CN110455966B - SiO (silicon dioxide)2Polymeric microspheres of urushiol ester, preparation method and application thereof in separation of gastrodin and derivatives thereof - Google Patents
SiO (silicon dioxide)2Polymeric microspheres of urushiol ester, preparation method and application thereof in separation of gastrodin and derivatives thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high performance liquid chromatography, and particularly relates to SiO2Polymeric microspheres of urushiol ester, preparation method and application in separation of gastrodin and its derivatives. The technical scheme comprises the following steps: using urushiol methacrylate as a monomer, fully mixing the urushiol methacrylate with a cross-linking agent and a free radical initiator, and coating the mixture on the surface of silica gel; free radical polymerization to obtain SiO2Polymeric microspheres of urushiol ester. Mixing SiO2The gastrodin and the derivatives thereof are separated by HPLC by filling a chromatographic column with urushiol ester high-molecular microspheres. The separation degree of gastrodin and phenyl-beta-D-glucopyranoside reaches more than 9.55, the separation degree of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside reaches more than 17.01, and the separation degree of phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside reaches more than 8.25.
Description
Technical Field
The invention belongs to the technical field of high performance liquid chromatography, and particularly relates to SiO2Polymeric microspheres of urushiol ester, preparation method and application in separation of gastrodin and its derivatives.
Background
The chemical structural formulas of the gastrodin and the derivatives of phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside are respectively as follows:
gastrodine:
phenyl- β -D-glucopyranoside:
4-nitrophenyl-beta-D-glucopyranoside:
gastrodine is the main active component of traditional Chinese medicinal material rhizoma Gastrodiae, and has effects of tranquilizing, hypnotizing, relieving convulsion, relieving pain, resisting epilepsia, and protecting nerve cell. Is mainly used for the auxiliary treatment of headache, dizziness, limb numbness, infantile convulsion, epilepsy and convulsion and hypertension clinically, and has obvious effect. phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside are important drug synthesis intermediates, have very similar structures with gastrodin, and have smaller polarity difference, so that the separation of gastrodin derivatives from gastrodin is of great significance.
At present, the following prior art is reported about the high performance liquid chromatography separation method of gastrodin and derivatives thereof:
1. application No.: 201710710292.1, title of the invention: a weak polarity rosinyl polymer microsphere, a preparation method and an application thereof are disclosed in the Chinese invention patent, wherein the weak polarity rosinyl polymer microsphere is used for separating gastrodin and phenyl-beta-D-glucopyranoside, and the mobile phase is as follows: methanol, detection wavelength: 265nm, temperature 28 ℃, flow rate of 0.35mL/min, and resolution of 1.6.
2. Wangwangjing, preparation of a rosin-based high performance liquid chromatography stationary phase and separation research on gastrodin [ D ], 2017. In the prior art, a rosin polymer microsphere is used as a chromatographic column stationary phase for separating gastrodin and phenyl-beta-D-glucopyranoside, and a mobile phase is as follows: methanol, detection wavelength: 220nm, temperature 25 ℃, flow rate of 0.3mL/min, and resolution of 1.54.
3. Liuyuhong, easily entering the sea, Chenyan, Huangqifang, Liuyunhua. RP-HPLC method for simultaneously determining free gastrodine, Baliximan and total gastrodine [ J ] in gastrodia elata]. Chinese patent medicine 2012, 34(01): 182-. Wherein the chromatographic column is LUNA C18(4.6mm multiplied by 150 mm), the mobile phase is methanol-1% glacial acetic acid, the gradient elution is carried out, the flow rate is 0.8mL/min, the column temperature is 35 ℃, and the detection wavelength is 270 nm.
4. Shen Shi Jing, jin Ji shan, xu Feng Qing, etc. High performance liquid chromatography for determining gastrodin and gastrodin aglycone content [ J ] in rhizoma Gastrodiae by different processing methods]. 70-73 of the university of traditional Chinese medicine 2014, 33 (6). Wherein the chromatographic column is Spursil C18EP (250 mm. times.4.6 mm), mobile phase methanol-0.1% phosphoric acid water (5: 95), flow rate 1mL/min, column temperature 40 ℃, detection wavelength 220 nm.
