Dynamic response of a ferromagnetic nanofilament under rotating fields: effects of flexibility, thermal fluctuations and hydrodynamics.

Using nonequilibrium computer simulations, we study the response of ferromagnetic nanofilaments, consisting of stabilized one dimensional chains of ferromagnetic nanoparticles, under external rotating magnetic fields. In difference with their analogous microscale and stiff counterparts, which have been actively studied in recent years, nonequilibrium properties of rather flexible nanoparticle filaments remain mostly unexplored. By progressively increasing the modeling details, we are able to evidence the qualitative impact of main interactions that can not be neglected at the nanoscale, showing that filament flexibility, thermal fluctuations and hydrodynamic interactions contribute independently to broaden the range of synchronous frequency response in this system. Furthermore, we also show the existence of a limited set of characteristic dynamic filament configurations and discuss in detail the asynchronous response, which at finite temperature becomes probabilistic.

Depletion Interactions at Interfaces Induced by Ferromagnetic Colloidal Polymers.

The pair-interaction force profiles for two non-magnetic colloids immersed in a suspension of ferromagnetic colloidal polymers are investigated via Langevin simulations. A quasi-two-dimensional approach is taken to study the interface case and a range of colloidal size ratios (non-magnetic:magnetic) from 6:1 up to 20:1 have been considered in this work. Simulations show that when compared with non-magnetic suspensions, the magnetic polymers strongly modify the depletion force profiles leading to strongly oscillatory behavior. Larger polymer densities and size ratios increase the range of the depletion forces, and in general, also their strength; the force barrier peaks at short distances show more complex behavior. As the length of the ferromagnetic polymers increases, the force profiles become more regular, and stable points with their corresponding attraction basins develop. The number of stable points and the distance at which they occur can be tuned through the modification of the field strength H and the angle θ formed by the field and the imaginary axis joining the centers of the two non-magnetic colloids. When not constrained, the net forces acting on the two colloids tend to align them with the field till θ=0∘. At this angle, the force profiles turn out to be purely attractive, and therefore, these systems could be used as a funneling tool to form long linear arrays of non-magnetic particles. Torsional forces peak at θ=45∘ and have minimums at θ=0∘ as well as θ=90∘ which is an unstable orientation as slight deviations will evolve towards θ→0∘. Nonetheless, results suggest that the θ=90∘ orientation could be easily stabilized in several ways. In such a case, the stable points that the radial force profiles exhibit for this orthogonal orientation to the field could be used to control the distance between the two large colloids: their position and number can be controlled via H. Therefore, suspensions made of ferromagnetic colloidal polymers can be also useful in the creation of magnetic colloidal tweezers or ratchets. A qualitative explanation of all the observed phenomena can be provided in terms of how the geometrical constraints and the external field modify the conformations of the ferromagnetic polymers near the two large particles, and in turn, how both factors combine to create unbalanced Kelvin forces that oscillate in strength with the distance between the two non-magnetic colloids.

Self-organized sulfide-driven traveling pulses shape seagrass meadows.

Seagrasses provide multiple ecosystem services and act as intense carbon sinks in coastal regions around the globe but are threatened by multiple anthropogenic pressures, leading to enhanced seagrass mortality that reflects in the spatial self-organization of the meadows. Spontaneous spatial vegetation patterns appear in such different ecosystems as drylands, peatlands, salt marshes, or seagrass meadows, and the mechanisms behind this phenomenon are still an open question in many cases. Here, we report on the formation of vegetation traveling pulses creating complex spatiotemporal patterns and rings in Mediterranean seagrass meadows. We show that these structures emerge due to an excitable behavior resulting from the coupled dynamics of vegetation and porewater hydrogen sulfide, toxic to seagrass, in the sediment. The resulting spatiotemporal patterns resemble those formed in other physical, chemical, and biological excitable media, but on a much larger scale. Based on theory, we derive a model that reproduces the observed seascapes and predicts the annihilation of these circular structures as they collide, a distinctive feature of excitable pulses. We show also that the patterns in field images and the empirically resolved radial profiles of vegetation density and sediment sulfide concentration across the structures are consistent with predictions from the theoretical model, which shows these structures to have diagnostic value, acting as a harbinger of the terminal state of the seagrass meadows prior to their collapse.

