Visualizable cylindrical macromolecules with controlled stiffness from backbones containing libraries of self-assembling dendritic side groups

被引:329
作者
Percec, V [1 ]
Ahn, CH
Cho, WD
Jamieson, AM
Kim, J
Leman, T
Schmidt, M
Gerle, M
Möller, M
Prokhorova, SA
Sheiko, SS
Cheng, SZD
Zhang, A
Ungar, G
Yeardley, DJP
机构
[1] Case Western Reserve Univ, Dept Macromol Sci, WM Keck Labs Organ Synth, Cleveland, OH 44106 USA
[2] Univ Mainz, Inst Chem Phys, D-55128 Mainz, Germany
[3] Univ Ulm, D-89069 Ulm, Germany
[4] Univ Akron, Maurice Morton Inst Polymer Sci, Akron, OH 44325 USA
[5] Univ Sheffield, Dept Mat Engn, Sheffield S1 3JD, S Yorkshire, England
[6] Univ Sheffield, Ctr Mol Mat, Sheffield S1 3JD, S Yorkshire, England
关键词
D O I
10.1021/ja981211v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The synthesis and structural analysis of a library containing 13 taper- and conical-shaped self-assembling dendrons, 16 dendritic monomers, and their corresponding polymers is reported. Fifteen of these polymers exhibit a well-defined cylindrical shape produced by the self-assembly of their dendritic side groups that self-organizes in a hexagonal columnar two-dimensional liquid crystalline lattice. The retrosynthetic analysis of this lattice by X-ray diffraction (XRD) showed that the diameter (60 to 41 Angstrom) and the number of repeat units forming the cylinder cross-section (7 to 1.9) of these polymers are determined by the structure of their dendritic side groups. This demonstrates that, in the hexagonal columnar lattice, the conformation (from helical to fully extended) and the stiffness of the polymer backbone penetrating through the center of the cylinder are controlled in a systematic and predictive way by the structure of the side groups. Dynamic and static light scattering experiments have demonstrated the same trend for the stiffness of these polymers in solution (Kuhn segment length from 200 to 1032 Angstrom). Single chains and monolayers of these polymers were visualized and quantitatively analyzed by scanning force microscopy (SFM) on a graphite surface to provide the first comparative study of the conformation, stiffness, and contour length in solution (by light scattering), in the disordered solid state on a flat substrate (by SFM), and in the hexagonal columnar lattice (by XRD). The elaboration of this library of visualizable cylindrical macromolecules with controlled chain conformation and stiffness accesses the elucidation of many fundamental problems of the field of polymer science at the molecular level and the design of multifunctional nanoscale systems based on single polymer chains.
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页码:8619 / 8631
页数:13
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