Self-Assembling Structures of Long-Chain Phenyl Glucoside Influenced by the Introduction of Double Bonds

Jung, Jong Hwa; John, George; Yoshida, Kaname; Shimizu, Toshimi

doi:10.1021/ja020752o

Cited by 128 publications

(115 citation statements)

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“…In the literature, some key chemical groups seem to promote chirality in glycolipids at the nanoscale. As shown in Table 2, non-bola compounds (e.g., samples 1 to 4) need an interaction-promoting (hydrogen bonding, π-π stacking) 63,64 linker (phenyl, phenylamide, amidopyridine) rather than specific saturation/unsaturation ratios. For instance, ether linkers only promote micelles but never lead to the formation of fibers (compound N°7 in Table 2).…”

Section: Discussionmentioning

confidence: 99%

pH-triggered formation of nanoribbons from yeast-derived glycolipid biosurfactants

et al. 2014

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International audienceIn the present paper, we show that the saturated form of acidic sophorolipids, a family of industrially scaled bolaform microbial glycolipids, unexpectedly forms chiral nanofibers only at pH below 7.5. In particular, we illustrate that this phenomenon derives from a subtle cooperative effect of molecular chirality, hydrogen bonding, van der Waals forces and steric hindrance. The pH-responsive behaviour was shown by Dynamic Light Scattering (DLS), pH-titration and Field Emission Scanning Electron Microscopy (FE-SEM) while the nanoscale chirality was evidenced by Circular Dichroism (CD) and cryo Transmission Electron Microscopy (cryo-TEM). The packing of sophorolipids within the ribbons was studied using Small Angle Neutron Scattering (SANS), Wide Angle X-ray Scattering (WAXS) and 2D H-1-H-1 through-space correlations via Nuclear Magnetic Resonance under very fast (67 kHz) Magic Angle Spinning (MAS-NMR)

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Section: Discussionmentioning

confidence: 99%

pH-triggered formation of nanoribbons from yeast-derived glycolipid biosurfactants

et al. 2014

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“…Furthermore, the recently developed, selfassembled nanotube structures from synthetic glycolipids 171 proved to be the final expression of molecular chirality at supramolecular level 172 since coiled helical ribbon structures as an intermediate finally transform into tubular structures (not mentioned). Organic selfassembled HARNs are, thus, now greatly contributing to the exploitation of quite novel nanostructures with well-controlled morphologies, [173][174][175][176] inorganic building blocks, 177,178 and diverse functionalities. 179 …”

Section: Discussionmentioning

confidence: 99%

Bottom-Up Synthesis and Morphological Control of High-Axial-Ratio Nanostructures through Molecular Self-Assembly

Shimizu

2003

Polym J

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ABSTRACT:Based on our recent results, the present paper overviews noncovalent formation of high-axial-ratio nanostructures (HARNs), such as fibers, rods, tubes and ropes, through molecular self-assembly of bola-form amphiphilic (bolaamphiphilic) monomers. A variety of bolaamphiphiles, in which sugars, peptides, or nucleobases as headgroups are connected to both ends of a hydrocarbon spacer, were newly designed and synthesized. Their self-assembling behavior was examined in aqueous solutions in terms of bottom-up fabrication of organic nanostructures. The morphologies proved to strongly depend on the headgroup structure, spacer chain lengths and even-odd carbon numbers of used oligo(methylene) spacers. Typical examples of self-assembled morphologies include nanofibers from 1-glucosamide-or thymidine-appended bolaamphiphiles, vesicle-encapsulated microtubes from glycylglycine-appended bolaamphiphiles, double-helical ropes from thymine-appended bolaamphiphiles. These self-assembled HARNs are constructed hierarchically in a manner similar to biological structures. On the basis of several solid-state analyses, molecular packing and orientation within the HARNs are discussed and compared with the single crystal structures in terms of hydrogen-bond networks. Furthermore, pH-dependent reversible polymer formation was achieved using the combination of glucuronamideand aromatic boronic acid-appended bola-form derivatives. Polymerization of bola-form 1-glucosamide derivatives with a 1,4-butadiyne group was performed in self-assembled nanometer-sized fibers, giving a single polydiacetylene chain of 64-mer that can be seen in TEM.KEY WORDS High-Axial-Ratio Nanostructure (HARN) / Bolaamphiphile / Self-Assembly / Noncovalent Synthesis / Hydrogen Bond / Nanofiber / Microtube / Nano-Rod / Rope / Hydrogel / Crystal Structure / Biomaterials possess highly organized non-covalent structures formed spontaneously in bottom-up fashion, 1 shaping natural body and functioning as energyconverting and information-converting materials. In contrast, conventional polymers are so-called linear macromolecules in which tens of thousands to millions of low-molecular-weight monomer units are connected to each other through covalent bonds. Very recently, a new family of polymers, including topologically complex polymers 2-13, 18-25 and self-assembled nanostructures, [14][15][16][17]26 has attracted much attention. 27,28 In particular, Kunitake and his co-worker built up the fundamental concept behind the polymolecular materials based on bilayer-containing molecular assemblies. 29,30 Stupp et al., 31, 32 Percec et al., 33 and Whitesides et al. 34,35 also succeeded in a molecule-up fabrication using polymer building blocks to realize nanometersized assemblies with well-defined shapes. The advantage of non-covalent self-assembly technique, unlike chemical reaction or polymerization, is in that it can directly produce ordered two-and three-dimensional structures like sheets, rods, fibers, tubes, disks, and spheres. It is more important that nanostruct...

