Asymmetric Growth in Polyelectrolyte Multilayers.

Radioactive counterions were used to track the ratio of positive to negative polymer repeat units within a polyelectrolyte multilayer made from poly(diallyldimethylammonium chloride), PDADMAC, and poly(styrene sulfonate), PSS. For this widely employed pair of "linearly" assembled polyelectrolytes it...

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Publicado en:Journal of the American Chemical Society Vol. 135; no. 20; pp. 7636 - 7647
Autores principales: Ghostine, Ramy A., Markarian, Marie Z., Schlenoff, Joseph B.
Formato: Artículo
Publicado: American Chemical Society 5/22/2013
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 5/22/2013
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      pub: American Chemical Society
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        87965049
        10.1021/ja401318m
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      tig:
        atl: Asymmetric Growth in Polyelectrolyte Multilayers.
      aug:
        au:
          Ghostine, Ramy A.
          Markarian, Marie Z.
          Schlenoff, Joseph B.
        affil: Department of Chemistry and Biochemistry, The Florida State University, Tallahassee, Florida 32306-4390, United States
      su:
        Polyelectrolytes
        Multilayers
        Polystyrene
        Sulfonates
        Reaction-diffusion equations
        Stoichiometry
        Cations
        Chlorides
      sug:
        subj:
          Polyelectrolytes
          Multilayers
          Polystyrene
          Sulfonates
          Reaction-diffusion equations
          Stoichiometry
          Cations
          Chlorides
      ab: Radioactive counterions were used to track the ratio of positive to negative polymer repeat units within a polyelectrolyte multilayer made from poly(diallyldimethylammonium chloride), PDADMAC, and poly(styrene sulfonate), PSS. For this widely employed pair of "linearly" assembled polyelectrolytes it was found that the accepted model of charge overcompensation for each layer is incorrect. In fact, overcompensation at the surface occurs only on the addition of the polycation, whereas PSS merely compensates the PDADMAC. After the assembly of about a dozen layers, excess positive sites begin to accrue in the multilayer. Treating the surface as a reaction–diffusion region for pairing of polymer charges, a model profile was constructed. It is shown that different reaction–diffusion ranges of positive and negative polyelectrolyte charge lead to a blanket of glassy, stoichiometric complex growing on top of a layer of rubbery, PDADMAC-rich complex. Though overcompensation and growth was highly asymmetric with respect to the layer number, entirely conventional "linear" assembly of the multilayer was observed. The impact of asymmetric growth on various properties of multilayers is discussed.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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