Polymer Depletion Research Articles

Stochastic model for the transfer of gaseous particles in polymer-carbon-nanotube nanocomposites with interfacial regions.

In this work, a stochastic model of gaseous transfer in polymer-carbon-nanotube (CNT) nanocomposites is presented. The model takes into account interfacial areas, i.e., polymer depletion regions. The local regime of transport is controlled by the density of the polymer. In a dense polymer, this regime corresponds to the ordinary diffusion, while in free volume regions, it corresponds to the ballistic transport. The introduction of a free volume and/or a depleted polymer layer near to a CNT wall leads to the emergence of anomalous diffusion. We have demonstrated how the anomalous diffusion regime changes in the presence of nanotubes for different distributions of polymer density. The presented approach allows us to describe the threshold effect in the diffusion coefficient as a function of CNTs density in polymer-CNT nanocomposites.

Reversible Microwheel Translation Induced by Polymer Depletion.

For in vivo applications, microbots (μbots) must move, which is a need that has led to designs, such as helical swimmers, that translate through the bulk fluid. We have previously demonstrated that, upon application of a rotating magnetic field, colloidal particles in aqueous systems can be reversibly assembled from superparamagnetic particles into μbots that translate along surfaces using wet friction. Here, we show that high-molecular-weight polymers of a size that approaches the length scale of the gap between the μbot and surface can be excluded, impacting μbot transport. Using xanthan gum as a convenient high-molecular-weight model, we determine that polymer depletion imparts only a weak effect on colloid-surface interactions but has a significant influence on local viscosity, which is an effect great enough to induce a reversal in the μbot translation direction.

A mechanistic model of cross-bridge migration in RBC aggregation and disaggregation.

Red blood cells (RBCs) clump together under low flow conditions in a process called RBC aggregation, which can alter RBC perfusion in a microvascular network. As elevated RBC aggregation is commonly associated with cardiovascular and inflammatory diseases, a better understanding of aggregation is essential. Unlike RBC aggregation in polymer solutions which can be well explained by polymer depletion theory, plasma-mediated RBC aggregation has features that best match explanations with cross-bridging mechanisms. Previous studies have demonstrated the dominant role of fibrinogen (Fg) in promoting aggregate formation and recent cell-force spectroscopy (CFS) experiments on interacting RBC doublets in plasma have reported an inverse relationship between disaggregation force and the adhesive contact area between RBCs. This has led investigators to revisit the hypothesis of inter-RBC cross-bridging which involves cross-bridge migration under interfacial tension during the forced disaggregation of RBC aggregates. In this study, we developed the cross-bridge migration model (CBMM) in plasma that mechanistically represents the migrating cross-bridge hypothesis. Transport of mobile Fg cross-bridges (mFg) was calculated using a convection-diffusion transport equation with our novel introduction of convective cross-bridge drift that arises due to intercellular friction. By parametrically transforming the diffusivity of mFg in the CBMM, we were able to match experimental observations of both RBC doublet formation kinematics and RBC doublet disaggregation forces under optical tweezers tension. We found that non-specific cross-bridging promotes spontaneous growth of adhesion area between RBC doublets whereas specific cross-bridging tends to prevent adhesion area growth. Our CBMM was also able to correlate Fg concentration shifts from healthy population blood plasma to SLE (lupus) condition blood plasma with the observed increase in doublet disaggregation forces for the RBC doublets in SLE plasma.

Protein-polymer mixtures in the colloid limit: Aggregation, sedimentation, and crystallization.

While proteins have been treated as particles with a spherically symmetric interaction, of course in reality, the situation is rather more complex. A simple step toward higher complexity is to treat the proteins as non-spherical particles and that is the approach we pursue here. We investigate the phase behavior of the enhanced green fluorescent protein (eGFP) under the addition of a non-adsorbing polymer, polyethylene glycol. From small angle x-ray scattering, we infer that the eGFP undergoes dimerization and we treat the dimers as spherocylinders with aspect ratio L/D - 1 = 1.05. Despite the complex nature of the proteins, we find that the phase behavior is similar to that of hard spherocylinders with an ideal polymer depletant, exhibiting aggregation and, in a small region of the phase diagram, crystallization. By comparing our measurements of the onset of aggregation with predictions for hard colloids and ideal polymers [S. V. Savenko and M. Dijkstra, J. Chem. Phys. 124, 234902 (2006) and Lo Verso et al., Phys. Rev. E 73, 061407 (2006)], we find good agreement, which suggests that the behavior of the eGFP is consistent with that of hard spherocylinders and ideal polymers.

