Interfacial polar molecules feature a strongly anisotropic response to applied electric field, favoring dipole orientations parallel to the interface. In water, in particular, this effect combines with generic orientational preferences induced by spatial asymmetry of water hydrogen bonding under confined geometry, which may give rise to a Janus interface. The two effects manifest themselves in considerable dependence of water polarization on both the field direction relative to the interface, and the polarity (sign) of the field. Using molecular simulations, we demonstrate strong field-induced orientational forces acting on apolar surfaces through water mediation. At a field strength comparable to electric fields around a DNA polyion, the torques we predict to act on an adjacent nanoparticle are sufficient to overcome thermal fluctuations. These torques can align a particle with surface as small as 1 nm2. The mechanism can support electrically controlled ordering of suspended nanoparticles as a means of tuning their properties, and can find application in electro-nanomechanical devices.
Ordering nanoparticles into a desired super-structure is often crucial for their technological applications. We use molecular dynamics simulations to study the assembly of nanoparticles in a polymer brush randomly grafted to a planar surface as the solvent evaporates. Initially, the nanoparticles are dispersed in a solvent that wets the polymer brush. After the solvent evaporates, the nanoparticles are either inside the brush or adsorbed at the surface of the brush, depending on the strength of the nanoparticle-polymer interaction. For strong nanoparticle-polymer interactions, a 2-dimensional …
We investigate the solvent mediated interactions between nanoparticles adsorbed at a liquid-vapor interface in comparison to the solvent mediated interactions in the bulk liquid and vapor phases of a Lennard-Jones solvent. Molecular dynamics simulation data for the latter are in good agreement with results from integral equations in the reference functional approximation and a simple geometric approximation. Simulation results for the solvent mediated interactions at the interface differ markedly from the interactions of the particles in the corresponding bulk phases. We find that at short int…
The combinations of particle aspect ratio and enthalpic-barrier templates that lead to translational and orientational ordering of monolayers of rectangular particles are determined using Monte Carlo simulations and density functional theory. For sufficiently high enthalpic barriers, we find that only specific combinations of particle sizes and template spacings lead to ordered arrays. The pattern multiplication factor provided by the template extends to approximately ten times the smallest dimension of the particle.
Nanoscopic pores are used in various systems to attract nanoparticles. In general the behaviour is a result of two types of interactions: the material specific affinity and the solvent-mediated influence also called the depletion force. The latter is more universal but also much more complex to understand since it requires modeling both the nanoparticle and the solvent. Here, we employed classical density functional theory to determine the forces acting on a nanoparticle near a nanoscopic pore as a function of its hydrophobicity and its size. A simple capillary model is constructed to predict …
The controlled self-assembly of thiol stabilized gold nanocrystals in a mediating solvent and confined within mesoporous alumina was probed in situ with small angle x-ray scattering. The evolution of the self-assembly process was controlled reversibly via regulated changes in the amount of solvent condensed from an undersaturated vapor. Analysis indicated that the nanoparticles self-assembled into cylindrical monolayers within the porous template. Nanoparticle nearest-neighbor separation within the monolayer increased and the ordering decreased with the controlled addition of solvent. The proc…
In recent years significant attention has been attracted to proposals which utilize DNA for nanotechnological applications. Potential applications of these ideas range from the programmable self-assembly of colloidal crystals, to biosensors and nanoparticle based drug delivery platforms. In Chapter I we introduce the system, which generically consists of colloidal particles functionalized with specially designed DNA markers. The sequence of bases on the DNA markers determines the particle type. Due to the hybridization between complementary single-stranded DNA, specific, type-dependent interac…
Nanoparticles introduced in living cells are capable of strongly promoting the aggregation of peptides and proteins. We use here molecular dynamics simulations to characterise in detail the process by which nanoparticle surfaces catalyse the self- assembly of peptides into fibrillar structures. The simulation of a system of hundreds of peptides over the millisecond timescale enables us to show that the mechanism of aggregation involves a first phase in which small structurally disordered oligomers assemble onto the nanoparticle and a second phase in which they evolve into highly ordered beta-s…
Charge Regulation Mediated Interaction of Amphoteric Nanoparticle Surfaces
Indian Institute of Technology, Jodhpur（印度理工学院乔德普尔分校）；Université Grenoble Alpes, CNRS, Grenoble INP, 3SR（格勒诺布尔阿尔卑斯大学）；Vellore Institute of Technology（维洛尔理工大学）
Effective and controlled drug delivery systems with on-demand release and targeting abilities have received enormous attention for biomedical applications. Here, we describe a novel enzyme-based cap system for mesoporous silica nanoparticles (MSNs) that is directly combined with a targeting ligand via bio-orthogonal click chemistry. The capping system is based on the pH-responsive binding of an aryl-sulfonamide-functionalized MSN and the enzyme carbonic anhydrase (CA). An unnatural amino acid (UAA) containing a norbornene moiety was genetically incorporated into CA. This UAA allowed for the si…
