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The hydrodynamics and mixing during the nonaxisymmetry impingement of a micro-droplet and a sessile droplet of the same fluid are investigated by many-body dissipative particle dynamics (MDPD) simulation. In this work, the range of the impingement angle (θi) between the impinging droplet and the sessile droplet is 0°–60° and the contact angle is set as 45° or 124°. The droplets impingement and mixing behavior is analyzed based on the droplet internal flow field, the concentration distribution and the time scale of the decay of the kinetic energy of the impinging droplet. The dimensionless total mixing time (τm) is calculated by a modified mixing function. With the Weber number (We) ranging from 5.65 to 22.7 and the Ohnesorge number (Oh) ranging from 0.136 to 0.214, we find τm hardly changes with We and Oh. Whereas, θi and surface wettability are found to have a significant effect on τm. We find that θi has no clear effect on τm on a hydrophobic surface, while on the hydrophilic surface, τm increase with the θi. Thus, reducing the impinging angle is a valid method to shorten the τm.

Hypothesis Delivery of multiple payloads using the same micelle is of significance to achieve multifunctional or synergistic effects. The interacting distribution of different payloads in micelles is expected to influence the loading stability and capacity. It is highly desirable to explore how intermolecular interactions affect the joint distribution of multi-payloads. Experiments Dissipative Particle Dynamics simulations were performed to probe the loading of three payloads: decane with a linear carbon chain, butylbenzene with an aromatic ring connected to carbon chain, and naphthalene with double aromatic rings, within poly(β-amino ester)-b-poly(ethylene glycol) micelles. Properties of core-shell micelles, e.g., morphological evolution, radial density distribution, mean square displacement, and contact statistics, were analyzed to reveal payloads loading stability and capacity. Explorations were extended to vesicular, multi-compartment, double helix, and layer-by-layer micelles with more complex inner structures. Findings Different payloads have their own preferred locations. Decane locates at the hydrophilic/hydrophobic interface, butylbenzene occupies both the hydrophilic/hydrophobic interface and the hydrophobic core, while naphthalene enters the hydrophobic core. More efficient delivery of multi-payloads is achieved since the competition of payloads occupying preferred locations is minimized. The fusion of micelles encapsulating different payloads suggests that specific payloads will move to their preferred positions without interfering other payloads.

Given the importance of preserving the mechanical properties of recycled isotactic polypropylene (iPP) during its processing, this work provides an improved understanding of the contribution of introducing physical or chemical crosslinks using the dissipative particle dynamics (DPD) method, which makes it possible to model iPP structures with a realistic range of crosslink densities. First, the protocol to build a coarse‐grained model of iPP from an all‐atom expression by Bayesian optimization is described. A Bayesian optimization procedure employing two different cutoff distances successfully provides optimal DPD parameters reproducing iPP's properties compared to the all‐atom system. Then, the coarse‐grained iPP model with optimal DPD parameters is applied to study structures containing a realistic range of crosslink densities to evaluate their mechanical properties. These calculations demonstrate that the mechanical properties such as the Young's modulus and ultimate strength increase while the fracture strain decreases with an increase in the crosslink density, which is consistent with experimental observations. The results also show that there is a critical crosslink density above which these properties start to be improved due to the introduction of crosslinks. These findings can help us to obtain targeted properties of recycled iPP by introducing physical or chemical crosslinks.

As a pH-sensitive nanomaterial, Eudragit S100 has good colon targeting. However, little research has been carried out on its mesoscopic scale. In this paper, the self-assembly behavior of Pulsatilla saponins D (PSD) and Eudragit S100, as well as the loading and release mechanism of PSD, was investigated via computer simulations. The effects of the self-assembly characteristics of PSD and Eudragit S100 in the dry powder state on the drug-carrier ratio were explored by the coarse-grained molecular dynamics (CGMD) method. According to the pH-responsive feature of Eudragit S100, the drug protection under gastric pH conditions and release in colonic pH conditions were simulated through the dissipative particle dynamics (DPD) method, which has provided insights into the microscopic morphological changes in the pH-sensitive drug delivery systems.

The mixing morphology control plays a crucial role in photovoltaic power generation, yet this specific effect on device performances remains elusive. Here, we employed computational approaches to delineate the photovoltaic properties of layered heterojunction polymer solar cells with tunable mixing morphologies. One-step quench and two-step quench strategies were proposed to adjust the mixing morphology by thermodynamic and kinetic effects. The computation for the one-step quench revealed that modulating interfacial widths and interfacial roughness could significantly promote the photovoltaic performance of layered heterojunction polymer solar cells. The two-step quench can provide a buffer at a lower temperature before the kinetic quenching, leading to the formation of small-length-scale islands connected to the interface and a further increase in photovoltaic performance. Our discoveries are supported by recent experimental evidence and are anticipated to guide the design of photovoltaic materials with optimal performance.

A mesoscopic model with molecular resolution is presented for dipalmitoyl phosphatidylcholine (DPPC) and palmitoyl oleoyl phosphatidylcholine (POPC) monolayer simulations at the air-water interface using many-body dissipative particle dynamics (MDPD). The parameterization scheme is rigorously based on reproducing the physical properties of water and alkane and the interfacial property of the phospholipid monolayer by comparison with experimental results. Using much less computing cost, these MDPD simulations yield a similar surface pressure-area isotherm as well as similar pressure-related morphologies as all-atom simulations and experiments. Moreover, the compressibility modulus, order parameter of lipid tails, and thickness of the phospholipid monolayer are quantitatively in line with the all-atom simulations and experiments. This model also captures the sensitive changes in the pressure-area isotherms of mixed DPPC/POPC monolayers with altered mixing ratios, indicating that the model is promising for applications with complex natural phospholipid monolayers. These results demonstrate a significant improvement of quantitative phospholipid monolayer simulations over previous coarse-grained models.