Influence of solvent quality on depletion potentials in colloid-polymer mixtures.

As first explained by the classic Asakura-Oosawa (AO) model, effective attractive forces between colloidal particles induced by depletion of nonadsorbing polymers can drive demixing of colloid-polymer mixtures into colloid-rich and colloid-poor phases, with practical relevance for purification of water, stability of foods and pharmaceuticals, and macromolecular crowding in biological cells. By idealizing polymer coils as effective penetrable spheres, the AO model qualitatively captures the influence of polymer depletion on thermodynamic phase behavior of colloidal suspensions. In previous work, we extended the AO model to incorporate aspherical polymer conformations and showed that fluctuating shapes of random-walk coils can significantly modify depletion potentials [W. K. Lim and A. R. Denton, Soft Matter 12, 2247 (2016); J. Chem. Phys. 144, 024904 (2016)]. We further demonstrated that the shapes of polymers in crowded environments sensitively depend on solvent quality [W. J. Davis and A. R. Denton, J. Chem. Phys. 149, 124901 (2018)]. Here, we apply Monte Carlo simulation to analyze the influence of solvent quality on depletion potentials in mixtures of hard-sphere colloids and nonadsorbing polymer coils, modeled as ellipsoids whose principal radii fluctuate according to random-walk statistics. We consider both self-avoiding and non-self-avoiding random walks, corresponding to polymers in good and theta solvents, respectively. Our simulation results demonstrate that depletion of polymers of equal molecular weight induces much stronger attraction between colloids in good solvents than in theta solvents and confirm that depletion interactions are significantly influenced by aspherical polymer conformations.

Polymerization/depolymerization of actin cooperates with the morphology and stability of cell-sized droplets generated in a polymer solution under a depletion effect.

Intercellular fluids in living organisms contain high concentrations of macromolecules such as nucleic acid and protein. Over the past few decades, several studies have examined membraneless organelles in terms of liquid-liquid phase separation. These studies have investigated aggregation/attraction among a rich variety of biomolecules. Here, we studied the association between the polymerization/depolymerization of actin, interconversion between monomeric (G-actin) and filamentous states (F-actin), and water/water phase separation in a binary polymer solution using polyethylene glycol (PEG) and dextran (DEX). We found that actin, which is a representative cytoskeleton, changes its distribution in a PEG/DEX binary solution depending on its polymerization state: monomeric G-actin is distributed homogeneously throughout the solution, whereas polymerized F-actin is localized only within the DEX-rich phase. We extended our study by using fragmin, which is a representative actin-severing and -depolymerizing factor. It took hours to restore a homogeneous actin distribution from localization within the DEX-rich phase, even with the addition of fragmin in an amount that causes complete depolymerization. In contrast, when actin that had been depolymerized by fragmin in advance was added to a solution with microphase-separation, F-actin was found in DEX-rich phase droplets. The micro-droplets tended to deform into a non-spherical morphology under conditions where they contained F-actin. These findings suggest that microphase-separation is associated with the dynamics of polymerization and localization of the actin cytoskeleton. We discuss our observations by taking into consideration the polymer depletion effect.

Impact of In-Cell and In-Vitro Crowding on the Conformations and Dynamics of an Intrinsically Disordered Protein.

The conformations and dynamics of proteins can be influenced by crowding from the large concentrations of macromolecules within cells. Intrinsically disordered proteins (IDPs) exhibit chain compaction in crowded solutions in vitro, but no such effects were observed in cultured mammalian cells. Here, to increase intracellular crowding, we reduced the cell volume by hyperosmotic stress and used an IDP as a crowding sensor for in-cell single-molecule spectroscopy. In these more crowded cells, the IDP exhibits compaction, slower chain dynamics, and much slower translational diffusion, indicating a pronounced concentration and length-scale dependence of crowding. In vitro, these effects cannot be reproduced with small but only with large polymeric crowders. The observations can be explained with polymer theory and depletion interactions and indicate that IDPs can diffuse much more efficiently through a crowded cytosol than a globular protein of similar dimensions.