However, the above-mentioned prior arts all have a problem that the effect of separating gastrodine and its derivatives is not satisfactory, and therefore, it is necessary to search for a more efficient method for separating gastrodine and its derivatives.
At present, no report about the separation of gastrodin and 4-nitrophenyl phenyl-beta-D-glucopyranoside exists.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides SiO2Polymeric microspheres of urushiol ester, preparation method and application in separation of gastrodin and its derivatives.
The invention is realized by the following steps of2The preparation method of the urushiol ester polymer microsphere comprises the following steps:
s1: uniformly mixing monomer methacrylic acid lacquer phenolic ester with a cross-linking agent and a free radical initiator;
s2: coating the mixture obtained in the step S1 on the surface of the silica gel;
s3: placing the silica gel compound obtained in the step S2 into an aqueous solution of a surfactant to perform a free radical polymerization reaction;
s4: soxhlet extraction of the product obtained in step S3 with anhydrous ethanol, and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
Further, in step S1, the crosslinking agent is ethylene glycol dimethacrylate.
Further, in step S1, the radical initiator is an azo-based radical initiator or an organic peroxide-based radical initiator.
Further, the azo radical initiator is azobisisobutyronitrile.
Further, the organic peroxide radical initiator is benzoyl peroxide.
Furthermore, the mass ratio of the monomers, the cross-linking agent and the free radical initiator is 0.1-1.5:0.5-15: 0.004-0.1.
SiO using the same2Preparation method of urushiol ester polymer microspheresSiO prepared by the method2Polymeric microspheres of urushiol ester.
SiO as above2Application of urushiol ester polymer microsphere in separation of gastrodin and its derivatives is provided.
Further, the application method is to mix SiO2The urushiol ester high molecular microspheres are used as stationary phase filler to be filled in a chromatographic column and applied to a liquid chromatograph to separate gastrodin and derivatives thereof.
Further, the derivative of gastrodin comprises phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside.
Further, SiO2The urushiol ester high molecular chromatographic column is connected into a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.3-1.0mL/min, the detection wavelength is 220nm, and the column temperature is 25 +/-5 ℃; starting the sample injection valve to make the mobile phase bring the gastrodin and the derivatives thereof into SiO2The separation of gastrodin and derivatives thereof is realized in a urushiol ester high molecular chromatographic column.
Further, the SiO2The particle size distribution of the urushiol ester polymer microsphere is 3-15 mu m, the pore size distribution is 5-10nm, and the specific surface area is 225-2/g。
Further, SiO is filled in a column by adopting a wet method and is pressed by a constant pressure pump2Filling urushiol ester polymer microspheres in a hollow chromatographic column, loading the column under 6000psi for 10min, loading the column under 4500psi for 10min, loading the column under 3000psi for 5min, loading the column under 1500psi for 5min, removing the chromatographic column after filling, loading the sieve plate and column head to obtain SiO2Polymeric chromatographic column of urushiol ester.
SiO2The mechanism of separating two substances by urushiol ester high-molecular microspheres is as follows: the fixed phase filler SiO of the chromatographic column used in the invention2The urushiol ester polymer microsphere not only keeps the characteristics of uniform particle size and good sphericity of the silicon dioxide microsphere, but also takes the advantages of regular pore structure and rich surface functional groups of the urushiol polymer microsphere into consideration, so that the SiO prepared by taking the microsphere as a stationary phase2The urushiol ester high molecular chromatographic column has more excellent separation performance on gastrodin and derivatives thereof.
Further, the reaction temperature of the free radical polymerization is 70-90 ℃, and the time is 8-10 h.
Further, the mass ratio of the monomer, the cross-linking agent and the silica gel is 1: 1-100.
Further, the surfactant is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate, and the mass fraction of the surfactant in the water phase is 0.3-5%.
