CN113332967A - Trapezoidal polyether modified and cysteine terminated chromatographic stationary phase, preparation method and application - Google Patents
Trapezoidal polyether modified and cysteine terminated chromatographic stationary phase, preparation method and application Download PDFInfo
- Publication number
- CN113332967A CN113332967A CN202110726660.8A CN202110726660A CN113332967A CN 113332967 A CN113332967 A CN 113332967A CN 202110726660 A CN202110726660 A CN 202110726660A CN 113332967 A CN113332967 A CN 113332967A
- Authority
- CN
- China
- Prior art keywords
- polyether
- trapezoidal
- cysteine
- stationary phase
- modified
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/30—Partition chromatography
- B01D15/305—Hydrophilic interaction chromatography [HILIC]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/32—Bonded phase chromatography
- B01D15/325—Reversed phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, a preparation method and application thereof, wherein the molecular structure of the trapezoidal polyether modified on the stationary phase comprises 11 rings and 23 chiral centers, has larger molecular volume and complex stereochemical structure, and can provide interaction among various molecules, thereby having excellent separation selectivity and larger sample loading capacity, and being suitable for various chromatographic separation modes such as hydrophilic action, reversed phase and the like. The end branched chain of the trapezoidal polyether molecule has aldehyde group, C ═ C double bond and openable lactone structure, and the ring has a plurality of active functional groups capable of reacting with other compounds, so that the trapezoidal polyether modification and the cysteine-terminated chromatographic stationary phase can be conveniently modified to prepare different types of novel stationary phases. The preparation method has the advantages of simple operation steps, high implementation feasibility and relatively low preparation cost.
Description
Technical Field
The invention relates to the technical field of chromatographic separation stationary phases, in particular to a trapezoidal polyether-modified cysteine-terminated chromatographic stationary phase, a preparation method and application thereof.
Background
The ether type bonded stationary phase is an important stationary phase, and the production process is mature. The Dashilu project group synthesized a 3- (aza-18-crown-6) propyl-bonded stationary phase with gamma-chloropropyl-bonded silica under the action of sodium hydride (chromatography, 1995, 13: 161). Chinese patent No. ZL01109965.8 discloses an ether-type bonded stationary phase and a preparation method thereof, wherein a silicon coupling agent containing a β - (3, 4-epoxycyclohexyl) group is adopted to react with alkyl alcohol and then covalently bond with a hydroxyl-containing particulate carrier, and since the epoxy ring in the β - (3, 4-epoxycyclohexyl) group is more active than the epoxy ring of a common γ -epoxypropyloxypropyl group, the bonding process of the present invention does not require a catalyst and the reaction process is simple, the stationary phase prepared by the method can be effectively used for liquid chromatography separation, especially for separation of alkaline organic compounds, and the separation effect is high.
Crown ethers are cyclic polyethers derived from aromatic vicinal diols, and since the polarity is concentrated on the intra-ring oxygen atom, they can be used in highly selective coordination with cations and polar compounds, and are a stationary phase that has been studied more by chromatographic workers. R-binaphthol is used as a raw material in the fields of Loganic syndrome and the like, R- (3,3 '-diphenyl-1, 1' -dinaphthyl) -20-crown-6 is synthesized by improving Suzuki reaction, and is coated on C18 silica gel to prepare a crown ether stationary phase (organic chemistry, 2015, 35, 217-222) for chiral resolution of high performance liquid chromatography.
Besides crown ether, the chinese patent application No. 201110079436.0 discloses a silica gel bonded with a single chiral helical polyether, a preparation method thereof and a use thereof as a chiral stationary phase of high performance liquid chromatography, which has the technical effects: the silica gel bonded with the single-chiral spiral polyether with the poly [3- (9-alkyl fluorene-9-yl) -1, 2-epoxypropane skeleton structure prepared by the invention can be used as a chiral stationary phase of high performance liquid chromatography to separate and analyze a plurality of racemes, wherein the racemes comprise alcohols, ketones, lipids, carboxylic acids, amines and the like. In addition, the preparation of other polyether chromatographic stationary phases is rarely reported.