Impact of In‐Cell and In‐Vitro Crowding on the Conformations and Dynamics of an Intrinsically Disordered Protein

AbstractThe conformations and dynamics of proteins can be influenced by crowding from the large concentrations of macromolecules within cells. Intrinsically disordered proteins (IDPs) exhibit chain compaction in crowded solutions in vitro, but no such effects were observed in cultured mammalian cells. Here, to increase intracellular crowding, we reduced the cell volume by hyperosmotic stress and used an IDP as a crowding sensor for in‐cell single‐molecule spectroscopy. In these more crowded cells, the IDP exhibits compaction, slower chain dynamics, and much slower translational diffusion, indicating a pronounced concentration and length‐scale dependence of crowding. In vitro, these effects cannot be reproduced with small but only with large polymeric crowders. The observations can be explained with polymer theory and depletion interactions and indicate that IDPs can diffuse much more efficiently through a crowded cytosol than a globular protein of similar dimensions.

Improving the Flocculation Performance of Clay-Based Tailings in Seawater: A Population Balance Modelling Approach

A population balance model described the flocculation of clay-based mining tailings in treated seawater with reduced magnesium content. For the treatment, 0.06 M of lime was added to the liquor, generating solid magnesium complexes that were subsequently removed by vacuum filtration. Magnesium content varied between 10–1440 ppm when mixing raw seawater with treated seawater. The aggregate size was analysed by the Focused Beam Reflectance Measurement (FBRM) technology. The model follows the dynamics of the aggregation-rupture and it provides a good approximation to the temporal evolution. A decrease in collision efficiency was implemented as an indicator of the polymer depletion, describing the size reduction. Lower magnesium content makes larger aggregates with a higher fractal dimension, but an increase in the concentration of clays reduces both the size of aggregates and the fractal dimension, indicating more open and porous structures, with higher permeability to the passage of fluid. The model efficiently illustrates the experimental data, with R-square (R2) greater than 0.9 and Goodness of Fit (GoF) greater than 95% in most cases, wherein the fitting parameters allowed for analysing the impact of magnesium and clays on the collision efficiency, collision frequency, and fragmentation rate. The model is predictive with few parameters, and it is potentially a powerful tool for water management optimisation.

Adsorption and Diffusion Moderated by Polycationic Polymers during Electrodeposition of Zinc.

Electrodeposition of metals is relevant to much of materials research including catalysis, batteries, antifouling, and anticorrosion coatings. The sacrificial characteristics of zinc used as a protection for ferrous substrates is a central corrosion protection strategy used in automotive, aviation, and DIY industries. Zinc layers are often used for protection by application to a base metal in a hot dip galvanizing step; however, there is a significant interest in less energy and material intense electroplating strategies for zinc. At present, large-scale electroplating is mostly done from acidic zinc solutions, which contain potentially toxic and harmful additives. Alkaline electroplating of zinc offers a route to using environment-friendly green additives. Within the scope of this study an electrolyte containing soluble zinc hydroxide compound and a polyquarternium polymer as additive were studied during zinc deposition on gold model surfaces. Cyclic voltammetry experiments and in-situ electrochemical quartz crystal microbalance with dissipation (QCM-D) measurements were combined to provide a detailed understanding of fundamental steps that occur during polymer-mediated alkaline zinc electroplating. Data indicate that a zincate-loaded polymer can adsorb within the inner sphere of the electric double layer, which lowers the electrostatic penalty of the zincate approach to a negatively charged surface. X-ray photoelectron spectroscopy also supports the assertion that the zincate-loaded polymer is brought tightly to the surface. We also find an initial polymer depletion followed by an active deposition moderation via control of the zincate diffusion through the adsorbed polymer.

Bio-Based Polymer Electrolytes for Electrochemical Devices: Insight into the Ionic Conductivity Performance.

With the continuing efforts to explore alternatives to petrochemical-based polymers and the escalating demand to minimize environmental impact, bio-based polymers have gained a massive amount of attention over the last few decades. The potential uses of these bio-based polymers are varied, from household goods to high end and advanced applications. To some extent, they can solve the depletion and sustainability issues of conventional polymers. As such, this article reviews the trends and developments of bio-based polymers for the preparation of polymer electrolytes that are intended for use in electrochemical device applications. A range of bio-based polymers are presented by focusing on the source, the general method of preparation, and the properties of the polymer electrolyte system, specifically with reference to the ionic conductivity. Some major applications of bio-based polymer electrolytes are discussed. This review examines the past studies and future prospects of these materials in the polymer electrolyte field.

