JPS59190657A - Specimen pretreating method and apparatus therefor - Google Patents
Specimen pretreating method and apparatus thereforInfo
- Publication number
- JPS59190657A JPS59190657A JP6420383A JP6420383A JPS59190657A JP S59190657 A JPS59190657 A JP S59190657A JP 6420383 A JP6420383 A JP 6420383A JP 6420383 A JP6420383 A JP 6420383A JP S59190657 A JPS59190657 A JP S59190657A
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- JP
- Japan
- Prior art keywords
- tube
- ion
- sample
- type
- syringe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、少量の試料の中に含まれる所望イオンを選択
的に除去する試料前処理方法およびその装置に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sample pretreatment method and apparatus for selectively removing desired ions contained in a small amount of sample.
一般に、クロマトグラフィーを用いて試料中のｅ′ｌ＃
、不純物などを測定する場合、主成分の大きなビーク釦
近接して溶出する成分の測定は極めて困難である。例え
ば、塩素イオンを多量に含む試料の中に存在する微量イ
オン（ＮＯ，−、Ｎｏ−、、、’ｓｏニー等）をイオン
クロマドグ２フイーを用いて測定する場合、塩素イオン
のピークが大きな障害となることが多い。このため、第
１図に示すような試料前処理方法により、塩素イオンを
除去する方法が採用されていた。即ち、第１図において
、銀型イオン交換樹脂粒子１が充填され出入口にグラス
ウール等２゜３が挿着されてなる管状部材４に、矢印方
向から試料を流し込むと、試料中の塩素イオンが粒子１
状部材４からの溶出液を容器５に受けると、塩化銀が沈
澱し塩素イオンが除去された試料が得られる。Generally, chromatography is used to determine e′l# in a sample.
When measuring , impurities, etc., it is extremely difficult to measure components that elute close to the large beak button of the main component. For example, when measuring trace ions (NO, -, No-, , 'sony, etc.) present in a sample containing a large amount of chlorine ions using Ion Chroma Dog 2 Fee, the peak of chlorine ions is large. It is often a hindrance. For this reason, a method of removing chlorine ions by a sample pretreatment method as shown in FIG. 1 has been adopted. That is, in FIG. 1, when a sample is poured from the direction of the arrow into a tubular member 4 filled with silver-type ion exchange resin particles 1 and glass wool etc. 1
When the eluate from the shaped member 4 is received in the container 5, a sample is obtained in which silver chloride is precipitated and chloride ions are removed.
然し乍ら、上記従来例においては、管状部材４内の粒子
１０間に水分が存在するため、試料を多量に注入しない
と希釈される欠点があった。このため、極少量の試料し
か得られないような場合には、この方法を採用できなか
った。また、イオン交換樹脂粒子を銀型にしてのち管状
部材４に充填し、その後（若しくは使用後周期的に）、
所定の洗浄液で洗浄して上記粒子１を得る必要があるた
め、それら一連の操作が極めて煩雑であるという欠点も
あった。However, in the conventional example described above, since moisture exists between the particles 10 in the tubular member 4, there is a drawback that the sample will be diluted unless a large amount is injected. For this reason, this method cannot be used in cases where only a very small amount of sample can be obtained. Alternatively, the ion exchange resin particles are made into a silver shape and then filled into the tubular member 4, and then (or periodically after use).
Since it is necessary to obtain the particles 1 by washing with a predetermined washing liquid, there is also the drawback that the series of operations is extremely complicated.
本発明はかかる欠点に鑑みてなされたものであり、その
目的は、少量の試料でも希釈されることなく且つ容易に
試料中の所望イオンを選択的に除去する方法およびその
装置を提供することにある。The present invention has been made in view of these drawbacks, and an object of the present invention is to provide a method and an apparatus for selectively removing desired ions from a sample even in a small amount without diluting the sample. be.
