Nanometer-sized clusters are often targeted due to their potential applications as nanoreactors or storage/delivery devices. One route to assemble and stabilize finite structures consists of imparting directional bonding patterns between the nanoparticles. When only a portion of the particle surface is able to form an inter-particle bond, finite-size aggregates such as micelles and vesicles may form.
View Article and Find Full Text PDFThe design of nano-functionalised membranes or channels, able to effectively adsorb pollutants in aqueous solutions, is a topic that is gaining a great deal of attention in the materials science community. With this work we explore, through a combination of scaling theories and molecular dynamics simulations, the adsorption of spherical non-deformable colloidal nanoparticles within planar polymeric brushes. Our strategy is twofold: first, we generalise the Alexander-de Gennes theory for planar homopolymeric brushes to the case of diblock copolymer brushes, then we map the adsorbing homopolymeric brushes onto a diblock copolymer system, where the adsorbed colloids and all interacting monomers are considered monomers in bad solvent and we apply the generalised scaling theory to this effective diblock copolymer.
View Article and Find Full Text PDFThe urgency to find complementary therapies to current SARS-CoV-2 vaccines, whose effectiveness is preserved over time and not compromised by the emergence of new and emerging variants, has become a critical health challenge. We investigate the possibility of jamming the opening of the Receptor Binding Domain (RBD) of the spike protein of SARS-CoV-2 with small compounds. Through in silico screening, we identified two potential candidates that would lock the Receptor Binding Domain (RBD) in a closed configuration, preventing the virus from infecting the host cells.
View Article and Find Full Text PDFThe rich and complex phase diagram typical of anisotropic biological or synthetic nanoparticles, has brought a great deal of interest over the equilibrium phase behaviour of non-spherical colloids. Amongst the class of anisotropic nanoparticles, hard spherocylindrical colloids have been, over the years, extensively studied because of their optical properties, for their rich phase diagrams, and their important industrial applications, as model particles for biological systems (viruses), or for example as potential drug carriers having the ability of surviving the attacks of the immune systems. As real anisotropic nanoparticles are often polydisperse in size and/or in shape, unveiling the effect of such a perturbation over their equilibrium phase diagram is of paramount importance.
View Article and Find Full Text PDFUnveiling a general law for adsorption within macromolecules sets an important step forward in the design of nanomaterials with tunable and controllable properties. Reaching such a generalised control would have an important outcome in a plethora of possible fields, from biomedical applications up to materials science. In fact, the definition of classes regrouping adsorbing macromolecules with different geometrical or chemical properties would enormously simplify the design of controllable adsorbing materials, especially when geometrical or chemical constraints are set by the particular application.
View Article and Find Full Text PDFBy means of multiscale molecular simulation, we show that solvophilic-solvophobic AB diblock copolymer brushes in the semi-dilute regime present a re-entrant disorder/order/disorder transition. The latter is fully controllable through two parameters: the grafting density and the solvophobic to solvophilic ratio of the tethered macromolecules. Upon increasing density, chains first aggregate into patches, then further order into a crystalline phase and finally melt into a disordered phase.
View Article and Find Full Text PDFWe study the adsorption properties in bottlebrush/colloid binary mixtures by combining scaling theories, theoretical predictions, self-consistent field computations (SCFC), and molecular dynamics simulations. In particular, we focus on adsorption in the case in which an attraction is set between the two species, by analysing the solution properties for a range of interactions and the size ratio between colloids and bottlebrushes, in the case in which colloids are smaller than the macromolecules. We show that the onset of adsorption is dominated by the local properties of the adsorbing guest particle.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2021
Herein, we show a comprehensive experimental, theoretical, and computational study aimed at designing macromolecules able to adsorb a cargo at the nanoscale. Specifically, we focus on the adsorption properties of star diblock copolymers, , macromolecules made by a number of diblock copolymer arms tethered on a central core; the monomeric heads, which are closer to the tethering point, are attractive toward a specific target, while the monomeric tails are neutral to the cargo. Experimentally, we exploited the adaptability of poly(2-oxazoline)s (POxs) to realize block copolymer-coated nanoparticles with a proper functionalization able to interact with heavy metals and show or exhibit a thermoresponsive behavior in aqueous solution.
View Article and Find Full Text PDFBottle brushes are polymeric macromolecules made of a linear polymeric backbone grafted with side chains. The choice of the grafting density σg, the length ns the grafted side chains and their chemical nature fully determines the properties of each macromolecule, such as its elasticity and its folding behaviour. Typically, experimental bottle brushes are systems made of tens of thousands of monomeric units, rendering a computational approach extremely expensive, especially in the case of bottle brush solutions.
View Article and Find Full Text PDFLimited bonding valence, usually accompanied by well-defined directional interactions and selective bonding mechanisms, is nowadays considered among the key ingredients to create complex structures with tailored properties: even though isotropically interacting units already guarantee access to a vast range of functional materials, anisotropic interactions can provide extra instructions to steer the assembly of specific architectures. The anisotropy of effective interactions gives rise to a wealth of self-assembled structures both in the realm of suitably synthesized nano- and micro-sized building blocks and in nature, where the isotropy of interactions is often a zero-th order description of the complicated reality. In this review, we span a vast range of systems characterized by limited bonding valence, from patchy colloids of new generation to polymer-based functionalized nanoparticles, DNA-based systems and proteins, and describe how the interaction patterns of the single building blocks can be designed to tailor the properties of the target final structures.
View Article and Find Full Text PDFSoft nanocomposites represent both a theoretical and an experimental challenge due to the high number of the microscopic constituents that strongly influence the behaviour of the systems. An effective theoretical description of such systems invokes a reduction of the degrees of freedom to be analysed, hence requiring the introduction of an efficient, quantitative, coarse-grained description. We here report on a novel coarse graining approach based on a set of transferable potentials that quantitatively reproduces properties of mixtures of linear and star-shaped homopolymeric nanocomposites.
