Evolution Kinetics of Stabilizing Pickering Emulsion by Brush-Modified Janus Particles: DPD Simulation and Experimental Insights.

In the present study, we report the evolution of stabilizing Pickering emulsions using brush-modified Janus particles (JPs), utilizing the dissipative particle dynamics (DPD) simulation technique. Our results are subsequently corroborated with experimental findings. Each JP has one-half of the hydrophobic surface, with the other half embedded with hydrophilic polymer brushes grown via atom transfer radical polymerization (ATRP). Our generic simulation model analyzes the chemical kinetics of polymer brush growth on one-half of the initiator-embedded microparticle (MP) surface, resulting in the formation of JP. This involves evaluating monomer conversion and reaction rates. Our results exhibit a substantial influence of the number of JPs, grafted brush density, and brush length on oil-in-water emulsion stability. We studied the evolution kinetics and stability of emulsion formation by analyzing the growth of average domain size and corresponding scaling functions up to a late time limit. This study aims to clarify the connection between the size, quantity, and functionality of JPs and the stability of Pickering emulsions.

Architecture dependent transport behavior of iron (0) entrapped biodegradable polymeric particles for groundwater remediation.

Polylactic acid based spherical particles with three architectural variations (Isotropic (P1), Semi porous (P2), and Janus (P3)) were employed to encapsulate zero valent iron nanoparticles (ZVINPs), and their performance was extensively evaluated in our previous studies. However, little was known about their transportability through saturated porous media of varying grain size kept under varying ionic strength. In this particular study, we aimed to investigate the architectural effect of polymeric particles (P1-P3) on their mobility through the sand column of varying grain size in presence of mono, di, and tri-valent ions of varying concentrations (25-200 mM (millimoles)). As per column breakthrough experiments (BTCs) using various types of sands, amphiphilic Janus type (P3) particles exhibited the maximum transportability among all the tested particles, irrespective of the nature of the sand. Owing to the narrower travel path, sands with lower porosity (31%) delayed the plateau by shifting it to a higher pore volume with a minimum retention of iron (C/Co: 0.94 for P3) in the column. The impact of mono (Na+, K+), di (Ca2+, Mg2+), and trivalent (Al3+) ions on their transportability was progressively increased from P3 to P1, especially at higher ionic concentrations (200 mM), with P3 being the most mobile particles (C/Co:0.54 for Al3+). Among all the ions, Al3+ exhibited maximum hindrance to their mobility through the sand column. This could be due to their strong charge screening effect coupled with cation bridging complex formation with moving particles. Experimental results obtained from BTCs were found to be well-fitted with a theoretical model based on advection-dispersion equation, showing minimum retention for P3 particles. Overall, it can be inferred that encapsulation of ZVINPs inside Janus particles (P3) with a right balance of amphiphilicity and highly negative surface charge would be required to achieve considerable transportability through sand aquifers to target contaminants in polluted groundwater existing under harsh conditions (high ionic concentrations).

Growth kinetics and morphology characterization of binary polymeric fluid under random photo-illumination.

We present a comprehensive study using dissipative particle dynamics simulations to investigate phase separation kinetics (PSK) in three-dimensional (3d) polymeric fluids under random photo-illumination. We consider two scenarios: polymer blends with active radicals at one end of each immiscible chain and block copolymer (BCP) melts with photosensitive bonds linking incompatible blocks. The phase separation (PS) is induced by temperature quench of the initial homogeneously mixed system. Simultaneously, the system experiences random photo-illumination, simulated by two concurrent random events: (a) the recombination of active radicals in polymer blends and (b) the breaking of photosensitive bonds in BCP chains. Variations in the bond-breaking probability, Pb, mimic the change in light intensity. The length scale follows power law growth, R(t) ∼ tϕ, where ϕ represents the growth exponent. Increasing Pb results in a gradual transition in growth kinetics from micro-PS to macro-PS, accompanied by corresponding transition probabilities for both systems. Micro-PSK dominates the evolution process at low Pb values. The scaling functions exhibit data overlap for most scaled distances, indicating the statistical self-similarity of evolving patterns. Our study enhances the understanding of PSK in polymeric fluids, revealing the impact of photosensitive bonds and active radicals. Furthermore, it suggests the potential for designing novel polymeric materials with desired properties.

Effect of amphiphilic polymers on phase separating binary mixtures: A DPD simulation study.

