Brush Height Research Articles

Mixed brushes consisting of oppositely charged Y‐shaped polymers in salt free, monovalent, and divalent salt solutions

AbstractThe conformation and the internal stratification of mixed brushes formed from oppositely charged Y(−) and Y(+)‐shaped chains in salt free, monovalent, and divalent salt solutions were studied by means of molecular dynamics simulations using the primitive model. Scaling relations of mixed brush height with respect to the grafting surface per chain, the ratio of the total positive to the total negative charge of polyelectrolyte chains, and salt concentrations were obtained. The simulations predicted that mixed brushes show a unique response to divalent salt (1:2) solutions. For symmetric brushes having the same spacer lengths, number of chains and charged units fractions the increase of the salt concentration leads to the enrichment of the outer brush surface with Y(+) units and the lamella microphase separation. For asymmetric brushes in high salt concentration cylindrical domain microphases are formed.

Density functional study of one- and two-component bottlebrush molecules in solvents of varying quality

Modified inhomogeneous statistical associating fluid theory (iSAFT) density functional theory is extended to bottlebrush polymers in both good and poor solvent. The detailed structures of side chains in the implicit solvent are calculated and have a semi-quantitative agreement with simulation. The average brush heights calculated from the theory agree with well-established scaling theories. iSAFT is easily extended to model bottlebrush polymers with two or more components. For an amphiphilic core-shell bottlebrush polymer, if the solvent-phobic block is much shorter than the solvent-philic block, it will fold towards the backbone even though it resides at the free end of the side chain. Similarly, for an amphiphilic mixed-type bottlebrush polymer, the chain length of different components has a great impact on the structure and properties of the molecule. The molecule may not have the response (the switch of outer layer) towards the solvent treatment if one component is significantly longer than the other. Our results provide insight into the conformation of bottlebrush polymers as well as guidance in practical applications.

Densely Grafted Polyelectrolyte Brushes Trigger “Water-in-Salt”-like Scenarios and Ultraconfinement Effect

Summary This paper presents an all-atom molecular dynamics (MD) simulation of highly charged and densely grafted polyelectrolyte (PE) brushes on a flat surface. Simulation findings for the variation of brush height with polymer size and grafting density are explained by the scaling laws for brushes in the non-linear osmotic regime. More importantly, this study establishes the triggering of an ultraconfinement effect by the densely grafted brushes. This effect leads to significant changes in the distribution, structure, and properties as well as a massive mobility reduction of both the counterions and water. Furthermore, the interplay of the ultraconfinement effect and the large counterion-PE electrostatic interactions trigger a “water-in-salt”-like scenario (witnessed in highly concentrated aqueous electrolyte solutions), which is characterized by the counterion-PE-functional group serving as the “salt” with the “salt” overwhelming the water in both mass and volume and affecting the solvation structure of the counterions by replacing the solvation water with the PE-functional group.

Influence of pore morphology on the diffusion of water in triblock copolymer membranes.

Understanding the transport properties of water in self-assembled block copolymer morphologies is important for furthering the use of such materials as water-purifying membranes. In this study, we used coarse-grained dissipative particle dynamics simulations to clarify the influence of pore morphology on the self-diffusion of water in linear-triblock-copolymer membranes. We considered representative lamellar, cylindrical, and gyroid morphologies and present results for both the global and local diffusivities of water in the pores. Our results suggest that the diffusivity of water in the confined, polymer-coated pores differs from that in the unconfined bulk. Explicitly, in confinement, the mobility of water is reduced by the hydrodynamic friction arising from the hydrophilic blocks coating the pore walls. We demonstrate that in lamella and cylindrical morphologies, the latter effects can be rendered as a universal function of the pore size relative to the brush height of the hydrophilic blocks.

