CN102033115A - Separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin - Google Patents
Separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin Download PDFInfo
- Publication number
- CN102033115A CN102033115A CN 201010535781 CN201010535781A CN102033115A CN 102033115 A CN102033115 A CN 102033115A CN 201010535781 CN201010535781 CN 201010535781 CN 201010535781 A CN201010535781 A CN 201010535781A CN 102033115 A CN102033115 A CN 102033115A
- Authority
- CN
- China
- Prior art keywords
- sodium
- hydroxyl
- sample
- reference substance
- butane sulfonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention relates to a separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin, aiming at solving a limit detecting problem of the 4-hydroxy butane sodium sulfonate (sodium) in the sulfobutyl ether-beta-cyclodextrin by adopting ion chromatography, using an anion analysis column as a separating means, adopting an electric conductivity detector, and using eluant as a sodium carbonate-sodium bicarbonate system or a sodium (potassium) carbonate-sodium (potassium) hydroxide system. The separating and measuring method comprises the following steps of: (1) preparing eluant with proper concentration, wherein the eluant is the sodium carbonate-sodium bicarbonate system or the sodium (potassium) carbonate-sodium (potassium) hydroxide system; (2) preparing a sulfobutyl ether-beta-cyclodextrin sample solution and a 4-hydroxy butane sodium sulfonate (sodium) reference substance solution with proper concentration; and (3) respectively carrying out the sample detection of the sample solution and the reference substance solution by the ion chromatography by adopting an anion chromatographic column and the electric conductivity detector, wherein in the sample solution, if the peak area of the 4-hydroxy butane sodium sulfonate (sodium) is lower than a reference peak area, a sample is qualified. The separating and measuring method is sensitive, has low sample dosage, high reproduction and reliable result and can control and detect the quality of the sulfobutyl ether-beta-cyclodextrin, thereby increasing product quality.
Description
Technical field
The present invention relates to a kind of separation and assay method, be specifically related to the separation and the assay method of 4-hydroxyl sodium butane sulfonate in a kind of sulphur butyl betadex.
Background technology
Sulphur butyl betadex (sulfobutyl ether-β-cyclodextrin, SBE-β-CD) is the beta-cyclodextrin derivative of the nineties in 20th century by the exploitation of U.S. CyDex company, is applied to increase drug solubility and stability, improves drug bioavailability, regulates drug releasing rate, prevents the volatile ingredient loss, improves bad smell, reduces pungency, reduces aspect such as bad reaction.Sulphur butyl betadex is β-CD and 1, the product of 4-butane sultones generation substitution reaction.SBE-β-CD commonly used is 7 SBE
7-β-CD, commodity are called Captisol, its sodium salt commonly used.4-hydroxyl butane sulfonic acid is 1, the accessory substance that the hydrolysis of 4-butane sultones produces.
The assay method of 4-hydroxyl sodium butane sulfonate is not seen the domestic and foreign literature report in the sulphur butyl betadex.
Sulphur butyl betadex is the cyclodextrine derivatives of an ion-type, contains foreign ions such as 4-hydroxyl sodium butane sulfonate, chlorion in the sulphur butyl betadex sample.4-hydroxyl sodium butane sulfonate limiting the quantity of in sulphur butyl betadex is very low, below per mille.Therefore needing to seek one can effectively separate sulphur butyl betadex, 4-hydroxyl sodium butane sulfonate, chlorion etc. in the sample, and the method that has higher detection sensitivity that 4-hydroxyl sodium butane sulfonate is detected.
The chromatography of ions genealogy of law adopts the high pressure pump system that the eluent of regulation is pumped into the chromatogram analysis method that the chromatographic column that filling agent is housed is carried out separation determination.The test sample that injects by eluent bring into separate in the chromatographic column after, enter detecting device through rejector or flavor, by integraph or data handling system record chromatographic signal.The chromatography of ions is used the qualitative and quantitative analysis with materials such as inorganic anion, inorganic cation, organic acid, pure carbohydrate, aminosugars, amino acid, protein, glycoprotein always.Its separating mechanism is mainly ion-exchange, promptly based on the reversible exchange of carrying out between the solute ions that has identical charges in ion that can dissociate on the ion exchange resin and the moving phase; Other separating mechanisms of the chromatography of ions form ion pair, ion exclusion etc. in addition.
