Self‐Assembly of Hybrid Dendrons with Complex Primary Structure Into Functional Helical Pores

Abstract

The synthesis of three libraries of self-assembling hybrid dendrons containing a primary structure based on the sequence (4-3,4-3,5)12G2-CO(2)CH(3) generated from benzyl ether, biphenyl-4-methyl ether, and AB(2) repeat units constructed from (AB)(y)--AB(2) combinations of benzyl ethers, is reported. The structural and retrostructural analysis of their supramolecular dendrimers facilitated the discovery of new architectural principles that lead to the assembly of functional helical pores. The self-assembly of an example of hybrid dendron containing -H, -CO(2)CH(3), -CH(2)OH, -COOH, -COOK, -CONH(2), -CONHCH(3), -CO(2)(CH(2))(2)OCH(3), -(R) and -(S)-CONHCH(CH(3))C(2)H(5) as X-groups at the apex demonstrated that these self-assembling dendrons provide the simplest strategy for the design and synthesis of porous columns containing a diversity of hydrophilic and hydrophobic functional groups in the inner part of the pore. The results reported here expand the scope and limitations of dendrons available for the self-assembly of functional pores that previously were generated mostly from dendritic dipeptides, to simpler architectures based on hybrid dendrons.

Histologic grade is correlated with outcome after resection of hepatic neuroendocrine neoplasms

“…They also have been shown to act as functional groups that mediate the self‐organization of ordered, mostly smectic liquid crystalline phases 17–29. Research from our laboratory has elaborated strategies for the design of self‐assembling dendritic building blocks based on ionic,30–37 H‐bonding,38–47 donor–acceptor,48–50 fluorophobic,51–53 covalent,54–59 and other specific and nonspecific interactions. This article reports the design, synthesis, and structural analysis of self‐assembling dendrons containing ionic‐liquid functionalities at their apex.…”

Nanoporous Membranes of Hydrogen‐bridged Smectic Networks with Nanometer Transverse Pore Dimensions

“…For reference, a smectic monomer with only covalent bonds did not rearrange in a similar way, which indicates that some dynamics around bond braking and reformation is involved. [26] When polymer formed from pure 1 is cooled from the polymerization temperature at 105 8C to room temperature its structure is maintained although the tilt angle between the average molecular long axis and the plane of the layer shows a marginal increase. When the same sample is heated to higher temperatures, however, large structural changes are observed.…”

“…[23][24][25] For smaller dimensions supramolecular dendritic structures can self-assemble into pores with a well-controlled inner chemical nature. [26,27] Bottom-up methods that are especially appealing are based on the self-organization of liquid crystals and their polymers because they decrease the pore sizes down to the order of molecular length scales, for example, around 1 nm and below, while the assemblies themselves can have much larger dimensions. For instance, nanoporous systems made from polymerized lyotropic systems have proven themselves to be useful for purification and desalination of water [28,29] or gas separation, [30] where dimensions down to the molecular level are essential.…”

Cubic and Other3DThermotropic Liquid Crystal Phases and Quasicrystals

“…Owing to limited solubility, only a small library of biphenyl-4-methyl ether dendrons was reported [85]. However, a full library of trisubstituted and two libraries of disubstituted biphenylpropyl ether dendrons were synthesized -see 21 as an example [86].…”