Protein corona composition of poly(ethylene glycol)- and poly(phosphoester)-coated nanoparticles correlates strongly with the amino acid composition of the protein surface

Extensive molecular dynamics simulations reveal that the interactions between proteins and poly(ethylene glycol) (PEG) can be described in terms of the surface composition of the proteins. PEG molecules accumulate around non-polar residues while avoiding the polar ones. A solvent-accessible-surface-area model of protein adsorption accurately fits a large set of data on the composition of the protein corona of poly(ethylene glycol)- and poly(phosphoester)-coated nanoparticles recently obtained by label-free proteomic mass spectrometry.

Blood Proteins and Their Interactions with Nanoparticles Investigated Using Molecular Dynamics Simulations

Blood proteins play a fundamental role in determining the response of the organism to the injection of drugs or, more in general, of therapeutic preparations in the blood stream. Some of these proteins are responsible for mediating immune response and coagulation. Nanoparticles, which are being intensely investigated as possible drug nanocarriers, heavily interact with blood proteins and their ultimate fate is determined by these interactions. Here we report the results of molecular dynamics simulations of several blood proteins aimed to determining their possible behavior at the nanoparticle surface. On one hand we investigated the behavior of fibrinogen, a glycoprotein, which polymerizes …

Critical Micelle Concentration of Micelles with Different Geometries in Diblock Copolymer/Homopolymer Blends

Summary In this paper, we have investigated the shape transition ofanisolatedmicelleformedintheAB-diblockcopolymerandA-homopolymer blends. SCFT has been employed tocompute the CMC for three different morphologies:lamellar, cylindrical and spherical. By comparing theCMC for different shapes, we can determine the preferredmicelle geometry. Several factors can influence the micellemorphology,andwehaveexploredtheeffectsofthediblockasymmetry, the homopolymer/copolymer length ratio andthe monomer–monomer interaction, on the micelle shapetransitions. It is found the micelle undergoes a sequenceof shape transitions, lamellar ! cylindrical ! spherical,when the A-block of the copolymer becomes longer.…

Shear Modulus of an Irreversible Diblock Copolymer Network from Self-Consistent Field Theory

Using self-consistent field theory, we investigate the stretching-induced microphase separation in an irreversibly cross-linked polymer network composed of diblock copolymer chains and estimate its...

An efficient dissipative particle dynamics-based algorithm for simulating electrolyte solutions

We propose an efficient simulation algorithm based on the dissipative particle dynamics (DPD) method for studying electrohydrodynamic phenomena in electrolyte fluids. The fluid flow is mimicked with DPD particles while the evolution of the concentration of the ionic species is described using Brownian pseudo particles. The method is designed especially for systems with high salt concentrations, as explicit treatment of the salt ions becomes computationally expensive. For illustration, we apply the method to electro-osmotic flow over patterned, superhydrophobic surfaces. The results are in good agreement with recent theoretical predictions.

Elastic Properties and Line Tension of Self-Assembled Bilayer Membranes

The elastic properties of a self-assembled bilayer membrane are studied using the self-consistent field theory, applied to a model system composed of flexible amphiphilic chains dissolved in hydrophilic polymeric solvents. Examining the free energy of bilayer membranes with different geometries allows us to calculate their bending modulus, Gaussian modulus, two fourth-order membrane moduli, and the line tension. The dependence of these parameters on the microscopic characteristics of the amphiphilic chain, characterized by the volume fraction of the hydrophilic component, is systematically studied. The theoretical predictions are compared with the results from a simple monolayer model, whic…

Complex Formation between Polyelectrolytes and Oppositely Charged Oligoelectrolytes

We study the complex formation between one long polyanion chain and many short oligocation chains by computer simulations. We employ a coarse-grained bead-spring model for the polyelectrolyte chains, and model explicitly the small salt ions. We systematically vary the concentration and the length of the oligocation, and examine how the oligocations affects the chain conformation, the static structure factor, the radial and axial distribution of various charged species, and the number of bound ions in the complex. At low oligocation concentration, the polyanion has an extended structure. Upon increasing the oligocation concentration, the polyanion chain collapses and forms a compact globule,…

Flows and mixing in channels with misaligned superhydrophobic walls.

Aligned superhydrophobic surfaces with the same texture orientation reduce drag in the channel and generate secondary flows transverse to the direction of the applied pressure gradient. Here we show that a transverse shear can be easily generated by using superhydrophobic channels with misaligned textured surfaces. We propose a general theoretical approach to quantify this transverse flow by introducing the concept of an effective shear tensor. To illustrate its use, we present approximate theoretical solutions and Dissipative Particle Dynamics simulations for striped superhydrophobic channels. Our results demonstrate that the transverse shear leads to complex flow patterns, which provide a…

Computer simulations of single particles in external electric fields

Applying electric fields is an attractive way to control and manipulate single particles or molecules, e.g., in lab-on-a-chip devices. However, the response of nanosize objects in electrolyte solution to external fields is far from trivial. It is the result of a variety of dynamical processes taking place in the ion cloud surrounding charged particles and in the bulk electrolyte, and it is governed by an intricate interplay of electrostatic and hydrodynamic interactions. Already systems composed of one single particle in electrolyte solution exhibit a complex dynamical behaviour. In this review, we discuss recent coarse-grained simulations that have been performed to obtain a molecular-leve…

