JP5565726B2 - Carbon nanotubes provided with polyamino acid and method for producing the same - Google Patents
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本発明は水中での分散性に優れた、ポリアミノ酸が施与されたカーボンナノチューブおよびその製造方法に関する。 The present invention relates to a carbon nanotube provided with a polyamino acid and excellent in dispersibility in water, and a method for producing the same.
黒鉛面が円筒の形状をなすカーボンナノチューブ（以下「ＣＮＴ」という）は、新しい機能材料として、様々な分野で近年注目されている。特にＣＮＴの表面は、化学的に不活性であり、かつ物理的な吸着を起こすという特性が注目されている。例えば、核酸、タンパク質等の生体物質の機能を損なうことなくＣＮＴの表面上に固定することができれば、バイオセンサー、診断機器、ドラッグデリバリー、微生物、動物細胞培養などのバイオテクノロジー分野における、核酸、タンパク質等の生体物質に対する良好な担体として応用することが期待されている。 Carbon nanotubes having a graphite surface in the shape of a cylinder (hereinafter referred to as “CNT”) have recently attracted attention in various fields as new functional materials. Particularly, the surface of CNT has been attracting attention because it is chemically inert and causes physical adsorption. For example, if it can be immobilized on the surface of CNT without impairing the function of biological materials such as nucleic acids and proteins, nucleic acids and proteins in biotechnology fields such as biosensors, diagnostic equipment, drug delivery, microorganisms, and animal cell culture It is expected to be applied as a good carrier for biological substances such as
しかしながら、ＣＮＴ自体は疎水性であるために、生体物質を施与するのに最適な環境である水中での分散性が著しく悪いという特性が問題となる。これまでにＣＮＴの水中の分散性を改善するために、超音波処理によるＣＮＴ分散法（特許文献１）、ＤＮＡなどの生体物質（特許文献２）、高分子化合物（特許文献３〜５）、又は界面活性剤などの化学物質（特許文献６〜１１）を分散剤として用いる方法が研究されてきた。 However, since CNT itself is hydrophobic, there is a problem that the dispersibility in water, which is an optimum environment for applying biological substances, is extremely poor. In order to improve the dispersibility of CNT in water so far, a CNT dispersion method by ultrasonic treatment (Patent Document 1), a biological material such as DNA (Patent Document 2), a polymer compound (Patent Documents 3 to 5), Alternatively, methods using chemical substances such as surfactants (Patent Documents 6 to 11) as dispersants have been studied.
しかしながら、超音波処理によるＣＮＴ分散法は、時間経過と共にＣＮＴの再集合が起こるという欠点がある。また、ＤＮＡ等の生体物質によるＣＮＴ分散法は、使用する生体物質の純度が一定せず、またＤＮａｓｅ等の分解酵素によって分解されるなどの欠点がある。さらに、高分子化合物および界面活性剤については、酵素反応、分子間相互作用等の生化学的な反応の阻害剤として作用する懸念がある。 However, the CNT dispersion method using ultrasonic treatment has a drawback in that CNT reassembly occurs over time. In addition, the CNT dispersion method using a biological material such as DNA has drawbacks such that the purity of the biological material used is not constant and is degraded by a degrading enzyme such as DNase. Furthermore, there is a concern that polymer compounds and surfactants act as inhibitors of biochemical reactions such as enzyme reactions and intermolecular interactions.
そこで、本発明は、化学的に安定で、酵素反応等の生化学的な反応の阻害剤として作用せず、かつ安定な分散性を有するＣＮＴおよびその製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a CNT that is chemically stable, does not act as an inhibitor of a biochemical reaction such as an enzyme reaction, and has a stable dispersibility, and a method for producing the same.
本発明者等は、上述の課題を解決するために、種々の分散剤を鋭意検討した。その結果、本発明者等は、ポリアミノ酸類、特にポリチロシンとポリトリプトファンがＣＮＴの分散性を著しく向上させることを見出した。
すなわち、本発明は、ポリアミノ酸が施与されたＣＮＴおよびその製造方法を提供する。
In order to solve the above-described problems, the present inventors have intensively studied various dispersants. As a result, the present inventors have found that polyamino acids, particularly polytyrosine and polytryptophan, remarkably improve the dispersibility of CNTs.
That is, the present invention provides a CNT provided with a polyamino acid and a method for producing the same.
