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.

We report the synthesis and self-assembling behaviour of coil–rod–coil molecules 1a–1c and 2a–2c, which incorporate lateral carboxyl or ester groups in the middle of the rod segment. The self-assembling behaviour of these molecules was investigated in the bulk using differential scanning calorimetry, polarised optical microscopy and small-angle X-ray scattering. Our results reveal that hydrogen bonds strongly influence the self-assembling behaviour of rod-like building blocks. Molecules 1a–1c, which incorporate carboxyl groups in the middle of rod segments, self-assemble into two-dimensional (2-D) columnar, three-dimensional (3-D) body-centred tetragonal and 3-D hexagonal close-packed assemblies in the crystalline state. However, molecules 2a–2c, which contain ester groups in the centre of rod segments, self-assemble into unexpected lamellar, hexagonal perforated lamellar and 2-D columnar nanostructures in the bulk, indicating that hydrogen bonds impede intermolecular stacking in this rod–coil system. © 2015 Society of Chemical Industry

A new class of π-conjugated, skewed H-shaped oligomers, consisting of biphenyl, phenylene vinylene, and phenylene ethynylene units as the rigid segment, were synthesized via Sonogashira coupling and Wittig reactions. The coil segments of these molecules were composed of poly(ethylene oxide) (PEO) or PEO with lateral methyl groups between the rod and coil segment, respectively. The experimental results revealed that the lateral methyl groups attached to the surface of the rod and coil segments dramatically influenced the self-assembling behavior of the molecules in the crystalline phase. H-shaped rod–coil molecules containing a lateral methyl group at the surface of the rod and PEO coil segments self-assemble into a two-dimensional columnar or a three-dimensional body-centered tetragonal nanostructures in the crystalline phase, whereas molecules lacking a lateral methyl group based on the PEO coil chain self-organize into lamellar or hexagonal perforated lamellar nanostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 85–92

Chiral β-hydroxy-β-arylalanine and β-methoxy-β-arylalanine derivatives, which occur widely in marine nature products, were stereoselectively synthesized with 99 % ee values. The two erythro isomers were prepared by L- or D-aminoacylase-catalyzed resolution of the corresponding N-acetyl derivatives, whereas the two threo isomers were obtained only by D-aminoacylase-catalyzed resolution of the derivatives. erythro-β-Hydroxy-β-arylalanine derivatives were prepared by diastereoselective hydrogenation of ethyl 2-(hydroxyimino)-3-oxo-3-arylpropanoates, which were in turn acquired by the oximation of ethyl 3-oxo-3-arylpropanoates with ethyl nitrite in the presence of nano-K₂CO₃ with yields of 72 % to 80 %. β-Methoxy-β-arylalanine derivatives were synthesized through Williamson reactions between the corresponding β-hydroxy-β-arylalanines and iodomethane with silver oxide as base.

Rod–coil molecules, consisting of flexible and rigid blocks, have a strong capacity to self-assemble into a variety of ordered nanostructures in the bulk state. In this article, we report the synthesis and the self-assembling behavior of coil–rod–coil rectilinear molecular isomers 1 and 2. These molecules consist of conjugated rod segments, which are composed of phenylene, biphenylene and carbon–carbon triple bonds, and poly(ethylene oxide) (PEO) with a degree of polymerization of 7 as coil segments. The molecular structures were characterized by ¹H NMR and matrix-assisted laser desorption ionization time-of-flight mass spectroscopy. Investigation of the self-organization of the two molecules by means of differential scanning calorimetry, polarized optical microscopy and X-ray diffraction reveals that, for the coil–rod–coil molecular isomers, rod components of phenylene or biphenylene units linked together with PEO coil chains dramatically influence the self-assembly behavior in the bulk state. Structural isomers 1 and 2 self-assemble into lamellar structures in the crystalline state. In the liquid crystalline phase, molecule 1 containing phenylene units connected to coil segments self-organizes into a hexagonal perforated lamellar structure, while molecule 2 incorporating biphenylene units linked with coil segments self-assembles into a lamellar structure. © 2013 Society of Chemical Industry

