RESUMEN

Singlet fission and triplet-triplet annihilation upconversion are two multiexciton processes intimately related to the dynamic interaction between one high-lying energy singlet and two low-lying energy triplet excitons. Here, we introduce a series of dendritic macromolecules that serve as platform to study the effect of interchromophore interactions on the dynamics of multiexciton generation and decay as a function of dendrimer generation. The dendrimers (generations 1-4) consist of trimethylolpropane core and 2,2-bis(methylol)propionic acid (bis-MPA) dendrons that provide exponential growth of the branches, leading to a corona decorated with pentacenes for SF or anthracenes for TTA-UC. The findings reveal a trend where a few highly ordered sites emerge as the dendrimer generation grows, dominating the multiexciton dynamics, as deduced from optical spectra, and transient absorption spectroscopy. While the dendritic structures enhance TTA-UC at low annihilator concentrations in the largest dendrimers, the paired chromophore interactions induce a broadened and red-shifted excimer emission. In SF dendrimers of higher generations, the triplet dynamics become increasingly dominated by pairwise sites exhibiting strong coupling (Type II), which can be readily distinguished from sites with weaker coupling (Type I) by their spectral dynamics and decay kinetics.

RESUMEN

Singlet fission has emerged as a key mechanism of exciton multiplication in organic chromophores, generating two triplet excitons from a single photon. Singlet fission is typically studied in crystalline films or in isolated dimers. Here, we investigate an intermediate regime where through-space interactions mediate singlet fission and triplet pair recombination within isolated polymer chains. Specifically, we investigate how appending pentacenes to a polynorbornene backbone can lead to macromolecules that take advantage of through-space π-π interactions for fast singlet fission and rapid triplet pair dissociation. Singlet fission in these systems is affected by molecular dynamics, and triplet-triplet recombination is a geminate process where the rate of recombination scales with molecular-weight. We find that these pendent pentacene polymers yield free triplets with lifetimes that surpass those of crystalline chromophores in both solution as isolated polymers and in thin films.

RESUMEN

Here, we describe a method for the enhanced self-assembly of triblock Janus colloids targeted to form a kagome lattice. Using computer simulations, we demonstrate that the formation of this elusive structure can be significantly improved by self-propelling or activating the colloids along the axis connecting their hydrophobic hemispheres. The process by which metastable aggregates are destabilized and transformed into the favored kagome lattice is quite general, and we argue this active approach provides a systematic pathway to improving the self-assembly of a large number of colloidal structures.

Asunto(s)

RESUMEN

Colloids grafted with a corona layer of polymers show glassy behavior that covers a wide range of fragilities, with this behavior being tunable through variations in grafting density and grafting chain length. We find that the corona roughness, which is maximized for long chain lengths and sparse grafting, is directly correlated to the concentration-dependence of the system relaxation time (fragility). Relatively rougher colloids result in stronger liquids because their rotational motions become orientationally correlated across the whole system even at low particle loadings leading to an essentially Arrhenius-like concentration-dependence of the relaxation times near the glass transition. The smoother colloids do not show as much orientational correlation except at higher densities leading to fragile behavior. We therefore propose that these materials are an ideal model to study the physical properties of the glass transition.

RESUMEN

In this review, we discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field, with a specific focus on dry active matter. We explore this phenomenology through the lens of the complexity of the colloidal building blocks. We begin by considering the behavior of isotropic spherical particles. We then discuss the case of amphiphilic and dipolar Janus particles. Finally, we show how the geometry of the colloids and/or the directionality of their interactions can be used to control the physical properties of the assembled active aggregates, and we suggest possible strategies for how to exploit activity as a tunable driving force for self-assembly. The unique properties of active colloids lend promise to the design of the next generation of functional, environment-sensing microstructures able to perform specific tasks in an autonomous and targeted manner.

RESUMEN

We explore the synthesis and photophysics of nanostructured block copolymers that mimic light-harvesting complexes. We find that the combination of a polar and electron-rich boron dipyrromethene (BODIPY) block with a nonpolar electron-poor perylene diimide (PDI) block yields a polymer that self-assembles into ordered "nanoworms". Numerical simulations are used to determine optimal compositions to achieve robust self-assembly. Photoluminescence spectroscopy is used to probe the rich exciton dynamics in these systems. Using controls, such as homopolymers and random copolymers, we analyze the mechanisms of the photoluminescence from these polymers. This understanding allows us to probe in detail the photophysics of the block copolymers, including the effects of their self-assembly into nanostructures on their excited-state properties. Similar to natural systems, ordered nanostructures result in properties that are starkly different than the properties of free polymers in solution, such as enhanced rates of electronic energy transfer and elimination of excitonic emission from disordered PDI trap states.