Self-regenerating giant hyaluronan polymer brushes

Tailoring interfaces with polymer brushes is a commonly used strategy to create functional materials for numerous applications. Existing methods are limited in brush thickness, the ability to generate high-density brushes of biopolymers, and the potential for regeneration. Here we introduce a scheme to synthesize ultra-thick regenerating hyaluronan polymer brushes using hyaluronan synthase. The platform provides a dynamic interface with tunable brush heights that extend up to 20 microns – two orders of magnitude thicker than standard brushes. The brushes are easily sculpted into micropatterned landscapes by photo-deactivation of the enzyme. Further, they provide a continuous source of megadalton hyaluronan or they can be covalently-stabilized to the surface. Stabilized brushes exhibit superb resistance to biofilms, yet are locally digested by fibroblasts. This brush technology provides opportunities in a range of arenas including regenerating tailorable biointerfaces for implants, wound healing or lubrication as well as fundamental studies of the glycocalyx and polymer physics.

Viscoelastic and dynamic properties of polymer grafted nanocomposites with high glass transition temperature graft chains

The viscoelastic and dynamic properties of dynamically asymmetric polymer-grafted nanocomposites (PGNs) are studied via molecular dynamics simulations. The model PGN is made up of two chains having a large glass transition temperature (Tg) difference, where the grafted chains have the higher Tg. The viscoelastic and dynamic properties were studied at temperatures between the Tgs of the graft and matrix polymers as a function of the average brush height. Simulation results showed that the static and dynamic properties of the glassy brush played an important role in reinforcing the overall nanocomposite. Although the bare nanofiller containing nanocomposite showed increased shear storage moduli compared to the neat low-Tg polymer, PGNs presented the greatest increases in the shear storage modulus. In addition, the shear storage modulus increased with increasing average brush height, reaching a maximum value at the brush height limit. Analysis of the simulation results revealed that the reinforcement of the shear storage modulus was mainly related to the slowing down of the dynamics of matrix polymer chains. The following mechanisms were identified that were responsible for this effect: (i) High-Tg grafted chains act as obstacles for matrix polymer chains. (ii) With increasing average brush height, grafted and matrix chains form a well-mixed morphology at the nanofiller interface, which leads to further slowing down of the matrix chain dynamics. (iii) Finally, at the brush height limit, grafted chains form a stiff and immobile percolated network, which leads to the observed maximum in the shear storage modulus.

Polymer Brushes Immersed in Two-Component Solvents with Pure Volume Exclusion: Effect of Solvent Molecular Shape

Polymer brushes have wide application in surface modification. We study dense, short polymer brushes immersed in a mixing solvent under athermal conditions using the classical density functional theory. The brush polymer is short so that the equilibrium behavior of the brush deviates far from the scaling laws for infinite brush chains. The excluded volume interaction is the only interaction in the system. We compare the excluded volume effect of solvent molecules of different shapes. Two types of mixing solvents are considered: solvent composed of linear oligomers and monomers, or that of spherical particles and monomers. The effects of grafting density, solvent molecular size, and solvent number density on the brush height, the density profiles, the relative excess adsorption, and the brush–solvent interface width are systematically analyzed. In the adsorption aspect, the spherical particles have stronger ability than the linear oligomers do to penetrate through the brush layer and gather at the substrate. In the screening aspect, the oligomers are more capable of screening the excluded volume interaction between the brush chains than the spherical particles. The brush–solvent interface width decreases monotonically with increasing oligomer length, but it has a minimum with the increasing spherical particle size. Our research differentiates the attractive-interaction-induced phenomenon and the volume-exclusion-induced phenomenon in dense brush systems and exhibits the difference in the antifouling properties of the brushes contacting solvent molecules of different shapes.