Amorphous solid dispersions (ASDs) are commonly used to orally deliver small-molecule drugs that are poorly water-soluble. ASDs consist of drug molecules in the amorphous form which are dispersed in a hydrophilic polymer matrix. Producing a high-performance ASD is critical for effective drug delivery and depends on many factors such as solubility of the drug in the matrix and the rate of drug release in aqueous medium (dissolution), which is linked to bioperformance. Often, researchers perform a large number of design iterations to achieve this objective. A detailed molecular-level understanding of the mechanisms behind ASD dissolution behavior would aid in the screening, designing, and optimization of ASD formulations and would minimize the need for testing a wide variety of prototype formulations. Molecular dynamics and related types of simulations, which model the collective behavior of molecules in condensed phase systems, can provide unique insights into these mechanisms. To study the effectiveness of these simulation techniques in ASD formulation dissolution, we carried out dissipative particle dynamics simulations, which are particularly an efficient form of molecular dynamics calculations. We studied two stages of the dissolution process: the early-stage of the dissolution process, which focuses on the dissolution at the ASD/water interface, and the late-stage of the dissolution process, where significant drug release would have occurred and there would be a mixture of drug and polymer molecules in a predominantly aqueous environment. Experimentally, we used Fourier transform infrared spectroscopy to study the interactions between drugs, polymers, and water in the dry and wet states and the chromatographic technique to study the rate of drug and polymer release. Both experiments and simulations provided evidence of polymer microstructures and drug-polymer interactions as important factors for the dissolution behavior of the investigated ASDs, consistent with previous work by Pudlas et al. (Eur. J. Pharm. Sci.2015, 67, 21-31). As experimental and simulation results are consistent and complementary, it is clear that there is significant potential for combined experimental and computational research for a detailed understanding of ASD formulations and, hence, formulation optimization.

We have studied the self-assembly of two types of amphiphiles with one or two blocks composed of giant “monomers” of the cubic cage using dissipative particle dynamics (DPD) simulations with the ai...

In the current work, atom transfer radical polymerization-induced self-assembly (ATRP PISA) phase diagrams were obtained by the means of dissipative particle dynamics simulations. A fast algorithm for determining the equilibrium morphology of block copolymer aggregates was developed. Our goal was to assess how the chemical nature of ATRP affects the self-assembly of diblock copolymers in the course of PISA. We discovered that the chain growth termination via recombination played a key role in determining the ATRP PISA phase diagrams. In particular, ATRP with turned off recombination yielded a PISA phase diagram very similar to that obtained for a simple ideal living polymerization process. However, an increase in the recombination probability led to a significant change of the phase diagram: the transition between cylindrical micelles and vesicles was strongly shifted, and a dependence of the aggregate morphology on the concentration was observed. We speculate that this effect occurred due to the simultaneous action of two factors: the triblock copolymer architecture of the terminated chains and the dispersity of the solvophobic blocks. We showed that these two factors affected the phase diagram weakly if they acted separately; however, their combination, which naturally occurs during ATRP, affected the ATRP PISA phase diagram strongly. We suggest that the recombination reaction is a key factor leading to the complexity of experimental PISA phase diagrams.

Rational design of thermotropic liquid crystal (LC)-based sensors utilizing different mesophases holds great promise to open up novel detection modalities for various chemical and biological applications. In this context, we present a dissipative particle dynamics study to explore the unique anchoring behavior of nematic and smectic LCs at amphiphile-laden aqueous-LC interface. By increasing the surface coverage of amphiphiles, two distinct anchoring sequences, a continuous planar-tilted-homeotropic transition and a discontinuous planar-to-homeotropic transition, can be observed for the nematic and smectic LCs, respectively. More importantly, the latter occurs at a much lower surface coverage of amphiphiles, demonstrating an outstanding sensitivity for the smectic-based sensors. The dynamics of reorientation further reveals that the formation of homeotropic smectic anchoring is mainly governed by the synchronous growth of smectic layers through the LCs, which is significantly different from the mechanism of interface-to-bulk ordering propagation in nematic anchoring. Furthermore, the smectic LCs have also been proven to possess a potential selectivity in response to a subtle change in the chain rigidity of amphiphiles. These simulation findings are promising and would be valuable for the development of novel smectic-based sensors.

To study the formation and stability of the O/W and reverse W/O microemulsion, dissipative particle dynamics (DPD) simulation was utilized to investigate the system composed of oil, water and Gemin...

It is generally agreed that the nuclei of eukaryotic cells at interphase are partitioned into disjointed territories, with distinct regions occupied by certain chromosomes. However, the underlying mechanism for such territorialization is still under debate. Here we model chromosomes as coarse-grained block copolymers and to investigate the effect of loop domains (LDs) on the formation of compartments and territories based on dissipative particle dynamics. A critical length of LDs, which depends sensitively on the length of polymeric blocks, is obtained to minimize the degree of phase separation. This also applies to the two-polymer system: The critical length not only maximizes the degree of territorialization but also minimizes the degree of phase separation. Interestingly, by comparing with experimental data, we find the critical length for LDs and the corresponding length of blocks to be respectively very close to the mean length of topologically associating domains (TADs) and chromosomal segments with different densities of CpG islands for human chromosomes. The results indicate that topological constraints with optimal length can contribute to the formation of territories by weakening the degree of phase separation, which likely promotes the chromosomal flexibility in response to genetic regulations.

