<sup>13</sup>C Solid-State NMR Study of Polyelectrolyte Multilayers

Smith, R. N.; Reven, Linda; Barrett, Christopher J.

doi:10.1021/ma0258408

Cited by 51 publications

(57 citation statements)

References 23 publications

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“…The sawtooth pattern of the dipolar coupling strength is superimposed on a monotonic increase, in complete agreement with the polymer T 1H data, indicating an increased mobility of PDADMAC when it is on the surface which seems to be heading for the PEC values for full bilayer films and grows from the value of bulk PDADMAC. These data complement the 13 C spin-lattice relaxation data, 31 with the PDADMAC becoming less mobile as the number of layers increases and the PSS mobility staying relatively constant. The lack of oscillation of the dried samples highlights the effect of water on the mobility of the polymers within the film.…”

Section: Effect Of Number Of Layers On Polymer Mobilitysupporting

confidence: 78%

NMR Studies of the Effect of Adsorbed Water on Polyelectrolyte Multilayer Films in the Solid State

et al. 2003

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Fast-MAS 1 H NMR is used to probe the structure and dynamics of the adsorbed water and polymer components in polyelectrolyte multilayer (PEM) films and the bulk polyelectrolyte complex (PEC). The films, ranging in size from a single layer to 5 bilayers, consist of poly(diallyl dimethylammonium chloride), PDADMAC, and poly(sodium-4-styrenesulfonate), PSS, adsorbed onto colloidal silica. Relaxation and line width measurements show that the adsorbed water is less mobile in the films than in the analogous PEC. The environment of the water throughout the film is found to be affected by the nature of the outer layer with the water displaying a higher mobility and chemical shift when PDADMAC forms the outer layer. Relaxation measurements, together with 1 H double-quantum (DQ) NMR experiments, reveal that polymer dynamics in the PEMs are strongly influenced by the layer number and water content. 2D spin diffusion and DQ NMR are used to detect polymer-polymer and water-polymer association. The results support the diffuse interpenetrating model of the different layers and a partitioning of the water to the PSS component and to the surface layer.

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Section: Effect Of Number Of Layers On Polymer Mobilitysupporting

confidence: 78%

NMR Studies of the Effect of Adsorbed Water on Polyelectrolyte Multilayer Films in the Solid State

et al. 2003

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“…19,36 Odd/even effects were also observed in the mobility of water in multilayers measured by NMR relaxation rates. 37–38 The adsorption of PAH on the surface decreased the water mobility for PAH/PSS systems. 38–40 …”

Section: Introductionmentioning

confidence: 99%

Homogeneity, Modulus, and Viscoelasticity of Polyelectrolyte Multilayers by Nanoindentation: Refining the Buildup Mechanism

2012

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Atomic force microscopy, AFM, and nanoindentation of polyelectrolyte multilayers, PEMUs, made from poly(diallyldimethylammonium), PDADMA, and poly(styrene sulfonate), PSS, provided new insight into their surface morphology and growth mechanism. A strong odd/even alternation of surface modulus revealed greater extrinsic (counterion-balanced) charge compensation for fully hydrated multilayers ending in the polycation, PDADMA. These swings in modulus indicate a much more asymmetric layer-by-layer growth mechanism than previously proposed. Viscoelastic properties of the PEMU, which may contribute to cell response, were highlighted by variable indentation rates and minimized by extrapolating to zero indentation rate, at which point the surface and bulk equilibrium moduli were comparable. Variations in surface composition were probed at high resolution using force mapping and the surface was found to be uniform, with no evidence of phase separation. AFM comparison of wet and dry films terminated with PSS and PDADMA revealed much greater swelling of the PDADMA-terminated PEMU by water, with collapse of surface roughness features in dry conditions. Dynamic and static contact angle measurements suggested less rearrangement for the glassy PSS surface.

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“…Although the formation of PEMs is simple, the internal structure, which has been probed by various techniques including neutron reflectometry [18,19], atomic force microscopy [20], and solid state NMR [21], reveals considerable complexity. The layers deposited consist of stratified structures in which polyanions and polycations of individual layers interpenetrate each other.…”

Section: Fundamental Aspects Of Polyelectrolyte Multilayer (Pem) Coatmentioning

confidence: 99%

Capillary electrochromatography using polyelectrolyte multilayer coatings

Kamande

Fletcher

Lowry

et al. 2005

J of Separation Science

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This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed.

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¹³C Solid-State NMR Study of Polyelectrolyte Multilayers

Cited by 51 publications

References 23 publications

NMR Studies of the Effect of Adsorbed Water on Polyelectrolyte Multilayer Films in the Solid State

NMR Studies of the Effect of Adsorbed Water on Polyelectrolyte Multilayer Films in the Solid State

Homogeneity, Modulus, and Viscoelasticity of Polyelectrolyte Multilayers by Nanoindentation: Refining the Buildup Mechanism

Capillary electrochromatography using polyelectrolyte multilayer coatings

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13C Solid-State NMR Study of Polyelectrolyte Multilayers

Cited by 51 publications

References 23 publications

NMR Studies of the Effect of Adsorbed Water on Polyelectrolyte Multilayer Films in the Solid State

NMR Studies of the Effect of Adsorbed Water on Polyelectrolyte Multilayer Films in the Solid State

Homogeneity, Modulus, and Viscoelasticity of Polyelectrolyte Multilayers by Nanoindentation: Refining the Buildup Mechanism

Capillary electrochromatography using polyelectrolyte multilayer coatings

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¹³C Solid-State NMR Study of Polyelectrolyte Multilayers