Three‐dimensional crystalline supramolecular nanostructures from self‐assembly of rod–coil molecules incorporating lateral carboxyl group in the middle of the rod segment

Yu, Shengsheng; Yang, Yuntian; Cheng-fan, LI; Chen, Tie; Jin, Long

doi:10.1002/pi.4933

Cited by 6 publications

(3 citation statements)

References 33 publications

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“…Amphiphilic rod–coil molecules consisting of rigid rod segments and flexible hydrophilic poly(ethylene oxide) (PEO) coil chains are also known to form various supramolecular aggregates with well-defined shapes and sizes, such as spherical micelles, cylindrical micelles, ribbons, vesicles, tubules, helices, and toroids in selected solutions. − These self-assembling nanostructures, constructed through noncovalent forces, including hydrophobic and hydrophilic effects, electrostatic interactions, hydrogen bonding, and van der Waals interactions, could be widely utilized as biomimetic or bioinspired materials in aqueous solutions. − We reported that supramolecular nanostructures can be accurately controlled by incorporating lateral alkyl groups at the surface of the rod and coil segments or at the center of the rod building block. This can significantly influence microphase separation of the rod–coil molecules and lead to the creation of hexagonal perforated layer, oblique columnar, and 3-D body-centered tetragonal nanostructures in bulk, and the formation of micelles, vesicles, and helical nanofibers in aqueous solutions, by tuning the self-assembling driving force of the rod building block. − These results indicate that the lateral chains in the rod domain can suppress the intermolecular π–π stacking interaction that leads to the relatively loose packing of the rod segments of different nanoassemblies.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of n-Shaped Rod–Coil Molecules into Thermoresponsive Nanoassemblies: Construction of Reversible Helical Nanofibers in Aqueous Environment

Yang

Cui

et al. 2016

Macromolecules

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Amphiphilic coil–rod–coil molecules 1–3, consisting of an n-shaped rod building block and poly(ethylene oxide) (PEO) with a degree of polymerization of 5 linked through a biphenyl unit as the coil segment, were synthesized. Molecule 1 self-assembles into lamellar and hexagonal perforated layer structures, in the crystalline and liquid crystalline phases, respectively. Remarkably, molecule 2 incorporating lateral methyl groups between the rod and coil segments spontaneously self-organizes into hexagonal perforated layer and oblique columnar structures. The additional incorporation of a lateral butyl group at the center of the rod segment of molecule 2 generates molecule 3, which assumes an exclusively oblique columnar structure in the solid state. In aqueous solutions, molecule 1 self-assembles into fibrous aggregates, whereas molecules 2 and 3 exhibit a self-organizing capacity to form helical fibers. Additionally, circular dichroism (CD) experiments and atomic force microscope (AFM) measurements of molecule 3 highlight a switch of the helical sense to the opposite handedness, depending on the temperature of the aqueous solution.

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Section: Introductionmentioning

confidence: 99%

Self-Assembly of n-Shaped Rod–Coil Molecules into Thermoresponsive Nanoassemblies: Construction of Reversible Helical Nanofibers in Aqueous Environment

Yang

Cui

et al. 2016

Macromolecules

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“…The peaks can be assigned to the (100), (010), (210), and (300) reflections of a two-dimensional oblique columnar structure with a characteristic angle γ = 64° (Figure a) and lattice constants a = 5.13 nm and b = 2.97 nm (Table S2). In addition, three peaks of 1a corresponding to the equidistant q-spacings in the small-angle region can be assigned to the (001), (002), and (003) reflections, indicating a lamellar structure in the crystalline phase. − The measured layer spacing of 4.7 nm is close to the estimated molecular length (the estimated lengths of the rod segment and coil chain are ∼3.1 and ∼4.1 nm from the Corey–Pauling–Koltun (CPK) molecular model, respectively). This suggests that a typical monomolecular layer structure was formed in which the rod segments are fully interdigitated with each other (Figure b).…”

