JP2005008715A

JP2005008715A - Method for controlling affinity of material surface and method for controlling affinity of immobilization carrier surface

Info

Publication number: JP2005008715A
Application number: JP2003172835A
Authority: JP
Inventors: Yasuji Igawa; 泰爾井川; Takashi Matsuyama; 崇松山; Osamu Watanabe; 修渡辺
Original assignee: Toyota Central R&D Labs Inc
Current assignee: Toyota Central R&D Labs Inc
Priority date: 2003-06-18
Filing date: 2003-06-18
Publication date: 2005-01-13

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for controlling affinity of the surface of an organic material by impressing a voltage to the organic material containing a polarization molecule equipped with a fixed condition. <P>SOLUTION: The affinity of a material surface is controlled on the basis of electric polarization and/or hydrophilicity or hydrophobicity at the end part of a polarization molecule oriented on the material surface by impressing positive and negative voltages in the direction crossing the surface of an organic material containing a polarization molecule which is electrically polarized in a natural state or electrically polarized by voltage impression, more preferably a polarization molecule having hydrophilicity at one end of the molecule and hydrophobicity at the other end. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０００１】
【発明の属する技術分野】
本発明は、材料表面の親和性の制御方法及び固定化担体表面の親和性の制御方法に関する。更に詳しくは、本発明は、一定の条件を備えた分極分子を含む有機材料に電圧を印加して分極分子を配向させることにより、親和性（親水性又は疎水性）を規定し得る分極分子端部を有機材料の表面に揃えさせて、有機材料の表面の親和性を制御する方法、及び、この制御方法の微小物体光固定化に対する好ましい適用に関する。
【０００２】
【従来の技術】
種々の産業分野において、材料表面の改質技術の一環として、材料表面の親和性（親水性及び疎水性、あるいは濡れ性）を制御する手段が求められている。
【０００３】
例えば、自動車業界や電子産業界で使用されるプラスチック類は複数の材料を複合化する方向に進んでいるため、材料表面の親和性の制御を要求される場合が多くなってきている。その一例として、基板となる材料への塗料の付着性を改善する手法が求められている。又、例えば医療機器業界において、生体と直接に接する部分に用いる材料の表面特性として、生体に対して低負荷である事が求められている。
【０００４】
【特許文献１】特表平１０−５０２８５７号公報
【特許文献２】米国特許第５，０２６，６０７号公報
上記の特許文献１や特許文献２には、材料表面の改質手段としてプラズマ処理等が開示されている。即ち、酸素の存在下で材料の表面に対してプラズマ処理あるいはコロナ放電を行うことにより、材料の表面に水酸基やカルボキシル基を導入して濡れ性（親水性）を向上させている。
【０００５】
【特許文献３】特開平１−２５５８５７号公報
【特許文献４】特開平８−２１６３６８号公報
上記の特許文献３や特許文献４には、複写機器等に用いる感光体において、高分子材料中に光異性化の可能なスピロピラン等の有機色素を導入し、有機色素の光吸収に基づく分子構造の変化（異性化）を利用して高分子材料表面の濡れ性を変化させる方法が開示されている。
【０００６】
一方、本件出願人は既に、特願２００２−５６７５２号及びこれに基づく優先権を主張した特願２００３−３８０３９号（これらの特許出願は未公開である）の願書に添付した明細書において、微小物体の光固定化方法や、この方法を有効に利用できる光固定化担体を提案している。この光固定化方法は、タンパク質、ＤＮＡ、生細胞等の極めて微小な生体物質を、それらの変性、失活あるいは破壊等を伴わない光照射によって担体上に固定化できると言う、有利でしかも応用範囲の広い新規技術である。
【０００７】
【発明が解決しようとする課題】
しかし、上記の特許文献１や特許文献２に開示された技術は、例えば、高価なプラズマ処理設備を必要とするとか、材料表面の親和性を親水性向上と言う方向にしか制御できないとか、材料表面の親和性を繰り返し可逆的に変化させることができないとかの多くの制約を伴う。又、表面改質処理の内容が苛酷であるため、例えば材料表面に生体分子等が位置する状態では、それらの分子の変性、失活あるいは破壊等が不可避である。
【０００８】
上記の特許文献３や特許文献４に開示された技術は、光照射と言う比較的温和な手段を用いる点で有利性を認めるが、本来的に色素分子の異性化状態は経時的な安定性を欠くものであるため、一定以上の時間経過にわたって表面改質状態を維持したい場合には、必ずしも好適な方法ではなかった。
【０００９】
更に、本件出願人の提案に係る前記微小物体の光固定化方法で利用する光固定化担体においても、次のような改善の余地があった。
【００１０】
即ち、第１に、材料の成形性や光固定化能力を考慮すると、光固定化担体の少なくとも表層部を所定の光反応性成分を含む高分子材料を以て形成することが有利である。ところが、担体に固定化すべき微小物体として特に重要なタンパク質、ＤＮＡ、生細胞等は大抵が親水性であり、担体表面の高分子材料との親和性が不十分となり易い。そのため、光固定化のために担体表面に配置された微小物体の、担体表面に対する配置状態あるいは接触状態が安定化し難い。
【００１１】
第２に、例えば既に担体表面に固定化され、酵素活性試験等の一定のプロセスを経た酵素を、担体表面から回収して残存活性等をチェックしたい場合がある。これらの場合、担体表面に固定化された酵素を超音波加振や強い水流への暴露のような強制手段で剥離させると、その剥離操作自体に起因して酵素が失活し、研究目的を達成できないと言う懸念がある。
【００１２】
そこで本発明は、上記各種の従来技術における欠点を解消できる材料表面の親和性の制御方法を提供し、併せて、この方法を上記微小物体の光固定化方法に適用することにより、光固定化方法について前記した改善の余地を埋めることを、解決すべき技術的課題とする。
【００１３】
【課題を解決するための手段】
（第１発明の構成）
上記課題を解決するための本願第１発明（請求項１に記載の発明）の構成は、自然状態において電気的に分極しており、又は電圧の印加によって電気的な分極が可能である分極分子を含む有機材料の表面の親和性を制御する方法であって、前記有機材料の表面に対して交差する方向に正負の電圧を印加して、有機材料における分極分子を電圧の印加方向沿いに配向させると同時に分極分子内の電気的分極を誘起あるいは強化させ、配向した分極分子における有機材料表面側の端部の前記電気的分極に基づく親水的性質によって、有機材料表面の親水性を増大させる、材料表面の親和性の制御方法である。
【００１４】
（第１発明の作用・効果）
第１発明によれば、所定の方向への電圧の印加によって、有機材料に含まれる分極分子における電気的分極を誘起／強化された端部が有機材料表面に配向して揃うため、有機材料表面の親水性が有効に増大する。
【００１５】
即ち、第１発明は、有機材料表面の改質処理の新たな手段を提供する。しかもこの手段は、プラズマ処理等に比較して、電圧の印加と言う装置面で簡易かつ低コストな手段により実現することができ、かつ表面改質処理の内容が温和であるし、分子の配向変化を利用するため材料表面の親水性を繰り返し可逆的に変化させることができる。又、前記の特許文献３や特許文献４に開示された、色素分子の異性化状態（構造異性体間の一定の平衡状態）を利用する技術との比較においては、表面改質状態が大幅に安定化すると考えられる。
【００１６】
次に、この第１発明の原理は、本件出願人の提案に係る前記微小物体の光固定化方法の一層の改善に極めて有効に利用できる。即ち、光固定化担体の表層部を構成する高分子材料の親水性を増大させることは容易であり、又、必要に応じて、例えば有機材料表面と平行な方向に電圧を印加すれば、高分子材料の親和性を元に戻す（親水性を低減させる）ことも容易である。
【００１７】
（第２発明の構成）
上記課題を解決するための本願第２発明（請求項２に記載の発明）の構成は、分子の一端部が親水性、他端部が疎水性であって、自然状態において電気的に分極しており、又は電圧の印加によって電気的な分極が可能である分極分子を含む有機材料の表面の親和性を制御する方法であって、前記有機材料の表面に対して交差する方向に正負の電圧を印加して、有機材料における分極分子を電圧の印加方向沿いに配向させることにより、分極分子における前記親水性又は疎水性のいずれかの端部を有機材料の表面側に揃えさせて、有機材料表面の親水性／疎水性を制御する、材料表面の親和性の制御方法である。
【００１８】
（第２発明の作用・効果）
第２発明においては、分極分子の端部での電気的分極の誘起又は強化を利用する第１発明とは異なり、分極分子が端部に備える親水性部分／疎水性部分を利用する材料表面の親和性の制御方法である。しかし、その作用・効果においては、少なくとも第１発明と同様のものを期待できる。
【００１９】
しかも第２発明においては、本来的に親水性／疎水性である分極分子の端部を利用するので、第１発明よりも親和性の制御効果が明確で、かつ大きいと考えられる。更に、単に有機材料表面の親水性を増減させるだけでなく、明確な親水性と明確な疎水性との間で有機材料表面の親和性を制御することができる。因みに、例えば有機材料表面と平行な方向に電圧を印加すれば、分極分子が有機材料表面上に寝た状態になって親水性端部と疎水性端部が均等に露出するので、有機材料表面を親水性と疎水性との中間状態に調整することもできる。
【００２０】
（第３発明の構成）
上記課題を解決するための本願第３発明（請求項３に記載の発明）の構成は、前記第２発明に係る有機材料表面を親水性／疎水性のいずれかの方向に制御するに当たり、前記分極分子の電気的分極の内容を考慮して印加する電圧の正負の方向を選択し、これによって分極分子の親水性端部／疎水性端部の内の選択された一方の端部を有機材料の表面側に揃えさせる、材料表面の親和性の制御方法である。
【００２１】
（第３発明の作用・効果）
第２発明においては、第１発明とは異なり、分極分子の任意の端部を有機材料の表面側に揃えさせるのではなく、親水性端部又は疎水性端部を選択的に有機材料の表面側に配向させる必要がある。そのため、分極分子の電気的分極の内容を考慮して、印加する電圧の正負の方向を選択することが好ましい。
【００２２】
即ち、例えば、電圧の印加によって誘起又は強化される分極分子の電気的分極状態において、δ＋側となる端部（分極分子全体における電子供与性側の端部）に親水性端部が設定されているのであれば、有機材料の表面側が負極であり裏面側が正極であるように電圧を印加することにより、有機材料の表面に分極分子の親水性端部が揃うから、該表面を親水性に変化させることができる。又、この親水性への変化は、分極分子の電気的分極により一層強化される。
【００２３】
（第４発明の構成）
上記課題を解決するための本願第４発明（請求項４に記載の発明）の構成は、前記第１発明〜第３発明のいずれかに係る有機材料が、以下の（１）〜（３）のいずれかの態様で分極分子を含むものである、材料表面の親和性の制御方法である。
（１）有機分子である分極分子からなる有機材料。
（２）適宜な材料からなるマトリクス中に分極分子を分散させた有機材料。
（３）適宜な材料からなるマトリクスの構成分子に対して分極分子が結合している有機材料。
【００２４】
（第４発明の作用・効果）
本発明に係る有機材料は、分極分子を含む必要があるが、その「含む」態様は限定されない。しかし、第４発明の（１）〜（３）のいずれかの態様を好ましく例示できる。有機材料のコスト、成形性、分極分子の制御された配向の安定的な維持等を考慮すると、とりわけ（３）の態様が好ましい。
【００２５】
（第５発明の構成）
上記課題を解決するための本願第５発明（請求項５に記載の発明）の構成は、前記第１発明〜第４発明のいずれかに係る分極分子が、少なくとも一つの芳香環を含む分子である、材料表面の親和性の制御方法である。
【００２６】
（第５発明の作用・効果）
分極分子の種類は限定されないが、自然状態において電気的に分極しており、又は電圧の印加によって電気的な分極が可能である分子であるために、少なくとも一つの芳香環を含む分子であることが好ましい。
【００２７】
（第６発明の構成）
上記課題を解決するための本願第６発明（請求項６に記載の発明）の構成は、前記第１発明〜第４発明のいずれかに係る分極分子が、少なくともアゾ基、アゾメチン基又はエチレン基を包含する群から選ばれるリンカー構造部を介して連結された二つの芳香環を含む分子である、材料表面の親和性の制御方法である。
