title: Tube-graft-Sheet Nano-Objects Created by A Stepwise Self-Assembly of Polymer-Polyoxometalate Hybrids.
abstract: In this work, we report the preparation of complex nano-objects by means of a stepwise self-assembly of two polymer-polyoxometalate hybrids (PPHs) in solution. The PPHs are designed and synthesized by tethering two linear poly(ε-caprolactone)s (PCL) of different molecular weights (MW) on a complex of a Wells-Dawson-type polyoxometalate (POM) cluster and its countraions. The higher MW PCL-POM self-assembled into nanosheets, while the lower MW PCL-POM assembled into nanotubes just by altering the ratio of water in the DMF-water mixed solvent system. The two nano-objects have a similar membrane structure in which a PCL layer is sandwiched by the two POM-based complex layers. The PCL layer in the nanosheets is semicrystalline, while the PCL layer in the nanotubes is amorphous. We further exploited this MW-dependence to self-assemble the nanotubes on the nanosheet edges to create complex tube-graft-sheet nano-objects. We found that the nanotubes nucleate on the four {110} faces of the PCL crystal and then further grow along the crystallographic b-axis of the PCL crystal. Our findings offer hope for the further development of nano-objects with increasing complexity.
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Jing
authors.initials: J
authors.lastname: Tang
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Xue-Ying
authors.initials: XY
authors.lastname: Li
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Han
authors.initials: H
authors.lastname: Wu
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Li-Jun
authors.initials: LJ
authors.lastname: Ren
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Yu-Qi
authors.initials: YQ
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Hai-Xia
authors.initials: HX
authors.lastname: Yao
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Min-Biao
authors.initials: MB
authors.lastname: Hu
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Wang