JP2004136236A - Tip for dispensation - Google Patents
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- JP2004136236A JP2004136236A JP2002305099A JP2002305099A JP2004136236A JP 2004136236 A JP2004136236 A JP 2004136236A JP 2002305099 A JP2002305099 A JP 2002305099A JP 2002305099 A JP2002305099 A JP 2002305099A JP 2004136236 A JP2004136236 A JP 2004136236A
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N2035/00178—Special arrangements of analysers
- G01N2035/00277—Special precautions to avoid contamination (e.g. enclosures, glove- boxes, sealed sample carriers, disposal of contaminated material)
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は生化学実験・臨床検査・薬剤の開発研究において蛋白質・ペプチド・核酸等の溶液を吸引・分注する際に使用する分注用チップに関する。
【０００２】
【従来の技術】
現在、ディスポーザブルの分注用チップとしては主にポリプロピレンの成型品が幅広く用いられており、耐溶剤性、液切れ性の面で好適に使用されている。
更に近年、バイオテクノロジーの進展に伴い生化学分野において今までに無い極微量のサンプルを分取・分注するケースが増加し、そのニーズに合わせて例えば、特許文献１に開示されている様な分注用チップ内面にシリコーン・フッ素系処理を施したもの、或いはシリコーンを含有するポリプロピレンコンパウンドを用いて成型する事でチップ内部を撥水性にした「低リテンションタイプ」と呼ばれる溶液残留量の少ない分注用チップが実用化されている。
現在分注用チップは幅広い用途に使用されており、プッシュボタン式連続分注装置、いわゆるディスペンサーと呼ばれる手に持って使用する分注量が可変式の分注装置の先端部に取り付けるディスポーザブルチップが最も一般的であるが、それ以外に臨床検査の自動分析器の様な大型の装置類に組み込まれて使用する場合や、更には特許文献２に開示されている様に分注用チップ内で微粒子を使用した反応測定をする系も考えられている。
【０００３】
微量物質が扱われるようになり、更に分注用チップの用途が広がるとともに従来の分注精度という要求性能に加えて、溶液中の物質のチップ内への吸着残留が問題としてクローズアップされてきた。
チップ内への吸着残留が引き起こす問題は第一に分取した溶液中の物質濃度の変化である。
分取−分注の溶液容量に変化が無くとも、溶液中の物質（溶質）がチップ壁面に吸着することで分注前後の溶液濃度に差が生じてしまい、その変化の割合は溶質の濃度が薄くなればなるほど大きくなり、分取−分注を繰り返すうちに最終的には溶質が全て吸着により失われるという事態も発生する。
【０００４】
第二の問題としては、自動分析器や反応系に使用する場合チップに吸着残留した物質が次の反応系に持ち越され、いわゆるキャリーオーバーという不必要な反応もしくはコンタミネーションを引き起こす可能性である。
蛋白質・ペプチド・核酸といった生体由来物質は特に従来のチップに使用されているポリプロピレン樹脂に対して強い吸着性を示し、低リテンションタイプの撥水性処理を施したチップにおいても見た目の液切れ性は向上し、溶液の残留は改善されるが、吸着を引き起こす最も大きな要因である疎水性相互作用は逆に強くなってしまう為、物質の種類によって溶質の吸着残留量は増加してしまう。
【０００５】
【特許文献１】
特開平８−８９８２０号公報
【特許文献２】
特開平１１−２６２６７８号公報
【０００６】