本発明の特徴は、少量の試料の中に含まれる所望イオン
を選択的に除去する試料前処理方法およびその装置にお
いて、中空繊維状のイオン交換膜チューブをシリンジに
装着し、該シリンジ内に前記チューブの内部を通過させ
て試料を採取することにより、前記チューブ内壁面のイ
オン交換基と前記試料中の所望イオンとをイオン交換さ
せ、前記シリンジ内に前記所望イオンが除去された試料
を得るようにしたことにある。A feature of the present invention is that in a sample pretreatment method and apparatus for selectively removing desired ions contained in a small amount of sample, a hollow fiber ion exchange membrane tube is attached to a syringe, and the ion exchange membrane tube is inserted into the syringe. By passing the sample through the inside of the tube and collecting the sample, the ion exchange groups on the inner wall surface of the tube and the desired ions in the sample are ion-exchanged, and a sample from which the desired ions have been removed is obtained in the syringe. It's because I did it.
以下、本発明について図を用いて詳細に説明する。第２
図および第３図は、本発明実施例の構成説明図であり、
図中、６はシリンジ、７はシリンジ６のピストン部、８
はシリンジ６のピストン操作部、９はシリンジ６の注射
針、１０は例えば長さ５〜２００ｃｍ内径０．０３〜０
．０８ ａｍのナフィオンチューブでなるイオン交換膜
チューブ、１２は内部に例えば０．２２μｍのフィルタ
１３を有するフィルタユニット、１４はインジェクタ注
入用針である。尚、上記注射針９がイオン交換膜チュー
ブ１０の一端に挿入されるが、挿入状態での密着度が十
分でないときには、該挿入部からの液もれを防ぐため接
着部材１１を用いて挿入部周辺を接着することが行なわ
れる。Hereinafter, the present invention will be explained in detail using figures. Second
3 and 3 are configuration explanatory diagrams of an embodiment of the present invention,
In the figure, 6 is a syringe, 7 is a piston part of syringe 6, and 8 is a syringe.
is a piston operation part of the syringe 6, 9 is an injection needle of the syringe 6, and 10 is, for example, a length of 5 to 200 cm and an inner diameter of 0.03 to 0.
．． An ion exchange membrane tube made of a 0.08 am Nafion tube, 12 a filter unit having a filter 13 of, for example, 0.22 μm inside, and 14 an injector injection needle. The injection needle 9 is inserted into one end of the ion exchange membrane tube 10, but if the degree of tightness in the inserted state is not sufficient, an adhesive member 11 is used to secure the insertion part to prevent liquid leakage from the insertion part. Gluing the periphery is done.
以下、上記構成からなる本発明実施例の動作について説
明する。最初、第２図のイオン交換膜チューブ１０を約
１Ｎの硝酸銀水溶液中に例えば３０分間浸す。該チュー
ブを構成する樹脂が下式（１）のように反応してＡｇ型
圧なる。The operation of the embodiment of the present invention having the above configuration will be described below. First, the ion exchange membrane tube 10 shown in FIG. 2 is immersed in an approximately 1N silver nitrate aqueous solution for, for example, 30 minutes. The resin constituting the tube reacts as shown in the following formula (1), resulting in an Ag-type pressure.
Ｒｅ５ｉｎ−８ｏ５・Ｘ ＋ＡｇＮ０Ｓ−＋ Ｒｅ５ｉ
ｎ−８ｏ、・Ａｇ 十Ｘ−Ｎ０． ・−−−・・（１１
ここで、Ｒｅ５ｉｎ ；樹脂、Ｘ；Ｈ＋などの各種イオ
ン次に、上記チューブ１０を脱イオン水で洗浄してのち
その水を十分にとり除く。その後、チューブ１０の一側
開孔に上記注射針９の先端を挿入しく必要な場合には、
注射針９の挿入部周辺に接着部材１１が接着される）、
第２図の状態となす。次に、チューブ１０の他側開孔を
被測定液たる試料の中に入れ、ピストン操作部８を操作
して、シリンジ６内に試料を吸入する。該試料がチーー
ブ１０内を通過することにより、下式（２）のような反
応を受ける。Re5in-8o5・X +AgNOS-+ Re5i
n-8o, ・Ag 10X-N0.・---・・(11
Here, various ions such as Re5in, resin, X, and H+ are then washed with deionized water, and the water is sufficiently removed. Thereafter, if necessary, insert the tip of the injection needle 9 into the opening on one side of the tube 10.