RESUMEN

Amphiphilic Janus particles self-assemble into complex metastructures, but little is known about how their assembly might be modified by weak interactions with a nearby biological membrane surface. Here, we report an integrated experimental and molecular dynamics simulation study to investigate the self-assembly of amphiphilic Janus particles on a lipid membrane. We created an experimental system in which Janus particles are allowed to self-assemble in the same medium where zwitterionic lipids form giant unilamellar vesicles (GUVs). Janus particles spontaneously concentrated on the inner leaflet of the GUVs. They exhibited biased orientation and heterogeneous rotational dynamics as revealed by single particle rotational tracking. The combined experimental and simulation results show that Janus particles concentrate on the lipid membranes due to weak particle-lipid attraction, whereas the biased orientation of particles is driven predominantly by inter-particle interactions. This study demonstrates the potential of using lipid membranes to influence the self-assembly of Janus particles.

Asunto(s)

RESUMEN

We establish a quantitative analogy between polymer grafted nanoparticles (PGNPs) and patchy nanoparticles (NPs). Over much of the experimentally relevant parameter space, we show that PGNPs behave quantitatively like Janus NPs, with the patch size having a universal dependence on the number of grafts and the ratio of the size of the NPs to the grafted chain size. The widely observed anisotropic self-assembly of PGNP into superstructures can thus be understood through simple geometric considerations of single patch models, in the same spirit as the geometry-based surfactant models of Israelachvili.

RESUMEN

We demonstrate that the self-assembly of spherical nanoparticles (NPs), grafted isotropically with polymeric ligands, into anisotropic structures is a manifestation of the fluctuations inherent in small number statistics. Computer simulations show that the organization of ligand atoms around an individual NP is not spatially isotropic for small numbers of grafts and ligand monomers. This inherent, spatially asymmetric ligand distribution causes the effective, two-body inter-NP potential to have a strong orientational dependence, which reproduces the anisotropic assembly observed ubiquitously for these systems. In contrast, ignoring this angular dependence does not permit us to capture NP self-assembly. This idea of fluctuation-driven behavior should be broadly relevant, and, for example, it should be important for the assembly of ligand-decorated quantum dots into arrays.

RESUMEN

We report numerical simulations of membrane tubulation driven by large colloidal particles. Using Monte Carlo simulations we study how the process depends on particle size and binding strength, and present accurate free energy calculations to sort out how tube formation compares with the competing budding process. We find that tube formation is a result of the collective behavior of the particles adhering on the surface, and it occurs for binding strengths that are smaller than those required for budding. We also find that long linear aggregates of particles forming on the membrane surface act as nucleation seeds for tubulation by lowering the free energy barrier associated to the process.

Asunto(s)

RESUMEN

Using computer simulations, we show that lipid membranes can mediate linear aggregation of spherical nanoparticles binding to it for a wide range of biologically relevant bending rigidities. This result is in net contrast with the isotropic aggregation of nanoparticles on fluid interfaces or the expected clustering of isotropic insertions in biological membranes. We present a phase diagram indicating where linear aggregation is expected and compute explicitly the free-energy barriers associated with linear and isotropic aggregation. Finally, we provide simple scaling arguments to explain this phenomenology.

Asunto(s)

RESUMEN

Elastic sheets with macroscopic dimensions are easy to deform by bending and stretching. Yet shaping nanometric sheets by mechanical manipulation is hard. Here we show that nanoparticle self-assembly could be used to this end. We demonstrate that spherical nanoparticles adhering to the outer surface of an elastic nanotube can self-assemble into linear structures: rings or helices on stretchable nanotubes, and axial strings on nanotubes with high rigidity to stretching. These self-assembled structures are inextricably linked to a variety of deformed nanotube profiles, which can be controlled by tuning the concentration of nanoparticles, the nanoparticle-nanotube diameter ratio and the elastic properties of the nanotube. Our results open the possibility of designing nanoparticle-laden tubular nanostructures with tailored shapes, for potential applications in materials science and nanomedicine.

