Hierarchical Growth of Chiral Self-Assembled Structures in Protic Media

Brunsveld, Luc; Zhang, H.; Glasbeek, M.; Vekemans, Jef A. J. M.; Meijer, E. W.

doi:10.1021/ja0005237

Cited by 223 publications

(261 citation statements)

References 37 publications

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“…The helicity of the columns selfassembled from achiral dendritic alcohols provides definitive demonstration for our previous hypothesis that the helicity of the dendritic dipeptides is induced by their achiral dendrons (15,16). This self-assembly system relates to other processes in which a stereocenter selects the twist sense of a racemic helical structure (10,23,24) and is in agreement with the principles elaborated by Green et al (25). However, it differs from those in which a stereocenter induces helicity in an achiral nonhelical system (26).…”

Section: Structural Analysis Of Oriented Fibers By Xrd and Self-assemsupporting

confidence: 86%

Principles of self-assembly of helical pores from dendritic dipeptides

Percéc

Dulcey

Peterca

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

127

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The self-assembly of the dendritic dipeptides (4-3,4-3,5)nG2-CH2-Boc-L-Tyr-L-Ala-OMe and their achiral dendritic alcohol (4-3,4-3,5)nG2-CH2OH precursors, both with n ‫؍‬ 1-16, where n represents the number of methylenic units in the alkyl groups of the dendron, are reported. All chiral dendritic dipeptides and achiral dendritic alcohols self-assemble into helical porous columns that are stable in both solution and solid state. The pore diameter (Dpore) of the columns self-assembled from dendritic dipeptides is Ϸ10 Å larger than that of structures assembled from dendritic alcohols. The increase of the Dpore at the transition from dendritic alcohol to dendritic dipeptide is accompanied by a decreased solid angle of the building block. This trend is in agreement with previous pore size-solid angle dependences observed with different protective groups of the dipeptide and primary structures of the dendron. However, within the series of dendritic alcohols and dendritic dipeptides with various n, the Dpore increases when the solid angle increases. The results of these investigations together with those of previous studies on the role of dipeptide stereochemistry and protective groups on this self-assembly process provide the molecular principles required to program the construction of supramolecular helical pores with diameter controlled at the Å level from a single dendritic dipeptide architecture. These principles are expected to be valid for libraries of dendritic dipeptides based on dendrons and dipeptides with various primary structures. chiral dendrons ͉ porous supramolecular columns ͉ protein mimics ͉ peptide stereochemistry N atural porous proteins function as viral helical coats (1), transmembrane channels (2, 3), antibiotics (4), and pathogens (5), and their remodeled structures are used in synthetic systems for reversible encapsulation (6) and stochastic sensing (7). With few exceptions (8-10) porous protein mimics do not assemble, as the natural porous proteins do, into periodically ordered structures that are stable in both solution and bulk (11)(12)(13)(14). This behavior limits their structural analysis by combinations of solution and solid-state complementary techniques. Recently our laboratory (15) reported the self-assembly of amphiphilic dendritic dipeptides into helical porous structures that are stable in both solution and bulk (15). Preliminary reports have demonstrated that the internal structure and the stability of the porous columns self-assembled from dendritic dipeptides are programmed by the structure and stereochemistry of the dipeptide (15, 16), the protective groups of the dipeptide (17), and the structure of the dendron (18) attached to the dipeptide. Here we are reporting a comparative study of the self-assembly and structural and retrostructural analysis of the supramolecular porous structures generated from libraries of (4-3,4-3,5)nG2-CH 2 -Boc-L-Tyr-L-Ala-OMe dendritic dipeptides and their achiral (4-3,4-3,5)nG2-CH 2 OH precursors with n ϭ 1-16. This series of experiments will prov...

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Section: Structural Analysis Of Oriented Fibers By Xrd and Self-assemsupporting

confidence: 86%

Principles of self-assembly of helical pores from dendritic dipeptides

Percéc

Dulcey

Peterca

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

127

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“…[28][29][30] Also, in some cases, chiral and strongly polar solute-solvent and solute-solute interactions are responsible for these helical assembled structures. 31,32 However, weak and/or invisible ultraweak intermolecular interactions of nonpolar systems have not been yet explored in synthetic helical structures.…”

Section: Michiya Fujiki 4638mentioning

confidence: 99%

Nonclassical forces: Seemingly insignificant but a powerful tool to control macromolecular structures

Fujiki

Saxena

2008

J. Polym. Sci. A Polym. Chem.

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Strong chemical forces such as covalent and ionic bonds are responsible for building discrete molecules, nature dwells on noncovalent forces weaker by three orders in magnitude, like the hydrophobic effect, hydrogen bonding, and van der Waals forces. Despite being weak, they possess the potential to drive spontaneous folding or unfolding of proteins and nucleic acids and the recognition between complimentary molecular surfaces. The power of these forces lies in the cooperativity with which they act, thereby generating a cumulative effect of many bonding interactions occurring together. Many ongoing research aims to translate the potential of these forces to the synthetic world to create desired structures with specific chemical functions. Achieving this offers unlimited opportunities for designing and synthesizing the most complex structures with specific applications. This highlight aims to reflect the critical role these noncovalent forces play in controlling macromolecular structures, which hold immense untapped potential for applications defying conventions, and briefly touches on the concept of homochirality in nature based on chiral and weak noncovalent interactions in synthetic nonpolar Si‐catenated polymers. It sheds some light on the discovery and characterization of Si/F‐C interactions in fluoroalkylated polysilanes in chemosensing of fluoride ions and nitroaromatics with a great sensitivity and selectivity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4637–4650, 2008

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“…[2] Columnar self-assemblies based on benzene-1,3,5-tricarboxamide (BTA) motif result from π-π stacking interactions and formation of maximal number of hydrogen bonds between the individual units. [3][4][5][6] These discotic systems [7] are characterized by a helical arrangement of units and have attracted attention as organic electronic elements due to their liquid crystal features. [8] Detailed studies of their aggregation process have highlighted the cooperative nature of these self-assemblies.…”

Section: Introductionmentioning

confidence: 99%