Cationic-anionic Synchronous Ring-opening Polymerization

Overview

Journal Nat Commun

Specialty Biology

Date 2025 Feb 22

PMID 39987195

Authors

Wenli Wang

Xue Liang

Hengxu Liu

Jiamin Zhang

Yuanzu Zhang

Beibei Zhang

Jianhua Li

Yunqing Zhu

Jianzhong Du

Affiliations

Soon will be listed here.

Abstract

Chemical reactions with incompatible mechanisms (such as nucleophilic reactions and electrophilic reactions, cationic polymerization and anionic polymerization) are usually difficult to perform simultaneously in one-pot. In particular, synchronous cationic-anionic polymerization has been an important challenge in the field of polymer synthesis due to possible coupling termination of both chain ends. We recently found that such terminal couplings can be significantly inhibited by a bismuth salt with a strong nucleophilic anion (e.g., BiCl) and disclosed the mechanism. Accordingly, we propose a cationic-anionic polymerization (CAP) method where cationic ring-opening polymerization (CROP) of 2-oxazolines (Ox) and anionic ring-opening polymerization (AROP) of cyclic esters (CE) can be initiated sequentially and propagated simultaneously in one-pot, using bismuth salts as the initial initiators, to afford a multifunctional copolymer polyoxazoline-block-polyester (POx-b-PCE). Furthermore, a block copolymer PAPOZ-b-PCL synthesized by CAP can self-assemble into micellar aggregates, which exhibit excellent intrinsic antibacterial activities without loading any extra antibiotic components. Overall, such a CAP method opens new avenues for synthesizing multi-component copolymers and biomaterials.

References

Yang Z, Hu C, Cui F, Pang X, Huang Y, Zhou Y . One-Pot Precision Synthesis of AB, ABA and ABC Block Copolymers via Switchable Catalysis. Angew Chem Int Ed Engl. 2022; 61(12):e202117533. DOI: 10.1002/anie.202117533. View

Sedlacek O, Lava K, Verbraeken B, Kasmi S, De Geest B, Hoogenboom R . Unexpected Reactivity Switch in the Statistical Copolymerization of 2-Oxazolines and 2-Oxazines Enabling the One-Step Synthesis of Amphiphilic Gradient Copolymers. J Am Chem Soc. 2019; 141(24):9617-9622. DOI: 10.1021/jacs.9b02607. View

Wei J, Diaconescu P . Redox-Switchable Ring-Opening Polymerization with Ferrocene Derivatives. Acc Chem Res. 2019; 52(2):415-424. DOI: 10.1021/acs.accounts.8b00523. View

Wan Y, He J, Zhang Y . An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs. Angew Chem Int Ed Engl. 2022; 62(8):e202218248. DOI: 10.1002/anie.202218248. View

Cui H, Chen Z, Zhong S, Wooley K, Pochan D . Block copolymer assembly via kinetic control. Science. 2007; 317(5838):647-50. DOI: 10.1126/science.1141768. View

Fu C, Xu J, Kokotovic M, Boyer C . One-Pot Synthesis of Block Copolymers by Orthogonal Ring-Opening Polymerization and PET-RAFT Polymerization at Ambient Temperature. ACS Macro Lett. 2022; 5(4):444-449. DOI: 10.1021/acsmacrolett.6b00121. View

Mecerreyes D, Moineau G, Dubois P, Jerome R, Hedrick J, Hawker C . Simultaneous Dual Living Polymerizations: A Novel One-Step Approach to Block and Graft Copolymers. Angew Chem Int Ed Engl. 2018; 37(9):1274-1276. DOI: 10.1002/(SICI)1521-3773(19980518)37:9<1274::AID-ANIE1274>3.0.CO;2-J. View

Jain S, Bates F . On the origins of morphological complexity in block copolymer surfactants. Science. 2003; 300(5618):460-4. DOI: 10.1126/science.1082193. View

Abubekerov M, Wei J, Swartz K, Xie Z, Pei Q, Diaconescu P . Preparation of multiblock copolymers step-wise addition of l-lactide and trimethylene carbonate. Chem Sci. 2018; 9(8):2168-2178. PMC: 5903370. DOI: 10.1039/c7sc04507g. View

10.

Zhu S, Zhao Y, Ni M, Xu J, Zhou X, Liao Y . One-Step and Metal-Free Synthesis of Triblock Quaterpolymers by Concurrent and Switchable Polymerization. ACS Macro Lett. 2022; 9(2):204-209. DOI: 10.1021/acsmacrolett.9b00895. View

11.

Hong M, Chen E . Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nat Chem. 2015; 8(1):42-9. DOI: 10.1038/nchem.2391. View

12.

Wu Y, Swager T . Living Polymerization of 2-Ethylthio-2-oxazoline and Postpolymerization Diversification. J Am Chem Soc. 2019; 141(32):12498-12501. PMC: 6727665. DOI: 10.1021/jacs.9b06009. View

13.

Xu J, Wang X, Hadjichristidis N . Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization. Nat Commun. 2021; 12(1):7124. PMC: 8655074. DOI: 10.1038/s41467-021-27377-3. View

14.

Dau H, Jones G, Tsogtgerel E, Nguyen D, Keyes A, Liu Y . Linear Block Copolymer Synthesis. Chem Rev. 2022; 122(18):14471-14553. DOI: 10.1021/acs.chemrev.2c00189. View

15.

Zhang X, Jones G, Hedrick J, Waymouth R . Fast and selective ring-opening polymerizations by alkoxides and thioureas. Nat Chem. 2016; 8(11):1047-1053. DOI: 10.1038/nchem.2574. View

16.

Li C, Li Q, Kaneti Y, Hou D, Yamauchi Y, Mai Y . Self-assembly of block copolymers towards mesoporous materials for energy storage and conversion systems. Chem Soc Rev. 2020; 49(14):4681-4736. DOI: 10.1039/d0cs00021c. View

17.

Zhou M, Qian Y, Xie J, Zhang W, Jiang W, Xiao X . Poly(2-Oxazoline)-Based Functional Peptide Mimics: Eradicating MRSA Infections and Persisters while Alleviating Antimicrobial Resistance. Angew Chem Int Ed Engl. 2020; 59(16):6412-6419. DOI: 10.1002/anie.202000505. View

18.

Adams N, Schubert U . Poly(2-oxazolines) in biological and biomedical application contexts. Adv Drug Deliv Rev. 2007; 59(15):1504-20. DOI: 10.1016/j.addr.2007.08.018. View

19.

Kim T, Zhou Z, Choi Y, Costanza V, Wang L, Bahng J . Flexible biomimetic block copolymer composite for temperature and long-wave infrared sensing. Sci Adv. 2023; 9(6):eade0423. PMC: 9916982. DOI: 10.1126/sciadv.ade0423. View

20.

Engelis N, Anastasaki A, Nurumbetov G, Truong N, Nikolaou V, Shegiwal A . Sequence-controlled methacrylic multiblock copolymers via sulfur-free RAFT emulsion polymerization. Nat Chem. 2017; 9(2):171-178. DOI: 10.1038/nchem.2634. View