Natural inspiration : Amphiphilic polysaccharide‐block‐polypeptide copolymers were synthesized by click chemistry from dextran end‐functionalized with an alkyne group and poly(γ‐benzyl L ‐glutamate) end‐functionalized with an azide group. The ability of these copolymers to self‐assemble into small vesicles (see picture) suggests the possibility of a new generation of drug‐ and gene‐delivery systems whose structure mimics that of viruses.
This review covers the literature concerning the modification of polysaccharides through controlled radical polymerizations (NMP, ATRP and RAFT). The different routes to well‐defined polysaccharide‐based macromolecules (block and graft copolymers) and graft‐functionalized polysaccharide surfaces as well as the applications of these polysaccharide‐based hybrids are extensively discussed.
Polysaccharides have emerged as important functional materials because of their unique properties such as biocompatibility, biodegradability, and availability of reactive sites for chemical modifications to optimize their properties. The overwhelming majority of the methods to modify polysaccharides employ random chemical modifications, which often improve certain properties while compromising others. On the other hand, the employed methods for selective modifications often require excess of coupling partners, long reaction times and are limited in their scope and wide applicability. To circumvent these drawbacks, aniline‐catalyzed oxime formation is developed for selective modification of a variety of polysaccharides through their reducing end. Notably, it is found that for efficient oxime formation, different conditions are required depending on the composition of the specific polysaccharide. It is also shown how our strategy can be applied to improve the physical and functional properties of alginate hydrogels, which are widely used in tissue engineering and regenerative medicine applications. While the randomly and selectively modified alginate exhibits similar viscoelastic properties, the latter forms significantly more stable hydrogel and superior cell adhesive and functional properties. Our results show that the developed conjugation reaction is robust and should open new opportunities for preparing polysaccharide‐based functional materials with unique properties.
Summary: Oligo- and polysaccharides are important macromolecules in living systems, showing their multifunctional characteristics in the construction of cell walls, energy storage, cell recognition and their immune response. Saccharides as organic raw materials can open new perspectives on the way to new biocompatible and biodegradable products which could help to overcome the problems resulting from the upcoming restrictions of petrochemical resources. Construction of well-defined carbohydrate polymer backbones is very challenging as it is difficult to realize complete regio and stereo-control of the glycosylating process. Most synthetic approaches are therefore based on the modification or degradation of naturally occurring polysaccharides resulting in less then perfect products. Enzymes have several remarkable catalytic properties compared with other types of catalysts in terms of their selectivity, high catalytic activity, lack of undesirable side reactions and operation under mild conditions. A biocatalytic pathway to synthesize saccharides is therefore very attractive as it results in well-defined polysaccharides avoiding the above drawbacks. When biogenic polysaccharides are combined with synthetic macromolecules, surfaces etc. materials with new interesting properties arise and the processability of the designed hybrid materials is facilitated. Amylose and amylopectin hybrid materials can be synthesized via enzymatic polymerization routes utilizing transferases. This approach opens access to well-defined hybrid structures bearing amylase or amylopectin moieties that cannot be synthesized by any other means. 相似文献