【００２８】
（第６発明の作用・効果）
分極分子が、第６発明のように所定のリンカー構造部を介して連結された二つの芳香環を含む場合、より大きな電気的分極を発現可能である。このような分極分子は、電圧の印加による分子配向がより顕著であるため、有機材料表面の親和性の変化もより顕著になる。
【００２９】
（第７発明の構成）
上記課題を解決するための本願第７発明（請求項７に記載の発明）の構成は、前記第５発明又は第６発明に係る芳香環を含む分極分子における当該芳香環が、電子供与性基及び／又は電子吸引性基を備える、材料表面の親和性の制御方法である。
【００３０】
（第７発明の作用・効果）
分極分子が、第７発明のように電子供与性基及び／又は電子吸引性基を備える芳香環を含む場合、自然状態及び電圧の印加時における分子内の電気的な分極がより強くなる。
【００３１】
（第８発明の構成）
上記課題を解決するための本願第８発明（請求項８に記載の発明）の構成は、前記第６発明又は第７発明に係る連結された二つの芳香環を含む分極分子において、一方の芳香環が電子供与性基を、他方の芳香環が電子吸引性基を備える、材料表面の親和性の制御方法である。
【００３２】
（第８発明の作用・効果）
分極分子が、第８発明のように電子供与性基と電子吸引性基をそれぞれ備える二つの芳香環を含む場合、自然状態及び電圧の印加時における分子内の電気的な分極が更に強くなる。
【００３３】
（第９発明の構成）
上記課題を解決するための本願第９発明（請求項９に記載の発明）の構成は、前記第７発明又は第８発明に係る一つ又は二つの芳香環が電子供与性基及び電子吸引性基を備える場合において、電子供与性基が親水性基又は疎水性基であり、電子吸引性基がその逆に疎水性基又は親水性基である、材料表面の親和性の制御方法である。
【００３４】
（第９発明の作用・効果）
第９発明のように、一つ又は二つの芳香環に備わる電子供与性基及び電子吸引性基の一方が親水性基で他方が疎水性基である場合（あるいは逆に、一方が疎水性基で他方が親水性基である場合）、分極分子の電気的な分極の大きさに加えて電子供与性基及び電子吸引性基の固有の親水性あるいは疎水性が発現する。
【００３５】
このため、有機材料表面における分極分子の配向による親和性の制御効果は、更に顕著なものとなる。とりわけ、親水性基を有機材料表面に揃えるようにして分極分子を配向させた場合、有機材料表面は例外的な程に顕著な親水性を発現し得る。
【００３６】
（第１０発明の構成）
上記課題を解決するための本願第１０発明（請求項１０に記載の発明）の構成は、前記第１発明〜第９発明のいずれかに係る有機材料に対する電圧の印加の際、有機材料をそのガラス転移点以上に加温する、材料表面の親和性の制御方法である。
【００３７】
（第１０発明の作用・効果）
有機材料をガラス転移点以上に加温すると、分極分子の配向の自由度が格段に高まるため、電圧の印加時における分子配向が著しく起こり易い。この点を有効に利用すると、有機材料表面の親和性制御の安定性が著しく向上する。
【００３８】
即ち、例えば前記特許文献３や特許文献４に開示された技術は表面改質状態の安定性を欠くと言う重大な欠点があるが、第１０発明においては分極分子の配向と言うロック状態を、有機材料をガラス転移点以上に加温すると言うアンロック手段によって変更可能にする。従って、有機材料表面の親和性を、安定化された制御状態と、アンロック手段によるその制御状態の変更又は緩和とに明確に使い分けることができる。
【００３９】
（第１１発明の構成）
上記課題を解決するための本願第１１発明（請求項１１に記載の発明）の構成は、前記第１発明〜第１０発明のいずれかに係る有機材料の表面に対する交差方向への電圧の印加を、有機材料の表面に対して交差する方向に沿って設けた正負の電極によって行い、あるいは、同軸上で発生すると共に倍数関係にある周波数を持った２種以上の照射光を有機材料の表面に対して斜め方向から照射することによって行う、材料表面の親和性の制御方法である。
【００４０】
（第１１発明の作用・効果）
有機材料の表面に対して交差方向への電圧を印加する手段は限定されないが、第１１発明に規定するように、正負の電極の利用、あるいは特定方向からの所定の光照射を好ましく例示できる。なお、第１３発明に係る固定化担体表面の親和性の制御方法においては有機材料として光固定化材料を用いるので、有機材料の表面に対する電圧印加手段としての照射光の利用は避けた方が良い。
【００４１】
（第１２発明の構成）
上記課題を解決するための本願第１２発明（請求項１２に記載の発明）の構成は、前記第１発明〜第１１発明のいずれかに係る材料表面の親和性の制御方法を、以下（４）〜（６）のいずれかの態様で行う、材料表面の親和性の制御方法である。
（４）商品あるいは商品部材として新規に製造され、又は既に使用されている有機材料に対して、加工プロセスとして電圧印加による有機材料表面の親和性の制御を行う。
（５）商品あるいは商品部材としての使用環境にある有機材料に対し、その表面に対して交差する方向に正負の電圧を印加し得る形態で電圧印加手段を付設することにより、有機材料表面の親和性の制御を常時可能とする。
（６）商品あるいは商品部材としての使用環境にある有機材料に対して、その表面に対して交差する方向に正負の電圧を印加し得る形態で、かつ、正負の電圧方向を逆転し得る形態で電圧印加手段を付設することにより、有機材料表面の親和性の制御を常時可能とする。
【００４２】
（第１２発明の作用・効果）
表面改質技術の一種としての材料表面の親和性の制御方法は、多種多様な技術分野で求められているが、その実施態様の好ましいカテゴリーとして、第１２発明の（４）〜（６）の態様を例示することができる。
【００４３】
（４）の態様は、有機材料に対する加工プロセスとして一過性の親和性制御を行うものであり、親和性の制御状態の経時的な安定性が求められる。（５）及び（６）の態様は、使用環境にある有機材料の表面の親和性制御を随時行うことが好ましい場合の制御であり、親和性の制御状態の安定性と共に、簡易な制御手段により迅速・確実に制御状態を切り替え可能であることが求められる。
【００４４】
（第１３発明の構成）
上記課題を解決するための本願第１３発明（請求項１３に記載の発明）の構成は、第１発明、第２発明、第４発明〜第９発明のいずれかに係る有機材料が、照射光によって光変形を誘起され、その表面に配置された微小物体を固定化できる光固定化材料でもある場合において、少なくとも表層部に前記有機材料を用いた固定化担体を構成し、正負の電極を用いて固定化担体の表面に対し交差する方向に電圧を印加することにより、下記の（７）又は（８）を目的として微小物体に対する固定化担体表面の親和性を制御する、固定化担体表面の親和性の制御方法である。
（７）前記微小物体の固定化に先立ち、固定化担体の表面に配置された微小物体の当該固定化担体に対する配置状態又は接触状態を安定化させる操作
（８）所定の技術的要求に応じて、既に固定化担体の表面に固定化されている微小物体の固定化状態を緩和する操作
（第１３発明の作用・効果）
第１３発明の（７）により、有機材料である光固定化材料を用いた固定化担体の表面に対する、タンパク質、ＤＮＡ、生細胞等の親水性の微小物体の配置状態又は接触状態を安定化させることができ、微小物体の光固定化をより正確に（例えば、固定化担体表面の正確な予定位置に）、しかも確実に（例えば、極めて高い固定化率で）固定化することができる。
【００４５】
第１３発明の（８）により、必要に応じて、担体表面に光固定化した微小物体を、超音波加振や強い水流への暴露のような苛酷な強制的手段に頼ることなく、温和な手段（緩やかな加振、弱い水流への暴露等）によって担体表面から離脱させ、回収することができる。このことは、例えば、担体表面に固定化した生細胞を回収する場合において、担体表面からの離脱操作が生細胞を失活させる恐れが少ないため、再生医療等の観点から非常に有利である。
【００４６】
【発明の実施の形態】
次に第１発明〜第１３発明の実施の形態について説明する。以下、「本発明」と言うときは、これらの各発明を包括的に指している。
【００４７】
〔分極分子〕
本発明において分極分子とは、自然状態において電気的に分極しており、又は電圧の印加によって電気的な分極が可能である分子を言う。更に、分極分子とは、分子の一端部が親水性、他端部が疎水性であって、自然状態において電気的に分極しており、又は電圧の印加によって電気的な分極が可能である分極分子をも言う。このような条件に該当する限りにおいて、分極分子の種類は限定されないが、以下に列挙するタイプの分極分子が特に好ましい。
【００４８】
即ち、まず、少なくとも一つの芳香環を含む分極分子が好ましい。所定のリンカー構造部を介して連結された二つの芳香環を含む分極分子は、更に好ましい。「所定のリンカー構造部」とは、例えば、二つの芳香環を連結するアゾ基、アゾメチン基又はエチレン基等を言う。芳香環を含む分極分子において、当該芳香環が電子供与性基及び／又は電子吸引性基を備えることが、更に好ましい。リンカー構造部を介して連結された二つの芳香環において、一方の芳香環が電子供与性基を、他方の芳香環が電子吸引性基を備えることが、とりわけ好ましい。更に、分極分子における一つ又は二つの芳香環が電子供与性基及び電子吸引性基を備える場合において、電子供与性基が親水性基又は疎水性基であり、電子吸引性基がその逆に疎水性基又は親水性基であることも、とりわけ好ましい。
【００４９】
なお、親水性の電子供与性基としては一級〜三級アミノ基、水酸基等を、疎水性の電子供与性基としてはアルキル基、アルコキシ基等を、親水性の電子吸引性基としてはカルボキシル基、アセチル基、スルホン酸基等を、疎水性の電子吸引性基としてはフルオロアルキル基、フッ素基、ニトロ基、シアノ基等を、それぞれ挙げることができる。
【００５０】
芳香環はそれ自体として疎水性であるため、単一の芳香環が単一の電子供与性基又は電子吸引性基を備える分極分子では、電子供与性基又は電子吸引性基は親水性であることが好ましい。又、単一の芳香環が電子供与性基及び電子吸引性基を備える分極分子では、これらがパラの位置に存在することが好ましい。
【００５１】
〔光反応性成分〕
光反応性成分の好ましい例示として、光照射によりアブレーション，フォトクロミズム，分子の光誘起配向等を起こし、結果的に光固定化材料の体積，密度，自由体積等が変化して光変形が生成されるような成分を挙げることができる。
【００５２】
光反応性成分の種類は限定されないが、例えば材料の形状変化を伴う異方的光反応を起こし得る成分である光異性化成分や光重合性成分を、好ましく例示することができる。固定化する微小物体が、担体材料との化学反応により活性が損なわれるような生体物質である場合には、光反応性成分として光異性化成分が好ましい。そして光異性化成分としては、例えばトランス−シス光異性化を生じる成分、特に代表的にはアゾ基（−Ｎ＝Ｎ−）を有する色素構造、とりわけ、アゾベンゼンやその誘導体の化学構造を持つ成分を好ましく例示できる。
【００５３】
従って、アゾベンゼンやその誘導体の化学構造を持つ成分は、好ましい分極分子であると共に好ましい光反応性成分でもあるため、このような成分を含む高分子材料は、本発明に係る好ましい有機材料であると共に好ましい光固定化材料でもある。
【００５４】
光固定化材料がアゾ基を有する色素構造を含む材料である場合において、その色素構造が、１又は２以上の電子吸引性官能基（電子吸引性置換基）、及び／又は、１又は２以上の電子供与性官能基（電子供与性置換基）を備えることが、特に好ましい。これらの電子吸引性官能基と電子供与性官能基とを併せ備えることが、とりわけ好ましい。このような電子吸引性官能基と電子供与性官能基とを併せ備えるアゾ基含有の色素構造は、前記したように、同時に好ましい分極分子でもある。
【００５５】
〔有機材料、光固定化材料〕
本発明に係る有機材料とは、分極分子を含み、有機材料の表面に対して交差する方向への電圧の印加により、分極分子の配向に起因する有機材料表面の親和性の制御が可能な材料を言う。本発明に係る有機材料には、光固定化材料でもある有機材料が含まれる。
【００５６】
光固定化材料とは、上記の分極分子と共に光反応性成分を含み、光反応性成分に起因する光変形を起こすことにより、表面に配置された微小物体に対して光照射時に固定化能力を示す材料である。前記のように、分極分子が同時に光反応性成分である場合もある。
【００５７】
有機材料や光固定化材料が分極分子や光反応性成分を含む態様は限定されないが、好ましい例示として、（１）有機材料や光固定化材料が、分極分子や有機分子である光反応性成分からなる場合を挙げることができる。次に、（２）適宜な有機材料からなるマトリクス中に分極分子や光反応性成分が分散している場合を挙げることができる。更に、（３）適宜な材料からなるマトリクスの構成分子に対して分極分子や光反応性成分が結合している場合を、とりわけ好ましく挙げることができる。
【００５８】
有機材料や光固定化材料のマトリクスを構成する材料としては、高分子材料が特に好ましい。高分子材料の種類は限定されないが、高分子の繰返し単位の中にウレタン基，ウレア基，又はアミド基を含んだものが、更には高分子の主鎖中にフェニレン基のような環構造を備えたものが、耐熱性の点では好ましい。高分子材料は必要な形状に成形可能である限りにおいて分子量や重合度を問わず、重合形態も直鎖状，分岐状，はしご状，星形等の任意の形態で良く、又、ホモポリマーでも共重合体であっても良い。
【００５９】
分極分子の配向状態の安定性や、光固定化材料における光変形の安定性（微小物体に対する経時的な固定力の維持）のためには、高分子材料のガラス転移温度が例えば１００°Ｃ以上と言った高いものの方が好ましいが、反面、水性媒体中で分極分子を配向させたい場合を考慮すると、ガラス転移温度が１００°Ｃ以下のものも好ましい。
【００６０】
以上の点から、本発明に係る有機材料（光固定化材料）として特に好ましい高分子材料の２，３の具体例として、実施例で述べるものの他、次の「化１」〜「化４」に示すものが挙げられる。これらの例において、−Ｘはニトロ基，シアノ基，トリフルオロメチル基，アルデヒド基又はカルボキシル基を、−Ｙ−は−Ｎ＝Ｎ−，−ＣＨ＝Ｎ−又は−ＣＨ＝ＣＨ−を、−Ｒ−はフェニレン基，オリゴメチレン基，ポリメチレン基又はシクロヘキサン基を、それぞれ示す。
【００６１】
【化１】