In summary, the advantages and positive effects of the invention are:
1. the fixed phase filler SiO of the chromatographic column used in the invention2The microsphere shape of the urushiol ester polymer is regular, the particle size distribution is uniform, the pore structure is rich and regular, the permeability of a chromatographic column is good, and the back pressure is low. At higher flow rates and pressures, no collapse occurred. And the stability is good, the device can be repeatedly used, and after the device is used for a long time, the filler in the chromatographic column is not damaged and dissolved.
2. The fixed phase filler SiO of the chromatographic column used in the invention2The urushiol ester polymer microsphere keeps the good characteristics of uniform particle size and high sphericity of the silicon dioxide microsphere, and also has the advantages of urushiol polymer, regular pore structure and rich surface functional groups, wherein saturated alkyl groups of C15-C17 on the side chain have a sieving effect on separated substances. The theoretical plate number is up to 60000, and the gastrodin and derivatives thereof have better separation effect.
3. The method of the invention has good separation effect on gastrodin and derivatives thereof. The separation degree of gastrodin and phenyl-beta-D-glucopyranoside in patent application No. 201710710292.1 is 1.60, while the separation degree in the invention can reach more than 9.55. In addition, the invention also well realizes the separation of the 4-nitrophenyl-beta-D-glucopyranoside with the polarity more similar to that of gastrodin, and the separation degree can reach more than 17.01. The separation degree of the phenyl-beta-D-glucopyranoside and the 4-nitrophenyl-beta-D-glucopyranoside can reach more than 8.25.
4. The prior art of application No. 201710710292.1, which uses organic solvent as mobile phase in rosin-based polymer chromatographic column, and the SiO of the present invention2Urushiol fractionThe sub-chromatographic column adopts water as a mobile phase, so that the pollution is less and the environment is more protected.
5. The fixed phase filler SiO of the chromatographic column used in the invention2The urushiol ester polymer microsphere has the advantages of simple preparation process, low cost and good application prospect.
6. The raw materials used by the invention are high-quality natural plant renewable resource raw lacquer peculiar to China, which has important significance for expanding the application field of raw lacquer.
7. Application of the invention to SiO2The method for efficiently separating gastrodin and derivatives thereof by the urushiol ester high-molecular chromatographic column has the advantages of high sensitivity, simple operation, rapidness and high efficiency.
Drawings
FIG. 1 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside at a flow rate of 0.3mL/min in application example 1 of the present invention;
FIG. 2 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside at a flow rate of 0.5mL/min in application example 2 of the present invention;
FIG. 3 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside at a flow rate of 0.3mL/min in application example 3 of the present invention;
FIG. 4 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside at a flow rate of 0.5mL/min in application example 4 of the present invention;
FIG. 5 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and phenyl- β -D-glucopyranoside at a flow rate of 0.7mL/min in application example 5 of the present invention;
FIG. 6 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside at a flow rate of 0.7mL/min in application example 6 of the present invention;
FIG. 7 is a High Performance Liquid Chromatography (HPLC) chromatogram of a mixed solution of p-phenyl- β -D-glucopyranoside and 4-nitrophenyl- β -D-glucopyranoside according to application example 7 of the present invention at a flow rate of 0.3 mL/min;
FIG. 8 is a High Performance Liquid Chromatography (HPLC) chromatogram of a mixed solution of p-phenyl- β -D-glucopyranoside and 4-nitrophenyl- β -D-glucopyranoside according to application example 8 of the present invention at a flow rate of 0.7 mL/min;
FIG. 9 is a High Performance Liquid Chromatography (HPLC) spectrum of a mixed solution of gastrodin, p-phenyl- β -D-glucopyranoside and 4-nitrophenyl- β -D-glucopyranoside at a flow rate of 1.0mL/min in EXAMPLE 9 of the present invention;
FIG. 10 is a high performance liquid chromatography chromatogram of a mixed solution of gastrodin and phenyl- β -D-glucopyranoside according to comparative example 1 of the present invention;
FIG. 11 is a HPLC chromatogram of a mixed solution of gastrodin and phenyl- β -D-glucopyranoside according to comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the devices and reagents used in the examples and test examples are commercially available unless otherwise specified. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
The invention discloses a SiO2Urushiol ester polymer microspheres, a preparation method and application thereof in separation of gastrodin and derivatives thereof are shown in the following examples.