The drug diffusion issue in microneedles is the focus of its medical application. It will not only affect the distribution of drugs in the needle body but will also have an impact on the drug release performance of the microneedle. The utilization of cross-linked polymer materials to obtain the drug diffusion control has been experimentally verified as a feasible method. However, the mechanism research on the molecular level is still incomplete. In this study, the dissipative particle dynamics (DPD) simulation has been applied to study the effect of the cross-linking reaction on drug diffusion in hyaluronic acid microneedles. We have discovered that when the cross-linking degree reaches 90%, the diffusion coefficient of the drug is 6.45 times lower than that of the uncross-linked system. The main reason for the decline in drug diffusion ability is that the cross-linking reaction varies the conformation of the polymer. The amplification in the cross-linking degree makes the polymer coils more compact and approach each other, finally forming a continuously distributed cross-linked network, which reduces its degradation rate in the body. Simultaneously, these cross-linked networks can also hinder the interaction of soluble drugs with water, thereby preventing the premature release of drugs. The simulation results are consistent with the data collected in the previous microneedle experiment. This work will be an extension of DPD simulation in the application of biological materials.

Microneedle (MN) technology has been proven to be promising to become an effective drug delivery route of insulin for diabetes treatment, with the advantages of high delivery efficiency, convenient management, and minimal risk of infection. However, efforts are still required to verify the insulin activity in MNs for further clinical application. Moreover, it is also essential to study the diffusion properties of insulin to understand the ability of various MN materials to control insulin release. Herein, we have combined all-atom molecular dynamics simulation and coarse-grained dissipative particle dynamics to systematically study insulin's structural stability and diffusion coefficient in polyvinyl alcohol and hyaluronic acid solutions. The all-atom simulation reveals the dissimilarities in the interaction mode between insulin and the two polymers. It also points out that the presence of the two polymers would not irreversibly impact the secondary structure of insulin, thereby ensuring regular insulin expression in vivo. Mesoscopic simulation results manifest that the diffusion coefficient of insulin in hyaluronic acid (HA) solution is greater than that of the polyvinyl alcohol (PVA) system. Meanwhile, through the study of insulin centroid trajectory, we have claimed two different diffusion mechanisms of insulin in polymer solution: The movement of insulin in the HA and water solution follows the Brownian motion rule. In comparison, the hopping effect of insulin has been observed in the PVA solution due to poor intermolecular affinity as well as lower polymer water solubility. By summarizing different diffusion mechanisms, this study can provide theoretical guidance for preparing insulin-loaded dissolvable MNs.

Dissipative particle dynamics simulations were adopted to study the mechanism of lyotropic liquid crystal (LLC) formation and the synthesis process of silica nanowires by LLC template method. Simul...

Technical challenges in precision medicine and environmental remediation create an increasing demand for smart materials that can select and deliver a probe load to targets with high precision. In this context, soft nanomaterials have attracted considerable attention due to their ability to simultaneously adapt their morphology and functionality to complex ambients. Two major challenges are to precisely control this adaptability under dynamic conditions and provide predesigned functionalities that can be manipulated by external stimuli. Here, we report on the computational design of a distinctive class of soft nanocarriers, built from armored nanodroplets, able to selectively encapsulate or release a probe load under specific flow conditions. First, we describe in detail the mechanisms at play in the formation of pocket-like structures in armored nanodroplets and their stability under external flow. Then we use that knowledge to test the capacity of these pockets to yield flow-assisted encapsulation or expulsion of a probe load. Finally, the rheological properties of these nanocarriers are put into perspective with those of delivery systems employed in pharmaceutical and cosmetic technology.

In this study, we developed a coarse-grained model based on the dissipative particle dynamics (DPD) method to investigate the aggregates of the cetyltrimethylammonium bromide (CTAB) molecules on go...

Elucidating the interactions between nanoparticles (NPs) and proteins can provide useful guidelines for the dictation of cell functions. In this paper, dissipative particle dynamics (DPD) simulatio...

Dissipative particle dynamics simulations were performed to investigate the self-assembly of dipalmitoylphosphatidylcholine (DPPC) as a model lipid membrane on the surface of carbon nanotubes (CNTs). The influence of surface curvature of CNTs on self-assembly was investigated by performing simulations on solutions of DPPC in water in contact with CNTs of different diameters: CNT (10, 10), CNT (14, 14), CNT (20, 20), and CNT (34, 34). DPPC solutions with a wide range of concentrations were chosen to allow for formation of lipid structures of various surface densities, ranging from a submonolayer to a well-organized monolayer and a CNT covered with a lipid monolayer immersed in a planar lipid bilayer. Our results are indicative of a sequence of phase-ordering processes for DPPC on the surface of CNTs. At low surface coverages, the majority of hydrocarbon tail groups of DPPC are in contact with the CNT surface. Increasing the surface coverage leads to the formation of hemimicellar aggregates, and at high surface coverages close to the saturation limit, an organized lipid monolayer self-assembles. An examination of the mechanism of self-assembly reveals a two-step mechanism. The first step involves densification of DPPC on the CNT surface. Here, the lipid molecules do not adopt the order of the target phase (lipid monolayer on the CNT surface). In the second step, when the lipid density on the CNT surface is above a threshold value (close to saturation), the lipid molecules reorient themselves to form an organized monolayer around the tube. Here, the DPPC molecules adopt stretched conformations normal to the surface, the end hydrocarbon groups adsorb on the surface, and the head groups occupy the outermost part of the monolayer. The saturation density and the degree of lipid ordering on the CNT surface depend on the surface curvature. The saturation density increases with increased surface curvature, and better-ordered structures are formed on less curved surfaces.

