Azide-Substituted Polylactide: A Biodegradable Substrate for Antimicrobial Materials via Click Chemistry Attachment of Quaternary Ammonium Groups

Abstract

Polylactide (PL) co-polymers substituted with pendant azide groups (azido-PL) were synthesized by the nucleophilic conjugate addition of 3-azido-1-propanethiol to a co-polymer of PL containing α,β-unsaturated ester units, poly(lactide-co-methylene glycolide) (ene-PL) that is obtained from the base-promoted dehydrochlorination of poly(lactide-cochlorolactide) (chloro-PL). Alternatively, azido-PL was prepared by the treatment of chloro-PL with 3-azido-1-propanethiol without isolation of the ene-PL intermediate. The azido-PL was functionalized by copper-catalyzed [3 + 2] cycloaddition reactions with four alkynes: propargyl 4-methoxybenzoate, N,N,N-trimethyl-N-propargylammonium bromide, N,N-dimethyl-Noctyl-N-propargylammonium bromide, and N,N,N-trioctyl-N-propargylammonium bromide. Polymer adducts with N,N,Ntrioctyl-N-propargylammonium bromide displayed potent antimicrobial activity both in suspension and as a polymer film.

Biobased polymers derived from itaconic acid bearing clickable groups with potent antibacterial activity and negligible hemolytic activity

“…Likewise, 1 H-NMR (Fig. 1B) and 13 C-NMR spectra show typical peaks of the introduced functional groups, confirming the success of the reaction and the formation of the monomer derivative with thiazole and triazole groups in its structure (TTI). See the ESI, Fig.…”

“…Characterization 1 H and 13 C NMR spectra were recorded on a Bruker Avance III HD-400AVIII spectrometer at room temperature using CDCl 3 , DMSO-d 6 and D 2 O as solvents ( purchased from Sigma-Aldrich). Fourier transform infrared (FTIR) spectra were recorded on a PerkinElmer Spectrum Two instrument, equipped with an attenuated total reflection (ATR) module.…”

“…Although little research has been performed until now on the synthesis of biobased/ biodegradable antimicrobial polymers, 9 recently, a few examples have been reported that include functionalized polycarbonates 10,11 polycaprolactone 12 and polylactides. 13 Biobased polymers such as polylactides also possess properties such as biocompatibility, environmental safety and sustainability, which could be essential in biomedical devices, wound dressing, food packaging, textiles and cosmetic applications. Therefore, research on sustainable antimicrobial materials is necessary and remains a challenge in the fields of polymer chemistry and materials science.…”

Click chemistry strategies for the accelerated synthesis of functional macromolecules

“…Chlorine-substituted polylactide could be converted into substituted polylactide through either direct substitution by azido-substituted alkanethiol or elimination-addition pathway under mild condition without concern of cleavage of ester groups in backbone. 541 To modify more inert commodity polymers, such as polypropylene (PP) and polyethylene (PE), high-energy irradiation has to be used to introduce halide groups while polymethacrylate/ polyacrylate/poly(vinyl alcohol) can take advantage of esterification/transesterification of side chains to install alkyne or azide groups. 542 In addition, nucleophilic ring-opening of the epoxides in poly(glycidyl methacrylate) (PGMA) by NaN 3 introduces azido and secondary hydroxyl groups for further functionalization (e.g., esterification; Scheme 23 (E)).…”

Challenges in Bone Tissue Regeneration: Stem Cell Therapy, Biofunctionality and Antimicrobial Properties of Novel Materials and Its Evolution

“…An optimized blend with a weight ratio of 70/30 PLA/PCL was found to be the best for osteoblast functionality, indicated by increased ALP activity. Similar to the studies described for non-biodegradable polymers, Kalelkar et al [100] used a click chemistry approach, modifying an azido-terminated PLA with different quaternary ammonium groups and creating a polymer showing antimicrobial activity against E. coli and S. aureus. The amino-functionalized polymer killed the cultured bacteria within 1 h of surface contact.…”