Because sulphur butyl betadex is the cyclodextrine derivatives of an ion-type, also contains other foreign ions such as chlorion in the sulphur butyl betadex sample.Adopt suitable eluent condition, 4-hydroxyl sodium butane sulfonate, sulphur butyl betadex, chlorion etc. are realized well separating in the chromatography of ions energy.
Summary of the invention
The separation and the assay method that the purpose of this invention is to provide 4-hydroxyl sodium butane sulfonate in a kind of sulphur butyl betadex, this method adopts the chromatography of ions, with the anion analysis post is separation means, with the electric conductivity detector is detection means, separates and the detection problem with this limit that solves 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex.4-hydroxyl sodium butane sulfonate is the important by-products that produces in the sulphur butyl betadex building-up process, should carry out rational quality control and check to the 4-hydroxyl sodium butane sulfonate in the product, thereby improves the quality and the quality of product.This method has that amount of samples is few, detection sensitivity is high, reappearance is high, the advantage of reliable results.
Technical scheme of the present invention is: the separation and the assay method of 4-hydroxyl sodium butane sulfonate in a kind of sulphur butyl betadex is characterized in that step is as follows:
⑴ prepare eluent;
⑵ preparation sulphur butyl betadex sample solution;
⑶ the reference substance solution of preparation 4-hydroxyl sodium butane sulfonate, or the reference substance solution of 4-hydroxyl butane sulfonic acid;
⑷ it is separation means that chromatography of ions adopts anion chromatographic column, adopts electric conductivity detector; Sample is sample introduction respectively, with the eluent wash-out sulphur butyl betadex sample or the reference substance solution of step ⑴ preparation;
⑸ detect respectively in the reference substance solution of the reference substance solution of 4-hydroxyl sodium butane sulfonate or 4-hydroxyl butane sulfonic acid, the peak area of 4-hydroxyl butane sulfonic acid (can think that perhaps this peak area is the peak area of reflection 4-hydroxyl butane sulfonate radical);
⑹ go out the content of 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex sample according to the data computation of step ⑸.
Described eluent can be sodium carbonate-sodium bicarbonate system, NaOH-sodium carbonate system or potassium hydroxide-sal tartari system;
Sodium carbonate in sodium carbonate-sodium bicarbonate eluent: sodium bicarbonate=0～30m mol/L:0～40m mol/L; In NaOH-sodium carbonate or potassium hydroxide-sal tartari eluent, NaOH-sodium carbonate, or potassium hydroxide-sal tartari=0～15m mol/L:0～15m mol/L.
The concentration of described sulphur butyl betadex sample solution and 4-hydroxyl sodium butane sulfonate reference substance solution can be 10mg/ml and 10 μ g/ml.
In other words, the concrete operation method of each step of the present invention is:
⑴ the preparation of eluent: sodium carbonate-sodium bicarbonate eluent preparation: weighing sodium carbonate, sodium bicarbonate are an amount of, are dissolved in deionized water, are mixed with sodium carbonate: the eluent of sodium bicarbonate=0～30m mol/L:0～40m mol/L;
NaOH-sodium carbonate, or the preparation of potassium hydroxide-sal tartari eluent: weighing sodium hydroxide, sodium carbonate, or potassium hydroxide, sal tartari are an amount of, be dissolved in deionized water, be mixed with NaOH: sodium carbonate, or potassium hydroxide: the eluent of sal tartari=0～15m mol/L:0～15m mol/L;
⑵ the preparation of sample solution: take by weighing sulphur butyl betadex, be dissolved in deionized water, be mixed with the sample solution of debita spissitudo;
⑶ the preparation of reference substance solution: take by weighing 4-hydroxyl sodium butane sulfonate, or 4-hydroxyl butane sulfonic acid, be dissolved in deionized water, be mixed with the reference substance solution of debita spissitudo;
⑷ it is separation means that chromatography of ions adopts the anion analysis post, adopts electric conductivity detector, respectively with sample solution and reference substance solution sample introduction;
⑸ detect respectively in the reference substance solution of the reference substance solution of 4-hydroxyl sodium butane sulfonate or 4-hydroxyl butane sulfonic acid, the peak area of 4-hydroxyl butane sulfonate radical;
⑹ go out the content of 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex sample according to the data computation of step ⑸.