View Article and Find Full Text PDFWe study the effective interactions and phase behavior of star polymer-colloid mixtures through theory and Monte Carlo simulations. We extend previous theoretical approaches for calculating the effective star-colloid pair potential to take into account attractive contributions, which become significant at worsening solvent conditions. In order to assess the validity of our simulation and theory, we compute the effective interactions via virtual move parallel tempering Monte Carlo simulations using a microscopic bead-spring model for the star polymer and achieve excellent agreement.
View Article and Find Full Text PDFThe fabrication of versatile building blocks that reliably self-assemble into desired ordered and disordered phases is amongst the hottest topics in contemporary materials science. To this end, microscopic units of varying complexity, aimed at assembling the target phases, have been thought, designed, investigated and built. Such a path usually requires laborious fabrication techniques, especially when specific functionalisation of the building blocks is required.
View Article and Find Full Text PDFWe present extensive experimental and theoretical investigations on the structure, phase behavior, dynamics and rheology of model soft-hard colloidal mixtures realized with large, multiarm star polymers as the soft component and smaller, compact stars as the hard one. The number and length of the arms in star polymers control their softness, whereas the size ratio, the overall density and the composition are additional parameters varied for the mixtures. A coarse-grained theoretical strategy is employed to predict the structure of the systems as well as their ergodicity properties on the basis of mode coupling theory, for comparison with rheological measurements on the samples.
View Article and Find Full Text PDFThe promising applications of core-shell nanoparticles in the biological and medical field have been well investigated in recent years. One remaining challenge is the characterization of the structure of the hydrated polymer shell. Here we use small-angle X-ray scattering (SAXS) to investigate iron oxide core-poly(ethylene glycol) brush shell nanoparticles with extremely high polymer grafting density.
View Article and Find Full Text PDFWe consider a novel class of patchy particles inspired by polymer-based complex units where the limited valence in bonding is accompanied by soft interactions and incessant fluctuations of the patch positions, possibly leading to reversible modifications of the patch number and size. We introduce a simple model that takes into account the aforementioned features and we focus on the role played by the patch flexibility on the self-organization of our patchy units in the bulk, with particular attention to the connectivity properties and the morphology of the aggregated networks.
View Article and Find Full Text PDFWe present a multi-scale molecular modeling of concentrated solutions of unknotted and non-concatenated ring polymers under good solvent conditions. The approach is based on a multi-blob representation of each ring polymer, which is capable of overcoming the shortcomings of single-blob approaches that lose their validity at concentrations exceeding the overlap density of the solution [A. Narros, A.
View Article and Find Full Text PDFBy employing rheological experiments, mode coupling theory, and computer simulations based on realistic coarse-grained models, we investigate the effects of small, hard colloids on the glassy states formed by large, soft colloids. Multiarm star polymers mimic hard and soft colloids by appropriately varying the number and size of their arms. The addition of hard colloids leads, depending on their concentration, to either melting of the soft glass or the emergence of two distinct glassy states.
View Article and Find Full Text PDFKnotted chains are a promising class of polymers with many applications for materials science and drug delivery. Here we introduce an experimentally realizable model for the design of chains with controllable topological properties. Recently, we have developed a systematic methodology to construct self-assembling chains of simple particles, with final structures fully controlled by the sequence of particles along the chain.
View Article and Find Full Text PDFBy means of multiscale molecular simulations, we show that telechelic-star polymers are a simple, robust, and tunable system, which hierarchically self-assembles into soft-patchy particles and mechanically stabilizes selected, open crystalline structures. The self-aggregating patchy behavior can be fully controlled by the number of arms per star and by the fraction of attractive monomeric units at the free ends of the arms. Such self-assembled soft-patchy particles while forming, upon augmenting density, gel-like percolating networks, preserve properties as particle size, number, and arrangement of patches per particle.
View Article and Find Full Text PDFWe consider mixtures of self-avoiding multiarm star polymers with hard colloids that are smaller than the star polymer size. By employing computer simulations, and by extending previous theoretical approaches, developed for the opposite limit of small star polymers [A. Jusufi et al.
View Article and Find Full Text PDFA systematic coarse-graining procedure is proposed for the description and simulation of AB diblock copolymers in selective solvents. Each block is represented by a small number, n(A) or n(B), of effective segments or blobs, containing a large number of microscopic monomers. n(A) and n(B) are unequivocally determined by imposing that blobs do not, on average, overlap, even if complete copolymer coils interpenetrate (semi-dilute regime).
View Article and Find Full Text PDFWe investigate the self-assembly of an athermal model of AB diblock copolymers into disordered and ordered micellar microphases. The original microscopic lattice model with ideal A strands and self-avoiding B strands is mapped onto a system of ultrasoft dumbbells, with monomer-averaged effective interactions between the centers of mass (CMs) of the two blocks. Extensive Monte Carlo simulations of this coarse-grained model are reported for several length ratios f = L(A)/(L(A) + L(B)) of the two strands of lengths L(A) and L(B).
View Article and Find Full Text PDFA coarse-grained effective segment description of polymer solutions is presented, based on soft, transferable effective interactions between bonded and nonbonded effective segments. The number of segments is chosen such that the segment density does not exceed their overlap threshold, allowing polymer concentrations to be explored deep into the semidilute regime. This quantitative effective segment description is shown to preserve known scaling laws of polymer solutions and provides accurate estimates of amplitudes, while leading to a orders-of-magnitude increase in the simulation efficiency and allowing analytic calculations of structural and thermodynamic properties.
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