Complementary Nucleobase Interactions Drive the Hierarchical Self-Assembly of Core-Shell Bottlebrush Block Copolymers toward Cylindrical Supramolecules

The self-assembly of amphiphilic block copolymers has facilitated the preparation of a wide variety of nano-objects of diverse morphology. Ready access to these nanostructures has opened up new possibilities in catalysis, sensing, and nanomedicine. In comparison, the self-assembly of large building blocks (i.e., amphiphilic bottlebrush polymers) has received less attention, owing in part to the relatively more challenging synthesis of these macromolecules. Bottlebrush amphiphiles can self-assemble into uniquely stable spherical nanostructures and can also produce dynamic cylinders with lengths modulated by environmental conditions, motivating further research in this area. Herein, we report the synthesis of core–shell bottlebrush polymers (BBPs) containing complementary nucleobase functionalities via a combination of ring-opening metathesis polymerization (ROMP) and reversible addition–fragmentation chain transfer (RAFT) polymerization, using a “grafting-from” approach, and their hierarchical self-assembly in aqueous media. Mixtures of BBPs containing thymine or adenine units in their core blocks were found to self-assemble into higher-order cylindrical supramolecules upon heating above a critical temperature. This temperature was demonstrated to correspond to the lower critical solution temperature (LCST) of the corona-forming poly(4-acryloylmorpholine) block, providing evidence for a unique one-dimensional BBP assembly mechanism. Moreover, the formation of extended supramolecular assemblies was preferentially observed when both thymine- and adenine-functionalized BBPs were present in equimolar concentrations, pointing toward an alternating, isodesmic mechanism of organization occurring via nucleobase interactions located at their chain termini. We anticipate that these discoveries will provide the basis for future studies regarding BBP self-assembly, especially with regard to the formation of stimuli-responsive anisotropic nanostructures

Latest LAPS developments Assimilating remote sensing data and its impact on LAPS predictability

Presentación realizada en la 3rd European Nowcasting Conference, celebrada en la sede central de AEMET en Madrid del 24 al 26 de abril de 2019

Structure and dynamics of Rh surfaces

Lattice relaxations, surface phonon spectra, surface energies, and work functions are calculated for Rh(100) and Rh(110) surfaces using density-functional theory and the full-potential linearized augmented plane wave method. Both, the local-density approximation and the generalized gradient approximation to the exchange-correlation functional are considered. The force constants are obtained from the directly calculated atomic forces, and the temperature dependence of the surface relaxation is evaluated by minimizing the free energy of the system. The anharmonicity of the atomic vibrations is taken into account within the quasiharmonic approximation. The importance of contributions from different phonons to the surface relaxation is analyzed.Comment: 9 pages, 7 figures, scheduled to appear in Phys. Rev. B, Feb. 15 (1998). Other related publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm

The impact of atmosphere–ocean–wave coupling on the near-surface wind speed in forecasts of extratropical cyclones

Accurate modelling of air–sea surface exchanges is crucial for reliable extreme surface windspeed forecasts. While atmosphere-only weather forecast models represent ocean and wave effects through sea-state independent parametrizations, coupled multi-model systems capture sea-state dynamics by integrating feedbacks between the atmosphere, ocean and wave model components. Here, we investigate the sensitivity of extreme surface wind speeds to air–sea exchanges at the kilometre scale using coupled and uncoupled configurations of the Met Office’s UK Regional Coupled Environmental Prediction system. The case period includes the passage of extra-tropical cyclones Helen, Ali, and Bronagh, which brought maximum gusts of 36 ms−1 over the UK. Compared with the atmosphere-only results, coupling to the ocean decreases the domain-average sea-surface temperature by up to 0.5 K. Inclusion of coupling to waves reduce the 98th percentile 10-m wind speed by up to 2 ms−1 as young, growing wind waves reduce the wind speed by increasing the sea-surface aerodynamic roughness. Impacts on gusts are more modest, with local reductions of up to 1 ms−1, due to enhanced boundary-layer turbulence which partially offsets air–sea momentum transfer. Using a new drag parametrization based on the Coupled Ocean–Atmosphere Response Experiment 4.0 parametrization, with a cap on the neutral drag coefficient and reduction for wind speeds exceeding 27 ms−1, the atmosphere-only model achieves equivalent impacts on 10-m wind speeds and gusts as from coupling to waves. Overall, the new drag parametrization achieves the same 20% improvement in forecast 10-m wind-speed skill as coupling to waves, with the advantage of saving the computational cost of the ocean and wave models

Optimal inventory control policies of a two-stage push–pull production inventory system with lost sales under stochastic production, transportation, and external demand

