A Novel Preparative Method of Silica Nanotubes by Utilizing Self-assembly and Disassembly of Peptide Amphiphiles

Shimada, Toshio; Tamura, Yasuhiro; Tirrell, Matthew; Kuroda, Kazuyuki

doi:10.1246/cl.2012.95

Cited by 5 publications

(4 citation statements)

References 19 publications

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“…Assembly and disassembly of another (PA)-system, where the (PA) self-assembled into worm-like micelles, was demonstrated to be useful in the preparation of silica nanotubes. 27,28 However, even though the studies with (PA) shed light on the formation and morphology of 1D structures, our study differs from them in the sense that our peptide has no surface-active behavior.…”

Section: Introductionmentioning

confidence: 75%

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Peptide nanotube formation: a crystal growth process

et al. 2012

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Above its critical aggregation concentration the tfa salt of the peptide A 6 K self-assembles into micron long, hollow nanotubes with uniform diameters of 52 nm and crystalline order. Here we combine the use of SAXS with cryoTEM and cryo-electron tomography (cryoET, 3D cryoTEM) to study the formation process of the 2D crystalline A 6 K nanotubes. This study reveals that the formation of these tubes in fact is a crystal growth process, involving different mechanisms depending on the conditions used. Inorganic crystals have been demonstrated to form not only through ion-by-ion addition but also through non-classical mechanisms including oriented attachment. Here we show an organic crystalline material that can form through molecule-by-molecule growth as well as through oriented attachment. We discuss the mechanisms in relation to the supersaturation levels of the peptide solutions and the molecular interactions between the peptide molecules in the tubular assemblies. The proposed mechanisms are supported by semi-empirical molecular orbital calculations and time resolved dissolution experiments.

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Section: Introductionmentioning

confidence: 75%

“…Single molecules which have a radius of gyration of $0.44 nm (ref. 28) are below the cryoTEM detection limit. Surprisingly, under these conditions sheet-like fragments were observed already after 15 min, and in this case no fibrous aggregates were observed (Fig.…”

Section: Nanotube Formation After Temperature Assisted Dissolutionmentioning

confidence: 94%

Peptide nanotube formation: a crystal growth process

et al. 2012

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“…Peptide surfactants can self-assemble into micelles, vesicles and a wide array of high-aspect-ratio nanostructures, such as nanobers, nanotapes, helical ribbons and tubules, with specic biological applications. [11][12][13][14][15][16][17][18][19][20] These attractive features of peptide surfactants are inherently related to hydrogen bonding between peptide sequences and hydrophobic interactions between alkyl chains. Therefore, variations in these factors can dramatically affect the aggregation behavior of peptide surfactants.…”

Section: Introductionmentioning

confidence: 99%

Aggregation behavior of a gemini surfactant with a tripeptide spacer

2015

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A peptide gemini surfactant, 12-G(NH2)LG(NH2)-12, has been constructed with two dodecyl chains separately attached to the two terminals of a glutamic acid-lysine-glutamic acid peptide and the aggregation behavior of the surfactant was studied in aqueous solution. The 12-G(NH2)LG(NH2)-12 molecules form fiber-like precipitates around pH 7.0, and the precipitation range is widened on increasing the concentration. At pHs 3.0 and 11.0, 12-G(NH2)LG(NH2)-12 forms soluble aggregates because each molecule carries two positively charged amino groups at the two ends of the peptide spacer at pH 3.0, while each molecule carries one negatively charged carboxyl group in the middle of the peptide spacer at pH 11.0. 12-G(NH2)LG(NH2)-12 displays a similar concentration-dependent process at these two pHs: forming small micelles above the critical micelle concentration and transferring to fibers at pH 3.0 or twisted ribbons at pH 11.0 above the second critical concentration. The fibers formed at pH 3.0 tend to aggregate into bundles with twisted structure. Both the twisted fibers at pH 3.0 and the twisted ribbons at pH 11.0 contain β-sheet structure formed by the peptide spacer.

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“…Therefore, a number of strategies to design self-assembled organic aggregates has been developed in order to make these organic matrices work as templates/scaffolds/catalysts for a deposition of silica at ambient conditions [ 20 ]. Recently, self-assembled fibrils of polypeptides [ 21 – 29 ] or amine-modified polysaccharides [ 30 ] have been used as template for the formation of silica nanotubes. For example, Yuwono et al [ 23 ] reported the use of peptide-amphiphile nanofiber templates in order to direct the synthesis of hollow silica nanotubes with outer diameters of 15–23 nm.…”

Section: Introductionmentioning

confidence: 99%

Controlled synthesis and tunable properties of ultrathin silica nanotubes through spontaneous polycondensation on polyamine fibrils

Yuan

Zhu

Noda

et al. 2013

Beilstein J. Nanotechnol.

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SummaryThis paper describes a facile approach to a biomimetic rapid fabrication of ultrathin silica nanotubes with a highly uniform diameter of 10 nm and inner hollow of around 3 nm. The synthesis is carried out through a spontaneous polycondensation of alkoxysilane on polyamine crystalline fibrils that were conveniently produced from the neutralization of a solution of protonated linear polyethyleneimine (LPEI–H+) by alkali compounds. A simple mixing the fibrils with alkoxysilane in aqueous solution allowed for the rapid formation of silica to produce LPEI@silica hybrid nanotubes. These 10-nm nanotubes were hierarchically organized in a mat-like morphology with a typical size of 1–2 micrometers. The subsequent removal of organic LPEI via calcination resulted in silica nanotubes that keep this morphology. The morphology, the structure, the pore properties and the formation mechanism of the silica nanotubes were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller measurements (BET), and X-ray diffraction (XRD). Detailed studies demonstrated that the formation of the nanotubes depends on the molar ratio of [OH]/[CH2CH2NH] during the neutralization as well as on the basicity of the alkali compound and on the concentration of the silica source. The synthesis of silica nanotubes established here could be easily applied to a fabrication on the kilogram scale. Silica nanotubes that were obtained from the calcination of hybrid nanotubes of LPEI@silica in an N2 atmosphere showed a distinct photoluminescence centered at 540 nm with a maximum excitation wavelength of 320 nm. Furthermore, LPEI@silica hybrid nanotubes were applied to create silica–carbon composite nanotubes by alternative adsorption of ionic polymers and subsequent carbonization.

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A Novel Preparative Method of Silica Nanotubes by Utilizing Self-assembly and Disassembly of Peptide Amphiphiles

Cited by 5 publications

References 19 publications

Peptide nanotube formation: a crystal growth process

Peptide nanotube formation: a crystal growth process

Aggregation behavior of a gemini surfactant with a tripeptide spacer

Controlled synthesis and tunable properties of ultrathin silica nanotubes through spontaneous polycondensation on polyamine fibrils

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