CN112604675B - Preparation method and application of azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase - Google Patents
Preparation method and application of azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase Download PDFInfo
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Abstract
The invention relates to the technical field of chiral stationary phases, in particular to a preparation method and application of an azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase. According to the invention, azobenzene dicarboxamide-based bridged beta-cyclodextrin is used as a second-generation supramolecular compound, azophenyl provides a pi-pi effect, amide is a hydrogen bond donor and a hydrogen bond acceptor, azo groups have a flexible structure and are beneficial to matching with a synergistic inclusion effect between two cyclodextrin cavities, the stationary phase surface prepared by bridged cyclodextrin contains abundant action sites, the spatial structure difference of levorotatory and dextrorotatory enantiomers can be identified in an omnibearing manner, more chiral substances can be resolved in a short time, the chiral separation efficiency is greatly improved, the method is applicable to normal phase, reverse phase and polar organic modes, the resolution range is widened, and the method has a good practical value.
Description
Technical Field
The invention relates to the technical field of chiral stationary phases, in particular to a preparation method and application of an azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase.
Background
Chirality is a common phenomenon in nature, and chiral compounds are widely applied in the fields of chemistry, medicine, food, pesticides and the like. Based on the authoritative study, it was shown that 57% of the pharmaceutically active ingredients were chiral in 1800 pesticides. The chiral problem caused by enantiomers has attracted a great deal of international social attention in the early 20 th century, and the teaching of the "thalidomide event" blood has brought people to the public vigilance, recognizing that chiral substances, although enantiomers have almost the same physical and chemical properties, may exhibit completely different biological activities, toxicity, toxicology, metabolic pathways and medicinal values when they act on natural life substances. In 1992 the FDA began to require chiral drugs to be marketed as single enantiomers, which not only doubled drug production, reduced clinical dose, but also more precise efficacy with less side effects. However, chiral resolution often suffers from difficulties due to the close similarity of the structures of the chiral species. The key point of chiral resolution is the material of the chiral stationary phase, and the preparation and application of the multimode chiral stationary phase are always the hot research field in separation and analysis. Therefore, establishing the effective and practical chiral stationary phase and the resolution method have important significance for food safety, medicine safety and environmental safety.
At present, the most effective and convenient methods for resolving enantiomers are membrane separation technology, chromatographic technology and the like, wherein High Performance Liquid Chromatography (HPLC) is one of the most effective chiral separation methods, the separation conditions of HPLC are mild, the conversion of sample enantiomers cannot be caused, the compatibility of the enantiomers with medicines is good, and the rapid development is achieved. The separation principle of high performance liquid chromatography is mainly based on the difference of the chiral substances with the chiral stationary phase and the mobile phase, whether the chiral substances can be separated or not and the relationship between the separation degree and the chromatographic column are the most compact. Commonly used chiral separation materials mainly include: brush type, protein, macrocyclic antibiotic, cellulose, cyclodextrin and metal organic framework immobilization are equal. The cyclodextrin stationary phase has low cost and no toxicity, is suitable for various chromatographic separation modes, is widely applied to various fields of chiral drugs, pesticide analysis and the like, and is partially commercialized in chiral separation.
The cyclodextrin is an oligomer consisting of a plurality of D-glucose, commonly comprises alpha-, beta-, gamma-cyclodextrin (n is 6,7 and 8), the cyclodextrin is similar to a bucket in shape, an inclusion hollow structure is arranged in the middle of the cyclodextrin, a carbon-oxygen skeleton and a plurality of polar hydroxyl groups are regularly arranged at two ports to form an inner hydrophobic cavity and an outer port hydrophilic structure, a plurality of chiral sites are contained in a molecule, and the cyclodextrin has strong space recognition capability, so that good conditions are created for chiral separation, and the cyclodextrin serving as a supramolecular object is widely applied to the aspects of artificial enzyme simulation, molecular recognition, drug carrier, chromatographic separation and the like. The former performed a series of partial and full derivatizations of the peripheral ports of cyclodextrins, such as: methylation, hydroxypropylation, benzoylation, benzene or naphthalene carbamation and the like, and introduces multiple actions such as hydrogen bond action, electrostatic action, dipole-dipole action, pi-pi action and the like into a cyclodextrin port, thereby being beneficial to the occurrence of inclusion action and greatly enhancing the chiral separation capability. However, derivatization of the port may somewhat crowd the port groups and may not facilitate the full encapsulation of the cavity. Therefore, the bridged cyclodextrin designed and synthesized by the method can make up the defects to a certain extent, two or more cyclodextrin cavities form a whole through the bridge group, the synergistic inclusion effect is achieved, the chiral substances with large volume can be identified through the 'false cavity' of the synergistic inclusion, and the chiral identification capability is further enhanced through the synergistic effect of the bridge group, so that the advantages of the natural cyclodextrin are fully exerted.