【００６２】
【化２】

【００６３】
【化３】

【００６４】
【化４】

〔材料表面の親和性の制御〕
本発明に係る材料表面の親和性の制御方法は、二つの方法に大別される。
【００６５】
第１の方法は、分極分子を含む有機材料の表面に対して交差する方向に正負の電圧を印加して、有機材料における分極分子を電圧の印加方向沿いに配向させると同時に分極分子内の電気的分極を誘起あるいは強化させる方法である。これにより、配向した分極分子における有機材料表面側の端部の前記電気的分極に基づく親水的性質によって、有機材料表面の親水性を増大させる。
【００６６】
第２の方法は、分子の一端部が親水性、他端部が疎水性であって、自然状態において電気的に分極しており、又は電圧の印加によって電気的な分極が可能である分極分子を含む有機材料の表面に対して交差する方向に正負の電圧を印加して、有機材料における分極分子を電圧の印加方向沿いに配向させる方法である。これにより、分極分子における前記親水性又は疎水性のいずれかの端部を有機材料の表面側に揃えさせて、有機材料表面の親水性／疎水性を制御する。
【００６７】
上記の第２の方法においては、有機材料表面を親水性／疎水性のいずれかの方向に制御するため、印加する電圧の正負の方向を選択できるようにすることが望ましい。電圧の正負の方向の選択は、電圧印加時の分極分子における電気的分極状態において、分極分子の例えば親水性の端部がδ＋／δ−のいずれであるかによって決定される。そのことによって、分極分子の親水性端部／疎水性端部の内の選択された一方の端部を有機材料の表面側に揃えさせることができる。
【００６８】
材料表面の親和性の制御方法の実施態様として、例えば、新規に製造され、又は既に商品として使用されている有機材料に対して、加工プロセスとして電圧印加による有機材料表面の親和性の制御を行うことができる。この実施態様は、具体的には、自動車の塗装プロセスにおいて、塗膜を積層する場合に塗膜間の接着性を向上させる場合等に利用できる。
【００６９】
他の実施態様として、例えば、商品としての使用環境にある有機材料に対し、その表面に対して交差する方向に正負の電圧を印加し得る形態で電圧印加手段を付設することにより、有機材料表面の親和性の制御を常時可能とすることができる。この実施態様は、具体的には、親水性や疎水性の物体、例えばタンパク質の分離や精製に用いることができる。予め疎水性に調整した有機材料の表面に疎水性の物質のみを付着させた後に、有機材料の表面を親水化してこれらの疎水性物質を脱離させ、回収すれば、当該疎水性物質を分離又は精製できる。
【００７０】
更に他の実施態様として、例えば、商品としての使用環境にある有機材料に対して、その表面に対して交差する方向に正負の電圧を印加し得る形態で、かつ、正負の電圧方向を逆転し得る形態で電圧印加手段を付設することにより、有機材料表面の親和性の制御を常時可能とすることができる。この実施態様は、具体的には、有機材料を自動車の窓ガラスのコーティングとして用いて、低速走行時には親水性に制御して（濡れ性を増大させて）雨滴による光の散乱を防止し、高速走行時には疎水性に制御して雨水をはじきとばすと言うアクティブワイパーとして利用する場合等に利用できる。
【００７１】
〔電圧の印加〕
有機材料に対する電圧印加の方法としては、例えば、有機材料の表面に対して交差する方向に沿って設けた正負の電極によって行うことができる。
【００７２】
又、例えば、同軸上で発生すると共に倍数関係にある周波数を持った２種以上の照射光を有機材料の表面に対して斜め方向から照射することによって行うこともできる。この方法の具体的な実施態様として、例えば図１に示すように、有機材料１の表面に対して、斜め方向から、第２高調波発生装置を備えたレーザー装置２からのレーザー光３を入射することができる。このレーザー光３は、ωの周波数の基本波と２ωの周波数を持った第２高調波が同軸上で発生する構成にしてあるため、２つの周波数の光の重ね合わせにより、有機材料１の表面に対して斜め方向の電場を誘起することができる。従って、有機材料１中の多数の分極分子４を、その電気的に分極した一端側が有機材料１の表面に揃うように配向させることができる。
【００７３】
電場における正／負方向の逆転は、正負の電極によって行う場合には容易であるし、上記した照射光により電場を誘起する場合には光の偏光方向を１／２波長板、１／４波長板を用いて回転させることによって可能である。そうすることによって、分極分子４の他端側が有機材料１の表面に揃うように配向させることもできる。
【００７４】
有機材料に対する電圧の印加の際、有機材料をそのガラス転移点以上に加温しておくと、分極分子の配向が著しく容易になり、有機材料表面の親和性の制御効果が著しく顕著になる。
【００７５】
〔固定化担体表面の親和性の制御〕
固定化担体表面の親和性の制御方法においては、前記光固定化材料である有機材料を少なくとも表層部に用いた固定化担体の表面に対して交差する方向に、正負の電極によって電圧を印加し、微小物体に対する固定化担体表面の親和性を制御する。そしてこの制御は、下記の（７）又は（８）の操作として行う。
（７）前記微小物体の固定化に先立ち、固定化担体の表面に配置された微小物体の当該固定化担体に対する配置状態又は接触状態を安定化させる操作。
（８）所定の技術的要求に応じて、既に固定化担体の表面に固定化されている微小物体の固定化状態を緩和する操作。
【００７６】
〔微小物体の光固定化〕
微小物体の光固定化には、少なくとも表層部に前記光固定化材料を用いた固定化担体を使用する。この固定化担体の表面に、大きさが５０μｍ以下程度の有形物体である微小物体を配置（接触）させたもとで、照射光によって微小物体を担体の表面に固定化するのである。
【００７７】
担体の表面に微小物体を配置させる形態は任意であるが、微小物体を水等の液状媒体中で担体表面に配置させることが好ましい。その具体的な形態として、例えば、微小物体を溶解又は懸濁させた液状媒体（水、緩衝液等）中へ担体を浸漬したり、又は少量の該液状媒体を担体表面に滴下する、等の実施形態を好ましく例示できる。微小物体の種類は限定されず、担体に固定化する微小物体の個数も限定されない。
【００７８】
微小物体及びこれを固定化した担体の技術的カテゴリーとしては、金属粒子、金属酸化物粒子、半導体粒子、セラミック粒子、プラスチック粒子又はこれらの内の２以上の材料からなる（例えば２種材料の混合体又は重層構造体）粒子を固定化した電界効果トランジスタ、２次元フォトニック結晶、電気的又は光学的な集積回路チップ等を例示できる。
【００７９】
又、ポリペプチド、より具体的には例えば酵素、抗原、抗体、細胞膜レセプタータンパク質あるいは生物細胞において発現する各種タンパク質群を固定化したバイオリアクターやバイオセンサー、集積化酵素トランジスタ、イムノアッセイ用の試験チップ、プロテオーム解析用の試験チップ等も例示できる。
【００８０】
更に、１本鎖又は２本鎖以上（３本鎖、４本鎖も含む）の核酸即ちポリヌクレオチド、より好ましくはハイブリダイゼーションが可能な１本鎖のポリヌクレオチドを固定化したＤＮＡチップ又はＤＮＡマイクロアレイも例示できる。細胞又は微生物、特に好ましくは生活状態にある細胞又は微生物を固定化した担体も例示できる。
【００８１】
担体としては、上記のような比較的小さなチップの形態の他、カラム等に充填するための粒体等の形態、表面で基質溶液等を流動させる大きな固定的反応床の形態、簡便なイムノアッセイ等に用いる小サイズの試験紙の如き形態、顕微鏡観察等に用いられるスライドガラスの如き形態、等が挙げられる。
【００８２】
光固定化用の照射光としては、光変形を起こす材料との組み合わせにおいてミスマッチングがない限り、伝搬光、近接場光又はエバネッセント光等の任意の照射光を利用できる。伝搬光としては、自然光、レーザー光等を利用できる。伝搬光、近接場光又はエバネッセント光として、その偏光特性を利用できる。
【００８３】
光照射の方法として、その照射領域あるいは照射強度に一定の分布を与えることも好ましい。その場合、多数の微小物体を一定の分布パターンに従って担体の表面に固定化することができるので、電気的又は光学的な集積回路チップ等を構成したり、集積化酵素トランジスタを構成したりする際に有効である。特に同一の担体に対して、種類の異なる微小物体を用いて異なる分布パターンに従って繰り返し固定化を行うことにより、機能的に複雑な回路等を形成できる。
【００８４】
このような照射光の照射領域あるいは照射強度の分布を与える手段として、例えばフォトマスクを利用することができる。微小物体を担体表面の特定部位に配置したり、多数の微小物体を一定の分布パターンに従って担体の表面に配置したりする手段として、微小物体を公知のレーザートラッピングによって所定位置へ移動させる手法も利用できる。
【００８５】
【実施例】
〔実施例１〕
（本発明に係る有機材料の合成）
所定のプロセスによりアゾベンゼン構造を含む下記「化５」に示すアゾ色素を合成した後、これを酸クロリド反応によりアクリル化して下記「化６」に示す化合物を合成した。次に、減圧蒸留により重合禁止剤を取り除いたメタクリル酸メチル（和光純薬製）と化６の化合物を共重合させ、下記「化７」に示す高分子化合物を得た。
【００８６】
【化５】