本発明のポリアミノ酸が施与されたＣＮＴは、従来の分散剤が施与されたＣＮＴに比べて、化学的に安定であり、かつ、生化学的な反応を阻害することなく、長期にわたる安定な分散性を有することから、バイオテクノロジー分野での利用に好適である。 The CNTs to which the polyamino acid of the present invention is applied are chemically stable and stable over a long period of time without inhibiting biochemical reactions, compared to CNTs to which conventional dispersants have been applied. Therefore, it is suitable for use in the biotechnology field.
以下に、本発明を説明する。 The present invention is described below.
本発明のポリアミノ酸が施与されたＣＮＴは、透過型電子顕微鏡などの電子顕微鏡を用いて、表面上にポリアミノ酸が存在することが確認できる。図１は、本発明のポリアミノ酸が施与されたＣＮＴの走査型プローブ顕微鏡の写真を示す。 The CNTs to which the polyamino acid of the present invention has been applied can be confirmed to be present on the surface using an electron microscope such as a transmission electron microscope. FIG. 1 shows a photograph of a scanning probe microscope of CNT to which the polyamino acid of the present invention has been applied.
図１の写真から、ポリチロシンはＳＷＣＮＴに覆うように吸着していることが確認できた。ＣＮＴはその表面が疎水性であるため、ポリアミノ酸を疎水性相互作用、および／またはπ電子スタッキングなどの相互作用様式で吸着しているものと考えられる。 From the photograph in FIG. 1, it was confirmed that polytyrosine was adsorbed so as to cover SWCNTs. Since the surface of CNT is hydrophobic, it is considered that polyamino acids are adsorbed in an interaction mode such as hydrophobic interaction and / or π-electron stacking.
本発明のポリアミノ酸が施与されたＣＮＴは、水中での分散性（以下これを単に「分散性」と称することがある）に優れる。該分散性は、６００ｎｍにおける濁度を測定することにより判定することができる。一実施例では、ポリチロシンが施与されたＳＷＮＴは、蒸留水中で、室温で１ヶ月間以上、初期の分散状態を維持した。 The CNT to which the polyamino acid of the present invention is applied is excellent in dispersibility in water (hereinafter, this may be simply referred to as “dispersibility”). The dispersibility can be determined by measuring the turbidity at 600 nm. In one example, SWNTs to which polytyrosine was applied maintained their initial dispersion in distilled water for more than a month at room temperature.
また、本発明のポリアミノ酸が施与されたカーボンナノチューブは、
（１）カーボンナノチューブ水分散液およびポリアミノ酸水溶液をそれぞれ個別に調製するステップと、
（２）該カーボンナノチューブ水分散液と該ポリアミノ酸水溶液とを混合して、カーボンナノチューブをポリアミノ酸により処理するステップと、
（３）カーボンナノチューブ−ポリアミノ酸混合液を遠心分離して、カーボンナノチューブを回収するステップ
とを含む方法により調製することができる。
In addition, the carbon nanotubes to which the polyamino acid of the present invention is applied,
(1) individually preparing a carbon nanotube aqueous dispersion and a polyamino acid aqueous solution,
(2) mixing the carbon nanotube aqueous dispersion and the polyamino acid aqueous solution, and treating the carbon nanotubes with the polyamino acid;
(3) Centrifugating the carbon nanotube-polyamino acid mixture to recover the carbon nanotubes.
上記ポリアミノ酸としては、例えば、ポリロイシン、ポリリシン、ポリセリン、ポリフェニルアラニン、ポリチロシン、及びポリトリプトファン等が挙げられ、これらの混合物であってもよい。好ましくは、ポリチロシン、及びポリトリプトファンが使用される。 Examples of the polyamino acid include polyleucine, polylysine, polyserine, polyphenylalanine, polytyrosine, and polytryptophan, and may be a mixture thereof. Preferably, polytyrosine and polytryptophan are used.
該ポリアミノ酸の分子量は、後述する可溶化処理を行うことができれば特に制限はないが、１０００〜５００００Ｄａの範囲が好ましく、より好ましくは１２０００〜３５０００Ｄａの範囲である。 The molecular weight of the polyamino acid is not particularly limited as long as the solubilization treatment described later can be performed, but is preferably in the range of 1000 to 50000 Da, more preferably in the range of 12000 to 35000 Da.
