Weak polyelectrolyte-based multilayers via layer-by-layer assembly: Approaches, properties, and applications

Layer-by-layer (LbL) assembly is a nanoscale technique with great versatility, simplicity and molecular-level processing of various nanoscopic materials. Weak polyelectrolytes have been used as major building blocks for LbL assembly providing a fundamental and versatile tool to study the underlying mechanisms and practical applications of LbL assembly due to its pH-responsive charge density and molecular conformation. Because of high-density uncompensated charges and high-chain mobility, weak polyelectrolyte exponential multilayer growth is considered one of the fastest developing areas for organized molecular films. In this article, we systematically review the current status and developments of weak polyelectrolyte-based multilayers including all-weak-polyelectrolyte multilayers, weak polyelectrolytes/other components (e.g. strong polyelectrolytes, neutral polymers, and nanoparticles) multilayers, and exponentially grown weak polyelectrolyte multilayers. Several key aspects of weak polyelectrolytes are highlighted including the pH-controllable properties, the responsiveness to environmental pH, and synergetic functions obtained from weak polyelectrolyte/other component multilayers. Throughout this review, useful applications of weak polyelectrolyte-based multilayers in drug delivery, tunable biointerfaces, nanoreactors for synthesis of nanostructures, solid state electrolytes, membrane separation, and sensors are highlighted, and promising future directions in the area of weak polyelectrolyte-based multilayer assembly such as fabrication of multi-responsive materials, adoption of unique building blocks, investigation of internal molecular-level structure and mechanism of exponentially grown multilayers, and exploration of novel biomedical and energy applications are proposed.