Structure and Properties of High-Density Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization

Tsujii, Yoshinobu; Ohno, Kohji; Yamamoto, Satoshi; Goto, Atsushi; Fukuda, Takeshi

doi:10.1007/12_063

Cited by 621 publications

(710 citation statements)

References 182 publications

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“…The distinct behaviors observed for (n-s)-N-6-CD-ICs made with α-and γ-CDs-lower T c s and ΔH c s for (n-s)-N-6-γ-CD-ICs-can in part be attributed to the differences in the constraints imposed on their un-included chains "dangling" from their CD-IC channels. Because, in fact, they form dense brushes [18] that do not significantly "dangle", but are largely extended and parallel, and will be discussed further below. Single and pairs of side-by-side N-6 chains included, respectively, in the nylon-α-and γ-CD-IC channels emerge from them immediately above their crystalline CD-IC surfaces, with initial channel densities of ~4 and ~3 nylon-6 chains/nm 2 of channel, respectively.…”

Section: Semi-crystalline Polymers In (N-s)-cd-ics and Coalesced Frommentioning

confidence: 99%

Non-Stoichiometric Polymer-Cyclodextrin Inclusion Compounds: Constraints Placed on Un-Included Chain Portions Tethered at Both Ends and Their Relation to Polymer Brushes

Tonelli

2014

Polymers

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When non-covalently bonded crystalline inclusion compounds (ICs) are formed by threading the host cyclic starches, cyclodextrins (CDs), onto guest polymer chains, and excess polymer is employed, non-stoichiometric (n-s)-polymer-CD-ICs, with partially uncovered and "dangling" chains result. The crystalline host CD lattice is stable to ~300 °C, and the uncovered, yet constrained, portions of the guest chains emanating from the CD-IC crystal surfaces behave very distinctly from their neat bulk samples. In CD-IC crystals formed with α-and γ-CD hosts, each containing, respectively, six and eight 1,4-α-linked glucose units, the channels constraining the threaded portions of the guest polymer chains are ~0.5 and 1.0 nm in diameter and are separated by ~1.4 and 1.7 nm. This results in dense brushes with ~0.6 and 0.4 chains/nm 2 (or 0.8 if two guest chains are included in each γ-CD channel) of the un-included portions of guest polymers emanating from the host CD-IC crystal surfaces. In addition, at least some of the guest chains leaving from a crystalline CD-IC surface re-enter another CD-IC crystal creating a network structure that leads to shape-memory behavior for (n-s)-polymer-CD-ICs. To some extent, (n-s)-polymer-CD-ICs can be considered as dense polymer brushes with chains that are tethered on both ends. Not surprisingly, the behavior of the un-included portions of the guest polymer chains in (n-s)-polymer-CD-ICs are quite different from those of their neat bulk samples, with higher glass-transition and melt crystallization temperatures and crystallinities. Here we additionally compare their behaviors to samples coalesced from their stoichiometric ICs, and more importantly to dense polymer brushes formed by polymer chains chemically bonded to surfaces at only one end. Judging on the basis of their glass-transition, crystallization and melting temperatures, and crystallinities, we generally find the un-included portions of OPEN ACCESSPolymers 2014, 6 2167 chains in (n-s)-polymer-CD-ICs to be more constrained than those in neat bulk as-received and coalesced samples and in high density brushes. The last observation is likely because many of the un-included chain portions in (n-s)-polymer-CD-ICs are tethered/constrained at both ends, while the chains in their dense brushes are tethered at only one end.

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Section: Semi-crystalline Polymers In (N-s)-cd-ics and Coalesced Frommentioning

confidence: 99%

Non-Stoichiometric Polymer-Cyclodextrin Inclusion Compounds: Constraints Placed on Un-Included Chain Portions Tethered at Both Ends and Their Relation to Polymer Brushes

Tonelli

2014

Polymers

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“…1,2) This surface-initiated polymerization technique, especially combined with a controlled radical polymerization system, enables us to prepare high-density grafted polymers due to the densely immobilized initiators and the high initiator efficiency. With increasing graft densities, polymer chains will be stretched away from the surface in order to avoid overlap of each polymer chain, forming a so-called ''polymer brush''.…”

Section: Introductionmentioning

confidence: 99%

Surface and Interface Analyses of Polymer Brushes by Synchrotron Radiation

et al. 2013

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In the present review, we focus on the characterization of polymer brushes by quantum beam, which is regarded as a promising probe of surface and interface analysis. The polymer brushes were prepared on various shapes of surface, and proved to be benefit to various applications. Among them, the polymer brushes grafted on sphere nanoparticles and flat substrates are investigated as representative cases. The static structure of polymer brushes, especially the chain dimension of polymer brushes grafted on nanoparticles and a flat substrate, have been studied by small angle X-ray scattering (SAXS) and neutron reflectivity (NR), respectively. The microscopic dynamical properties of polymer brushes are also expected to be revealed by quantum beam. X-ray photon correlation spectroscopy (XPCS), a technique using a coherent X-ray, is one of the promising methods for microscopically understanding of dynamical properties of polymer brushes. Some of our recent studies about dynamical behavior of polymer brush immobilized nanoparticle by XPCS are also presented.

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“…P olymer brushes form when macromolecular chains are end-tethered to surfaces at high grafting densities 1,2 . The swelling and mutual steric repulsion of the polymers cause the chains to stretch and extend into the solvent, producing a molecular coating that can reduce non-specific interactions of the underlying surface with cells and biological macromolecules 3 .…”

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confidence: 99%

Stimuli-sensitive intrinsically disordered protein brushes

et al. 2014

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Grafting polymers onto surfaces at high density to yield polymer brush coatings is a widely employed strategy to reduce biofouling and interfacial friction. These brushes almost universally feature synthetic polymers, which are often heterogeneous and do not readily allow incorporation of chemical functionalities at precise sites along the constituent chains. To complement these synthetic systems, we introduce a biomimetic, recombinant intrinsically disordered protein that can assemble into an environment-sensitive brush. This macromolecule adopts an extended conformation and can be grafted to solid supports to form oriented protein brushes that swell and collapse dramatically with changes in solution pH and ionic strength. We illustrate the value of sequence specificity by using proteases with mutually orthogonal recognition sites to modulate brush height in situ to predictable values. This study demonstrates that stimuli-responsive brushes can be fabricated from proteins and introduces them as a new class of smart biomaterial building blocks.

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Structure and Properties of High-Density Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization

Cited by 621 publications

References 182 publications

Non-Stoichiometric Polymer-Cyclodextrin Inclusion Compounds: Constraints Placed on Un-Included Chain Portions Tethered at Both Ends and Their Relation to Polymer Brushes

Non-Stoichiometric Polymer-Cyclodextrin Inclusion Compounds: Constraints Placed on Un-Included Chain Portions Tethered at Both Ends and Their Relation to Polymer Brushes

Surface and Interface Analyses of Polymer Brushes by Synchrotron Radiation

Stimuli-sensitive intrinsically disordered protein brushes

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