An adhesive member 11 is adhered around the insertion portion of the injection needle 9),
Make the state shown in Figure 2. Next, the opening on the other side of the tube 10 is placed into a sample, which is a liquid to be measured, and the piston operating section 8 is operated to aspirate the sample into the syringe 6. When the sample passes through the tube 10, it undergoes a reaction as expressed by the following formula (2).
Ｒｅ５ｉｎ Ｓｏ、・Ａｇ＋Ｘ（Ｊ −＋ Ｒｅ５
ｉｎ Ｓｏ、・Ｘ＋ＡｇＣ７！ ＝−・−・・（２１こ
こで、ｋｃｌ’ｃ 塩化銀）の溶解度は極めて小さい（
２０°Ｃのときの溶解度積はわずか１．７８ＸｉＯであ
る）ため、々ＣＩ！は容易に沈澱する。従って、チュー
ブ１０内を通過してシリンジ６内に吸入された試料の中
には、塩素イオン（ＣＺ−）が殆んど存在しない。Re5in So, ・Ag+X(J −+ Re5
in So,・X+AgC7! =-・-・(21 Here, the solubility of kcl'c silver chloride) is extremely small (
The solubility product at 20°C is only 1.78XiO), so CI! precipitates easily. Therefore, almost no chloride ions (CZ-) are present in the sample passed through the tube 10 and sucked into the syringe 6.
その後、第２図の注射針９をチューブ１０と一緒にとり
はずし、第３図に示すようにインジェクタ注入用針１４
が装着されたフィルタユニット１２をシリンジ６忙とり
つげる。次に、インジェクタ注入用針１４の先端を、例
えばイオンクロマトグラフのサンプルインジェクタなど
に挿入する。ピストン操作部８を押し込むと、シリンジ
６内の試料がフィルタ１３を経てインジェクタ注入用針
１４から上記インジェクタ内などに注入される。尚、シ
リンジ６内の試料の中に被測定成分妨害物質（例えばＡ
ｇ（Ｊ沈澱物など）が含まれていないか、もし含まれて
いても微量であって測定上支障のないよ５な場合には、
第３図のフィルタユニット１２を除去しシリンジ注入用
針１４を直接シリンジ６にとりつげるようにしてもよい
。また、本発明は上記チューブ１０を銀型にして塩素イ
オンを試料からとり除く上述の実施例に限定されるもの
でなく種々の変形が可能であり、例えばバリウム型にし
て硫酸イオンをとり除いたり水素型にして金属イオンを
とり除いたり、鍛型にしてリン酸イオンをとり除いたり
、若しくはカルシウム型にしてフッ素イオンを除いたり
するようにしてもよいものとする。Thereafter, the injection needle 9 shown in FIG. 2 is removed together with the tube 10, and the injector injection needle 14 is removed as shown in FIG.
The filter unit 12 equipped with the filter unit 12 is attached to the syringe 6. Next, the tip of the injector injection needle 14 is inserted into, for example, a sample injector of an ion chromatograph. When the piston operating portion 8 is pushed in, the sample in the syringe 6 is injected into the injector through the filter 13 and the injector injection needle 14. Note that the sample in the syringe 6 contains substances interfering with the component to be measured (for example, A
If it does not contain g (J precipitate, etc.), or if it does, it is in a very small amount and does not pose a problem for measurement,
The filter unit 12 shown in FIG. 3 may be removed and the syringe injection needle 14 may be directly attached to the syringe 6. Further, the present invention is not limited to the above-described embodiment in which the tube 10 is made into a silver type to remove chloride ions from the sample, but various modifications are possible.For example, the tube 10 is made into a barium type to remove sulfate ions, or hydrogen It is also possible to use a mold to remove metal ions, a forge to remove phosphate ions, or a calcium mold to remove fluorine ions.