【００８７】
【化６】

【００８８】
【化７】

化７の高分子化合物に結合した状態で含まれている化６の化合物は、そのアゾベンゼン構造の一端側に電子供与性で親水性であるアミノ基を含み、他端側に電子吸引性で疎水性であるシアノ基を含む。そして、化６の化合物は分極分子であると共に光反応性成分でもあるため、化７の高分子化合物は、本発明に係る有機材料であると共に光固定化材料でもあり、そのガラス転移温度は約１２０°Ｃである。
【００８９】
（有機材料膜の作製と分極分子の配向）
上記した化７の高分子化合物５０ｍｇをピリジン２ｍＬに溶解させた溶液を調製し、この溶液をスライドガラス基板上に１ｍＬほど滴下した。そしてスライドガラス基板を２０００ｒｐｍで回転させて溶媒を除去し、約１１０ｎｍの均一な膜厚の有機材料膜を作製した。
【００９０】
次に、図２に示すように、上記の有機材料膜５を形成したスライドガラス基板６を、基板加熱用のヒーター７を備えた平板電極８上に設置した。この平板電極８は、高電圧電源９を介して、有機材料膜５の上方に架設した針状電極１０につながれている。
【００９１】
（接触角の測定）
電極８，１０による電圧印加の前に、有機材料膜５に水を滴下して、有機材料膜５の表面における水との接触角を測定したところ、その接触角は６７度であった。次に、有機材料膜５をヒーター７で加熱することなく、平板電極８を正極とし針状電極１０を負極として、電圧を３００秒間印加したもとで同上の接触角を測定したところ、その接触角は５０度であった（実施例１−１）。更に、有機材料膜５をヒーター７で１５０°Ｃに加熱した状態において電極８，１０による電圧を３００秒間印加した後、常温に冷却して同上の接触角を測定したところ、その接触角は２５度であった（実施例１−２）。
【００９２】
次に、上記２５度の接触角を示した有機材料膜５をスライドガラス基板６ごと直立させ（電圧が有機材料膜５の表面と水平に印加するように設定し）、その上で上記と同様に有機材料膜５を加熱した状態において電圧印加した後、常温に冷却して同上の接触角を測定したところ、その接触角は、ほぼ６７度に戻っていた（実施例１−３）。更に、スライドガラス基板６を元の（図２に示す）状態に戻して、上記とは逆に平板電極８を負極とし針状電極１０を正極として、上記と同様に有機材料膜５を加熱し電圧印加した後、常温に冷却して有機材料膜５表面の接触角を測定したところ、その接触角は当初の接触角よりも大きい８０度であった（実施例１−４）。
【００９３】
以上の結果から明らかなように、分極分子を含む有機材料に対して所定の方向に電圧を印加すると、その有機材料表面の親水性が有意に向上する。特に、その有機材料のガラス転移温度以上の温度に加熱しながら電圧を印加すると、有機材料表面の親水性が著しく向上する。又、電圧の印加方法を変えることにより、有機材料表面の親和性をいろいろと制御することができる。
【００９４】
なお、実施例１−１及び１−２の結果は、有機材料膜５に含まれる化６の化合物における電子供与性で親水性であるアミノ基が有機材料膜５の表面に配向して揃ったものであり、実施例１−３の結果は、化６の化合物が有機材料膜５の表面と平行に配向したことによるものであり、実施例１−４の結果は、化６の化合物における電子吸引性で疎水性であるシアノ基が有機材料膜５の表面に配向して揃ったものである、と考えられる。
【００９５】
一方、比較例１として、分極分子（光反応性成分）を含まないアクリル系の高分子材料で、ガラス転移温度が１２０°Ｃであるメタクリル酸メチルを用いて実施例１と同様のガラス基板上の材料膜を構成した。この材料膜に対して電圧印加の前に同上の方法で接触角を測定したところ、その接触角は７０度であった。次に、このガラス基板を図２の電圧印加装置に持ち込み、１５０°Ｃに加熱した状態で平面電極８（正極）、針状電極１０（負極）による電圧を３００秒間印加した後、常温に冷却して同上の接触角を測定したところ、その接触角は、７０度であった。
【００９６】
以上の結果から明らかなように、分極分子を含まない有機材料においては、ガラス転移温度以上の温度に加熱しながら電圧を印加しても、有機材料表面の親和性を変化させて制御することは困難である。
【００９７】
〔実施例２〕
上記の有機材料膜を担体として用い、ＤＮＡマイクロアレイの作製と蛍光検出とを行った。本例の実施に当たり、実施例１において当初に作製された（電圧印加前の）有機材料膜を比較例２とし、前記実施例１−２の状態の有機材料膜を実施例２とした。
【００９８】
λ−ＤＮＡ（ニッポンジーン社製４８Ｋ塩基対）をｐＨ８．０の緩衝液に溶解させた溶液（０．５μｇ／μＬ）１００μＬをエッペンドルフチューブに入れ、更にＤＮＡ染色用の蛍光色素（ＭｏｌｅｃｕｌａｒＰｒｏｂｅ社製）ＴＯ−ＰＲＯ−３ｉｏｄｉｄｅの原液１μＬを加えて攪拌し、λ−ＤＮＡを蛍光物質で染色した。
【００９９】
こうして蛍光色素で染色したλ−ＤＮＡをＡｆｆｉｍｅｔｒｉｘ社製の４１７Ａｒｒａｙｅｒを用いて、上記実施例２及び比較例２に係る有機材料膜上にスポットした。各スポットの直径は１２５μｍ、スポット間隔は３７５μｍである。次に有機材料膜上にスポットしたλ−ＤＮＡからの蛍光をＡｆｆｉｍｅｔｒｉｘ社製の４２８ＡｒｒａｙＳｃａｎｎｅｒを用いて解析した。Ｃｙ５用のフィルターセット（励起６３２ｎｍ、蛍光６６０−６８０ｎｍ）を用いて解析した。
【０１００】
実施例２についてのものを図２に示すが、実施例２では直径１２５μｍの円形で均一なスポットが観察されたのに対して、図３に示す比較例２ではスポットの周辺部に蛍光強度の強い部分が偏り、実施例２との比較においてはスポットの均一性が不十分であった。この差異は、λ−ＤＮＡ溶液をスポットした際の有機材料膜の相対的な親水性の違いに起因すると考えている。即ち、水との濡れ性に優れた実施例２ではλ−ＤＮＡ溶液がスポットの全面で均一に乾燥して行くのに対して、比較例２では水との濡れ性が不足するために、λ−ＤＮＡ溶液が乾燥するにつれてλ−ＤＮＡ溶液がスポットの周縁部に偏ったものと考えられる。
【０１０１】
〔実施例３〕
実施例１における電圧印加前の状態の有機材料膜を比較例３とし、実施例１−２に係る有機材料膜を実施例３として、これらを光固定化担体とする酵素の光固定化を試みた。そのために、これらの有機材料膜をそれぞれ１ｃｍ×１ｃｍの大きさに切り取って、比較例３及び実施例３に係る固定用担体基板とした。
【０１０２】
タンパク質分解酵素〔Ｐｒｏｔｅａｓｅ（ＳｕｂｔｉｌｌｉｓｉｎＣａｒｌｓｂｅｒｇ）〕１０ｍｇを１０ｍＬのイオン交換水に溶解した。この酵素水溶液にそれぞれ上記の比較例３及び実施例３に係る固定用担体基板を浸漬した状態にし、これらの固定用担体基板の表面に対して、波長４８８ｎｍ、強度８０ｍＷ／ｃｍ^２のレーザー光を３０分間照射した。
【０１０３】
次に、これらの固定用担体基板を酵素水溶液から取り出し、それぞれ別のイオン交換水に浸漬して３０分間攪拌した。更にその後、それぞれ新しいイオン交換水でこれらの固定用担体基板の洗浄を行った。
【０１０４】
一方、人工基質（ＢＯＣ−ＧＧＬ−ＰＮＡ）４ｍｇをジメチルホルムアミド１ｍＬに溶解した。この人工基質は、タンパク質分解酵素により分解されるとｐ−ニトロアニリドが溶け出して波長３８０ｎｍの吸収が増大するため、溶液が黄色に呈色する。この人工基質溶液を５０μＬ採取して４５０μＬの１０ｍＭトリス塩酸緩衝液（ｐＨ８．０）に加え、反応溶液を得た。
【０１０５】
この反応溶液を比較例３及び実施例３に係る固定用担体基板の表面に各５０μＬ滴下し、３７°Ｃで１時間保持した。その後、それぞれの反応溶液を吸い取り、ＵＶ／ＶＩＳスプクトロメーターを用いて３８０ｎｍの吸光度を測定した。その結果、実施例３に係る固定用担体基板に滴下した溶液では吸光度が０．２４５増加し、比較例３に係る固定用担体基板に滴下した溶液では吸光度が０．１１７増加していた。
【０１０６】
いずれの固定用担体基板においてもイオン交換水で洗浄していることから、上記の吸光度の増加量の違いは、固定用担体基板における親水性の違いが光照射時における酵素の固定量の相違となって現れ、実施例３に係る固定用担体基板では比較例３に係る固定用担体基板よりも多量の酵素が光固定化された結果であると考えることができる。
【０１０７】
〔実施例４〕
上記の実施例３に係る固定用担体基板であって、実施例３の通りに酵素を固定化したものを２枚準備した。その内の１枚は、図２に示した電圧印加装置に図２に示す状態で持ち込み、平板電極８を負極、針状電極１０を正極として、室温で電圧を３００秒間印加した（実施例４−１）。他の１枚の固定用担体基板は電圧印加処理を行わなかった（実施例４−２）。
【０１０８】
実施例４−１及び実施例４−２に係る固定用担体基板をそれぞれ３００μＬのイオン交換水に浸漬して３０分間攪拌した。次に、この浸漬及び攪拌に供した各３００μＬのイオン交換水からそれぞれ５０μＬを取り出し、実施例３で使用したものと同じ反応溶液の各５０μＬと混合した。
【０１０９】
これらの混合液につき、ＵＶ／ＶＩＳスプクトロメーターを用いた３８０ｎｍの吸光度を、混合直後と、混合後３７°Ｃで１時間保持した後とについて測定し、その間の吸光度変化を調べた。その結果、実施例４−１に使用したイオン交換水では吸光度が０．０５増加したが、実施例４−２に使用したイオン交換水では吸光度が変化していなかった。
【０１１０】
以上の結果から、実施例４−１に係る固定用担体基板では、電圧印加処理により固定用担体基板の表面が疎水化して酵素が緩和な条件で脱離し易くなったこと、脱離した酵素は活性を維持していたことが分かる。又、実施例４−１との対比考察から、実施例４−２に係る固定用担体基板では、イオン交換水への浸漬及び攪拌によって酵素が脱離していないことが分かる。
【図面の簡単な説明】
【図１】本発明の実施形態を示す図である。
【図２】本発明の実施形態を示す図である。
【図３】実施例のλ−ＤＮＡスポットを示す図である。
【図４】実施例のλ−ＤＮＡスポットを示す図である。
【符号の説明】
１有機材料
３レーザー光
４分極分子
５有機材料膜
８，１０電極[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for controlling the affinity of a material surface and a method for controlling the affinity of an immobilized carrier surface. More specifically, the present invention relates to a polarized molecular end capable of defining affinity (hydrophilicity or hydrophobicity) by applying a voltage to an organic material containing a polarized molecule having a certain condition to orient the polarized molecule. The present invention relates to a method for controlling the affinity of the surface of the organic material by aligning the surface with the surface of the organic material, and a preferred application of this control method to immobilization of micro object light.
[0002]
[Prior art]
In various industrial fields, a means for controlling the affinity (hydrophilicity and hydrophobicity or wettability) of the material surface is required as part of the material surface modification technique.
[0003]
For example, plastics used in the automobile industry and the electronic industry are progressing in the direction of compounding a plurality of materials, and thus there is an increasing demand for controlling the affinity of the material surface. As an example, there is a need for a technique for improving the adhesion of a paint to a material that becomes a substrate. Further, for example, in the medical device industry, as a surface property of a material used for a portion in direct contact with a living body, a low load on the living body is required.
[0004]
[Patent Document 1] Japanese Patent Publication No. 10-502857
[Patent Document 2] US Pat. No. 5,026,607
Patent Document 1 and Patent Document 2 described above disclose plasma processing and the like as material surface modification means. That is, by performing plasma treatment or corona discharge on the surface of the material in the presence of oxygen, a hydroxyl group or a carboxyl group is introduced into the surface of the material to improve wettability (hydrophilicity).
[0005]
[Patent Document 3] JP-A-1-255857
[Patent Document 4] JP-A-8-216368
In Patent Document 3 and Patent Document 4 described above, in a photoconductor used for a copying machine or the like, an organic dye such as spiropyran capable of photoisomerization is introduced into a polymer material, and a molecular structure based on light absorption of the organic dye A method of changing the wettability of the surface of a polymer material by utilizing the change (isomerization) of the polymer is disclosed.
[0006]
On the other hand, the applicant of the present application already described in Japanese Patent Application No. 2002-56752 and Japanese Patent Application No. 2003-38039 which claimed the priority based on this application (these patent applications have not been published). Proposals have been made on a method for light immobilization of an object and a light immobilization carrier capable of effectively using this method. This light immobilization method is advantageous in that it can be used to immobilize extremely minute biological materials such as proteins, DNA, and living cells on a carrier by light irradiation without degeneration, inactivation or destruction thereof. It is a new technology with a wide range.
[0007]
[Problems to be solved by the invention]
However, the techniques disclosed in Patent Document 1 and Patent Document 2 described above require, for example, an expensive plasma processing facility, can control the affinity of the material surface only in the direction of improving hydrophilicity, This is accompanied by many limitations such that the surface affinity cannot be reversibly changed repeatedly. Further, since the content of the surface modification treatment is severe, for example, in the state where biomolecules are located on the surface of the material, modification, deactivation or destruction of those molecules is unavoidable.
[0008]
The techniques disclosed in Patent Document 3 and Patent Document 4 described above are advantageous in that they use a relatively mild means called light irradiation, but the isomerization state of the dye molecule is inherently stable over time. Therefore, when it is desired to maintain the surface modification state over a certain period of time, it is not necessarily a suitable method.
[0009]
Furthermore, the light immobilization carrier used in the method for immobilizing a micro object according to the proposal of the present applicant also has room for improvement as follows.
[0010]
That is, first, considering the moldability and light immobilization ability of the material, it is advantageous to form at least the surface layer portion of the light immobilization carrier with a polymer material containing a predetermined photoreactive component. However, proteins, DNA, living cells and the like that are particularly important as minute objects to be immobilized on the carrier are mostly hydrophilic and tend to have insufficient affinity with the polymer material on the surface of the carrier. For this reason, it is difficult to stabilize the arrangement state or contact state of the minute object arranged on the carrier surface for light fixation with respect to the carrier surface.
[0011]
Secondly, for example, there is a case where an enzyme that has already been immobilized on the surface of the carrier and has undergone a certain process such as an enzyme activity test is collected from the surface of the carrier to check the residual activity. In these cases, if the enzyme immobilized on the carrier surface is peeled off by forced means such as ultrasonic vibration or exposure to strong water flow, the enzyme is deactivated due to the peeling operation itself, There is concern that it cannot be achieved.
[0012]
Therefore, the present invention provides a method for controlling the affinity of the material surface that can eliminate the drawbacks of the above-mentioned various conventional techniques, and at the same time, this method is applied to the light immobilization method for a micro object, thereby light immobilization. It is a technical problem to be solved to fill the room for improvement described above.
[0013]
[Means for Solving the Problems]
(Configuration of the first invention)
The configuration of the first invention of the present application (the invention described in claim 1) for solving the above problem is a polarized molecule that is electrically polarized in a natural state or that can be electrically polarized by applying a voltage. A method for controlling the affinity of the surface of an organic material containing an organic material, wherein positive and negative voltages are applied in a direction crossing the surface of the organic material to orient the polarized molecules in the organic material along the direction in which the voltage is applied. At the same time, induces or enhances the electric polarization in the polarized molecule, and increases the hydrophilicity of the organic material surface by the hydrophilic property based on the electric polarization at the end of the oriented polarized molecule on the organic material surface side, This is a method for controlling the affinity of the material surface.
[0014]
(Operation and effect of the first invention)
According to the first aspect of the present invention, the end of the polarized / polarized molecule contained in the organic material induced / strengthened by applying a voltage in a predetermined direction is aligned and aligned on the surface of the organic material. The hydrophilicity of the is effectively increased.
[0015]
That is, the first invention provides a new means for modifying the surface of the organic material. Moreover, this means can be realized by a simple and low-cost means in terms of voltage application compared to plasma treatment, etc., and the contents of the surface modification treatment are mild, and the molecular orientation Since the change is utilized, the hydrophilicity of the material surface can be repeatedly and reversibly changed. In addition, in comparison with the technique disclosed in Patent Document 3 and Patent Document 4 that utilizes the isomerization state of dye molecules (a constant equilibrium state between structural isomers), the surface modification state is greatly increased. It is thought to stabilize.
[0016]
Next, the principle of the first invention can be used extremely effectively for further improvement of the method of fixing the microscopic object according to the proposal of the applicant. That is, it is easy to increase the hydrophilicity of the polymer material that constitutes the surface layer portion of the light-immobilized carrier, and if necessary, for example, if a voltage is applied in a direction parallel to the surface of the organic material, It is also easy to restore the affinity of the molecular material (reducing hydrophilicity).