Adopt ion chromatography system of the present invention, can effectively separate between sample and impurity are straight, detection sensitivity is very high, and the lowest detectable limit of 4-hydroxyl sodium butane sulfonate can reach the rank of ng/ml.Owing to limiting the quantity of of 4-hydroxyl sodium butane sulfonate in the sample is very low, below per mille, so the sensitivity of detecting device is had higher requirement.Select for use electric conductivity detector can reach the detection requirement preferably.
Description of drawings
Fig. 1 is the typical curve of embodiment 3 sodium carbonate-sodium bicarbonate system;
Fig. 2 is the sample solution sample introduction of embodiment 3 concentration 10.007mg/ml, chromatogram;
Fig. 3 is embodiment 3 concentration 10.18 μ g/ml reference substance chromatograms;
Fig. 4 is the typical curve of embodiment 4 NaOH system eluents;
Fig. 5 is the sample solution sample introduction of embodiment 4 concentration 5.011mg/ml, chromatogram;
Fig. 6 is embodiment 4 concentration 5.062 μ g/ml reference substance chromatograms.
Embodiment
Below in conjunction with embodiment the present invention is discussed in detail.
Weighing sodium carbonate 0.214g, sodium bicarbonate 1.026g adds deionized water 2000ml dissolving, and getting concentration is 1m mol/L sodium carbonate+6m mol/L sodium bicarbonate, and total concentration is the eluent of 7m mol/L.
Weighing sodium hydroxide 0.443g adds deionized water 2000ml dissolving, and getting concentration is the eluent of 5.5m mol/L.
Embodiment 3, the detection of the sodium carbonate-4-of sodium bicarbonate system hydroxyl sodium butane sulfonate,
Ion chromatograph: DIONEX ICS-90 type ion chromatograph (U.S. Dai An company),
The negative ion guard column of IonPac AG23(4 * 50mm),
ASRS300(4 mm) negative ion rejector,
Chromatographic column: IonPac AS23 anion analysis post (4 * 250 mm),
Electric conductivity detector.
1) preparation of 4-hydroxyl sodium butane sulfonate reference substance solution:
Precision takes by weighing the 4-hydroxyl sodium butane sulfonate of 101.81mg to the 100ml measuring bottle, and constant volume gets the 4-hydroxyl sodium butane sulfonate of 0.1018mg/ml, and precision pipettes 0.1ml respectively, 0.3ml, 0.5ml 0.7ml is in 0.9ml to the 50ml volumetric flask, use the deionized water constant volume, obtain concentration and be respectively 2.036,6.108,10.18,14.25, the 4-hydroxyl sodium butane sulfonate of 18.32 μ g/ml.
2) preparation of sulphur butyl betadex sample solution:
Precision takes by weighing sample 500.36mg, and deionized water dissolving is settled to 50ml, and getting concentration is 10.007mg/ml solution.
3) drafting of typical curve:
Concentration is respectively 2.036,6.108, and the 4-hydroxyl sodium butane sulfonate sample introduction of 10.18,14.25,18.32 μ g/ml, eluent are the sodium carbonate-sodium bicarbonate system solution among the embodiment 1, the drawing standard curve, and the result is linear good, typical curve such as Fig. 1.
