Nanoconfined Polyelectrolyte Multilayers: From Nanostripes to Multisegmented Functional Nanotubes

Roy, Cécile; Buron, C.C.; Demoustier‐Champagne, Sophie; Jonas, Alain M.

doi:10.1002/9783527646746.ch25

Cited by 5 publications

(6 citation statements)

References 92 publications

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“…The PVCL/PMAA growth was linear after two bilayers, with an average thickness increment per bilayer of 35 nm (Figure S3). This is much larger than the growth increment measured for flat multilayers (4.1 nm/bilayer, Figure a), which is typical for LbL assembly in nanopores as extensively reported previously for electrostatic multilayers; ,,,− apparently, the same phenomena (crowding of chains leading to gel formation, bridging of chains between opposite pore walls, etc.) happen for H-bonded multilayers as well.…”

Section: Resultssupporting

confidence: 78%

Hydrogen-Bonded Multilayers for the Release of Polyelectrolyte Nanotubes in Biocompatible Conditions

Ferain

Demoustier‐Champagne

et al. 2019

ACS Appl. Polym. Mater.

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The growth and disaggregation of hydrogen-bonded layer-by-layer (LbL) multilayers based on poly(methacrylic acid) (PMAA) and poly(N-vinylcaprolactam) (PVCL) are studied depending on pH, NaCl concentration, and PVCL molar mass. Whereas multilayer growth is essentially insensitive to salt and PVCL molar mass, the critical pH for disaggregation strongly depends on salt concentration. The PMAA/PVCL multilayers are then used as sacrificial compartments for the release of LbL nanostructures in biocompatible close-to-neutral 0.15 M NaCl aqueous conditions. We particularly demonstrate the liberation of LbL nanotubes grown inside the nanopores of templating polymer membranes without having to dissolve the membrane template in nonbiocompatible organic solvents and show that the amount of released nanotubes is close to the amount of noncrossing nanopores in the membrane.

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Section: Resultssupporting

confidence: 78%

Hydrogen-Bonded Multilayers for the Release of Polyelectrolyte Nanotubes in Biocompatible Conditions

Ferain

Demoustier‐Champagne

et al. 2019

ACS Appl. Polym. Mater.

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“…The high intensity of CN – and SO 3 – fragments until 120 nm and their low intensity afterward suggest that LbL assembly happens on the membrane surface with limited penetration into the pores. Steric hindrance likely leads to slow diffusion of PEI and CS chains into 10 nm nanochannels and consequently the limited depth of LbL adsorption in the nanochannels. The average hydrodynamic sizes of PEI and CS are 1 order of magnitude larger than the pore size (Figure S10).…”

Section: Results and Discussionmentioning

confidence: 99%

Highly Rectifying Fluidic Diodes Based on Asymmetric Layer-by-Layer Nanofilms on Nanochannel Membranes

et al. 2021

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Nanochannel-based fluidic diodes display ion selectivity and ion current rectification (ICR), which may prove to be important in energy-harvesting devices and biosensors. This paper reports asymmetric functionalization of the outer surface of a flexible nanochannel polymer membrane to create fluidic diodes that give ICR. Layer-by-layer (LbL) adsorption with cross-linking of only the underlying part of the polyelectrolyte nanofilm leads to a porosity step across the film. The combination of a high effective surface charge density and the porosity step in the film leads to a remarkable maximum ICR factor of ∼200 with a pH gradient across the film. Incorporation of pH-sensitive polyelectrolyte components enables the ICR factor to increase an order of magnitude on going from pH 8 to pH 3. Moreover, the coated membrane shows excellent anion selectivity. Thus, LbL adsorption with partial cross-linking provides a simple method for creating coated nanochannel membranes that serve as pH-responsive ionic diodes for potential chemical/biosensors.

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“…Although the liberated nanotubes retained the enzymatic activity of immobilized GOX, most of them were broken during the template dissolution process due to the harsh conditions required for the removal of AAO (phosphoric acid solution). The soft extraction of nanotubes from the template framework is indeed still a challenge for template-assisted synthesis . As for nanoporous polymer membranes, which can be more easily dissolved in organic solvents, the difficulty is to separate the nanotubes from the dissolved polymer solution.…”

Section: Introductionmentioning

confidence: 99%

Quantitative Collection and Enzymatic Activity of Glucose Oxidase Nanotubes Fabricated by Templated Layer-by-Layer Assembly

2015

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We report on the fabrication of enzyme nanotubes in nanoporous polycarbonate membranes via the layer-by-layer (LbL) alternate assembly of polyethylenimine (PEI) and glucose oxidase (GOX), followed by dissolution of the sacrificial template in CH2Cl2, collection, and final dispersion in water. An adjuvant-assisted filtration methodology is exploited to extract quantitatively the nanotubes without loss of activity and morphology. Different water-soluble CH2Cl2-insoluble adjuvants are tested for maximal enzyme activity and nanotube stability; whereas NaCl disrupts the tubes by screening electrostatic interactions, the high osmotic pressure created by fructose also contributes to loosening the nanotubular structures. These issues are solved when using neutral, high molar mass dextran. The enzymatic activity of intact free nanotubes in water is then quantitatively compared to membrane-embedded nanotubes, showing that the liberated nanotubes have a higher catalytic activity in proportion to their larger exposed surface. Our study thus discloses a robust and general methodology for the fabrication and quantitative collection of enzymatic nanotubes and shows that LbL assembly provides access to efficient enzyme carriers for use as catalytic swarming agents.

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Nanoconfined Polyelectrolyte Multilayers: From Nanostripes to Multisegmented Functional Nanotubes

Cited by 5 publications

References 92 publications

Hydrogen-Bonded Multilayers for the Release of Polyelectrolyte Nanotubes in Biocompatible Conditions

Hydrogen-Bonded Multilayers for the Release of Polyelectrolyte Nanotubes in Biocompatible Conditions

Highly Rectifying Fluidic Diodes Based on Asymmetric Layer-by-Layer Nanofilms on Nanochannel Membranes

Quantitative Collection and Enzymatic Activity of Glucose Oxidase Nanotubes Fabricated by Templated Layer-by-Layer Assembly

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