We explore the use of coarse-grained dissipative particle dynamics simulations to predict critical micelle concentrations (CMCs) in polydisperse surfactant mixtures and blends. By fitting pseudo-phase separation models (PSMs) to aqueous solutions of binary surfactant mixtures at selected compositions above the CMC, we avoid the need for expensive simulations of more complex multicomponent mixtures performed as a function of dilution. The approach is demonstrated for sodium laureth sulfate (SLES) surfactants with polydispersity in the ethoxylate spacer. For this system, we find a modest degree of cooperativity in micelle formation, which we attribute to the reduced repulsion between charged headgroups for surfactants with dissimilar ethoxylate spacer lengths. However, this is insufficient to explain the lowered CMC often observed in commercial SLES samples, which we attribute to the presence of small amounts of unsulfated alkyl ethoxylates and/or traces of salt.

Investigation of drug encapsulation behavior is important to design efficient drug delivery materials. With this aim, we strive to perform coarse-grained simulations to study the drug encapsulation behavior of a particular micelle-forming co-polymer composed of hydrophilic PEG and hydrophobic PLGA units. The study is performed at the mesoscopic scale to overcome the time scale problem associated with the micelle formation at the atomistic scale. The structure and drug loading properties are studied at different polymer concentrations and drug loading. The resulting micellar structures that are obtained via dissipative particle dynamics simulations are observed to encapsulate the drug with high efficiency values. Moreover, the DPD simulations performed in this work reveal physical insight on the interactions and molecular structure as well as the temporal evolution of the encapsulation process. Our work can be considered as an attempt to computationally characterize the drug encapsulation behavior and structure of a prospective drug delivery system.

The objective of investigating macroscopic polymer properties with a low computing cost and a high resolution has led to the development of efficient hybrid simulation tools. Systems generated from such simulation tools can fail in service if the effect of uncertainty of model inputs on its outputs is not accounted for. This work focuses on quantifying the effect of parametric uncertainty in our coarse-grained molecular dynamics-finite element coupling approach using uncertainty quantification. We consider uniaxial deformation simulations of a polystyrene sample at T = 100 K in our study. Parametric uncertainty is assumed to originate from parameters in the molecular dynamics model with a nonperiodic boundary (the force constant between polymer beads and anchor points, the number of anchor points, and the size of the surrounding dissipative particle dynamics domain) and a parameter to blend the energies of particles and continuum (weighting factor). Key issues that arise in uncertainty quantification are discussed on the basis of the quantities of interest including mass density, end-to-end distance, and radial distribution function. This work reveals the influence of key input parameters on the properties of polymer structure and facilitates the determination of those parameters in the application of this hybrid molecular dynamics-finite element approach.

Dissipative particle dynamics (DPD) simulations were applied to investigate the effect of SiO2 nanoparticles (SNPs) modified with different tertiary amine chain length and concentration on O/W emulsion properties, the influence mechanism was also revealed from the molecular level. On this basis, the influence of the modified SNPs volume fraction in the emulsion system was studied. The results showed that with the increase number of tertiary amine chain alkyl carbon, the stability of the original emulsion system was first enhanced and then weakened while the responsiveness of the protonated emulsion system was first weakened and then slightly enhanced, the number of tertiary amine chains modified on SNPs has the same influence rule on emulsion performance, which was determined by the hydrophobicity of modified SNPs. In addition, with the increase of the modified SNPs volume fraction in the emulsion system, the stability of the emulsion is gradually enhanced. However, when the volume fraction of SiO2 exceeds 3%, the amplitude of stability enhancement decreases. The increase in the interaction energy between oil droplets in the equilibrium process is caused by emulsion fusion, which in turn is affected by SNPs. The repulsive force between oil and water is greater than that between two oil drops, which is the reason for the oil drop fusion. The presence of SNPs can reduce the repulsive force between oil and water to different degrees, thus slowing down the fusion of emulsion.

We developed a multiscale model for simulating aggregation of multiple, free-flowing platelets in low-intermediate shear viscous flow, in which aggregation is mediated by the interaction of α(IIb)β(3) receptors on the platelets membrane and fibrinogen (Fg). This multiscale model uses coarse grained molecular dynamics (CGMD) for platelets at the microscales, and dissipative particle dynamics (DPD) for the shear flow at the macroscales, employing our hybrid aggregation force field for modeling molecular level receptor ligand bonds. We define an aggregation tensor and use it to quantify the molecular level contact characteristics between platelets in an aggregate. We perform numerical studies under different flow conditions for platelet doublets and triplets and evaluate the contact area, detaching force, and minimum distance between different pairs of platelets in an aggregate. We also present the dynamics of applied stress and velocity magnitude distributions on the platelet membrane during aggregation and quantify the increase in stress in the contact region under different flow conditions. Integrating the knowledge from our previously validated models, together with new aggregation scenarios, our model can dynamically quantify aggregation characteristics and map stress and velocity distribution on the platelet membrane which are difficult to measure in vitro, thus providing an insight into mechanotransduction bond formation response of platelets to flow induced shear stresses. This modeling framework, together with the tensor method for quantifying inter-platelet contact, can be extended to simulate and analyze larger aggregates and their adhesive properties.