[0017]
(Configuration of the second invention)
The structure of the second invention of the present application (the invention according to claim 2) for solving the above problem is that one end of the molecule is hydrophilic and the other end is hydrophobic, and is electrically polarized in a natural state. A method for controlling the affinity of the surface of an organic material containing a polarized molecule that can be electrically polarized by application of a voltage, the voltage being positive or negative in a direction intersecting the surface of the organic material Is applied to orient the polarized molecules in the organic material along the voltage application direction so that either the hydrophilic or hydrophobic ends of the polarized molecules are aligned with the surface side of the organic material. This is a method for controlling the affinity of the material surface to control the hydrophilicity / hydrophobicity of the surface.
[0018]
(Operation and effect of the second invention)
In the second invention, unlike the first invention that uses the induction or enhancement of electrical polarization at the end of the polarized molecule, the surface of the material that uses the hydrophilic part / hydrophobic part provided at the end of the polarized molecule. This is a method for controlling affinity. However, at least the same actions and effects as those of the first invention can be expected.
[0019]
In addition, in the second invention, the end of the polarization molecule that is inherently hydrophilic / hydrophobic is used, so that the affinity control effect is clearer and larger than in the first invention. Furthermore, it is possible not only to increase or decrease the hydrophilicity of the surface of the organic material, but also to control the affinity of the surface of the organic material between clear hydrophilicity and clear hydrophobicity. For example, if a voltage is applied in a direction parallel to the surface of the organic material, the polarized molecules will lie on the surface of the organic material and the hydrophilic end and the hydrophobic end will be evenly exposed. Can be adjusted to an intermediate state between hydrophilicity and hydrophobicity.
[0020]
(Configuration of the third invention)
The configuration of the third invention of the present application (the invention described in claim 3) for solving the above-described problem is that, in controlling the surface of the organic material according to the second invention in either the hydrophilic / hydrophobic direction, The direction of the voltage to be applied is selected in consideration of the electric polarization content of the polarized molecule, so that one of the hydrophilic end / hydrophobic end of the polarized molecule is made an organic material. This is a method for controlling the affinity of the material surface to be aligned on the surface side of the material.
[0021]
(Operation and effect of the third invention)
In the second invention, unlike the first invention, the end of the polarized molecule is not aligned with the surface of the organic material, but the hydrophilic end or the hydrophobic end is selectively placed on the surface of the organic material. It must be oriented sideways. Therefore, it is preferable to select the positive / negative direction of the voltage to be applied in consideration of the content of the electric polarization of the polarized molecule.
[0022]
That is, for example, in an electrically polarized state of a polarized molecule that is induced or strengthened by application of a voltage, a hydrophilic end is set at an end on the δ + side (an end on the electron donating side in the entire polarized molecule). If so, by applying a voltage so that the surface of the organic material is the negative electrode and the back surface is the positive electrode, the hydrophilic end of the polarized molecule is aligned on the surface of the organic material, so that the surface changes to hydrophilic. Can be made. Moreover, this change to hydrophilicity is further enhanced by the electrical polarization of the polarized molecules.
[0023]
(Configuration of the fourth invention)
The structure of the fourth invention of the present application (the invention described in claim 4) for solving the above problems is that the organic material according to any one of the first invention to the third invention is the following (1) to (3). The method for controlling the affinity of the material surface, which comprises a polarized molecule in any of the above aspects.
(1) An organic material composed of polarized molecules that are organic molecules.
(2) An organic material in which polarized molecules are dispersed in a matrix made of an appropriate material.
(3) An organic material in which polarization molecules are bonded to constituent molecules of a matrix made of an appropriate material.
[0024]
(Operation and effect of the fourth invention)
The organic material according to the present invention needs to contain a polarized molecule, but its “including” aspect is not limited. However, any one of the aspects (1) to (3) of the fourth invention can be preferably exemplified. In view of the cost of the organic material, moldability, stable maintenance of the controlled orientation of the polarized molecules, etc., the aspect (3) is particularly preferable.
[0025]
(Structure of the fifth invention)
In order to solve the above problems, the fifth invention of the present application (the invention according to claim 5) is a molecule in which the polarized molecule according to any one of the first to fourth inventions contains at least one aromatic ring. This is a method for controlling the affinity of the material surface.
[0026]
(Operation and effect of the fifth invention)
There are no limitations on the type of polarized molecule, but it is a molecule that contains at least one aromatic ring because it is electrically polarized in the natural state or can be electrically polarized by applying a voltage. Is preferred.
[0027]
(Structure of the sixth invention)
The structure of the sixth invention of the present application (the invention according to claim 6) for solving the above problem is that the polarization molecule according to any of the first to fourth inventions is at least an azo group, an azomethine group or an ethylene group. Is a molecule containing two aromatic rings linked via a linker structure part selected from the group comprising: a material surface affinity control method.
[0028]
(Operation and effect of the sixth invention)
When the polarized molecule includes two aromatic rings connected via a predetermined linker structure as in the sixth invention, a larger electrical polarization can be expressed. In such a polarized molecule, since the molecular orientation due to the application of voltage is more remarkable, the change in the affinity of the organic material surface becomes more significant.
[0029]
(Structure of the seventh invention)
The structure of the seventh invention of the present application (the invention according to claim 7) for solving the above problem is that the aromatic ring in the polarized molecule containing the aromatic ring according to the fifth or sixth invention is an electron donating group. And / or a material surface affinity control method comprising an electron-withdrawing group.
[0030]
(Operation and effect of the seventh invention)
When the polarized molecule includes an aromatic ring having an electron donating group and / or an electron withdrawing group as in the seventh invention, the electric polarization in the molecule at the time of application of a natural state and voltage becomes stronger.
[0031]
(Configuration of the eighth invention)
The structure of the eighth invention of the present application (the invention according to claim 8) for solving the above-described problem is that in the polarized molecule containing two linked aromatic rings according to the sixth invention or the seventh invention, one fragrance This is a method for controlling the affinity of the material surface, in which the ring has an electron-donating group and the other aromatic ring has an electron-withdrawing group.
[0032]
(Operation and effect of the eighth invention)
When the polarized molecule includes two aromatic rings each having an electron donating group and an electron withdrawing group as in the eighth invention, the electric polarization in the molecule at the time of application of a natural state and voltage is further increased.
[0033]
(Structure of the ninth invention)
The structure of the ninth invention of the present application (the invention according to claim 9) for solving the above problem is that one or two aromatic rings according to the seventh invention or the eighth invention are an electron donating group and an electron withdrawing property. In the case of providing a group, the electron-donating group is a hydrophilic group or a hydrophobic group, and the electron-withdrawing group is conversely a hydrophobic group or a hydrophilic group.
[0034]
(Operation and effect of the ninth invention)
As in the ninth invention, when one of the electron donating group and the electron withdrawing group in one or two aromatic rings is a hydrophilic group and the other is a hydrophobic group (or conversely, one is a hydrophobic group When the other is a hydrophilic group), the intrinsic hydrophilicity or hydrophobicity of the electron donating group and the electron withdrawing group develops in addition to the magnitude of the electric polarization of the polarized molecule.
[0035]
For this reason, the effect of controlling the affinity by the orientation of the polarized molecules on the surface of the organic material becomes even more remarkable. In particular, when the polarized molecules are oriented so that the hydrophilic group is aligned with the surface of the organic material, the surface of the organic material can exhibit exceptionally significant hydrophilicity.
[0036]
(Configuration of the tenth invention)
The structure of the tenth invention of the present application (the invention according to claim 10) for solving the above-mentioned problems is that the organic material is applied when a voltage is applied to the organic material according to any one of the first to ninth inventions. This is a method for controlling the affinity of the material surface, which heats the glass transition point or higher.
[0037]
(Operation and effect of the tenth invention)
When the organic material is heated to a temperature higher than the glass transition point, the degree of freedom of orientation of the polarized molecules is remarkably increased, so that molecular orientation is extremely likely to occur when a voltage is applied. When this point is effectively used, the stability of the affinity control on the surface of the organic material is remarkably improved.
[0038]
That is, for example, the techniques disclosed in Patent Document 3 and Patent Document 4 have a serious drawback of lacking the stability of the surface modification state, but in the tenth invention, the locked state called the orientation of polarized molecules is It can be changed by an unlocking means that heats the organic material above the glass transition point. Therefore, the affinity of the organic material surface can be clearly used for the stabilized control state and the change or relaxation of the control state by the unlocking means.
[0039]
(Structure of 11th invention)
The configuration of the eleventh invention of the present application (the invention according to the eleventh aspect) for solving the above-described problem is that a voltage is applied in the cross direction to the surface of the organic material according to any one of the first to tenth inventions. This is performed by positive and negative electrodes provided along the direction intersecting the surface of the organic material, or two or more kinds of irradiation light generated on the same axis and having a frequency having a multiple relation are applied to the surface of the organic material. On the other hand, this is a method for controlling the affinity of the material surface by irradiating from an oblique direction.
[0040]
(Operation and effect of the eleventh invention)
A means for applying a voltage in the cross direction to the surface of the organic material is not limited, but as defined in the eleventh invention, the use of positive and negative electrodes or predetermined light irradiation from a specific direction can be preferably exemplified. In the method for controlling the affinity of the surface of the immobilization carrier according to the thirteenth aspect of the invention, since the light immobilization material is used as the organic material, it is better to avoid using irradiation light as voltage applying means for the surface of the organic material. .
[0041]
(Configuration of the twelfth invention)