【発明が解決しようとする課題】
本発明の目的は、分注用チップの基本的な要求性能である分注精度を低下させる事無く、溶液中の物質のチップ壁面への吸着を抑え、分取溶液の濃度変化が無くキャリーオーバー・コンタミネーションを引き起こさない分注用チップを提供する事である。
【課題を解決するための手段】
【０００７】
即ち本発明は、
（１）内面の少なくとも溶液が接触する部分が水との接触角が０度の超親水性材料で被覆され、少なくともチップ先端部分の外面が水との接触角が６０度以上の樹脂からなる分注用チップ、
（２）水との接触角が６０度以上の樹脂がポリプロピレンである（１）記載の分注用チップ、
（３）超親水性材料が、ポリヒドロキシアルキルメタクリレート、ポリオキシＣ２−Ｃ４アルキレン基含有メタクリレート重合体又はこれを含む共重合体、ポリビニルピロリドン、リン脂質・高分子複合体、及び２−メタクリロイルオキシエチルホスホリルコリンを含む重合体又はこれを含む共重合体、から選ばれる少なくとも１つである（１）又は（２）記載の分注用チップ、
である。
【０００８】
【発明の実施の形態】
分注用チップ壁面と溶液中の物質の吸着を防止する為には疎水性相互作用を無くす事が最も効果的であり、分注用チップ壁面の疎水性部位を無くす、即ち親水化するという分注用チップの表面処理として全く新規の方法を本発明において選択した。
親水化の際、吸着をより高度に抑えるためには接触角が０度の超親水性表面にする事が重要である。
ここで、単にディスペンサーチップ表面を超親水性表面にしてしまうと基本的な要求性能である分注精度が低下するという問題が発生する。
本発明者は、いかにして分注精度を下げる事無く超親水性表面により吸着を防止させるかという点について鋭意検討の結果、少なくともディスペンサーチップ先端部分の外面を接触角６０度以上の表面にする事によって分注精度の問題を解決できる事を見出した。
【０００９】
検討の結果、分注の際精度が低下する要因は２つあり、一つはチップ内面への溶液の残留によるものと、もう一つはチップ先端部外面への溶液の巻き込み付着である。
前者については、当然チップ内面が撥水性であるほど溶液は残留せずに精度良く排出されるのであるが、超親水性にした場合でも分注速度に注意してゆっくりと排出する事で残留量を抑える事が可能で、寧ろ条件によってはポリプロピレンの様に液滴状に溶液が残留する場合よりも効率的に溶液が排出される事も確認した。
【００１０】
一方後者すなわちチップ先端部外面への溶液の巻き込みについてはチップ外面を超親水性にした場合、先端から排出された溶液が滴下されずにチップ外面に付着残留する割合が大きくなり分注精度が低下してしまう。
よって、分注用チップ内面の溶液が接触する部分を接触角０度の超親水性材料で被覆し、チップ先端部の外面を接触角６０度以上の樹脂とする事で分注精度を低下させる事無く、壁面への吸着残留を改善させる事が出来る。
【００１１】
本発明の分注用チップは量産性を考慮した場合水との接触角が６０度以上のポリプロピレンで成型したチップ成型品の内面に水との接触角が０度の超親水性材料を被覆するのが好ましく、該超親水性材料としてはポリヒドロキシアルキルメタクリレート、ポリオキシＣ２−Ｃ４アルキレン基含有メタクリレート重合体又はこれを含む共重合体、ポリビニルピロリドン、リン脂質・高分子複合体、又は２−メタクリロイルオキシエチルホスホリルコリン重合体又はこれを含む共重合体から選ばれる少なくとも１つであることが好ましい。
【００１２】
前述の通りチップ内面への溶液残留が少ないほど分注速度を上げる事ができるので、超親水性材料としては出来るだけ自由水の保持率が低いものが好ましく、前述の２−メタクリロイルオキシエチルホスホリルコリンを含む共重合体のコーティング層で可能な限り薄く被覆するのが吸着防止効果、分注精度のバランスの面で最も好ましい。
２−メタクリロイルオキシエチルホスホリルコリンを含む化合物の共重合体としては特に限定するものでは無いが、２−メタクリロイルオキシエチルホスホリルコリン・ブチルメタクリレート共重合体（「ハイドロゲルの血液適合性に及ぼす親水性基構造の影響」生体材料Ｖｏｌ．９、Ｎｏ．６ 石原一彦、中林宣男他参照）を好適に使用する事が出来る。