Shearing of nanocomposites has shown to produce ordered nanostructures and orientation in the polymeric matrix. Due to the importance of the formation of an ordered structure of nanoparticles in a polymeric matrix to device wearable, flexible and photonic materials, its useful to get an insight of the shear-induced ordering and other properties of the polymeric nanocomposites. In this paper, we use a model Wormlike micellar matrix to study the arrangement and morphology of nanoparticles in the composite when the system is sheared using a hybrid multiparticle dynamics and molecular dynamics sim…
We present results of Brownian dynamics simulations of tethered nanospheres and tethered nanorods. Immiscibility between tether and nanoparticle facilitates microphase separation into the bicontinuous, double gyroid structure (first reported by Iacovella et al. [Phys. Rev. E 75 (2007)] and Horsch et al. [J. Chem. Phys. 125 (2006)] respectively). We demonstrate the ability of these nanoparticles to adopt distinct, minimal energy local packings, in which nanospheres form icosahedral-like clusters and nanorods form splayed hexagonal bundles. These local structures reduce packing frustration withi…
We present a new convenient and efficient "grafting from" method to obtain well defined polystyrene (PS) silica nanoparticles. The method, based on Nitroxide-Mediated Polymerization (NMP), consists to bind covalently the alkoxyamine, which acts as initiator controller agent, at the silica nanoparticles surface in two steps. The first step is a reaction between the aminopropylsilane and the silica particles in order to functionalize the particles surface with amino group. In a second step, the initiating-controlling alkoxyamine moiety is introduced via an over grafting reaction between the amin…
Charge Regulation Effect on Nanoparticles Interaction Mediated by Polyelectrolyte
Indian Institute of Technology Jodhpur（印度焦浦尔理工学院）；University of Chinese Academy of Sciences（中国科学院大学）；Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所）；University of Ljubljana（卢布尔雅那大学）
Orientational ordering driven by mechanical distortion of soft substrates plays a major role in material transformation processes such as elastocapillarity and surface anchoring. We present a theoretical model of the orientational response of anisotropic rods deposited onto a surface of a soft, elastic substrate of finite thickness. We show that anisotropic rods exhibit a continuous isotropic-nematic phase transition, driven by orientational interactions between surface deposited rods. This interaction is mediated by the deformation of the underlying elastic substrate, and is quantified by the…
The organization of nano-particles inside grafted polymer layers is governed by the interplay of polymer-induced entropic interactions and the action of externally applied fields. Earlier work had shown that strong external forces can drive the formation of colloidal structures in polymer brushes. Here we show that external fields are not essential to obtain such colloidal patterns: we report Monte Carlo and Molecular dynamics simulations that demonstrate that ordered structures can be achieved by compressing a `sandwich' of two grafted polymer layers, or by squeezing a coated nanotube, with n…
We study experimentally the impact of spherical nanoparticles on the orientational order parameters of a host nematic liquid crystal. We use spherical core-shell quantum dots that are surface functionalized to promote homeotropic anchoring on their interface with the liquid crystal host. We show experimentally that the orientational order may be strongly affected by the presence of spherical nanoparticles even at low concentrations. The orientational order of the composite system is probed by means of polarised micro-Raman spectroscopy and by optical birefringence measurements as function of t…
Internalization of particles by cells plays a crucial role for adsorbing nutrients and fighting infection. Endocytosis is one of the most important mechanisms of the particles uptake which encompass multiple pathways. Although endocytosis is a complex mechanism involving biochemical signaling and active force generation, the energetic cost associated to the large deformations of the cell membrane wrapping around the foreign particle is an important factor controlling this process, which can be studied using quantitative physical models. Of particular interest is the competition between membran…
Taking into account simultaneously the Vicsek short range ordering and also the far-field hydrodynamic interactions mediated by the ambient fluid, we investigate the role of long range interactions in the ordering phenomena in a quasi 2-dimensional active suspension. By studying the number fluctuations, the velocity correlation functions and cluster size distribution function, we observe that depending on the number density of swimmers and the strength of noise, the hydrodynamic interactions affect the ordering in a suspension. For a fixed value of noise, at large density of particles, long ra…
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 by Monte Carlo simulation that spherical nanoparticles adhering to the outer surface of an elastic nanotube can self-assemble into linear structures as a result of curvature-mediated interactions. We find that nanoparticles arrange into rings or helices on stretchable nanotubes, and as axial strings on nanotubes with high rigidity to stretching. These self…
Crystallization of supersaturated liquids usually starts by heterogeneous nucleation. Mounting evidence shows that even homogeneous nucleation in simple liquids takes place in two steps; first a dense amorphous precursor forms, and the crystalline phase appears via heterogeneous nucleation in/on the precursor cluster. Herein, we review recent results by a simple dynamical density functional theory, the phase-field crystal model, for (precursor-mediated) homogeneous and heterogeneous nucleation of nanocrystals. It will be shown that the mismatch between the lattice constants of the nucleating c…