The structure of the twelfth invention of the present invention (the invention according to claim 12) for solving the above-described problems is the following (4). The method for controlling the affinity of the material surface according to any one of the first to eleventh inventions. ) To (6), which is a method for controlling the affinity of the material surface.
(4) Controlling the affinity of the surface of the organic material by applying a voltage as a processing process for an organic material newly manufactured or used as a product or product member.
(5) By attaching voltage application means in a form that allows positive and negative voltages to be applied to the organic material in the usage environment as a product or product member in a direction crossing the surface, the affinity of the organic material surface Sexual control is always possible.
(6) With respect to an organic material in a use environment as a product or a product member, a positive / negative voltage can be applied in a direction crossing the surface, and a positive / negative voltage direction can be reversed. By attaching the voltage application means, it is possible to always control the affinity of the organic material surface.
[0042]
(Operation and effect of the twelfth invention)
A method for controlling the affinity of the material surface as a kind of surface modification technique is required in a wide variety of technical fields. As a preferred category of the embodiment, (4) to (6) of the twelfth invention Embodiments can be illustrated.
[0043]
In the aspect (4), transient affinity control is performed as a processing process for an organic material, and stability over time of the affinity control state is required. Aspects (5) and (6) are controls when it is preferable to perform the affinity control of the surface of the organic material in the usage environment as needed, and with a simple control means along with the stability of the affinity control state. It is required that the control state can be switched quickly and reliably.
[0044]
(Structure of the thirteenth invention)
The structure of the thirteenth invention of the present application (the invention described in claim 13) for solving the above problems is that the organic material according to any one of the first invention, the second invention, and the fourth invention to the ninth invention is irradiated light. In the case where it is also a light immobilization material that is capable of immobilizing a micro object arranged on the surface thereof, the immobilization support using the organic material is formed at least on the surface layer portion, and positive and negative electrodes are used. By applying a voltage in a direction crossing the surface of the immobilization carrier, the affinity of the immobilization carrier surface with respect to a micro object is controlled for the purpose of (7) or (8) below. This is a method for controlling affinity.
(7) Prior to immobilization of the minute object, an operation of stabilizing the arrangement state or contact state of the minute object arranged on the surface of the immobilization carrier with respect to the immobilization carrier.
(8) An operation for relaxing the immobilization state of a minute object already immobilized on the surface of the immobilization carrier in accordance with a predetermined technical requirement.
(Operation and effect of the thirteenth invention)
According to (7) of the thirteenth aspect of the present invention, the arrangement state or contact state of hydrophilic micro objects such as proteins, DNA, living cells, etc. is stabilized with respect to the surface of the immobilization carrier using the light immobilization material that is an organic material The light immobilization of the minute object can be performed more accurately (for example, at a precise predetermined position on the surface of the immobilization carrier) and reliably (for example, at a very high immobilization rate).
[0045]
According to (8) of the thirteenth invention, if necessary, a minute object light-immobilized on the surface of the carrier can be gently used without relying on severe forced means such as ultrasonic vibration or exposure to a strong water flow. It can be detached from the surface of the carrier and collected by means (slow vibration, exposure to a weak water flow, etc.). This is very advantageous from the viewpoint of regenerative medicine and the like because, for example, when recovering viable cells immobilized on the surface of the carrier, there is little fear that the detachment operation from the surface of the carrier will inactivate the viable cells.
[0046]
DETAILED DESCRIPTION OF THE INVENTION
Next, embodiments of the first to thirteenth inventions will be described. Hereinafter, the term “present invention” refers to each of these inventions comprehensively.
[0047]
[Polarized molecule]
In the present invention, a polarized molecule refers to a molecule that is electrically polarized in a natural state or that can be electrically polarized by application of a voltage. Furthermore, a polarized molecule is a polarized molecule in which one end of the molecule is hydrophilic and the other end is hydrophobic, and is electrically polarized in a natural state, or can be electrically polarized by applying a voltage. Also refers to molecules. As long as it corresponds to such conditions, the kind of polarization molecule is not limited, but the following types of polarization molecules are particularly preferable.
[0048]
That is, first, a polarized molecule containing at least one aromatic ring is preferred. More preferred is a polarized molecule comprising two aromatic rings linked via a predetermined linker structure. The “predetermined linker structure” refers to, for example, an azo group, an azomethine group, an ethylene group, or the like that connects two aromatic rings. In a polarized molecule containing an aromatic ring, it is more preferable that the aromatic ring has an electron donating group and / or an electron withdrawing group. Of the two aromatic rings linked via the linker structure, it is particularly preferred that one aromatic ring has an electron donating group and the other aromatic ring has an electron withdrawing group. Further, in the case where one or two aromatic rings in the polarization molecule have an electron donating group and an electron withdrawing group, the electron donating group is a hydrophilic group or a hydrophobic group, and the electron withdrawing group is vice versa. It is also particularly preferable that it is a hydrophobic group or a hydrophilic group.
[0049]
The hydrophilic electron-donating group is a primary to tertiary amino group, a hydroxyl group, the hydrophobic electron-donating group is an alkyl group, an alkoxy group, or the like, and the hydrophilic electron-withdrawing group is a carboxyl group. Acetyl group, sulfonic acid group and the like, and hydrophobic electron withdrawing groups include fluoroalkyl group, fluorine group, nitro group, cyano group and the like.
[0050]
Since an aromatic ring is itself hydrophobic, in a polarized molecule where a single aromatic ring has a single electron donating group or electron withdrawing group, the electron donating group or electron withdrawing group is hydrophilic It is preferable. In a polarized molecule in which a single aromatic ring is provided with an electron donating group and an electron withdrawing group, it is preferable that these exist at the para position.
[0051]
(Photoreactive component)
As a preferable example of the photoreactive component, ablation, photochromism, photo-induced orientation of molecules, etc. are caused by light irradiation, and as a result, the volume, density, free volume, etc. of the photo-immobilized material are changed to generate photo deformation. Such components can be mentioned.
[0052]
Although the kind of photoreactive component is not limited, For example, the photoisomerization component and photopolymerizable component which are components which can raise | generate anisotropic photoreaction accompanying the shape change of material can be illustrated preferably. When the micro object to be immobilized is a biological substance whose activity is impaired by a chemical reaction with the carrier material, a photoisomerization component is preferable as the photoreactive component. As the photoisomerization component, for example, a component causing trans-cis photoisomerization, particularly typically a dye structure having an azo group (—N═N—), particularly a component having a chemical structure of azobenzene or a derivative thereof. Can be preferably exemplified.
[0053]
Therefore, the component having a chemical structure of azobenzene or its derivative is a preferable polarization molecule and a preferable photoreactive component. Therefore, the polymer material containing such a component is a preferable organic material according to the present invention. It is also a preferred light immobilization material.
[0054]
When the photofixation material is a material including a dye structure having an azo group, the dye structure has one or more electron-withdrawing functional groups (electron-withdrawing substituents) and / or one or two or more. It is particularly preferable to have an electron donating functional group (electron donating substituent). It is particularly preferable to combine these electron-withdrawing functional group and electron-donating functional group. Such an azo group-containing dye structure having both an electron-withdrawing functional group and an electron-donating functional group is simultaneously a preferable polarized molecule as described above.
[0055]
[Organic materials, light immobilization materials]
The organic material according to the present invention includes a polarized molecule, and can control the affinity of the surface of the organic material due to the orientation of the polarized molecule by applying a voltage in a direction crossing the surface of the organic material. Say. The organic material according to the present invention includes an organic material that is also a light fixing material.
[0056]
A light immobilization material contains a photoreactive component together with the above-mentioned polarized molecules, and causes light deformation caused by the photoreactive component, thereby immobilizing a minute object placed on the surface during light irradiation. It is a material to show. As mentioned above, the polarization molecule may be a photoreactive component at the same time.
[0057]
Although the aspect in which an organic material or a light immobilization material contains a polarization molecule or a photoreactive component is not limited, preferred examples include (1) a photoreactive component in which the organic material or the light immobilization material is a polarization molecule or an organic molecule. The case where it consists of can be mentioned. Next, (2) a case where polarized molecules and photoreactive components are dispersed in a matrix made of an appropriate organic material can be mentioned. Furthermore, (3) the case where a polarized molecule or a photoreactive component is bonded to a constituent molecule of a matrix made of an appropriate material can be particularly preferably mentioned.
[0058]
As a material constituting the matrix of the organic material or the light fixing material, a polymer material is particularly preferable. The type of polymer material is not limited, but those containing a urethane group, urea group, or amide group in the repeating unit of the polymer, and a ring structure such as a phenylene group in the polymer main chain. It is preferable in terms of heat resistance. As long as the polymer material can be molded into the required shape, the polymerization form may be any form such as linear, branched, ladder or star shape, regardless of molecular weight or degree of polymerization. A copolymer may also be used.
[0059]
The glass transition temperature of the polymer material is, for example, 100 ° C. or higher for the stability of the orientation state of the polarized molecules and the stability of the optical deformation of the light-immobilized material (maintaining the fixing force with respect to the minute object over time). However, considering the case where it is desired to orient the polarized molecules in an aqueous medium, those having a glass transition temperature of 100 ° C. or lower are also preferable.
[0060]
From the above points, as specific examples of the polymer material particularly preferable as the organic material (light-fixing material) according to the present invention, the following “Chemical Formula 1” to “Chemical Formula 4” are described in addition to those described in Examples. The following are listed. In these examples, -X represents a nitro group, a cyano group, a trifluoromethyl group, an aldehyde group or a carboxyl group, -Y- represents -N = N-, -CH = N- or -CH = CH-, R- represents a phenylene group, an oligomethylene group, a polymethylene group or a cyclohexane group, respectively.
[0061]
[Chemical 1]