The self-assembly of block copolymers in a confined space has been proven to be a facile and robust strategy for fabricating assembled structures with various potential applications. Herein, we employed a new pH-responsive polymer self-assembly method to regulate ion transport inside artificial nanochannels. The track-etched asymmetric nanochannels were functionalized with PS22k-b-P4VP17k/hPS4k blend polymers, and the ionic conductance and rectification properties of the proposed system were investigated. The pH-actuated changes in the surface charge and wettability resulted in the selective pH-gated ionic transport behavior. The designed system showed a good switching property to the pH stimulus and could recover during the repetitive experiments. The gating ability of the polymer-nanochannel system increased with increasing the weight of the homopolymer, and the proposed platform demonstrated robust stability and reusability. Numerical and the dissipative particle dynamics simulations were implemented to emulate the pH-dependent self-assembling behavior of diblock copolymers in a confined space, which were consistent with the experimental observations. As an example of the self-assembly of polymers in nanoconfinements, this work provides a facile and robust strategy for the regulation of ion transport in synthetic nanochannels. Meanwhile, this work can be further extended to design artificial smart nanogates for various applications such as mass delivery and energy harvesting.

The implementation of solid-fluid boundary condition has been a major challenge for dissipative particle dynamics (DPD) method. Current implementations of boundary conditions usually try to approach a uniform density distribution and a velocity profile close to analytical solution. The density oscillations and slip velocity are intentionally eliminated, and different wall properties disappear in the same analytical solution. This paper develops a new wall model that combines image and frozen particles and a new strategy to emphasize different wall properties especially wettabilities. The strategy first studies the realistic wall-fluid system by molecular dynamics (MD) simulation depending on physical parameters. Then, a DPD simulation is used to match the density and velocity profiles with the new wall model. The obtained DPD parameters can simulate the systems with the same wall and fluid materials. With this method, a simulation of the Poiseuille flow of liquid argon with copper walls is presented. Other walls with super-hydrophilic, hydrophilic, and hydrophobic wettabilities are also simulated. The limitations of the analytical solution and the effect of the wall-fluid interaction are discussed. The results show that the method suggested in this paper can simulate the mesoscale behavior of the microchannel flow related to realistic systems.

In this paper, we investigate the application of smoothed particle hydrodynamics (SPH) to the computation of 3-D flows in channels with sudden expansion or contraction. In the same context, we also discuss 2-D SPH computations applicable to channels characterized by cross-sections of large aspect ratios. The particle nature of SPH allows us to treat macro-systems similarly to atomic systems, transferring knowledge from molecular dynamics (MD) and dissipative particle dynamics (DPD) and suggesting a common framework for simulations at different scales. Computations are carried out by making use of tools previously used for atomic-scale systems (usually MD) and mesoscopic systems (usually DPD). The results obtained suggest that SPH captures the main flow characteristics and achieves good accuracy both in 2-D and 3-D, at least for Re values in the range 0.0177 to 55.4 investigated here. Minor numerical artifacts may be observed near the solid boundaries, especially at corner discontinuities. Such localized inaccuracies near points of geometric discontinuity are common in all numerical simulation methods.

Morphology transition of block copolymer assemblies in response to external stimuli has attracted considerable attention. However, our knowledge about the mechanism of such a transition is still limited, especially for rod-coil block copolymers. Here, we report a programmable morphology evolution of assemblies induced by variation of chain ordering for rod-coil-rod triblock copolymers. A sequence of morphology transition from ellipsoids to disks, bowls, and vesicles is observed by increasing the solution temperature. At high temperatures, the mobility of the rod chain increases and the rigidity of the rod chain decreases. This gives rise to an ellipsoid-to-vesicle morphology transition. Dissipative particle dynamics theoretical simulations were performed to reveal the mechanism of this morphology transition process. It was found that the increase of rod chain mobility and the decrease of rod chain rigidity induce a decrease of chain ordering of rod blocks as temperature increases, which results in an ellipsoid-to-vesicle morphology transition. The gained information can guide the construction of nanoassemblies based on the rod-coil block copolymers.

Polymers can increase the viscosity of water, reduce the relative permeability of the water phase, and enhance the flowability of the oil phase; surfactants can form molecular films at the oil–water interface boundaries, thereby reducing interfacial tension. Surfactant/polymer (S/P) flooding technology for enhancing oil recovery has become a major way to increase crude oil production. This study used dissipative particle dynamics (DPD) technology to simulate the emulsification process of a four-component composite system consisting of oil, water, sodium dodecylbenzene sulfonate (SDBS), and partially hydrolyzed polyacrylamide (HPAM). By changing the concentration of the S/P system, the effect on emulsification behavior was analyzed. Combined with particle distribution diagrams and interfacial tension parameters, the effect of the emulsification behavior on the performance of the S/P binary system was analyzed. On this basis, the effect of different emulsion performances on the recovery factor was evaluated using micro-experiments. The study found that the S/P system that produced stable emulsification had a lower interfacial tension and relatively good effect on improving the recovery factor. Increasing the concentration of the polymer and surfactant may cause changes in the interfacial film of the emulsion, thereby affecting the ability of the S/P system to reduce interfacial tension and may not improve the oil recovery factor. The research results help to better analyze and screen the S/P system used for oil extraction and improve crude oil recovery.

