Adhesion dynamics of functionalized nanocarriers to endothelial cells: a dissipative particle dynamics study.

Targeted drug delivery to endothelial cells utilizing functionalized nanocarriers (NCs) is an essential procedure in therapeutic and diagnosis therapies. Using dissipative particle dynamics simulation, NCs have been designed and combined with an endothelial environment, such as the endothelial glycocalyx (EG) layer, receptors, water, and cell wall. Furthermore, the energy landscapes of the functionalized NC with the endothelial cell have been analyzed as a function of properties such as the shape, size, initial orientation, and ligand density of NCs. Our results show that an appropriate higher ligand density for each particular NC provides more driving forces than barriers for the penetration of the NCs. Herein we report the importance of shell entropy loss for the NC shape effect on the adhesion and penetration into the EG layer. Moreover, the rotation of the disc shape NC as a wheel during the penetration is an extra driving force for its further inclusion. By increasing the NCs' size larger than the appropriate size for each particular ligand density, due to an increase in the NCs' shell entropy loss, the barriers surpass the driving forces for NC penetration. Furthermore, the parallel orientation provides the NCs with the best penetration capabilities. However, the rotation of the disc shape NCs enhances their diffusion in the perpendicular orientation too. Overall, our findings highlight the crucial role of the shell entropy loss in governing the penetration of NCs. Besides, studying NCs with a homogeneous ligand composition enabled us to cross barriers and probe energetics after the complete inclusion of the NCs.

Dynamic Interfacial Trapping of Janus Nanorod Aggregates.

Taking advantage of both shape and chemical anisotropy on the same nanoparticle offers rich self-assembly possibilities for nanotechnology. Through dissipative particle dynamics calculations, in the present work, the directed assembly of Janus nanorod aggregates and their capability to assemble into metastable novel structures at an interfacial level have been assessed. Symmetric Janus rods become kinetically trapped and exhibit either parallel or antiparallel alignment with respect to their long axis (different compositions). This depends on several factors that have been mapped herein and that can be precisely tuned: Flory-Huggins interaction parameter χ between polymer phases; concentration; shear rate; and even aggregate shape. Ultimately, two different aggregate structures result from rod tumbling that are not observed under quiescent conditions: monolayer-like aggregates exhibiting trapped rods with antiparallel configuration; and stacked nanorod arrays similar to superlattice sheets. These different structures can be controlled by the likelihood with which tumbling Janus rods encounter other aggregate portions showing parallel alignment. Hence, the present study offers fundamental insight into relevant parameters that govern the directed assembly of Janus nanoparticles at an interfacial level. Novel applications may potentially derive from the resulting aggregate structures, such as peculiar displays and sensors.

Slip and momentum transfer mechanisms mediated by Janus rods at polymer interfaces.

As an incipient but preeminent technology for multiphase nanomaterials/fluids, exact compatibilizing mechanisms of Janus particles in polymer blends and the consequent morphology remain unknown. The contributions of Janus nanorods to slip suppression and momentum transfer across the interface have been explored through dissipative particle dynamics simulations under shear flow at unentangled polymer-polymer interfaces. Rods have been then grafted with flexible polymer chains to unveil interfacial structure-property relationships at a molecular level when compared with flexible diblock copolymer surfactants. When Janus rods are sparsely grafted with necessarily longer grafts, they favor a greater degree of graft interpenetration with polymer phases. This yields less effective momentum transfer that impacts droplet coalescence processes; dynamic heterogeneities at complex interfaces; and helps map their efficiency as compatibilizers.

Polymer-mediated nanorod self-assembly predicted by dissipative particle dynamics simulations.

