Brush Grafting Density Research Articles

Glycopolymer Brushes for the Affinity Adsorption of RCA120: Effects of Thickness, Grafting Density, and Epitope Density

The interactions between glycopolymer brushes and lectin are very important for the development of affinity membrane chromatography in protein separation. Here, we report the combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and surface plasmon resonance (SPR) to investigate the relationship between the structure of glycopolymer brushes and the affinity adsorption of lectin. The glycopolymer brushes were fabricated from self-assembly of 11-mercapto-1-undecanol (MUD)/1-undecanethiol (UDT) mixture, immobilization of ATRP initiators, and then SI-ATRP of 2-lactobionamidoethyl methacrylate (LAMA). Brush thickness and grafting density were adjusted by controlling polymerization time and thiol ratio in MUD/UDT mixture, respectively. Sugar epitope density was also controlled through copolymerization of 2-hydroxylethyl methacrylate (HEMA) with LAMA. Ricinus communis agglutinin (RCA(120)), one kind of lectin that can bind galactose specifically, was chosen to study the effects of brush architectures on lectin adsorption. SPR results indicate not only the thickness but also the grafting density and the epitope density of glycopolymer brushes can achieve the best performance of sugar cluster effect in affinity adsorption of lectin. In addition, the mass transport effect is crucial in the adsorption process. We propose that it is important to keep the balance between the sugar cluster effect and the mass transport effect in the preparation of high-performance affinity membrane chromatography.

Bioadhesive Control of Plasma Proteins and Blood Cells from Umbilical Cord Blood onto the Interface Grafted with Zwitterionic Polymer Brushes

In this work, bioadhesive behavior of plasma proteins and blood cells from umbilical cord blood (UCB) onto zwitterionic poly(sulfobetaine methacrylate) (polySBMA) polymer brushes was studied. The surface coverage of polySBMA brushes on a hydrophobic polystyrene (PS) well plate with surface grafting weights ranging from 0.02 mg/cm(2) to 0.69 mg/cm(2) can be effectively controlled using the ozone pretreatment and thermal-induced radical graft-polymerization. The chemical composition, grafting structure, surface hydrophilicity, and hydration capability of prepared polySBMA brushes were determined to illustrate the correlations between grafting properties and blood compatibility of zwitterionic-grafted surfaces in contact with human UCB. The protein adsorption of fibrinogen in single-protein solutions and at complex medium of 100% UCB plasma onto different polySBMA brushes with different grafting coverage was measured by enzyme-linked immunosorbent assay (ELISA) with monoclonal antibodies. The grafting density of the zwitterionic brushes greatly affects the PS surface, thus controlling the adsorption of fibrinogen, the adhesion of platelets, and the preservation of hematopoietic stem and progenitor cells (HSPCs) in UCB. The results showed that PS surfaces grafted with polySBMA brushes possess controllable hydration properties through the binding of water molecules, regulating the bioadhesive and bioinert characteristics of plasma proteins and blood platelets in UCB. Interestingly, it was found that the polySBMA brushes with an optimized grafting weight of approximately 0.1 mg/cm(2) at physiologic temperatures show significant hydrated chain flexibility and balanced hydrophilicity to provide the best preservation capacity for HSPCs stored in 100% UCB solution for 2 weeks. This work suggests that, through controlling grafting structures, the hemocompatible nature of grafted zwitterionic polymer brushes makes them well suited to the molecular design of regulated bioadhesive interfaces for use in the preservation of HSPCs from human UCB.

