Polymer chain ends play an important role in the glassy dynamics of polymeric materials. In this study, a combination of single molecule defocus fluorescence microscopy and well-controlled atom transfer radical polyme...Polymer chain ends play an important role in the glassy dynamics of polymeric materials. In this study, a combination of single molecule defocus fluorescence microscopy and well-controlled atom transfer radical polymerization was used to investigate site-dependent segmental mobility of poly（n-butyl methacrylate）. As the temperature increased, the rotation of fluorophores, which were selectively labelled in chain end and chain middle, was gradually activated. The power spectra of rotation trajectories, the distribution of angular displacement as well as the population of rotating fluorophores demonstrated that the local dynamics was more activated at the chain ends than the middles, showing the unique contribution of the chain end to the dynamics of the system.展开更多
Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics ...Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.展开更多
基金financially supported by National Basic Research Program of China(No.2014CB643601)
文摘Polymer chain ends play an important role in the glassy dynamics of polymeric materials. In this study, a combination of single molecule defocus fluorescence microscopy and well-controlled atom transfer radical polymerization was used to investigate site-dependent segmental mobility of poly（n-butyl methacrylate）. As the temperature increased, the rotation of fluorophores, which were selectively labelled in chain end and chain middle, was gradually activated. The power spectra of rotation trajectories, the distribution of angular displacement as well as the population of rotating fluorophores demonstrated that the local dynamics was more activated at the chain ends than the middles, showing the unique contribution of the chain end to the dynamics of the system.
基金supported by National Basic Research Program of China(No. 2014CB643601)
文摘Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.