The bridged cyclodextrin is formed by connecting two or more than two monocyclodextrins through a spacer arm, and is a new generation of supramolecular compound. Two adjacent cyclodextrin cavities may cooperate to participate in an inclusion coordination of guest molecules of suitable shape and size, thereby extending the bonding ability of the molecules and giving the highest binding constant of supramolecular complexes (c>1011L/mol) is favorable for increasing the difference of the binding constants of levorotatory and dextrorotatory compounds and the bridged cyclodextrin, thereby showing higher chiral selectivity, overcoming the defect that a single cyclodextrin has a small cavity (about 0.65nm), and separating chiral compounds with larger molecular volume.
The choice of the bridge group is also important, the azobenzene diformyl bridge group contains a large pi-conjugated system, a hydrogen bond providing body and an acceptor, particularly the forward-reverse conversion barrier of the azo group is low, and the flexible bridge group can be better matched with the synergistic inclusion effect of two adjacent cyclodextrin cavities. The method comprises the steps of synthesizing an azobenzene dicarboxamide bridged beta-cyclodextrin chiral ligand by using mono-6-amino-beta-cyclodextrin as an intermediate and azobenzene-4, 4' -diformyl group as a bridging group, and preparing the novel azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase by using 3-isocyanatopropyl triethoxysilane as a coupling agent and ordered mesoporous SBA-15 silica gel as a matrix. The flexible azobenzene-4, 4' -diformyl is used as a bridging group to form a pincer-type structure with two cyclodextrin molecules, which is beneficial to cooperative inclusion and identification of chiral compounds. In addition, the ordered mesoporous SBA-15 silica gel is used as a substrate, the fixed phase pore channel is regular, the eddy diffusion is small, the mass transfer speed is high, and the rapid analysis is facilitated.
The azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase synthesized by the method has obvious advantages in chiral substance separation, and is used for chiral compounds which are difficult to split by the traditional beta-cyclodextrin stationary phase: the 3' -hydroxyflavanone (a), the dansyl leucine (b), the carvedilol (c) and the uniconazole (d) can be completely resolved on the azobenzene dicarboxamide-bridged beta-cyclodextrin chiral stationary phase within a short time.
Disclosure of Invention
The invention aims to provide a preparation method of an azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase and application thereof in separation of chiral compounds.
In order to achieve the purpose, the invention provides an azobenzene dicarboxamide bridged beta-cyclodextrin bonded chiral stationary phase, and a preparation method of the chiral stationary phase comprises the following steps:
(1) mixing azobenzene dicarboxylic acid, mono-6-amino-beta-cyclodextrin, N, N' -dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and N, N-dimethylformamide, magnetically stirring at normal temperature for reaction for 48 hours to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, adding acetone into the reaction solution, precipitating, filtering, dissolving the solid with water, separating and purifying by a carboxymethyl sephadex C-25 column, adding acetone into the eluate to precipitate a product, and drying to obtain an azobenzene dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous N, N-dimethylformamide, slowly adding 0.2-0.5mL of gamma-isocyanatopropyl triethoxysilane, magnetically stirring at 80 ℃ for reaction for 2h to obtain a triethoxysilane reaction liquid containing azobenzene dicarboxamide bridged beta-cyclodextrin;
(3) adding azobenzene dicarboxamide bridged beta-cyclodextrin under the protection of nitrogen: adding dry SBA-15 with the ratio of the mesoporous molecular sieve SBA-15 to the reaction liquid in the step (2) at 1:3.5, heating to 105-125 ℃ for reaction for 12 hours, filtering, repeatedly washing the solid with N, N-dimethylformamide, methanol and water, and drying in vacuum to obtain an azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase crude product;
(4) azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase crude product: adding acetone at the ratio of 1:100 for extraction, performing Soxhlet extraction for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then performing vacuum drying for 8h at 50 ℃ to obtain the azobenzene dimethylamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
Preferably, in the step (1), the molar ratio of azobenzene dicarboxylic acid: mono-6-amino- β -cyclodextrin: n, N' -dicyclohexylcarbodiimide: 1-hydroxybenzotriazole: the ratio of N, N-dimethylformamide is 1: 1.5-3.0: 15-30.
