JP2008069086A - Synthesis of super-ultrafine hose having supermolecular structure - Google Patents
Synthesis of super-ultrafine hose having supermolecular structure Download PDFInfo
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Abstract
Description
本発明は超分子構造を有する超極細ホースの合成に関する。 The present invention relates to the synthesis of a superfine hose having a supramolecular structure.
従来、特許文献１開示の窒素含有基が互いに連結してマクロサイクルを形成した多座配位子が開示されている。また、特許文献２開示の中空構造を有する炭素繊維であって、その中空部に水等を内包する高分子が開示されている。さらにまた、特許文献３開示の機能性ナノ構造体が開示されている。
しかし、上記従来例には、オキサジアゾール基を骨格の一部とする（オキサジアゾール基の数は３〜４）マクロサイクル、このマクロサイクルが積層したナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤおよびこれらの製造方法、並びに、オキサジアゾール基を骨格の一部とするマクロサイクル（オキサジアゾール基の数は３〜４）が積層したナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤであって、ホース内に水分子を内包するナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤが開示されていない。 However, in the above conventional example, an oxadiazole group is part of the skeleton (the number of oxadiazole groups is 3 to 4), a macrocycle, and a nanohose (or nanotube-like) supermolecule in which the macrocycle is stacked Nanowires in which bundles of nanowires and production methods thereof, and macrocycles having oxadiazole groups as a part of the skeleton (number of oxadiazole groups is 3 to 4) are stacked in a nanohose shape (or nanotube shape) A nanowire in which supramolecules are bundled and a nanohose-like (or nanotube-like) supramolecule enclosing water molecules in a hose is not disclosed.
また、従来の代表的なナノチューブとしてカーボンナノチューブがあるが、これは、カーボンナノチューブが１分子からなっているためこれ以上分割することは、不可能であった。 Further, there is a carbon nanotube as a typical conventional nanotube. However, since the carbon nanotube is composed of one molecule, it is impossible to further divide it.
本発明は、オキサジアゾール基を骨格の一部とする新しいマクロサイクル（オキサジアゾール基の数は３〜４）の合成により、超分子構造を有する超極細ホースの合成を提供することを解決すべき課題としている。 The present invention solves the problem of providing a superfine hose having a supramolecular structure by synthesizing a new macrocycle (the number of oxadiazole groups is 3 to 4) having an oxadiazole group as a part of the skeleton. It is an issue that should be done.
第１発明は、オキサジアゾール基を骨格の一部とする（オキサジアゾール基の数は３〜４）マクロサイクル、このマクロサイクルが積層したナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤおよびこれらの製造方法である。この新規マクロサイクルは、超分子化機能を有しこれが積層してナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤを形成するのである。前記したように、従来のカーボンナノチューブが、１分子からなっているためこれ以上分割することは、不可能であるのに対し、本発明では、
超分子化機能を有しこれが積層しナノホース状（又はナノチューブ状）を形成するためチューブの構成成分に再分割することが可能である。
The first invention is a macrocycle having an oxadiazole group as a part of the skeleton (the number of oxadiazole groups is 3 to 4), and a nanohose-like (or nanotube-like) supermolecule in which the macrocycle is laminated. Nanowires and methods of manufacturing them. This new macrocycle has a supramolecularization function and is laminated to form a nanowire in which nanohose-like (or nanotube-like) supramolecules are bundled. As described above, since the conventional carbon nanotube is composed of one molecule, it is impossible to further divide it.
Since it has a supramolecularization function and is laminated to form a nanohose shape (or nanotube shape), it can be subdivided into the constituent components of the tube.