Interactions between proteins and poly(ethylene-glycol) investigated using molecular dynamics simulations

Poly(ethylene-glycol) (PEG) is a polymer used to coat therapeutic preparations, like drugs or drug nanocarriers, and improve their efficacy. This effect is probably due to a reduction of the interactions of the coated species with the host organism. Nevertheless, experiments show that PEGylated materials do interact with the surrounding biological milieu, and in particular with blood proteins. Here, we use atomistic molecular dynamics simulations to characterize the interactions between the polymer and several blood proteins. In these simulations, the proteins are immersed in a mixture of PEG and water molecules. We observe how PEG distributes around the protein surface and measure PEG-prot…

Application of Tunable-Slip Boundary Conditions in Particle-Based Simulations

Compared to macroscopic systems, fluids on the micro- and nanoscales have a larger surface-to-volume ratio, thus the boundary condition becomes crucial in determining the fluid properties. No-slip boundary condition has been applied successfully to wide ranges of macroscopic phenomena, but its validity in microscopic scale is questionable. A more realistic description is that the flow exhibits slippage at the surface, which can be characterized by a Navier slip length. We present a tunable-slip method by implementing Navier boundary condition in particle-based computer simulations (Dissipative Particle Dynamics as an example). To demonstrate the validity and versatility of our method, we ha…

Dielectric response of nanoscopic spherical colloids in alternating electric fields: a dissipative particle dynamics simulation.

We study the response of single nanosized spherical colloids in electrolyte solution to an alternating electric field (AC field) by computer simulations. We use a coarse-grained mesoscopic simulation approach that accounts in full for hydrodynamic and electrostatic interactions as well as for thermal fluctuations. The solvent is modeled as a fluid of single Dissipative Particle Dynamics (DPD) beads, and the colloidal particle is modeled as a rigid body made of DPD beads. We compute the mobility and the polarizability of a single colloid and investigate systematically the effect of amplitude and frequency of the AC-fields. Even though the thickness of the Debye layer is not "thin" compared t…

Solvent Determines Nature of Effective Interactions between Nanoparticles in Polymer Brushes

We study the effective interaction between two parallel rod-like nanoparticles in swollen and collapsed polymer brushes as a function of penetration depth by 2D self-consistent field calculations. In vertical direction, the interaction is always attractive. In lateral direction, the behavior under good and poor solvent conditions is qualitatively different. In swollen brushes (good solvent), nanoparticles always repel each other. In collapsed brushes (poor solvent), we identify two different regimes: an immersed regime, where the nanoparticles are fully surrounded by the brush, and an interfacial regime, where they are located in the interface between brush and solvent. In the immersed regi…

Tuning Transition Properties of Stimuli-Responsive Brushes by Polydispersity

Anisotropic flow in striped superhydrophobic channels

We report results of dissipative particle dynamics simulations and develop a semi-analytical theory of an anisotropic flow in a parallel-plate channel with two superhydrophobic striped walls. Our approach is valid for any local slip at the gas sectors and an arbitrary distance between the plates, ranging from a thick to a thin channel. It allows us to optimize area fractions, slip lengths, channel thickness and texture orientation to maximize a transverse flow. Our results may be useful for extracting effective slip tensors from global measurements, such as the permeability of a channel, in experiments or simulations, and may also find applications in passive microfluidic mixing.

The Influence of Block Ionomer Microstructure on Polyplex Properties: Can Simulations Help to Understand Differences in Transfection Efficiency?

Gene therapies enable therapeutic interventions at gene transcription and translation level, providing enormous potential to improve standards of care for multiple diseases. Nonviral transfection agents and in particular polyplexes based on block ionomers are-besides viral vectors and cationic lipid formulations-among the most promising systems for this purpose. Block ionomers combine a hydrophilic noncharged block, e.g., polyethylene glycol (PEG), with a hydrophilic cationic block. For efficient transfection, however, endosomolytic moieties, e.g., imidazoles, are additionally required to facilitate endosomal escape, which raises the general question how to distribute these functionalities …

Effective slippage on superhydrophobic trapezoidal grooves

We study the effective slippage on superhydrophobic grooves with trapezoidal cross-sections of various geometries (including the limiting cases of triangles and rectangular stripes), by using two complementary approaches. First, dissipative particle dynamics (DPD) simulations of a flow past such surfaces have been performed to validate an expression [E.S.Asmolov and O.I.Vinogradova, J. Fluid Mech. \textbf{706}, 108 (2012)] that relates the eigenvalues of the effective slip-length tensor for one-dimensional textures. Second, we propose theoretical estimates for the effective slip length and calculate it numerically by solving the Stokes equation based on a collocation method. The comparison …

A New Colloid Model for Dissipative-Particle-Dynamics Simulations

We propose a new model to simulate spherical colloids. This is a mesoscopic method based on the dissipative particle dynamics. The colloid is represented by a large spherical bead, and its surface interacts with the solvent beads through a pair of dissipative and stochastic forces. This new model extends the tunable-slip boundary condition [Eur. Phys. J. E 26, 115 (2008)] from planar surfaces to curved geometry, thus allows one to study colloids with slippery surfaces. Simulation results show good agreement with the prediction of hydrodynamic theories, indicating the hydrodynamic interactions are properly accounted in our new model.