4) detection of sample:
With concentration is the sample solution sample introduction of 10.007mg/ml, and chromatogram is Fig. 2, and concentration is that 10.18 μ g/ml reference substance chromatograms are Fig. 3.
Ion chromatograph: DIONEX ICS2000 type ion chromatograph (U.S. Dai An company),
The negative ion guard column of IonPac AG19(4 * 50mm),
ASRS300(4 mm) negative ion rejector,
Chromatographic column: IonPac AS19 anion analysis post (4 * 250 mm).
Electric conductivity detector.
1) preparation of 4-hydroxyl sodium butane sulfonate reference substance solution:
Precision takes by weighing 50.62 mg 4-hydroxyl sodium butane sulfonates to the 100ml measuring bottle, and constant volume gets 506.2 μ g/ml 4-hydroxyl sodium butane sulfonates, and precision pipettes 0.25ml respectively, 0.5ml, 1ml, 2ml is in 3ml to the 100ml volumetric flask, use the deionized water constant volume, obtain concentration and be respectively 1.266,2.531,5.062,10.12, the 4-hydroxyl sodium butane sulfonate of 15.19 μ g/ml.
2) preparation of sulphur butyl betadex sample solution:
Precision takes by weighing sample 501.12mg, and deionized water dissolving is settled to 100ml, and getting concentration is 5.011mg/ml solution.
3) drafting of typical curve:
Concentration is respectively 2.036,6.108, and the 4-hydroxyl sodium butane sulfonate sample introduction of 10.18,14.25,18.32 μ g/ml, eluent are the NaOH system solution among the embodiment 2, the drawing standard curve, and the result is linear good, typical curve such as Fig. 4.
4) detection of sample:
With concentration is the sample solution sample introduction of 5.011mg/ml, and chromatogram is Fig. 5, and concentration is that 5.062 μ g/ml reference substance chromatograms are Fig. 6.
More than the description of better embodiment of the present invention is not limited the present invention, those skilled in the art can make various changes or distortion according to the present invention, only otherwise break away from spirit of the present invention, all should belong to the scope of claims of the present invention.
Claims (4)
1. the separation and the assay method of 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex is characterized in that, separate with determination step to be:
⑴ prepare eluent;
⑵ preparation sulphur butyl betadex sample solution;
⑶ the reference substance solution of preparation 4-hydroxyl sodium butane sulfonate, or the reference substance solution of 4-hydroxyl butane sulfonic acid;
⑷ it is separation means that chromatography of ions adopts anion chromatographic column, adopts electric conductivity detector; Sample is sample introduction respectively, with the eluent wash-out sulphur butyl betadex sample or the reference substance solution of step ⑴ preparation;
⑸ detect respectively in the reference substance solution of the reference substance solution of 4-hydroxyl sodium butane sulfonate or 4-hydroxyl butane sulfonic acid, the peak area of 4-hydroxyl butane sulfonate radical;
⑹ go out the content of 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex sample according to the data computation of step ⑸.
2. the separation and the assay method of 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex according to claim 1 is characterized in that the concrete operation method of each step is:
⑴ the preparation of eluent: sodium carbonate-sodium bicarbonate eluent preparation: weighing sodium carbonate, sodium bicarbonate are an amount of, are dissolved in deionized water, are mixed with sodium carbonate: the eluent of sodium bicarbonate=0～30m mol/L:0～40m mol/L;
NaOH-sodium carbonate, or the preparation of potassium hydroxide-sal tartari eluent: weighing sodium hydroxide, sodium carbonate, or potassium hydroxide, sal tartari are an amount of, be dissolved in deionized water, be mixed with NaOH: sodium carbonate, or potassium hydroxide: the eluent of sal tartari=0～15m mol/L:0～15m mol/L;
⑵ the preparation of sample solution: take by weighing sulphur butyl betadex, be dissolved in deionized water, be mixed with the sample solution of debita spissitudo;
⑶ the preparation of reference substance solution: take by weighing 4-hydroxyl sodium butane sulfonate, or 4-hydroxyl butane sulfonic acid, be dissolved in deionized water, be mixed with the reference substance solution of debita spissitudo;
⑷ it is separation means that chromatography of ions adopts the anion analysis post, adopts electric conductivity detector, respectively with sample solution and reference substance solution sample introduction;
⑸ detect respectively in the reference substance solution of the reference substance solution of 4-hydroxyl sodium butane sulfonate or 4-hydroxyl butane sulfonic acid, the peak area of 4-hydroxyl butane sulfonate radical;
⑹ go out the content of 4-hydroxyl sodium butane sulfonate in the sulphur butyl betadex sample according to the data computation of step ⑸.