SiO2Preparation of urushiol ester polymer microspheres
Preparation of example 1
0.35g of methacrylic lacquer phenolic ester as a monomer, 0.75g of ethylene glycol dimethacrylate as a cross-linking agent and 3mg of azobisisobutyronitrile were mixed thoroughly and then coated uniformly onto the surface of 5.00g of silica gel. In the present embodiment, azobisisobutyronitrile is used as the azo radical initiator, and in other embodiments, an organic peroxide radical initiator such as benzoyl peroxide may be used. Then placing the mixture into 250mL of aqueous solution with the mass fraction of 0.1 percent and taking sodium dodecyl sulfate as a surfactant, carrying out free radical polymerization reaction for 8 hours at 90 ℃, then carrying out Soxhlet extraction on the product by absolute ethyl alcohol, and then carrying out vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microspheres is 3-10 μm, the average pore diameter is 6.36nm, and the specific surface area is 275m2/g。
Preparation of example 2
1.50g of methacrylic lacquer phenolic ester as a monomer, 3.35g of ethylene glycol dimethacrylate as a cross-linking agent and 15mg of azodiisobutyronitrile are fully mixed, uniformly coated on the surface of 50.00g of silica gel, then placed in 1000mL of aqueous solution with the mass fraction of 1% of lauryl sodium sulfate as a surfactant for free radical polymerization reaction at 75 ℃ for 8 hours, and then the product is subjected to Soxhlet extraction by absolute ethyl alcohol and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microspheres is 5-10 mu m, the average pore diameter is 6.59nm, and the specific surface area is 295m2/g。
Preparation of example 3
1.5g of methacrylic lacquer phenolic ester as a monomer, 6.5g of ethylene glycol dimethacrylate as a cross-linking agent and 100mg of benzoyl peroxide are fully mixed, uniformly coated on the surface of 90.00g of silica gel, then placed in 1000mL of aqueous solution with the mass fraction of 3 percent and the mass fraction of sodium dodecyl sulfate as a surfactant for free radical polymerization reaction for 8 hours at 85 ℃, and then the product is subjected to Soxhlet extraction by absolute ethyl alcohol and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microsphere is 10-15 μm, the average pore diameter is 7.23nm, and the specific surface area is 300.65m2/g。
Preparation of example 4
1.0g of lacquer phenol methacrylate was used asFully mixing a monomer, 5.0g of ethylene glycol dimethacrylate serving as a cross-linking agent and 50mg of benzoyl peroxide, uniformly coating the mixture on the surface of 600.0g of silica gel, then placing the mixture in 1000mL of aqueous solution with the mass fraction of 3% of sodium dodecyl sulfate serving as a surfactant to perform free radical polymerization reaction for 10 hours at 85 ℃, then performing Soxhlet extraction on the product by using absolute ethyl alcohol, and performing vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microsphere is 5-15 μm, the average pore diameter is 10.05nm, and the specific surface area is 350.15m2/g。
Preparation of example 5
0.1g of methacrylic lacquer phenolic ester as a monomer, 8.0g of ethylene glycol dimethacrylate as a cross-linking agent and 40mg of benzoyl peroxide are fully mixed, uniformly coated on the surface of 90.00g of silica gel, then placed in 1000mL of aqueous solution with the mass fraction of 3 percent and the mass fraction of sodium dodecyl sulfate as a surfactant for free radical polymerization reaction for 8 hours at 70 ℃, and then subjected to Soxhlet extraction by absolute ethyl alcohol and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microsphere is 3-10 μm, the average pore diameter is 9.56nm, and the specific surface area is 320.50m2/g。
Preparation of example 6