Friction between Brush Layers of Charged and Neutral Bottle-Brush Macromolecules. Molecular Dynamics Simulations

Using molecular dynamics simulations, we study the lubricating properties of neutral and charged bottle-brush coatings as a function of the compression and shear stresses and brush grafting density. Our simulations have shown that in charged bottle-brush systems under shear there is a layer with excess counterions located in the middle between brush-bearing surfaces. The main deformation mode of the charged bottle-brush layers is associated with the backbone deformation, resulting in the backbone deformation ratio, α, and shear viscosity, η, being universal functions of the Weissenberg number. In the case of neutral bottle-brush systems, in addition to the backbone deformation there is also side chain deformation. The coupling between backbone and side chain deformation violates universality in the deformation ratio, α, dependence on the Weissenberg number and results in scaling exponents varying with the compression stress and brush grafting density. The existence of different length scales controlling deformation of neutral bottle brushes manifests itself in the shear viscosity, η, dependence on the shear rate, ̇γ. Shear viscosity, η, as a function of the shear rate, ̇γ, has two plateaus and two shear thinning regimes. The low shear rate plateau and shear thinning regime correspond to the backbone deformation, while the second plateau and shear thinning regime at moderate shear rates are due to side chain deformation. For both systems the value of the friction coefficient increases with increasing shear rate. The values of the friction coefficient for charged bottle-brush systems are about ten times smaller than corresponding values for neutral systems at the same shear rate.

Nanomechanical properties of polymer brushes by colloidal AFM probes

Nanomechanical properties of end grafted polymer layers were studied by AFM based, colloidal probe compression measurements. Zwitterionic poly(sulfobetaine methacrylate) (PSBMA) brush was grafted from planar Si surface and poly(methyl methacrylate) (PMAA) brush was grown on colloidal probe by surface initiated atom transfer radical polymerization. PMAA brush was further modified with adhesion promoting arginyl-glycyl-aspartic acid (RGD) peptide sequences. Force–distance curves were obtained for systems where the polymer brushes were probed on unmodified surfaces or face to each other. For each systems the grafting density of the polymer brush was determined applying a ‘box’ like polymer brush model based on the theory by de Gennes. ‘Average’ grafting density was calculated in cases when two polymer brushes face each other: RGD functionalized PMAA or PMAA against PSBMA. For our systems the values for the grafting density was between 0.04 and 0.11 nm −2. Furthermore the measured approach force–distance curves were fitted according to the Hertz model and the apparent Young’s modulus was determined for all measurements being in a range of around 250 kPa at physiological conditions.

Neutron Reflectivity Study on the Postpolymerization Modification of Poly(2-hydroxyethyl methacrylate) Brushes

Postpolymerization modification reactions are widely employed to prepare functional polymer brushes. Relatively little is known, however, about the distribution of functional groups in such postmodified brushes. Using neutron reflectometry and UV–vis spectroscopy as principal tools, this article investigates the p-nitrophenyl chloroformate (NPC)-mediated postpolymerization modification of poly(2-hydroxyethyl methacrylate) (PHEMA) brushes, prepared via surface-initiated atom transfer radical polymerization, with D-10 leucine and D-3 serine. The neutron reflectometry experiments indicate that the postpolymerization modification depends both on brush thickness and grafting density. Whereas for dense brushes, postpolymerization modification with D-10 leucine is limited to the top ∼200 Å of the brush, independently of the brush thickness, the extent of postmodification can be significantly enhanced by decreasing the grafting density of the brush or by using the more hydrophilic and sterically less demanding D-3 serine, which reflects the ability of this amino acid to more readily penetrate the brush. UV–vis experiments revealed that the NPC activation is also nonuniform, but brush thickness and grafting density dependent, which adds to brush thickness and density and the nature of the amino acid as another of a complex set of variables that determine the final distribution of functional groups in postmodified brushes.

Polyelectrolyte Brushes Grafted from Cellulose Nanocrystals Using Cu-Mediated Surface-Initiated Controlled Radical Polymerization

Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.

Molecular Dynamics Simulations of Grafted Layers of Bottle-Brush Polyelectrolytes

Using molecular dynamics simulations, we study the effect of the brush grafting density and degree of polymerization of the side chains on conformations of brush layers made of charged bottle-brush macromolecules. The thickness of the brush layer first decreases with increasing brush grafting density; then, it saturates and remains constant in the wide interval of the brush grafting densities. The brush layers consisting of the bottle-brush macromolecules with longer side chains have a larger layer thickness. The elongation of the side chains of the bottle-brush macromolecules decreases with increasing brush grafting density. This contraction of the side chains is due to counterion condensation inside the volume occupied by bottle-brushes. Our simulations showed that counterion condensation is a multiscale process reflecting different symmetries of the bottle-brush layer.