The transient elongational viscosity ηe(t) of the polymer melt is known to exhibit strain hardening, which depends on the strain rate ε˙. This phenomenon was elucidated by the difference of chain stretching in the entanglement network between extension and shear. However, to date, the microscopic evolution of polymer melt has not been fully statistically analyzed. In this work, the radial size distributions P(Rg,t) of linear polymers are explored by dissipative particle dynamics during the stretching processes. In uniaxial extensional flow, it is observed that the mean radius of gyration R¯g(t) and standard deviation σ(t) remain unchanged until the onset of strain hardening, corresponding to linear viscoelasticity. Both R¯g and σ rise rapidly in the non-linear regime, and bimodal size distribution can emerge. Moreover, the onset of strain hardening is found to be insensitive to the Hencky strain (ε˙Ht) and chain length (N).

The reason for the formation of an anhydrous and surfactant-free deep eutectic solvent (DES)-based microemulsion system has been widely explored so far. Dissipative dynamism (DPD) is used to simula...

The many-body dissipative particle dynamics (mDPD) is a prominent mesoscopic multiphase model for fluid transport in mesoconfinement. However, it has been a long-standing challenge for mDPD (and ot...

In this work, the effects of polarization of confining charged planar dielectric surfaces on induced electroosmotic flow are investigated. To this end, we use dissipative particle dynamics to model solvent and ionic particles together with a modified Ewald sum method to model electrostatic interactions and surfaces polarization. A relevant difference between counterions number density profiles, velocity profiles, and volumetric flow rates obtained with and without surface polarization for moderate and high electrostatic coupling parameters is observed. For low coupling parameters, the effect is negligible. An increase of almost 500% in volumetric flow rate for moderate/high electrostatic coupling and surface separation is found when polarizable surfaces are considered. The most important result is that the increase in electrostatic coupling substantially increases the electroosmotic flow in all studied range of separations when the dielectric constant of electrolytes is much higher than the dielectric constant of confining walls. For the higher separation simulated, an increase of around 340% in volumetric flow rate when the electrostatic coupling is increased by a factor of two orders of magnitude is obtained.

A model, including the chemical details of core nanoparticles as well as explicit surface charges and hydrophobic patches, of triblock Janus particles is employed to simulate nucleation and solid-solid phase transitions in two-dimensional layers. An explicit solvent and a substrate are included in the model, and hydrodynamic and many-body interactions were taken into account within many-body dissipative particle dynamics simulation. In order not to impose a mechanism a priori, we performed free (unbiased) simulations, leaving the system the freedom to choose its own pathways. In agreement with the experiment and previous biased simulations, a two-step mechanism for the nucleation of a kagome lattice from solution was detected. However, a distinct feature of the present unbiased versus biased simulations is that multiple nuclei emerge from the solution; upon their growth, the aligned and misaligned facets at the grain boundaries are introduced into the system. The liquid-like particles trapped between the neighboring nuclei connect them together. A mismatch in the symmetry planes of neighboring nuclei hinders the growth of less stable (smaller) nuclei. Unification of such nuclei at the grain boundaries of misaligned facets obeys a two-step mechanism: melting of the smaller nuclei, followed by subsequent nucleation of liquid-like particles at the interface of bigger neighboring nuclei. Besides, multiple postcritical nuclei are formed in the simulation box; the growth of some of which stops due to introduction of a strain in the system. Such an incomplete nucleation/growth mechanism is in complete agreement with the recent experiments. The solid-solid (hexagonal-to-kagome) phase transition, at weak superheatings, obeys a two-step mechanism: a slower step (formation of a liquid droplet), followed by a faster step (nucleation of kagome from the liquid droplet).

Janus particles have drawn considerable interest as colloidal surfactants, microswimmers, and building blocks for colloidal lattices. So far, research primarily focused on spherical Janus particles for which a number of fabrication methods are well established. Janus particles with geometric anisotropy offer shape-dependent properties in addition to surface anisotropy, but their synthesis is more challenging. Here, we report a variety of polymeric Janus nanoparticles synthesized from ABC triblock terpolymer microphases in microemulsion droplets. Evaporation-induced assembly of the ABC triblock terpolymers led to prolate microparticles with A/C lamellae stacked along the particle’s major axis. By admixing a B homopolymer during microphase separation, the morphology of the B microphase was gradually tuned in between the A/C lamellae. Cross-linking of the B microdomain created Janus nanodiscs, where the topology could be controlled to unconventional inner structures. We follow the morphology evolution and rationalize their stability with theoretical considerations in the strong segregation limit and dissipative particle dynamics simulations.

In this work, we study the hydrodynamic behavior of monoclonal antibodies in the presence of silicone oil-water interfaces. We model the antibody molecules using a coarse-grained 24-bead model, where two beads are used to represent each antibody domain. We consider the spatial variation of the antibody polarity in our model as each bead represents a set of hydrophilic or hydrophobic amino acids. We use the dissipative particle dynamics scheme to represent the coarse-grained force field which governs the motion of the beads. In addition, interprotein interactions are modeled using an electrostatic force field. The model parameters are determined by comparing the structure factor against experimental structure factor data ranging from a low concentration regime (10 mg/mL) to a high concentration regime (150 mg/mL). Next, we conduct simulations for a suspension of antibody molecules in the presence of silicone oil-water interfaces. Protein loss from the bulk solution is noticed as the molecules adsorb at the interface. We observe dynamic cluster formation in the solution bulk and at the interface, as the antibody molecules self-associate along their trajectories. We quantify the aggregation using a density clustering algorithm and investigate the effect of the antibody concentration on the diffusivity of the antibody solution, aggregation propensity, and protein loss from the bulk. Our study shows that numerical simulations can be an important tool for understanding the molecular mechanisms driving protein aggregation near hydrophobic interfaces.

