Responsive polymer materials can adapt to surrounding environments, regulate transport of ions and molecules, change wettability and adhesion of different species on external stimuli, or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals, and vice versa. These materials are playing an increasingly important part in a diverse range of applications, such as drug delivery, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings and textiles. We review recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks. We also provide a critical outline of emerging developments.

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A new approach to fabricate polyelectrolyte microcapsules is based on exploiting porous inorganic microparticles of calcium carbonate. Porous CaCO3 microparticles (4.5−5.0 microns) were synthesized and characterized by scanning electron microscopy and the Brunauer−Emmett−Teller method of nitrogen adsorption/desorption to get a surface area of 8.8 m2/g and an average pore size of 35 nm. These particles were used as templates for polyelectrolyte layer-by-layer assembly of two oppositely charged polyelectrolytes, poly(styrene sulfonate) and poly(allylamine hydrochloride). Calcium carbonate core dissolution resulted in formation of polyelectrolyte microcapsules with an internal matrix consisting of a polyelectrolyte complex. Microcapsules with an internal matrix were analyzed by confocal Raman spectroscopy, scanning electron microscopy, force microscopy, and confocal laser-scanning fluorescence microscopy. The structure was found to be dependent on a number of polyelectrolyte adsorption treatments. Capsules have a very high loading capacity for macromolecules, which can be incorporated into the capsules by capturing them from the surrounding medium into the capsules. In this paper, we investigated the loading by dextran and bovine serum albumin as macromolecules. The amount of entrapped macromolecules was determined by two independent methods and found to be up to 15 pg per microcapsule.

Polyelectrolyte multilayers were deposited onto polystyrene and melamine formaldehyde latex particles by means of consecutive adsorption. Two different methods of multilayer growth were employed. First, adsorption of polyelectrolytes at a concentration exceeding saturation amounts was combined with the removal of the nonbound polyelectrolyte by means of centrifugation. Second, adsorption of polyelectrolyte was performed at a concentration just sufficient for saturation coverage. Both methods yielded continuous layer growth. The process of film formation was followed by electrophoresis, dynamic light scattering, single particle light scattering and fluorescence intensity measurements. Layer deposition onto partially crosslinked melamine resin latex particles, which were soluble at pH values of less than 1.6, resulted in the production of three‐dimensional thin polyelectrolyte shells upon dissolving the core. The ultrathin shells were observed by means of scanning and transmission electron microscopy. © 1998 John Wiley & Sons, Ltd.

Porous microparticles of calcium carbonate with an average diameter of 4.75 microm were prepared and used for protein encapsulation in polymer-filled microcapsules by means of electrostatic layer-by-layer assembly (ELbL). Loading of macromolecules in porous CaCO3 particles is affected by their molecular weight due to diffusion-limited permeation inside the particles and also by the affinity to the carbonate surface. Adsorption of various proteins and dextran was examined as a function of pH and was found to be dependent both on the charge of the microparticles and macromolecules. The electrostatic effect was shown to govern this interaction. This paper discusses the factors which can influence the adsorption capacity of proteins. A new way of protein encapsulation in polyelectrolyte microcapsules is proposed exploiting the porous, biocompatible, and decomposable microparticles from CaCO3. It consists of protein adsorption in the pores of the microparticles followed by ELbL of oppositely charged polyelectrolytes and further core dissolution. This resulted in formation of polyelectrolyte-filled capsules with protein incorporated in interpenetrating polyelectrolyte network. The properties of CaCO3 microparticles and capsules prepared were characterized by scanning electron microscopy, microelectrophoresis, and confocal laser scanning microscopy. Lactalbumin was encapsulated by means of the proposed technique yielding a content of 0.6 pg protein per microcapsule. Horseradish peroxidase saves 37% of activity after encapsulation. However, the thermostability of the enzyme was improved by encapsulation. The results demonstrate that porous CaCO3 microparticles can be applied as microtemplates for encapsulation of proteins into polyelectrolyte capsules at neutral pH as an optimal medium for a variety of bioactive material, which can also be encapsulated by the proposed method. Microcapsules filled with encapsulated material may find applications in the field of biotechnology, biochemistry, and medicine.

Laser mediated remote release of encapsulated fluorescently labeled polymers from nanoengineered polyelectrolyte multilayer capsules containing gold sulfide core/gold shell nanoparticles in their walls is observed in real time on a single capsule level. We have developed a method for measuring the temperature increase and have quantitatively investigated the influence of absorption, size, and surface density of metal nanoparticles using an analytical model. Experimental measurements and numerical simulations agree with the model. The treatment presented in this work is of general nature, and it is applicable to any system where nanoparticles are used as absorbing centers. Potential biomedical applications are highlighted.

Stable hollow polyelectrolyte capsules were produced by means of the layer-by-layer assembling of poly(allylamine), PAH, and poly-(styrenesulfonate), PSS, on melamine formaldehyde microcores followed by the core decomposition at low pH. These capsules are nonpermeable for urease in water and become permeable in a water/ethanol mixture. The capsules were loaded with urease in water/ethanol mixture and then resuspended in water. The urease molecules are kept in the capsule, whereas the small urea molecules rapidly diffuse through the capsule wall providing a substrate for the biocatalytic reaction.