Epitaxial Adsorption of Monodendron-Jacketed Linear Polymers on Highly Oriented Pyrolytic Graphite

Prokhorova, S. A.; Sheiko, Sergei S.; Mourran, Ahmed; Azumi, Reiko; Beginn, Uwe; Zipp, Gabriela; Ahn, Cheol Hee; Holerca, Marian N.; Percéc, Virgil; Möller, Martin

doi:10.1021/la000141e

Cited by 74 publications

(75 citation statements)

References 30 publications

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“…Due to the presence of hydrophilic and hydrophobic residues, the adsorption of proteins and associating polymers on a surface is more complicated than the adsorption of homopolymers. 14 For example, Bauerle et al 15 and Prokhorova et al 16 observed monolayers with long-range order when oligo͑thiophenes͒ or comblike polymers adsorb on graphite, while Sheiko et al 17 reported first-order rod-globule phase transitions in adsorbed polymer films. When adsorbed on a surface, proteins often undergo conformational changes in an attempt to lower the global free energy.…”

Section: Introductionmentioning

confidence: 99%

Adsorption of comb copolymers on weakly attractive solid surfaces

Striolo

Jayaraman²,

Genzer³

et al. 2005

The Journal of Chemical Physics

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In this work continuum and lattice Monte Carlo simulation methods are used to study the adsorption of linear and comb polymers on flat surfaces. Selected polymer segments, located at the tips of the side chains in comb polymers or equally spaced along the linear polymers, are attracted to each other and to the surface via square-well potentials. The rest of the polymer segments are modeled as tangent hard spheres in the continuum model and as self-avoiding random walks in the lattice model. Results are presented in terms of segment-density profiles, distribution functions, and radii of gyration of the adsorbed polymers. At infinite dilution the presence of short side chains promotes the adsorption of polymers favoring both a decrease in the depletion-layer thickness and a spreading of the polymer molecule on the surface. The presence of long side chains favors the adsorption of polymers on the surface, but does not permit the spreading of the polymers. At finite concentration linear polymers and comb polymers with long side chains readily adsorb on the solid surface, while comb polymers with short side chains are unlikely to adsorb. The simple models of comb copolymers with short side chains used here show properties similar to those of associating polymers and of globular proteins in aqueous solutions, and can be used as a first approximation to investigate the mechanism of adsorption of proteins onto hydrophobic surfaces.

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Section: Introductionmentioning

confidence: 99%

Adsorption of comb copolymers on weakly attractive solid surfaces

Striolo

Jayaraman²,

Genzer³

et al. 2005

The Journal of Chemical Physics

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“…[1] SFM is now routinely used to visualise rather stiff and thick synthetic macromolecules, e.g., of monodendron-jacketed, dendronized, helical, and hyperbranched polymers, etc. [2] Certain progress has been also achieved in the SFM-imaging of flexible synthetic polymer chains: their conformational transitions have been studied ex situ, provided that strong binding (e.g., by electrostatic forces) of the macromolecules to the supporting substrate has been ensured. [3] But the in situ SFM-visualisation of the macromolecular conformational dynamics remains a rather challenging task requiring a search for more appropriate experiments.…”

Section: Introductionmentioning

confidence: 99%

Real‐Time Scanning Force Microscopy of Macromolecular Conformational Transitions

Gallyamov

Tartsch

Khokhlov

et al. 2004

Macromol. Rapid Commun.

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Summary: Comb‐like macromolecules were adsorbed on mica and imaged by scanning force microscopy in real time as they underwent a transition from an extended worm‐like conformation to globuli and vice versa. The conformational transition was effected by coadsorption of ethanol and water molecules. Coadsorption of the small molecules allowed manipulation of the adherence and spreading of the macromolecules, thus effecting the reptation like stretching and collapse of the single molecules.SFM images of three individual PMA‐g‐PnBuA brush molecules on mica 27 min (left, first collapse cycle) and 18 min (right, second collapse cycle) after injection of ethanol into the sample space.imageSFM images of three individual PMA‐g‐PnBuA brush molecules on mica 27 min (left, first collapse cycle) and 18 min (right, second collapse cycle) after injection of ethanol into the sample space.

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“…[33,34] In addition, the dendron provides a significant mechanical barrier to rotation about bonds in a central unit when the conjugates are in a conformationally restricted environment, such as in a solid-state lattice or on a surface. We have shown that when monolayers of these systems form, not only a pattern containing one molecular conformation (in a global energy minimum), but a range of conformations may be found in surface-bound domains.…”

mentioning

confidence: 99%

Self‐Organized Monolayers: A Route to Conformational Switching and Read‐Out of Functional Supramolecular Assemblies by Scanning Probe Methods

Hermann

Scherer

Housecroft

et al. 2006

Adv Funct Materials

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Self‐organized molecular layers provide a promising route to constructing new (switchable) nanodevices and optimizing nanosensors. The design of such molecules involves control of structure and stabilization on the surface, as well as control of functionality. The search for a potentially universal “adapter”, which can control the self‐organization and stabilization on a particular type of surface, is a unique challenge. High‐quality nanoscale imaging using scanning tunneling microscopy (STM) provides the means to further such studies. This article reviews our recent STM work on single molecules, self‐assembled monolayers, and self‐organized monolayers, highlighting our application of a general “self‐organizer” for graphite surfaces, i.e., a Fréchet‐type dendron. How powerfully this self‐organizing motif can affect various central components (catalytic, switchable, redox‐active) on a graphite surface is addressed by analyzing self‐organized monolayers of nine different molecules, each containing at least one first‐ or second‐generation Fréchet‐type dendron. In molecular layers containing a “switchable” core, we can detect a large conformational change upon protonation with HCl gas. Last, but not least, the dynamic surface organization properties of the Fréchet‐type dendrons are described.

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Epitaxial Adsorption of Monodendron-Jacketed Linear Polymers on Highly Oriented Pyrolytic Graphite

Cited by 74 publications

References 30 publications

Adsorption of comb copolymers on weakly attractive solid surfaces

Adsorption of comb copolymers on weakly attractive solid surfaces

Real‐Time Scanning Force Microscopy of Macromolecular Conformational Transitions

Self‐Organized Monolayers: A Route to Conformational Switching and Read‐Out of Functional Supramolecular Assemblies by Scanning Probe Methods

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