Surface‐initiated PET‐RAFT polymerization under metal‐free and ambient conditions using enzyme degassing

ABSTRACTAn open‐to‐air method for the efficient synthesis of surface‐tethered polymer brushes based on photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization is reported. Key to this approach is an enzyme‐assisted strategy using glucose oxidase to facilitate the in situ removal of oxygen during the polymerization process. Control experiments in the absence of glucose oxidase confirm the importance of enzymatic deoxygenation for successful polymerization of a variety of acrylamide, methacrylate, and acrylate monomers. In accordance with controlled polymerization kinetics, a linear increase in brush height as a function of irradiation time for a range of light intensities is demonstrated. Importantly, the use of light to mediate growth and the inherent monomer versatility of PET‐RAFT allow for the facile fabrication of well‐defined polymer brushes under aqueous conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 70–76

Effects of thiocyanate anions on switching and structure of poly(N-isopropylacrylamide) brushes**Project supported by the Joint Funds of Xinjiang Natural Science Foundation (Grant No. 2019D01C333), the National Natural Science Foundation of China (Grant Nos. 11847610 and 21764015), the National Basic Research Program of China (Grant No. 2015CB857100).

In this work, we investigate the effects of thiocyanate anions on the switching and the structure of poly (N-isopropylacrylamide) (PNIPAM) brushes using a molecular theory. Our model takes into consideration the PNIPAM–anion bonds, the electrostatic effects and their explicit coupling to the PNIPAM conformations. It is found that at low thiocyanate anion concentration, as the anion concentration of thiocyanate increases, thiocyanate anions are more associated with PNIPAM chains through the PNIPAM–anion bonds, which contributes to stronger electrostatic repulsion and leads to an increase of lower critical solution temperature (LCST). By analyzing the average volume fractions of PNIPAM brushes, it is found that the PNIPAM brush presents a plateau structure. Our results show that the thiocyanate anions promote phase segregation due to the PNIPAM–anion bonds and the electrostatic effect. According to our model, the reduction of LCST can be explained as follows: at high thiocyanate anion concentration, with the increase of thiocyanate concentration, more ion bindings occurring between thiocyanate anions and PNIPAM chains will result in the increase of the hydrophobicity of PNIPAM chains; when the increase of electrostatic repulsion is insufficient to overcome the hydrophobic interaction of PNIPAM chains, it will lead to the reduction of brush height and LCST at high thiocyanate anion concentration. Our theoretical results are consistent with the experimental observations, and provide a fundamental understanding of the effects of thiocyanate on the LCST of PNIPAM brushes.

Flame stabilization of supersonic ethylene jet in fuel-rich hot coflow

The stability limit of a supersonic ethylene jet flame in a fuel-rich hot coflow was examined by investigating the influence of the injection pressure, which was varied from 2.0 atm to 4.5 atm, and of the equivalence ratio of the coflow, which was varied from 1.2 to 1.6. The flames were investigated with time-resolved chemiluminescence and schlieren images, as well as a large-eddy simulation of combustion. The results show that, with increasing injection pressure, the flame state changes from stable to unstable and blow-off, and the flame brush thickness, heat release, and height of coflow decrease. The flame stability limits decrease as the equivalence ratio of coflow increases. Lastly, a large-eddy simulation was performed to investigate the mechanism of flame stabilization, and the numerical simulation results are in good agreement with the experimental results. It was found that the stability of a supersonic flame is affected by the chemical time scale and flow time scale.

Electrokinetic energy conversion in nanochannels grafted with pH-responsive polyelectrolyte brushes modelled using augmented strong stretching theory.

In this paper, we develop a theory to quantify the electrokinetic energy conversion in electrolyte-filled nanochannels grafted with pH-responsive polyelectrolyte (PE) brushes. A pressure-driven flow drives the mobile electrolyte ions of the electric double layer (EDL) supported by the charged PE brushes leading to the generation of a streaming current, a streaming electric field and eventually an electrical energy. The salient feature of this study is that the brushes are described using our recently developed augmented Strong Stretching Theory (SST) model. In all the previous theoretical studies on liquid transport in PE-brush-grafted nanochannels, the brushes have either been assumed to be of constant height (independent of salt concentration or pH) or modelled using the Alexander-de-Gennes model that considers uniform monomer distribution along the brush height. Such simplifications have meant that the salt and the pH dependence of the brush height, the monomer distribution, and the resulting electrostatics have not been appropriately accounted for in the transport calculations. This paper addresses these limitations and provides a much more detailed description of the brushes while capturing the corresponding electrokinetic energy conversion. The results establish that the presence of the PE brushes ensures a localization of the average EDL charge density away from the grafting surface, thereby enabling the migration of the EDL ions with a larger background flow velocity; as a consequence, there is an enhancement of the streaming current, streaming electric field, and the resulting electrical energy generation under certain grafting densities of the PE brushes.

