The slowly formed Guiselin brush

O’Shaughnessy, Ben; Vavylonis, Dimitrios

doi:10.1209/epl/i2003-00602-4

Cited by 14 publications

(21 citation statements)

References 21 publications

(30 reference statements)

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“…Under this condition, the reaction rate defined as the number of surface bonds created per unit time and area Q decomposes into the product of the (intrinsic) reaction rate (frequency) q for monomers within the reaction distance from the surface and the concentration of monomers c0 within the reaction distance (z<b). The latter is to be calculated for polymer configurations equilibrated under the constraints imposed by already bound monomers [100,101,102,103]. Below, we consider chemisorption from a dilute solution.…”

Section: Adsorption Of Wlcmentioning

confidence: 99%

Semiflexible Chains at Surfaces: Worm-Like Chains and beyond

et al. 2016

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Abstract:We give an extended review of recent numerical and analytical studies on semiflexible chains near surfaces undertaken at Institut Charles Sadron (sometimes in collaboration) with a focus on static properties. The statistical physics of thin confined layers, strict two-dimensional (2D) layers and adsorption layers (both at equilibrium with the dilute bath and from irreversible chemisorption) are discussed for the well-known worm-like-chain (WLC) model. There is mounting evidence that biofilaments (except stable d-DNA) are not fully described by the WLC model. A number of augmented models, like the (super) helical WLC model, the polymorphic model of microtubules (MT) and a model with (strongly) nonlinear flexural elasticity are presented, and some aspects of their surface behavior are analyzed. In many cases, we use approaches different from those in our previous work, give additional results and try to adopt a more general point of view with the hope to shed some light on this complex field.

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Section: Adsorption Of Wlcmentioning

confidence: 99%

Semiflexible Chains at Surfaces: Worm-Like Chains and beyond

et al. 2016

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“…This process has been studied theoretically by O'Shaughnessy and Vavylonis [209]. Single chain chemisorption kinetics was analyzed in a similar way to that for dilute solutions (section 5.1).…”

Section: Chemisorption: the Slow Guiselin Brushmentioning

confidence: 99%

“…(a) Hierachichal loop structure after adsorption from the melt. For slow chemisorption [209] successive loop size scales are frozen in as their critical density is reached. Beyond this their formation would force chain stetching and hence is strongly suppressed.…”

Section: Physisorption: the Guiselin Brushmentioning

confidence: 99%

“…The blob structure of the swollen layer in good solvent is shown. It consists of two regions separated at z * ∼ s * 3/5 corresponding to loop size s * [55,209], each region having a different density profile. For irrversible physisorption from a melt there is no inner region.…”

Section: Physisorption: the Guiselin Brushmentioning

confidence: 99%

“…Since chemical bond formation requires many surface-monomer collisions, chemisorption from melts can be thought of as a slow version of Guiselin's case which involved immediate bond formation. This process has been studied theoretically by O'Shaughnessy and Vavylonis [209]. Single chain chemisorption kinetics was analyzed in a similar way to that for dilute solutions (section 5.1).…”

Section: Chemisorption: the Slow Guiselin Brushmentioning

confidence: 99%

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Non-equilibrium in adsorbed polymer layers

O’Shaughnessy

Vavylonis

2005

J. Phys.: Condens. Matter

122

152

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Abstract.High molecular weight polymer solutions have a powerful tendency to deposit adsorbed layers when exposed to even mildly attractive surfaces. The equilibrium properties of these dense interfacial layers have been extensively studied theoretically. A large body of experimental evidence, however, indicates that non-equilibrium effects are dominant whenever monomer-surface sticking energies are somewhat larger than kT , a common case. Polymer relaxation kinetics within the layer are then severely retarded, leading to non-equilibrium layers whose structure and dynamics depend on adsorption kinetics and layer ageing. Here we review experimental and theoretical work exploring these non-equilibrium effects, with emphasis on recent developments. The discussion addresses the structure and dynamics in non-equilibrium polymer layers adsorbed from dilute polymer solutions and from polymer melts and more concentrated solutions. Two distinct classes of behaviour arise, depending on whether physisorption or chemisorption is involved. A given adsorbed chain belonging to the layer has a certain fraction of its monomers bound to the surface, f , and the remainder belonging to loops making bulk excursions. A natural classification scheme for layers adsorbed from solution is the distribution of single chain f values, P (f ), which may hold the key to quantifying the degree of irreversibility in adsorbed polymer layers. Here we calculate P (f ) for equilibrium layers; we find its form is very different to the theoretical P (f ) for non-equilibrium layers which are predicted to have infinitely many statistical classes of chain. Experimental measurements of P (f ) are compared to these theoretical predictions.

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