Computer Simulation of Concurrent Bulk- and Surface-Initiated Living Polymerization

We use Monte Carlo simulation implementing the bond fluctuation model formalism in the canonical (NVT) ensemble to study living polymerization initiated concurrently in bulk and on flat substrates. Our results reveal that the molecular weights and molecular weight distributions of both classes of polymers depend on the grafting density of the surface-bound polymers (σ) and the fraction of polymers on the surface (η) relative to that in bulk. In general, polymer grafts on the surface possess lower molecular weight and higher polydispersity index compared to their bulk counterparts. The difference between the molecular weight of the two populations of polymers decreases with decreasing σ and increasing η. Our work provides evidence that the common practice of using the molecular weight of bulk-initiated polymers in estimating the grafting density of polymeric anchors on flat substrates is not generally valid

Swelling of Hydrophilic Polymer Brushes by Water and Alcohol Vapors

We examine the effect of end-tethering, grafting density (σ), chemistry of polymer side chain, and solvent type on the vapor swelling of hydrophilic polymer brushes. Using a library of samples derived by postpolymerization modification of a poly­(2-(dimethylamino)­ethyl methacrylate) (PDMAEMA) brush, we determine the extent of vapor swelling and solvent uptake at different vapor pressures of water, methanol, and ethanol using spectroscopic ellipsometry. We compare the results from neat PDMAEMA and PDMAEMA quaternized by methyl iodide with chemically analogous samples prepared by spincasting bulk PDMAEMA. We find that brush samples swell to greater extents than spuncast samples, indicating a role for end-tethering in the vapor uptake process. Furthermore, vapor swelling of polymer brushes depends strongly on both polymer and solvent chemistry. We demonstrate that the extent to which σ affects vapor sorption inside the brush depends on polymer side chain chemistry, indicating an interdependence of the observed parameters on each other. The implications of these findings for the use of polymer brushes in technologies such as vapor sensing applications are discussed

Surface-Anchored Poly(<i>N</i>‑isopropylacrylamide) Orthogonal Gradient Networks

We present a versatile synthetic route leading toward generating surface-attached polyacrylamide gels, in which the cross-link density varies continuously and gradually across the substrate in two orthogonal directions. We employ free radical polymerization to synthesize random copolymers comprising ∼5% of photoactive methacrylyl­oxybenzo­phenone (MABP), ∼5% of thermally active styrene sulfonyl azide (SSAz), and ∼90% of <i>N</i>-isopropyl­acrylamide (NIPAAm) units. The presence of MABP and SSAz in the copolymer facilitates control over the cross-link density of the gel in an orthogonal manner using photoactivated and thermally activated cross-linking chemistries, respectively. Spectroscopic ellipsometry is employed to determine the degree of swelling of the gel in water and methanol as a function of position on the substrate. Network swelling varies continuously and gradually across the substrate and is high in regions of low gel fractions and low in regions of high gel fractions

Effect of Protein-like Copolymers Composition on the Phase Separation Dynamics of a Polymer Blend: A Monte Carlo Simulation

We use kinetic Monte Carlo simulation based on the bond fluctuation model to investigate the dynamics of phase separation in immiscible 80/20 A/B binary polymer blends, comprising 80% and 20% of A and B components, respectively, in the presence of ≈4.92% 30-mer protein-like copolymer (PLC) made of C and D segments. The molecular interactions are chosen such that there is an attraction between A and C and between B and D segments and no interaction between like segments; all other interaction energies have been chosen to be repulsive. The PLC migration to and presence at the A/B interface effectively slow down the process of phase separation in binary blends, thereby minimizing the unfavorable A/B contacts and reducing the A/B interfacial tension. The ability of PLCs to effectively retard the process of phase separation depends sensitively on the PLC composition. PLCs with 0.3 ≤ <i>x</i>_C ≤ 0.5, where <i>x</i>_C is the mole fraction of C, are most effective in compatibilizing the 80/20 A/B binary blend. The growth of phase-separated domains follows a dynamical scaling law for both the binary and ternary blends compatibilized by PLCs in the late stage of phase separation with universal scaling functions that are nearly independent of PLC composition

Proteinlike Copolymers as Encapsulating Agents for Small-Molecule Solutes

We describe the utilization of proteinlike copolymers (PLCs) as encapsulating agents for small-molecule solutes. We perform Monte Carlo simulations on systems containing PLCs and model solute molecules in order to understand how PLCs assemble in solution and what system conditions promote solute encapsulation. Specifically, we explore how the chemical composition of the PLCs and the range and strength of molecular interactions between hydrophobic segments on the PLC and solute molecules affect the solute encapsulation efficiency. The composition profiles of the hydrophobic and hydrophilic segments, the solute, and implicit solvent (or voids) within the PLC globule are evaluated to gain a complete understanding of the behavior in the PLC/solute system. We find that a single-chain PLC encapsulates solute successfully by collapsing the macromolecule to a well-defined globular conformation when the hydrophobic/solute interaction is at least as strong as the interaction strength among hydrophobic segments and the interaction among solute molecules is at most as strong as the hydrophobic/solute interaction strength. Our results can be used by experimentalists as a framework for optimizing unimolecular PLC solute encapsulation and can be extended potentially to applications such as “drug” delivery via PLCs

Formation and Antifouling Properties of Amphiphilic Coatings on Polypropylene Fibers