We present the phase separation dynamics of a binary (AB), simple fluid (SF), and amphiphilic polymer (AP) mixture using dissipative particle dynamics simulation at d = 3. We study the effect of different AP topologies, including block copolymers, ring block copolymers (RCP), and miktoarm star polymers, on the evolution morphologies, dynamic scaling functions, and length scale of the AB mixture. Our results demonstrate that the presence of APs leads to significantly different evolution morphologies in SF. However, the deviation from dynamical scaling is prominent, mainly for RCP. Typically, the characteristic length scale for SF follows the power law R(t) ∼ tϕ, where ϕ is the growth exponent. In the presence of high AP, we observe diffusive growth (ϕ → 1/3) at early times, followed by saturation in length scale (ϕ → 0) at late times. The extent of saturation varies with constraints imposed on the APs, such as topology, composition ratio, chain length, and stiffness. At lower composition ratios, the system exhibits inertial hydrodynamic growth (ϕ → 2/3) at asymptotic times without clearly exhibiting the viscous hydrodynamic regime (ϕ → 1) at earlier times in our simulations. Our results firmly establish the existence of hydrodynamic growth regimes in low surfactant-influenced phase separation kinetics of binary fluids and settle the related ambiguity in d = 3 systems.

Segregation of fluids with polymer additives at domain interfaces: a dissipative particle dynamics study.

This paper investigates the phase separation kinetics of ternary fluid mixtures composed of a polymeric component (C) and two simple fluids (A and B) using dissipative particle dynamics simulations with a system dimensionality of d = 3. We model the affinities between the components to enable the settling of the polymeric component at the interface of fluids A and B. Thus, the system evolves to form polymer coated morphologies, enabling alteration of the fluids' interfacial properties. This manipulation can be utilized across various disciplines, such as the stabilization of emulsions and foams, rheological control, biomimetic design, and surface modification. We probe the effects of various parameters, such as the polymeric concentration, chain stiffness, and length, on the phase separation kinetics of the system. The simulation results show that changes in the concentration of flexible polymers exhibit perfect dynamic scaling for coated morphologies. The growth rate decreases as the polymeric composition is increased due to reduced surface tension and restricted connectivity between A- and B-rich clusters. Variations in the polymer chain rigidity at fixed composition ratios and degrees of polymerization slow the evolution kinetics of AB fluids marginally, although the effect is more pronounced for perfectly rigid chains. Whereas flexible polymer chain lengths at fixed composition ratios slow down the segregation kinetics of AB fluids slightly, varying the chain lengths of perfectly rigid polymers leads to a significant deviation in the length scale and dynamic scaling for the evolved coated morphologies. The characteristic length scale follows a power-law growth with a growth exponent ϕ that shows a crossover from the viscous to the inertial hydrodynamic regime, where the values of ϕ depend on the constraints imposed on the system.

Dissipative particle dynamics simulation study on ATRP-brush modification of variably shaped surfaces and biopolymer adsorption.

We present a dissipative particle dynamics (DPD) simulation study on the surface modification of initiator embedded microparticles (MPs) of different shapes via atom transfer radical polymerization (ATRP) brush growth. The surface-initiated ATRP-brush growth leads to the formation of a more globular MP shape. We perform the comparative analysis of ATRP-brush growth on three different forms of particle surfaces: cup surface, spherical surface, and flat surface (rectangular/disk-shaped). First, we establish the chemical kinetics of the brush growth: the monomer conversion and the reaction rates. Next, we discuss the structural changes (shape-modification) of brush-modified surfaces by computing the radial distribution function, spatial density distribution, radius of gyration, hydrodynamic radius, and shape factor. The polymer brush-modified particles are well known as the carrier materials for enzyme immobilization. Finally, we study the biopolymer adsorption on ATRP-brush modified particles in a compatible solution. In particular, we explore the effect of ATRP-brush length, biopolymer chain length, and concentration on the adsorption process. Our results illustrate the enhanced biopolymer adsorption with increased brush length, initiator concentration, and biopolymer concentration. Most importantly, when adsorption reaches saturation, the flat surface loads more biopolymers than the other two surfaces. The experimental results verified the same, considering the disk-shaped flat surface particles, cup-shaped particles, and spherical particles.

Photo-induced bond breaking during phase separation kinetics of block copolymer melts: a dissipative particle dynamics study.