An analytical model based on Markov processes is proposed for the analysis of a linear, horizontally integrated, two stages, push–pull inventory system. Uncertainty about both supply and demand is taken into consideration. Exponentially distributed lead times, compound Poisson external demand and lost sales are assumed. An algorithm that creates the infinitesimal generator matrix of the system is developed and an exact numerical solution of the system performance measures is also provided. The proposed model can be either used to evaluate what if scenarios exploring the behavior of the system or to optimize performance measures of the considered system. As an example, the model is used to analyze and get insights of the behavior of a supply–demand balanced system. © 2021, Sociedad de Estadística e Investigación Operativa

Synthesis and Characterization of Charge-Stabilized Poly(4-hydroxybutyl acrylate) Latex by RAFT Aqueous Dispersion Polymerization: A New Precursor for Reverse Sequence Polymerization-Induced Self-Assembly

 The reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 4-hydroxybutyl acrylate (HBA) is conducted using a water-soluble RAFT agent bearing a carboxylic acid group. This confers charge stabilization when such syntheses are conducted at pH 8, which leads to the formation of polydisperse anionic PHBA latex particles of approximately 200 nm diameter. The weakly hydrophobic nature of the PHBA chains confers stimulus-responsive behavior on such latexes, which are characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, and 1H NMR spectroscopy. Addition of a suitable water-miscible hydrophilic monomer such as 2-(N-(acryloyloxy)ethyl pyrrolidone) (NAEP) leads to in situ molecular dissolution of the PHBA latex, with subsequent RAFT polymerization leading to the formation of sterically stabilized PHBA–PNAEP diblock copolymer nanoparticles of approximately 57 nm diameter. Such formulations constitute a new approach to reverse sequence polymerization-induced self-assembly, whereby the hydrophobic block is prepared first in aqueous media. </p

Forecasting soil erosion and sediment yields during flash floods: The disastrous case of Mandra, Greece, 2017

Flash floods, among the most destructive natural hazards, are commonly studied as to their catastrophic power in terms of fatalities, infrastructure damages and economic losses. A devastating aftermath of flash floods, which has not received much-deserved attention in the literature, is the sizeable and permanent soil loss due to soil erosion and sediment yields. This study aims at forecasting soil erosion and sediment yields due to the disastrous storm event that occurred in Mandra town (western Attica, Greece) on 15 November 2017. Gridded hydrometeorological forecasts were conducted at 5-min and 1-h time steps by means of the chemical hydrological atmospheric ocean wave system (CHAOS). The forecasts of soil erosion and sediment yields were achieved by a high-resolution geographic information system (GIS) application of the modified universal soil loss equation (MUSLE) on the basis of the forecasted surface runoff hydrographs. The entire event lasted from the afternoon of 14 November until noon of 15 November, but the bulk of the disastrous storm occurred in the morning of 15 November 2017, flooding two torrent basins. As a result of the extreme flash flood, 2195 tons and 1435 tons of sediment were forecasted to be detached from the body of the soil's surface and transported to the stream networks of the Soures and Agia Aikaterini Torrent basins which cross Mandra. Soil erosion maps were constructed for every hour and the spatial and temporal evolution of soil erosion was shown throughout the event. This study provides concrete insights on the erosion-prone areas of the study basins, which can inform actions against erosion

Predicted skeletal muscle mass and 4-year cardiovascular disease incidence in middle-aged and elderly participants of ikaria prospective epidemiological study: The mediating effect of sex and cardiometabolic factors

The sex-specific effect of skeletal muscle mass (SMM) index (SMI) on 4-year first fatal/nonfatal cardiovascular disease (CVD) event in free-of-disease individuals was examined. In 2009, n = 1411 inhabitants (mean age = 64(12)) from Ikaria were selected. Follow-up was performed in 2013. SMI was created to reflect SMM through appendicular skeletal muscle mass (indirectly calculated through formulas) divided by body mass index (BMI). Fifteen and six tenths percent of participants exhibited CVD (19.8% in men/12% in women, p = 0.002). Significant U-shape trends were observed in participants &gt;65 years old and women irrespective to age confirmed through multi-adjusted Cox regression analysis; in age &gt;65 years, Hazard Ratio (HR)(2nd vs. 1st SMI tertile) = 0.80, 95% Confidence Interval (95%CI) (0.45, 0.96) and in women HR(2nd vs. 1st SMI tertile) = 0.71, 95% CI (0.33, 0.95), while, as for the 3rd SMI tertile, no significant trends were observed. Mediation analysis revealed that mediators of the aforementioned associations in men were the arterial distensibility and total testosterone, while, in women, inflammation, insulin resistance, and arterial distensibility. High SMM accompanied by obesity may not guarantee lower CVD risk. Specific cardiometabolic factors seem to explain this need for balance between lean and fat mass. © 2020 by the authors. Licensee MDPI, Basel, Switzerland