本発明のポリアミノ酸が施与されたＣＮＴに用いるＣＮＴ類としては、単層ＣＮＴ（ＳＷＣＮＴ）、二層ＣＮＴ（ＤＷＣＮＴ）、複層ＣＮＴ（ＭＷＣＮＴ）のいずれであってもよい。 The CNTs used for the CNT to which the polyamino acid of the present invention is applied may be any of single-wall CNT (SWCNT), double-wall CNT (DWCNT), and multi-wall CNT (MWCNT).
該ＣＮＴの長さは、約１〜１５μｍが好ましく、より好ましくは約５〜１５μｍである。該ＣＮＴの直径は、約０．５〜２ｎｍであることが好ましい。市販されているものは凝集体を形成している場合が多いので、好ましくは、メノウ乳鉢等で細かくした後、処理に付する。 The length of the CNT is preferably about 1 to 15 μm, more preferably about 5 to 15 μm. The diameter of the CNT is preferably about 0.5 to 2 nm. Since what is marketed often forms aggregates, it is preferably subjected to treatment after being made fine with an agate mortar or the like.
本発明において、使用する水としては、特に限定はされないが、蒸留水、脱イオン水、滅菌水、超純水等を使用できる。 In the present invention, the water to be used is not particularly limited, but distilled water, deionized water, sterilized water, ultrapure water, and the like can be used.
ＣＮＴの水分散液は、ＣＮＴと水とを０．０１：１００〜１０：１００の重量比で混合した後、公知の分散手段、例えば超音波により分散して調製することができる。 The aqueous dispersion of CNTs can be prepared by mixing CNTs and water in a weight ratio of 0.01: 100 to 10: 100, and then dispersing them by a known dispersing means such as ultrasonic waves.
また、ポリアミノ酸としてはポリロイシン、ポリセリン、ポリフェニルアラニン、ポリチロシン、ポリトリプトファン等を使用することができる。これらのポリアミノ酸は水難溶性であるので、それぞれのポリアミノ酸の性質に適し、かつ本発明の目的に沿った各種の可溶化処理を行う。一例として、ポリチロシン（分子量１２０００〜３５０００）の可溶化処理には、０．００５〜０．０５Ｍの水酸化カリウム溶液を用いる。 Moreover, polyleucine, polyserine, polyphenylalanine, polytyrosine, polytryptophan, etc. can be used as a polyamino acid. Since these polyamino acids are sparingly soluble in water, various solubilization treatments are performed in accordance with the properties of each polyamino acid and in accordance with the object of the present invention. As an example, a 0.005-0.05M potassium hydroxide solution is used for the solubilization treatment of polytyrosine (molecular weight 12000-35000).
ステップ（２）における混合液は、ポリアミノ酸とＣＮＴの重量混合比が、０．１：１〜５：１、好ましくは０．５:１〜２:１、より好ましくは１．５:１〜２:１となるような比で、ＣＮＴ水分散液とポリアミノ酸水溶液とを混合して調製する。 The mixed solution in step (2) has a polyamino acid / CNT weight mixing ratio of 0.1: 1 to 5: 1, preferably 0.5: 1 to 2: 1, more preferably 1.5: 1. It is prepared by mixing a CNT aqueous dispersion and an aqueous polyamino acid solution at a ratio of 2: 1.
ステップ（２）における処理は、例えば、混合液を振とうすることにより行うことができる。該処理の温度は、２０〜９０℃の範囲であり、２５〜３０℃が好ましい。また、該処理の時間は０．２５〜３時間、好ましくは０．８〜１時間行う。 The process in step (2) can be performed, for example, by shaking the mixed solution. The temperature of the treatment is in the range of 20 to 90 ° C, and preferably 25 to 30 ° C. The treatment time is 0.25 to 3 hours, preferably 0.8 to 1 hour.
上記のカーボンナノチューブを回収するステップの後に、遠心分離等でカーボンナノチューブを洗浄するステップを含むことが好ましい。該洗浄は、蒸留水等で行う。該洗浄するステップの回数に制限はないが、１〜５回行えば十分である。 It is preferable to include a step of washing the carbon nanotubes by centrifugation or the like after the step of collecting the carbon nanotubes. The washing is performed with distilled water or the like. Although there is no restriction | limiting in the frequency | count of this washing | cleaning step, it is enough to perform 1-5 times.
本発明のさらなる詳細を、以下の非限定的な実施例により説明する。 Further details of the invention are illustrated by the following non-limiting examples.