The uninterrupted ring ladder structure of the ladder polyether prevents the molecular chain from freely rotating, and the rotation (or degradation) must break two chemical bonds on the same ring at the same time. However, this simultaneous cleavage of two bonds on the same ring gives the molecule a much smaller chance of chain scission than the corresponding single bond cleavage. Therefore, the trapezoidal polyether has higher thermal, mechanical, radiation and chemical stability than the traditional single-chain polymer due to the unique double-chain structure. At present, chromatographic stationary phases modified by trapezoidal polyether and terminated by cysteine are not reported, so that the invention aims to provide the chromatographic stationary phases modified by trapezoidal polyether and terminated by cysteine, a preparation method and application so as to expand the types and application prospects of the chromatographic stationary phases.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, a preparation method and application thereof.
The first purpose of the technical scheme of the invention is to design a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, wherein the chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine has a structure shown in a formula I, and the trapezoidal polyether (Brevitoxin B) has a structure shown in a formula II:
the second objective of the technical scheme of the invention is to provide a preparation method of the chromatographic stationary phase modified by the trapezoidal polyether and terminated by cysteine, wherein the reaction process is shown as the following formula III, and the preparation method comprises the following steps:
s1: dispersing aminopropyl bonded silica gel microspheres (structural formula 1) in 30-50 mL of aqueous solution, adding 10-100 mL of aqueous solution of trapezoidal polyether (Brevitoxin B), heating and refluxing for 0.5-2 days at 70-80 ℃, and washing with methanol to obtain trapezoidal polyether modified silica gel microspheres (structural formula 2);
s2: dispersing the trapezoidal polyether modified silica gel microspheres prepared in the step S1 in a container filled with 10-100 mL of dipotassium hydrogen phosphate aqueous solution, adding 1-3 g of sodium borohydride, stirring at room temperature for 1-2 h, filtering, washing with water to be neutral, and drying to obtain reductive trapezoidal polyether modified silica gel microspheres (structural formula 3);
s3: and (4) dispersing the reductive trapezoidal polyether modified silica gel microspheres prepared in the step (S2) in a cysteine aqueous solution, carrying out heating reflux reaction for 10-12 h at the temperature of 70-80 ℃, washing with methanol, and drying to obtain a chromatographic stationary phase (structural formula 4) modified by trapezoidal polyether and terminated by cysteine, wherein the mass feed ratio of cysteine to the reductive trapezoidal polyether modified silica gel microspheres is 1: 0.5-5.
In the preferred technical scheme, in the step S1, the mass concentration of the trapezoidal polyether in the aqueous solution of the trapezoidal polyether (Brevetoxin B) is 15-20%, and the mass feeding ratio of the aminopropyl bonded silica gel microspheres (structural formula 1) to the trapezoidal polyether is 1: 0.5-10.
Preferably, in the step S2, the molar concentration of the dipotassium hydrogen phosphate in the aqueous solution of the dipotassium hydrogen phosphate is 0.01 to 0.1 mol/L.
Preferably, in the step S3, the mass concentration of cysteine in the aqueous solution of cysteine is 25 to 30%.
The third purpose of the technical scheme of the invention is to provide an application of the chromatographic stationary phase modified by the trapezoidal polyether and terminated by the cysteine, wherein the chromatographic stationary phase modified by the trapezoidal polyether and terminated by the cysteine is used as a stationary phase of hydrophilic chromatography or a stationary phase of reversed-phase chromatography.
The invention has the advantages and beneficial effects that:
1. the invention discloses a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, wherein the molecular structure of the modified trapezoidal polyether comprises 11 rings and 23 chiral centers, has larger molecular volume and complex stereochemistry structure, can provide interaction among various molecules, has excellent separation selectivity and larger sample loading capacity, and is suitable for various chromatographic separation modes such as hydrophilic action (embodiment 2), reversed phase (embodiments 3 and 4) and the like.
2. The invention discloses a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, wherein the modified trapezoidal polyether is specially terminated by micromolecular amino acid (cysteine), so that the influence of silicon hydroxyl is effectively shielded, an end branched chain of a trapezoidal polyether molecule has an aldehyde group, a C ═ C double bond and an openable lactone structure, and a plurality of active functional groups capable of reacting with other compounds are arranged on a ring, so that the chromatographic stationary phase modified by the trapezoidal polyether and terminated by cysteine can be further modified to prepare different novel stationary phases.