Preferably, the ratio is in the following ratio: mono-6-amino- β -cyclodextrin: n, N' -dicyclohexylcarbodiimide: 1-hydroxybenzotriazole: n, N-dimethylformamide is preferably 1.0:2.0:2.0:2.0: 20.
Preferably, the azobenzene dicarboxylic acid in the step (1) is one of azobenzene-4, 4' -dicarboxylic acid, azobenzene-3, 3' -dicarboxylic acid or azobenzene-2, 2' -dicarboxylic acid.
Preferably, the amount of the gamma-isocyanatopropyltriethoxysilane used in the step (2) is 0.4mL as the most preferable amount.
Preferably, the reaction temperature in the step (3) is 115 ℃.
Preferably, the azobenzene dicarboxamide-bridged beta-cyclodextrin chiral stationary phase is used for the enantiomer resolution of 3' -hydroxyflavanone, dansyl leucine, carvedilol and uniconazole chiral compounds.
The invention has the beneficial effects that:
(1) the invention uses 3' -hydroxy flavanone, dansyl leucine, carvedilol and uniconazole as chiral solute probes, and evaluates the chiral chromatographic performance of the stationary phase under various modes to obtain the following results: the underivatized azobenzene dicarboxamide bridged beta-cyclodextrin chiral fixed relative enantiomer can reach better separation degree in a short time, and the bridged bicyclic dextrin has the capability of synergistic recognition.
(2) The new stationary phase cyclodextrin port reserves a large amount of hydroxyl groups and has strong hydrogen bond effect, a benzene ring provides pi-pi effect, amide is a hydrogen bond donor and a hydrogen bond acceptor, azo is a flexible structure, molecules integrally present a pincer-type structure, and can be used for cooperatively inclusion of analytes in the resolution process of chiral substances, so that the stability difference of inclusion compounds formed by enantiomers and cyclodextrin is increased, and more possibility is provided for resolution of the chiral substances.
(3) The preparation method of the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase has the advantages of simple process, low cost of raw materials, good solute selectivity, suitability for various chromatographic modes, stable chromatographic performance, good reproducibility and the like.
Drawings
FIG. 1 is a schematic structural diagram of an azobenzene dicarboxamide-bridged beta-cyclodextrin chiral stationary phase;
FIG. 2 is the chemical structure of the resolved chiral compound;
FIG. 3 is a chromatogram of chiral separation of 3' -hydroxyflavanone (a), dansyl leucine (b), carvedilol (c), and uniconazole (d).
Detailed Description
The present invention will be further described with reference to examples.
Example 1
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): n, N' -dicyclohexylcarbodiimide (DCC, mmol): 1-hydroxybenzotriazole (HOBT, mmol): mixing N, N-dimethylformamide (DMF, mL) according to the proportion of 1.0:1.5:1.5:1.5:15, reacting for 48h at normal temperature to obtain a solution of azobenzene dicarboxamido bridged beta-cyclodextrin, adding acetone into the reaction solution, precipitating, filtering, dissolving the solid with water, separating and purifying through a carboxymethyl dextran gel (C-25) column, adding acetone into the eluate to precipitate a product, and drying to obtain an azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
Calculating the bonding amount of the prepared azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase through the carbon content in the element analysis result, and actually measured data are as follows:
example 2
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15(g) into the reaction liquid obtained in the step (2) directly according to the proportion of 1:3.5, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing the fixed solid with DMF, methanol and water, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamido bridged beta-cyclodextrin bonded SBA-15;
(4) azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
Calculating the bonding amount of the prepared azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase through the carbon content in the element analysis result, and actually measured data are as follows:
example 3
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.5:2.5:2.5:25, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
The carbon content in the element analysis result is calculated to obtain the bonding amount of the azobenzene-4, 4' -diformylamido-bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase, and the actual measurement data is as follows:
example 4
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:3.0:3.0:3.0:30, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
The carbon content in the element analysis result is calculated to obtain the bonding amount of the azobenzene-4, 4' -diformylamido-bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase, and the actual measurement data is as follows:
example 5
(1) Azobenzene-3, 3' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-3, 3' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-3, 3' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-3, 3' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-3, 3' -dimethylamido bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
Calculating the bonding amount of the prepared azobenzene-3, 3' -dicarboxamido bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase through the carbon content in the element analysis result, and actually measured data are as follows:
example 6
(1) Azobenzene-2, 2' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-2, 2' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-2, 2' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-2, 2' -dimethylamino-bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-2, 2' -dimethylamido bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