［実施例１］ＳＷＣＮＴ及びポリチロシンの調製
Ｓｈｅｎｚｈｅｎ Ｎａｎｏｔｅｃｈ Ｐｏｒｔ Ｃｏ.,Ｌｔｄ.より購入したＳＷＣＮＴ（長さ約５〜１５μｍ、直径約＜２ｎｍ）をメノウ乳鉢でよくすりつぶした後、１ｍｇ／ｍｌとなるように蒸留水で調製し、８時間超音波処理（Ｗ−１１３ Ｕｌｔｒａｓｏｎｉｃ ｍｕｌｔｉｃｌｅａｎｅｒ、ＨＯＮＤＡ社製）を行った。また、ポリチロシンは、１２０００〜３５０００ＤａのＭＰ Ｂｉｏｍｅｄｉｃａｌｓ ＬＬＣ社製を使用し、０．０２５ＭのＫＯＨに溶解して、１ｍｇ／ｍｌポリチロシン溶液を調製した。
[Example 1] Preparation of SWCNT and polytyrosine SWCNT purchased from Shenzhen Nanotech Port Co., Ltd. (length of about 5 to 15 μm, diameter of about <2 nm) is well ground in an agate mortar to 1 mg / ml In this way, it was prepared with distilled water and subjected to ultrasonic treatment (W-113 Ultrasonic multi-layer, manufactured by HONDA) for 8 hours. Polytyrosine used was 12000-35000 Da manufactured by MP Biomedicals LLC, and dissolved in 0.025 M KOH to prepare a 1 mg / ml polytyrosine solution.
［実施例２］ポリチロシンが施与されたＳＷＣＮＴの作製
２０μｌの超音波処理した１ｍｇ／ｍｌ ＳＷＣＮＴ、３０μｌのポリチロシン溶液、５０μｌの蒸留水を混合し、３０℃で１時間、１２００ｒｐｍで振とうした。ＳＷＣＮＴを４℃、１５０００ｒｐｍで３０分遠心分離した後、上清を除去した。残った沈殿層に滅菌水を１００μｌ加え、ボルテックスミキサー（Ｓｃｉｅｎｔｉｆｉｃ Ｉｎｄｕｓｔｒｉｅｓ Ｖｏｒｔｅｘ-ｇｅｎｅ２）で５〜１０秒程度攪拌した後、再度４℃、１５０００ｒｐｍで３０分間遠心分離した。この操作を５回繰り返して、ポリチロシンが施与されたＳＷＣＮＴを調製した。
[Example 2] Preparation of SWCNTs to which polytyrosine was applied 20 μl of ultrasonically treated 1 mg / ml SWCNT, 30 μl of polytyrosine solution and 50 μl of distilled water were mixed and shaken at 30 ° C. for 1 hour at 1200 rpm. did. After SWCNT was centrifuged at 4 ° C. and 15000 rpm for 30 minutes, the supernatant was removed. 100 μl of sterilized water was added to the remaining precipitate layer, and the mixture was stirred for 5 to 10 seconds with a vortex mixer (Scientific Industries Vortex-gene 2), and then centrifuged again at 4 ° C. and 15000 rpm for 30 minutes. This operation was repeated 5 times to prepare SWCNT to which polytyrosine was applied.
得られたポリチロシンが施与されたＳＷＣＮＴを蒸留水に懸濁後、室温で１ヶ月静置した。図３に示すように、ポリチロシンが施与されていないＳＷＣＮＴと比較して、ポリチロシンが施与されたＳＷＣＮＴは著しく良好な分散性を有していた。 The obtained SWCNTs coated with polytyrosine were suspended in distilled water and allowed to stand at room temperature for 1 month. As shown in FIG. 3, the SWCNTs to which polytyrosine was applied had remarkably good dispersibility as compared to SWCNTs to which polytyrosine was not applied.
［比較例１］ＴｒｉｔｏｎＸ−１００が施与されたＳＷＣＮＴの作製
ポリチロシン溶液に代えて０．１重量％ ＴｒｉｔｏｎＸ‐１００溶液を用いたことを除き、実施例２と同様にＳＷＣＮＴを処理した。
[Comparative Example 1] Preparation of SWCNT to which Triton X-100 was applied SWCNT was treated in the same manner as in Example 2 except that a 0.1 wt% Triton X-100 solution was used instead of the polytyrosine solution.