第２発明は、オキサジアゾール基を骨格の一部とするマクロサイクル（オキサジアゾール基の数は３〜４）が積層したナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤであって、ホース内に水分子を内包するナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤである。この新規マクロサイクルは、超分子化機能を有しこれが積層してナノホース状（又はナノチューブ状）の超分子が束となったナノワイヤは、水分子を内包しているのである。 The second invention is a nanowire in which nano-horse-like (or nanotube-like) supramolecules in which macrocycles (the number of oxadiazole groups is 3 to 4) having an oxadiazole group as a part of the skeleton are stacked. The nanowire is a bundle of nano-hose (or nanotube-like) supramolecules enclosing water molecules in the hose. This new macrocycle has a supramolecular function, and the nanowire in which nanohose-like (or nanotube-like) supramolecules are laminated to form a bundle contains water molecules.
以下、本発明を具体化した実施例１について図面を参照しつつ説明する。 Hereinafter, a first exemplary embodiment of the present invention will be described with reference to the drawings.
オキサジアゾールを有するマクロサイクルを次のように合成する。
5-tert-ブチルイソフタル酸(13.33 g, 60 mmol)とチオセミカルバジド(5.47 g, 60 mmol)をポリりん酸(180 g)に加え、メカニカルスタラーを使用して180 ℃で4時間かき混ぜた。これを室温付近まで放冷した後、氷水（300 mL）に注ぎ、１時間かき混ぜた。沈殿をハイフロスーパーセルでろ過し、固体を水とメタノールで洗浄した。これをアルミナクロマトグラフィー（溶出液：クロロホルム）で分離精製した。得られた固体は、オキサジアゾール基３および４個を有しているマクロサイクルの混合物であった。これを再結晶（溶媒クロロホルム/酢酸エチル=2:1）によって分離精製すると、オキサジアゾール基４個を含有するマクロサイクル(0.26 g, 収率2%)が得られた。これを昇華精製すると無水物が得られ、元素分析によって確認された。
ナノワイヤ(I) を次のように作製する。
マクロサイクル(2.5 mg)をクロロホルム(12.5 mL)に溶解し、酢酸エチル（12.5 mL）を注いだ。1時間室温で放置し、析出した固体を基板に分取した。これを乾燥したのち、走査型電子顕微鏡による観察を行ったところ、直径1 μm−100 nmの分子ワイヤーが観測された（図１）。元素分析の測定を行った結果、測定値C, 70.40; H, 6.02; N, 13.71%, 理論値（C48H48N8O4・H2O）C, 70.40; H, 6.15; N, 13.68%の分析結果が得られ、水分子を内包することが明らかになった。
ナノワイヤのＸ線結晶構造解析を次のように行った。
マクロサイクルをクロロホルム−メタノールの混合溶液に溶解し、再結晶を行った結果、0.18×0.05×0.05 mmの単結晶が得られた。これを-100 ℃でＸ線結晶構造解析を行った結果、図２のような分子配列を有するナノホース構造が観測された。このナノホースは水分子を内包しており、水分子は大きく振動している様子が明らかになった。さらに、このナノホースは自己集合して、図３に示すナノホースの束を形成していた。このナノホースの束は大きく成長し、図１のナノワイヤを構築したものと考えられる。このため、図３はナノワイヤの断面構造図と考えられる。
ナノワイヤ(II) を次のように作製する。
マクロサイクル(2.5 mg)をクロロホルム(12.5 mL)に溶解し、ヘキサン（12.5 mL）を注いだ。1時間室温で放置し、析出した固体を基板に分取した。これを乾燥したのち、走査型電子顕微鏡による観察を行った結果、直径500 nm−50 nmの分子ナノワイヤが観測された（図４）。
以上において、本発明を実施例１に即して説明したが、本発明は上記実施例１に制限されるものではなく、その趣旨を逸脱しない範囲で適宜変更して適用できることはいうまでもない。
A macrocycle with oxadiazole is synthesized as follows.