Colloidal magnetic brushes: influence of the magnetic content and presence of short-range attractive forces in the micro-structure and field response.

The behaviour of supramolecular brushes, whose filaments are composed of sequences of magnetic and non-magnetic colloidal particles, has been studied using Langevin dynamics simulations. Two types of brushes have been considered: sticky or Stockmayer brushes (SB) and non-sticky magnetic brushes (NSB). In both cases, the microstructure and the collective behaviour have been analysed for a wide range of magnetic field strengths including the zero-field case, and negative fields. The results show that, for the same magnetic content, SB placed in a magnetic field present an extensibility up to two times larger than NSB. The analysis of the microstructure of SB at zero field shows that magnetic particles belonging to different filaments in the brush self-organize into ring and chain aggregates, while magnetic colloids in NSB mainly remain in a non-aggregated state. Clustering among magnetic particles belonging to different filaments is observed to gradually fade away as the magnetic content of SB filaments increases towards 100%. Under an external field, SB are observed to form chains, threads and sheets depending on the magnetic content and the applied field strength. The chain-like clusters in SB are observed to decrease in size as the magnetic content in the filaments increases. A non-monotonic field dependence is observed for the average size of these clusters. In spite of the very different microstructure, both NSB and SB are observed to have a very similar magnetization, especially in high strength fields.

Adsorption transition of a grafted ferromagnetic filament controlled by external magnetic fields.

Extensive Langevin dynamics simulations are used to characterize the adsorption transition of a flexible magnetic filament grafted onto an attractive planar surface. Our results identify different structural transitions at different ratios of the thermal energy to the surface attraction strength: filament straightening, adsorption, and the magnetic flux closure. The adsorption temperature of a magnetic filament is found to be higher in comparison to an equivalent nonmagnetic chain. The adsorption has been also investigated under the application of a static homogeneous external magnetic field. We found that the strength and the orientation of the field can be used to control the adsorption process, providing a precise switching mechanism. Interestingly, we have observed that the characteristic field strength and tilt angle at the adsorption point are related by a simple power law.

Magnetic responsive brushes under flow in strongly confined slits: external field control of brush structure and flowing particle mixture separation.

In the present work magnetic brushes under flow conditions and confined inside narrow slits have been studied using Langevin dynamics simulations. It has been observed that the structural properties of these confined magnetic brushes can be tuned via the application of an external magnetic field, and this control can be exerted with a relatively low content of magnetic colloidal particles in the filaments that form the brushes (20% in the present study). The potential of these brushes to perform a separation process of a size-bidispersed mixture of free non-magnetic colloidal particles flowing through the slit has also been explored. Numerical results show that it is possible to induce a two-fold effect on the bidispersed particle flow: a lateral separation of the two types of flowing colloidal particles and an enhancement of the differences in their velocities. These two features are key elements sought in separation processes and could be very relevant in the design of new chromatographic columns and microfluid separation devices.

Fairy circle landscapes under the sea.

Short-scale interactions yield large-scale vegetation patterns that, in turn, shape ecosystem function across landscapes. Fairy circles, which are circular patches bare of vegetation within otherwise continuous landscapes, are characteristic features of semiarid grasslands. We report the occurrence of submarine fairy circle seascapes in seagrass meadows and propose a simple model that reproduces the diversity of seascapes observed in these ecosystems as emerging from plant interactions within the meadow. These seascapes include two extreme cases, a continuous meadow and a bare landscape, along with intermediate states that range from the occurrence of persistent but isolated fairy circles, or solitons, to seascapes with multiple fairy circles, banded vegetation, and "leopard skin" patterns consisting of bare seascapes dotted with plant patches. The model predicts that these intermediate seascapes extending across kilometers emerge as a consequence of local demographic imbalances along with facilitative and competitive interactions among the plants with a characteristic spatial scale of 20 to 30 m, consistent with known drivers of seagrass performance. The model, which can be extended to clonal growth plants in other landscapes showing fairy rings, reveals that the different seascapes observed hold diagnostic power as to the proximity of seagrass meadows to extinction points that can be used to identify ecosystems at risks.

