{"title":"Polymerization-Induced Sulfone-Bond-Driven Self-Assembly","authors":"Junrui Zhang, Qili Li, Tanrong Yu, Yijian Ma, Zizhuo Zhao, Chengshuo Shen, Xunshan Liu, Meng Huo","doi":"10.1021/acs.macromol.4c02860","DOIUrl":null,"url":null,"abstract":"Sulfone bonding refers to dipole–dipole interactions between sulfone groups, which have been long overlooked. Herein, sulfone bonding was employed for the first time as the driving force for the self-assembly of block copolymers via a polymerization-induced sulfone-bond-driven self-assembly (PI-SDSA) strategy. The presence of sulfone bonding in a sulfone-functionalized monomer was first confirmed by scanning tunneling microscopy break junction measurements at the single-molecule level. Successful PI-SDSA was achieved in toluene, and the polymerization kinetics confirmed the polymerization-enhanced sulfone bonding as the driving force. The PI-SDSA was demonstrated to possess a peculiar monomer/solvent library by the successful PI-SDSA of a series of sulfone-containing monomers in solvents with varying dipole moments. The as-prepared sulfone-functionalized polymer assemblies manifested unique salt-responsiveness because of the competitive ion–dipole interactions between the ions and sulfone groups, enabling the salt-responsive payload release. The use of sulfone bonding as the driving force for self-assembly has provided a new perspective for both the polymerization-induced self-assembly and the self-assembly of block copolymers and will inspire the design of stimuli-responsive supramolecular materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"33 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c02860","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
引用次数: 0
Abstract
Sulfone bonding refers to dipole–dipole interactions between sulfone groups, which have been long overlooked. Herein, sulfone bonding was employed for the first time as the driving force for the self-assembly of block copolymers via a polymerization-induced sulfone-bond-driven self-assembly (PI-SDSA) strategy. The presence of sulfone bonding in a sulfone-functionalized monomer was first confirmed by scanning tunneling microscopy break junction measurements at the single-molecule level. Successful PI-SDSA was achieved in toluene, and the polymerization kinetics confirmed the polymerization-enhanced sulfone bonding as the driving force. The PI-SDSA was demonstrated to possess a peculiar monomer/solvent library by the successful PI-SDSA of a series of sulfone-containing monomers in solvents with varying dipole moments. The as-prepared sulfone-functionalized polymer assemblies manifested unique salt-responsiveness because of the competitive ion–dipole interactions between the ions and sulfone groups, enabling the salt-responsive payload release. The use of sulfone bonding as the driving force for self-assembly has provided a new perspective for both the polymerization-induced self-assembly and the self-assembly of block copolymers and will inspire the design of stimuli-responsive supramolecular materials.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.