- Tunable asymmetric catalysis through ligand stacking in chiral rigid rods
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Chiral benzene-1,3,5-tricarboxamide (BTA) ligands, comprising one diphenylphosphino group and one or two remote chiral 1-methylheptyl side chains, were evaluated in the rhodium-catalyzed asymmetric hydrogenation of dimethyl itaconate. Despite the fact that the rhodium atom and the chiral center(s) are separated by more than 12 covalent bonds, up to 82% ee was observed. A series of control and spectroscopic experiments confirmed that the selectivity arises from the formation of chiral helical polymers by self-association of the BTA monomers through noncovalent interactions. The addition of a phosphine-free chiral BTA, acting as a comonomer for the chiral BTA ligands, increases the level of enantioselectivity (up to 88% ee). It illustrates how the selectivity of the reaction can be increased in a simple fashion by mixing two different BTA monomers. The concept was further probed by performing the same experiment with an achiral BTA ligand, i.e. a phosphine-functionalized BTA that contains two remote octyl side chains. It afforded an encouraging 31% ee, thus demonstrating the catalytically relevant transfer of chirality between the self-assembled units. It constitutes a unique example of the sergeants-and-soldiers principle applied to catalysis.
- Raynal, Matthieu,Portier, Francois,Van Leeuwen, Piet W. N. M.,Bouteiller, Laurent
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- Benzene tricarboxamide derivatives with lipid and ethylene glycol chains self-assemble into distinct nanostructures driven by molecular packing
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The self-assembly in aqueous solution of benzene-1,3,5-tricarboxamide (BTA) bearing one alkyl chain and two PEG (polyethylene glycol) chains or two alkyl chains and one PEG chain yields completely distinct nanostructures. Two series of derivatives were sy
- Aljuaid, Nada,Hamley, Ian W.,Ruokolainen, Janne,Seitsonen, Jani,Tully, Mark
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p. 8360 - 8363
(2021/08/25)
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- Triple helix formation in amphiphilic discotics: Demystifying solvent effects in supramolecular self-assembly
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A set of chiral, amphiphilic, self-assembling discotic molecules based on the 3,3′-bis(acylamino)-2,2′-bipyridine-substituted benzene-1,3,5-tricarboxamide motif (BiPy-BTA) was prepared. Amphiphilicity was induced into the discotic molecules by an asymmetrical distribution of alkyl and oligo(ethylene oxide) groups in the periphery of the molecules. Small-angle X-ray scattering, cryogenic transmission electron microscopy, and circular dichroism spectroscopy measurements were performed on the discotic amphiphiles in mixtures of water and alcohol at temperatures between 0 C an 90 C. The combined results show that these amphiphilic discotic molecules self-assemble into supramolecular fibers consisting of either one or three discotic molecules in the fiber cross-section and that the presence of water induces the bundling of the supramolecular fibers. The rich phase behavior observed for these molecules proves to be intimately connected to the mixing thermodynamics of the water-alcohol mixtures.
- Gillissen, Martijn A. J.,Koenigs, Marcel M. E.,Spiering, Jolanda J. H.,Vekemans, Jef A. J. M.,Palmans, Anja R. A.,Voets, Ilja K.,Meijer
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supporting information
p. 336 - 343
(2014/01/23)
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- Dynamic and bio-orthogonal protein assembly along a supramolecular polymer
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Dynamic protein assembly along supramolecular columnar polymers has been achieved through the site-specific covalent attachment of different SNAP-tag fusion proteins to self-assembled benzylguanine-decorated discotics. The self-assembly of monovalent discotics into supramolecular polymers creates a multivalent, bio-orthogonal and self-regulating framework for protein assembly. The intrinsic reversibility of supramolecular interactions results in reorganization and exchange of building blocks allowing for dynamic intermixing of protein-functionalized discotics between different self-assembled polymers, leading to self-optimization of protein arrangement and distance as evidenced by efficient energy transfer between fluorescent proteins.
- Petkau-Milroy, Katja,Uhlenheuer, Dana A.,Spiering,Vekemans, Jef A. J. M.,Brunsveld, Luc
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p. 2886 - 2891
(2013/07/27)
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- Symmetry breaking in the self-assembly of partially fluorinated benzene-1,3,5-tricarboxamides
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The interplay of two subsequent aggregation processes results in a symmetry-breaking phenomenon in an achiral self-assembling system. Partially fluorinated benzene-1,3,5-tricarboxamide molecules self-assemble into a racemic mixture of one-dimensional P- and M-helical aggregates, followed by bundling into optically active higher-order aggregates or fibers (see picture). Copyright
- Stals, Patrick J. M.,Korevaar, Peter A.,Gillissen, Martijn A. J.,De Greef, Tom F. A.,Fitie, Carel F. C.,Sijbesma, Rint P.,Palmans, Anja R. A.,Meijer
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p. 11297 - 11301
(2013/01/15)
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- Supramolecular materials from benzene-1,3,5-tricarboxamide-based nanorods
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Telechelic polymers end-capped or copolymerized with the benzene-1,3,5-tricarboxamide (BTA) moiety lead to supramolecular materials. The intrinsic phase segregation of BTA nanorods with an amorphous polymer such as poly(ethylene butylene) results in therm
- Roosma, Jorg,Mes, Tristan,Leclere, Philippe,Palmans, Anja R. A.,Meijer
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p. 1120 - 1121
(2008/10/09)
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