JP2004210578A - Nanofibrous boric acid, and production method therefor - Google Patents
Nanofibrous boric acid, and production method therefor Download PDFInfo
- Publication number
- JP2004210578A JP2004210578A JP2002380789A JP2002380789A JP2004210578A JP 2004210578 A JP2004210578 A JP 2004210578A JP 2002380789 A JP2002380789 A JP 2002380789A JP 2002380789 A JP2002380789 A JP 2002380789A JP 2004210578 A JP2004210578 A JP 2004210578A
- Authority
- JP
- Japan
- Prior art keywords
- boric acid
- nanofibrous
- trimethyl borate
- production method
- whiskers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、ナノファイバー状ホウ酸とその製造方法に関するものである。さらに詳しくは、この出願の発明は、変容しにくく、比較的安定なナノファイバー状ホウ酸とこれを簡便かつ大量に得ることのできる製造方法に関するものである。
【０００２】
【従来の技術】
炭素ナノチューブが発見されて以来、多くの一次元ナノスケール物質が合成されている。ナノチューブ構造の物質としては窒化ホウ素（ＢＮ）等、ナノロッド又はナノワイヤー構造の物質としては酸化マグネシウム（ＭｇＯ）、窒化ガリウム（ＧａＮ）等が合成されている。
【０００３】
ところで、ホウ素とその化合物は、強磁性体、超伝導材料、高強度材料、触媒、生物化学等の広範な分野に適用可能な優れた特性を有し、無機化学及び材料の開発においては重要な位置を占める物質である。その一つとしてのホウ酸は、たとえば滑剤（たとえば、非特許文献１参照）、抗菌剤（たとえば、非特許文献２参照）、癌細胞を選択的に破壊又は弱体化させることのできる医薬（たとえば、非特許文献３参照）等に広く応用されている。また、ホウ酸とその誘導体は、すべての動物組織に必要な構成成分であり、このことからホウ酸の潜在的価値が注目されている。
【０００４】
【非特許文献１】
ジャーナル・オブ・マテリアルズ・リサーチ（Ｊ． Ｍａｔｅｒ． Ｒｅｓ．），１９９９年，第１４巻，ｐ．３４５５
【非特許文献２】
アンナーレン・デア・ヘミー（Ａｎｎ． Ｃｈｅｍ．），１９９４年，第３巻，ｐ．２８３
【非特許文献３】
ジャーナル・オブ・ファーマシューティカル・アンド・バイオメディカル・アナリシス（Ｊ． Ｐｈａｒｍａｃｅｕｔ． Ｂｉｏｍｅｄ．），１９９８年，第１７巻，ｐ．４２７
【０００５】
【発明が解決しようとする課題】
しかしながら、ホウ酸とその誘導体に関し、変容しなく、安定した形態を有するナノスケール状の物質はこれまでに提供されていない。
【０００６】
この出願の発明は、このような事情に鑑みてなされたものであり、変容しにくく、比較的安定なナノファイバー状ホウ酸とこれを簡便かつ大量に得ることのできる製造方法を提供することを解決すべき課題としている。
【０００７】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、直径が数ｎｍ〜数十ｎｍの範囲にあるファイバー状の正ホウ酸（Ｂ（ＯＨ）３）であることを特徴とするナノファイバー状ホウ酸（請求項１）を提供する。
【０００８】
また、この出願の発明は、ホウ素酸化物（Ｂ２Ｏ３）とメタノール（ＭｅＯＨ）を反応させてエステル化させ、ホウ酸トリメチルを生成させた後、室温でホウ酸トリメチルの蒸気に蒸留水を噴霧し、加水分解させてホウ酸のウィスカーを生成させ、次いでそのウィスカーに希塩酸水溶液を噴霧して請求項１記載のナノファーバー状ホウ酸を得ることを特徴とするナノファイバー状ホウ酸の製造方法（請求項２）を提供する。
【０００９】
以下、実施例を示しつつ、この出願の発明のナノファイバー状ホウ酸とその製造方法についてさらに詳しく説明する。
【００１０】
【発明の実施の形態】
この出願の発明のナノファイバー状ホウ酸は、直径が数ｎｍ〜数十ｎｍの範囲にあるファイバー状の正ホウ酸（Ｂ（ＯＨ）３）である。このナノファイバー状ホウ酸は、極性の水素結合を持つため、強い相互作用を有する。したがって、形態保持力を有しており、比較的安定な物質である。
【００１１】
このようなナノファイバー状ホウ酸は、この出願の発明では、ホウ素酸化物（Ｂ２Ｏ３）とメタノール（ＭｅＯＨ）を反応させてエステル化させ、ホウ酸トリメチルを生成させた後、室温でホウ酸トリメチルの蒸気に蒸留水を噴霧し、加水分解させてホウ酸のウィスカーを生成させ、次いでそのウィスカーに希塩酸水溶液を噴霧することにより得られる。ナノファイバー状ホウ酸は、噴霧する希塩酸水溶液のｐＨを制御することにより、ミクロ導管、樹木状運動筋肉抹消、筋肉組織にそれぞれ類似した三種類の網状形態を有する。この場合の希塩酸水溶液のｐＨは、２．５〜４．５の範囲が好ましい。これにより、ホウ酸トリメチルの過度の加水分解が抑制される。
【００１２】
【実施例】