5-tert-butylisophthalic acid (13.33 g, 60 mmol) and thiosemicarbazide (5.47 g, 60 mmol) were added to polyphosphoric acid (180 g), and the mixture was stirred at 180 ° C. for 4 hours using a mechanical stirrer. This was allowed to cool to near room temperature, poured into ice water (300 mL), and stirred for 1 hour. The precipitate was filtered through Hyflo Supercell, and the solid was washed with water and methanol. This was separated and purified by alumina chromatography (eluent: chloroform). The resulting solid was a mixture of macrocycles having 3 and 4 oxadiazole groups. This was separated and purified by recrystallization (solvent chloroform / ethyl acetate = 2: 1) to obtain a macrocycle (0.26 g, yield 2%) containing 4 oxadiazole groups. This was purified by sublimation to obtain the anhydride, which was confirmed by elemental analysis.
Nanowire (I) is prepared as follows.
Macrocycle (2.5 mg) was dissolved in chloroform (12.5 mL), and ethyl acetate (12.5 mL) was poured. The mixture was allowed to stand at room temperature for 1 hour, and the precipitated solid was collected on a substrate. When this was dried and observed with a scanning electron microscope, molecular wires with a diameter of 1 μm-100 nm were observed (FIG. 1). As a result of measurement of elemental analysis, measured value C, 70.40; H, 6.02; N, 13.71%, theoretical value (C 48 H 48 N 8 O 4 · H 2 O) C, 70.40; H, 6.15; N, An analysis result of 13.68% was obtained, and it was revealed that water molecules were included.
The X-ray crystal structure analysis of the nanowire was performed as follows.
The macrocycle was dissolved in a mixed solution of chloroform-methanol and recrystallized. As a result, a single crystal of 0.18 × 0.05 × 0.05 mm was obtained. As a result of X-ray crystal structure analysis at −100 ° C., a nanohose structure having a molecular arrangement as shown in FIG. 2 was observed. This nanohose contained water molecules, and it became clear that the water molecules vibrated greatly. Furthermore, the nanohose self-assembled to form a bundle of nanohose shown in FIG. This bundle of nanohose grows greatly and is considered to have built the nanowire of FIG. Therefore, FIG. 3 is considered to be a cross-sectional structure diagram of the nanowire.
Nanowire (II) is prepared as follows.
Macrocycle (2.5 mg) was dissolved in chloroform (12.5 mL), and hexane (12.5 mL) was poured. The mixture was allowed to stand at room temperature for 1 hour, and the precipitated solid was collected on a substrate. After drying this, observation with a scanning electron microscope revealed that molecular nanowires having a diameter of 500 nm to 50 nm were observed (FIG. 4).
In the above, the present invention has been described with reference to the first embodiment. However, the present invention is not limited to the first embodiment, and it is needless to say that the present invention can be appropriately modified and applied without departing from the spirit of the present invention. .
本発明のホース状（又はチューブ状）の超分子は、分子導線として超小型ＬＳＩへの応用、分子ポンプとして人工毛管血管などの生体材料への応用、分子カプセルとしてドラッグデリバリー・システムへの応用などが考えられる。 The hose-like (or tube-like) supramolecules of the present invention can be applied to ultra-small LSIs as molecular conductors, applied to biomaterials such as artificial capillary blood vessels as molecular pumps, and applied to drug delivery systems as molecular capsules. Can be considered.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010061474A1 (en) * | 2008-11-28 | 2010-06-03 | 独立行政法人国立病院機構 西多賀病院 | Connecting magnetic element, connecting magnetic element manufacturing method, connecting magnetic element injecting device, connecting magnetic element injection control system, magnetic field control device, and connecting magnetic element injection control method |
| CN112974796A (en) * | 2021-02-07 | 2021-06-18 | 南京大学 | Composite structure of single silver nanowire and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010061474A1 (en) * | 2008-11-28 | 2010-06-03 | 独立行政法人国立病院機構 西多賀病院 | Connecting magnetic element, connecting magnetic element manufacturing method, connecting magnetic element injecting device, connecting magnetic element injection control system, magnetic field control device, and connecting magnetic element injection control method |
| CN112974796A (en) * | 2021-02-07 | 2021-06-18 | 南京大学 | Composite structure of single silver nanowire and preparation method and application thereof |
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