Nucleotide-Promoted Morphogenesis in Amphiphile Assemblies: Kinetic Control of Micrometric Helix Formation
Carole AiméRumi TamotoTakao SatohAxelle GrélardÉrick J. DufourcThierry BuffeteauHirotaka IharaReïko Oda
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Abstract:
Anionic nucleotides adenosine monophosphate or guanosine monophosphate interact with cationic vesicles, exchange with the counteranions of the amphiphiles in situ, and organize themselves at the membrane surfaces. Such organized nucleotides reciprocally transfer their chirality to membranes of nonchiral amphiphiles to induce the formation of right-handed micrometric helices on the time scale of hours. The kinetics of the nucleotide molecular organization and the formation of supramolecular helices was followed. We have shown that helix formation is a kinetic-dependent process that does not primarily result from ion exchange but from conformational reorganization and formation of weak interactions between confined nucleotides.Keywords:
Helix (gastropod)
Chirality
Cationic polymerization
Supramolecular chirality
Guanosine monophosphate
A new approach to second-order nonlinear optical (NLO) materials is reported, in which chirality and supramolecular organization play key roles. Langmuir-Blodgett films of a chiral helicene are composed of supramolecular arrays of the molecules. The chiral supramolecular organization makes the second-order NLO susceptibility about 30 times larger for the nonracemic material than for the racemic material with the same chemical structure. The susceptibility of the nonracemic films is a respectable 50 picometers per volt, even though the helicene structure lacks features commonly associated with high nonlinearity. Susceptibility components that are allowed only by chirality dominate the second-order NLO response.
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Abstract A C 3 ‐symmetric benzene‐1,3,5‐tricarboxamide substituted with ethyl cinnamate was found to self‐assemble into supramolecular gels with macroscopic chirality in a DMF/H 2 O mixture. The achiral compound simultaneously formed left‐ and right‐handed twists in an unequal number, thus resulting in the macroscopic chirality of the gels without any chiral additives. Furthermore, ester–amide exchange reactions with chiral amines enabled the control of both the handedness of the twists and the macroscopic chirality of the gels, depending on the structures of the chiral amines. These results provide new prospects for understanding and regulating symmetry breaking in assemblies of supramolecular gels formed from achiral molecular building blocks.
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An L- or D-glutamic acid based bolaamphiphile was found to form uniform helical nanotubes in water, which were used as the template to generate silica nanotubes. The formed silica nanotubes have supramolecular chirality in the inner walls, and were further used to load photoactive azobenzene moieties to realize a chiroptical switch.
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Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.
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Abstract By constructing a supramolecular light‐harvesting chiral nanotube in the aqueous phase, we demonstrate a cooperative energy and chirality transfer. It was found that a cyanostilbene‐appended glutamate compound (CG) self‐assembled into helical nanotubes exhibiting both supramolecular chirality and circularly polarized luminescence (CPL). When two achiral acceptors, ThT and AO, with different energy bands were co‐assembled with the nanotube, the CG nanotube could transfer its chirality to both of the acceptors. The excitation energy could be transferred to ThT but only be sequentially transferred to AO. During this process, the CPL ascribed to the acceptor could be sequentially amplified. This work provides a new insight into the understanding the cooperative chirality and energy transfer in a chiral supramolecular system, which is similar to the natural light‐harvesting antennas.
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The chirality of TPPS J aggregates followed the supramolecular chirality of assemblies from chiral molecules rather than the molecular chirality.
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Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π–π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.
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Chirality is rapidly induced in a fractal aggregate of the porphyrin t-CuPagg by addition of α-helical poly-glutamate. These results demonstrate a facile transfer of chirality via noncovalent interactions to preformed supramolecular assemblies grown in the absence of a chiral template.
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The emergence, transference, amplification, and memory of chiroptical activity in supramolecular assemblies, including circularly polarized absorbance and circularly polarized luminescence, remain significant challenges. Herein, an achiral pyridine-substituted coumarin derivative and chiral additives can coassemble into helical nanostructures with fine chiroptical activity via subtle hydrogen-bonding interactions. The resulting supramolecular assemblies remain optically active even after the removal of chiral additives, demonstrating supramolecular chirality can be remembered in the assemblies. More importantly, the removed chiral elements can be reused to achieve continuous circulation and amplification of chirality. This work presents insight into the emergence, transference, amplification, and memory of chirality in a supramolecular assembly system and could be applied to the manufacturing of chiroptical materials.
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