Scattering properties and internal structure of magnetic filament brushes.

Practical applications of polymer brush-like systems rely on a clear understanding of their internal structure. In the case of magnetic nanoparticle filament brushes, the competition between bonding and nonbonding interactions-including long range magnetic dipole-dipole interactions-makes the microstructure of these polymer brush-like systems rather complex. On the other hand, the same interactions open up the possibility to manipulate the meso- and macroscopic responses of these systems by applying external magnetic fields or by changing the background temperature. In this study, we put forward an approach to extract information about the internal structure of a magnetic filament brush from scattering experiments. Our method is based on the mapping of the scattering profiles to the information about the internal equilibrium configurations of the brushes obtained from computer simulations. We show that the structure of the magnetic filament brush is strongly anisotropic in the direction perpendicular to the grafting surface, especially at low temperatures and external fields. This makes slice-by-slice scattering measurements a technique very useful for the study of such systems.

The behavior of a magnetic filament in flow under the influence of an external magnetic field.

We present an extensive numerical study of the behaviour of a filament made of ferromagnetic colloidal particles subjected to the simultaneous action of a fluid flow and a stationary external magnetic field perpendicular to the flow lines. We found that in the presence of a shear flow, the tumbling motion observed at zero field is strongly inhibited when the external magnetic field is applied. The field is able to stabilise the filament with a well defined degree of alignment that depends on the balance between hydrodynamic and magnetic torques. In addition, for a Poiseuille flow, it has been found that the initial position has a long lasting influence on the behaviour of the magnetic filament when the external field is applied.

Flexible magnetic filaments under the influence of external magnetic fields in the limit of infinite dilution.

In the present work we use Langevin dynamics computer simulations to understand how the presence of a constant external magnetic field modifies the conformational phase diagram of magnetic filaments in the limit of infinite dilution. We have considered the filaments immersed in either a good (non-sticky filaments) or a poor (Stockmayer polymers) solvent. It has been found that in the presence of an applied field, filaments turn out to be much more susceptible to parameters such as temperature and solvent conditions. Filaments owe this increased susceptibility to the fact that the external magnetic field tends to level the free energy landscape as compared to the zero-field case. The field induces equalization in the free energy of competing conformational states that were separated by large energy differences in the zero-field limit. In this new scenario multistability arises, and manifests itself in the existence of broad regions in the phase diagram where two or more equilibrium configurations coexist. The existence of multistability greatly enhances the possibility of tuning the properties of the filament.

Magnetic filament brushes: tuning the properties of a magnetoresponsive supracolloidal coating.

We present a theoretical study on the design of a supramolecular magnetoresponsive coating. The coating is formed by a relatively dense array of supracolloidal magnetic filaments grafted to a surface in a polymer brush-like arrangement. In order to determine and optimise the properties of the magnetic filament brush, we perform extensive computer simulations with a coarse-grained model that takes into account the correlations between the magnetic moments of the particles and the backbone crosslinks. We show that the self-assembly of magnetic beads from neighbouring filaments defines the equilibrium structural properties of the complete brush. In order to control this self-assembly, we highlight two external stimuli that can lead to significant effects: temperature of the system and an externally applied magnetic field. Our study reveals self-assembly scenarios inherently driven by the crosslinking and grafting constraints. Finally, we explain the mechanisms of structural changeovers in the magnetic filament brushes and confirm the possibility of controlling them by changing the temperature or the intensity of an external magnetic field.

