First Insights into Electrografted Polymers by AFM-Based Force Spectroscopy

Cuenot, Stéphane; Gabriel, Sabine; Jérôme, Robert; Jérôme, Christine; Fustin, Charles-André; Jonas, Alain M.; Duwez, Anne‐Sophie

doi:10.1021/ma060824m

Cited by 38 publications

(59 citation statements)

References 43 publications

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“…The observed profile at pH = 9 (exponentially increasing repulsive forces during the approach) is the typical signature of a polymer brush under compression in a good solvent [33]. The linear increase of forces close to the contact point observed at pH = 5 is characteristic of a more collapsed state [34].…”

Section: Figurementioning

confidence: 85%

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Poly(acrylic acid) with disulfide bond for the elaboration of pH-responsive brush surfaces

Camp¹,

Prez²,

Alem³

et al. 2010

European Polymer Journal

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We report on a new route for the facile preparation of pH-responsive tethered brushes on metallic surfaces, starting from poly(acrylic acid) (PAA) containing a disulfide (S-S) bond (PAA-S-S-PAA). First, atom transfer radical polymerization (ATRP) of 1-ethoxyethyl acrylate (EEA) with a disulfide containing initiator was performed to obtain the poly(EEA) precursor polymer (PEEA-S-S-PEEA). Deprotection of PEEA by a heating step resulted in the desired PAA-chains without any further purification. The brushes, obtained by the 'grafting to' of PAA-S-S-PAA onto gold, were then characterized by atomic force microscopy in water at various pH values. The results evidence a large collapsing/swelling capacity.

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Section: Figurementioning

confidence: 85%

“…Indeed, for a high grafting density regime, the difference between collapsed and swollen brush thickness would be smaller. A crude estimation of the grafting density can be obtained from the measured thickness in the swollen state using the scaling concept based on the Alexander-de Gennes model [14,33,34]. Binding Energy (eV) …”

Section: Figurementioning

confidence: 99%

Poly(acrylic acid) with disulfide bond for the elaboration of pH-responsive brush surfaces

Camp¹,

Prez²,

Alem³

et al. 2010

European Polymer Journal

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“…However, as Duwez and coworkers showed, the electrografting of NHSA from an AFM tip could be used to deliver and immobilize individual molecules on a surface. 91,92 In this remarkable study, they electrografted the polymeric activated ester PNHSA from a gold coated AFM tip, which was then brought in contact with an amino functionalized surface. The formation of a covalent amide bond linked the polymer chain to the surface.…”

Section: Electrochemical Polymerizationmentioning

confidence: 99%

Synthesis of well‐defined polymeric activated esters

Théato

2008

J. Polym. Sci. A Polym. Chem.

277

260

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Monomers bearing an activated ester group can be polymerized under various controlled polymerization techniques, such as ATRP, NMP, RAFT polymerization, or ROMP. Combining the functionalization of polymers via polymeric activated esters with these controlled polymerization techniques generate possibilities to realize highly functionalized polymer architectures. Within this highlight two different research areas of activated esters in polymer science will be discussed: (i) the preparation of defined reactive polymer architectures by controlled polymerization techniques and (ii) the preparation of defined reactive thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6677–6687, 2008

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“…Among the few techniques that were used to characterize the molar mass of grafted polyelectrolytes, atomic force microscope-based single molecule force spectroscopy (SMFS) has been demonstrated to possess good potential [28][29][30][31]. By stretching single molecules between an atomic force microscope (AFM) tip and a supporting substrate, not only will intermolecular interactions be revealed, but also the contour length of the chain, and the conformation of the molecules on the surface or interface [10,[32][33][34][35][36].…”

Section: Introductionmentioning

confidence: 99%

Determination of the molar mass of surface-grafted weak polyelectrolyte brushes using force spectroscopy

Al-Baradi

Tomlinson

Zhang³

et al. 2015

Polymer

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The molar mass and dispersity of a polycation, poly[2-(dimethyl amino)ethyl methacrylate)] (PDMAEMA) grafted from a poly(methyl methacrylate) (PMMA) backbone, was measured by single-molecule force spectroscopy (SMFS) and shown to be consistent with results from gel permeation chromatography for the same comb polymer in aqueous solution. Comparison was then made between the comb polymer and PDMAEMA brushes that were grown from the substrate, as a function of the pH and ionic strength of the surrounding medium, and the limits of reliable characterization of the polymers are determined. A large discrepancy was observed between the responses of the comb and brush layer at low pH when the PDMAEMA molecules are extended from the supporting substrate. Here it is believed that the atomic force microscope (AFM) tip can penetrate the comb layer and selectively desorb side-chains of the comb. In the case of the well solvated PDMAEMA brushes at high pH, the tip preferentially selects larger chains, resulting in an over-estimate of the brush molar mass. The addition of salt also influenced the molar mass obtained by this technique. It is believed that salted brushes did not adhere well to the AFM tip, with subsequent desorption resulting in an underestimate of the molar mass. However, SMFS was shown to be capable of demonstrating the effect of salt on brush conformation, with greater swelling after the addition of a small amount of NaCl, but a significant decrease when 100 mM is added.

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First Insights into Electrografted Polymers by AFM-Based Force Spectroscopy

Cited by 38 publications

References 43 publications

Poly(acrylic acid) with disulfide bond for the elaboration of pH-responsive brush surfaces

Poly(acrylic acid) with disulfide bond for the elaboration of pH-responsive brush surfaces

Synthesis of well‐defined polymeric activated esters

Determination of the molar mass of surface-grafted weak polyelectrolyte brushes using force spectroscopy

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