Knäuel-Ring-Knäuel-Blockcopolymere als Bausteine supramolekularer hohler Polymerbürsten

Abstract

Die lösungsmittelunterstützte Selbstorganisation Oligomer‐substituierter formtreuer Makrocyclen führt zur Bildung von Zylinderaggregaten (siehe schematische Darstellung), die in Lösung vollständig charakterisiert wurden und sich als supramolekulare hohle Polymerbürsten bezeichnen lassen.

Shape-Persistent, Nano-Sized Macrocycles

“…[42] Cycle 14g, another member of this type of cycle, was incorporated into the coil-ring-coil block copolymer 14h. [41] Tobe further supplemented his work [94][95] by cyclization of dimer 58a and [43] Unlike the Breslow and Hay methods, which did not give any cyclic material, the Eglinton coupling did give product, though not in very high yields (see above). Astonishingly, both the cyclic tetramer 15a and the octamer 15e were isolated from dimer 58a (25 and 13% yield, respectively), but none of the thermodynamically favored hexameric analogue 15c was obtained.…”

“…[41] Its induced aggregation is based on an effect similar to that described above for 14cϪe, [42] a solvent that dissolves the polymeric chain, but not the cycle. It is reasonable to assume that the cycles are stacked one on top of the other in a ''hollow'' cylinder ( Figure 6).…”

“…B 2 MS, 1 H NMR 9a [33] 14% 209 mg B 2 GPC, MS, 1H NMR, EA 9b [33] 5% 79 mg B 4 GPC, MS, 1H NMR, EA 10a [34] 54% 220 mg B [c] 2 MS, NMR, UV, EA 10b [34] 32% 90mg D 2 UV, (EA), charact. as complex 11a [35] 28% 383 mg B 2 GPC, MS, NMR, EA, X-ray 11b [35] 25% 250 mg B 2 GPC, MS, NMR, X-ray 11c* [36] 14% 160 mg B 2 GPC, MS, NMR, X-ray 11d [37] 18% 83 mg B 2 GPC, MS, NMR 11e [37] 21% 340 mg B 2 GPC, MS, NMR 12a [38] 21% 25mg B 2 MS, NMR, X-ray 12b [38] 14% 42mg B 2 MS, NMR, STM, X-ray 12c [38] 25% 114 mg B 2 MS, NMR, X-ray 12d* [38] 18% 135 mg B 2 MS, NMR 12e [38] 18% 216 mg B 2 MS, NMR 13a [38] 27% 40 mg B 2 MS, 1H NMR 13b [38] 8% 28 mg D 2 MS, 1H NMR 13c [38] 18% 39 mg B 2 MS 13d* [38] 19% 46 mg B 2 MS 13e [38] 11% 45 mg B 2 MS, NMR 14a [39] 48% 860 mg D 2 m.p., MS, NMR 14b [39] R m.p., MS, NMR 14c [39] R m.p., MS, NMR 14d [39] R m.p., MS, NMR, STM 14e [39] R MALDI, NMR, m.p., STM 14f [40] R X-ray 14g [41] n.s. n.s.…”

“…n.s. 14h [41] R DLS, TEM, AFM 14i [42] R 14j [42] R 15a [43] 25% 18mg D 2 HPLC, m.p., MS, NMR, IR, UV, EA 73% 219 mg D 1 15b [44] 50% 150 mg D 1 HPLC, m.p., MS, NMR, IR, EA 15d [44] 29% 64 mg D 1 HPLC, m.p., MS, NMR, IR, UV 15e [43] 18% [31] n.s. n.s.…”

Tunable Length of Cyclic Peptide–Polymer Conjugate Self-Assemblies in Water

“…A relatively new class of self-assembled nanostructures are supramolecular polymer brushes, which are formed either by strong hydrogen bonds or π-π interactions. [14][15][16][17][18] These materials combine flexible polymer chains with a supramolecular backbone to create rigid anisotropic hairy nanoparticles, often having a rod-like shape. In particular, polymers conjugated to self-assembling cyclic peptides have attracted considerable attention for designing functional supramolecular nanotubes.…”