[0062]
[Chemical 2]

[0063]
[Chemical 3]

[0064]
[Formula 4]

[Control of material surface affinity]
The method for controlling the affinity of the material surface according to the present invention is roughly classified into two methods.
[0065]
In the first method, a positive and negative voltage is applied in a direction crossing the surface of the organic material containing the polarized molecule to orient the polarized molecule in the organic material along the direction in which the voltage is applied. This is a method for inducing or strengthening the local polarization. Thereby, the hydrophilic property on the surface of the organic material is increased by the hydrophilic property based on the electric polarization at the end of the oriented polarized molecule on the surface side of the organic material.
[0066]
The second method is a polarized molecule in which one end of the molecule is hydrophilic and the other end is hydrophobic and is electrically polarized in a natural state or can be electrically polarized by applying a voltage. In this method, positive and negative voltages are applied in a direction crossing the surface of the organic material containing, so that polarized molecules in the organic material are aligned along the voltage application direction. Thus, the hydrophilic / hydrophobic property of the surface of the organic material is controlled by aligning either the hydrophilic or hydrophobic end of the polarized molecule with the surface side of the organic material.
[0067]
In the second method, it is desirable that the positive / negative direction of the applied voltage can be selected in order to control the surface of the organic material in either the hydrophilic / hydrophobic direction. The selection of the positive / negative direction of the voltage is determined by whether the hydrophilic end of the polarized molecule is δ + / δ− in the electrically polarized state of the polarized molecule at the time of voltage application. This makes it possible to align one selected end of the hydrophilic / hydrophobic ends of the polarized molecule with the surface side of the organic material.
[0068]
As an embodiment of the method for controlling the affinity of the surface of the material, for example, the affinity of the surface of the organic material is controlled by applying a voltage as a processing process to an organic material that is newly manufactured or already used as a product. be able to. Specifically, this embodiment can be used when, for example, the adhesion between the coating films is improved when the coating films are laminated in an automobile painting process.
[0069]
As another embodiment, for example, the surface of the organic material is provided by attaching voltage applying means in a form in which positive and negative voltages can be applied in a direction crossing the surface of the organic material in a use environment as a product. It is possible to always control the affinity. Specifically, this embodiment can be used for separation and purification of hydrophilic and hydrophobic objects such as proteins. After attaching only hydrophobic substances to the surface of the organic material that has been adjusted to be hydrophobic beforehand, the hydrophobic surface of the organic material is hydrophilized to remove these hydrophobic substances. Or it can be purified.
[0070]
In still another embodiment, for example, a positive / negative voltage direction can be applied to an organic material in a use environment as a product in a direction crossing the surface, and the positive / negative voltage direction is reversed. By attaching the voltage application means in the form to be obtained, it is possible to always control the affinity of the organic material surface. Specifically, this embodiment uses an organic material as a coating on a window glass of an automobile, and is controlled to be hydrophilic (increase wettability) during low-speed driving to prevent light scattering by raindrops. It can be used as an active wiper that repels rainwater by controlling it to be hydrophobic during traveling.
[0071]
[Application of voltage]
As a method for applying a voltage to the organic material, for example, positive and negative electrodes provided along a direction intersecting the surface of the organic material can be used.
[0072]
Also, for example, it can be performed by irradiating the surface of the organic material with two or more types of irradiation light generated on the same axis and having a frequency having a multiple relation from an oblique direction. As a specific embodiment of this method, for example, as shown in FIG. 1, a laser beam 3 from a laser device 2 provided with a second harmonic generator is incident on the surface of the organic material 1 from an oblique direction. can do. Since this laser beam 3 has a configuration in which a fundamental wave having a frequency of ω and a second harmonic having a frequency of 2ω are generated on the same axis, the surface of the organic material 1 is obtained by superimposing the light of the two frequencies. An electric field in an oblique direction can be induced. Therefore, a large number of polarized molecules 4 in the organic material 1 can be oriented so that one end side of the electrically polarized molecules is aligned with the surface of the organic material 1.
[0073]
The reversal of the positive / negative direction in the electric field is easy when the positive / negative electrodes are used, and when the electric field is induced by the irradiation light described above, the polarization direction of the light is set to a ½ wavelength plate and a ¼ wavelength. This is possible by rotating the plate. By doing so, it can be oriented so that the other end side of the polarization molecule 4 is aligned with the surface of the organic material 1.
[0074]
When applying a voltage to the organic material, if the organic material is heated above its glass transition point, the orientation of the polarized molecules becomes remarkably easy and the effect of controlling the affinity of the organic material surface becomes remarkably remarkable.
[0075]
[Controlling the affinity of the surface of the immobilized carrier]
In the method for controlling the affinity of the surface of the immobilization carrier, a voltage is applied by positive and negative electrodes in a direction intersecting with the surface of the immobilization carrier using at least the organic material as the light immobilization material for the surface layer. , To control the affinity of the surface of the immobilization carrier for the minute object. This control is performed as the following operation (7) or (8).
(7) An operation of stabilizing the arrangement state or the contact state of the minute object arranged on the surface of the immobilization carrier with respect to the immobilization carrier prior to the immobilization of the minute object.
(8) An operation for relaxing the immobilization state of the minute object that has already been immobilized on the surface of the immobilization carrier according to a predetermined technical requirement.
[0076]
[Light immobilization of minute objects]
For light immobilization of a micro object, an immobilization carrier using the light immobilization material for at least a surface layer portion is used. A minute object, which is a tangible object having a size of about 50 μm or less, is placed (contacted) on the surface of the immobilization carrier, and the minute object is immobilized on the surface of the carrier by irradiation light.
[0077]
Although the form which arrange | positions a micro object on the surface of a support | carrier is arbitrary, it is preferable to arrange a micro object on the support | carrier surface in liquid media, such as water. As its specific form, for example, the carrier is immersed in a liquid medium (water, buffer solution, etc.) in which a minute object is dissolved or suspended, or a small amount of the liquid medium is dropped on the surface of the carrier. Embodiments can be preferably exemplified. The kind of micro object is not limited, and the number of micro objects to be immobilized on the carrier is not limited.
[0078]
The technical category of the micro object and the carrier on which it is immobilized includes metal particles, metal oxide particles, semiconductor particles, ceramic particles, plastic particles, or two or more of these materials (for example, mixing of two materials) Body or multi-layer structure) field effect transistor with fixed particles, two-dimensional photonic crystal, electrical or optical integrated circuit chip, and the like.
[0079]
In addition, polypeptides, more specifically, bioreactors and biosensors, integrated enzyme transistors, immunoassay test chips in which various groups of proteins expressed in enzymes, antigens, antibodies, cell membrane receptor proteins or biological cells are immobilized, Examples include a test chip for proteome analysis.
[0080]
Further, a DNA chip or DNA microarray on which a single-stranded or double-stranded or more (including triple-stranded, four-stranded) nucleic acid, that is, a polynucleotide, more preferably a single-stranded polynucleotide capable of hybridization is immobilized. Can also be illustrated. Examples also include a carrier on which cells or microorganisms, particularly preferably cells or microorganisms in a living state, are immobilized.
[0081]
As a carrier, in addition to the above-mentioned relatively small chip form, a form such as a granule for filling a column or the like, a form of a large fixed reaction bed in which a substrate solution etc. flows on the surface, a simple immunoassay, etc. For example, a form like a small-sized test paper, a form like a slide glass used for microscopic observation, and the like.
[0082]
As irradiation light for light fixation, any irradiation light such as propagating light, near-field light, or evanescent light can be used as long as there is no mismatch in combination with a material that causes optical deformation. Natural light, laser light, or the like can be used as the propagating light. The polarization characteristics can be used as propagating light, near-field light, or evanescent light.
[0083]
As a light irradiation method, it is also preferable to give a certain distribution to the irradiation region or irradiation intensity. In that case, a large number of minute objects can be immobilized on the surface of the carrier according to a certain distribution pattern. Therefore, when configuring an electrical or optical integrated circuit chip or the like, or configuring an integrated enzyme transistor, etc. It is effective for. In particular, a functionally complex circuit or the like can be formed by repeatedly immobilizing the same carrier according to different distribution patterns using different types of minute objects.
[0084]
For example, a photomask can be used as a means for providing such irradiation light irradiation region or irradiation intensity distribution. A method of moving micro objects to a predetermined position by known laser trapping is also used as a means to place micro objects on a specific part of the surface of the carrier or to arrange many micro objects on the surface of the carrier according to a certain distribution pattern. it can.
[0085]
【Example】
[Example 1]
(Synthesis of organic material according to the present invention)
An azo dye represented by the following “Chemical Formula 5” containing an azobenzene structure was synthesized by a predetermined process and then acrylated by an acid chloride reaction to synthesize a compound represented by the following “Chemical Formula 6”. Next, methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) from which the polymerization inhibitor had been removed by vacuum distillation was copolymerized with the compound of Chemical Formula 6 to obtain a polymer compound represented by the following “Chemical Formula 7”.
[0086]
[Chemical formula 5]

[0087]
[Chemical 6]

[0088]
[Chemical 7]

The compound of Chemical Formula 6 contained in a state bonded to the polymer compound of Chemical Formula 7 includes an amino group that is electron-donating and hydrophilic at one end of the azobenzene structure, and is electron-withdrawing and hydrophobic at the other end. A cyano group which is Since the compound of Chemical formula 6 is both a polarized molecule and a photoreactive component, the chemical compound of Chemical formula 7 is both an organic material according to the present invention and a light-fixing material, and its glass transition temperature is about 120 ° C.
[0089]
(Preparation of organic material film and orientation of polarized molecules)
A solution in which 50 mg of the polymer compound of Chemical Formula 7 was dissolved in 2 mL of pyridine was prepared, and about 1 mL of this solution was dropped on a slide glass substrate. Then, the solvent was removed by rotating the slide glass substrate at 2000 rpm to produce an organic material film having a uniform film thickness of about 110 nm.
[0090]
Next, as shown in FIG. 2, the slide glass substrate 6 on which the organic material film 5 was formed was placed on a plate electrode 8 provided with a heater 7 for heating the substrate. The flat plate electrode 8 is connected to a needle electrode 10 installed above the organic material film 5 via a high voltage power source 9.
[0091]
(Measurement of contact angle)
Before voltage application by the

electrodes

8 and 10, water was dropped on the organic material film 5, and the contact angle with water on the surface of the organic material film 5 was measured. The contact angle was 67 degrees. Next, when the organic material film 5 was not heated by the heater 7 and the flat electrode 8 was used as a positive electrode and the needle electrode 10 was used as a negative electrode, the contact angle was measured while applying a voltage for 300 seconds. The angle was 50 degrees (Example 1-1). Further, when the organic material film 5 was heated to 150 ° C. with the heater 7 and the voltage applied by the