Pickering Emulsions Stabilized by Nanoparticles with Thermally Responsive Grafted Polymer Brushes

A study is presented of emulsification by silica nanoparticles with poly(2-(dimethylamino)ethyl methacrylate) brushes grafted from their surfaces (SiO(2)-PDMAEMA) by atom-transfer radical polymerization (ATRP). The grafted nanoparticles were used to stabilize xylene-in-water and cyclohexane-in-water Pickering emulsions. PDMAEMA is a water-soluble weak polyelectrolyte with a pH-dependent lower critical solution temperature (LCST). Accordingly, SiO(2)-PDMAEMA nanoparticles were thermally responsive, as shown by the fact that they displayed a critical flocculation temperature (CFT) when heated. ATRP provides a high degree of control over the brush grafting density and degree of polymerization, two of the principal variables examined in this study. The effects of the solvent quality of the "oil" for the PDMAEMA brush were studied in addition to the effects of aqueous pH, ionic strength, and temperature relative to the CFT. The preferred emulsion type was oil in water in all cases. The lowest grafting density particles (0.077 chains/nm(2)) proved to be the most efficient and robust emulsifiers, producing stable emulsions using as little as 0.05 wt % particles in the aqueous phase and successfully emulsifying over a broader range of solution conditions than for the higher grafting density particles (0.36 and 1.27 chain/nm(2)). Both good (xylene) and poor (cyclohexane) solvents could be emulsified, but the poor solvent could be emulsified over a broader range of conditions than the good solvent. Emulsions have been stable for over 13 months, and some have dispersed as much as 83 vol % oil in the emulsion phase. Thermally responsive emulsions were created with the SiO(2)-PDMAEMA particles such that stable emulsions prepared at low temperature were rapidly broken by increasing the temperature above the CFT.

Substrate Heterogeneity Induced Instability and Slip in Polymer Thin Films: Dewetting on Silanized Surfaces with Variable Grafting Density

We employ dewetting behavior of thin polystyrene films to investigate the stability and slippage on the silanized Si wafers with different grafting density of silane brush. PS films are stable on our nonsilanized substrate, but an increase in the grafting density increases the contact angle from zero, causing the appearance and growth of holes. A clear signature of slippage (hole radius ∼ time2/3) is obtained at low grafting density and low contact angles, which changes to no-slip behavior (hole radius ∼ time) on a uniform high density brush. It is also found that the molecular weight of PS does not influence the slippage implying that the slippage observed is caused neither by the entanglement of polymer chains, nor by high nonwettability of the substrate, but by the substrate heterogeneity or physicochemical roughness imparted by the incomplete, low density brush with intervening adsorbed PS chains.

Janus gold nanoparticle with bicompartment polymer brushes templated by polymer single crystals

Janus particles have attracted increasing attention from the communities of materials science, chemistry, physics and biology. While large size Janus particles are readily achieved, synthesizing Janus nanoparticles (JNP) with diameters smaller than ∼20 nm remains a challenging task. In this article, we report a systematic study on growing polymer brushes on polymer-single-crystal-immobilized 6 and 15 nm diameter gold nanoparticles (AuNPs) using atom transfer radical polymerization. JNPs with bicompartment polymer brushes, such as poly(ethylene oxide) (PEO)/poly(methyl methacrylate), PEO/poly(tert-butyl acrylate), and PEO/poly(acrylic acid), were synthesized. The grafting densities can be carefully controlled. The Janus feature of these particles was confirmed using both platinum nanoparticle decoration and UV/Vis spectroscopy analysis. The surface plasmon resonance absorbance of Janus particles exhibited a blue shift compared with that of symmetric AuNPs with either homopolymer or mixed polymer brushes. This work demonstrated that using polymer single crystal as the templates, small size (<20 nm diameter) JNPs having bicompartment polymer brushes can be readily obtained. The ability to tune grafting density and molecular weight of polymer brushes can lead to controlled particle amphiphilicity.