Morphologies of a polyelectrolyte brush grafted onto a cubic colloid in the presence of trivalent ions.

We study the morphologies of a polyelectrolyte brush grafted onto a surface of cubic geometry under good solvent conditions in the presence of trivalent counterions, using molecular dynamics simulations. The electrostatic correlation effect and excluded volume effect on the morphologies are studied through varying the charge fraction and grafting density, respectively. Combining snapshots of surface morphologies, brush height, distribution profiles of polymer monomers, and monomer-monomer/counterion pair correlation functions, it is clearly shown that the electrostatic correlation effect, represented by the trivalent-counterion-mediated bridging effect, can induce lateral microphase separation of the cubic polyelectrolyte brush, resulting in the formation of pinned patches. These structures then lead to multi-scale ordering in the brush system and, thereby, a non-monotonic dependence of the brush height, corresponding to a collapse-to-swell transition, on the grafting density. Our simulation results demonstrate that, with the sequence of surface morphologies responsive to adjusting external parameters, the cubic polyelectrolyte brush can serve as a candidate system for the manufacturing of smart stimuli-responsive materials.

Effect of Formulation and Processing Parameters on the Size of mPEG- b-p(HPMA-Bz) Polymeric Micelles.

Micelles composed of block copolymers of poly(ethylene glycol)-b-poly(N-2-benzoyloxypropyl methacrylamide) (mPEG-b-p(HPMA-Bz)) have shown great promise as drug-delivery carriers due to their excellent stability and high loading capacity. In the present study, parameters influencing micelle size were investigated to tailor sizes in the range of 25–100 nm. Micelles were prepared by a nanoprecipitation method, and their size was modulated by the block copolymer properties such as molecular weight, their hydrophilic-to-hydrophobic ratio, homopolymer content, as well as formulation and processing parameters. It was shown that the micelles have a core–shell structure using a combination of dynamic light scattering and transmission electron microscopy analysis. By varying the degree of polymerization of the hydrophobic block (NB) between 68 and 10, at a fixed hydrophilic block mPEG5k (NA = 114), it was shown that the hydrophobic core of the micelle was collapsed following the power law of (NB × Nagg)1/3. Further, the calculated brush height was similar for all the micelles examined (10 nm), indicating that crew-cut micelles were made. Both addition of homopolymer and preparation of micelles at lower concentrations or lower rates of addition of the organic solvent to the aqueous phase increased the size of micelles due to partitioning of the hydrophobic homopolymer chains to the core of the micelles and lower nucleation rates, respectively. Furthermore, it was shown that by using different solvents, the size of the micelles substantially changed. The use of acetone, acetonitrile, ethanol, tetrahydrofuran, and dioxane resulted in micelles in the size range of 45–60 nm after removal of the organic solvents. The use of dimethylformamide and dimethylsulfoxide led to markedly larger sizes of 75 and 180 nm, respectively. In conclusion, the results show that by modulating polymer properties and processing conditions, micelles with tailorable sizes can be obtained.