Supramolecular Magnetic Brushes: The Impact of Dipolar Interactions on the Equilibrium Structure.

The equilibrium structure of supramolecular magnetic filament brushes is analyzed at two different scales. First, we study the density and height distributions for brushes with various grafting densities and chain lengths. We use Langevin dynamics simulations with a bead-spring model that takes into account the cross-links between the surface of the ferromagnetic particles, whose magnetization is characterized by a point dipole. Magnetic filament brushes are shown to be more compact near the substrate than nonmagnetic ones, with a bimodal height distribution for large grafting densities. This latter feature makes them also different from brushes with electric dipoles. Next, in order to explain the observed behavior at the filament scale, we introduce a graph theory analysis to elucidate for the first time the structure of the brush at the scale of individual beads. It turns out that, in contrast to nonmagnetic brushes, in which the internal structure is determined by random density fluctuations, magnetic forces introduce a certain order in the system. Because of their highly directional nature, magnetic dipolar interactions prevent some of the random connections to be formed. On the other hand, they favor a higher connectivity of the chains' free and grafted ends. We show that this complex dipolar brush microstructure has a strong impact on the magnetic response of the brush, as any weak applied field has to compete with the dipole-dipole interactions within the crowded environment.

The effect of links on the interparticle dipolar correlations in supramolecular magnetic filaments.

We present a combined computational and analytical study of supramolecular magnetic filaments, i.e., permanently linked chains of ferromagnetic nanocolloids. We put forward two different models for the interparticle connectivity within the chain. In the first model, the magnetic dipoles of the particles are free to rotate independently from the permanent links. The second model penalises the misalignment of the dipoles by coupling their orientations to the chain backbone. We show that the effect of the long-range magnetic dipolar interactions on the zero field net magnetic moment of the chain becomes less significant in the second case. However, the overall magnetic response in the model of freely rotating dipoles is much weaker.

Effects of the dipolar interaction on the equilibrium morphologies of a single supramolecular magnetic filament in bulk.

We study the equilibrium morphologies of a single supramolecular magnetic filament in a three-dimensional system as a function of the effective strength of the magnetic dipolar interactions. The study is performed by means of Langevin dynamics simulations with a bead-spring chain model of freely rotating dipoles. We demonstrate the existence of three structural regimes as the value of the dipolar coupling parameter is increased: a coil compaction regime, a coil expansion regime, and a closed chain regime in which the structures tend progressively to an ideal ring configuration. We discuss the governing effects of each regime, the structural transition between open and closed morphologies, and the reasons why we see no multiloop configurations that have been observed in two-dimensional systems under similar conditions.

Implications of extreme life span in clonal organisms: millenary clones in meadows of the threatened seagrass Posidonia oceanica.

The maximum size and age that clonal organisms can reach remains poorly known, although we do know that the largest natural clones can extend over hundreds or thousands of metres and potentially live for centuries. We made a review of findings to date, which reveal that the maximum clone age and size estimates reported in the literature are typically limited by the scale of sampling, and may grossly underestimate the maximum age and size of clonal organisms. A case study presented here shows the occurrence of clones of slow-growing marine angiosperm Posidonia oceanica at spatial scales ranging from metres to hundreds of kilometres, using microsatellites on 1544 sampling units from a total of 40 locations across the Mediterranean Sea. This analysis revealed the presence, with a prevalence of 3.5 to 8.9%, of very large clones spreading over one to several (up to 15) kilometres at the different locations. Using estimates from field studies and models of the clonal growth of P. oceanica, we estimated these large clones to be hundreds to thousands of years old, suggesting the evolution of general purpose genotypes with large phenotypic plasticity in this species. These results, obtained combining genetics, demography and model-based calculations, question present knowledge and understanding of the spreading capacity and life span of plant clones. These findings call for further research on these life history traits associated with clonality, considering their possible ecological and evolutionary implications.

