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JPS62221467A - Method for preparing purple membrane-containing membrane - Google Patents

Method for preparing purple membrane-containing membrane

Info

Publication number
JPS62221467A
JPS62221467A JP6300086A JP6300086A JPS62221467A JP S62221467 A JPS62221467 A JP S62221467A JP 6300086 A JP6300086 A JP 6300086A JP 6300086 A JP6300086 A JP 6300086A JP S62221467 A JPS62221467 A JP S62221467A
Authority
JP
Japan
Prior art keywords
purple
substrate
membrane
acrylamide
coupling agent
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
Application number
JP6300086A
Other languages
Japanese (ja)
Other versions
JPH0586273B2 (en
Inventor
Tatsuo Sora
曽良 達生
Hideatsu Maeda
前田 秀篤
Tsukasa Sakai
坂井 士
Keishiro Tsuda
津田 圭四郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Agency of Industrial Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agency of Industrial Science and Technology filed Critical Agency of Industrial Science and Technology
Priority to JP6300086A priority Critical patent/JPS62221467A/en
Publication of JPS62221467A publication Critical patent/JPS62221467A/en
Publication of JPH0586273B2 publication Critical patent/JPH0586273B2/ja
Granted legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

PURPOSE:To efficiently form a highly homogenous membrane layer, by treating the surface of a substrate with a coupling agent and forming a purple membrane-containing membrane layer due to the polymerization of acrylamide to the treated surface. CONSTITUTION:A purple membrane is the one isolated from Halobacterium halobium being one kind of halophil and contains bacteriorhodopsin being chromoprotein and is dissolved in an aqueous solution containing 5-15wt% of acrylamide to obtain a desired acrylamide solution. A substrate such as a glass substrate, an ITO electrode substrate or a metal plate is treated with a silane coupling agent and acrylamide is polymerized while the acrylamide solution containing the purple membrane is contacted with the surface of the surface treated substrate to form a homogenous membrane layer of a purple membrane-containing acrylamide gel.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は紫膜含有薄膜を製造するための新規な方法に関
するものである。さらに詳しくいえば。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a new method for producing purple film-containing thin films. In more detail.

本発明は、光応答機能を有するバイオ素子として有用な
、優れた均質性含有する紫膜含有薄膜の層をガラス、金
属などの基板上に効率よく形成させる方法に関するもの
である。
The present invention relates to a method for efficiently forming a purple membrane-containing thin film layer with excellent homogeneity on a substrate such as glass or metal, which is useful as a biodevice having a photoresponsive function.

従来の技術 最近、シリコンを利用した電子素子1例えば超LSIな
どの微細加工技術に限界が見えはじめ、また素子自体に
も物理的な限界が予想されていることから1分子レベル
で素子を組み立てようとする分子電子素子の概念が提案
され、これに伴って。
Conventional technology Recently, the limits of microfabrication technology for electronic devices using silicon 1, such as ultra-LSI, have begun to appear, and the physical limits of the devices themselves are expected, so we are trying to assemble devices at the single molecule level. Along with this, the concept of molecular electronic devices was proposed.

タンパク質や脂質、神経細胞などの生体物質を見習った
新しい素子、いわゆるバイオ素子の研究が積極的に行わ
れるようになった。このバイオ素子は信号の伝達や加工
などを分子レベルで行えるため、10  μm以下の大
きさの素子が可能といわれている。
Research into new devices that imitate biological materials such as proteins, lipids, and nerve cells, so-called bio-devices, has begun to be actively conducted. Since this biodevice can perform signal transmission and processing at the molecular level, it is said that it is possible to create a device with a size of 10 μm or less.

ところで、高度好塩菌の1種である・・ロバクテリウム
・ハロビウム(Halobacterium halo
bi−um)から見出された紫膜は色素タンパク質のバ
クテリオロドプシンを含み、特殊な光応答機能をMする
ところから、バイオ素子として1例えば元スイッチング
素子やメモリー素子などとしての利用が期待されており
、現在その利用研究が盛んに行われている。
By the way, one type of highly halophilic bacterium...Halobacterium halo
Since the purple membrane discovered from the bioluminescence membrane contains the pigment protein bacteriorhodopsin and has a special light-responsive function, it is expected to be used as a biodevice, such as a switching element or a memory element. Currently, research on its use is actively being conducted.