Quantitative Analysis of Thickness and pH Actuation of Weak Polyelectrolyte Brushes

Polymer brushes are widely used as surface coatings for various inert, functional, or responsive interfaces. If the polymer can alter its protonation state (a polyelectrolyte (PE)), the brush can switch between a collapsed and swollen state with pH, which enables applications such as nanoscale actuators. However, changes in brush height as the polymer alters its charge state are not straightforward to measure accurately. Here, we show how surface plasmon resonance can be used to determine the thickness of PE brushes both in their charged and neutral states. We use different methods to measure the heights of brushes consisting of poly(acrylic acid) and the polybasic poly(2-(diethylamino)ethyl methacrylate), both prepared by atom transfer radical polymerization. We find polymers in solution that can act as refractive index probes, which do not interact with the grafted polyelectrolytes, thus providing an “exclusion height” of the brush. Importantly, the angular reflection spectrum can be used to directly id...

Fast growing greater amberjack post-larvae require a high energy-high protein weaning diet

Larvae and early juveniles of fast-growing fish species show tremendous growth potential, leading to higher requirements for protein, high-unsaturated fatty acids, and other nutrients. Several commercial weaning diets with relatively high success have been developed for low/moderate-growing species; however, additional challenges are outlined to meet growth potential and energy requirements of such fast-growing species. The objective of the present study was to evaluate two commercial microdiets for marine fish, one having simultaneously a very high protein and high lipid contents (HIGH), and another (MOD) with a high protein and moderate lipid content, in a growth performance trial with greater amberjack post-larvae from 33 to 78 days after hatching. Moreover, histological preparations of liver, anterior and posterior intestine were assessed for hepatic and intestinal lipid inclusions quantification and gut epithelial brush height measurement. Activities of the digestive enzymes: pepsin, trypsin, chymotrypsin, lipase and amylase were also analyzed. Post-larvae fed HIGH microdiet exhibited higher final weight and lower feed conversion ratio that those fed on MOD microdiet. Liver displayed a higher level of lipid inclusions for the MOD diet than for HIGH diet. Moreover, enterocytes of posterior intestine presented a much higher level of supranuclear vacuoles for the HIGH diet compared to MOD diet. The lower Trypsin/Chymotrypsin ratio observed at the end of the experiment in larvae fed on MOD diet may indicate a deficiency in protein of this diet. Together, these results support that larvae of greater amberjack, and likely other fast-growing marine fish species, require high protein–high lipid microdiets. The use of microdiets developed targeting slower growing marine species may lead to sub-optimal performances in fast-growing larvae.

Lubrication in polymer-brush bilayers in the weak interpenetration regime: Molecular dynamics simulations and scaling theories.

We conduct molecular dynamics (MD) simulations and develop scaling laws to quantify the lubrication behavior of weakly interpenetrated polymer brush bilayers in the presence of an external shear force. The weakly interpenetrated regime is characterized by 1<d_{g}/d_{0}<2, where d_{g} is the gap between the opposing surfaces (where the brushes are grafted) and d_{0} is the unperturbed brush height. MD simulations predict that in the shear thinning regime, characterized by a larger shear force or a large Weissenberg number (W), R_{g}^{2}∼W^{0.19} and η∼W^{-0.38}, where R_{g} is the chain extension in the direction of the shear and η is the viscosity. These scaling behaviors, which are distinctly different from that witnessed in strongly compressed regime (for such a regime, characterized by d_{g}/d_{0}<1, R_{g}^{2}∼W^{0.53}, and η∼W^{-0.46}), match excellently with those predicted by our scaling theory.

Understanding the effects of symmetric salt on the structure of a planar dipolar polymer brush.

The effects of added salt on a planar dipolar polymer brush immersed in a polar solvent are studied using a field theoretic approach. The field theory developed in this work provides a unified framework for capturing effects of the inhomogeneous dielectric function, translational entropy of ions, crowding due to finite sized ions, ionic size asymmetry, and ion solvation. In this paper, we use the theory to study the effects of ion sizes, their concentration, and ion-solvation on the polymer segment density profiles of a dipolar brush immersed in a solution containing symmetric salt ions. The interplay of crowding effects, translational entropy, and ion solvation is shown to exhibit either an increase or decrease in the brush height. Translational entropy and crowding effects due to finite sizes of the ions tend to cause expansion of the brush as well as uniform distribution of the ions. By contrast, ion-solvation effects, which tend to be stronger for smaller ions, are shown to cause shrinkage of the brush and inhomogeneous distribution of the ions.