3. the separation and the assay method of 4-hydroxyl sodium butane sulfonate is characterized in that in the sulphur butyl betadex according to claim 2, described sodium carbonate-sodium bicarbonate eluent, sodium carbonate: sodium bicarbonate=0～10m mol/L:0～15m mol/L.
4. according to the separation and the assay method of 4-hydroxyl sodium butane sulfonate in the claim 3 sulphur butyl according to claim 2 betadex, it is characterized in that, described NaOH-sodium carbonate, or potassium hydroxide-sal tartari eluent, NaOH: sodium carbonate, or potassium hydroxide: sal tartari=3～10m mol/L:0～10m mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010535781 CN102033115B (en) | 2010-11-09 | 2010-11-09 | Separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010535781 CN102033115B (en) | 2010-11-09 | 2010-11-09 | Separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102033115A true CN102033115A (en) | 2011-04-27 |
| CN102033115B CN102033115B (en) | 2013-03-20 |
Family
ID=43886286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010535781 Expired - Fee Related CN102033115B (en) | 2010-11-09 | 2010-11-09 | Separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102033115B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108845044A (en) * | 2018-05-03 | 2018-11-20 | 山东滨州智源生物科技有限公司 | The detection method of sodium content in a kind of sulfobutyl ether betadex sodium |
| CN112147188A (en) * | 2020-09-24 | 2020-12-29 | 青岛科技大学 | Method for rapidly determining ash content in vulcanization accelerator MBTS |
| CN114624346A (en) * | 2020-12-11 | 2022-06-14 | 诺莱特电池材料(苏州)有限公司 | Method for detecting content of methylene methanedisulfonate in lithium ion battery electrolyte |
| WO2022259091A1 (en) * | 2021-06-10 | 2022-12-15 | Cyclolab Cyclodextrin Research And Development Laboratory Ltd | Purification of sulfobutylated cyclodextrins with specific ion exchange resins |
-
2010
- 2010-11-09 CN CN 201010535781 patent/CN102033115B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 《CHROMATOGRAPHIA》 19991231 S.GRARD等 Sulfobutyl ether-beta-cyclodextrin fingerprint using ion pair reversed-phase chromatography 695-700 1-4 第50卷, 第11/12期 * |
| 《J.SEP.SCI.》 20041231 ROMAIN JACQUET等 Liquid chromatography analysis of monosubstituted sulfobutyl ether-beta-cyclodextrin isomers on porous graphitic carbon 1221-1228 1-4 第27卷, * |
| 《药物分析杂志》 20071231 张培敏等 离子色谱在制药分析中的新进展 151-155 1-4 第27卷, 第1期 * |
| 《药物分析杂志》 20091231 葛文娜等 羟丙基-磺丁基-beta-环糊精包合物冻干粉中多烯紫杉醇的含量及其有关物质测定 582-586 1-4 第29卷, 第4期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108845044A (en) * | 2018-05-03 | 2018-11-20 | 山东滨州智源生物科技有限公司 | The detection method of sodium content in a kind of sulfobutyl ether betadex sodium |
| CN112147188A (en) * | 2020-09-24 | 2020-12-29 | 青岛科技大学 | Method for rapidly determining ash content in vulcanization accelerator MBTS |
| CN114624346A (en) * | 2020-12-11 | 2022-06-14 | 诺莱特电池材料(苏州)有限公司 | Method for detecting content of methylene methanedisulfonate in lithium ion battery electrolyte |
| CN114624346B (en) * | 2020-12-11 | 2024-03-29 | 诺莱特电池材料(苏州)有限公司 | Method for detecting content of methane disulfonic acid methylene ester in lithium ion battery electrolyte |
| WO2022259091A1 (en) * | 2021-06-10 | 2022-12-15 | Cyclolab Cyclodextrin Research And Development Laboratory Ltd | Purification of sulfobutylated cyclodextrins with specific ion exchange resins |
