Facile Preparation of Polysaccharide−Polypeptide Conjugates via a Biphasic Solution Ring-Opening Polymerization

Abstract

Polysaccharide−polypeptide conjugates have gained a broad interest in mimicking the structure and bioactivity of peptidoglycans or proteoglycans for biomedical applications. Efficient and precise preparation of the conjugates is challenging and unresolved, mainly because of the mismatched solubility between polysaccharide initiators and N-carboxyanhydrides (NCAs), which frequently results in competing side reactions and oligomeric polypeptide chain. Herein, we report a facile and efficient strategy to prepare the conjugates with well-controlled polypeptide chain length (l p ) directly from unmodified polysaccharides via a biphasic solution ring-opening polymerization. The effect of l p on surface antibacterial properties has been investigated. Elongating the l p can significantly potentiate the antibiofilm property of the conjugate coatings. Our results may provide opportunities to develop various polypeptide-based conjugates with well-defined structures toward versatile uses.

Recent Advance in Polymer Coatings Combating Bacterial Adhesion and Biofilm Formation†

“…Later, they prepared a series of chitosan‐ poly( L ‐glutamic acid) conjugates (CS‐g‐Es) by a biphasic solution ring‐opening polymerization (bsROP) and subsequent hydrolysis. [ 67 ] CS‐g‐Es were coated on polydopamine (PDA) modified polydimethylsiloxane (PDMS) surface with the assistance of dopamine (DA). The antibacterial adhesion and antibiofilm growth of the CS‐g‐E coatings were enhanced by elongating the poly( L ‐glutamic acid) chain length.…”

“…In addition, cationic brush‐like chitosan‐poly( L ‐lysine) conjugates (CS‐g‐Ks) were prepared by Tang et al . [ 67 ] CS‐g‐Ks modified PDMS surfaces were prepared by PDA co‐deposition method. Both killing efficacy and inhibition of biofilm growth of CS‐g‐K coatings were improved by increasing the cationic polypeptide chain length that >99.9% killing efficacy and ≤ 2.8% biofilm growth can be readily achieved (Figure 4a).…”

“…Reproduced with permission. [ 67 ] Copyright 2022, American Chemical Society. (b) Synergistic antibacterial effect of the homopolypeptide coating with cationic pendant groups and antibiotic counteranions.…”

One-pot preparation of polypeptide nanogels in aqueous solutionviaring-opening polymerization-induced nano-gelation

“…33 In most cases, the preparation process is performed in organic solvents. [34][35][36][37] For example, Du et al proposed a one-pot opento-air ROP of N-carboxyanhydride (NCA)-induced self-assembly for the preparation of poly(ethylene oxide)polyphenylalanine vesicles in tetrahydrofuran at 10 °C. 38 Duro-Castano and Battaglia et al reported the one-step synthesis of oxidationsensitive polypeptide-based nanoparticles in dimethyl sulfoxide (DMSO) by ROPISA of methionine NCA.…”

Cooperative Covalent Polymerization of N-carboxyanhydrides: from Kinetic Studies to Efficient Synthesis of Polypeptide Materials

“…The desired polymerization of NCA outpaces various side reactions including the water-induced side reactions, 33,38,43,45 enabling the preparation of well-defined polypeptides even in the presence of an aqueous phase. 38,43,48 Additionally, the accelerated polymerization allows the efficient synthesis of polypeptides with versatile architectures, 31,32,35,42,49 high MWs, 32,34,42,46 and predictable multiblock sequences, 39,45 which is difficult, if not impossible, to obtain with conventional polymerization methods.…”