Synthesis and Self‐Assembly of Rod–Rod Hybrid Poly(γ‐benzyl L‐glutamate)‐block‐Polyisocyanide Copolymers

Abstract

Connecting rods: Rigid rod–rod block copolymers are synthesized from peptide and polyisocyanide blocks (see picture: blue=poly(γ‐benzyl L‐glutamate); red=poly(methylbenzyl isocyanide) or poly(L‐isocyanoalanyl‐L‐alanine methyl ester). The polyisocyanide helix has side arms organized in a parallel β‐sheet (light blue). Some copolymers self‐assemble into ordered layers of hollow capsules.

Self‐Assembly of a Hydrophobic Polypeptide Containing a Short Hydrophilic Middle Segment: Vesicles to Large Compound Micelles

“…Great efforts have been made to incorporate proteins or polypeptides into synthetic materials. [6][7][8][9][10][11] For example, recently: Akashi et al reported a one-step preparation of polypeptide nanospheres with dual initiators in a mixture of water/DMSO; [12] Lecommandoux et al studied stimuliresponsive vesicles from a peptide-based diblock copolymer polybutadiene-block-poly(L-glutamic acid) (PB-b-PGA); [13] Deming et al demonstrated the charged polypeptide vesicles with promising biomimetic encapsulants; [14] and, This report describes a facile route to prepare the vesicles and large compound micelles (LCMs) from a series of poly(e-benzyloxycarbonyl L-lysine)-block-poly[diethylene glycol bis(3-amino propyl) ether]-block-poly(e-benzyloxycarbonyl L-lysine) (PZLL-DGBE-PZLL) in their water solution, depending on molecular weight of the polypeptides. A pyrene probe is used to demonstrate the aggregate formation of PZLL-DGBE-PZLL in solution, and also to measure their critical micelle concentration as a function of molecular weight of the polymer.…”

All‐Conjugated, Rod‐Rod Block Copolymers‐Generation and Self‐Assembly Properties

“…One nice example of vesicle formation in nonconjugated, rod-rod diblock copolymers was reported in 2005 by Kros et al [6] They investigated synthesis and nanostructure formation of a nonconjugated polyisocyanide-block-polybenzylglutamate diblock copolymer. The authors could observe the formation of large vesicles with a diameter of > 5 mm as illustrated in laser scanning confocal and optical microscopy images ( Figure 2).…”

“…Confocal laser scanning (left) and optical (right) microscopy images of a nonconjugated polyisocyanide-block-polybenzylglutamate diblock copolymer of the rod-rod type (drop casting of a chloroform solution of the diblock copolymer onto glass slides, chemical structure of the diblock copolymer shown in the inset); images after ref. [6] Scheme 2. Synthesis of a P3HT-b-P3EHT in a chain-growth polycondensation after Zhang et al; [20] THF, tetrahydrofuran; dppe, 1,2-bis(diphenylphosphino)ethane; i-C 3 H 7 , isopropyl; C 6 H 13 , n-hexyl; C 8 H 17 , 2-ethylhexyl.…”

Synthesis of Block Copolypeptides by Click Chemistry

“…[1][2][3][4][5][6][7][8] Block copolymers possessing at least one block with a conformation distinct from a coil have been less considered. For instance, rod-coils, [9][10][11][12][13][14] rod-dendrons, [15,16] or rod-rod [17][18][19] block copolymers undergo phase separation in unique and nonpredicted morphologies, in general at a smaller characteristic length scale than coil-coil block copolymers. This is explained by the high-level incompatibility of the two blocks, sometimes referred to as the conformational asymmetry.…”