RESUMEN

We use numerical simulations to study the phase behavior of a system of purely repulsive soft dumbbells as a function of size ratio of the two components and their relative degree of deformability. We find a plethora of different phases, which includes most of the mesophases observed in self-assembly of block copolymers but also crystalline structures formed by asymmetric, hard binary mixtures. Our results detail the phenomenological behavior of these systems when softness is introduced in terms of two different classes of interparticle interactions: (a) the elastic Hertz potential, which has a finite energy cost for complete overlap of any two components, and (b) a generic power-law repulsion with tunable exponent. We discuss how simple geometric arguments can be used to account for the large structural variety observed in these systems and detail the similarities and differences in the phase behavior for the two classes of potentials under consideration.

RESUMEN

How accurate is pair additivity in describing interactions between soft polymer-based nanoparticles? Using numerical simulations we compute the free energy cost required to overlap multiple chains in the same region of space, and provide a quantitative measure of the effectiveness of pair additivity as a function of chain number and length. Our data suggest that pair additivity can indeed become quite inadequate as the chain density in the overlapping region increases. We also show that even a scaling theory based on polymer confinement can only partially account for the complexity of the problem. In fact, we unveil and characterize an isotropic to star-polymer crossover taking place for large number of chains, and propose a revised scaling theory that better captures the physics of the problem.

RESUMEN

We use computer simulations to investigate the stability of a two-component polymer brush de-mixing on a curved template into phases of different morphological properties. It has been previously shown via molecular dynamics simulations that immiscible chains having different length and anchored to a cylindrical template will phase separate into stripes of different widths oriented perpendicularly to the cylindrical axis. We calculate free energy differences for a variety of stripe widths, and extract simple relationships between the sizes of the two polymers, N(1) and N(2), and the free energy dependence on the stripe width. We explain these relationships using simple physical arguments based upon previous theoretical work on the free energy of polymer brushes.

RESUMEN

In this paper we introduce a new method to design interparticle interactions to target arbitrary crystal structures via the process of self-assembly. We show that it is possible to exploit the slope of the crystal nucleation free-energy barrier to sample and select optimal interparticle interactions for self-assembly into a desired structure. We apply this method to find interactions to target two simple crystal structures: a crystal with simple cubic symmetry and a two-dimensional plane with square symmetry embedded in a three-dimensional space. Finally, we discuss the potential and limits of our method and propose a general model by which a functionally infinite number of different interaction geometries may be constructed and to which our reverse self-assembly method could in principle be applied.

RESUMEN

We use numerical simulations to understand how random deviations from the ideal spherical shape affect the ability of hard particles to form fcc crystalline structures. Using a system of hard spheres as a reference, we determine the fluid-solid coexistence pressures of both shape-polydisperse and monodisperse systems of aspherical hard particles. We find that when particles are sufficiently isotropic, the coexistence pressure can be predicted from a linear relation involving the product of two simple geometric parameters characterizing the asphericity of the particles. Finally, our results allow us to gain direct insight into the crystallizability limits of these systems by rationalizing empirical data obtained for analogous monodisperse systems.

RESUMEN

We use numerical simulations to show how a fully flexible filament binding to a deformable cylindrical surface may acquire a macroscopic persistence length and a helical conformation. This is a result of the nontrivial elastic response to deformations of elastic sheets. We find that the filament's helical pitch is completely determined by the mechanical properties of the surface, and can be easily tuned by varying the surface stretching rigidity. We propose simple scaling arguments to understand the physical mechanism behind this phenomenon and present a phase diagram indicating under what conditions one should expect a fully flexible chain to behave as a helical semiflexible filament. Finally, we discuss the implications of our results.

Asunto(s)

RESUMEN

We use numerical simulations to study the crystallization of monodisperse systems of hard aspherical particles. We find that particle shape and crystallizability can be easily related to each other when particles are characterized in terms of two simple and experimentally accessible order parameters: one based on the particle surface-to-volume ratio and the other on the angular distribution of the perturbations away from the ideal spherical shape. We present a phase diagram obtained by exploring the crystallizability of 487 different particle shapes across the two-order-parameter spectrum. Finally, we consider the physical properties of the crystalline structures accessible to aspherical particles and discuss limits and relevance of our results.

RESUMEN

We report molecular dynamics simulations of a system of repulsive, polymer-tethered colloidal particles. We use an explicit polymer model to explore how the length and the behavior of the polymer (ideal or self-avoiding) affect the ability of the particles to organize into ordered structures when the system is compressed to moderate volume fractions. We find a variety of different phases whose origin can be explained in terms of the configurational entropy of polymers and colloids. Finally, we discuss and compare our results to those obtained for similar systems using simplified coarse-grained polymer models, and set the limits of their applicability.

Asunto(s)