ホウ素酸化物（Ｂ２Ｏ３）１モルとメタノール（ＭｅＯＨ）５．７モルを反応させてエステル化させ、ホウ酸トリメチル（Ｂ（ＯＭＥ）３）を生成させた。このホウ酸トリメチルを蓋を取り付けていない反応容器に入れ、室温２７℃、湿度５０％の条件でホウ酸トリメチルの揮発蒸気に蒸留水を噴霧し、加水分解させ、ホウ酸のウィスカーを得た。そして、このウィスカーに０．０５モルの希塩酸水溶液を噴霧した。その結果、図１に示したようなマッシュルーム状の集合体が生成した。Ｘ線回折の結果、生成物は正ホウ酸（Ｂ（ＯＨ）３）であることが確認された。操作型電子顕微鏡を用いた観察により、生成物は、直径数ｎｍ〜数十ｎｍの範囲にあるファイバー状であることが確認された。得られたこのナノファイバー状ホウ酸は、極性の水素結合を持っているため、強い相互作用があり、したがって、形態保持力を有し、比較的安定な物質である。
【００１３】
ナノファイバー状ホウ酸は、噴霧する希塩酸水溶液のｐＨにより大別して三種類の網状形態を有する。一つは、図２（ａ）に示したミクロ導管に類似した形態であり、これは、希塩酸水溶液のｐＨが２．８程度で得られた。もう一つは、図２（ｂ）に示した樹木状運動筋肉抹消に類似した形態であり、希塩酸水溶液のｐＨが３．２程度で得られた。残る一つは、図２（ｃ）に示した筋肉組織に類似した形態であり、希塩酸水溶液のｐＨが３．４程度で得られた。
【００１４】
なお、容器内のホウ酸トリメチルには、少量の塩化アルミニウム（ＡｌＣｌ３）を添加することにより容器内の加水分解が抑制された。
【００１５】
もちろん、この出願の発明は、以上の実施形態及び実施例によって限定されるものではない。細部については様々な態様が可能であることはいうまでもない。
【００１６】
【発明の効果】
以上詳しく説明した通り、この出願の発明によって、変容しにくく、安定なナノファイバー状ホウ酸とこれを簡便かつ大量に得ることのできる製造方法が提供される。
【図面の簡単な説明】
【図１】実施例で得られたマッシュルーム状の集合体を示した写真である。
【図２】（ａ）（ｂ）（ｃ）は、それぞれ、ナノファイバー状ホウ酸の網状形態を示した透過型電子顕微鏡（ＴＥＭ）像である。[0001]
TECHNICAL FIELD OF THE INVENTION
The invention of this application relates to a nanofiber boric acid and a method for producing the same. More specifically, the invention of this application relates to a relatively stable nanofibrous boric acid which is hardly transformed and a method for producing the same, which can be obtained easily and in large quantities.
[0002]
[Prior art]
Since the discovery of carbon nanotubes, many one-dimensional nanoscale materials have been synthesized. As a material having a nanotube structure, boron nitride (BN) or the like is synthesized, and as a material having a nanorod or nanowire structure, magnesium oxide (MgO), gallium nitride (GaN), or the like is synthesized.
[0003]
By the way, boron and its compounds have excellent properties applicable to a wide range of fields such as ferromagnetic materials, superconducting materials, high-strength materials, catalysts, and biochemistry, and are important in inorganic chemistry and material development. It is a substance that occupies a position. Boric acid as one of them is, for example, a lubricant (for example, see Non-Patent Document 1), an antibacterial agent (for example, see Non-Patent Document 2), a drug capable of selectively destroying or weakening cancer cells (for example, , Non-Patent Document 3) and the like. Further, boric acid and its derivatives are necessary components for all animal tissues, and thus the potential value of boric acid has been attracting attention.
