Synthetic strategies, sustainability and biological applications of malic acid–based polymers

Abstract

This review summarises the recent developments in the synthesis and applications of polymers derived from malic acid. There has been an increased interest in the design of sustainable and biodegradable polymers as a result of the drive to use renewable feedstocks as an alternative to petrochemicals in addition to their significant potential in biomedical applications. Synthetic strategies to access polymers from malic acid based on both condensation and ring-opening polymerization, across a broad range of conditions, are reviewed along with their advantages and limits. The role that such materials are studied for in biomedical applications is discussed, and their environmental impact based on the biodegradability of the malic polymer backbone is outlined.

New promising biodegradable polyesters derived from poly((R,S)-3,3-dimethylmalic acid) for cardiovascular applications

“…Therewith, it can be able to adduce to the same chain in the lateral position a drug to release lastly during its degradation; we hypothesize that the grafting of the drug can be done during the synthesis of the monomer; it can be attached to the monomer once synthesized or to the polymer after deprotection [20,95].…”

“…The co-monomers relative contents (10,20, and 30 %) were obtained by 1 H NMR using the integration ratio of peak at 4.15 ppm corresponding to -CH 2 -O-hexyl and that at 5.20 ppm corresponding to -CH 2 -O-benzyl (Figure 12). After a catalytic hydrogenolysis in presence of 10 % of palladium on charcoal on the polyester, it is possible to obtain carboxylic acid group (when R = −CH 2 Ph) and alcohol group (when R = −(CH 2 ) 3 -O-CH 2 Ph) (Scheme 5).…”

“…Among this class of polymers, the PMLA is known to present good biocompatibility, non-toxicity in vitro and in vivo, non--immunogenic properties, and stability in the bloodstream [5,[16][17][18][19]. The particularity of this family of polyesters is the presence of functionalized groups in their side chain which, furthermore, allow chemical modification for grafting, thus delivering drugs [20].…”

Poly(trimethylene carbonate)/Poly(malic acid) Amphiphilic Diblock Copolymers as Biocompatible Nanoparticles

“…PMLA(Be)-based copolymers have thus been investigated as amphiphilic self-assembled PHA copolymers for thed esign of drug nanocarriers. [68][69][70] PCs and PHAs can be synthesized through controlled ROP of cyclic carbonates [8][9][10][11][12] and b-lactones, [71][72][73][74][75] respectively. [76] The ROP process enables fine-tuning of macromolecular features, such as achieving ap redictable molar mass;l ow dispersity; limiting undesirable side reactions, such as transesterifications/ transcarbonations; end-group fidelity;a nd tailored microstructures (regio-/stereoregularity of the macromolecule).…”

“…[8][9][10][11][12] Similarly,t he ROP of MLABeh as been successfully achieved from either organic or metallicc atalysts/initiators. [65,66,68,82,88,89] In ap reviousa pproach,P TMC-b-PMLABe hydrophobic copolymersw ere synthesized on the scale of af ew milligrams (ca. < 20 mg) throughs equential ROP of TMC and MLABeb yu sing the homemade zinc b-diketiminate [(BDI)Zn{N(SiMe 3 ) 2 }]/iPrOH (BDI = CH(CMeNC 6 H 3 -2,6-iPr 2 ) 2 )c atalytic system.…”