この紫膜をデバイス化するために、ガラスのような基板
上に、これを薄膜状に積層する必要があるが、これまで
、紫膜を含む薄膜層を基板上に形成させる方法としては
1例えば(1)紫膜含有懸濁液を用いるキャスト法、(
2)電着法、(3)遠心力を利用する方法などが知られ
ている。これらの方法のうち、キャスト法は比較的簡単
に行うことができ、また電着法や遠心力を利用する方法
は紫膜の配向薄膜が得られる点で有利であるが、いずれ
の方法も光応答機能を有するバイオ素子として利用する
場合、得られる薄膜層の均質性が不十分であるという欠
点を有している。
In order to make this purple film into a device, it is necessary to laminate it in the form of a thin film on a substrate such as glass. To date, there have been only 1 methods for forming a thin film layer containing the purple film on a substrate, for example. (1) Casting method using a purple membrane-containing suspension (
2) Electrodeposition method, (3) method using centrifugal force, etc. are known. Among these methods, the casting method is relatively easy to perform, and the electrodeposition method and the method using centrifugal force are advantageous in that they can produce an oriented thin film of purple film, but neither method is sensitive to light. When used as a biodevice having a response function, the resulting thin film layer has insufficient homogeneity.

発明が解決しようとする問題点 本発明の目的は、このような従来の方法がMする問題を
解決し、光応答機能を有するバイオ素子として有用な優
れた均質性をMする紫膜含有薄膜の層をガラスなどの基
板上に効率よく形成させる方法を提供することにある。
Problems to be Solved by the Invention The purpose of the present invention is to solve the problems of the conventional methods and to develop a thin film containing a violet membrane that has excellent homogeneity and is useful as a biodevice having a photoresponsive function. An object of the present invention is to provide a method for efficiently forming a layer on a substrate such as glass.

問題点全解決するための手段 本発明者らは、鋭意研究を重ねた結果、基板の表面をカ
ップリング剤で処理し、この表面にアクリルアミドの重
合反応を利用して、紫膜含有薄膜層を形成させることに
より、その目的を達成しうろことを見出し、この知見に
基づいて本発明を完成するに至った。
Means to Solve All Problems As a result of extensive research, the present inventors treated the surface of the substrate with a coupling agent, and created a thin film layer containing a purple film on this surface by utilizing the polymerization reaction of acrylamide. The inventors have found that the object can be achieved by forming such a structure, and have completed the present invention based on this knowledge.

すなわち、本発明は、好塩菌より単離した紫膜を含有す
るアクリルアミド溶液に、あらかじめカップリング剤で
表面処理した基板を接触させ、次いでアクリルアミドの
重合条件にもたらすことにより前記基板表面に紫膜含有
ポリアクリルアミドゲル層を形成させることを特徴とす
る紫膜含有薄膜の製造方法を提供するものである。
That is, in the present invention, a purple film is formed on the surface of the substrate by contacting a substrate whose surface has been previously treated with a coupling agent with an acrylamide solution containing a purple film isolated from a halophilic bacterium, and then bringing the substrate to polymerization conditions for acrylamide. The present invention provides a method for producing a thin film containing purple membrane, which comprises forming a polyacrylamide-containing gel layer.

本発明方法で用いる紫膜は、高度好塩菌の1種であるハ
ロバクテリウム・ハロビウム(Haloba−cter
ium halobium )から単離されたものであ
って1色素タンパク質のバクテリオロドプシンを含有し
ている。このバクテリオロドプシンは色素のビタミンA
とタンパク質とが結合したものであり、ビタミンA単独
では380 nm近辺にある吸収帯カ、タンパク質との
結合によってオプンンシフトを受け、570 nm近辺
にシフトしたものである。
The purple membrane used in the method of the present invention is produced by Halobacterium halobium, a type of highly halophilic bacterium.
halobium) and contains one chromoprotein, bacteriorhodopsin. This bacteriorhodopsin is the pigment vitamin A
Vitamin A alone has an absorption band around 380 nm, which undergoes an open shift due to binding with protein and is shifted to around 570 nm.