第４図は上述の本発明実施例の効果の一例を示すクロマ
ドグ２ムであり、図中、（４）は前処理を施こすことな
く試料を直接上記インジェクタに注入して得たクロマド
グ２ムであり、（Ｂ）は上述の本発明実施例による前処
理を施こした試料を上記インジェクタに注入して得たク
ロマトグラムである。FIG. 4 shows a chroma dog 2m showing an example of the effect of the embodiment of the present invention described above. and (B) is a chromatogram obtained by injecting a sample pretreated according to the above-described example of the present invention into the injector.
また、これらの試料としてはいずれの場合も、臭素イオ
ン５００ ｐｐｍ 、硝酸イオン１０ ｐｐｍ 、およ
び硫酸イオン２５ ｐｐｍを含む標準溶液が使用されて
いる。Further, in each case, standard solutions containing 500 ppm of bromide ions, 10 ppm of nitrate ions, and 25 ppm of sulfate ions are used as these samples.
更に、これらのクロマドグ２人を得るため、横河北辰電
機製イオンクロマトアナライザＩＣ−１００を用い、溶
離液として４ ｍＭ ”２ＣＯ３／４ｍＭＮａＨｃＯｓ
ヲ２ ｍ’４１゜で流し除去液として０．０５ Ｍの
ドデシルベンゼンスルホン酸溶液を２鴨品で流して実験
を行なった。第に隠れて測定不可能だった硝酸イオンが
（Ｂ）でははっきりと現われている。従って、臭素イオ
ンのような主成分ピークに隣接して溶出する硝酸イオン
の如き微量成分ピークを高精度に測定することが、本発
明実施例を用いることによって容易に可能となる。Furthermore, in order to obtain these two chromadogs, 4mM 2CO3/4mM NaHcOs was used as an eluent using Yokogawa Hokushin Electric's ion chromato analyzer IC-100.
An experiment was carried out by flowing a 0.05 M dodecylbenzenesulfonic acid solution as a removal liquid through a 2-layer tube at a temperature of 41 degrees. Nitrate ions, which were hidden and could not be measured, are clearly visible in (B). Therefore, by using the embodiments of the present invention, it is easily possible to measure with high precision the trace component peak such as nitrate ion which elutes adjacent to the main component peak such as bromide ion.
以上詳しく説明したような本発明の実施例によれば、内
容積の小さいイオン交換膜チューブ１ｏ内を通過させて
試料中の所望イオンを選択的に除去するような構成であ
るため、前記従来例に比し極少量の試料を前処理するこ
とができるという利点がある。このため、イオンクロマ
トグラフのインジェクタ等に使用する量だけ、試料を前
処理でき、微量の試料しか得られないときのイオン成分
の測定に用いるのに好適である。また、上記チー−プ１
０は洗浄後十分水をと９除くことができるため、前記従
来例のように試料が水で希釈される心配もない。更に、
上記チューブ１Ｄは十分細長であるため、チューブ１０
の内壁面と試料との接触が充分であり、Ｏ４Ｊ記（２）
式のような反応も万遍なく速く完了する利点がある。According to the embodiment of the present invention as described in detail above, the desired ions in the sample are selectively removed by passing through the ion exchange membrane tube 1o having a small internal volume, so that it is different from the conventional example. This method has the advantage that a very small amount of sample can be pretreated compared to the previous method. Therefore, the sample can be pretreated in the amount required for the injector of an ion chromatograph, etc., and is suitable for use in measuring ionic components when only a small amount of sample is obtained. Also, the above Cheap 1
Since water can be removed sufficiently after washing, there is no need to worry about the sample being diluted with water as in the conventional example. Furthermore,
Since the tube 1D is sufficiently elongated, the tube 10
There is sufficient contact between the inner wall surface of the sample and the sample, and O4J (2)
Reactions like the one shown in the formula also have the advantage of completing quickly and uniformly.