3. The invention discloses a preparation method of a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, which is characterized in that the trapezoidal polyether (Brevetoxin B) is bonded to the surface of a modified silicon sphere through Schiff base reaction, and the chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine is prepared by carrying out tail sealing treatment on cysteine.
Drawings
FIG. 1 is a chromatogram obtained by separating uracil, thiourea, melamine, ammeline and deoxyuridine in a hydrophilic interaction chromatography mode in a liquid chromatography column made of a trapezoidal polyether-modified, cysteine-terminated chromatographic stationary phase prepared by the method of the present invention in example 2;
FIG. 2 is a chromatogram obtained by separating an ecdysone extract from a liquid chromatography column prepared from a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine according to the method of the invention in example 3;
FIG. 3 is a chromatogram obtained by separating a carnosol extract from a liquid chromatographic column prepared from a stationary chromatographic phase modified with trapezoidal polyether and terminated with cysteine according to the method of the present invention in example 4.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The method for preparing the chromatographic stationary phase modified by the trapezoidal polyether and terminated by the cysteine has the reaction process shown in the formula III and comprises the following steps:
s1: dispersing aminopropyl bonded silica gel microspheres (structural formula 1) in 50mL of aqueous solution, adding 10-100 mL of aqueous solution of trapezoidal polyether (Brevitoxin B), heating and refluxing at 80 ℃ for 12h, and washing with methanol to obtain trapezoidal polyether modified silica gel microspheres (structural formula 2);
s2: dispersing the trapezoidal polyether modified silica gel microspheres (structural formula 2) prepared in the step S1 in a container filled with 80mL of dipotassium hydrogen phosphate aqueous solution, adding 1.5g of sodium borohydride, stirring at room temperature for 1.5h, filtering, washing with water to be neutral, and drying to obtain the reductive trapezoidal polyether modified silica gel microspheres (structural formula 3);
s3: and (4) dispersing the reductive trapezoidal polyether modified silica gel microspheres prepared in the step (S2) in a cysteine aqueous solution, heating and refluxing for 10h at 80 ℃, washing with methanol, and drying to obtain a chromatographic stationary phase modified by trapezoidal polyether and terminated by cysteine, wherein the mass feed ratio of cysteine to the reductive trapezoidal polyether modified silica gel microspheres is 1: 1.5.
In the preferred technical scheme, in the step S1, the mass concentration of the trapezoidal polyether in the aqueous solution of the trapezoidal polyether (Brevetoxin B) is 18%, and the mass feeding ratio of the aminopropyl bonded silica gel microspheres to the trapezoidal polyether is 1: 3.
In step S2, the molar concentration of dipotassium hydrogen phosphate in the aqueous solution of dipotassium hydrogen phosphate is preferably 0.05 mol/L.
In step S3, the mass concentration of cysteine in the aqueous solution of cysteine is preferably 25%.
Example 2
2.2g of the trapezoidal polyether-modified cysteine-terminated chromatographic stationary phase prepared in example 1 was taken at 150kg/cm3Loading into stainless steel chromatographic column with inner diameter of 4.6mm and length of 150mm by slurry method under pressure to obtain cysteine-terminated trapezoidal polyether-modified liquid chromatographic column. Under a hydrophilic interaction chromatography mode, a mixed solution of 5mmol/L ammonium acetate solution (solvent A) and pure acetonitrile (solvent B) is used as a mobile phase, linear gradient elution is adopted (0-30min, the proportion of the solvent A is 12-40%), the flow rate is 0.8mL/min, the column temperature is 25 ℃, the detection wavelength is 240nm, the sample injection amount is 8 mu L, and uracil, thiourea, melamine, ammeline and deoxyuridine are separated to obtain a chromatogram shown in figure 1.
The chromatographic data in figure 1 shows: the baselines of the 5 compounds are completely separated, and the peak sequences are 1-uracil, 2-deoxyuridine, 3-thiourea, 4-melamine and 5-cyanuric acid diamide, so that the chromatographic stationary phase modified by the trapezoidal polyether and terminated by cysteine, which is prepared by the method disclosed by the invention, can be applied to a hydrophilic interaction chromatographic mode and has special selectivity and a good separation effect.