Fluorescence microscopy tracking of dyes, nanoparticles and quantum dots during growth of polymer spherulites

The distribution of additives and nanoparticles in a semicrystalline polymer is largely dependent on the complex hierarchical polymer morphology and the kinetics of its development. Here we show by in-situ fluorescence microscopy (FM), coupled with polarized optical and scanning electron microscopy, that a substantial fraction of the additive (Nile Red, NR) and even NR-labelled silica nanoparticles (NP) and quantum dots (QD) was pushed ahead of the growing spherulites during melt-crystallization. For the 35 and 200 nm NPs this was unexpected because their diffusion coefficient based on Stokes-Einstein equation should have been 2–3 orders of magnitude slower than the rate at which spherulites were growing. Another surprising finding was that much of the initially rejected NR and some QDs subsequently re-entered the spherulites through back-diffusion, posing the question why they were then rejected in the first place. The excessive initial rejection of NR and QDs and the unexpectedly rapid migration of NPs are both explained by the additive preferentially filling and being carried along by the polymer depletion zone in the melt ahead of the growing spherulite, and the high negative pressure in these zones. The effectiveness of FM in detecting minute cracks and cavities is also demonstrated. The results also show that the most severe clustering of additives occurs where spherulites did not nucleate, a problem preventable by the addition of nucleating agent.

Flow induced by an oscillating sphere in probing complex viscosity of polymer solutions

A theoretical investigation is presented for a linear viscoelastic flow induced by an oscillatory colloidal particle in nonadsorbing polymer solutions. At small-amplitude oscillations, the polymer distribution is assumed to be at equilibrium and forms a depletion zone around the particle based on the mean-field approximation. The goal of the theoretical approach is to predict the apparent complex viscosity sensed by the particle and compare this with the actual viscosity of the bulk fluid. Due to the local inhomogeneity, substantial deviation between the apparent and true viscosity in the bulk needs to be corrected quantitatively. The resulting apparent complex viscosity or friction coefficient in the Fourier domain will help to interpret active and passive microrheological measurements of colloid-polymer mixtures that take polymer depletion into account.

Sea Shell: A Marine Waste to Filler in Polymer Composite

This work focuses on the sea shell and its source and application of known clam shells. These clam shells are marine waste which is made of calcium carbonates .Its utilization is highly required to make a value added product and waste minimization. The depletion of polymer has motivated the researcher to search the alternative to reduce the consumption of polymer. Thus the recent studies on the clam shells have been done to understand its utilization in polymer and other application. Some of the important applications may include potential of seashell as filler materials in different polymeric composites, which would enhance its mechanical properties along with its applications in mechanical industries.

Economic Analysis of Low Salinity Polymer Flooding Potential in the Niger Delta Oil Fields

With the current growing demand for oil, oil price and the concerns about future oil supplies increases the pressure in securing oil resources. Enhanced oil recovery processes are applied to recover oil not produced by natural and secondary energy drive of the reservoir. In this study, Simulation has been carried out on a hypothetical model using (ECLIPSE 100) as the simulator. Three cases natural depletion, waterflooding, and injection of low saline polymer were considered.5-spot pattern of four vertical producers wells and one vertical injector well was used as a hypothetical well model. Economics analysis were carried out in this three scenario to determine their net present value, profit per dollar invested, payout and Discounted flow-rate of return. The results shows that low salinity polymer flooding has the highest recovery of 62% and profit with NPV @ 10 ($412.9MM), payout 0.9 years, profit per dollar invested $25.9 and dcf-ror 82%. However, waterflooding gave recovery of 42%. NPV @10 ($ 317.3MM), payout 1.2 years, profit per dollar invested $20.8, dcf-ror 78%. Natural depletion gave recovery of 16.5 %, profit with NPV @10 (230.0MM), payout 1.0 years, profit per dollar invested $9.3, dcf-ror 78%. Decision rule was applied using NPV, DCF-ROR, NCR and payout which states that project with higher NPV, DCF-ROR, NCR and less Payout are more economically viable. The result of the three cases considered shows that low salinity polymer injection is more profitable followed by waterflooding and natural depletion.

Assembly of Microparticles to Patterned Trenches Using the Depletion Volume Effect.

In this paper, we demonstrate that 20 μm microbeads can be preferentially assembled into substrate trenches of similar width by employing a polymer (depletant) that induces the depletion volume effect (depletion attraction). In previous works, we proved that this strategy is useful to assemble mesoscale parts in a site-specific manner. Here, we show that it is also applicable to assemble functional parts, such as fluorescent particles, into trenches engraved on the surface of two- and three-dimensional template components. A convenient advantage of this strategy is that it is independent of material properties for assembling mesoscale functional components into desired patterns.

