We propose dextran and dextran polyaldehyde (DPA) coatings for modification of layer-by-layer (LbL) assembled polyelectrolyte microcapsules which provide stability against aggregation in 0.75 M aqueous solutions of mono- and bivalent ions (Na~+, Cl~-, Ca~(2+), HPO_4~(2-)). The microcapsules were prepared of three bilayers of poly(4-styrenesulfonate) (PSS) and poly(allylamine) (PAH). Dextran and its derivatives were attached to amino-terminated surface of the microcapsules via three types of chemical bonds of subsequently increasing strength: (1) hydrogen bonds, (2) hydrolyzable covalent cross-links resulting from aldehydes and primary amines coupling, and (3) nonhydrolyzable covalent C-N single bonds of secondary amines. Attachment of the DPA materials via the latter two types of bonds resulted in strengthening the capsules walls which preserved a fraction of the microcapsules from disintegration upon electrostatic swelling in 0.1 M NaOH. The non-disintegrated fraction of the DPA-coated microcapsules restored their initial size after pH was decreased back to neutral. The microcapsules coated with the original dextran immobilized via hydrogen bonds and the bare microcapsules were fully dissolved under the alkaline conditions. The preserved fraction of the microcapsules was higher for the DPA materials with higher contents of the aldehyde groups and after conversion of the hydrolyzable covalent cross-links to the nonhydrolyzable secondary amines via reduction with NaBH_4. The higher contents of the aldehyde groups and the reduction led to the lower limiting swelling degree of the DPA-coated microcapsules at alkaline pH. The proposed coatings can be used for colloid stabilization of polyelectrolyte microcapsules in aqueous medium, encapsulation of pH-insensitive macromolecules at the postpreparation stage, and pH-triggered release of encapsulated material.
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