Example 3
2.2g of the trapezoidal polyether-modified cysteine-terminated chromatographic stationary phase prepared in example 1 was taken at 150kg/cm3Loading into stainless steel chromatographic column with inner diameter of 4.6mm and length of 250mm under pressure by slurry method to obtain cysteine-terminated trapezoidal polyether-modified liquid chromatographic column. The liquid chromatographic column modified by trapezoidal polyether with cysteine sealed end is applied to chromatographic separation of traditional Chinese medicine ecdysone extract, and a chromatogram shown in figure 2 is obtained.
Dissolving ecdysone extract sample of Chinese medicinal materials with methanol, performing isocratic elution (the proportion of solvent B is 40%) in a mobile phase system of water (solvent A) and methanol (solvent B), wherein the flow rate is 0.8mL/min, the column temperature is 35 ℃, the detection wavelength is 254nm, the sample injection amount is 10 μ L, and the chromatogram of figure 2 shows that 9 components are separated (S1, S2, P1, S3, S4, P2, S5, P3 and P4).
Example 4
2.2g of the trapezoidal polyether-modified cysteine-terminated chromatographic stationary phase prepared in example 1 was taken at 150kg/cm3Loading into stainless steel chromatographic column with inner diameter of 4.6mm and length of 250mm under pressure by slurry method to obtain cysteine-terminated trapezoidal polyether-modified liquid chromatographic column. The liquid chromatographic column modified by trapezoidal polyether with cysteine sealed end is applied to chromatographic separation of the traditional Chinese medicine carnosic acid extract, and a chromatogram shown in figure 3 is obtained.
Dissolving a traditional Chinese medicine carnosol extract sample with methanol, performing gradient elution (0-8min, the proportion of solvent B is 50%; 8-60min, the proportion of solvent B is 50-70%) under a mobile phase system of water (solvent A) and methanol (solvent B), wherein the flow rate is 0.8mL/min, the column temperature is 35 ℃, the detection wavelength is 230nm, the sample injection amount is 20 mu L, and the chromatogram in FIG. 3 shows that 12 components (P1, S1, P2, S2, S3, S4, S5, S6, S7, S8, S9 and S11) are separated.
The results of the chromatographic data in examples 3 and 4 show that: the chromatographic stationary phase modified by the trapezoidal polyether and terminated by the cysteine prepared by the method can be applied to a reversed phase mode, has larger volume and complicated stereochemistry, and has good separation effect on traditional Chinese medicine extracts with more complicated components.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A ladder-shaped polyether-modified cysteine-terminated chromatographic stationary phase is characterized in that the ladder-shaped polyether-modified cysteine-terminated chromatographic stationary phase has a structure shown in a formula I, and the ladder-shaped polyether (Brevetoxin B) has a structure shown in a formula II:
2. a method for preparing the ladder-shaped polyether-modified cysteine-terminated chromatographic stationary phase according to claim 1, wherein the reaction scheme is shown as the following formula III, comprising the following steps:
s1: dispersing aminopropyl bonded silica gel microspheres (structural formula 1) in 30-50 mL of aqueous solution, adding 10-100 mL of aqueous solution of trapezoidal polyether (Brevitoxin B), heating and refluxing for 0.5-2 days at 70-80 ℃, and washing with methanol to obtain trapezoidal polyether modified silica gel microspheres (structural formula 2);
s2: dispersing the trapezoidal polyether modified silica gel microspheres prepared in the step S1 in a container filled with 10-100 mL of dipotassium hydrogen phosphate aqueous solution, adding 1-3 g of sodium borohydride, stirring at room temperature for 1-2 h, filtering, washing with water to be neutral, and drying to obtain reductive trapezoidal polyether modified silica gel microspheres (structural formula 3);
s3: and (4) dispersing the reductive trapezoidal polyether modified silica gel microspheres prepared in the step (S2) in a Cysteine (Cysteine) aqueous solution, carrying out heating reflux reaction for 10-12 h at 70-80 ℃, washing with methanol, and drying to obtain a chromatographic stationary phase (structural formula 4) modified by trapezoidal polyether and terminated by Cysteine, wherein the mass feed ratio of Cysteine to the reductive trapezoidal polyether modified silica gel microspheres is 1: 0.5-5.