0.1g of methacrylic lacquer phenolic ester as a monomer, 15.0g of ethylene glycol dimethacrylate as a cross-linking agent and 15mg of benzoyl peroxide are fully mixed, uniformly coated on the surface of 80.00g of silica gel, then placed in 1000mL of aqueous solution with the mass fraction of 3 percent and the mass fraction of sodium dodecyl sulfate as a surfactant for free radical polymerization reaction for 8 hours at 85 ℃, and then the product is subjected to Soxhlet extraction by absolute ethyl alcohol and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microspheres is 3-5 μm, the average pore diameter is 10.56nm, and the specific surface area is 340.00m2/g。
Preparation of example 7
1.5g of methacrylic lacquer phenolic ester as a monomer, 0.5g of ethylene glycol dimethacrylate as a cross-linking agent and 4mg of azodiisobutyronitrile are fully mixed, uniformly coated on the surface of 100.00g of silica gel, then placed in 1000mL of aqueous solution with the mass fraction of 3 percent of lauryl sodium sulfate as a surfactant for free radical polymerization reaction for 8 hours at 90 ℃, and then subjected to Soxhlet extraction by absolute ethyl alcohol and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microspheres is 5-10 μm, the average pore diameter is 9.47nm, and the specific surface area is 305m2/g。
Preparation of example 8
1.5g of methacrylic lacquer phenolic ester as a monomer, 10.0g of ethylene glycol dimethacrylate as a cross-linking agent and 70mg of azodiisobutyronitrile are fully mixed, uniformly coated on the surface of 11.50g of silica gel, then placed in 1000mL of aqueous solution with the mass fraction of 3 percent of lauryl sodium sulfate as a surfactant for free radical polymerization reaction for 8 hours at 85 ℃, and then subjected to Soxhlet extraction by absolute ethyl alcohol and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microsphere is 5-15 μm, the average pore diameter is 5.05nm, and the specific surface area is 225.00m2/g。
Preparation of example 9
1.5g of urushiol methacrylateEster is taken as a monomer, 15.0g of ethylene glycol dimethacrylate is taken as a cross-linking agent to be fully mixed with 100mg of azodiisobutyronitrile, the mixture is uniformly coated on the surface of 90.00g of silica gel, then the mixture is placed in 1000mL of aqueous solution with the mass fraction of 3 percent of sodium dodecyl sulfate taken as a surfactant to carry out free radical polymerization reaction for 10 hours at the temperature of 90 ℃, then the product is subjected to Soxhlet extraction by absolute ethyl alcohol, and vacuum drying is carried out to obtain SiO2Polymeric microspheres of urushiol ester.
The particle size distribution of the microspheres is measured by a laser particle sizer, and the specific surface area and the pore structure of the microspheres are measured by a micro-porous and mesoporous physical adsorption instrument. Through detection and analysis, the particle size distribution of the microspheres is 3-10 μm, the average pore diameter is 6.86nm, and the specific surface area is 265m2/g。
Using SiO2Gastrodin separated by urushiol ester high molecular chromatographic column and its derivatives
Application example 1
The SiO obtained in preparation example 1 was added2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2Polymeric chromatographic column of urushiol ester. Then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodin and phenyl-beta-D-glucopyranoside in acetonitrile-0.05% phosphoric acid water (3:97, V/V) solution to obtain a solution containing 5 × 10 per 1L-4Injecting a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside in mol;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.3mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting the sample injection valve to make acetonitrileAqueous phosphoric acid solution carried the sample into SiO2The sample loading amount in the urushiol ester high molecular chromatographic column is 4 mu L, the separation of gastrodin and phenyl-beta-D-glucopyranoside is realized, the obtained result is shown in figure 1, a gastrodin peak appears when the retention time is 13.28min, a phenyl-beta-D-glucopyranoside peak appears when the retention time is 18.76min, and the separation degree is 11.47.