［比較例２］サケ***二本鎖ＤＮＡが施与されたＳＷＣＮＴの作製
ポリチロシン溶液に代えて、超音波処理した０．５ｍｇ／ｍｌ サケ***二本鎖ＤＮＡ水溶液を用いたことを除き、実施例２と同様にＳＷＣＮＴを処理した。
[Comparative Example 2] Preparation of SWCNT to which salmon sperm double-stranded DNA was applied Except that a 0.5 mg / ml salmon sperm double-stranded DNA aqueous solution treated with ultrasonic waves was used instead of the polytyrosine solution. SWCNTs were treated as in Example 2.
［実施例３］ ポリチロシンが施与されたＳＷＣＮＴの分散状態の安定性
実施例１で得られたポリチロシンが施与されたＳＷＣＮＴの分散状態の安定性を、分光光度計（Ｕ‐２００１，Ｓｐｅｃｔｒｏｍｅｔｅｒ，ＨＩＴＡＴＩ社製）を用いて、６００ｎｍにおける濁度を測定することにより、検討した。濁度の測定は、静置時間毎（０時間、１時間、１日、７日、１４日）に行った。
[Example 3] Stability of dispersed state of SWCNT applied with polytyrosine The stability of dispersed state of SWCNT applied with polytyrosine obtained in Example 1 was measured with a spectrophotometer (U-2001). It was examined by measuring the turbidity at 600 nm using Spectrometer (manufactured by HITATI). The turbidity was measured every stationary time (0 hour, 1 hour, 1 day, 7 days, 14 days).
結果を図４に示す。比較対照として、０．０２Ｍ ＫＯＨまたは蒸留水にそれぞれ分散させたＳＷＣＮＴを用いた。ポリチロシンが施与されたＳＷＣＮＴは、ＴｒｉｔｏｎＸ−１００が施与されたＳＷＣＮＴ、および超音波処理したサケ***二本鎖ＤＮＡが施与されたＳＷＣＮＴとほぼ同等の分散性を有することが確認できた。 The results are shown in FIG. As a comparative control, SWCNT dispersed in 0.02M KOH or distilled water was used. It was confirmed that the SWCNTs applied with polytyrosine had almost the same dispersibility as SWCNTs applied with Triton X-100 and SWCNTs applied with sonicated salmon sperm double-stranded DNA. .
本発明のポリアミノ酸が施与されたＣＮＴは、化学的に安定であり、かつ、生化学的な反応を阻害することなく、長期にわたる安定な分散性を有するため、バイオテクノロジー分野での利用に好適である。 The CNTs to which the polyamino acid of the present invention has been applied are chemically stable and have a long-term stable dispersibility without inhibiting biochemical reactions, so that they can be used in the biotechnology field. Is preferred.
Claims (10)
前記ポリアミノ酸がポリチロシンおよびポリトリプトファンからなる群より選択され、
蒸留水に懸濁させて静置した場合に１日以上分散状態を維持することを特徴とする
カーボンナノチューブ。 A carbon nanotube provided with a polyamino acid ,
The polyamino acid is selected from the group consisting of polytyrosine and polytryptophan;
When dispersed in distilled water and allowed to stand, the dispersion state is maintained for one day or longer.
Carbon nanotube .
（２）前記カーボンナノチューブ水分散液と前記ポリアミノ酸水溶液とを混合して、カーボンナノチューブをポリアミノ酸により処理するステップと、
（３）カーボンナノチューブ−ポリアミノ酸混合液を遠心分離して、カーボンナノチューブを回収するステップ
とを含む、ポリアミノ酸が施与されたカーボンナノチューブの製造方法であって、
前記ポリアミノ酸はポリチロシンおよびポリトリプトファンからなる群より選択され、
前記ポリアミノ酸水溶液は、０．００５〜０．０５Ｍの水酸化カリウム水溶液に前記ポリアミノ酸を溶解することにより調製される
製造方法。 (1) individually preparing a carbon nanotube aqueous dispersion and a polyamino acid aqueous solution,
(2) mixing the carbon nanotube aqueous dispersion and the polyamino acid aqueous solution, and treating the carbon nanotubes with the polyamino acid;
(3) centrifuging the carbon nanotube-polyamino acid mixture to recover the carbon nanotubes, and a method for producing the carbon nanotubes to which the polyamino acid has been applied ,
The polyamino acid is selected from the group consisting of polytyrosine and polytryptophan;
The polyamino acid aqueous solution is prepared by dissolving the polyamino acid in a 0.005-0.05M potassium hydroxide aqueous solution.
Manufacturing method .
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