Hierarchical self-assembly of columnar aggregates

Abstract

Biology often uses hierarchical self-assembly to produce complex functional structures from smaller components. At each level of this stepwise process, non-covalent interactions bring together the subunits of a lower level of complexity, using the information encoded in their structures. Applying this approach to synthetic systems represents a formidable challenge, because it requires a high degree of command of non-covalent interactions. In this tutorial review, recent developments in the hierarchical self-assembly of discrete columnar aggregates are discussed.

Helicity Induction on a Poly(phenylacetylene) Derivative Bearing a Sulfonic Acid Pendant with Chiral Amines and Memory of the Macromolecular Helicity in Dimethyl Sulfoxide

“…The macromolecular helicity memory of poly-1 assisted by the interaction with an achiral diamine 15 lasted for over six months as observed for the helical PCPA, PPPA, and PEPPA with a helicity memory after the SEC fractionation, 31,[35][36][37][38] but the memory gradually declined with time at ambient temperature (20)(21)(22)(23)(24)(25) C) and the ICD intensity of the fractionated poly-1 showed a decrease of about 20% at room temperature after 185 d. The stability of the memory was highly dependent on the concentration of the salts and the decreasing rate was accelerated in the presence of the common salts; the ICD completely disappeared after 12 h in the presence of 15 . TosOH ([15 .…”

“…Constructing artificial helical polymers [1][2][3][4][5][6][7][8][9][10][11][12][13] and oligomers (foldamers) [14][15][16][17][18] or supramolecular helical assemblies [19][20][21][22][23][24][25] with controlled helicity has attracted significant interest in recent years in the fields of polymer and supramolecular chemistry because of their potential applications for novel chiral materials. In a series of our studies, we reported the helicity induction in optically inactive, cis-transoidal poly((4-carboxyphenyl)acetylene) (PCPA), [26][27][28][29] poly((4-phosphonophenyl)acetylene) (PPPA), [30][31][32] and poly(ethyl(4-ethynylphenyl)phosphonate) (PEPPA) 30,31,33,34 ( Figure 1) with chiral amines in dimethyl sulfoxide (DMSO) and some amino acids in water.…”

End-evaporation dynamics revisited

“…123, 144912 ͑2005͒ chiral discotics, where the discotic polymers hierarchically self-assemble to form long one-dimensional columns. 2 We have derived a master equation for the reactions and diffusion of the rods on a lattice, focussing on the special case in which the system remains homogeneous, which corresponds to the reaction-limited scenario. This is equivalent to the mean-field description that is commonly used to study living polymers.…”

“…Another important example of equilibrium polymers is given by self-assembled stacks of discotic molecules, 1,2 which have possible applications in plastic transistors and photovoltaics. A large number of studies on the equilibrium properties of equilibrium polymers have been published, both theoretical 3,4 and experimental; 5,6 for recent reviews on this subject see Refs.…”

“…A typical example is, for instance, given by supramolecular structures consisting of discotic molecules that self-assemble into rigid linear stacks ͑see Ref. 2 for a review͒ and that exhibit an extremely slow relaxation. Actually, the example of stacks of discotic molecules belongs to the more general class of rods that align in a magnetic field or in a nematic liquid-crystalline phase.…”