Nanopatterning of Solvent between Apposing Planar Brushes under Pressure

Using computer simulation of a coarse-grained, bead–spring model as well as scanning-probe microscopy of polytBA brushes in ethanol, we demonstrate that upon compression a poor solvent between two apposing polymer brushes does not remain a uniform thin film but, instead, forms a lateral, nanoscopic structure. The characteristic lateral length scale of the solvent domains scales with the brush height that, in turn, can be controlled by the grafting density, molecular weight, or pressure. These findings are rationalized in terms of geometric considerations, accounting for the interfacial free energy between the solvent and the brush and the spatial arrangement of the grafted chains. The phenomenon offers a general strategy to laterally structure confined fluids.

Structural Regulation of a Neurofilament-Inspired Intrinsically Disordered Protein Brush by Multisite Phosphorylation.

Intrinsically disordered proteins (IDPs) play central roles in numerous cellular processes. While IDP structure and function are often regulated by multisite phosphorylation, the biophysical mechanisms linking these post-translational modifications to IDP structure remain elusive. For example, the intrinsically disordered C-terminal sidearm domain of the neurofilament heavy subunit (NFH-SA) forms a dense brush along axonal NF backbones and is subject to extensive serine phosphorylation. Yet, biophysical insight into the relationship between phosphorylation and structure has been limited by the lack of paradigms in which NF brush conformational responses can be measured in the setting of controlled phosphorylation. Here, we approach this question by immobilizing a recombinant NFH-SA (rNFH-SA) as IDP brushes onto glass, and controllably phosphorylating the sequence in situ with mitogen-activated protein kinase 1 (ERK2) preactivated by mitogen-activated protein kinase kinase (MKK). We then monitor brush height changes using atomic force microscopy, which shows that phosphorylation induces significant brush swelling to an extent that strongly depends upon pH and ionic strength, consistent with a mechanism in which phosphorylation regulates brush structure through local electrostatic interactions. Further consistent with this mechanism, the phosphorylated rNFH-SA brush may be dramatically condensed with micromolar concentrations of divalent cations. Phosphorylation-induced height changes are qualitatively reversible via alkaline phosphatase-mediated dephosphorylation. Our study demonstrates that multisite phosphorylation controls NFH-SA structure through modulation of chain electrostatics and points to a general strategy for engineering IDP-based interfaces that can be reversibly and dynamically modulated by enzymes.

Polyelectrolyte brush bilayers in weak interpenetration regime: Scaling theory and molecular dynamics simulations

We employ molecular dynamics (MD) simulations and develop scaling theories to quantify the equilibrium behavior of polyelectrolyte (PE) brush bilayers (BBLs) in the weakly interpenetrated regime, which is characterized by d_{0}<d_{g}<2d_{0}, where d_{g} is the gap between the opposing plates where the PE brushes are grafted and d_{0} is the unperturbed height of a PE brush grafted at a single plate. Scaling predictions establish that, for the weakly interpenetrated osmotic PE BBLs δ∼N^{1/2}(2-d_{g}/d_{0})^{1/2} (where δ is the interpenetration length and N is the number of Kuhn segments in PE brush). MD simulations excellently recover this dependence of δ on N and the extent of interpenetration (quantified by d_{g}/d_{0}). These predictions, unlike the existing studies, establish a finite interpenetration for all values of d_{g}/d_{0} as long as d_{g}<2d_{0}. Finally, we quantify the monomer and counterion concentration distributions and point out that these two distributions may quantitatively deviate from each other at locations very close to the channel centerline, where the interpenetration-induced monomer concentration can be significantly low.