A promising approach of designing mesostructured materials with novel physical behavior is to combine unique optical and electronic properties of solid nanoparticles with long-range ordering and facile response of soft matter to weak external stimuli. Here we design, practically realize, and characterize orientationally ordered nematic liquid crystalline dispersions of rod-like upconversion nanoparticles. Boundary conditions on particle surfaces, defined through surface functionalization, promote spontaneous unidirectional self-alignment of the dispersed rod-like nanoparticles, mechanically co…
A theoretical analysis of homeotropic alignment induced by nanoparticles (NPs) in a nematic liquid crystal (NLC) sample cell is presented. It is found that such alignment on the surface of a NP causes a change in the orientation of the molecular director near the surface, which in turn induces variations in the elastic constants and free energy. The induced NLC properties allow coupling between nearby NPs, mediated by the NLC molecules. The rotation of the coupled NPs close to the substrate tends to induce a long-range orientation of the NLC molecular director, leading to modification in the a…
Using non-equilibrium molecular dynamics simulations, we study the rheology of a model hybrid mixture of liquid crystals (LCs) and dipolar soft spheres (DSS) representing magnetic nanoparticles. The bulk isotropic LC-DSS mixture is sheared with different shear rates using Lees-Edwards periodic boundary conditions. The steady-state rheological properties and the effect of the shear on the microstructure of the mixture are studied for different strengths of the dipolar coupling, $λ$, among the DSS. We find that at large shear rates, the mixture shows a shear-thinning behavior for all considered …
The aggregation of clay particles in aqueous solution is a ubiquitous everyday process of broad environmental and technological importance. However, it is poorly understood at the all-important atomistic level since it depends on a complex and dynamic interplay of solvent-mediated electrostatic, hydrogen-bonding, and dispersion interactions. With this in mind we have performed an extensive set of classical molecular dynamics simulations (included enhanced sampling simulations) on the interactions between model kaolinite nanoparticles in pure and salty water. Our simulations reveal highly aniso…
A suspension of nanoparticles with very low volume fraction is found to assemble into a macroscopic cellular phase under the collective influence of AC and DC voltages. Systematic study of this phase transition shows that it was the result of electrophoretic assembly into a two-dimensional configuration followed by spinodal decomposition into particle-rich walls and particle-poor cells mediated principally by electrohydrodynamic flow. This mechanistic understanding reveals two characteristics needed for a cellular phase to form, namely 1) a system that is considered two dimensional and 2) shor…
We investigate the impact of nanoparticle roughness on the phase behaviour of suspensions in models of calcium carbonate nanoparticles. We use a Derjaguin approach that incorporates roughness effects and interactions between the nanoparticles modelled with a combination of DLVO forces and hydration forces, derived using experimental data and atomistic molecular dynamics simulations, respectively. Roughness effects, such as atomic steps or terraces appearing in mineral surfaces result in very different effective inter-nanoparticle potentials. Using stochastic Langevin Dynamics computer simulati…
In biomimetic and biological systems, interactions between surfaces are often mediated by adhesive molecules, nanoparticles, or colloids dispersed in the surrounding solution. We present here a general, statistical-mechanical model for two surfaces that interact via adhesive particles. The effective, particle-mediated interaction potential of the surfaces is obtained by integrating over the particles' degrees of freedom in the partition function. Interestingly, the effective adhesion energy of the surfaces exhibits a maximum at intermediate particle concentrations, and is considerably smaller …
We study the dynamics of orientational phase ordering in fluid membranes. Through numerical simulation we find an unusually slow coarsening of topological texture, which is limited by subdiffusive propagation of membrane curvature. The growth of the orientational correlation length $ξ$ obeys a power law $ξ\propto t^w$ with $w < 1/4$ in the late stage. We also discuss defect profiles and correlation patterns in terms of long-range interaction mediated by curvature elasticity.
Ion-mediated interaction is important for the properties of polyelectrolytes such as colloids and nucleic acids. The effective pair interactions between two polyelectrolytes have been investigated extensively, but the many-body effect for multiple polyelectrolytes still remains elusive. In this work, the many-body effect in potential of mean force (PMF) between like-charged nanoparticles in various salt solutions has been comprehensively examined by Monte Carlo simulation and the nonlinear Poisson-Boltzmann theory. Our calculations show that, at high 1:1 salt, the PMF is weakly repulsive and a…
A hybrid block copolymer(BCP) nanocomposite computational model is proposed to study nanoparticles(NPs) with a generalised shape including squares, rectangles and rhombus. Simulations are used to study the role of anisotropy in the assembly of colloids within BCPs, ranging from NPs that are compatible with one phase, to neutral NPs. The ordering of square-like NPs into grid configurations within a minority BCP domain was investigated, as well as the alignment of nanorods in a lamellar-forming BCP, comparing the simulation results with experiments of mixtures of nanoplates and PS-\textit{b}-PMM…
