QOPNA UID/QUI/00062/2019), Spanish Ministry Science and Research (MINECO RTI2018-094356-B-C21)info:eu-repo/semantics/publishedVersio

Interactive impacts of meteorological and hydrological conditions on the physical and biogeochemical structure of a coastal system

The German Bight was exposed to record high riverine discharges in June 2013, as a result of flooding of the Elbe and Weser rivers. Several anomalous observations suggested that the hydrodynamical and biogeochemical states of the system were impacted by this event. In this study, we developed a biogeochemical model and coupled it with a previously introduced high-resolution hydrodynamical model of the southern North Sea in order to better characterize these impacts and gain insight into the underlying processes. Performance of the model was assessed using an extensive set of in situ measurements for the period 2011–2014. We first improved the realism of the hydrodynamic model with regard to the representation of cross-shore gradients, mainly through inclusion of flow-dependent horizontal mixing. Among other characteristic features of the system, the coupled model system can reproduce the low salinities, high nutrient concentrations and low oxygen concentrations in the bottom layers observed within the German Bight following the flood event. Through a scenario analysis, we examined the sensitivity of the patterns observed during July 2013 to the hydrological and meteorological forcing in isolation. Within the region of freshwater influence (ROFI) of the Elbe–Weser rivers, the flood event clearly dominated the changes in salinity and nutrient concentrations, as expected. However, our findings point to the relevance of the peculiarities in the meteorological conditions in 2013 as well: a combination of low wind speeds, warm air temperatures and cold bottom-water temperatures resulted in a strong thermal stratification in the outer regions and limited vertical nutrient transport to the surface layers. Within the central region, the thermal and haline dynamics interactively resulted in an intense density stratification. This intense stratification, in turn, led to enhanced primary production within the central region enriched by nutrients due to the flood but led to reduction within the nutrient-limited outer region, and it caused a widespread oxygen depletion in bottom waters. Our results further point to the enhancement of the current velocities at the surface as a result of haline stratification and to intensification of the thermohaline estuarine-like circulation in the Wadden Sea, both driven by the flood event

Wissenschaftliche Monitoringkonzepte für die Deutsche Bucht (WIMO) - Abschlussbericht

The state and development of coastal marine systems and an understanding of the interaction of organisms, sea floor, water column, and biochemical and physical processes can only be obtained by a combination of long-term monitoring and modelling approaches of different complexity. A need for the development and evaluation of monitoring strategies is driven by a framework of different European and German regulations. The research project WIMO (Scientific Monitoring Concepts for the German Bight) has developed concepts and methods that aim at a fundamental scientific understanding of marine systems and also meet monitoring requirements of European legislation and regulations like the EU Marine Strategy Framework Directive. In this final report examples of common descriptors of ecosystem state like seabed integrity, eutrophication, and biodiversity are discussed. It has been assessed to what extent established measuring procedures used to survey the characteristics of the sea floor, and newly developed technologies are eligible for governmental monitoring. The significance of integrative modelling for linking and visualising results of measurements and models is illustrated. It is shown how new concepts have been implemented into governmental monitoring in the form of web based data sheets. These insights enable continuous analyses and developments in the future

Communication of pharmacogenetic research results to HIV-infected treated patients: standpoints of professionals and patients.

International audienceThe aim of pharmacogenetic studies is to adapt therapeutic strategies to individual genetic profiles, thus maximising their efficacy and minimising the likelihood of adverse side effects. Since the advent of personalised medicine, the issue of communicating research results to participants has become increasingly important. We addressed this question in the context of HIV infection, as patients and associations are particularly concerned by research and therapeutic advances. We explored the standpoints of both research professionals and participants involved in a pharmacogenetic study conducted in a cohort of HIV-infected patients. The setting of the research protocol was followed over a 2-year period. Participants' standpoints were collected through a questionnaire and interviews were conducted with research professionals. Of 125 participants, 76% wished to receive individual results and 71% wished to receive collective results; 39% did not know when results might be expected. Communication of global research results is a principle that is generally accepted by professionals. Concerning individual feedback, the professionals felt that it was necessary if it could be of direct benefit to the participant, but they expressed doubts for situations with no recognised benefit. Our results highlight the necessity to consider this issue in greater detail. We suggest the need to anticipate the debates concerning individual feedback, to differentiate between situations and the importance of further investigations on the opportunities and modalities of communication. Finally, our work emphasised the opposite pressures between the pursuit of scientific knowledge and the therapeutic orientation of clinical trials

Biophysical Assessment of Single Cell Cytotoxicity: Diesel Exhaust Particle-Treated Human Aortic Endothelial Cells

