Synthesis of Polymer Brushes Using Atom Transfer Radical Polymerization

Pyun, Jeffrey; Kowalewski, Tomasz; Matyjaszewski, Krzysztof

doi:10.1002/marc.200300078

Cited by 684 publications

(601 citation statements)

References 136 publications

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“…32 Moreover, it is a convenient indirect reporter for the molecular weight and polydispersity (PDI) of the surfaces grafted polymers provided there is a good correlation between the polymer growth from the surface and in solution. 33,34,35,36,37 In our case the sacrificial initiator EBiB is a α-halogen ester whereas the surface initiator is an amide. The latter have been reported to be prone to a higher termination rate in the initial phase of conventional ATRP resulting in higher PDIs and molecular weighs.…”

Section: Grafting Of Polymer From Atrp Functional Polyhipesmentioning

confidence: 95%

Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP

et al. 2012

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Amino-functional macroporous monoliths from polymerized high internal phase emulsion (polyHIPE) were surface modified with initiators for atom transfer radical polymerization (ATRP). The ATRP initiator groups on the polyHIPE surface were successfully used to initiate activator regeneration by electron transfer (ARGET) ATRP of (meth)acrylic monomers, such as methyl methacrylate (MMA) or tert-butyl acrylate (tBA) resulting in a dense coating of polymers on the polyHIPE surface. Addition of sacrificial initiator permitted control of the amount of polymer grafted onto the monolith surface. Subsequent removal of the tertbutyl protecting groups yielded highly functional polyHIPE-g-poly(acrylic acid). The versatility to use the high density of carboxylic acid groups for secondary reactions was demonstrated by the successful conjugation of enhanced green fluorescent protein (eGFP) and coral derived red fluorescent protein (DsRed) using EDC/sulfo-NHS chemistry, on the polymer 3D-scaffold surface. The materials and methodologies presented here are simple and robust, thus, opening new possibilities for the bioconjugation of highly porous polyHIPE for bioseparation applications.

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Section: Grafting Of Polymer From Atrp Functional Polyhipesmentioning

confidence: 95%

Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP

et al. 2012

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“…We estimate the polydispersity in our polyelectrolyte layer from literature values to be in range M n /M w = 1.2 -1.5 33 . Such a polydispersity should lead to a slower decay of the steric force at high distances than predicted by the scaling model, due to the tendency of longer polymer chains to extend further away from the substrate surface.…”

Section: Normal Forces In Pure Watermentioning

confidence: 99%

Direct Measurement of Normal and Shear Forces between Surface-Grown Polyelectrolyte Layers

et al. 2009

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This paper presents measurements, using the surface force balance (SFB), of the normal and shear forces in aqueous solutions between polyelectrolyte layers grown directly on mica substrates (grafted-from). The grafting-from was via surface-initiated atom transfer radical polymerization (surface-initiated ATRP) using a positively-charged methacrylate monomer. Xray reflectometry measurements confim the successful formation of polyelectrolyte layers by this method. Surface-inititated ATRP has the advantages that the polymer chains can be strongly grafted to the substrate, and that high grafting densities should be achievable. Measured normal forces in water showed a long-range repulsion arising from an electrical double layer that extended beyond the polyelectrolyte layers, and a stronger, shorter-range repulsion when the polyelectrolyte brushes were in contact. Swollen layer thicknesses were in the range 15 -40 nm. Upon addition of ~10 -2 M -10 -1 M sodium nitrate, screening effects reduced the electrical double layer force to an undetectable level. Shear force measurements in pure water were performed, and the measured friction may arise from polymer chains bridging between the surfaces.2

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“…Notably, acrylate-and methacrylate-based ATRP has been used to create a wide variety of brushes with different functionalities and architectures, based on a common synthetic approach (for reviews, see e.g. [28][29][30] ). The advantages of grafted-from brushes include the ability to access higher density regimes, due to by-passing the kinetic limitations on graftedto brush density that arise from the slow diffusion of pre-existing polymer chains through a partiallyformed brush 18,[31][32][33] .…”

Section: Introductionmentioning

confidence: 99%

Structure and Collapse of a Surface-Grown Strong Polyelectrolyte Brush on Sapphire

et al. 2012

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We have used neutron reflectometry to investigate the behavior of a strong polyelectrolyte brush on a sapphire substrate, grown by atom transfer radical polymerization (ATRP) from a silane-anchored initiator layer. The initiator layer was deposited from vapor, following treatment of the substrate with an Ar/H 2 O plasma to improve surface reactivity. The deposition process was characterized using X-ray reflectometry, indicating the formation of a complete, cross-linked layer. The brush was grown from the monomer [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC), which carries a strong positive charge. The neutron reflectivity profile of the swollen brush in pure water (D 2 O) showed that it adopted a two-region structure, consisting of a dense surface region ∼ 100 Å thick, in combination with a diffuse brush region extending to around 1000 Å from the surface. The existence of the diffuse brush region may be attributed to electrostatic repulsion from the positively-charged surface region, while the surface region itself most probably forms due to polyelectrolyte adsorption to the hydrophobic initiator layer. The importance of electrostatic interactions in maintaining the brush region is confirmed by measurements at high (1 M) added 1:1 electrolyte, which show a substantial transfer of polymer from the brush to the surface region, together with a strong reduction in brush height. On addition of 10 -4 M oppositely-charged surfactant (sodium dodecyl sulfate SDS), the brush undergoes a dramatic collapse, forming a single dense layer about 200 Å in thickness, which may be attributed to the neutralization of the monomers by adsorbed dodecyl sulfate ions in combination with hydrophobic interactions between these dodecyl chains. Subsequent increases in surfactant concentration result in slow increases in brush height, which may be caused by stiffening of the polyelectrolyte chains due to further dodecyl sulfate adsorption.3

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Synthesis of Polymer Brushes Using Atom Transfer Radical Polymerization

Cited by 684 publications

References 136 publications

Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP

Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP

Direct Measurement of Normal and Shear Forces between Surface-Grown Polyelectrolyte Layers

Structure and Collapse of a Surface-Grown Strong Polyelectrolyte Brush on Sapphire

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