Using a dissipative particle dynamics (DPD) simulation method, we study the phase separation dynamics in block copolymer (BCP) melts in d = 3, subjected to external stimuli such as light. An initial homogeneous BCP melt is rapidly quenched to a temperature T < Tc, where Tc is the critical temperature. We then allow the system to undergo alternate light "on" and "off" cycles. An on-cycle breaks the stimuli-sensitive bonds connecting both the blocks A and B in the BCP melt, and during the off-cycle, the broken bonds recombine. By simulating the effect of light, we isolate scenarios where phase separation begins with the light off (set 1); the cooperative interactions within the system allow it to undergo microphase separation. When the phase separation starts with the light on (set 2), the system undergoes macrophase separation due to bond breaking. Here, we report the role of alternate cycles on domain morphology by varying the bond-breaking probability for both set 1 and set 2, respectively. We observe that the scaling functions depend upon the conditions mentioned above that change the time scale of the evolving morphologies in various cycles. However, in all the cases, the average domain size respects the power-law growth: R(t) ∼tφ at late times, where φ is the dynamic growth exponent. After a short-lived diffusive growth (φ∼ 1/3) at early times, φ illustrates a crossover from the viscous hydrodynamic (φ∼ 1) to the inertial hydrodynamic (φ∼ 2/3) regimes at late times.

High Adsorption of α-Glucosidase on Polymer Brush-Modified Anisotropic Particles Acquired by Electrospraying-A Combined Experimental and Simulation Study.

In this particular contribution, we aim to immobilize a model enzyme such as α-glucosidase onto poly(DMAEMA) [poly(2-dimethyl amino ethyl methacrylate)] brush-modified anisotropic (cup- and disc-shaped) biocompatible polymeric particles. The anisotropic particles comprising a blend of PLA [poly(lactide)] and poly(MMA-co-BEMA) [poly((methyl methacrylate)-co-(2-(2-bromopropionyloxy) ethyl methacrylate)] were acquired by electrospraying, a scalable and convenient technique. We have also demonstrated the role of a swollen polymer brush grafted on the surface of cup-/disc-shaped particles via surface-initiated atom transfer radical polymerization in immobilizing an unprecedentedly high loading of enzyme [441 mg/g (cup)-589 mg/g (disc) of particles, 15-20 times higher than that of the literature-reported system] as compared to non-brush-modified particles. Circular dichroism spectroscopy was used to predict the structural changes of the enzyme upon immobilization onto the carrier particles. An enormously high amount of enzymes with preserved activity (∼85 ± 13% for cups and ∼78 ± 15% for discs) was found to adhere onto brush-modified particles at pH 7 via electrostatic adsorption. These findings were further explored at the atomistic level using a coarse-grained dissipative particle dynamics simulation approach, which exhibited excellent correlation with experimental results. In addition, accelerated particle separation was also achieved via magnetic force-induced aggregation within 20 min (without a centrifuge) by incorporating magnetic nanoparticles into disc-shaped particles while electrojetting. This further strengthens the technical feasibility of the process, which holds immense potential to be applied for various enzymes intended for several applications.

Role of a polymeric component in the phase separation of ternary fluid mixtures: a dissipative particle dynamics study.

We present the results from dissipative particle dynamics (DPD) simulations of phase separation dynamics in ternary (ABC) fluids mixture in d = 3 where components A and B represent the simple fluids, and component C represents a polymeric fluid. Here, we study the role of polymeric fluid (C) on domain morphology by varying composition ratio, polymer chain length, and polymer stiffness. We observe that the system under consideration lies in the same dynamical universality class as a simple ternary fluids mixture. However, the scaling functions depend upon the parameters mentioned above as they change the time scale of the evolution morphologies. In all cases, the characteristic domain size follows l(t) ∼ tφ with dynamic growth exponent φ, showing a crossover from the viscous hydrodynamic regime (φ = 1) to the inertial hydrodynamic regime (φ = 2/3) in the system at late times.

Designing polymer gels and composites that undergo bio-inspired phototactic reconfiguration and motion.