| US11649299B2 (en) | 2021-06-10 | 2023-05-16 | Cyclolab Cyclodextrin Research And Development Laboratory Ltd. | Purification of sulfobutylated cyclodextrins with specific ion exchange resins |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102033115B (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102033115B (en) | Separating and measuring method of 4-hydroxy butane sodium sulfonate in sulfobutyl ether-beta-cyclodextrin | |
| EP3748340B1 (en) | Methods for the rapid preparation of labeled glycosylamines and for the analysis of glycosylated biomolecules producing the same | |
| CN102914600A (en) | Method for measuring trace chloridion and sulfate radical in loprazolam samples by ion chromatography | |
| EP3106224A1 (en) | Ion exchange chromatography column, method, and system thereof | |
| CN102539564A (en) | Detection method for ornidazole injection impurities and content measuring method | |
| CN101699281B (en) | Detection method of acetylcysteine and related substances thereof | |
| Fernández et al. | Modulation of mobile phase composition in flow-injection/sequential-injection chromatography exploiting multisyringe flow analysis | |
| US20170007981A1 (en) | Packing material for liquid chromatography and column for liquid chromatography | |
| CN105510511B (en) | HPLC (High Performance Liquid Chromatography) separation and detection method of 2-aminobutanol enantiomer | |
| CN1441248A (en) | Detection method of glyoxalic acid, glycolic acid, glyoxal and oxalic acid | |
| CN103175930B (en) | A kind of HPLC analytical method measuring sodium sulphite content | |
| CN106226454A (en) | A kind of measure the ion chromatographic method of trace chloro ion in trimethyl gallium | |
| Shen et al. | Enantiomeric separation of naphthalene-2, 3-dicarboxaldehyde derivatized dl-3, 4-dihydroxyphenylalanine and optical purity analysis of l-3, 4-dihydroxyphenylalanine drug by cyclodextrin-modified micellar electrokinetic chromatography | |
| Haddad | Peer Reviewed: Ion Chromatography Retrospective | |
| CN108845044A (en) | The detection method of sodium content in a kind of sulfobutyl ether betadex sodium | |
| CN103852542A (en) | Method for detecting complete degradation product of low molecular weight heparin based on post-column derivatization | |
| Hamilton et al. | Analytical methods for the quantification of free melamine and cyanuric acid in Nylon 6/6, 6 co‐polymer | |
| CN103995062B (en) | Method for testing exenatide and impurities thereof by using high performance liquid chromatography | |
| CN102901783A (en) | Content determination method for pranoprofen eye drops | |
| CN103048407A (en) | Content detection method for lysine of compound ketoacid tablet | |
| CN105974037A (en) | Pretreatment method for determining trace quantity of anions in ammonium sebate through ion chromatography | |
| Shelor et al. | Automated Programmable Generation of Broad pH Range Volatile Ionic Eluents for Liquid Chromatography | |
| Mitsumori et al. | Quantitative analysis of cyclodextrins by electrochemical detector and column with core-shell type filler | |
| JP6597138B2 (en) | Ion conversion method and ion conversion apparatus for ionic compounds | |
| US11845769B2 (en) | Anion exchange stationary phases based on a polyalkylpolyamine polymer layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130320 Termination date: 20171109 |