したがって、タンパク質とビタミンAとの相互作用様式
を変化させることにより、色変化を生じさせることがで
きる。この相互作用様式を変化させるには、例えばタン
パク質の熱変性が有効に用いられる。
Therefore, by changing the interaction mode between protein and vitamin A, a color change can be caused. To change this interaction mode, for example, thermal denaturation of proteins can be effectively used.

本発明方法においては、基板としてガラス基板やITO
電極板、  5n02電極板などの透明基板、あるいは
金属板やプラスチック板などが用いられる。
In the method of the present invention, a glass substrate or an ITO substrate is used as the substrate.
An electrode plate, a transparent substrate such as a 5n02 electrode plate, a metal plate, a plastic plate, etc. are used.

また、これらの基板の表面処理に用いられるカップリン
グ剤としては、シラン系、チタネート系、アルミニウム
系などのカップリング剤があるが、特にガラス基板につ
いてはこれらの中でシラン系カップリング剤が好適であ
る。この上うなシラン系カップリング剤としては、例え
ばビニルトリクロルシラン、ビニルトリメトキシシラン
、ビニルトリス(2−メトキシエトキシ)シラン、ビニ
ルトリアセトキシシラン、γ−メタクリルオキシプロピ
ルトリメトキシシランなどが挙げられる。
In addition, coupling agents used for surface treatment of these substrates include silane-based, titanate-based, and aluminum-based coupling agents, among which silane-based coupling agents are particularly suitable for glass substrates. It is. Examples of such silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, and γ-methacryloxypropyltrimethoxysilane.

基板表面のカップリング剤による処理は1例えば所望の
カップリング剤を溶剤に溶解し、この溶液中に基板を浸
せきしたのち、該基板に付着する溶剤を蒸発させ、次い
で加熱乾燥することにょシ行われる。
The treatment of the substrate surface with a coupling agent is carried out by, for example, dissolving the desired coupling agent in a solvent, immersing the substrate in this solution, evaporating the solvent adhering to the substrate, and then heating and drying. be exposed.

本発明方法においては、このようにしてカップリング剤
で表面処理した基板表面に、紫膜を含有するアクリルア
ミド溶液を接触させながら、該アクリルアミド之重合さ
せることにより、該基板表面に紫膜含有ポリアクリルア
ミドゲルの薄膜層全形成させる。この際用いられる前記
紫膜を含有すルアクリルアミド溶液は、アクリルアばド
ラ、5〜15重量係の範囲で含有する水溶液中に紫膜を
溶解させることによって調製することができる。
In the method of the present invention, the acrylamide solution containing a purple film is brought into contact with the substrate surface treated with a coupling agent in this way, and the acrylamide is polymerized, thereby forming a polyacrylamide containing a purple film on the substrate surface. A thin layer of gel is formed. The acrylamide solution containing the purple membrane used in this case can be prepared by dissolving the purple membrane in an aqueous solution containing acrylic abadola in a range of 5 to 15 weight percent.

紫膜の濃度については特に制限はなく広範囲に選択可能
である。この場合、媒質としては必要に応じ酢酸緩衝液
のような緩衝液を用いることもできる。
The concentration of the purple membrane is not particularly limited and can be selected from a wide range. In this case, a buffer such as an acetate buffer can be used as the medium, if necessary.

基板表面に前記紫膜を含有するアクリルアミドモノマー
溶液を接触させる方法については特に制限はないが、例
えば該基板とアクリル樹脂などの樹脂板とでセルを作成
し、これに該アクリルアミド浴液を注入するといった方
法を用いることができる。
There are no particular restrictions on the method of bringing the acrylamide monomer solution containing the purple film into contact with the substrate surface, but for example, a cell is created with the substrate and a resin plate such as an acrylic resin, and the acrylamide bath liquid is injected into this cell. A method such as this can be used.

アクリルアミドの重合は、従来性われている方法と同様
に、過硫酸アンモニウムのようなラジカル発生剤やりポ
フラビンのような光ラジカル発生剤などによって開始さ
れ、通常は室温で行われる。
Polymerization of acrylamide is initiated by a radical generator such as ammonium persulfate or a photoradical generator such as poflavin, as in conventional methods, and is usually carried out at room temperature.