Application example 2
SiO obtained in preparation example 2 was pressed with a constant pressure pump2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodin and phenyl-beta-D-glucopyranoside in acetonitrile-0.05% phosphoric acid water (3:97, V/V) solution to obtain a solution containing 5 × 10 per 1L-4Injecting a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside in mol;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.5mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2In a urushiol ester high-molecular chromatographic column, the sample introduction amount is 4 mu L, the separation of gastrodin and phenyl-beta-D-glucopyranoside is realized, the obtained result is shown in figure 2, a gastrodin peak appears when the retention time is 7.97min, a phenyl-beta-D-glucopyranoside peak appears when the retention time is 11.16min, and the separation degree is 10.89.
Application example 3
SiO obtained in preparation example 3 was pressed with a constant pressure pump2Urushiol ester polymerFilling the balls in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, disassembling the chromatographic column, loading the sieve plate and column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside in 3:97, V/V acetonitrile-0.05% phosphoric acid water solution to obtain a solution containing 5 × 10 per 1L-4mixing the mol gastrodin and 4-nitrophenyl-beta-D glucopyranoside solution, and injecting a sample;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.3mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2The sample introduction amount in the urushiol ester high molecular chromatographic column is 4 mu L, the separation of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside is realized, the obtained result is shown in figure 3, a gastrodin peak appears when the retention time is 13.12min, a 4-nitrophenyl-beta-D-glucopyranoside peak appears when the retention time is 25.33min, and the separation degree is 20.71.
Application example 4
SiO obtained in preparation example 4 was pressed with a constant pressure pump2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside in 3:97, V/V acetonitrile-0.05% phosphoric acid water solution to obtain a solution containing 5 × 10 per 1L-4mixing the mol gastrodin and 4-nitrophenyl-beta-D-glucopyranoside solution, and injecting a sample;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.5mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2The sample introduction amount in the urushiol ester high molecular chromatographic column is 4 mu L, the separation of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside is realized, the obtained result is shown in figure 4, a gastrodin peak appears when the retention time is 7.97min, a 4-nitrophenyl-beta-D-glucopyranoside peak appears when the retention time is 15.30min, and the separation degree is 19.59.
Application example 5
SiO obtained in preparation example 5 was pressed with a constant pressure pump2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodin and phenyl-beta-D-glucopyranoside in acetonitrile-0.05% phosphoric acid water (3:97, V/V) solution to obtain a solution containing 5 × 10 per 1L-4Injecting a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside in mol;
(2) setting parameters: mixing SiO2Liquid chromatography of urushiol ester high molecular chromatographic columnThe flow rate of a mobile phase of the liquid chromatograph is set to be 0.7mL/min, the detection wavelength is 220nm, and the temperature of a column oven is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2The sample introduction amount in the urushiol ester high molecular chromatographic column was 4. mu.L, and the separation of gastrodin and phenyl-beta-D-glucopyranoside was achieved, and the obtained results are shown in FIG. 5, wherein a gastrodin peak appeared at a retention time of 5.72min, a phenyl-beta-D-glucopyranoside peak appeared at a retention time of 7.98min, and the degree of separation was 10.11.
Application example 6
SiO obtained in production example 6 was pressed with a constant pressure pump2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside in 3:97, V/V acetonitrile-0.05% phosphoric acid water solution to obtain a solution containing 5 × 10 per 1L-4mixing the mol gastrodin and 4-nitrophenyl-beta-D-glucopyranoside solution, and injecting a sample;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.7mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2The sample introduction amount in the urushiol ester high molecular chromatographic column is 4 mu L, the separation of gastrodin and 4-nitrophenyl-beta-D-glucopyranoside is realized, the obtained result is shown in figure 6, a gastrodin peak appears when the retention time is 5.72min, and 4-nitrophenyl-beta-gamma-aminobutyric acid ion salt appears when the retention time is 10.93minD-glucopyranoside peak, degree of separation 18.33.