Inspired by the adaptive behavior of photo-responsive biological organisms, we develop analytical and computational models to design polymer gels and composites that can be dynamically reconfigured and driven to move with the application of light. We focus on gels formed from poly(N-isopropylacrylamide) and functionalized with spirobenzopyran (SP) chromophores, which become hydrophobic under blue light in acidic aqueous solution. Using our modeling approaches, we irradiate the gels through photomasks and demonstrate that the shapes of the samples can be reversibly and remotely 'remolded' by varying the apertures in the masks. By simulating the effect of repeatedly moving the light across the sample, we also show that the gel can undergo directed motion. We then examine gels that contain both SP chromophores and the ruthenium catalysts that drive the oscillatory Belousov-Zhabotinsky reaction. These dual-functionalized gels undergo spontaneous, self-sustained motion even when the lights are held stationary. We also simulate the behavior of composites formed from SP-functionalized fibers embedded in the poly(N-isopropylacrylamide) gel. With the SP-functionalization confined to the fibers, light and heat act as orthogonal stimuli and thus the composites display distinctly different modes of movement when the different cues are applied to the samples. Overall, our findings provide guidelines for using light to controllably reconfigure the shape and drive the movement of gel-based materials and thus, tailor the material to display different functionalities.

Effect of bond-disorder on the phase-separation kinetics of binary mixtures: A Monte Carlo simulation study.

We present Monte Carlo (MC) simulation studies of phase separation in binary (AB) mixtures with bond-disorder that is introduced in two different ways: (i) at randomly selected lattice sites and (ii) at regularly selected sites. The Ising model with spin exchange (Kawasaki) dynamics represents the segregation kinetics in conserved binary mixtures. We find that the dynamical scaling changes significantly by varying the number of disordered sites in the case where bond-disorder is introduced at the randomly selected sites. On the other hand, when we introduce the bond-disorder in a regular fashion, the system follows the dynamical scaling for the modest number of disordered sites. For a higher number of disordered sites, the evolution morphology illustrates a lamellar pattern formation. Our MC results are consistent with the Lifshitz-Slyozov power-law growth in all the cases.

Living Additive Manufacturing: Transformation of Parent Gels into Diversely Functionalized Daughter Gels Made Possible by Visible Light Photoredox Catalysis.

Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials "dead" toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative "living additive manufacturing" strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant "parent" materials to generate more complex and diversely functionalized "daughter" materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinduced single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent's average composition, strand length, and/or cross-linking density. Daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized.

Photo-regeneration of severed gel with iniferter-mediated photo-growth.

Using dissipative particle dynamics (DPD), we developed a computational approach to model the light-induced regeneration of a gel matrix when a significant portion of the material is severed. We considered photo-controlled radical polymerization (photo-CRP) within polymer networks with embedded iniferter groups: the "photo-growth" strategy. Absorption of light by the iniferter groups turns on the polymerization process, which inserts monomers and cross-linkers into the network strands. Photo-growth allows us to effectively regenerate a severed gel under the application of light even when the severed parts are not in direct contact. The growth process can be turned off once the polymerization is near completion to yield a new cross-linked gel that resembles the uncut material.

Combining ATRP and FRP Gels: Soft Gluing of Polymeric Materials for the Fabrication of Stackable Gels.

Stackable gels comprised of layers of dissimilar polymers were synthesized by combining conventional free radical polymerization (FRP) and atom transfer radical polymerization (ATRP) using two approaches: (i) polymerization of a pre-gel solution containing a monomer and cross-linker introduced on top of a previously prepared gel, and (ii) simultaneous polymerization of two immiscible pre-gel solutions remaining in contact. All permutations of FRP and ATRP yielded single-piece, connected, amphiphilic gels regardless of the order of polymerization. Furthermore, multi-layer ATRP gels combining different polymers were synthesized with the FRP layer as a gluing agent. A 10-layer amphiphilic stackable gel combining n-butyl methacrylate (BMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA), and a 10-layer stackable gel combining BMA, DMAEMA and di(ethylene glycol) methyl ether methacrylate (PEO2MA) were synthesized. This patching method, combining conventional FRP gels with ATRP ones, offers an efficient path to the formation of complex stackable gel architectures.

Embedding flexible fibers into responsive gels to create composites with controllable dexterity.