3. The method for preparing the stationary phase for chromatography of trapezoid polyether modification and cysteine capping as claimed in claim 2, wherein in step S1, the mass concentration of trapezoid polyether in the aqueous solution of trapezoid polyether (Brevetoxin B) is 15-20%, and the mass ratio of aminopropyl bonded silica gel microspheres (formula 1) to trapezoid polyether is 1: 0.5-10.
4. The method for preparing the stationary phase for trapezoidal polyether modification and cysteine capping of claim 2, wherein in the step S2, the molar concentration of the dipotassium hydrogen phosphate in the aqueous solution of the dipotassium hydrogen phosphate is 0.01-0.1 mol/L.
5. The method for preparing the trapezoidal polyether modified and cysteine-terminated chromatographic stationary phase according to claim 2, wherein in the step S3, the mass concentration of cysteine in the cysteine aqueous solution is 25-30%.
6. Use of a trapezoidal polyether modified, cysteine terminated chromatographic stationary phase according to claim 1 as a stationary phase for hydrophilic chromatography or a stationary phase for reverse phase chromatography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110726660.8A CN113332967B (en) | 2021-06-29 | 2021-06-29 | Trapezoidal polyether modified and cysteine terminated chromatographic stationary phase, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110726660.8A CN113332967B (en) | 2021-06-29 | 2021-06-29 | Trapezoidal polyether modified and cysteine terminated chromatographic stationary phase, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113332967A true CN113332967A (en) | 2021-09-03 |
| CN113332967B CN113332967B (en) | 2023-04-07 |
Family
ID=77481365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110726660.8A Active CN113332967B (en) | 2021-06-29 | 2021-06-29 | Trapezoidal polyether modified and cysteine terminated chromatographic stationary phase, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113332967B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090233791A1 (en) * | 2008-03-14 | 2009-09-17 | Gorkovenko Alexander A | Carbohydrate Polyethers for Chromatographic Media |
| US20120077778A1 (en) * | 2010-09-29 | 2012-03-29 | Andrea Bourdelais | Ladder-Frame Polyether Conjugates |
| EP2545989A1 (en) * | 2011-07-13 | 2013-01-16 | InstrAction GmbH | Composite material for chromatographic applications |
| CN103041792A (en) * | 2013-01-23 | 2013-04-17 | 常州南京大学高新技术研究院 | Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof |
| US20160108169A1 (en) * | 2014-09-30 | 2016-04-21 | Board Of Trustees Of The Leland Stanford Junior University | Efficient synthesis of rigid ladder polymers |
| CN106750251A (en) * | 2016-11-11 | 2017-05-31 | 中国科学院化学研究所 | A kind of new material and its application containing polyether amide block copolymer with inierpeneirating network structure |
| CN107349636A (en) * | 2017-07-12 | 2017-11-17 | 北京大学 | Capillary and its preparation and application of the biomaterial as interaction phase |
| CN108043375A (en) * | 2017-11-07 | 2018-05-18 | 南京赢点色谱分离技术有限公司 | A kind of preparation method of multi-mode combination vancomycin chromatographic stationary phases |
| US20190060871A1 (en) * | 2016-03-23 | 2019-02-28 | Daicel Corporation | Chromatography stationary phase |
| CN111308077A (en) * | 2020-03-02 | 2020-06-19 | 品测(上海)检测科技有限公司 | Preparation method and application of nerve shellfish toxin immunoaffinity column |
| DE102019120455A1 (en) * | 2019-07-29 | 2021-02-04 | Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) | Method for the simultaneous determination of different analytes in an environmental sample, based on core / shell microparticles |
-
2021
- 2021-06-29 CN CN202110726660.8A patent/CN113332967B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090233791A1 (en) * | 2008-03-14 | 2009-09-17 | Gorkovenko Alexander A | Carbohydrate Polyethers for Chromatographic Media |
| US20120077778A1 (en) * | 2010-09-29 | 2012-03-29 | Andrea Bourdelais | Ladder-Frame Polyether Conjugates |
| EP2545989A1 (en) * | 2011-07-13 | 2013-01-16 | InstrAction GmbH | Composite material for chromatographic applications |
| CN103041792A (en) * | 2013-01-23 | 2013-04-17 | 常州南京大学高新技术研究院 | Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof |
| US20160108169A1 (en) * | 2014-09-30 | 2016-04-21 | Board Of Trustees Of The Leland Stanford Junior University | Efficient synthesis of rigid ladder polymers |
| US20190060871A1 (en) * | 2016-03-23 | 2019-02-28 | Daicel Corporation | Chromatography stationary phase |
| CN106750251A (en) * | 2016-11-11 | 2017-05-31 | 中国科学院化学研究所 | A kind of new material and its application containing polyether amide block copolymer with inierpeneirating network structure |
| CN107349636A (en) * | 2017-07-12 | 2017-11-17 | 北京大学 | Capillary and its preparation and application of the biomaterial as interaction phase |
| CN108043375A (en) * | 2017-11-07 | 2018-05-18 | 南京赢点色谱分离技术有限公司 | A kind of preparation method of multi-mode combination vancomycin chromatographic stationary phases |
| DE102019120455A1 (en) * | 2019-07-29 | 2021-02-04 | Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) | Method for the simultaneous determination of different analytes in an environmental sample, based on core / shell microparticles |
| CN111308077A (en) * | 2020-03-02 | 2020-06-19 | 品测(上海)检测科技有限公司 | Preparation method and application of nerve shellfish toxin immunoaffinity column |
Non-Patent Citations (2)
| Title |
|---|
| ZHIHONG WANG ET AL.: "Analysis of Interactions of Brevetoxin-B and Human Serum Albumin by Liquid Chromatography/Mass Spectrometry" * |
| 徐文 等: "高效液相色谱手性冠醚固定相的制备研究" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113332967B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Gas chromatographic separation of enantiomers on novel chiral stationary phases | |
| Zhang et al. | Highly selective separation of enantiomers using a chiral porous organic cage | |
| CN101274270B (en) | Method for preparing bonding type cyclodextrin stationary phase with click chemistry reaction | |
| CN110560170B (en) | Pd @ MOF material, preparation method thereof and application thereof in biphenyl preparation | |
| CN101745371A (en) | Preparation method of cyclodextrin bonded stationary phase | |
| CN111592442B (en) | Preparation method of benzene-d 6 | |
| CN111013194B (en) | Chiral POC separation column capable of resolving various racemic compounds of different types | |
| CN113332967B (en) | Trapezoidal polyether modified and cysteine terminated chromatographic stationary phase, preparation method and application | |
| Liu et al. | A chiral metal-organic cage [Fe4L6](ClO4) 8 used for capillary gas chromatographic separations | |
| CN111889087B (en) | Preparation and application of pyridine ionic liquid functionalized beta-cyclodextrin silica gel chromatographic stationary phase | |
| CN111440041B (en) | Synthesis method of toluene-d 8 | |
| CN107537576B (en) | Immobilized catalyst of silane coupling molecular sieve and double-salt ionic liquid | |
| CN110918076B (en) | Preparation method and application of naphthaloyl bridged bis-beta-cyclodextrin bonded chiral stationary phase | |
| CN103193898A (en) | Synthesis and application of L-phenylalanine derived Beta-cyclodextrin bonded silica gel for separating alanine enantiomer | |
| CN113350970A (en) | Porous organic small molecule liquid absorbent, preparation method and application | |
| CN109096412B (en) | Amino chromatography medium and preparation method thereof | |
| CN113388128B (en) | Imidazole dimethylamide bridged bis-beta-cyclodextrin stationary phase and preparation method and application thereof | |
| CN101152624B (en) | Alcoholic hydroxyl group hydrophily color spectrum stationary phase and method for preparing the same | |
| CN104628892B (en) | Preparation method and use of 6-benzyl phenylethylamine derivative beta-cyclodextrin bonded SBA-15 | |
| CN107674112B (en) | Affinity chromatography medium using heparin as ligand | |
| CN102489276A (en) | Benzyl nitrogen bridged calix[2]arene[2]triazine bonded silica stationary phase, its preparation method and its purpose | |
| CN102101045B (en) | Method for preparing glycosyl fixed phase | |
| CN102101044B (en) | Method for preparing oligomeric ethylene glycol stationary phase | |
| CN113797905B (en) | Pyridine dicarboxamide bridged bis-beta-cyclodextrin stationary phase and preparation method and application thereof | |
| CN114797809B (en) | Porous liquid gas chromatography chiral column for separating racemic compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |