A quantitative study of tethered chains in various solution conditions using Langmuir diblock copolymer monolayers

Kent, Michael S.

doi:10.1002/(sici)1521-3927(20000301)21:6<243::aid-marc243>3.0.co;2-r

Cited by 92 publications

(118 citation statements)

References 81 publications

(172 reference statements)

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“…[29][30][31] The surface and solvent were chosen to maximize preferential adsorption of one block to a solid surface while the solvent was chosen to preferentially interact with the other block. One example is the physisorption of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) from a toluene solution.…”

Section: Synthesis Of Grafted Polymer Chainsmentioning

confidence: 99%

“…However, this value is strongly affected by excluded volume and can vary from system to system. For example, Kent 29 studied Langmuir-Blodgett layers of poly(dimethylsiloxane)-b-PS block copolymers and reported that the highly stretched regime occurs for S [ 12. A study was reported by Cheng and coworkers 36,37 in which they studied PS brushes formed by the block-selective crystallization of PEO-b-PS and poly(L-lactic acid)-b-PS copolymers.…”

Section: The Definition Of a Polymer Brush By Characteristic Parametementioning

confidence: 99%

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A structural definition of polymer brushes

Brittain

Minko

2007

J. Polym. Sci. A Polym. Chem.

569

652

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ABSTRACT:In this article, we consolidate several literature reports in an attempt to provide a structural definition of a polymer brush as a tethered polymer layer with a high grafting density of polymer chains. We will try to distinguish a brush from grafted polymer layers and coated layers and provide a reasonable approach to the description of the brush regime with a single parameter S-reduced grafting density. Furthermore, we will attempt to describe the relevance of this description to applications. This article is timely given the continuing interest relating to brushes on flat substrates, nanoparticles, and the walls of micro-channels.

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Section: Synthesis Of Grafted Polymer Chainsmentioning

confidence: 99%

Section: The Definition Of a Polymer Brush By Characteristic Parametementioning

confidence: 99%

A structural definition of polymer brushes

Brittain

Minko

2007

J. Polym. Sci. A Polym. Chem.

569

652

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“…The new signal demonstrates the line broadening expected when the 1,1,1-trifluorobutane fragment is bound to the rigid network backbone of 1. The absence of other signals in the 19 F NMR spectrum indicated that no significant side reactions involving TFIB took place. Therefore, it was concluded that there were little to no 1,1,1-trifluorobutane radical fragments formed in solution, indicating that the primary reactive sites in the reaction solution were at the surface of 1.…”

Section: Resultsmentioning

confidence: 99%

“…18 Physisorption is characterized by adsorption of one polymer chain onto another, [19][20][21] whereas both grafting methods involve a chemical reaction between the substrate surface and the polymer chain forming a covalent bond attachment (chemisorption). 18 Although each method produces interesting physical characteristics at the substrate surface, the 'grafting from' method is of particular interest.…”

Section: Introductionmentioning

confidence: 85%

“…Such a small amount of monomer was expected to produce short oligomeric chains that were surface grafted to 1, and thus have a similar effect on the 19 F NMR spectrum that was observed for the reaction of 1 with TFIB. Analysis of the product, 1/PFS, with 1 H NMR and UV-visible spectroscopy confirmed the presence of 1.…”

Section: Surface-initiated Graft Polymerization Studiesmentioning

confidence: 99%

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A carbon network backbone polymer functionalized with polymer brushes