Application example 7
SiO obtained in production example 7 was pressed with a constant pressure pump2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: taking appropriate amount of phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside, dissolving with acetonitrile-0.05% phosphoric acid water (3:97, V/V) solution, preparing to contain 5 × 10 per 1L-4Injecting a mixed solution of mol phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.3mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2In a urushiol ester high molecular chromatographic column, the sample introduction amount is 4 mu L, the separation of phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside is realized, and the obtained result is shown in figure 7, wherein a phenyl-beta-D-glucopyranoside peak appears when the retention time is 18.32min, a 4-nitrophenyl-beta-D-glucopyranoside peak appears when the retention time is 25.20, and the separation degree is 10.09.
Application example 8
SiO obtained in production example 8 was pressed with a constant pressure pump2Filling urushiol ester polymer microsphere in stainless steel hollow chromatographic column, loading at 6000psi for 10min, 4500psi for 10min, 3000psi for 5min, and 1500pLoading the column under si pressure for 5min, removing the chromatographic column, and loading the sieve plate and column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside in 3:97, V/V acetonitrile-0.05% phosphoric acid water solution to obtain a solution containing 5 × 10 per 1L-4mol of a mixed solution of phenyl-beta-D-glucopyranoside and phenyl-beta-D-glucopyranoside, and sample injection;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 0.7mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2In a urushiol ester high molecular chromatographic column, the sample introduction amount is 4 mu L, the separation of phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside is realized, and the obtained result is shown in figure 8, wherein a phenyl-beta-D-glucopyranoside peak appears when the retention time is 7.97min, a 4-nitrophenyl-beta-D-glucopyranoside peak appears when the retention time is 10.89min, and the separation degree is 8.92.
Application example 9
SiO obtained in production example 9 was pressed with a constant pressure pump2Filling urushiol ester polymer microspheres in a stainless steel hollow chromatographic column, loading the column for 10min under 6000psi, loading the column for 10min under 4500psi, loading the column for 5min under 3000psi, loading the column for 5min under 1500psi, removing the chromatographic column, loading the sieve plate and the column head to obtain SiO2/urushiol ester high molecular chromatographic column, then SiO2The urushiol ester high molecular chromatographic column is connected to a high performance liquid chromatograph, and is washed by acetonitrile-0.05 percent phosphoric acid water (3:97, V/V) solution until the baseline is balanced, and then the sample can be injected.
The detection method comprises the following steps:
(1) preparing a sample solution: dissolving appropriate amount of gastrodine, phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside in acetonitrile-0.05% phosphoric acid water (3:97, V/V) solution to obtain a solution containing 5 × 10 per 1L-4Injecting a mixed solution of gastrodin, phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside in mol;
(2) setting parameters: mixing SiO2The urushiol ester high molecular chromatographic column is connected to a liquid chromatograph, the flow rate of a mobile phase of the liquid chromatograph is set to be 1.0mL/min, the detection wavelength is 220nm, and the column temperature is 25 ℃;
(3) separation: starting a sample injection valve to enable the acetonitrile-phosphoric acid aqueous solution to bring the sample into SiO2In a urushiol ester high-molecular chromatographic column, the sample introduction amount is 4 mu L, the separation of gastrodin, phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside is realized, the obtained result is shown in figure 9, a gastrodin peak appears when the retention time is 4.01min, a phenyl-beta-D-glucopyranoside peak appears when the retention time is 5.59min, a 4-nitrophenyl-beta-D-glucopyranoside peak appears when the retention time is 7.65min, and the separation degree is 9.45 and 8.30.
Comparative application example 1 method for separating gastrodin and derivative phenyl-beta-D glucopyranoside by using rosin-based polymer chromatographic column
The rosin-based polymer chromatographic column is prepared according to the method disclosed by the invention patent application with the application number of 201710710292.1.