In this study, N-doping porous carbons (NPCs) with a 3D aperiodic hierarchical and layered structure were prepared by the sodium hydride (NaOH) activation of graphite nanofibers (GNFs)/polypyrrole (PPY) composites. The effects of the N groups and structural features on the CO₂ adsorption capacity of NPCs were investigated by N₂ full isotherms, XRD, SEM, and TEM. The CO₂ adsorption capacity was measured by the CO₂ isothermal adsorption at 25°C and 1 atm. It was found that GNFs served as a substrate and layered graphitic carbons were formed by the thermal annealing of PPY. The content of N groups and textural properties of NPCs were enhanced with increasing activation temperature, resulting in improved CO₂ adsorption capacity. The CO₂ adsorption isotherms showed that GPK-600 exhibited the best CO₂ adsorption capacity of 88.8 mg/g when the activation temperature was 600°C. The result indicates that the pore size and its distribution of NPCs lead to feasible contact CO₂, and the presence of high N groups on the NPCs could have resulted in further stabilization of the surface effect. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40517.

T-shaped coil–rod–coil oligomers, consisting of a dibenzo[a,c]phenazine unit and phenyl groups linked together with acetylenyl bonds at the 2,7-position of dibenzo[a,c]phenazine as a rigid segment have been synthesized. The coil segments of these new molecules composed of poly(ethylene oxide) (PEO)–poly(propylene oxide) (PPO) incorporating lateral methyl groups between the rod and coil segment and two flexible alkyl groups connecting with the rigid segment at the 4,6-position of dibenzo[a,c]phenazine, respectively. The experimental results reveal that the length of the flexible PEO coil chain influence construction of various supra-nanostructures from lamellar structure to rectangular columnar structure. It is also shown that introduction of different length of alkyl side chain groups in the backbone of the T-shaped molecules affect the self-organization behavior to form hexagonal perforate layer or oblique columnar structures. In addition, lateral methyl groups attached to the surface of rod and coil segments, dramatically influence the self-assembling behavior in the crystalline phase. T-shaped molecules containing a lateral methyl group at the surface of rod and PEO coil segments, self-assemble into 3D body-centered tetragonal structures in the crystalline phase, while molecules without a lateral methyl group based on PEO coil chain self-organize into 2D oblique columnar crystalline structures. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 5021–5028

We report the synthesis and self-assembly behavior of coil–rod–coil molecules. These molecules each consist of two biphenyl groups and an anthracene unit connected with ethynyl bonds at the 1,8-position of anthracene as a rod segment, with methoxy or octyl groups at the 10-position of anthracene, and poly(ethylene oxide) with degrees of polymerization of 12 and 17 linked to the biphenyls as coil segments. Structural investigation of these molecules by means of differential scanning calorimetry, polarized optical microscopy and X-ray diffraction in the bulk state reveals that these molecules self-assemble into lamellar structures in the solid state, while, in the liquid-crystalline phase, they self-organize into various columnar assemblies depending on the volume fraction of coil segments. Copyright © 2011 Society of Chemical Industry

The rod-coil molecules with n-shaped rod building block, consisting of an anthracene unit and two biphenyl groups linked together with acetylenyl bonds at the 1,8-position of anthracene as a rigid rod segment, and the alkyl or alkyloxy chains with various length (i.e., methoxy- (1), octyl- (2), hexadecyl- (3)) at the 10-position of anthracene and poly(ethylene oxide) with the number of repeating units of 7 connected with biphenyl as coil segments were synthesized. The molecular structures were characterized by ¹H NMR and MALDI-TOF mass spectroscopy. The self-assembling behavior of new type of molecules 1–3 was investigated by means of DSC, POM, and SAXS at the bulk state. These molecules with a n-shaped rod building block segment self-assemble into supramolecular structures through the combination of π–π stacking of rigid rod building blocks and microphase separation of the rod and coil blocks. SAXS studies reveal that molecules 1 and 2 show hexagonal columnar and rectangular columnar structures in the liquid crystalline phase, respectively; meanwhile, molecules 1–3 self-organize into lamellar structures in the crystalline state. In addition, self-assembling studies of molecules 1–3 by DLS and TEM indicated that these molecules self-assemble into elongated nanofibers in aqueous medium. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1415–1422, 2010