Greco

Bianconi

2010

Polym J

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The surface-initiated graft polymerization of polymer brushes attached to an sp 3 random carbon network backbone structure is demonstrated. Poly(ethyl acrylate) (PEA), poly(4-fluorostyrene) (PFS) and poly(acrylonitrile) (PAN) brushes were grafted from the network backbone polymer poly(hydridocarbyne), 1, illustrating the breadth of reactivity of the network backbone. Attachment of polymeric/oligomeric chains to the network backbone was observed through two different methods with different polymer systems. First, selective solvent extraction separated a homogeneous mixture of PEA and 1, dissolving PEA in diethyl ether, but leaving 1 behind as a brown precipitate. In contrast, 1 functionalized with PEA brushes completely dissolved, showing that it was not a homogenous mixture of the substrate and free polymeric chains, but a system of covalently bound polymer chains originating from 1. Formation of short chains of PFS at the surface of 1 allowed the use of 19 F nuclear magnetic resonance to observe the change in resonance shift and shape for the polymer side chains. Solvent extraction was used to demonstrate that tetrahydrofuran (THF) was able to separate a homogeneous mixture of PAN and 1, dissolving 1 in THF, but leaving PAN behind as a white precipitate.

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Self‐Assembly and Properties of Main‐Chain Reversible Polymer Brushes

et al. 2005

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in the potential range between 0 and 0.6 V. Impedance spectra were taken between 100 kHz and 50 MHz under sinusoidal potentials with an amplitude of 10 mV. To estimate the electrochemical parameters from the data, the whole system was represented by ideal elements of a simplified equivalent-circuit model composed of serial resistance, interface capacitance, and interface resistance. [4] and very limited experimental work has been reported. [5] Using DNA-based modules, we investigate here the compressive and adhesive mechanical properties of self-assembled polymer brushes, and we report the effects of surface anchor density, association strength, and monomer flexibility on those properties. Reversible polymer brush properties ( Fig. 1) were examined using atomic force microscopy (AFM). Patterned gold substrates were prepared using scanning electron microscopy (SEM), photolithography, and chemical vapor deposition. The patterning provided a background reference height and also allowed multiple samples to be introduced simultaneously into the AFM. Isolated gold dots (~1.4 lm in diameter) were spaced among quadrants of a ca. 1 cm 2 silicon surface. Each quadrant and its associated gold pattern were addressed independently with a solution of an oligonucleotide±thiol RP anchor 1, (5¢®3¢)GGTATACC±(CH 2 ) 3 ±SH, and a 6-mercapto-1-hexanol backlayer that resists non-specific adsorption of the RPs on the surface.[6] The relative concentration of the two components determined the surface density (0±1.2 10 12 cm ±2 )of the RP anchor within a self-assembled monolayer (SAM) on the pattern in each quadrant.[6] Using tapping-mode AFM in 1 M NaCl and phosphate buffer (pH 7.0), the heights of the gold dots in each quadrant were measured and found to be roughly equivalent at~40 nm (Table 1). All four quadrants were then immersed simultaneously into the RP solutions of interest and probed in rapid succession with a single gold-coated AFM tip that had also been treated with 1.The anchor 1 is complementary to the oligonucleotide RP monomer 2 ((5¢®3¢)GGTATACCGCTTAAGC). End-to-end duplex formation of 2 creates a linear, polymeric assembly that resembles larger duplex DNA, but in which the main chain is defined by the reversible base pairing.[7] The equilibrium RP solution structure of 2 has been thoroughly characterized, [8] and reversible polymers formed from oligonucleotide-based monomers have been found to be a useful model system for delineating molecule-to-material relationships in RPs. Polymer-brush synthesis is a facile, one-step self-assembly process. Immersing the 1-modified substrate into an 11 lM solution of 2 led, within minutes, to the formation of RP brushes, as revealed by changes in the AFM images (Table 1). The effective thickness of the brush is indicated by the difference in the height of the features in the two solutions, which increased with increasing surface density of anchors; the apparent brush thicknesses are 6 ± 2, 16 ± 2, and 23 ± 2 nm for surface anchor densities of 0.6 ± 0.1 10 11 , 1.1 ± 0.1 10 11 , ...

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A quantitative study of tethered chains in various solution conditions using Langmuir diblock copolymer monolayers

Cited by 92 publications

References 81 publications

A structural definition of polymer brushes

A structural definition of polymer brushes

A carbon network backbone polymer functionalized with polymer brushes

Self‐Assembly and Properties of Main‐Chain Reversible Polymer Brushes

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