Surface-Initiated Polymerization by Means of Novel, Stable, Non-Ester-Based Radical Initiator

Bain, Erich D.; Dawes, K.; Özçam, A. Evren; Hu, Xinfang; Gorman, Christopher B.; Šrogl, Jiří; Genzer, Jan

doi:10.1021/ma300491e

Cited by 53 publications

(70 citation statements)

References 77 publications

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“…These two counterbalancing effects resulted in maximum degrafting at pH 7.4. This was further supported by the [161]. Copyright 2012 American Chemical Society experimental observation that the degrafting rate of qPDMAEMA brushes increased with increasing pH.…”

Section: Charged Polymer Brushessupporting

confidence: 53%

“…Genzer and co-workers studied the effects of weak linkers (e.g., ester bond) on the stability of surface-grafted PDMAEMA (a weak polyelectrolyte) brushes at varying conditions of pH [161]. Two sets of PDMAEMA brushes were prepared by surface-initiated free radical polymerization (SI-FRP) from the so-called BAIN initiator and SI-ATRP from [11-(2-bromo-2-methyl)propionyloxy]-undecyltrichlorosilane (BMPUS) initiator, respectively.…”

Section: Charged Polymer Brushesmentioning

confidence: 99%

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Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Sheiko

2015

Topics in Current Chemistry

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Mechanical activation of chemical bonds is usually achieved by applying external forces. However, nearly all molecules exhibit inherent strain of their chemical bonds and angles as a result of constraints imposed by covalent bonding and interactions with the surrounding environment. Particularly strong deformation of bonds and angles is observed in hyperbranched macromolecules caused by steric repulsion of densely grafted polymer branches. In addition to the tension amplification, macromolecular architecture allows for accurate control of strain distribution, which enables focusing of the internal mechanical tension to specific chemical bonds and angles. As such, chemically identical bonds in self-strained macromolecules become physically distinct because the difference in bond tension leads to the corresponding difference in the electronic structure and chemical reactivity of individual bonds within the same macromolecule. In this review, we outline different approaches to the design of strained macromolecules along with physical principles of tension management, including generation, amplification, and focusing of mechanical tension at specific chemical bonds.

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Section: Charged Polymer Brushessupporting

confidence: 53%

Section: Charged Polymer Brushesmentioning

confidence: 99%

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Sheiko

2015

Topics in Current Chemistry

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“…The polymerization was carried out for 6 min and terminated by adding a saturated solution of CuCl 2 in water/ methanol. For the preparation of the block copolymer P(NIPAMb-DMAEMA), the PNIPAM-modified substrates were transferred into a mixture of 33 mL of N,N-dimethylaminoethyl methacrylate (DMAEMA) 11.6 g of H 2 O, 0.45 g of methanol, 2.00 g of bipyridyl and 0.40/0.04 g of CuCl/CuCl 2 , according to the protocol reported by Bain et al 31 The polymerization was run for 2 h, followed by sonication in methanol, rinsing in Milli-Q water and drying in a N 2 stream. Polyelectrolyte solutions were prepared by dissolving the required amount of polyelectrolyte, PSS or PDADMAC, in 0.1 M NaCl solution to obtain the concentration of 0.01 (mono)mol L…”

Section: Materials and Sample Preparationmentioning

confidence: 99%

Temperature responsive behavior of polymer brush/polyelectrolyte multilayer composites

et al. 2016

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aThe complex interaction of polyelectrolyte multilayers (PEMs) physisorbed onto end-grafted polymer brushes with focus on the temperature-responsive behavior of the system is addressed in this work. The investigated brush/multilayer composite consists of a poly(styrene sulfonate)/poly(diallyldimethylammonium chloride) (PSS/PDADMAC) multilayer deposited onto the poly(N-isopropylacrylamide-bdimethylaminoethyl methacrylate) P(NIPAM-b-DMAEMA) brush. Ellipsometry and neutron reflectometry were used to monitor the brush collapse with the thickness decrease as a function of temperature and the change in the monomer distribution perpendicular to the substrate at temperatures below, across and above the phase transition, respectively. It was found that the adsorption of PEMs onto polymer brushes had a hydrophobization effect on PDMAEMA, inducing the shift of its phase transition to lower temperatures, but without suppressing its temperature-responsiveness. Moreover, the diffusion of the free polyelectrolyte chains inside the charged brush was proved by comparing the neutron scattering length density profile of pure and the corresponding PEM-capped brushes, eased by the enhanced contrast between hydrogenated brushes and deuterated PSS chains. The results presented herein demonstrate the possibility of combining a temperature-responsive brush with polyelectrolyte multilayers without quenching the responsive behavior, even though significant interpolyelectrolyte interactions are present. This is of importance for the design of multicompartment coatings, where the brush can be used as a reservoir for the controlled release of substances and the multilayer on the top as a membrane to control the diffusion in/out by applying different stimuli.

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“…ATRP of poly-(N,N-(dimethylamino ethyl) methacrylate (PDMAEMA): The synthesis was carried out following the literature [58], but with the difference of using the new reactor. Further, the literature recipe was modified by changing the CuCl/CuCl 2 ratio in order to slow down the reaction to achieve more dense polymer brushes [59].…”

Section: Synthesismentioning

confidence: 99%

Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

et al. 2014

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The effect of brush thickness on the loading of gold nanoparticles (AuNPs) within stimuli-responsive poly-(N,N-(dimethylamino ethyl) methacrylate) (PDMAEMA) polyelectrolyte brushes is reported. Atom transfer radical polymerization (ATRP) was used to grow polymer brushes via a "grafting from" approach. The brush thickness was tuned by varying the polymerization time. Using a new type of sealed reactor, thick brushes were synthesized. A systematic study was performed by varying a single parameter (brush thickness), while keeping all other parameters constant. AuNPs of 13 nm in diameter were attached by incubation. X-ray reflectivity, electron scanning microscopy and ellipsometry were used to study the particle loading, particle distribution and interpenetration of the particles within the brush matrix. A model for the structure of the brush/particle hybrids was derived. The particle number densities of attached AuNPs depend on the brush thickness, as do the optical properties of the hybrids. An increasing particle number density was found for increasing brush thickness, due to an increased surface roughness.

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Surface-Initiated Polymerization by Means of Novel, Stable, Non-Ester-Based Radical Initiator

Cited by 53 publications

References 77 publications

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Molecular Mechanochemistry: Engineering and Implications of Inherently Strained Architectures

Temperature responsive behavior of polymer brush/polyelectrolyte multilayer composites

Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

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