Ice polyamorphism in the minimal Mercedes-Benz model of water.

We investigate ice polyamorphism in the context of the two-dimensional Mercedes-Benz model of water. We find a first-order phase transition between a crystalline phase and a high-density amorphous phase. Furthermore, we find a reversible transformation between two amorphous structures of high and low density; however, we find this to be a continuous and not an abrupt transition, as the low-density amorphous phase does not show structural stability. We discuss the origin of this behavior and its implications with regard to the minimal generic modeling of polyamorphism.

Influence of microstructure on the transitions between mesoscopic thin-film morphologies in ballistic-diffusive models.

We study the influence of the symmetries of competing microstructures on the emergence of different mesoscopic morphologies in the growth by vapor deposition of thin solid films. We show the results of numerical simulations in (1+1) - and (2+1) -dimensional systems including different microstructures, as well as thermally activated surface diffusion in combination with a ballistic algorithm to model the deposition process. We focus on the characterization of the transitional structures that appear in the empirical structure zone model (SZM) through the evaluation of the mean packing density and the mean coordination number. We show that the maximum coordination number of the underlying microstructure classifies the statistics of the transitional morphologies at the border between zone I in the SZM, characterized by the formation of fractal-like patterns, and zone II, where pronounced faceting develops. We analyze the appearance of lattice frustration and texture competition effects in complex microstructures having mutually exclusive symmetries.

Spherical brushes within spherical cavities: a self-consistent field and Monte Carlo study.

We present an extensive numerical study on the behavior of spherical brushes confined into a spherical cavity. Self-consistent field (SCF) and off-lattice Monte Carlo (MC) techniques are used in order to determine the monomer and end-chain density profiles and the cavity pressure as a function of the brush properties. A comparison of the results obtained via SCF, MC, and the Flory theory for polymer solutions reveals SCF calculations to be a valuable alternative to MC simulations in the case of free and softly compressed brushes, while the Flory's theory accounts remarkably well for the pressure in the strongly compressed regime. In the range of high compressions, we have found the cavity pressure P to follow a scale relationship with the monomer volume fraction v, P approximately v(alpha). SCF calculations give alpha=2.15+/-0.05, whereas MC simulations lead to alpha=2.73+/-0.04. The underestimation of alpha by the SCF method is explained in terms of the inappropriate account of the monomer density correlations when a mean field approach is used.

Shear effects on crystal nucleation in colloidal suspensions.

Extensive two-dimensional Langevin dynamics simulations are used to determine the effect of steady shear flows on the crystal nucleation kinetics of charge stabilized colloids and colloids whose pair potential possess an attractive shallow well of a few k_{B}T 's (attractive colloids). Results show that in both types of systems small amounts of shear speeds up the crystallization process and enhances the quality of the growing crystal significantly. Moderate shear rates, on the other hand, destroy the ordering in the system. The very high shear rate regime where a reentering transition to the ordered state could exist is not considered in this work. In addition to the crystal nucleation phenomena, the analysis of the transport properties and the characterization of the steady state regime under shear are performed.

Stiff polymer adsorption. Onset to pattern recognition.

We present the results of extensive off-lattice Monte-Carlo simulations of a stiff polymer chain adsorbing onto a sticky periodic stripe-like pattern of variable width. We have analyzed, in terms of the chain length and rigidity, the adsorption and the pattern recognition process as a function of the stripe width. We have seen that this process is twofold: (i) the chain adsorbs rather isotropically onto the surface at a characteristic temperature T(c) and (ii) a further reduction in the temperature is needed for the chain to reorganize and adjust to the specific pattern. Such polymer reorganization has been studied through the evaluation of the chain degree of stretching and asphericity. We have found an optimal stripe width that maximizes the stretching. We have introduced a criteria to estimate the characteristic temperature at which the pattern recognition takes place T(r)