It is known that the adhesive property and mechanical strength of an apolar polymer can be improved by grafting with polar side chains, whereas the underlying mechanism is still elusive. In this work, the equilibrium structure and mechanical moduli of the melt of graft copolymers have been explored by dissipative particle dynamics. Due to the strong immiscibility of the non-polar backbone and polar side chains, nano-clusters of side chains formed and acted as physical crosslinkers. Moreover, non-affinity adsorption of polar side chains in the melt to the wall was observed, revealing an improvement in the adhesion property. Subjecting graft copolymers to cyclic deformation, the storage and loss moduli were acquired, and they grew with increasing grafting density. The melt strength in terms of the crossover frequency ascended with more side chains on the backbone. Our findings reveal that the strengthening of the mechanical properties of graft copolymers can be attributed to the formation of weakly cross-linked structures, thus offering an insight into the molecular design to aid the development of stronger graft copolymers.

Bilayers, self-assembled by cationic surfactants and fatty alcohols in water, are the basic units of lamellar gel networks - creamy formulations extensively used in cosmetics and pharmaceutics. Mesoscopic modelling and study of the bilayers formed by single- or double-tail cationic surfactants (CTAC or DHDAC), and fatty alcohols (FAs) in the lamellar fluid and gel phases were employed. Fatty alcohols with alkyl tail equal to or greater than the surfactant alkyl tail, i.e., C16FA or C18FA and C22FA, were considered. A model formulation was explored with the FA concentration greater than that of the surfactant and the structure of the fluid and gel bilayers in tensionless state characterised via the density profiles across the bilayers, orientational order parameters of the surfactant and FA chains, intrinsic analysis of the bilayer interfaces, and bending rigidity. The intrinsic analysis allows identification and quantification of the coexistence of the interdigitated and non-interdigitated phases present within the gel bilayers. The FA chains were found to conform the primary scaffolding of the bilayers while the surfactant chains tessellate bilayer monolayers from their water-hydrophobic interface. Further, the overlap of the FA chains from the apposed monolayers of the fluid bilayers rises with increasing FA length. Finally, the prevalence of the non-interdigitated phase over the interdigitated phase within the gel bilayers becomes enhanced upon the FA length increase with a preference of the surfactant chains to reside in the non-interdigitated phase rather than the interdigitated phase.

The design of mixed polymeric micelles by a combination of two or more dissimilar polymers is a potential strategy to achieve multiple stimuli-response for anti-cancer drug delivery. However, their drug loading co-micellization behavior and multiple stimuli-responsive drug release mechanism have been poorly understood at the mesoscopic level, especially in the system that involves reduction-response due to the difficulty of simulation on the cleavage of chemical bonds. In this work, the co-micellization behavior, drug distribution regularities and dual pH/reduction-responsive drug release process of mixed micelles formed by disulfide-linked polycaprolactone-b-polyethylene glycol methyl ether methacrylate (PCL-SS-PPEGMA) and poly(ethylene glycol) methyl ether-b-poly(N,N-diethylamino ethyl methacrylate) (PDEA–PPEGMA) were studied by dissipative particle dynamics (DPD) mesoscopic simulations. A dedicated bond-breaking script was employed to accomplish the disulfide bond-breaking simulations. The results showed that PCL55-SS-PPEGMA10 and PDEA34–PPEGMA11 could be well mixed to form superior DOX-loaded micelles with good drug-loading capacity and drug-controlled release performance. To prepare the DOX-loaded micelles with optimized properties, the simulation results suggested the feed ratio of DOX:PCL55-SS-PPEGMA10:PDEA34–PPEGMA11 set to 3:4:4. Compared with the two single stimuli-response, the dual pH/reduction-response process perfectly combined both pH-response and reduction-response together, providing a higher release rate of DOX. Therefore, this study provides theoretical guidance aimed at the property optimization and micellar structure design of the dual pH/reduction-responsive mixed micelles.

In this work using dissipative particle dynamics simulations with explicit treatment of polar species we demonstrate that the molecular nature of dielectric media has a significant impact on swelling and collapse of a polyelectrolyte chain in a dilute solution. We show that the small-scale effects related to the presence of polar species lead to the intensification of the electrostatic interactions when the charges are close to each other and/or their density is high enough. As a result, the electrostatic strength , usually regarded as the main parameter governing the polyelectrolyte chain collapse, does not have a universal meaning: the value of λ at which the coil-to-globule transition occurs is found to be dependent on the specific fixed value of the solvent bulk permittivity e while varying the monomer unit charge Q and vice versa. This effect is observed even when the backbone and the counterions have the same polarity as the solvent beads, i.e. no dielectric mismatch is present. The reason for such behavior is rationalized in terms of the “effective” dielectric permittivity eeff which depends on the volume fraction φ of charged units inside the polymer chain volume; using eeff instead of e collapses all data onto one master curve describing the chain shrinking with λ. Furthermore, it is shown that a polar chain adopts less swollen conformations in the polyelectrolyte regime and collapses more easily compared to a non-polar chain.