２−メタクリロイルオキシエチルホスホリルコリン重合体又は共重合体においては、共重合体中の２−メタクリロイルオキシエチルホスホリルコリンの含有率が高いほど優れた吸着制御効果が期待できるが、２−メタクリロイルオキシエチルホスホリルコリンの含有率が高ければ共重合体は水溶性となる為、目的に応じて共重合比率を調節する必要がある。
【００１３】
【実施例】
以下、実施例によって本発明を更に具体的に説明する。
（実施例１）
ポリプロピレン製分注用チップ（住友ベークライト製 ＳＵＭＩＬＯＮ ＭＳ−６３１６０Ｇ）のディスペンサー接続側開口部から２−メタクリロイルオキシエチルホスホリルコリン−ブチルメタクリレート共重合体の０．５ｗｔ／ｖｏｌ％エタノール溶液を分注し、５分間分注状態を保持した後に真空ポンプに接続した吸引用ノズルをディスペンサー接続側開口部に接続し、１０秒間吸引後、７０℃で４Ｈｒ真空乾燥させた。
２−メタクリロイルオキシエチルホスホリルコリン−ブチルメタクリレート共重合体は、「リン脂質類似構造を有するハイドロゲル膜からの薬物放出 高分子論文集，４６，５９１−５９５（１９８９）」の内容に従い２−メタクリロイルオキシエチルホスホリルコリンとブチルメタクリレート比＝３／７の共重合体を合成し使用した。
【００１４】
（比較例１）
ポリプロピレン製分注用チップ（住友ベークライト製 ＳＵＭＩＬＯＮ ＭＳ−６３１６０Ｇ）を比較例１とした。
【００１５】
（比較例２）
ポリプロピレン製分注用チップ（住友ベークライト製 ＳＵＭＩＬＯＮ ＭＳ−６３１６０Ｇ）に特開平８−８９９２０号公報「ディスペンサー用チップ及びその製造方法」に従いフッ素系撥水剤をコートしたものを比較例２とした。
【００１６】
（水との接触角の比較）
実施例１及び比較例１、比較例２の分注用チップの内面及び外面の水との接触角を測定した結果を表１に示す。
【００１７】
【表１】
（分注精度の評価）
実施例１及び比較例１、比較例２の分注用チップの分注精度を評価した。評価法は日本工業規格 Ｋ０９７０（プッシュボタン式液体用微量検体体積計）に従った。
【００１９】
【表２】
比較例２が変動係数、正確さ共に最も優れていたが、実施例１も比較例１と同等レベルであり、何れも日本工業規格を満たしていた。
【００２１】
（蛋白質溶液濃度変化率の評価）
蛋白質溶液を使用して、分注前後の濃度変化を測定した。
使用した蛋白質ペルオキシターゼ標識アビジンとペルオキシターゼ標識牛血清アルブミンの２種類で、各々３水準の濃度の溶液を実施例１、比較例１、比較例２を用いて１０回分取−分注操作を繰り返した後の溶液中の蛋白質量をペルオキシターゼの酵素活性をＴＭＢＺとの反応により吸光度値として求めた。
【００２２】
結果は図１、図２に示した。図１は０．０１６、０．０８、０．４μｇ／ｍＬのペルオキシターゼ標識アビジン溶液を１０回分取−分注操作を繰り返した後の溶液中の酵素活性量を示したグラフである。図２は０．１、０．５、１．０μｇ／ｍＬのペルオキシターゼ標識牛血清アルブミン溶液を１０回分取−分注操作を繰り返した後の溶液中の酵素活性量を示したグラフである。これら結果、比較例１及び比較例２に比べて実施例１の蛋白質濃度は高く、分取−分注操作による溶質の減少が抑えられている事が確認された。
【００２３】
【発明の効果】
本発明の分注用チップを使用する事で溶質の分注チップへの吸着が無く、分取溶液の濃度変化及びコンタミネーションの無い分取−分注操作を精度良く行なう事が出来る。
【図面の簡単な説明】
【図１】ペルオキシターゼ標識アビジン溶液を１０回分取−分注操作を繰り返した後の溶液中の酵素活性量を示したグラフである。
【図２】ペルオキシターゼ標識牛血清アルブミン溶液を１０回分取−分注操作を繰り返した後の溶液中の酵素活性量を示したグラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a dispensing tip used for aspirating and dispensing solutions of proteins, peptides, nucleic acids, etc. in biochemical experiments, clinical tests, and drug development research.
[0002]
[Prior art]
At present, molded products of polypropylene are widely used as disposable dispensing tips, and are preferably used in terms of solvent resistance and liquid drainage.
Furthermore, in recent years, with the progress of biotechnology, the number of cases of dispensing and dispensing an extremely small amount of sample in the field of biochemistry has increased, and according to the needs, for example, as disclosed in Patent Document 1 A low-retention type, called "low retention type", in which the inside of the tip is made water-repellent by molding it with a silicone-fluorine treatment on the inner surface of the dispensing tip or by molding using a silicone-containing polypropylene compound. Note chips have been put to practical use.
Currently, dispensing tips are used for a wide range of applications.Disposable tips that are attached to the tip of a push-button type continuous dispensing device, a dispenser with a variable dispensing amount used in the hand called a dispenser, are used. It is the most common, but when it is used by being incorporated into a large-sized device such as an automatic analyzer for a clinical test, or in a dispensing tip as disclosed in Patent Document 2 A system for measuring the reaction using fine particles has also been considered.
[0003]
Trace substances have been handled, and the use of dispensing tips has expanded, and in addition to the required performance of conventional dispensing accuracy, residual adsorption of substances in solution into chips has been highlighted as a problem. .
The first problem caused by the residual adsorption in the chip is a change in the concentration of the substance in the separated solution.
Even if there is no change in the solution volume between the dispensing and dispensing, a difference occurs in the solution concentration before and after dispensing due to the substance (solute) adsorbing on the chip wall surface, and the rate of the change is the solute concentration. The thinner becomes, the larger it becomes, and during the repetition of preparative-dispensing, a situation occurs in which all the solutes are eventually lost by adsorption.
[0004]
The second problem is that when used in an automatic analyzer or a reaction system, the substance adsorbed and remaining on the chip is carried over to the next reaction system, and may cause an unnecessary reaction or contamination called carryover.
Biological substances such as proteins, peptides, and nucleic acids show strong adsorptive properties especially to the polypropylene resin used in conventional chips, and the improved liquid repellency of low-retention type water-repellent chips is improved. Although the solution retention is improved, the hydrophobic interaction, which is the largest factor causing the adsorption, becomes stronger on the contrary, so that the adsorption residue of the solute increases depending on the type of the substance.
[0005]
[Patent Document 1]
JP-A-8-89820 [Patent Document 2]
JP-A-11-262678 [0006]
[Problems to be solved by the invention]
An object of the present invention is to suppress the adsorption of substances in a solution to a chip wall without lowering dispensing accuracy, which is a basic required performance of a dispensing tip, and to prevent carry-over without a change in the concentration of a dispensing solution.・ Provide a dispensing tip that does not cause contamination.
[Means for Solving the Problems]
[0007]
That is, the present invention
(1) At least a portion of the inner surface that comes into contact with the solution is coated with a superhydrophilic material having a contact angle with water of 0 °, and at least an outer surface of the tip end portion is made of a resin with a contact angle with water of 60 ° or more. Injection tip,
(2) The dispensing tip according to (1), wherein the resin having a contact angle with water of 60 degrees or more is polypropylene.
(3) superhydrophilic material, polyhydroxyalkyl methacrylates, polyoxy C 2 -C 4 alkylene group containing methacrylate polymers or copolymers comprising the same, polyvinylpyrrolidone, phospholipid-polymer composite, and 2-methacryloyloxy A dispensing tip according to (1) or (2), which is at least one selected from a polymer containing ethyl phosphorylcholine or a copolymer containing the same;
It is.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The most effective way to prevent the adsorption of the substance in the solution to the dispensing tip wall is to eliminate the hydrophobic interaction, and to eliminate the hydrophobic part of the dispensing tip wall, that is, to make it hydrophilic. A completely new method was selected in the present invention for the surface treatment of injection chips.
At the time of hydrophilization, in order to suppress the adsorption to a higher degree, it is important to provide a superhydrophilic surface having a contact angle of 0 degree.
Here, if the dispenser tip surface is simply made a superhydrophilic surface, there arises a problem that the dispensing accuracy, which is a basic required performance, is reduced.
The present inventor has conducted intensive studies on how to prevent adsorption by a superhydrophilic surface without lowering the dispensing accuracy, and as a result, at least the outer surface of the tip portion of the dispenser tip has a contact angle of 60 degrees or more. It has been found that the problem of dispensing accuracy can be solved.
[0009]
As a result of the study, there are two factors that lower the accuracy in dispensing, one is due to the solution remaining on the inner surface of the chip, and the other is the entrainment of the solution on the outer surface of the tip end.
For the former, naturally, the more water-repellent the inner surface of the chip, the more accurately the solution is discharged without remaining.However, even when the surface is super-hydrophilic, the solution can be discharged slowly by paying attention to the dispensing speed. It was also confirmed that depending on the conditions, the solution was discharged more efficiently than when the solution remained in the form of droplets like polypropylene.
[0010]
On the other hand, regarding the latter, that is, entrapment of the solution into the outer surface of the tip of the chip, when the outer surface of the chip is made superhydrophilic, the rate of the solution discharged from the tip not adhering to the outer surface of the chip without being dripped increases, resulting in a lower dispensing accuracy. Resulting in.
Therefore, the dispensing tip is coated with a super-hydrophilic material having a contact angle of 0 °, and the outer surface of the tip of the tip is made of a resin having a contact angle of 60 ° or more, thereby lowering dispensing accuracy. It is possible to improve the residual adsorption on the wall without any problem.
[0011]
The dispensing tip of the present invention covers the inner surface of a tip molded product made of polypropylene having a contact angle with water of 60 degrees or more in consideration of mass productivity with a superhydrophilic material having a contact angle with water of 0 degrees. Preferably, the superhydrophilic material is a polyhydroxyalkyl methacrylate, a polyoxy C 2 -C 4 alkylene group-containing methacrylate polymer or a copolymer containing the same, polyvinylpyrrolidone, a phospholipid / polymer composite, or 2-hydroxyalkyl methacrylate. It is preferably at least one selected from a methacryloyloxyethyl phosphorylcholine polymer and a copolymer containing the same.
[0012]
As described above, since the dispensing rate can be increased as the solution remaining on the inner surface of the chip is smaller, it is preferable that the superhydrophilic material has a retention rate of free water as low as possible, and the above-mentioned 2-methacryloyloxyethyl phosphorylcholine is preferable. It is most preferable to coat as thin as possible with a coating layer of a copolymer containing the same in view of the balance between the adsorption prevention effect and the dispensing accuracy.
The copolymer of the compound containing 2-methacryloyloxyethyl phosphorylcholine is not particularly limited, but a 2-methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer (“having a hydrophilic group structure that affects the blood compatibility of a hydrogel”). Influence "Biomaterial Vol. 9, No. 6 Kazuhiko Ishihara, Nobuo Nakabayashi et al.) Can be suitably used.
In the 2-methacryloyloxyethyl phosphorylcholine polymer or copolymer, the higher the content of 2-methacryloyloxyethyl phosphorylcholine in the copolymer, the higher the adsorption control effect can be expected, but the higher the content of 2-methacryloyloxyethyl phosphorylcholine, the better. If the ratio is high, the copolymer becomes water-soluble, so it is necessary to adjust the copolymerization ratio according to the purpose.
[0013]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
(Example 1)
A 0.5 wt / vol% ethanol solution of 2-methacryloyloxyethyl phosphorylcholine-butyl methacrylate copolymer is dispensed from an opening on the dispenser connection side of a polypropylene dispensing tip (SUMILON MS-63160G manufactured by Sumitomo Bakelite) and 5 minutes. After maintaining the dispensing state, a suction nozzle connected to a vacuum pump was connected to the opening on the dispenser connection side, and after suction for 10 seconds, vacuum drying was performed at 70 ° C. for 4 hours.
2-methacryloyloxyethyl phosphorylcholine-butyl methacrylate copolymer is a 2-methacryloyloxyethyl compound according to the content of “Drug Release from Hydrogel Membrane Having Phospholipid-Like Structure, Journal of Polymers, 46, 591-595 (1989)”. A copolymer having a phosphorylcholine / butyl methacrylate ratio of 3/7 was synthesized and used.
[0014]
(Comparative Example 1)
A polypropylene dispensing tip (SUMILON MS-63160G manufactured by Sumitomo Bakelite) was used as Comparative Example 1.
[0015]
(Comparative Example 2)
Comparative Example 2 was prepared by coating a polypropylene dispensing tip (SUMILON MS-63160G, manufactured by Sumitomo Bakelite) with a fluorine-based water repellent in accordance with JP-A-8-89920, "Dispenser Tips and Production Method".
[0016]
(Comparison of contact angle with water)
Table 1 shows the measurement results of the contact angles of the inner and outer surfaces of the dispensing tips of Example 1 and Comparative Examples 1 and 2 with water.
[0017]
[Table 1]
(Evaluation of dispensing accuracy)
The dispensing accuracy of the dispensing tips of Example 1, Comparative Example 1, and Comparative Example 2 was evaluated. The evaluation method was in accordance with Japanese Industrial Standard K0970 (push button type micro sample volume meter for liquid).
[0019]
[Table 2]
Comparative Example 2 had the best coefficient of variation and accuracy, but Example 1 was at the same level as Comparative Example 1 and all satisfied the Japanese Industrial Standards.
[0021]
(Evaluation of protein solution concentration change rate)
Using the protein solution, the change in concentration before and after dispensing was measured.
Using two kinds of protein peroxidase-labeled avidin and peroxidase-labeled bovine serum albumin, each having a concentration of three levels, the procedure of Example 1, Comparative Example 1 and Comparative Example 2 was repeated 10 times for the dispensing-dispensing operation. The amount of protein in the solution was determined as an absorbance value by reacting the enzyme activity of peroxidase with TMBZ.
[0022]
The results are shown in FIGS. FIG. 1 is a graph showing the amount of enzyme activity in a solution obtained by repeating the dispensing-dispensing operation of 0.016, 0.08, and 0.4 μg / mL peroxidase-labeled avidin solution 10 times. FIG. 2 is a graph showing the amount of enzyme activity in a 0.1, 0.5, and 1.0 μg / mL peroxidase-labeled bovine serum albumin solution after repeating the dispensing-dispensing operation 10 times. As a result, it was confirmed that the protein concentration of Example 1 was higher than that of Comparative Example 1 and Comparative Example 2, and a decrease in solute due to the fractionation-dispensing operation was suppressed.
[0023]
【The invention's effect】
By using the dispensing tip of the present invention, there is no adsorption of the solute to the dispensing tip, and the dispensing-dispensing operation without concentration change and contamination of the dispensing solution can be performed accurately.
[Brief description of the drawings]
FIG. 1 is a graph showing the amount of enzyme activity in a peroxidase-labeled avidin solution after repeating a dispensing-dispensing operation 10 times.
FIG. 2 is a graph showing the amount of enzyme activity in a peroxidase-labeled bovine serum albumin solution after repeating the dispensing-dispensing operation 10 times.
Claims (3)
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| JP2002305099A JP4162969B2 (en) | 2002-10-18 | 2002-10-18 | Dispensing tip |
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| JP2002305099A JP4162969B2 (en) | 2002-10-18 | 2002-10-18 | Dispensing tip |
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| JP2004136236A true JP2004136236A (en) | 2004-05-13 |
| JP4162969B2 JP4162969B2 (en) | 2008-10-08 |
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| JP2009210562A (en) * | 2008-02-08 | 2009-09-17 | Fujifilm Corp | Pipette chip |
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