Monolayers of diblock copolymer at the air-water interface: the attractive monomer-surface case

Fauré, Marie-Claude; Bassereau, Patricia; Carignano, Marcelo A.; Szleifer, Igal; Gallot, Yves; Andelman, David

doi:10.1007/s100510050324

Cited by 111 publications

(230 citation statements)

References 24 publications

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“…Bijsterbosch and coworkers 19 estimated an effective adsorption energy of 0.4 k B T per monomer using scaling estimates of the surface density of EO monomers. Faure and co-workers 21 found optimal agreement between their measured isotherms and ones obtained from single chain mean-field calculations when their adsorption energy parameter was chosen to be about 1 k B T per monomer. Given the smooth transition to the pseudoplateau in the experimental data (as opposed to a sharp transition in the SCMF predictions), it is difficult to estimate the onset of segment desorption with high accuracy.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…19,21 The appearance of a pseudoplateau at a surface pressure of approximately 10 mN/m is linked to the onset of solubilization of PEO segments and the transition between a fully adsorbed copolymer layer to a configuration where the PS blocks stay anchored at the interface and PEO chains form a brush in the water subphase. Bijsterbosch and coworkers 19 estimated an effective adsorption energy of 0.4 k B T per monomer using scaling estimates of the surface density of EO monomers.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Adsorption Energies of Poly(ethylene oxide)-Based Surfactants and Nanoparticles on an Air–Water Surface

et al. 2013

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The self-assembly of polymer-based surfactants and nanoparticles on fluid–fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure–density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼103 k B T.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Adsorption Energies of Poly(ethylene oxide)-Based Surfactants and Nanoparticles on an Air–Water Surface

et al. 2013

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“…Poly(styrene) block of the copolymer exists in a collapsed state because both water (or K 2 SO 4 subphases) is a nonsolvent for PS. Fig 2 shows that increasing K 2 SO 4 concentration makes the solvent quality for PEO incrementally worse, which, in turn, results in more PEO segments attached to the interface and in higher surface pressures [19,20].…”

Section: Pressure -Area Isotherms Of Ps-b-peomentioning

confidence: 99%

“…The conformation of PEO chains at each subphase condition can be deduced from the π-A isotherm. At low surface pressures (π < 5 mN/m) PEO chains are known to be adsorbed to the air-water interface in so-called "pancake" configuration [11,19,20]. Poly(styrene) block of the copolymer exists in a collapsed state because both water (or K 2 SO 4 subphases) is a nonsolvent for PS.…”

Section: Pressure -Area Isotherms Of Ps-b-peomentioning

confidence: 99%

Albumin binding and insertion into PS-b-PEO monolayers at air–water interface

Hlady

Jogikalmath

2007

Colloids and Surfaces B: Biointerfaces

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Interaction of human serum albumin with poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO) monolayer at air/solution interface was studied by measuring surface pressure. The density of PEO chains in the monolayer was controlled using Langmuir trough barriers. The thickness of PS-b-PEO monolayer prior to and after albumin adsorption was computed from in situ surface plasmon resonance (SPR) measurements. Depending on the initial PEO surface density the surface pressure kinetics of albumin insertion displayed two different regimes: below the PEO "pancake-brush" transition albumin binding was initially very rapid and itself induced the "pancake-brush" transition in the monolayer, and above the "pancake-brush" transition where some albumin penetration into the free PS-b-PEO monolayer still occurred into the PEO "brush". In the case of SPR-immobilized monolayer, more than 0.1 PEO chain/nm 2 was required to inhibit albumin or ferritin adsorption. A half-reduction of albumin adsorption required approx. threefold higher PEO surface density than the half-reduction of ferritin adsorption.

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“…Pioneering work in this field has been made by Szleifer and coworkers, which in a series of papers [97][98][99][100][114][115][116] systematically addressed how the thermodynamics and the kinetics of protein adsorption are affected by the presence of polymer brushes. Considering equilibrium properties, it was found that a higher grafting density better prevents protein adsorption due to steric repulsion and the competition between monomers and polymer to adsorb on the surface, a result also suggested in an earlier work of de Gennes.…”

Section: Predicting and Controlling Protein Adsorptionmentioning

confidence: 99%

Theory, simulations and the design of functionalized nanoparticles for biomedical applications: A Soft Matter Perspective

Angioletti‐Uberti

2017

npj Comput Mater

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Functionalised nanoparticles for biomedical applications represents an incredibly exciting and rapidly growing field of research. Considering the complexity of the nano-bio interface, an important question is to what extent can theory and simulations be used to study these systems in a realistic, meaningful way. In this review, we will argue for a positive answer to this question. Approaching the issue from a "Soft Matter" perspective, we will consider those properties of functionalised nanoparticles that can be captured within a classical description. We will thus not concentrate on optical and electronic properties, but rather on the way nanoparticles' interactions with the biological environment can be tuned by functionalising their surface and exploited in different contexts relevant to applications. In particular, we wish to provide a critical overview of theoretical and computational coarsegrained models, developed to describe these interactions and present to the readers some of the latest results in this fascinating area of research.

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Monolayers of diblock copolymer at the air-water interface: the attractive monomer-surface case

Cited by 111 publications

References 24 publications

Adsorption Energies of Poly(ethylene oxide)-Based Surfactants and Nanoparticles on an Air–Water Surface

Adsorption Energies of Poly(ethylene oxide)-Based Surfactants and Nanoparticles on an Air–Water Surface

Albumin binding and insertion into PS-b-PEO monolayers at air–water interface

Theory, simulations and the design of functionalized nanoparticles for biomedical applications: A Soft Matter Perspective

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