0000000000424701
AUTHOR
A. Dieter Schlüter
3D Conformations of Thick Synthetic Polymer Chains Observed by Cryogenic Electron Microscopy.
The backbone conformations of individual, unperturbed synthetic macromolecules have so far not been observed directly in spite of their fundamental importance to polymer physics. Here we report the dilute solution conformations of two types of linear dendronized polymers, obtained by cryogenic transmission electron stereography and tomography. The three-dimensional trajectories show that the wormlike chain model fails to adequately describe the scaling of these thick macromolecules already beyond a few nanometers in chain length, in spite of large apparent persistence lengths and long before a signature of self-avoidance appears. This insight is essential for understanding the limitations o…
The Largest Synthetic Structure with Molecular Precision: Towards a Molecular Object
Pushing the limits: A 200A - 10 Da structurally defined, linear macromolecule (PG5) has a molar mass, cross-section dimension, and cylindrical shape that are comparable to some naturally occurring objects, such as amyloid fibrils or certain plant viruses. The macromolecule is resistant against flattening out on a surface; the picture shows PG5 embracing the tobacco mosaic virus (TMV).
Efficient Synthesis of High Molar Mass, First- to Fourth-Generation Distributed Dendronized Polymers by the Macromonomer Approach
A homologous series of first- to fourth-generation (G1±G4) dendronized macromonomers, 5, 7, 10, and 12, was synthesized, and their poly- merization behavior under radical con- ditions investigated. These conditions were thermally induced radical poly- merization (TRP) and atom-transfer radical poymerization (ATRP). TRP was applied to all monomers and gave polymers PG1±PG4, whose molar masses range from several millions for PG1 to estimated several hundreds of thousands for PG2 and PG3, and to the oligomeric regime for PG4. ATRP was applied only to the G1 and G2 monomers 5 and 7. Kinetic studies on monomer 5 provide evidence that its polymerization proceeds in a control- led fashion. The hig…
The Next 100 Years of Polymer Science
International audience; The year 2020 marks the 100th anniversary of the first article on poly merization, published by Hermann Staudinger. It is Staudinger who realized that polymers consist of long chains of covalently linked building blocks. Polymers have had a tremendous impact on the society ever since this initial publication. People live in a world that is almost impossible to imagine without synthetic polymers. But what does the future hold for polymer science? In this article, the editors and advisory board of Macromolecular Chemistry and Physics reflect on this question.
Ion-Induced Stretching of Low Generation Dendronized Polymers with Crown Ether Branching Units
Synthesis of the first (G1) and second generation (G2) dendronized macromonomers MG1 and MG2 with the dibenzo-24-crown-8 moiety as branching unit is reported. The corresponding dendronized polymers, the polymethacrylates PG1 and PG2, were synthesized by free radical polymerization using AIBN as initiator at 60−80 °C. Static and dynamic light scattering revealed a significant chain expansion upon complexation of these polymers’ crown ether side chains with K+ ions. It is concluded that electrostatic repulsion does not significantly contribute to the chain expansion because of excessive counterion binding even well below the Manning limit, as evidenced by 19F NMR and 1H−19F NOE experiments. R…
Iron(II) Spin Transition Complexes with Dendritic Ligands, Part I
The ligands G1- and G2-oligo (benzyl ether) (PBE) dendrons and their iron(II) complexes [Fe(Gn-PBE)3]A2·xH2O (with n = 1, 2 and A = triflate, tosylate) were prepared. The magnetic properties of the complexes were investigated by a SQUID magnetometer. All complexes exhibit gradual spin transition below room temperature. At very low temperatures the magnetic behaviour reflects zero-field splitting (ZFS) effects. 57Fe-Mossbauer spectroscopy was performed to distinguish between ZFS of high spin species and spin state conversion into the low spin state. Further characterisation was carried out by thermogravimetric analysis (TGA) and FT-IR spectroscopy. Structural features have been determined by…
Suzuki polycondensation with a hairpin monomer.
Two straight monomers were subjected to an AA/BB-type Suzuki polycondensation with a hairpin-shaped 1,8-anthrylene monomer as the counterpart leading to a novel polyarylene which should have the preferred conformation of a folded chain. The molar masses were determined by gel permeation chromatography and dynamic light scattering and found to be M(w) = 14,000 and M(n) = 7,000. MALDI-TOF MS analysis of a fraction provides a fingerprint of the step-growth nature of this polymerization.