Producing High-Density High-Molecular-Weight Polymer Brushes by a “Grafting to” Method from a Concentrated Homopolymer Solution

Here, a new procedure and method are presented for the production of highly grafted polymer brushes. Thiol-terminated polyethylene oxide (PEO-SH) of molecular weight (M(w)) 20,000 (20k) is grafted to a gold surface from highly concentrated aqueous solutions of nonthiolated polyethylene oxide homopolymer. The M(w) and volume fraction of the homopolymer solution are varied in order to control the grafting density of the resulting PEO-SH brush. As a result, 20k M(w) PEO-SH brushes with grafting densities up to 0.3 chains/nm(2) are achieved, as determined by ellipsometry. Highly concentrated homopolymer solutions of volume fraction greater than approximately 12% and M(w) greater than approximately 938 produce near-ideal solvent conditions for the 20k M(w) PEO-SH chains; we have found that this facilitates the achievement of higher grafting densities of end-functionalized polymer brushes than would be possible from simple solutions. We propose this as a suitable method for applications where the grafting density of a brush surface must be accurately varied and controlled consistently. The effect of chemisorption time and cleaning procedure on the resulting brush grafting density are also explored.

Magnetic particle-loaded polymer brushes induced by external magnetic field: A Monte Carlo simulation

The effects of applied magnetic field on the system composed of polymer brushes and magnetic particles are studied by means of Monte Carlo simulation. The direction of the applied magnetic field is chosen to be perpendicular to the substrate plane. Polymer brushes and magnetic particles are attracted to each other. The average heights of polymer brushes depend not only on the strength of applied magnetic field (H) but also on the brush grafting density (σ) and the chain length (N). The applied magnetic field influences the arrangement of magnetic particles, and in turn, the arrangement of magnetic particles affects the spatial distribution of polymer brush monomers. When the strength of the magnetic field is increased, the average height of polymer brushes will be increased accordingly. The reason is that the orientations of the magnetic moments of particles must be along the magnetic field direction, and this leads polymer brushes to rearrange along the magnetic field direction. At the same time, the chain length and the grafting density of polymer brushes have also effects on the properties of the magnetic particles, such as the magnetic particles distribution, magnetic susceptibility, and pair correlation functions. Comparisons with the experimental ones are also made, and this investigation can provide some insights into statistical properties of magnetic particle-loaded brushes induced by external magnetic field. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1873–1881, 2010

Synthesis of Spherical Polyelectrolyte Brushes by Thermo‐controlled Emulsion Polymerization

A novel method of thermo-controlled emulsion polymerization has been employed to synthesize spherical polyelectrolyte brushes that consist of a solid polystyrene core and a poly (acrylic acid) (PAA) shell covalently attached on the core surface densely by one end. The growth of brushes from the core surface was monitored by dynamic light scattering (DLS). The particle size of PS core latex showed a narrow size distribution when observed by scanning electron microscopy (SEM). The brush size changed significantly upon changing pH value and ionic strength, and displayed similar behavior to brushes prepared by photo-emulsion polymerization. The grafting density of the PAA brush, which was determined by cutting off the PAA chains using alkali hydrolysis, confirmed the formation of PAA brushes.

Atomic force microscopy study of immunosensor surface to scale down the size ofELISA-type sensors

Here we describe the use of atomic force microscopy (AFM) to study the nanoscalemechanics of the molecular layers of a popular immunosensor, ELISA (enzyme-linkedimmunosorbent assay) type. We characterize the sensor surface in terms of brush lengthand grafting density of the molecular layers. The obtained data demonstrated that areliable reading of the immunosignal (a suggested dimensionless combinationof brush length and grafting density) can be attained from an area as small as ∼ 3 µm2. This is approximately 4 million times smaller compared to typical ELISA sensors. Theimmunosensor described is composed of a molecular mix of two different antigens.Intriguingly, we find that AFM can reliably distinguish between having the immunosignalfrom either antibody and from both antibodies together. This was impossible to get byusing standard optical detection methods.