The carbon content in the element analysis result is calculated to obtain the bonding amount of the azobenzene-2, 2' -diformylamido-bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase, and the actual measurement data is as follows:
example 7
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 105 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
Calculating the bonding amount of the prepared azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase through the carbon content in the element analysis result, and actually measured data are as follows:
example 8
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamido bridged beta-cyclodextrin, acetone is added into the reaction solution to precipitate a precipitate, the precipitate is filtered, the solid is dissolved by water, the solution is separated and purified by a carboxymethyl dextran gel (C-25) column, acetone is added into the eluent to precipitate a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.4mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 125 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
The carbon content in the element analysis result is calculated to obtain the bonding amount of the azobenzene-4, 4' -diformylamido-bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase, and the actual measurement data is as follows:
example 9
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.2mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
The patent calculates the bonding amount of the prepared azobenzene-4, 4' -dimethylamido-bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase through the carbon content in the element analysis result, and the actual measurement data is as follows:
example 10
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.3mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
Calculating the bonding amount of the prepared azobenzene-4, 4' -dicarboxamido bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase through the carbon content in the element analysis result, and actually measured data are as follows:
example 11
(1) Azobenzene-4, 4' -dicarboxylic acid (mmol): mono-6-amino- β -cyclodextrin (mmol): DCC (mmol): HOBT (mmol): DMF (mL) is mixed according to the proportion of 1.0:2.0:2.0:2.0:20, the mixture is reacted for 48 hours at normal temperature to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, acetone is added into the reaction solution to separate out a precipitate, the precipitate is filtered, the solid is dissolved by water, the separation and purification are carried out through a carboxymethyl dextran gel (C-25) column, the acetone is added into the eluent to separate out a product, and the product is dried to obtain the azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous DMF, slowly adding 0.5mL of gamma-isocyanatopropyl triethoxysilane into the solution, and reacting at 80 ℃ for 2h to obtain a reaction solution containing azobenzene-4, 4' -dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) under the protection of nitrogen, the azobenzene dicarboxamide group in the step (2) is bridged to beta-cyclodextrin (mmol): adding dry SBA-15 into the reaction liquid obtained in the step (2) directly, heating to 115 ℃ for reaction for 12 hours, filtering, repeatedly washing with DMF, methanol and water for fixation, and drying to obtain a crude product of the chiral stationary phase of the azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded SBA-15, wherein the ratio of SBA-15(g) to SBA-15 is 1: 3.5;
(4) azobenzene-4, 4' -dimethylamide bridged beta-cyclodextrin bonded phase (g) synthesized according to (3): acetone (mL) is used as a proportion of 1:100, acetone is used as an extracting agent, Soxhlet extraction is carried out for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then vacuum drying is carried out for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
The carbon content in the element analysis result is calculated to obtain the bonding amount of the azobenzene-4, 4' -diformylamido-bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase, and the actual measurement data is as follows:
example 12
Chiral separation experiment of high performance liquid chromatography
The azobenzene-4, 4' -dimethylamido-bridged beta-cyclodextrin chiral stationary phase, the azobenzene-3, 3' -dimethylamido-bridged beta-cyclodextrin chiral stationary phase and the azobenzene-2, 2' -dimethylamido-bridged beta-cyclodextrin chiral stationary phase prepared in the embodiments 2, 5 and 6 are respectively used as high performance liquid chromatography column packing materials to separate some chiral compounds.
Resolved chiral species: 3' -hydroxyflavanone, dansyl leucine, carvedilol, uniconazole.
The method comprises the following specific steps: the column packing was done by homogenization. Wherein the homogenizing agent is acetone; the displacing agent is methanol. Filling the homogenate into a stainless steel chromatographic column (4.6mm multiplied by 250mm), maintaining the pressure of 35.0MPa for 30 minutes, then gradually releasing the pressure to finish column filling, flushing for half an hour by taking 100% acetonitrile, 100% methanol, water and methanol with different volume ratios as mobile phases at low flow rate respectively, starting sample injection after the base line is stable, dissolving all standard products by using methanol, preparing into 100-200 mug/mL stock solution, and storing in a dark place at 4 ℃. Before injection, the mixture was filtered through a 0.22 μm filter and degassed by ultrasound. The reversed phase chromatography mode takes methanol/water or acetonitrile/water as a mobile phase, and the flow rate is 0.8 mL/min; the column temperature is 20 ℃; the sample injection amount is 5 mu L; the detection wavelength range is 200-380 nm. The polar organic mode uses methanol/acetonitrile/triethylamine/acetic acid in the appropriate ratio as the mobile phase. The remaining chromatographic parameters were the same as for the reverse phase chromatography mode.
