Glassy phases in Random Heteropolymers with correlated sequences

We develop a new analytic approach for the study of lattice heteropolymers, and apply it to copolymers with correlated Markovian sequences. According to our analysis, heteropolymers present three different dense phases depending upon the temperature, the nature of the monomer interactions, and the sequence correlations: (i) a liquid phase, (ii) a ``soft glass'' phase, and (iii) a ``frozen glass'' phase. The presence of the new intermediate ``soft glass'' phase is predicted for instance in the case of polyampholytes with sequences that favor the alternation of monomers. Our approach is based on the cavity method, a refined Bethe Peierls approximation adapted to frustrated systems. It amounts to a mean field treatment in which the nearest neighbor correlations, which are crucial in the dense phases of heteropolymers, are handled exactly. This approach is powerful and versatile, it can be improved systematically and generalized to other polymeric systems

Hidden potential in predicting wintertime temperature anomalies in the Northern Hemisphere

Variability of the North Atlantic Oscillation (NAO) drives wintertime temperature anomalies in the Northern Hemisphere. Dynamical seasonal prediction systems can skilfully predict the winter NAO. However, prediction of the NAO-dependent air temperature anomalies remains elusive, partially due to the low variability of predicted NAO. Here, we demonstrate a hidden potential of a multi-model ensemble of operational seasonal prediction systems for predicting wintertime temperature by increasing the variability of predicted NAO. We identify and subsample those ensemble members which are close to NAO index statistically estimated from initial autumn conditions. In our novel multi-model approach, the correlation prediction skill for wintertime Central Europe temperature is improved from 0.25 to 0.66, accompanied by an increased winter NAO prediction skill of 0.9. Thereby, temperature anomalies can be skilfully predicted for the upcoming winter over a large part of the Northern Hemisphere through increased variability and skill of predicted NAO

Hidden Potential in Predicting Wintertime Temperature Anomalies in the Northern Hemisphere

Variability of the North Atlantic Oscillation (NAO) drives wintertime temperature anomalies in the Northern Hemisphere. Dynamical seasonal prediction systems can skilfully predict the winter NAO. However, prediction of the NAO-dependent air temperature anomalies remains elusive, partially due to the low variability of predicted NAO. Here, we demonstrate a hidden potential of a multi-model ensemble of operational seasonal prediction systems for predicting wintertime temperature by increasing the variability of predicted NAO. We identify and subsample those ensemble members which are close to NAO index statistically estimated from initial autumn conditions. In our novel multi-model approach, the correlation prediction skill for wintertime Central Europe temperature is improved from 0.25 to 0.66, accompanied by an increased winter NAO prediction skill of 0.9. Thereby, temperature anomalies can be skilfully predicted for the upcoming winter over a large part of the Northern Hemisphere through increased variability and skill of predicted NAO

Increase in Arctic coastal erosion and its sensitivity to warming in the twenty-first century

Arctic coastal erosion damages infrastructure, threatens coastal communities and releases organic carbon from permafrost. However, the magnitude, timing and sensitivity of coastal erosion increase to global warming remain unknown. Here we project the Arctic-mean erosion rate to increase and very likely exceed its historical range of variability before the end of the century in a wide range of emission scenarios. The sensitivity of erosion to warming roughly doubles, reaching 0.4–0.8 m yr−1 °C−1 and 2.3–4.2 TgC yr−1 °C−1 by the end of the century. We develop a simplified semi-empirical model to produce twenty-first-century pan-Arctic coastal erosion rate projections. Our results will inform policymakers on coastal conservation and socioeconomic planning, and organic carbon flux projections lay out the path for future work to investigate the impact of Arctic coastal erosion on the changing Arctic Ocean, its role as a global carbon sink, and the permafrost–carbon feedback. © 2022, The Author(s)

Deviations from the mean field predictions for the phase behaviour of random copolymers melts

We investigate the phase behaviour of random copolymers melts via large scale Monte Carlo simulations. We observe macrophase separation into A and B--rich phases as predicted by mean field theory only for systems with a very large correlation lambda of blocks along the polymer chains, far away from the Lifshitz point. For smaller values of lambda, we find that a locally segregated, disordered microemulsion--like structure gradually forms as the temperature decreases. As we increase the number of blocks in the polymers, the region of macrophase separation further shrinks. The results of our Monte Carlo simulation are in agreement with a Ginzburg criterium, which suggests that mean field theory becomes worse as the number of blocks in polymers increases.Comment: 6 pages, 4 figures, Late