第１図は試料前処理方法の従来例説明図、第２図および
第３図は、本発明実施例の構成説明図、第４図は本発明
実施例の効果の一例を示すクロマトグラムである。
１・・・イオン交換樹脂粒子、４・・・管状部材、６・
・・シリンジ、７・・・ピストン部、８・・・ピストン
操作部、９・・・注射針、１ｏ川イオン交換膜チー−プ
、旧°°接着部材、１２・・・フィルタユニット、１３
・・・フィルタ、１４・・・インジェクタ注入用針。
ｆｉｒ ロ
アＺＩ１２］
オ ３ 圓FIG. 1 is an explanatory diagram of a conventional example of a sample pretreatment method, FIGS. 2 and 3 are illustrations of the configuration of an embodiment of the present invention, and FIG. 4 is a chromatogram showing an example of the effect of an embodiment of the present invention. . 1... Ion exchange resin particles, 4... Tubular member, 6.
... Syringe, 7... Piston part, 8... Piston operating part, 9... Syringe needle, 1o River ion exchange membrane cheap, old °° adhesive member, 12... Filter unit, 13
...filter, 14...injector injection needle. fir Roa ZI12] O 3 En
Claims (1)
オン交換膜チューブをシリンジに装着し、該シリンジ内
に前記チューブの内部を通過させて試料を採取すること
により、前記チューブ内壁面のイオン交換基と前記試料
中の所望イオンとをイオン交換させ、前記シリンジ内に
前記所望イオンが除去された試料を得ることを特徴とす
る試料前処理方法。 （２） 前記所望の型は銀型であり、ＩＩＪ記所望イ
オンは塩素イオン、臭素イオン、若しくはヨウ素イオン
である特許請求範囲第（１）項記載の試料前処理方法。 （６） 前記所望の型はバリウム型であり、前記所望
イオンは硫酸イオン若しくはシュウ酸イオンである特許
請求範囲第（１）項記載の試料前処理方法。 （４） 前記所望の型はカルシウム型であり、前記所
望イオンはフッ素イオン若しくはシュウ酸イオンである
特許請求範囲第（１）項記載の試料前処理方法。 （５） 前記所望の型は水素型であり、前記所望イオ
ンは金属イオンである特許請求範囲第（１）項記載の試
料前処理方法。 （６） 前記所望の型は鉄型であり、前記所望イオン
はリン酸イオンである特許請求範囲第（１）項記載の試
料前処理方法。 （７）所望の型のイオン交換基を有する中空繊維状のイ
オン交換膜チー−ブと、該チューブの一側開口に注射針
を挿入して密着させるシリンジとを具備し、前記チュー
ブの他側開口を試料に浸し前記チューブの内部を通過さ
せて前記シリンジ内に所望イオンが除去された前記試料
を吸入するように構成されたことを特徴とする試料前処
理装置。 （８） 前記所望の型は、銀型、バリウム型、カルシ
ウム型、鉄型、若しくは水素型のいずれかでなる特許請
求範囲第（ワ）項記載の試料前処理装置。 （９） 前記チューブは、長さ５ ｃｍ乃至２ＱＯｃ
ｍ１内径０．０５ｃｍ乃至０．０８ｃｍのチューブでな
る特許請求範囲第（７１項若しくは（８）項記載の試料
前処理装置。[Claims] (1) By attaching a hollow fibrous ion exchange membrane tube having a desired type of ion exchange group to a syringe, and collecting a sample by passing it through the inside of the tube into the syringe. A sample pretreatment method, characterized in that the ion exchange group on the inner wall surface of the tube and the desired ions in the sample are ion-exchanged, and the sample from which the desired ions have been removed is obtained in the syringe. (2) The sample pretreatment method according to claim (1), wherein the desired type is a silver type, and the desired ion IIJ is a chloride ion, a bromide ion, or an iodine ion. (6) The sample pretreatment method according to claim (1), wherein the desired type is a barium type, and the desired ion is a sulfate ion or an oxalate ion. (4) The sample pretreatment method according to claim (1), wherein the desired type is a calcium type, and the desired ion is a fluorine ion or an oxalate ion. (5) The sample pretreatment method according to claim (1), wherein the desired type is a hydrogen type, and the desired ion is a metal ion. (6) The sample pretreatment method according to claim (1), wherein the desired type is an iron type, and the desired ion is a phosphate ion. (7) A hollow fibrous ion exchange membrane tube having a desired type of ion exchange group, and a syringe for inserting an injection needle into an opening on one side of the tube and bringing it into close contact with the tube, and the other side of the tube A sample pretreatment device, characterized in that the sample pretreatment device is configured to immerse the sample into the sample through the opening, pass the sample through the tube, and suck the sample from which desired ions have been removed into the syringe. (8) The sample pretreatment apparatus according to claim 1, wherein the desired type is any one of a silver type, a barium type, a calcium type, an iron type, or a hydrogen type. (9) The tube has a length of 5 cm to 2 QOc.