Using computational modeling, we design a composite that encompasses a thermo-responsive gel and photo-responsive fibers that extend from the surface of the gel. By simulating the effect of light and heat on the sample, we isolate scenarios where cooperative interactions within the system allow the gel to actuate the "finger-like" motion of the embedded fibers. To achieve this distinctive behavior, we consider a gel formed from poly(N-isopropylacrylamide) (PNIPAAm), which shrinks when heated above the lower critical solution temperature (LCST). The fibers are functionalized with spirobenzopyran (SP) chromophores that extend a finite region into the polymer network. The application of heat causes the entire gel to shrink, while the application of light causes the regions around the functionalized fibers to collapse. With the fibers arranged in a square or circular pattern in the center of the gel, heating the non-illuminated samples drives the fibers to move apart as they bend outward (away from the center). With the application of light, the tips of fibers come together as the fibers bend inward. In this configuration, the fibers could act as grippers that bind objects in the presence of light. With the illumination turned off, the grippers could controllably release the objects. By placing the fibers closer to the edge of the sample, the combination of heat and light could be harnessed to bind and release larger objects. We also show that by illuminating the fibers separately, we can manipulate the motion of the individual finger-like objects, and thus, potentially expand the utility of the system. Overall, our findings provide guidelines for controllably reconfiguring the shape of soft materials and thus, tailoring the material to display different functionalities in different environments.

Ordering Dynamics in Neuron Activity Pattern Model: An Insight to Brain Functionality.

We study the domain ordering kinetics in d = 2 ferromagnets which corresponds to populated neuron activities with both long-ranged interactions, V(r) ∼ r-n and short-ranged interactions. We present the results from comprehensive Monte Carlo (MC) simulations for the nonconserved Ising model with n ≥ 2, interaction range considering near and far neighbors. Our model results could represent the long-ranged neuron kinetics (n ≤ 4) in consistent with the same dynamical behaviour of short-ranged case (n ≥ 4) at far below and near criticality. We found that emergence of fast and slow kinetics of long and short ranged case could imitate the formation of connections among near and distant neurons. The calculated characteristic length scale in long-ranged interaction is found to be n independent (L(t) ∼ t1/(n-2)), whereas short-ranged interaction follows L(t) ∼ t1/2 law and approximately preserve universality in domain kinetics. Further, we did the comparative study of phase ordering near the critical temperature which follows different behaviours of domain ordering near and far critical temperature but follows universal scaling law.

Phase separation in ternary fluid mixtures: a molecular dynamics study.

We present detailed results from molecular dynamics (MD) simulations of phase separation in ternary (ABC) fluid mixtures for d = 2 and d = 3 systems. Our MD simulations naturally incorporate hydrodynamic effects. The domain growth law is l(t) ∼ t(ϕ) with dynamic growth exponent ϕ. Our data clearly indicate that a ternary fluid mixture reaches a dynamical scaling regime at late times with a gradual crossover from ϕ = 1/3 → 1/2 → 2/3 in d = 2 and ϕ = 1/3 → 1 in d = 3 resulting from the hydrodynamic effect in the system. These MD simulations do not yet access the inertial hydrodynamic regime (with l(t) ∼ t(2/3)) of phase separation in ternary fluid mixtures in d = 3.

Kinetics of phase separation in polymer mixtures: a molecular dynamics study.

We present detailed results from a molecular dynamics (MD) simulation of phase-separation kinetics in polymer mixtures. Our MD simulations naturally incorporate hydrodynamic effects. We find that polymeric phase separation (with dynamically symmetric components) is in the same universality class as segregation of simple fluids: the degree of polymerization only slows down the segregation kinetics. For d = 2 polymeric fluids, the domain growth law is L(t) ∼ t(ϕ) with ϕ showing a crossover from 1/3 → 1/2 → 2/3. For d = 3 polymeric fluids, we see the crossover ϕ = 1/3 → 1. Our MD simulations do not yet access the inertial hydrodynamic regime (with L ∼ t(2/3)) of phase separation in 3-d fluids.

Growth kinetics of nanoclusters in solution.

We study the growth kinetics of nanoclusters in solution. There are two generic factors that drive growth: (a) reactions that produce the nanomaterial; and (b) diffusion of the nanomaterial due to chemical-potential gradients. We model the growth kinetics of ZnO nanoparticles via coupled dynamical equations for the relevant order parameters. We study this model both analytically and numerically. We find that there is a crossover in the nanocluster growth law: from L(t) ∼ t(1/2) in the reaction-controlled regime to L(t) ∼ t(1/3) in the diffusion-controlled regime.

Control of structure formation in phase-separating systems.

In this paper, we study the evolution of phase-separating binary mixtures which are subjected to alternate cooling and heating cycles. An initially homogeneous mixture is rapidly quenched to a temperature T(1)T(c). These cycles are repeated to create a domain morphology with multiple length scales, i.e., the structure factor is characterized by multiple peaks. For phase separation in d = 2 systems, we present numerical and analytical results for the emergence and growth of this multiple-scale morphology.