[0004]
[Non-patent document 1]
Journal of Materials Research (J. Mater. Res.), 1999, Vol. 14, p. 3455
[Non-patent document 2]
Annalen der Chemie (Ann. Chem.), 1994, Volume 3, p. 283
[Non-Patent Document 3]
Journal of Pharmaceutical and Biomedical Analysis (J. Pharmaceut. Biomed.), 1998, Vol. 17, p. 427
[0005]
[Problems to be solved by the invention]
However, regarding boric acid and its derivatives, a nanoscale-like substance having a stable and stable morphology has not been provided so far.
[0006]
The invention of this application has been made in view of such circumstances, and it is an object of the present invention to provide a nanofiber boric acid which is hard to change and is relatively stable, and a method for producing the same, which can be obtained easily and in large quantities. It is an issue to be solved.
[0007]
[Means for Solving the Problems]
The invention of this application solves the above-mentioned problem, and is characterized in that it is a fiber-like regular boric acid (B (OH) 3 ) having a diameter in a range of several nm to several tens nm. Boric acid (claim 1) is provided.
[0008]
In addition, the invention of this application is to react ester of boron oxide (B 2 O 3 ) with methanol (MeOH) to form trimethyl borate, and then distill distilled water into trimethyl borate vapor at room temperature. Spraying and hydrolyzing to form boric acid whiskers, and then spraying a dilute hydrochloric acid aqueous solution on the whiskers to obtain the nanofiber boric acid according to claim 1, wherein the method is a method for producing nanofibrous boric acid. (Claim 2) is provided.
[0009]
Hereinafter, the nanofibrous boric acid of the invention of the present application and a method for producing the same will be described in more detail with reference to examples.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The nanofibrous boric acid of the invention of this application is fiber-shaped positive boric acid (B (OH) 3 ) having a diameter ranging from several nm to several tens of nm. This nanofibrous boric acid has a strong interaction because it has polar hydrogen bonds. Therefore, it is a relatively stable substance having shape retention.
[0011]
In the invention of this application, such nanofibrous boric acid is esterified by reacting boron oxide (B 2 O 3 ) with methanol (MeOH) to form trimethyl borate, and then borate at room temperature. It is obtained by spraying distilled water onto the vapor of trimethyl acid, hydrolyzing it to form whiskers of boric acid, and then spraying the whiskers with a dilute aqueous hydrochloric acid solution. The nanofibrous boric acid has three types of reticulated morphologies similar to microconduit, dendritic musculoskeletal muscle, and muscle tissue by controlling the pH of the diluted hydrochloric acid aqueous solution to be sprayed. In this case, the pH of the diluted hydrochloric acid aqueous solution is preferably in the range of 2.5 to 4.5. This suppresses excessive hydrolysis of trimethyl borate.
[0012]
【Example】
1 mol of boron oxide (B 2 O 3 ) was reacted with 5.7 mol of methanol (MeOH) to perform esterification, thereby producing trimethyl borate (B (OME) 3 ). The trimethyl borate was placed in a reaction vessel without a lid, and distilled water was sprayed on the volatile vapor of trimethyl borate at room temperature of 27 ° C. and a humidity of 50% to hydrolyze to obtain whiskers of boric acid. Then, the whiskers were sprayed with a 0.05 molar diluted hydrochloric acid aqueous solution. As a result, a mushroom-like aggregate as shown in FIG. 1 was generated. As a result of X-ray diffraction, it was confirmed that the product was normal boric acid (B (OH) 3 ). Observation using an operating electron microscope confirmed that the product was in the form of a fiber having a diameter ranging from several nm to several tens nm. Since the obtained nanofibrous boric acid has a polar hydrogen bond, it has a strong interaction, and therefore has a shape-retaining power and is a relatively stable substance.
[0013]
The nanofiber-like boric acid has three types of net forms roughly classified according to the pH of the diluted hydrochloric acid aqueous solution to be sprayed. One is a form similar to the microconduit shown in FIG. 2 (a), which was obtained when the pH of the dilute hydrochloric acid aqueous solution was about 2.8. The other is a form similar to the dendritic motor muscle elimination shown in FIG. 2 (b), and was obtained when the pH of the diluted hydrochloric acid aqueous solution was about 3.2. The other one has a form similar to the muscle tissue shown in FIG. 2 (c), and was obtained when the pH of the dilute hydrochloric acid aqueous solution was about 3.4.
[0014]
The hydrolysis in the container was suppressed by adding a small amount of aluminum chloride (AlCl 3 ) to the trimethyl borate in the container.
[0015]
Of course, the invention of this application is not limited by the above embodiments and examples. It goes without saying that various aspects are possible for the details.
[0016]
【The invention's effect】
As described in detail above, the invention of this application provides a stable nanofiber-like boric acid which is hard to be transformed and a method for producing the same, which can be obtained easily and in large quantities.