Exposure to diesel exhaust particles (DEPs), a major source of traffic-related air pollution, has become a serious health concern due to its adverse influences on human health including cardiovascular and respiratory disorders. To elucidate the relationship between biophysical properties (cell topography, cytoskeleton organizations, and cell mechanics) and functions of endothelial cells exposed to DEPs, atomic force microscope (AFM) was applied to analyze the toxic effects of DEPs on a model cell line from human aortic endothelial cells (HAECs). Fluorescence microscopy and flow cytometry were also applied to further explore DEP-induced cytotoxicity in HAECs. Results revealed that DEPs could negatively impair cell viability and alter membrane nanostructures and cytoskeleton components in a dosage- and a time-dependent manner; and analyses suggested that DEPs-induced hyperpolarization in HAECs appeared in a time-dependent manner, implying DEP treatment would lead to vasodilation, which could be supported by down-regulation of cell biophysical properties (e.g., cell elasticity). These findings are consistent with the conclusion that DEP exposure triggers important biochemical and biophysical changes that would negatively impact the pathological development of cardiovascular diseases. For example, DEP intervention would be one cause of vasodilation, which will expand understanding of biophysical aspects associated with DEP cytotoxicity in HAECs

Submesoscale Instabilities in Mesoscale Eddies

Submesoscale processes have been extensively studied in observations and simulations of fronts. Recent idealized simulations show that submesoscale instabilities also occur in baroclinic mesoscale cyclones and anticyclones. The instabilities in the anticyclone grow faster and at coarser grid resolution than in the cyclone. The instabilities lead to larger restratification in the anticyclone than in the cyclone. The instabilities also lead to changes in the mean azimuthal jet around the anticyclone from 2-km resolution, but a similar effect only occurs in the cyclone at 0.25-km resolution. A numerical passive tracer experiment shows that submesoscale instabilities lead to deeper subduction in the interior of anticyclonic than cyclonic eddies because of outcropping isopycnals extending deeper into the thermocline in anticyclones. An energetic analysis suggests that both vertical shear production and vertical buoyancy fluxes are important in anticyclones but primarily vertical buoyancy fluxes occur in cyclones at these resolutions. The energy sources and sinks vary azimuthally around the eddies caused by the asymmetric effects of the Ekman buoyancy flux. Glider transects of a mesoscale anticyclone in the Tasman Sea show that water with low stratification and high oxygen concentrations is found in an anticyclone, in a manner that may be consistent with the model predictions for submesoscale subduction in mesoscale eddies

The LatMix summer campaign : submesoscale stirring in the upper ocean

Author Posting. © American Meteorological Society, 2015. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Bulletin of the American Meteorological Society 96 (2015): 1257–1279, doi:10.1175/BAMS-D-14-00015.1.Lateral stirring is a basic oceanographic phenomenon affecting the distribution of physical, chemical, and biological fields. Eddy stirring at scales on the order of 100 km (the mesoscale) is fairly well understood and explicitly represented in modern eddy-resolving numerical models of global ocean circulation. The same cannot be said for smaller-scale stirring processes. Here, the authors describe a major oceanographic field experiment aimed at observing and understanding the processes responsible for stirring at scales of 0.1–10 km. Stirring processes of varying intensity were studied in the Sargasso Sea eddy field approximately 250 km southeast of Cape Hatteras. Lateral variability of water-mass properties, the distribution of microscale turbulence, and the evolution of several patches of inert dye were studied with an array of shipboard, autonomous, and airborne instruments. Observations were made at two sites, characterized by weak and moderate background mesoscale straining, to contrast different regimes of lateral stirring. Analyses to date suggest that, in both cases, the lateral dispersion of natural and deliberately released tracers was O(1) m2 s–1 as found elsewhere, which is faster than might be expected from traditional shear dispersion by persistent mesoscale flow and linear internal waves. These findings point to the possible importance of kilometer-scale stirring by submesoscale eddies and nonlinear internal-wave processes or the need to modify the traditional shear-dispersion paradigm to include higher-order effects. A unique aspect of the Scalable Lateral Mixing and Coherent Turbulence (LatMix) field experiment is the combination of direct measurements of dye dispersion with the concurrent multiscale hydrographic and turbulence observations, enabling evaluation of the underlying mechanisms responsible for the observed dispersion at a new level.The bulk of this work was funded under the Scalable Lateral Mixing and Coherent Turbulence Departmental Research Initiative and the Physical Oceanography Program. The dye experiments were supported jointly by the Office of Naval Research and the National Science Foundation Physical Oceanography Program (Grants OCE-0751653 and OCE-0751734).2016-02-0