Bolaamphiphiles and monolayer lipid membranes made from 1,6,19,24-tetraoxa-3,21-cyclohexatriacontadiene-2,5,20,23-tetrone

Fuhrhop, Jürgen‐Hinrich; David, Hans Hermann; Mathieu, Joachim; Liman, Ulrich; Winter, H.-J.; Boekema, Egbert J.

doi:10.1021/ja00268a013

Cited by 145 publications

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“…We then newly designed and synthesized bola-form amphiphiles ("bolaamphiphile") 53 carrying sugar, peptide, and nucleobase moieties with potential multiple hydrogen bond functionalities as a hydrophilic group at both ends, which are separated by linear oligo(methylene) spacer as a hydrophobic moiety. 28 The linkage we mainly used between the hydrophobic and hydrophilic moieties is an amide linkage that is known to form a linear hydrogen bond chain.…”

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“…Since they have two hydrophilic headgroups separated by one or two hydrophobic spacers, (i) they exhibit no polymorphism as compared to amphiphiles with a single head and a single tail, (ii) they can form relatively thinner monolayers than bilayer membranes, (iii) they can produce spherical vesicles by incorporating the unsymmetrical hydrophilic headgroups, and (iv) the membrane fusion common to usual bilayer membranes hardly takes place. 53 These structural advantages of bolaamphiphilic monomers should increase the stability of the self-assembled membranes as compared to mono-head amphiphiles. By tuning the interlayer interaction based on the hydrogen bond networks between the hydrophilic headgroups, bolaamphiphiles can self-assemble to form supramolecular high-axialratio nanostructures including linear ribbons, helical ribbons, and tubular structures, depending on the molecular chirality, as shown in Figure 1.…”

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

Shimizu

2003

Polym J

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“…cis 42 tetradec-2-enedioic acid 14-benzyl ester, 8 5-methyl-2,2'-bipyridine [23][24][25] and (2-amino-ethyl)-carbamic acid tert-butyl ester 17 were prepared by literature methods. …”

Section: Methodsmentioning

confidence: 99%

Functionalisation of bolaamphiphiles with mononuclear bis(2,2′-bipyridyl)ruthenium(ii) complexes for application in self assembled monolayers

et al. 2003

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This submission was created using the RSC Article Template (DO NOT DELETE THIS TEXT) (LINE INCLUDED FOR SPACING ONLY -DO NOT DELETE THIS TEXT)A novel ruthenium(II) polypyridyl complex connected covalently to a bolaamphiphile, containing amide linkages to provide rigidity via hydrogen bonding in the monolayer, has been prepared. The ruthenium(II) complexes of this ligand and of the intermediates in the synthesis were prepared by modification of the coordinated ligands, demonstrating the synthetic versatility and robustness of this family of complexes. All ruthenium complexes were characterised by electrochemical and spectroscopic techniques and were found to have similar properties to the parent complex [Ru(bipy) 3 ] 2+, and remain versatile photosensitisers, with well-defined properties, despite extensive substitution of the bipy ligand.

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“…51 Bolaamphiphiles which consist of two hydrophilic groups connected via a hydrophobic spacer tend to form stable monolayer membranes. 52 Archaea species, microbes which are able to survive in harsh environments such as high temperatures or acidic conditions, contain bolaamphiphiles in their plasma membranes. Synthetic bolaamphiphiles with amide-linked head groups have been developed to increase the stability of bilayer membranes.…”

Section: Glycolipidsmentioning

confidence: 99%

Chiral Molecular Self‐Assembly

Spector¹,

Selinger²,

Schnur³

2003

Topics in Stereochemistry

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Bolaamphiphiles and monolayer lipid membranes made from 1,6,19,24-tetraoxa-3,21-cyclohexatriacontadiene-2,5,20,23-tetrone

Cited by 145 publications

References 0 publications

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

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

Functionalisation of bolaamphiphiles with mononuclear bis(2,2′-bipyridyl)ruthenium(ii) complexes for application in self assembled monolayers

Chiral Molecular Self‐Assembly

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