[Brief description of the drawings]
FIG. 1 is a photograph showing a mushroom-like aggregate obtained in an example.
FIGS. 2 (a), (b), and (c) are transmission electron microscope (TEM) images showing the reticulated morphology of boric acid in the form of nanofibers.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002380789A JP3890409B2 (en) | 2002-12-27 | 2002-12-27 | Aggregates of nanofibrous boric acid and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002380789A JP3890409B2 (en) | 2002-12-27 | 2002-12-27 | Aggregates of nanofibrous boric acid and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004210578A true JP2004210578A (en) | 2004-07-29 |
| JP3890409B2 JP3890409B2 (en) | 2007-03-07 |
Family
ID=32816915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002380789A Expired - Lifetime JP3890409B2 (en) | 2002-12-27 | 2002-12-27 | Aggregates of nanofibrous boric acid and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3890409B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007521664A (en) * | 2003-12-11 | 2007-08-02 | イエール ユニバーシティ | Growth of boron nanostructures with controlled diameter |
| CN103130235A (en) * | 2013-03-22 | 2013-06-05 | 天津大学 | Method for preparing boron-10 acid through boron trifluoride-10 one-step method |
-
2002
- 2002-12-27 JP JP2002380789A patent/JP3890409B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007521664A (en) * | 2003-12-11 | 2007-08-02 | イエール ユニバーシティ | Growth of boron nanostructures with controlled diameter |
| CN103130235A (en) * | 2013-03-22 | 2013-06-05 | 天津大学 | Method for preparing boron-10 acid through boron trifluoride-10 one-step method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3890409B2 (en) | 2007-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | A mild and efficient biomimetic synthesis of rodlike hydroxyapatite particles with a high aspect ratio using polyvinylpyrrolidone as capping agent | |
| Zhang et al. | Morphologically controlled synthesis of hydroxyapatite with partial substitution of fluorine | |
| Minus et al. | Single wall carbon nanotube templated oriented crystallization of poly (vinyl alcohol) | |
| Kajbafvala et al. | Nanostructure sword-like ZnO wires: rapid synthesis and characterization through a microwave-assisted route | |
| Darroudi et al. | Biopolymer-assisted green synthesis and characterization of calcium hydroxide nanoparticles | |
| Sun et al. | Monodisperse selenium-substituted hydroxyapatite: Controllable synthesis and biocompatibility | |
| WO2002072930A1 (en) | Metallic nanowire and process for producing the same | |
| Wang et al. | Amorphous calcium carbonate stabilized by a flexible biomimetic polymer inspired by marine mussels | |
| Ding et al. | In-situ generation of chitosan/hydroxyapatite composite microspheres for biomedical application | |
| Chook et al. | Antibacterial hybrid cellulose–graphene oxide nanocomposite immobilized with silver nanoparticles | |
| Uyar et al. | Electrospun polyethylene oxide (PEO) nanofibers containing cyclodextrin inclusion complex | |
| Shtansky et al. | Recent progress in fabrication and application of BN nanostructures and BN-based nanohybrids | |
| Chen et al. | Rapid synthesis of hollow nano-structured hydroxyapatite microspheres via microwave transformation method using hollow CaCO3 precursor microspheres | |
| Zhao et al. | Crystallization control of CaCO3 by ionic liquids in aqueous solution | |
| Ma et al. | Delicate assembly of ultrathin hydroxyapatite nanobelts with nanoneedles directed by dissolved cellulose | |
| Joy et al. | Polycaprolactone/graphene oxide–silver nanocomposite: a multifunctional agent for biomedical applications | |
| CN102874820A (en) | Method for preparing cellular silicon dioxide nanotubes | |
| Qian et al. | Controlled synthesis of light rare-earth hydroxide nanorods via a simple solution route | |
| Lee et al. | Redox-active tyrosine-mediated peptide template for large-scale single-crystalline two-dimensional silver nanosheets | |
| Li et al. | Controllable growth of ZnO nanowhiskers by a simple solution route | |
| JP2004210578A (en) | Nanofibrous boric acid, and production method therefor | |
| Baby et al. | Enhanced luminescence of silver nanoparticles decorated on hydrothermally synthesized exfoliated MoS2 nanosheets | |
| CN102351532B (en) | Preparation method of ZrO2-Al2O3 composite ceramics | |
| Joy et al. | Facile synthesis of visible region luminescent silver decorated graphene oxide nanohybrid for biomedical applications: in combination with DFT calculations | |
| Li et al. | A novel hydrothermal route to the synthesis of xonotlite nanofibers and investigation on their bioactivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060425 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060801 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060919 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20061107 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3890409 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |