JP4162969B2 - Dispensing tip - Google Patents
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- JP4162969B2 JP4162969B2 JP2002305099A JP2002305099A JP4162969B2 JP 4162969 B2 JP4162969 B2 JP 4162969B2 JP 2002305099 A JP2002305099 A JP 2002305099A JP 2002305099 A JP2002305099 A JP 2002305099A JP 4162969 B2 JP4162969 B2 JP 4162969B2
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- G—PHYSICS
- 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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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】
【0018】
(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】
【0020】
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]
BACKGROUND OF THE INVENTION
The present invention relates to a dispensing chip used when aspirating and dispensing a solution of protein, peptide, nucleic acid or the like in biochemical experiments, clinical tests, and drug development research.
[0002]
[Prior art]
Currently, polypropylene molded products are widely used as disposable dispensing tips, and are preferably used in terms of solvent resistance and liquid breakage.
Further, in recent years, with the progress of biotechnology, the number of cases in which an extremely small amount of sample has not been collected in the biochemical field has increased, and according to the needs, for example, as disclosed in Patent Document 1 A small amount of residual solution called “low-retention type” where the inside of the tip for dispensing is treated with silicone / fluorine or molded with a polypropylene compound containing silicone to make the inside of the tip water-repellent An injection tip has been put into practical use.
Dispensing tips are currently used in a wide range of applications. Disposable tips that can be attached to the tip of push-button continuous dispensing devices, so-called dispensers with a variable dispensing amount that can be used by hand. Although most commonly used, other than that, when incorporated into a large-scale apparatus such as an automatic analyzer for clinical examinations, or in a dispensing tip as disclosed in Patent Document 2, A system for measuring reaction using fine particles is also considered.
[0003]
Trace substances have been handled, and the application of dispensing tips has further expanded. In addition to the required performance of conventional dispensing accuracy, residual adsorption of substances in solution in the chips has been highlighted as a problem. .
The problem caused by the adsorption residue in the chip is firstly the change in the substance concentration in the collected solution.
Even if there is no change in the volume of the preparative-dispensing solution, the substance concentration (solute) in the solution is adsorbed on the chip wall, resulting in a difference in the solution concentration before and after dispensing, and the rate of change is the concentration of the solute. As the thickness becomes thinner, it becomes larger, and eventually, all of the solute is lost by adsorption while repeating the preparative-dispensing.
[0004]
The second problem is that when used in an automatic analyzer or reaction system, the substance adsorbed and remaining on the chip is carried over to the next reaction system, which may cause unnecessary reaction or contamination called so-called carryover.
Biological substances such as proteins, peptides, and nucleic acids exhibit strong adsorptivity to the polypropylene resin used in conventional chips, and the appearance of liquid drainage is improved even with low-retention type water-repellent treatment chips. However, although the residual of the solution is improved, the hydrophobic interaction, which is the largest factor causing the adsorption, becomes stronger on the contrary, and the residual amount of adsorption of the solute increases depending on the kind 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]
The purpose of the present invention is to suppress the adsorption of substances in the solution to the tip wall surface without reducing the dispensing accuracy, which is the basic required performance of the dispensing tip, and carry over without changing the concentration of the dispensing solution.・ To provide dispensing tips that do not cause contamination.
[Means for Solving the Problems]
[0007]
That is, the present invention
(1) At least the portion of the inner surface that is in contact with the solution is coated with a superhydrophilic material having a contact angle with water of 0 °, and at least the outer surface of the tip portion of the chip is made of a resin having a contact angle with water of 60 ° or more. Tip for injection,
(2) The dispensing tip according to (1), wherein the resin having a contact angle with water of 60 ° or more is polypropylene,
(3) The superhydrophilic material is polyhydroxyalkyl methacrylate, polyoxy C 2 -C 4 alkylene group-containing methacrylate polymer or a copolymer containing the same, polyvinyl pyrrolidone, phospholipid / polymer composite, and 2-methacryloyloxy The dispensing tip according to (1) or (2), which is at least one selected from a polymer containing ethylphosphorylcholine or a copolymer containing the same,
It is.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The most effective way to prevent the adsorption of substances in the dispensing tip wall and the solution is to eliminate the hydrophobic interaction. The hydrophobic part of the dispensing tip wall is eliminated, that is, it is made hydrophilic. An entirely new method was selected in the present invention for the surface treatment of the casting tip.
In order to suppress the adsorption to a higher degree during hydrophilization, it is important to use a superhydrophilic surface with a contact angle of 0 degree.
Here, if the surface of the dispenser chip is simply made to be a superhydrophilic surface, there arises a problem that the dispensing accuracy, which is a basic required performance, is lowered.
As a result of intensive studies on how to prevent adsorption with a superhydrophilic surface without lowering the dispensing accuracy, the present inventor has made at least the outer surface of the tip of the dispenser tip a surface having a contact angle of 60 degrees or more. I found out that the problem of dispensing accuracy can be solved.
[0009]
As a result of the examination, there are two factors that cause the accuracy to drop during dispensing, one is due to the remaining of the solution on the inner surface of the tip, and the other is the entanglement of the solution on the outer surface of the tip of the tip.
As for the former, naturally, the more water-repellent the inner surface of the tip, the more accurately the solution will be discharged, but even if it is made super hydrophilic, the remaining amount can be reduced by slowly discharging it while 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, with regard to the latter, that is, when the solution is entrained on the outer surface of the tip of the tip, if the tip outer surface is made super-hydrophilic, the proportion of the solution discharged from the tip is not dripped and remains on the outer surface of the tip increases, and the dispensing accuracy decreases. Resulting in.