Charge-driven and reversible assembly of ultra-dense polymer brushes: formation and antifouling properties of a zipper brush

We investigated a new type of polymer brushes: the zipper brush. By adsorbing a diblock-copolymer with one charged block and one neutral block to an oppositely charged polyelectrolyte brush, a neutral polymer brush is formed on top of an almost neutral complex layer of polyelectrolytes. This neutral brush can be adsorbed in minutes and desorbed in seconds to restore the original polyelectrolyte brush. The zipper brush can be used, for example, as an antifouling layer to prevent protein adsorption. These characteristics are shown by fixed-angle optical reflectometry for the system of poly(N-methyl-2-vinyl pyridinium)-block-poly(ethylene oxide) (P2MVP-PEO) adsorbed to a poly(acrylic acid) (PAA) brush. After the diblock-copolymer has adsorbed (at pH 6), the charges of the PAA brush are almost completely compensated by the charges of the P2MVP block. The grafting density of the formed neutral brush can be controlled by the chain length and grafting density of the PAA brush, and by the chain length of P2MVP block. As the P2MVP blocks used in this study are much smaller than the PAA chains in the brush, the grafting density of the PEO brushes are found to be a multiplication of that of the PAA brush, and much higher grafting densities (up to 1.59 chains per nm2) can be obtained than previously reported for polymer brushes prepared by adsorption. At low pH, when the PAA is uncharged, only a few mg m−2 adsorb probably because of hydrogen bonding between uncharged PAA and PEO. As the pH increases the PAA becomes more charged and the adsorbed amount of diblock-copolymer increases strongly until pH 6 and then levels off between pH 6 and pH 10. At pH 6 and 10 high salt concentrations (above 250 mM) are needed to significantly reduce the adsorbed amount. The antifouling properties of the zipper brush were tested by exposing the brush to a number of different protein solutions. For the proteins lysozyme, fibrinogen, bovine serum albumin, and b-lactoglobuline the zipper brush completely prevented any adsorption, for cytochrome C a small amount of adsorption was observed.

Programming nanostructures of polymer brushes by dip-pen nanodisplacement lithography (DNL)

We report a facile and versatile scanning probe based approach-dip-pen nanodisplacement lithography (DNL)--for manipulating nanostructures of polymer brushes. Nanostructured polymer brushes with sizes as small as 25 nm are made by DNL patterning of the initiator molecules and subsequent surface-initiated polymerization. Nanoconfinement effects including chain collapsing and spreading are observed in the nanopatterned polymer brushes. In addition to chemical structure, size, topography and shape, our approach can also readily program the grafting density, chain configuration, hierarchical structure and multiplexing of the polymer brushes, which allows for the realization of complex chemical surfaces.

Facile Method to Prepare Smooth and Homogeneous Polymer Brush Surfaces of Varied Brush Thickness and Grafting Density

This Article describes a facile method to prepare smooth and homogeneous polymer brush surfaces of variable grafting density from a solid surface by combining Langmuir-Blodgett (LB) deposition with surface-initiated atom transfer radical polymerization (SI-ATRP). This method is successfully demonstrated by the preparation of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brush surfaces on smooth silicon and quartz substrates. With the custom-synthesized inert diluent whose chemical structure, except end-functionality, is the same as that of the reactive initiator, smooth and chemically homogeneous mixed monolayers of initiators and inert diluents are immobilized on a solid surface by LB deposition, allowing the further variation of the grafting density of PNIPAM brushes grafted from the initiator monolayers of varied initiator coverage. With the optimized molar ratio of deactivator, Cu(II) in the Cu(I)-ligand catalyst complex, the brush thickness of PNIPAM brushes at varied grafting density is controlled to grow nearly linearly with reaction time while smoothness and chemical homogeneity of PNIPAM brushes are achieved. For the demonstrated PNIPAM brush surfaces, the thermoresponsive characteristics of PNIPAM brushes are also verified. This combined LB-ATRP method can be applied to graft a variety of polymer brushes, including polyelectrolytes and block copolymers, from different solid substrates.