Section: Resultsmentioning

confidence: 99%

Morphological Control of Coil–Rod–Coil Molecules Containing m-Terphenyl Group: Construction of Helical Fibers and Helical Nanorings in Aqueous Solution

et al. 2018

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Rod-coil molecules, composed of rigid segments and flexible coil chains, have a strong intrinsic ability to self-assemble into diverse supramolecular nanostructures. Herein, we report the synthesis and the morphological control of a new series of amphiphilic coil-rod-coil molecular isomers 1-2 containing flexible oligoether chains. These molecules are comprised of m-terphenyl and biphenyl groups, along with triple bonds, and possess lateral methyl or butyl groups at the coil or rod segments. The results of this study suggest that the morphology of supramolecular aggregates is significantly influenced by the lateral alkyl groups and by the sequence of the rigid fragments in the bulk and in aqueous solution. The molecules with different coils self-assemble into lamellar or oblique columnar structures in the bulk state. In aqueous solution, molecule 1a, with a lack of lateral groups, self-assembled into large strips of sheets, whereas exquisite nanostructures of helical fibers were obtained from molecule 1b, which incorporated lateral methyl groups between the rod and coil segments. Interestingly, molecule 1c with lateral butyl and methyl groups exhibited a strong self-organizing capacity to form helical nanorings. Nanoribbons, helical fibers, and small nanorings were simultaneously formed from the 2a-2c, which are structural isomers of 1a, 1b, and 1c. Accurate control of these supramolecular nanostructures can be achieved by tuning the synergistic interactions of the noncovalent driving force with hydrophilic-hydrophobic interactions in aqueous solution.

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“…Compounds 3 and 4 were prepared according to the references described elsewhere (see the Supporting Information). [14] Characterization:F lash column chromatography was performed using silica gel (200-300 mesh). 1 HNMR(300 MHz) was recorded in CDCl 3 on Bruker AM-300 instruments.…”

Section: Methodsmentioning

confidence: 99%

Construction of Supramolecular Assemblies from Self‐Organization of Amphiphilic Molecular Isomers

Yang

Wang

et al. 2016

Chemistry An Asian Journal

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Amphiphilic coil-rod-coil molecules, incorporating flexible and rigid blocks, have a strong affinity to self-organize into various supramolecular aggregates in bulk and in aqueous solutions. In this paper, we report the self-assembling behavior of amphiphilic coil-rod-coil molecular isomers. These molecules consist of biphenyl and phenyl units connected by ether bonds as the rod segment, and poly(ethylene oxide) (PEO) with a degree of polymerization of 7 and 12 as the flexible chains. Their aggregation behavior was investigated by differential scanning calorimetry, thermal optical polarized microscopy, small-angle X-ray scattering spectroscopy, and transmission electron microscopy. The results imply that the molecular structure of the rod building block and the length of the PEO chains dramatically influence the creation of supramolecular aggregates in bulk and in aqueous solutions. In the bulk state, these molecules self-organize into a hexagonal perforated lamellar and an oblique columnar structure, respectively, depending on the sequence of the rod building block. In aqueous solution, the molecule with a linear rod segment self-assembles into sheet-like nanoribbons. In contrast, its isomer, with a rod building block substituted at the meta-position of the aryl group, self-organizes into nanofibers. This is achieved through the control of the non-covalent interactions of the rod building blocks.

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Three‐dimensional crystalline supramolecular nanostructures from self‐assembly of rod–coil molecules incorporating lateral carboxyl group in the middle of the rod segment

Cited by 6 publications

References 33 publications

Self-Assembly of n-Shaped Rod–Coil Molecules into Thermoresponsive Nanoassemblies: Construction of Reversible Helical Nanofibers in Aqueous Environment

Self-Assembly of n-Shaped Rod–Coil Molecules into Thermoresponsive Nanoassemblies: Construction of Reversible Helical Nanofibers in Aqueous Environment

Morphological Control of Coil–Rod–Coil Molecules Containing m-Terphenyl Group: Construction of Helical Fibers and Helical Nanorings in Aqueous Solution

Construction of Supramolecular Assemblies from Self‐Organization of Amphiphilic Molecular Isomers

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