Design of malolactonic acid esters with a large spectrum of specified pendant groups in the engineering of biofunctional and hydrolyzable polyesters

The development of multimeric functionalized macromolecules with the strict adjustment of their structure and their properties, aimed at biological ap plications, leads to complex architecture and puts on the diversification o f hydrolyzable polymers. Poly(beta-malic acid) derivatives are very good ca ndidates in the preparation of smart molecules for a large spectrum of appl ications in the release of bioactive molecules, due to the presence of a la teral carboxylic acid function besides stereogenic centers in the repeating units and main chain cleavable bonds. The opportunity for accessing to the se structures comes from mastery of the corresponding functionalized beta-s ubstituted beta-lactones synthesis. Two different synthesis routes have bee n established and the functional pendant groups is attached at the step pre ceding the lactone formation. A third way consists in the synthesis of malo lactonic acid which is reacted with a specific molecule in presence of a co upling reagent. II is therefore possible to dispose of an important wealth of monomers and to tailor-make polymeric materials having a well-defined co mposition. Multimeric structures have been elaborated aimed at degradable m icelles from block copolymers, nanoparticles starting from hydrophobic poly esters, biomimetic architecture for interacting with fibroblast growth fact ors and amphiphilic associating polymers for hydrogel networks. Biodegradab le graft copolymers have been elaborated for bioactive molecules encapsulat ion and bioartificial membranes, including cholesterol and diacylglycerol, have been tailor-made.