Transport potential of super-hydrophobic organic contaminants in anionic-nonionic surfactant mixture micelles

Surfactant mixtures are commonly used in agricultural and soil remediation applications, necessitating an understanding of their micellization behavior and associated impact on the fate of co-existing chemicals in the subsurface. A polymer-water sorption isotherm approach was shown to present an alternative to traditional methods for quantifying, understanding and predicting surfactant mixture properties. Micelle compositions were measured for anionic-nonionic surfactant mixtures. This is important since micelle composition can alter the apparent aqueous solubility of super-hydrophobic organic contaminants (SHOCs) resulting in surfactant facilitated transport (SFT). A key parameter in predicting SFT for SHOCs is their micelle-water partition constant (KMI). These were determined for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated biphenyls (PCBs) with representative anionic-nonionic surfactant mixtures using a polymer depletion method. These previously unreported constants were intermediate between those for pure anionic and nonionic surfactant solutions, with magnitude depending on micelle composition. Separate linear relationships were found between log KMI and log KOW for PCDDs and PCBs. This work provides new methods and preliminary results relating to binary surfactant mixtures (e.g. critical micelle concentration and micelle composition) and SHOCs (KMI) that are important in the evaluation of the fate and transport of SHOCs in the subsurface environment and provide insight into the environmental mobility of these important contaminants.

Enhanced bacterial swimming speeds in macromolecular polymer solutions

The locomotion of swimming bacteria in simple Newtonian fluids can successfully be described within the framework of low Reynolds number hydrodynamics. The presence of polymers in biofluids generally increases the viscosity, which is expected to lead to slower swimming for a constant bacterial motor torque. Surprisingly, however, several experiments have shown that bacterial speeds increase in polymeric fluids, and there is no clear understanding why. Therefore we perform extensive coarse-grained simulations of a bacterium swimming in explicitly modeled solutions of macromolecular polymers of different lengths and densities. We observe an increase of up to 60% in swimming speed with polymer density and demonstrate that this is due to a depletion of polymers in the vicinity of the bacterium leading to an effective slip. However this in itself cannot predict the large increase in swimming velocity: coupling to the chirality of the bacterial flagellum is also necessary.

Red blood cell adhesion can be reduced by non-reactive macromolecules.

To date, the mechanisms behind red blood cell (RBC) adhesion remain unclear. However, polymer depletion at the red cell surface has been shown to play a significant role. Interestingly, most previous studies have focused on the adhesion-promoting effects of one type of large polymer or plasma protein. However, the situation in vivo is more complex in that one needs to consider a mixture of various bio-macromolecules. To explore this complexity, Interference Reflection Microscopy was used to investigate how mixtures of various polymers affect RBC adhesion. RBC adhesion to albumin-coated glass coverslips was studied in the presence of two pro-adhesion polymers [dextran70 kDa and 35 kDa poly(ethylene glycol) (PEG 35)] with and without three types of smaller polymers: dextran 10 kDa, PEG 10 kDa and Poloxamer 188. Our findings show that the presence of small polymers can inhibit the adhesion-promoting effects of dextran 70 and PEG 35, with a more pronounced reduction for heterogeneous mixtures. Interpretation of our results in terms of the depletion model appears appropriate, in that our findings are consistent with the assumption that this reduction occurs because of an increase of small molecules in the depletion region. This study thus suggests that depletion interaction can control cell-cell interactions in complex environments (e.g., in vivo), and indicates that considering the interplay of all plasma constituents is important in order to understand the pathophysiology of diseases associated with cell adhesion and vascular complications.

Effects of polymer adsorption on the effective viscosity in microchannel flows: phenomenological slip layer model from molecular simulations

Molecular simulations (Dissipative Particle Dynamics - DPD) were used to quantify the effect of polymer adsorption on the effective shear viscosity of a semi-dilute polymer solution in microchannel Poseuille flow. It is well known that polymer depletion layers develop adjacent to solid walls due to hydrodynamic forces, causing an apparent wall slip and reduced effective viscosity (increased total flow rate). We found that depletion layers also developed in the presence of hydrodynamically rough adsorbed layers on the wall. Polymer-polymer (steric) repulsion between flowing and adsorbed polymer expanded the depletion layer compared to no-adsorption cases, and the effective viscosity was reduced further. Desorption occurred for higher shear rates, reducing the repulsion effect and shrinking the depletion layers. A phenomenological algebraic model for the depletion layer thickness, including a shear modified adsorption isotherm, was developed based on the simulation data. The depletion layer model can be used together with the effective viscosity model we developed earlier.