Single-walled carbon nanotube (SWCNT) transmembrane channel formation in a pure 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) bilayer, and the spontaneous internalization of single-stranded DNA (ssDNA) into the formed pore were simulated. A combination of computational techniques, Dissipative Particle Dynamics-Monte Carlo hybrid simulations and quantum mechanical calculations at the hybrid-DFT level, was used as a new proposal to perform DPD simulations granting specific chemical identity to the model particles. The simulated transmembrane channels showed that, in the case of pristine SWCNTs and upon increasing the nanotube length, a higher tilt angle with respect to the bilayer normal is observed and more time is needed for the nanotube to stabilize. On the other hand, for SWCNTs with polar rims an almost perpendicular orientation is preferred with less than 15° of tilt with respect to the bilayer normal once the nanotubes have pierced both monolayers. These findings are supported by experimental observations where CNTs of average inner diameters of 1.51 ± 0.21 nm and lengths in the 5-15 nm range were inserted in DOPC membranes [J. Geng, et al., Nature, 2014, 514(7524), 612-615]. Moreover, the narrower the SWCNTs, the slower the spontaneous internalization of ssDNA becomes, and ssDNA ends hydrophobically trapped inside the artificial pore. A dependence on the nucleotide content is found indicating that the higher the presence of adenine and thymine in the ssDNA chains the slower the internalization becomes, in agreement with the experimental [A. M. Ababneh, et al., Biophys. J., 2003, 85(2), 1111-1127] and predicted solvation tendency in water for nucleic acid bases.

The phase behavior and interfacial tension of ternary polymeric mixtures (polystyrene/polystyrene-b-poly(methyl methacrylate)/poly(methyl methacrylate), PS/PS-b-PMMA/PMMA) are investigated by dissipative particle dynamics (DPD) simulations. Our simulation results show that, as the PS-b-PMMA diblock copolymer concentration increases, the interfacial tension decreases due to the decayed correlations between homopolymers PS and PMMA. When the chain lengths of copolymers are fixed, with the increase of the chain lengths of PS and PMMA homopolymers the interfacial width becomes wider and the interfacial tension becomes smaller, due to the copolymers presenting more stretched and swollen structures in the mixtures with the short length of homopolymers. However, with simultaneously increasing chain lengths of both diblock copolymer and homopolymers with a fixed ratio, the interfacial tension increases because the copolymer chains with longer chain length penetrate more deeply into the homopolymer phase and the interactions between diblock copolymers become weaker. These results will provide a way to mix incompatible homopolymers to improve material performances.

We studied the crystallization of semiflexible polymer chains in melts and poor-solvent solutions with different concentrations using dissipative particle dynamics (DPD) computer simulation techniques. We used the coarse-grained polymer model to reveal the general principles and microscopic scenario of crystallization in such systems at large time and length scales. It covers both primary and secondary nucleation as well as crystallites' merging. The parameters of the DPD model were chosen appropriately to reproduce the entanglements of polymer chains. We started from an initial homogeneous disordered solution of Gaussian chains and observed the initial stages of crystallization process caused in our model by orientational ordering of polymer chains and polymer-solvent phase separation. We found that the overall crystalline fraction at the end of the crystallization process decreases with the increasing polymer volume fraction while the steady-state crystallization speed at later stages does not depend on the polymer volume fraction. The average crystallite size has a maximal value in the systems with a polymer volume fraction from 0.7 to 0.95. In our model, these polymer concentrations represent an optimal value in the sense of balance between the amount of polymer material available to increase the crystallite size and chain entanglements, that prevent crystallites' growth and merging. On large time scales, our model allows us to observe lamellar thickening linear in logarithmic time scale.

Triblock Janus nanoparticles (TJPs) have demonstrated unique physical properties that make them beneficial for versatile biomedical applications, but there is a lack of understanding on the effect of hydrophobic–hydrophilic patch arrangement on TJP–bilayer interactions. Here, by adopting dissipative particle dynamics simulations, the interplay between the bilayer and TJPs with different hydrophobic–hydrophilic patches is systematically studied. By scrutinizing the complete transmembrane process of different TJPs, we reveal that the hydrophobic–hydrophilic patch arrangement of TJPs significantly affects the internalization pathway of TJPs, as well as the dynamic behaviors and stability of internalized TJPs. The TJPs with hydrophilic patches on two poles are more stable within the bilayer but their internalization process is more time-consuming. The TJPs with hydrophilic patches on two poles possess better penetration capability across the lipid bilayer due to their metastable configuration within the bilayer. Meanwhile, the ratio of hydrophobic–hydrophilic patches of TJPs is a secondary factor influencing the TJP–bilayer interactions. These findings demonstrate that the interactions between TJPs and the bilayer can be regulated by manipulating the hydrophobic–hydrophilic patch arrangement of TJPs, which provide valuable information for designing hybrid nanocomposites and facilitate the potential application of TJPs.

We study numerical methods for dissipative particle dynamics (DPD), which is a system of stochastic differential equations and a popular stochastic momentum-conserving thermostat for simulating complex hydrodynamic behavior at mesoscales. We propose a new splitting method that is able to substantially improve the accuracy and efficiency of DPD simulations in a wide range of the friction coefficients, particularly in the extremely large friction limit that corresponds to a fluid-like Schmidt number, a key issue in DPD. Various numerical experiments on both equilibrium and transport properties are performed to demonstrate the superiority of the newly proposed method over popular alternative schemes in the literature.