Synthesis of Helical Polymers by Polycondensation of Diboronic Acid and Chiral Tetrols

Mikami, Masafumi; Shinkai, Seiji

doi:10.1246/cl.1995.603

Cited by 26 publications

(17 citation statements)

References 10 publications

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“…30 Boronate-based systems have been recognized as one of the most promising approaches towards this end. Since they were first reported by S. Shinkai et al, 31 these related linear polymers have been widely developed. 32 The current trend is to build hierarchical supramolecular polymers where multiple kinds of intermolecular interactions, both in the polymeric backbone and those oriented orthogonally, combine to form 3D aggregates.…”

Section: Supramolecular Polymersmentioning

confidence: 98%

Hierarchical supramolecules and organization using boronic acid building blocks

2015

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Current progress on hierarchical supramolecules using boronic acids has been highlighted in this feature article. Boronic acids can participate in "click reactions" with diols and their congeners with dynamic covalent functionality. By comprehensively exploring versatile sequential boronate esterification linkages between plural boronic acid-appended molecules and multiple hydroxyl counterparts, not only versatile supramolecular polymers but also structurally well-defined network nanostructures have been developed. In addition orthogonal interactions such as dative bonds of the boron center with Lewis bases have led to the formation of hierarchical nano/microstructures. Boronate systems have the potential to be used as materials for smart gels, chemosensors, active architectures for electronics, heterogeneous catalysts, chemical-stimulus responsive systems for drug delivery, etc. Here, we fully discuss the feasibility of the structure-directing ability of boronic acids from the standpoint of the generation of new smart materials.

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Section: Supramolecular Polymersmentioning

confidence: 98%

Hierarchical supramolecules and organization using boronic acid building blocks

2015

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“…Shinkai and co-workers constructed a boronic acid linear polymer by polycondensation of a diboronic acid and chiral tetraol. 91 Spectroscopic studies and theoretical calculations established that the polymeric structures possess a DNA-like helical structure (Scheme 42).…”

Section: Polymeric 1d Structuresmentioning

confidence: 99%

Boronic acid building blocks: tools for self assembly

et al. 2011

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Dynamic covalent functionality has been acknowledged as a powerful tool for the construction of organised architectures, the reversible nature thermodynamically facilitates self-control and self-correction. The use of boronic acids complexation with diols and their congeners has already shown great promise in realising and developing reversible boron-containing multicomponent systems with dynamic covalent functionality. The structure-directing potential has lead to the development of a variety of self-organisation involving not only macrocycles, cages and capsules, but also porous covalent organic frameworks and polymers. Structure controls as well as remarkable synthesis are highlighted in this feature article.

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“…[81][82][83] Mikami and Shinkai first achieved the synthesis of main-chain sugar-containing polymers through self-condensation with diboronic acid under nonaqueous conditions. 84,85 Based on our continued interest in sugar-based bolaamphiphiles, we have newly synthesized glucuronamideappended bolaamphiphiles 6(n) possessing free 1,2-diols available for ester formation with a bola-form aromatic boronic acid derivative. In order to confirm linear complex formation between the glucuronamideand boronic acid-appended bola-form derivatives, we employed 11 B NMR spectroscopy since it is very sensitive to the spin state of the boron atom, such as neutral sp 2 , anionic sp 3 , and coordinated sp 3 states.…”

Section: Ph-dependent Reversible Polymer Formation From Bola-form Dermentioning

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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Synthesis of Helical Polymers by Polycondensation of Diboronic Acid and Chiral Tetrols

Abstract: Polymers containing sugar units in the main chain were synthesized by polycondensation of diboronic acid and C2-symmetrical chiral tetrols. Spectroscopic studies and theoretical calculations established that they possess a DNA-like helical structure.

Cited by 26 publications

References 10 publications

Hierarchical supramolecules and organization using boronic acid building blocks

Hierarchical supramolecules and organization using boronic acid building blocks

Boronic acid building blocks: tools for self assembly

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

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