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“…All the chemicals were of analytical grade and were used as received. The molecular structure of NCT was determined by 1 H and 13 C NMR (Vega-300 Varian Inc, USA) and FT-IR (Nicolet 380 FT-IR) spectroscopic techniques. NMR experiments were done on a Vega-600 Varian spectrometer using the WATERGATE program (Varian Inc. USA).…”

Section: Methodsmentioning

confidence: 99%

Adhesive Vesicles through Adaptive Response of a Biobased Surfactant

et al. 2010

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Adaptive response in functional systems of nature is best exemplified by the homeostasis (homeoviscous alterations) or the tropism observed in flora and fauna. The term "homeoviscous alteration" describes the process whereby the fluidity of the membrane is adjusted in response to a perturbation such as temperature, pressure, etc. [1,2] Most of the natural lipids utilize their characteristic unsaturations as a tool to execute such elegant processes. The biophysical properties of the membranes thus depend on the subtle adjustments in the structure and composition of the alkyl chains that are attached to glycerol backbones. [3] Chilling sensitivity in plants is the direct repercussion of the membrane dynamics in plants that involves conformational changes and variations in unsaturation component of the lipid membranes.[4] Deciphering the stimuli-responsive character in such biological systems not only sheds light on the underlying mechanism in the race for survival of the fittest, but also provides clues to generate unique functional materials in the laboratory. Amphiphilic molecules rich in unsaturations in their side chain are expected to display such interesting phenomena and provide vistas for new soft materials.[5] Taking cue from this, we designed an amphiphile from a naturally available raw material-cardanol-that possesses structural features akin to natural lipidic systems.Cardanol is a biobased non-isoprene lipid obtained from cashew nut shell liquid (CNSL). It consists of a rich mixture of phenolic lipids: 5 % of 3-(pentadecyl)phenol, 49 % of 3-(8Z-pentadecenyl)phenol, 17 % of 3-(8Z,11Z-pentadecadienyl)-phenol and 29 % of 3-(8Z,11Z,14-pentadecatrienyl)phenol. [6] The unique feature of cardanol is that it contains 1) lipid chains with varying degree of allylic cis double bonds, 2) alkyl chains with odd numbers of carbon atoms, 3) a reactive phenolic group in the meta position for further functionalization, and 4) saturated/unsaturated versions of hydrocarbon chains. Hence one can envision an amphiphilic building block from cardanol, which show a stimuli-responsive behavior that could be utilized to reconfigure them into functional architectures. Herein, we report vesicle formation and vesicular adhesion from a biobased surfactant, N-cardanyl tauramide (NCT), obtained by the judicious combination of cardanol as the hydrophobic part and taurine (a vital aminosulfonic acid) as the hydrophilic head group. The molecular structure of NCT is shown in Figure 1 c.NCT behaved as a surfactant in aqueous solution with a critical micelle concentration (CMC) of 1.2 mm at 25 8C. Typically, when a 5 mm micellar solution was warmed to 55 8C and annealed, the solution transformed into a viscous phase at 45 8C with a restricted flow. Upon reaching room temperature, the solution resumed back to the micellar phase. Interestingly, the viscous phase appeared elastic and could be pulled into a "wet string" (Figure 1 d). In order to understand this behavior, we performed a cryo-TEM analysis of the sample at 45 8C in the cooling ...

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Self-Assembling Structures of Long-Chain Phenyl Glucoside Influenced by the Introduction of Double Bonds

Cited by 128 publications

References 21 publications

pH-triggered formation of nanoribbons from yeast-derived glycolipid biosurfactants

pH-triggered formation of nanoribbons from yeast-derived glycolipid biosurfactants

Bottom-Up Synthesis and Morphological Control of High-Axial-Ratio Nanostructures through Molecular Self-Assembly

Adhesive Vesicles through Adaptive Response of a Biobased Surfactant

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