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Bionanocomposites represent an emerging group of nanostructured hybrid materials. They are formed by the combination of natural polymers and inorganic solids and show at least one dimension on the nanometer scale. Similar to conventional nanocomposites, which involve synthetic polymers, these biohybrid materials also exhibit improved structural and functional properties of great interest for different applications. The properties inherent to the biopolymers, that is, biocompatibility and biodegradability, open new prospects for these hybrid materials with special incidence in regenerative medicine and in environmentally friendly materials (green nanocomposites). Research on bionanocomposites can be regarded as a new interdisciplinary field closely related to significant topics such as biomineralization processes, bioinspired materials, and biomimetic systems. The upcoming development of novel bionanocomposites introducing multifunctionality represents a promising research topic that takes advantage of the synergistic assembling of biopolymers with inorganic nanometer‐sized solids.

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The rapid increase of interest in the field of biohybrid and biomimetic materials that exhibit improved structural and functional properties is attracting more and more researchers from life science, materials science, and nanoscience. Concomitant results offer valuable opportunities for applications that involve disciplines dealing with engineering, biotechnology, medicine and pharmacy, agriculture, nanotechnology, and others. In the current contribution we collect recent illustrative examples of assemblies between materials of biological origin and inorganic solids of different characteristics (texture, structure, and particle size). We introduce here a general overview on strategies for the preparation and conformation of biohybrids, the synergistic effects that determine the final properties of these materials, and their diverse applications, which cover areas as different as tissue engineering, drug delivery systems, biosensing devices, biocatalysis, green nanocomposites, etc.

A new family of functional hybrid nanocomposites based on the intercalation of naturally occurring anionic biopolymers including alginic acid, pectin, κ-carrageenan, ι-carrageenan, and xanthan gum in [Zn 2 Al(OH) 6 ]Cl‚nH 2 O layered double hydroxide (LDH), have been synthesized. The "coprecipitation" or "co-organized assembly" method has been successfully employed for the intercalation of such polysaccharides within the [Zn 2 Al] LDH. However, the "reconstruction" procedure from the calcined LDH in the presence of the anionic polysaccharides only resulted in a partial intercalation of the organic guest. Particular effort was devoted to the study of ι-carrageenan-[Zn 2 Al] systems. An essential feature of the prepared biopolymer-[Zn 2 Al] nanocomposites is that the anionic exchange capacity of the pristine LDH is turned into a cationic exchange capacity due to negatively charged groups in the polysaccharide structure that do not interact with the positively charged LDH layers. In agreement with the fact that most of the studied biopolymers interact strongly with calcium ions producing homogeneous gels, the prepared biopolymer-[Zn 2 Al] nanocomposites were operative as active phases of sensors for the recognition of calcium ions. Hence, the biopolymer-[Zn 2 Al] nanocomposites have been incorporated in carbon paste or PVC matrixes for the development of potentiometric sensors. These devices were applied to calcium determination by direct potentiometry and the best responses were obtained for the sensors based on alginate-LDH and ι-carrageenan-LDH nanocomposites.