We describe the formation of amphiphilic polymeric assemblies via a three-step functionalization process applied to polypropylene (PP) nonwovens and to reference hydrophobic self-assembled <i>n</i>-octadecyltrichlorosilane (ODTS) monolayer surfaces. In the first step, denatured proteins (lysozyme or fibrinogen) are adsorbed onto the hydrophobic PP or the ODTS surfaces, followed by cross-linking with glutaraldehyde in the presence of sodium borohydride (NaBH₄). The hydroxyl and amine functional groups of the proteins permit the attachment of initiator molecules, from which poly (2-hydroxyethyl methacrylate) (PHEMA) polymer grafts are grown directly through “grafting from” atom transfer radical polymerization. The terminal hydroxyls of HEMA’s pendent groups are modified with fluorinating moieties of different chain lengths, resulting in amphiphilic brushes. A palette of analytical tools, including ellipsometry, contact angle goniometry, Fourier transform infrared spectroscopy in the attenuated total reflection mode, and X-ray photoelectron spectroscopy is employed to determine the changes in physicochemical properties of the functionalized surfaces after each modification step. Antifouling properties of the resultant amphiphilic coatings on PP are analyzed by following the adsorption of fluorescein isothiocyanate-labeled bovine serum albumin as a model fouling protein. Our results suggest that amphiphilic coatings suppress significantly adsorption of proteins as compared with PP fibers or PP surfaces coated with PHEMA brushes. The type of fluorinated chain grafted to PHEMA allows modulation of the surface composition of the topmost layer of the amphiphilic coating and its antifouling capability

Formation and Antifouling Properties of Amphiphilic Coatings on Polypropylene Fibers

We describe the formation of amphiphilic polymeric assemblies via a three-step functionalization process applied to polypropylene (PP) nonwovens and to reference hydrophobic self-assembled <i>n</i>-octadecyltrichlorosilane (ODTS) monolayer surfaces. In the first step, denatured proteins (lysozyme or fibrinogen) are adsorbed onto the hydrophobic PP or the ODTS surfaces, followed by cross-linking with glutaraldehyde in the presence of sodium borohydride (NaBH₄). The hydroxyl and amine functional groups of the proteins permit the attachment of initiator molecules, from which poly (2-hydroxyethyl methacrylate) (PHEMA) polymer grafts are grown directly through “grafting from” atom transfer radical polymerization. The terminal hydroxyls of HEMA’s pendent groups are modified with fluorinating moieties of different chain lengths, resulting in amphiphilic brushes. A palette of analytical tools, including ellipsometry, contact angle goniometry, Fourier transform infrared spectroscopy in the attenuated total reflection mode, and X-ray photoelectron spectroscopy is employed to determine the changes in physicochemical properties of the functionalized surfaces after each modification step. Antifouling properties of the resultant amphiphilic coatings on PP are analyzed by following the adsorption of fluorescein isothiocyanate-labeled bovine serum albumin as a model fouling protein. Our results suggest that amphiphilic coatings suppress significantly adsorption of proteins as compared with PP fibers or PP surfaces coated with PHEMA brushes. The type of fluorinated chain grafted to PHEMA allows modulation of the surface composition of the topmost layer of the amphiphilic coating and its antifouling capability

Toward the Development of a Versatile Functionalized Silicone Coating

The development of a versatile silicone copolymer coating prepared by the chemical coupling of trichlorosilane (TCS) to the vinyl groups of poly­(vinylmethylsiloxane) (PVMS) is reported. The resultant PVMS-TCS copolymer can be deposited as a functional organic layer on a hydrophobic poly­(dimethylsiloxane) substrate and its mechanical modulus can be regulated by varying the TCS coupling ratio. In this paper, several case studies demonstrating the versatile properties of these PVMS-TCS functional coatings on PDMS elastomer substrates are presented. Numerous experimental probes, including optical microscopy, Fourier-transform infrared spectroscopy, surface contact angle, ellipsometry, and nanoindentation, are utilized to interrogate the physical and chemical characteristics of these PVMS-TCS coatings

Instability of Surface-Grafted Weak Polyacid Brushes on Flat Substrates

We study the stability of weak polyacid brush (WPAB) gradients in aqueous media covering a range in grafting density (σ) spanning 0.05–0.5 chains/nm² using two analogous surface-anchored bromoisobutyrate-based initiators for atom transfer radical polymerization (ATRP) bearing either an ester or amide linker. Variations in dry thickness of ester-based WPABs as a function of time and pH are consistent with WPAB degrafting via linker hydrolysis catalyzed by mechanical tension in the grafted chains. Sources of tension considered include high σ, as well as swelling and electrostatic repulsion associated with increasing degree of deprotonation (α) of repeat units in the WPAB. Normalized thickness of the WPAB decreases by a maximum amount at intermediate σ between ∼0.05−0.15 chains/nm², implying that contributions to tension by α are counterbalanced by charge regulation in the WPAB at high σ. Amide-based WPABs are more stable up to 264 h incubation, suggesting that commonly used ester-bearing ATRP initiators are more susceptible to hydrolysis over the time scales examined

Swelling of Polyelectrolyte and Polyzwitterion Brushes by Humid Vapors

Swelling behavior of polyelectrolyte and polyzwitterion brushes derived from poly­(2-(dimethylamino)­ethyl methacrylate) (PDMAEMA) in water vapor is investigated using a combination of neutron and X-ray reflectivity and spectroscopic ellipsometry over a wide range of relative humidity (RH) levels. The extent of swelling depends strongly on the nature of the side-chain chemistry. For parent PDMAEMA, there is an apparent enrichment of water vapor at the polymer/air interface. Despite extensive swelling at high humidity level, no evidence of charge repulsion is found in weak or strong polyelectrolyte brushes. Polyzwitterionic brushes swell to a greater extent than the quaternized brushes studied. However, for RH levels beyond 70%, the polyzwitterionic brushes take up less water molecules, leading to a decline in water volume fraction from the maximum of ∼0.30 down to ∼0.10. Using a gradient in polymer chain grafting density (σ), we provide evidence that this behavior stems from the formation of inter- and intramolecular zwitterionic complexes