Self-assembly of nanoparticles in polymer matrices is an interesting and growing subject in the field of nanoscience and technology. We report herein on modelling studies of the self-assembly and phase behavior of nanorods in a homopolymer matrix, with the specific goal of evaluating the role of deterministic entropic and enthalpic factors that control the aggregation/dispersion in such systems. Grafting polymer brushes from the nanorods is one approach to control/impact their self-assembly capabilities within a polymer matrix. From an energetic point of view, miscible interactions between the brush and the matrix are required for achieving a better dispersibility; however, grafting density and brush length are the two important parameters in dictating the morphology. Unlike in previous computational studies, the present Dissipative Particle Dynamics (DPD) simulation framework is able to both predict dispersion or aggregation of nanorods and determine the self-assembled structure, allowing for the determination of a phase diagram, which takes all of these factors into account. Three types of morphologies are predicted: dispersion, aggregation and partial aggregation. Moreover, favorable enthalpic interactions between the brush and the matrix are found to be essential for expanding the window for achieving a well-dispersed morphology. A three-dimensional phase diagram is mapped on which all the afore-mentioned parameters are taken into account. Additionally, in the case of immiscibility between brushes and the matrix, simulations predict the formation of some new and tunable structures.

Generalized mapping of multi-body dissipative particle dynamics onto fluid compressibility and the Flory-Huggins theory.

In this work, a generalized relation between the fluid compressibility, the Flory-Huggins interaction parameter (χ), and the simulation parameters in multi-body dissipative particle dynamics (MDPD) is established. This required revisiting the MDPD equation of state previously reported in the literature and developing general relationships between the parameters used in the MDPD model. We derive a relationship to the Flory-Huggins χ parameter for incompressible fluids similar to the work previously done in dissipative particle dynamics by Groot and Warren. The accuracy of this relationship is evaluated using phase separation in small molecules and the solubility of polymers in dilute solvent solutions via monitoring the scaling of the radius of gyration (Rg) for different solvent qualities. Finally, the dynamics of the MDPD fluid is studied with respect to the diffusion coefficient and the zero shear viscosity.

The Lowe-Andersen thermostat as an alternative to the dissipative particle dynamics in the mesoscopic simulation of entangled polymers.

Dissipative Particle Dynamics (DPD) has shown a great potential in studying the dynamics and rheological properties of soft matter; however, it is associated with deficiencies in describing the characteristics of entangled polymer melts. DPD deficiencies are usually correlated to the time integrating method and the unphysical bond crossings due to utilization of soft potentials. One shortcoming of DPD thermostat is the inability to produce real values of Schmidt number for fluids. In order to overcome this, an alternative Lowe-Anderson (LA) method, which successfully stabilizes the temperature, is used in the present work. Additionally, a segmental repulsive potential was introduced to avoid unphysical bond crossings. The performance of the method in simulating polymer systems is discussed by monitoring the static and dynamic characteristics of polymer chains and the results from the LA method are compared to standard DPD simulations. The performance of the model is evaluated on capturing the main shear flow properties of entangled polymer systems. Finally the linear and nonlinear viscoelastic properties of such systems are discussed.

Biomimetic Reversible Heat-Stiffening Polymer Nanocomposites.

Inspired by the ability of the sea cucumber to (reversibly) increase the stiffness of its dermis upon exposure to a stimulus, we herein report a stimuli-responsive nanocomposite that can reversibly increase its stiffness upon exposure to warm water. Nanocomposites composed of cellulose nanocrystals (CNCs) that are grafted with a lower critical solution temperature (LCST) polymer embedded within a poly(vinyl acetate) (PVAc) matrix show a dramatic increase in modulus, for example, from 1 to 350 MPa upon exposure to warm water, the hypothesis being that grafting the polymers from the CNCs disrupts the interactions between the nanofibers and minimizes the mechanical reinforcement of the film. However, exposure to water above the LCST leads to the collapse of the polymer chains and subsequent stiffening of the nanocomposite as a result of the enhanced CNC interactions. Backing up this hypothesis are energy conserving dissipative particle dynamics (EDPD) simulations which show that the attractive interactions between CNCs are switched on upon the temperature-induced collapse of the grafted polymer chains, resulting in the formation of a percolating reinforcing network.