electrodes

8 and 10 was applied for 300 seconds, and then cooled to room temperature and the contact angle was measured, the contact angle was 25. (Example 1-2).
[0092]
Next, the organic material film 5 showing the contact angle of 25 degrees is set upright together with the slide glass substrate 6 (the voltage is set so as to be applied horizontally to the surface of the organic material film 5), and the same as above When a voltage was applied while the organic material film 5 was heated, and the contact angle was measured after cooling to room temperature, the contact angle returned to approximately 67 degrees (Example 1-3). Further, the slide glass substrate 6 is returned to the original state (shown in FIG. 2), and the organic material film 5 is heated in the same manner as described above, with the plate electrode 8 as the negative electrode and the needle electrode 10 as the positive electrode, contrary to the above. After applying the voltage, the contact angle on the surface of the organic material film 5 was measured by cooling to room temperature, and the contact angle was 80 degrees larger than the initial contact angle (Example 1-4).
[0093]
As is clear from the above results, when a voltage is applied in a predetermined direction to an organic material containing polarized molecules, the hydrophilicity of the organic material surface is significantly improved. In particular, when a voltage is applied while heating to a temperature equal to or higher than the glass transition temperature of the organic material, the hydrophilicity of the organic material surface is significantly improved. In addition, the affinity of the organic material surface can be controlled in various ways by changing the voltage application method.
[0094]
The results of Examples 1-1 and 1-2 were obtained by aligning the electron donating and hydrophilic amino groups in the compound of Chemical Formula 6 contained in the organic material film 5 on the surface of the organic material film 5. The result of Example 1-3 is due to the fact that the compound of Chemical Formula 6 is aligned in parallel with the surface of the organic material film 5, and the result of Example 1-4 is the electron in the compound of Chemical Formula 6 It is thought that cyano groups that are attractive and hydrophobic are aligned and aligned on the surface of the organic material film 5.
[0095]
On the other hand, as Comparative Example 1, on a glass substrate similar to Example 1 using methyl methacrylate, which is an acrylic polymer material that does not contain polarized molecules (photoreactive components) and has a glass transition temperature of 120 ° C. The material film was constructed. When a contact angle was measured by the same method as described above before applying a voltage to the material film, the contact angle was 70 degrees. Next, this glass substrate is brought into the voltage application device of FIG. 2 and, after being heated to 150 ° C., a voltage is applied by the plane electrode 8 (positive electrode) and the needle electrode 10 (negative electrode) for 300 seconds, and then cooled to room temperature. When the contact angle was measured, the contact angle was 70 degrees.
[0096]
As is clear from the above results, in organic materials that do not contain polarized molecules, even if a voltage is applied while heating to a temperature above the glass transition temperature, it is possible to change and control the affinity of the organic material surface. Have difficulty.
[0097]
[Example 2]
Using the organic material film as a carrier, a DNA microarray was prepared and fluorescence was detected. In carrying out this example, the organic material film that was initially produced in Example 1 (before voltage application) was referred to as Comparative Example 2, and the organic material film in the state of Example 1-2 was referred to as Example 2.
[0098]
100 μL of a solution (0.5 μg / μL) in which λ-DNA (48K base pair manufactured by Nippon Gene Co., Ltd.) was dissolved in a pH 8.0 buffer solution was placed in an Eppendorf tube, and further a fluorescent dye for DNA staining (manufactured by Molecular Probe) 1 μL of a stock solution of TO-PRO-3 iodide was added and stirred, and λ-DNA was stained with a fluorescent substance.
[0099]
The λ-DNA thus stained with the fluorescent dye was spotted on the organic material films according to Example 2 and Comparative Example 2 using 417 Arrayer manufactured by Affymetrix. Each spot has a diameter of 125 μm and a spot interval of 375 μm. Next, the fluorescence from λ-DNA spotted on the organic material film was analyzed using a 428 Array Scanner manufactured by Affymetrix. Analysis was performed using a Cy5 filter set (excitation 632 nm, fluorescence 660-680 nm).
[0100]
FIG. 2 shows the results for Example 2. In Example 2, a circular and uniform spot having a diameter of 125 μm was observed, whereas in Comparative Example 2 shown in FIG. Strong portions were biased, and the uniformity of the spot was insufficient in comparison with Example 2. This difference is considered to be due to the difference in the relative hydrophilicity of the organic material film when the λ-DNA solution is spotted. That is, in Example 2 excellent in wettability with water, the λ-DNA solution is uniformly dried over the entire surface of the spot, whereas in Comparative Example 2, the wettability with water is insufficient. -It is considered that the λ-DNA solution is biased toward the periphery of the spot as the DNA solution dries.
[0101]
Example 3
In Example 1, the organic material film in the state before voltage application was set as Comparative Example 3, and the organic material film according to Example 1-2 was set as Example 3. It was. Therefore, each of these organic material films was cut into a size of 1 cm × 1 cm to obtain a fixing carrier substrate according to Comparative Example 3 and Example 3.
[0102]
10 mg of proteolytic enzyme [Protease (Subtilisin Carlsberg)] was dissolved in 10 mL of ion-exchanged water. In this enzyme aqueous solution, the fixing carrier substrate according to Comparative Example 3 and Example 3 described above was immersed, and the wavelength of the fixing carrier substrate was 488 nm and the intensity was 80 mW / cm. ² Was irradiated for 30 minutes.
[0103]
Next, these immobilizing carrier substrates were taken out of the enzyme aqueous solution, immersed in different ion exchange water, and stirred for 30 minutes. Thereafter, these immobilizing carrier substrates were washed with fresh ion exchange water.
[0104]
On the other hand, 4 mg of artificial substrate (BOC-GGL-PNA) was dissolved in 1 mL of dimethylformamide. When this artificial substrate is decomposed by a proteolytic enzyme, p-nitroanilide is dissolved and absorption at a wavelength of 380 nm is increased, so that the solution is colored yellow. 50 μL of this artificial substrate solution was collected and added to 450 μL of 10 mM Tris-HCl buffer (pH 8.0) to obtain a reaction solution.
[0105]
50 μL of each reaction solution was dropped on the surface of the fixing carrier substrate according to Comparative Example 3 and Example 3, and held at 37 ° C. for 1 hour. Thereafter, each reaction solution was blotted out and the absorbance at 380 nm was measured using a UV / VIS spectrometer. As a result, the absorbance of the solution dropped onto the fixing carrier substrate according to Example 3 increased by 0.245, and the absorbance of the solution dropped onto the fixing carrier substrate according to Comparative Example 3 increased by 0.117.
[0106]
Since any immobilization carrier substrate is washed with ion-exchanged water, the difference in the amount of increase in the absorbance is different from the difference in hydrophilicity in the immobilization carrier substrate due to the difference in the amount of enzyme immobilized upon light irradiation. Thus, it can be considered that the immobilization carrier substrate according to Example 3 is a result of photoimmobilization of a larger amount of enzyme than the immobilization carrier substrate according to Comparative Example 3.
[0107]
Example 4
Two immobilization carrier substrates according to Example 3 above, on which an enzyme was immobilized as in Example 3, were prepared. One of them is brought into the voltage application device shown in FIG. 2 in the state shown in FIG. 2, and the plate electrode 8 is used as a negative electrode and the needle electrode 10 is used as a positive electrode, and a voltage is applied for 300 seconds at room temperature (Example 4). -1). The other fixing carrier substrate was not subjected to the voltage application process (Example 4-2).
[0108]
The fixing carrier substrates according to Example 4-1 and Example 4-2 were each immersed in 300 μL of ion exchange water and stirred for 30 minutes. Next, 50 μL was taken out from each 300 μL of ion-exchanged water subjected to the immersion and stirring, and mixed with 50 μL of each of the same reaction solutions used in Example 3.
[0109]
With respect to these mixed solutions, the absorbance at 380 nm using a UV / VIS spectrometer was measured immediately after mixing and after being held at 37 ° C. for 1 hour after mixing, and the change in absorbance during that time was examined. As a result, the absorbance increased by 0.05 in the ion-exchanged water used in Example 4-1, but the absorbance did not change in the ion-exchanged water used in Example 4-2.
[0110]
From the above results, in the fixing carrier substrate according to Example 4-1, the surface of the fixing carrier substrate was hydrophobized by the voltage application process, and the enzyme was easily detached under mild conditions. It can be seen that the activity was maintained. Further, from the comparison with Example 4-1, it can be seen that the enzyme was not detached by immersion and stirring in ion-exchanged water in the immobilizing carrier substrate according to Example 4-2.
[Brief description of the drawings]
FIG. 1 is a diagram showing an embodiment of the present invention.
FIG. 2 is a diagram showing an embodiment of the present invention.
FIG. 3 is a diagram showing λ-DNA spots in Examples.
FIG. 4 is a diagram showing λ-DNA spots in Examples.
[Explanation of symbols]
1 Organic materials
3 Laser light
4 Polarized molecules
5 Organic material film
8,10 electrodes

Claims

A method for controlling the affinity of a surface of an organic material comprising a polarized molecule that is electrically polarized in nature or that can be electrically polarized by application of a voltage, comprising:
By applying positive and negative voltages in a direction crossing the surface of the organic material, the polarized molecules in the organic material are aligned along the direction of voltage application, and at the same time, the electric polarization in the polarized molecules is induced or strengthened, A method for controlling the affinity of a material surface, wherein the hydrophilic property of the surface of the organic material is increased by the hydrophilic property based on the electric polarization at the end of the polarized molecule on the organic material surface side.

The surface of an organic material containing a polarized molecule in which one end of the molecule is hydrophilic and the other end is hydrophobic and is electrically polarized in a natural state or can be electrically polarized by applying a voltage A method for controlling the affinity of
By applying a positive or negative voltage in a direction crossing the surface of the organic material and orienting the polarized molecules in the organic material along the direction of voltage application, either the hydrophilic or hydrophobic in the polarized molecules A method for controlling the affinity of a material surface, wherein the edge portion is aligned with the surface side of the organic material to control hydrophilicity / hydrophobicity of the organic material surface.

In controlling the surface of the organic material in one of the hydrophilic / hydrophobic directions, the positive / negative direction of the voltage to be applied is selected in consideration of the electric polarization content of the polarized molecule, and thereby the hydrophilicity of the polarized molecule is selected. 3. The method for controlling the affinity of a material surface according to claim 2, wherein one selected end of the hydrophobic end / hydrophobic end is aligned with the surface side of the organic material.

The method for controlling affinity of a material surface according to any one of claims 1 to 3, wherein the organic material contains a polarized molecule in any of the following modes (1) to (3).
(1) An organic material composed of polarized molecules that are organic molecules.
(2) An organic material in which polarized molecules are dispersed in a matrix made of an appropriate material.
(3) An organic material in which polarization molecules are bonded to constituent molecules of a matrix made of an appropriate material.

The method for controlling affinity of a material surface according to any one of claims 1 to 4, wherein the polarized molecule is a molecule containing at least one aromatic ring.

The polarizable molecule is a molecule comprising two aromatic rings linked via a linker structure part selected from the group including at least an azo group, an azomethine group or an ethylene group. 5. The method for controlling the affinity of the material surface according to any one of 4 above.

The material surface affinity control method according to claim 5 or 6, wherein the aromatic ring in the polarized molecule containing the aromatic ring has an electron donating group and / or an electron withdrawing group.

8. The polarized molecule containing two linked aromatic rings, wherein one aromatic ring has an electron donating group and the other aromatic ring has an electron withdrawing group. Control method of material surface affinity.

In the case where the one or two aromatic rings have an electron donating group and an electron withdrawing group, the electron donating group is a hydrophilic group or a hydrophobic group, and the electron withdrawing group is conversely a hydrophobic group or 9. The method for controlling the affinity of the material surface according to claim 7 or 8, wherein the material is a hydrophilic group.

The method for controlling affinity of a material surface according to any one of claims 1 to 9, wherein the organic material is heated to a glass transition point or higher when a voltage is applied to the organic material.

The application of the voltage in the crossing direction to the surface of the organic material is performed by positive and negative electrodes provided along the direction crossing the surface of the organic material, or the frequency generated on the same axis and having a multiple relationship is set. The control of the affinity of the material surface according to any one of claims 1 to 10, wherein the irradiation is performed by irradiating the surface of the organic material with two or more kinds of irradiated light from an oblique direction. Method.

The material surface affinity control method according to any one of claims 1 to 11, wherein the method for controlling the affinity of the material surface is performed in any of the following modes (4) to (6). Control method.
(4) Controlling the affinity of the surface of the organic material by applying a voltage as a processing process for an organic material newly manufactured or used as a product or product member.
(5) By attaching voltage application means in a form that allows positive and negative voltages to be applied to the organic material in the usage environment as a product or product member in a direction crossing the surface, the affinity of the organic material surface Sexual control is always possible.
(6) With respect to an organic material in a use environment as a product or a product member, a positive / negative voltage can be applied in a direction crossing the surface, and a positive / negative voltage direction can be reversed. By attaching the voltage application means, it is possible to always control the affinity of the organic material surface.

A light immobilization material, wherein the organic material according to any one of claims 1, 2, and 4 to 9 is induced to undergo light deformation by irradiation light and can immobilize a minute object disposed on the surface thereof. But in some cases,
By forming an immobilization carrier using the organic material at least on the surface layer portion and applying a voltage in a direction crossing the surface of the immobilization carrier using positive and negative electrodes, the following (7) or (8) A method for controlling the affinity of the surface of the immobilization carrier for controlling the affinity of the surface of the immobilization carrier to a minute object.
(7) An operation of stabilizing the arrangement state or the contact state of the minute object arranged on the surface of the immobilization carrier with respect to the immobilization carrier prior to the immobilization of the minute object.
(8) An operation for relaxing the immobilization state of the minute object that has already been immobilized on the surface of the immobilization carrier according to a predetermined technical requirement.