Understanding the structure and dynamics of polymers under confinement has been of widespread interest, and one class of polymers that have received comparatively little attention under confinement is that of ring polymers. The properties of non-concatenated ring polymers can also be important in biological fields because ring polymers have been proven to be a good model to study DNA organization in the cell nucleus. From our previous study, linear polymers in a cylindrically confined polymer melt were found to segregate from each other as a result of the strong correlation hole effect that is enhanced by the confining surfaces. By comparison, our subsequent study of linear polymers in confined thin films at similar levels of confinements found only the onset of segregation. In this study, we use molecular dynamics simulation to investigate the chain conformations and dynamics of ring polymers under planar (1D) confinement as a function of film thickness. Our results show that conformations of ring polymers are similar to the linear polymers under planar confinement, except that ring polymers are less compressed in the direction normal to the walls. While we find that the correlation hole effect is enhanced under confinement, it is not as pronounced as the linear polymers under 2D confinement. Finally, we show that chain dynamics far above Tg are primarily affected by the friction from walls based on the monomeric friction coefficient we get from the Rouse mode analysis.
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http://dx.doi.org/10.1063/5.0024729 | DOI Listing |
J Am Chem Soc
January 2025
Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, 1098 XH Amsterdam, Netherlands.
We present the synthesis, structural analysis, and remarkable reactivity of the first carbon nanohoop that fully incorporates ferrocene in the macrocyclic backbone. The high strain imposed on the ferrocene by the curved nanohoop structure enables unprecedented photochemical reactivity of this otherwise photochemically inert metallocene complex. Visible light activation triggers a ring-opening of the nanohoop structure, fully dissociating the Fe-cyclopentadienyl bonds in the presence of 1,10-phenanthroline.
View Article and Find Full Text PDFChem Sci
January 2025
Université Paris-Saclay, CNRS, Institut Galien Paris-Saclay 91400 Orsay France +33-180006081.
The synthesis of degradable polymer prodrug nanoparticles is still a challenge to be met, which would make it possible to remedy both the shortcomings of traditional formulation of preformed polymers (, low nanoparticle concentrations) and those of the physical encapsulation of drugs (, burst release and poor drug loadings). Herein, through the combination of radical ring-opening polymerization (rROP) and polymerization-induced self-assembly (PISA) under appropriate experimental conditions, we report the successful preparation of high-solid content, degradable polymer prodrug nanoparticles, exhibiting multiple drug moieties covalently linked to a degradable vinyl copolymer backbone. Such a rROPISA process relied on the chain extension of a biocompatible poly(ethylene glycol)-based solvophilic block with a mixture of lauryl methacrylate (LMA), cyclic ketene acetal (CKA) and drug-bearing methacrylic esters by reversible addition fragmentation chain transfer (RAFT) copolymerization at 20 wt% solid content.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
The unique reactivity of molecules under force commands an understanding of structure-mechanochemical activity relationships. While conceptual frameworks for understanding force transduction in many systems are established, systematic investigations into force-coupled molecular torsions are limited. Here, we describe a novel fluorenyl naphthopyran mechanophore for which mechanical force is uniquely coupled to the torsional motions associated with the overall chemical transformation as a result of the conformational rigidity imposed by the fluorene group.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Graft-through ring-opening metathesis polymerization (ROMP) of norbornene-terminated macromonomers (MMs) prepared using various polymerization methods has been extensively used for the synthesis of bottlebrush (co)polymers, yet the potential of ROMP for the synthesis of MMs that can subsequently be polymerized by graft-through ROMP to produce new bottlebrush compositions remains untapped. Here, we report an efficient "ROMP-of-ROMP" method that involves the synthesis of norbornene-terminated poly(norbornene imide) (PNI)-based MMs that, following ROMP, provide new families of bottlebrush (co)polymers and "brush-on-brush" hierarchical architectures. In the bulk state, the organization of the PNI pendants drives bottlebrush backbone extension to enable rapid assembly of asymmetric lamellar morphologies with large asymmetry factors.
View Article and Find Full Text PDFMacromol Rapid Commun
January 2025
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun, 130022, China.
The demand for insulating materials with superior dielectric properties has increased. Among these materials, polymers containing cyclic structure including cyclic olefin copolymer (COC) and cyclic olefin polymer (COP) stand out because of their excellent dielectric properties originating from the pure hydrocarbon structure. Introducing fluorine into polymers is one efficient strategy for optimizing the dielectric and the related important properties.
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