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Mucosal delivery of complex molecules such as peptides, proteins, oligonucleotides, and plasmids is one of the most intensively studied subjects. The use of colloidal carriers made of hydrophilic polysaccharides, i.e. chitosan, has arisen as a promising alternative for improving the transport of such macromolecules across biological surfaces. This article reviews the approaches which have aimed to associate macromolecules to chitosan in the form of colloidal structures and analyzes the evidence of their efficacy in improving the transport of the associated molecule through mucosae and epithelia. Chitosan has been shown to form colloidal particles and entrap macromolecules through a number of mechanisms, including ionic crosslinking, desolvation, or ionic complexation, though some of these systems have been realized only in conjunction with DNA molecules. An alternative involving the chemical modification …