A sample pretreatment device according to claim 71 or (8), which comprises a tube having an inner diameter of m1 of 0.05 cm to 0.08 cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6420383A JPS59190657A (en) | 1983-04-12 | 1983-04-12 | Specimen pretreating method and apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6420383A JPS59190657A (en) | 1983-04-12 | 1983-04-12 | Specimen pretreating method and apparatus therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59190657A true JPS59190657A (en) | 1984-10-29 |
Family
ID=13251271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6420383A Pending JPS59190657A (en) | 1983-04-12 | 1983-04-12 | Specimen pretreating method and apparatus therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59190657A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01114754A (en) * | 1987-10-29 | 1989-05-08 | Yokogawa Electric Corp | Method for measuring cn- ion |
| EP1178312A2 (en) * | 2000-08-02 | 2002-02-06 | Macherey-Nagel GmbH & Co. KG | Apparatus and its use for eliminating halide ions from aqueous solutions |
| EP1217102A3 (en) * | 2000-11-29 | 2004-08-11 | Ebara Corporation | Plating apparatus and method of managing plating liquid composition |
| JP2015219009A (en) * | 2014-05-13 | 2015-12-07 | 四国電力株式会社 | Continuous detection method and detection device of seawater leak |
| US20170038283A1 (en) * | 2015-08-04 | 2017-02-09 | Adam Tokarski | Sampling device |
| CN111417420A (en) * | 2017-11-17 | 2020-07-14 | 瑞典孤儿比奥维特鲁姆有限公司 | Syringe assembly with ion exchange material |
-
1983
- 1983-04-12 JP JP6420383A patent/JPS59190657A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01114754A (en) * | 1987-10-29 | 1989-05-08 | Yokogawa Electric Corp | Method for measuring cn- ion |
| EP1178312A2 (en) * | 2000-08-02 | 2002-02-06 | Macherey-Nagel GmbH & Co. KG | Apparatus and its use for eliminating halide ions from aqueous solutions |
| EP1178312A3 (en) * | 2000-08-02 | 2002-06-26 | Macherey-Nagel GmbH & Co. KG | Apparatus and its use for eliminating halide ions from aqueous solutions |
| US6602717B2 (en) | 2000-08-02 | 2003-08-05 | Macherey-Nagel Gmbh & Co. Kg | Apparatus for eliminating halide ions from aqueous solutions and method to remove halide ions from liquid aqueous samples |
| EP1217102A3 (en) * | 2000-11-29 | 2004-08-11 | Ebara Corporation | Plating apparatus and method of managing plating liquid composition |
| JP2015219009A (en) * | 2014-05-13 | 2015-12-07 | 四国電力株式会社 | Continuous detection method and detection device of seawater leak |
| US20170038283A1 (en) * | 2015-08-04 | 2017-02-09 | Adam Tokarski | Sampling device |
| US10006838B2 (en) * | 2015-08-04 | 2018-06-26 | Adam Tokarski | Sampling device |
| CN111417420A (en) * | 2017-11-17 | 2020-07-14 | 瑞典孤儿比奥维特鲁姆有限公司 | Syringe assembly with ion exchange material |
| CN111417420B (en) * | 2017-11-17 | 2024-02-02 | 瑞典孤儿比奥维特鲁姆有限公司 | Injector assembly with ion exchange material |
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