The results of the experiment and their corresponding optimized chromatographic conditions are shown in the figure, and it can be seen that the above solutes are completely separated. Obviously, the azobenzene dicarboxamide bridged beta-cyclodextrin chiral stationary phase can be used for separating partial chiral drugs such as flavanones, amino acids, beta-receptor blockers and the like and enantiomers of triazole chiral pesticides by high performance liquid chromatography.
Claims (7)
1. A preparation method of azobenzene dicarboxamide bridged beta-cyclodextrin bonded chiral stationary phase is characterized by comprising the following steps: the preparation method of the chiral stationary phase comprises the following steps:
(1) mixing azobenzene dicarboxylic acid, mono-6-amino-beta-cyclodextrin, N, N' -dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and N, N-dimethylformamide, magnetically stirring at normal temperature for reaction for 48 hours to obtain a solution of azobenzene dicarboxamide bridged beta-cyclodextrin, adding acetone into the reaction solution, precipitating, filtering, dissolving the solid with water, separating and purifying by a carboxymethyl sephadex C-25 column, adding acetone into the eluate to precipitate a product, and drying to obtain an azobenzene dicarboxamide bridged beta-cyclodextrin chiral ligand;
(2) under the protection of nitrogen, dissolving azobenzene dicarboxamide bridged beta-cyclodextrin in anhydrous N, N-dimethylformamide, slowly adding 0.2-0.5mL of gamma-isocyanatopropyl triethoxysilane, and magnetically stirring at 80 ℃ for reaction for 2h to obtain a reaction solution containing the azobenzene dicarboxamide bridged beta-cyclodextrin triethoxysilane;
(3) adding azobenzene dicarboxamide bridged beta-cyclodextrin under the protection of nitrogen: the ratio of the mesoporous molecular sieve SBA-15 is 1mmol: adding 3.5g of dry SBA-15 into the reaction solution obtained in the step (2), heating to 105-125 ℃, reacting for 12 hours, filtering, repeatedly washing the solid with N, N-dimethylformamide, methanol and water, and drying in vacuum to obtain a crude product of the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase;
(4) azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase crude product: acetone was 1 g: adding acetone for extraction according to the proportion of 100mL, performing Soxhlet extraction for 12h to remove unreacted reagents in a cavity and pores of the crude product, and then performing vacuum drying for 8h at 50 ℃ to obtain the azobenzene dicarboxamide bridged beta-cyclodextrin bonded SBA-15 chiral stationary phase product.
2. The method of claim 1, wherein: in the step (1), the ratio of azobenzene dicarboxylic acid: mono-6-amino- β -cyclodextrin: n, N' -dicyclohexylcarbodiimide: 1-hydroxybenzotriazole: the proportion of N, N-dimethylformamide is 1.5-3.0 mmol: 15-30 mL.
3. The method of claim 2, wherein: azobenzene dicarboxylic acid: mono-6-amino- β -cyclodextrin: n, N' -dicyclohexylcarbodiimide: 1-hydroxybenzotriazole: n, N-dimethylformamide was 1.0mmol, 2.0mmol, 20 mL.
4. The method of claim 1, wherein: in the step (1), the azobenzene dicarboxylic acid is one of azobenzene-4, 4' -dicarboxylic acid, azobenzene-3, 3' -dicarboxylic acid or azobenzene-2, 2' -dicarboxylic acid.
5. The method of claim 1, wherein: the dosage of the gamma-isocyanatopropyl triethoxysilane in the step (2) is 0.4 mL.
6. The method of claim 1, wherein: the reaction temperature in the step (3) is 115 ℃.
7. The azobenzene dicarboxamide-bridged beta-cyclodextrin chiral stationary phase prepared by the method of any one of claims 1-6 is used for the enantiomeric resolution of 3' -hydroxyflavanone, dansyl leucine, carvedilol and uniconazole chiral compounds.
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