このようにして製造した紫膜含有ポリアクリルアミドゲ
ルは、カップリング剤により強固に基板表面に結合して
いるので、該基板をそのまま水洗して未重合モノマーな
どの低分子物質を除去し、次いで乾燥することにより、
該基板上に紫膜含有ポリアクリルアミドゲルの薄膜層を
形成させることができる。
The purple film-containing polyacrylamide gel produced in this way is firmly bonded to the substrate surface by the coupling agent, so the substrate is washed with water to remove low molecular substances such as unpolymerized monomers, and then dried. By doing so,
A thin layer of purple film-containing polyacrylamide gel can be formed on the substrate.

このような方法によって基板上に形成された紫膜含有ポ
リアクリルアミドゲルの薄膜層は透明な紫色を示し、均
質性も良好であり、これに1例えばアルゴンイオンレー
ザ−やヘリウムイオンレーザ−などのレーザー光を照射
すると、紫膜中の色素タンパク質バクテリオロドプシン
のタンパク質が熱変性を起こし、照射部位のみが紫色か
ら黄色に変化する。
The thin layer of purple-containing polyacrylamide gel formed on the substrate by this method exhibits a transparent purple color and has good homogeneity. When irradiated with light, the pigment protein bacteriorhodopsin in the purple membrane undergoes thermal denaturation, and only the irradiated area changes from purple to yellow.

このようにして、紫膜含有薄膜層上に記録したレーザー
照射スポットは、通常の環境下では長時間安定である。
In this way, the laser irradiation spot recorded on the purple film-containing thin film layer is stable for a long time under normal circumstances.

実施例 次に実施例によって本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.

例 好塩菌より紫膜ヲ、「プレパラテイプ・バイオケミスト
リー(Preparative Biochem、  
) J第5巻、第161〜171ページ(1975年)
に記載されている方法に従って単離した。
For example, from halophilic bacteria to purple membrane, ``Preparative Biochemistry''.
) J Vol. 5, pp. 161-171 (1975)
It was isolated according to the method described in .

一万、シラン系カップリング剤のγ−メタクリルオキシ
プロピルトリメトキシシラン2.0重機チを含有するエ
タノール溶液中に% 50X50X1m11のガラス基
板を浸せきし、風乾したのち、乾燥器中で50℃、10
分間加熱乾燥した。
A glass substrate of 50 x 50 x 1 m was immersed in an ethanol solution containing 2.0% of γ-methacryloxypropyltrimethoxysilane, a silane coupling agent, and air-dried.
It was dried by heating for a minute.

次に、このようにしてカップリング剤により表面処理さ
れたガラス基板ft10.511冨厚のスペーサーを介
してアクリル樹脂板に装着してゲル作製用のセルを構成
し、これに、前記紫膜8■を含有するアクリルアミドモ
ノマー液(アクリルアミドモノマー7.5重量%、\0
.05モル酢酸緩衝液pH5,5)1.2m/’(H注
入し、通常の方法により室温で重合させた。
Next, the glass substrate whose surface was treated with a coupling agent in this way is attached to an acrylic resin plate via a spacer with a thickness of 10.511 ft to constitute a cell for gel production. Acrylamide monomer liquid containing (acrylamide monomer 7.5% by weight, \0
.. 05 molar acetate buffer pH 5.5) 1.2 m/' (H) was injected and polymerization was carried out at room temperature in a conventional manner.

重合開始して約30分後に1重合が完了したのを確認し
てから、セルを分解してガラス基板を取り出し、次いで
蒸留水で浸せき洗浄して、未重合モノマーなどの低分子
物質を除いたのち、乾燥器中で乾燥脱水することにより
、ガラス基板上に紫膜含有ポリアクリルアミドゲルの薄
膜層を形成することができた。
After confirming that one polymerization was completed approximately 30 minutes after the start of polymerization, the cell was disassembled and the glass substrate was taken out, and then washed by immersion in distilled water to remove low-molecular substances such as unpolymerized monomers. Thereafter, by drying and dehydrating in a dryer, a thin layer of purple membrane-containing polyacrylamide gel could be formed on the glass substrate.

このようにして形成された紫膜含有薄膜層は透明な紫色
を呈し、均質性も良好であり、これに。
The purple film-containing thin film layer formed in this way exhibits a transparent purple color and has good homogeneity.

適当なレンズ系により100mWのアルゴンイオンレー
ザ−を用い、レーザー光を照射したところ、照射部位の
みが紫色から黄色に変化した。レーザー光の照射時間は
2ミリ秒、照射部位の大きさは、顕微鏡観察によると約
20μm径であった。
When laser light was irradiated using a 100 mW argon ion laser using an appropriate lens system, only the irradiated area changed from purple to yellow. The laser beam irradiation time was 2 milliseconds, and the size of the irradiated area was approximately 20 μm in diameter according to microscopic observation.

このようにして、紫膜含有薄膜層上に記録したレーザー
照射スポットは、通常の環境下では長時間安定であった
In this way, the laser irradiation spot recorded on the purple film-containing thin film layer was stable for a long time under normal circumstances.

発明の効果 本発明方法によると、ガラスなどの基板上に、優れた均
質性を有する紫膜含有薄膜it極めて容易に形成させる
ことができ、この薄膜層はレーザー光などの照射により
、微少部品の色変化を起こすことが可能で、光応答機能
含有するバイオ素子として、μμ勘−ソリLL乙力こな
どへの応用が期待できる。
Effects of the Invention According to the method of the present invention, it is possible to form a purple film-containing thin film with excellent homogeneity on a substrate such as glass very easily. It is possible to cause a color change, and as a biodevice containing a photoresponsive function, it can be expected to be applied to μμ Kan-Sori LL Otsuriko, etc.

Claims (1)

【特許請求の範囲】[Claims] 1 好塩菌より単離した紫膜を含有するアクリルアミド
溶液に、あらかじめカップリング剤で表面処理した基板
を接触させ、次いでアクリルアミドの重合条件にもたら
すことにより前記基板表面に紫膜含有ポリアクリルアミ
ドゲル層を形成させることを特徴とする紫膜含有薄膜の
製造方法。
1. A substrate whose surface has been previously treated with a coupling agent is brought into contact with an acrylamide solution containing a purple membrane isolated from a halophilic bacterium, and then brought to polymerization conditions for acrylamide to form a purple membrane-containing polyacrylamide gel layer on the surface of the substrate. A method for producing a thin film containing a purple film, the method comprising: forming a thin film containing a purple film.
JP6300086A 1986-03-20 1986-03-20 Method for preparing purple membrane-containing membrane Granted JPS62221467A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6300086A JPS62221467A (en) 1986-03-20 1986-03-20 Method for preparing purple membrane-containing membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6300086A JPS62221467A (en) 1986-03-20 1986-03-20 Method for preparing purple membrane-containing membrane

Publications (2)

Publication Number Publication Date
JPS62221467A true JPS62221467A (en) 1987-09-29
JPH0586273B2 JPH0586273B2 (en) 1993-12-10

Family

ID=13216614

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6300086A Granted JPS62221467A (en) 1986-03-20 1986-03-20 Method for preparing purple membrane-containing membrane

Country Status (1)

Country Link
JP (1) JPS62221467A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1572958A4 (en) * 2002-07-29 2005-09-14 Mt Technologies Inc Biomimetic membranes
CN101825744A (en) * 2010-04-02 2010-09-08 电子科技大学 High-nonlinearity composite-structure micro-nano optical wave conducting wire and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111016466A (en) * 2019-12-20 2020-04-17 广州铂高标识技术有限公司 Novel high-speed thermal transfer ribbon

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1572958A4 (en) * 2002-07-29 2005-09-14 Mt Technologies Inc Biomimetic membranes
US7208089B2 (en) 2002-07-29 2007-04-24 Mt Technologies, Inc. Biomimetic membranes
CN101825744A (en) * 2010-04-02 2010-09-08 电子科技大学 High-nonlinearity composite-structure micro-nano optical wave conducting wire and preparation method thereof

Also Published As

Publication number Publication date
JPH0586273B2 (en) 1993-12-10

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