Counterion Penetration and Effective Electrostatic Interactions in Solutions of Polyelectrolyte Stars and Microgels

Counterion distributions and effective electrostatic interactions between spherical macroions in polyelectrolyte solutions are calculated via second-order perturbation (linear response) theory. By modelling the macroions as continuous charge distributions that are permeable to counterions, analytical expressions are obtained for counterion profiles and effective pair interactions in solutions of star-branched and microgel macroions. The counterions are found to penetrate stars more easily than microgels, with important implications for screening of bare macroion interactions. The effective pair interactions are Yukawa in form for separated macroions, but are softly repulsive and bounded for overlapping macroions. A one-body volume energy, which depends on the average macroion concentration, emerges naturally in the theory and contributes to the total free energy.Comment: 15 pages, 5 figure

Domains in Melts of Comb-Coil Diblock Copolymers: Superstrong Segregation Regime

Conditions for the crossover from the strong to the superstrong segregation regime are analyzed for the case of comb-coil diblock copolymers. It is shown that the critical interaction energy between the components required to induce the crossover to the superstrong segregation regime is inversely proportional to mb = 1 + n/m, where n is the degree of polymerization of the side chain and m is the distance between successive grafting points. As a result, the superstrong segregation regime, being rather rare in the case of ordinary block copolymers, has a much better chance to be realized in the case of diblock copolymers with combs grafted to one of the blocks.

Conformational transitions of heteropolymers in dilute solutions

In this paper we extend the Gaussian self-consistent method to permit study of the equilibrium and kinetics of conformational transitions for heteropolymers with any given primary sequence. The kinetic equations earlier derived by us are transformed to a form containing only the mean squared distances between pairs of monomers. These equations are further expressed in terms of instantaneous gradients of the variational free energy. The method allowed us to study exhaustively the stability and conformational structure of some periodic and random aperiodic sequences. A typical phase diagram of a fairly long amphiphilic heteropolymer chain is found to contain phases of the extended coil, the homogeneous globule, the micro-phase separated globule, and a large number of frustrated states, which result in conformational phases of the random coil and the frozen globule. We have also found that for a certain class of sequences the frustrated phases are suppressed. The kinetics of folding from the extended coil to the globule proceeds through non-equilibrium states possessing locally compacted, but partially misfolded and frustrated, structure. This results in a rather complicated multistep kinetic process typical of glassy systems.Comment: 15 pages, RevTeX, 20 ps figures, accepted for publication in Phys. Rev.

Molecular Dynamics Simulation of Semiflexible Polyampholyte Brushes - The Effect of Charged Monomers Sequence

Planar brushes formed by end-grafted semiflexible polyampholyte chains, each chain containing equal number of positively and negatively charged monomers is studied using molecular dynamics simulations. Keeping the length of the chains fixed, dependence of the average brush thickness and equilibrium statistics of the brush conformations on the grafting density and the salt concentration are obtained with various sequences of charged monomers. When similarly charged monomers of the chains are arranged in longer blocks, the average brush thickness is smaller and dependence of brush properties on the grafting density and the salt concentration is stronger. With such long blocks of similarly charged monomers, the anchored chains bond to each other in the vicinity of the grafting surface at low grafting densities and buckle toward the grafting surface at high grafting densities.Comment: 8 pages,7 figure

Programming temporal shapeshifting

Shapeshifting enables a wide range of engineering and biomedical applications, but until now transformations have required external triggers. This prerequisite limits viability in closed or inert systems and puts forward the challenge of developing materials with intrinsically encoded shape evolution. Herein we demonstrate programmable shape-memory materials that perform a sequence of encoded actuations under constant environment conditions without using an external trigger. We employ dual network hydrogels: in the first network, covalent crosslinks are introduced for elastic energy storage, and in the second one, temporary hydrogen-bonds regulate the energy release rate. Through strain-induced and time-dependent reorganization of the reversible hydrogen-bonds, this dual network allows for encoding both the rate and pathway of shape transformations on timescales from seconds to hours. This generic mechanism for programming trigger-free shapeshifting opens new ways to design autonomous actuators, drug-release systems and active implants