Interaction of Particles with a Polydisperse Brush: A Self-Consistent-Field Analysis

Two complementary theoretical approaches are used to study the effect of polydispersity oil (anti)fouling properties of a neutral polymer brush. Polydispersity is described using the Schulz-Zimm distribution. The Scheutjens-Fleer self-consistent-field (SF-SCF) formalism is used to consider the interaction between a single particle and a polydisperse brush with grafting density sigma, focusing on the influence of the polydispersity index. The larger the polydispersity, the easier it is for a small particle (with radius R similar to 1/(2 root sigma)) to penetrate the brush. Hence, the monodisperse brush is better suited to protect a surface against the adsorption of small particles compared to a corresponding polydisperse brush. The brush grafting density, however, remains the most important parameter for timing the brush antifouling properties against small particles. For large particles (modeled as a flat wall.) an opposite effect of polydispersity is found: it is harder to compress a polydisperse brush than it corresponding monodisperse brush, and thus a polydisperse brush is better suited to protect the Surface against adsorption of large particles. A less-detailed approach, based on the stacking of Alexander-de Gennes boxes, is used to study the adsorption of many particles into a polydisperse brush. Consistent with the single-particle data generated by the SF-SCF theory, for weak attraction between the particles and the brush the absolute adsorbed amount remains low but increases strongly as a function of polydispersity (from M-w/M-n = 1-2 by a factor of 2-4). Obviously, at higher attraction between the particles and the brush the adsorption increases, but a less strong dependence on the polydispersity index is observed.

Morphologies of Planar Polyelectrolyte Brushes in a Poor Solvent: Molecular Dynamics Simulations and Scaling Analysis

Using molecular dynamics simulations and scaling analysis, we study the effect of the solvent quality for the polymer backbone, the strength of the electrostatic interactions, the chain degree of polymerization, and the brush grafting density on conformations of the planar polyelectrolyte brushes in salt-free solutions. Polyelectrolyte brush forms: (1) vertically oriented cylindrical aggregates (bundles of chains), (2) maze-like aggregate structures, or (3) thin polymeric layer covering a substrate. These different brush morphologies appear as a result of the fine interplay between electrostatic and short-range monomer-monomer interactions. The brush thickness shows nonmonotonic dependence on the value of the Bjerrum length. It first increases with the increasing value of the Bjerrum length, and then it begins to decrease. This behavior is a result of counterion condensation within a brush volume.

Adsorption of Nonuniformly Charged Fullerene-like Nanoparticles on Planar Polyelectrolyte Brushes in Aqueous Solutions

On the basis of the coarse grained model, we investigated the adsorption of nonuniformly charged fullerene-like nanoparticles on planar polyelectrolyte brushes (PEBs) in aqueous solution by using Brownian dynamics simulation. It is found that the electroneutral nanoparticles can be adsorbed by the PEB, which is attributed to the asymmetrical electrostatic interactions of the PEB with the positively charged sites and negatively charged sites of the fullerene-like nanoparticles. The simulation results indicated that the adsorption amount exhibits non-monotonic behavior with the dipole moment of nanoparticles. First, the adsorption amount increases with the dipole moment and then reaches the maximum at the dipole moment of micro = 10.45. Finally, the adsorption falls at the dipole moment of micro = 14.39. The reason may be that, at the extremely large dipole moment of micro = 14.39, the fullerene-like nanoparticles aggregate together to form a big cluster in the bulk phase, which can be confirmed by the extremely high peak in the radial distribution function between nanoparticles. Accordingly, it is difficult for nanoparticles to enter into the PEB at the dipole moment of micro = 14.39. In addition, it is also found that the brush grafting density is an important factor affecting the brush thickness.