Therefore, the portion of the tip of the dispensing tip where the solution comes into contact is covered with a superhydrophilic material having a contact angle of 0 degrees, and the outer surface of the tip of the tip is made of resin having a contact angle of 60 degrees or more, thereby reducing the dispensing accuracy. It is possible to improve the adsorption residue on the wall without any problems.
[0011]
In the dispensing tip of the present invention, in consideration of mass productivity, the inner surface of a chip molded product molded with polypropylene having a contact angle with water of 60 ° or more is coated with a superhydrophilic material having a contact angle with water of 0 °. The superhydrophilic material is preferably a polyhydroxyalkyl methacrylate, a polyoxy C 2 -C 4 alkylene group-containing methacrylate polymer or a copolymer containing the same, polyvinyl pyrrolidone, a phospholipid / polymer composite, or 2- It is preferably at least one selected from a methacryloyloxyethyl phosphorylcholine polymer or a copolymer containing the same.
[0012]
As described above, the smaller the amount of solution remaining on the inner surface of the chip, the higher the dispensing speed. Therefore, it is preferable that the superhydrophilic material has a low free water retention rate as much as possible, and the aforementioned 2-methacryloyloxyethyl phosphorylcholine is used. It is most preferable that the coating layer of the copolymer to be coated is as thin as possible in terms of the balance between the anti-adsorption 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 (“the hydrophilic group structure affecting the blood compatibility of the hydrogel” "Influence" Biomaterials Vol.9, No.6 Kazuhiko Ishihara, Nobuo Nakabayashi et al.) Can be used suitably.
In 2-methacryloyloxyethyl phosphorylcholine polymer or copolymer, the higher the content of 2-methacryloyloxyethyl phosphorylcholine in the copolymer, the better the adsorption control effect can be expected, but the inclusion of 2-methacryloyloxyethyl phosphorylcholine If the rate is high, the copolymer becomes water-soluble, so the copolymerization ratio needs to be adjusted 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-butylmethacrylate copolymer is dispensed from the dispenser connection side opening of a polypropylene dispensing tip (SUMILON MS-63160G manufactured by Sumitomo Bakelite) for 5 minutes. After maintaining the dispensing state, the suction nozzle connected to the vacuum pump was connected to the opening on the dispenser connection side, suctioned for 10 seconds, and then vacuum dried at 70 ° C. for 4 hours.
2-Methacryloyloxyethyl phosphorylcholine-butyl methacrylate copolymer is produced according to the content of “Drug Release from Hydrogel Membranes Having a Phospholipid-like Structure, 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 Co., Ltd.) with a fluorine-based water repellent according to JP-A-8-89920, “Dispenser Chip and its Manufacturing Method”.
[0016]
(Comparison of contact angle with water)
Table 1 shows the results of measuring the contact angles of the inner and outer surfaces of the dispensing tips of Example 1, Comparative Example 1 and Comparative Example 2 with water.
[0017]
[Table 1]
[0018]
(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 liquid trace sample volume meter).
[0019]
[Table 2]
[0020]
Comparative Example 2 was the most excellent in both coefficient of variation and accuracy, but Example 1 was also at the same level as Comparative Example 1, and both satisfied Japanese Industrial Standards.
[0021]
(Evaluation of protein solution concentration change rate)
Using the protein solution, the concentration change before and after dispensing was measured.
After repeating the dispensing-dispensing operation 10 times using Example 1, Comparative Example 1 and Comparative Example 2 with three kinds of solutions of the protein peroxidase-labeled avidin and the peroxidase-labeled bovine serum albumin used, respectively. The amount of protein in the solution was determined as the absorbance value of the enzyme activity of peroxidase by reaction with TMBZ.
[0022]
The results are shown in FIGS. FIG. 1 is a graph showing the amount of enzyme activity in a solution after repeating the dispensing-dispensing operation of 0.016, 0.08, 0.4 μg / mL peroxidase-labeled avidin solution 10 times. FIG. 2 is a graph showing the amount of enzyme activity in the solution after repeating the fraction-dispensing operation of 0.1, 0.5, 1.0 μg / mL peroxidase-labeled bovine serum albumin solution 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 the decrease in solute due to the preparative-dispensing operation was suppressed.
[0023]
【The invention's effect】
By using the tip for dispensing of the present invention, there is no adsorption of the solute to the tip for dispensing, and the dispensing-dispensing operation without change in the concentration of the sorting solution and contamination can be performed with high accuracy.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing the amount of enzyme activity in a solution after a peroxidase-labeled avidin solution has been subjected to 10 times of dispensing and dispensing operations.
FIG. 2 is a graph showing the amount of enzyme activity in a solution after a peroxidase-labeled bovine serum albumin solution was subjected to 10 times of dispensing and dispensing operations.
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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JP4162969B2 true JP4162969B2 (en) | 2008-10-08 |
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JP2009058437A (en) * | 2007-08-31 | 2009-03-19 | Olympus Corp | Dispense nozzle and automatic analyzer |
JP5129729B2 (en) * | 2008-02-08 | 2013-01-30 | 富士フイルム株式会社 | Pipette tip |
JP5097737B2 (en) * | 2009-03-27 | 2012-12-12 | 株式会社日立ハイテクノロジーズ | Automatic analyzer and sample dispensing nozzle |
JP6493883B2 (en) * | 2016-01-22 | 2019-04-03 | 富士フイルム株式会社 | Film forming method and adapter manufacturing method |
EP3562933B1 (en) * | 2016-12-30 | 2021-08-18 | Molecular Machines & Industries AG | Method for the isolation and treatment of particulate targets |
CN112384799B (en) * | 2018-08-06 | 2023-06-20 | 株式会社岛津制作所 | Sample injection device |
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