(1) Preparing a sample solution: dissolving appropriate amount of gastrodine and phenyl-beta-D-glucopyranoside with methanol to obtain a solution containing gastrodine 2.5 × 10 per 1L-4Injecting a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside in mol;
(2) setting parameters: connecting the esterified rosin-based polymer chromatographic column to a liquid chromatograph, setting the flow rate of a mobile phase of the liquid chromatograph to be 0.3mL/min, the detection wavelength to be 254nm, and the column temperature to be 25 ℃;
(3) separation: starting a sample injection valve to enable methanol to bring a sample into the rosin-based polymer chromatographic column modified by esterification, so as to realize the separation of gastrodin, wherein the obtained result is shown as 10, a gastrodin peak appears when the retention time is 9.97min, a phenyl-beta-D-glucopyranoside peak appears when the retention time is 10.94min, and the separation degree is 1.60.
Comparative application example 2 method for separating gastrodin and derivative phenyl-beta-D-glucopyranoside by using rosin polymer chromatographic column
The rosin macromolecule chromatographic column is prepared according to the method disclosed by Wangwangjing, the preparation of the rosin-based high performance liquid chromatography stationary phase and the separation research on gastrodin [ D ], the article.
(1) Preparing a sample solution: dissolving appropriate amount of gastrodine and phenyl-beta-D-glucopyranoside with methanol to obtain a solution containing gastrodine 2.5 × 10 per 1L-4Injecting a mixed solution of gastrodin and phenyl-beta-D-glucopyranoside in mol;
(2) setting parameters: connecting the esterified and modified rosin macromolecule chromatographic column into a liquid chromatograph, setting the flow rate of a mobile phase of the liquid chromatograph to be 0.3mL/min, the detection wavelength to be 220nm, and the column temperature to be 25 ℃;
(3) separation: starting a sample injection valve to enable methanol to bring a sample into the esterification modified rosin polymer chromatographic column to realize gastrodin separation, wherein the obtained result is shown in figure 11, a gastrodin peak appears when the retention time is 11.16min, a phenyl-beta-D-glucopyranoside peak appears when the retention time is 12.39min, and the separation degree is 1.54.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. SiO (silicon dioxide)2Application of gastrodin and its derivatives in separation of gastrodin and its derivatives, wherein the gastrodin derivatives comprise phenyl-beta-D-glucopyranoside and 4-nitrophenyl-beta-D-glucopyranoside; the SiO2The preparation method of the urushiol ester polymer microsphere comprises the following steps:
s1: uniformly mixing monomer methacrylic acid lacquer phenolic ester with a cross-linking agent and a free radical initiator; the cross-linking agent is ethylene glycol dimethacrylate; the mass ratio of the monomers to the cross-linking agent to the free radical initiator is 0.1-1.5:0.5-15: 0.004-0.1;
s2: coating the mixture obtained in the step S1 on the surface of the silica gel;
s3: placing the silica gel compound obtained in the step S2 in an aqueous solution of a surfactant to perform free radical polymerization;
s4: soxhlet extraction of the product obtained in step S3 with anhydrous ethanol, and vacuum drying to obtain SiO2Polymeric microspheres of urushiol ester;
the mass ratio of the monomer to the cross-linking agent to the silica gel is 1: 1-100; the surfactant is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate, and the mass fraction of the surfactant in the water phase is 0.3-5%; the reaction temperature of the free radical polymerization is 70-90 ℃, and the time is 8-10 h; preparation of the resulting SiO2The particle size distribution of the urushiol ester polymer microsphere is 3-15 mu m, the pore size distribution is 5-10nm, and the specific surface area is 225-2(ii)/g; SiO is filled in a column by adopting a wet method and is pressed by a constant pressure pump2Filling urushiol ester polymer microspheres in a hollow chromatographic column, loading the column under 6000psi for 10min, loading the column under 4500psi for 10min, loading the column under 3000psi for 5min, loading the column under 1500psi for 5min, removing the chromatographic column after filling, loading the sieve plate and column head to obtain SiO2Polymeric chromatographic columns of urushiol esters;
the liquid chromatogram conditions for separating gastrodin and derivatives thereof are as follows: the mobile phase is acetonitrile-0.05% phosphoric acid water =3:97, V/V, the flow rate is 0.3-1.0mL/min, the detection wavelength is 220nm, and the column incubator is 25 +/-5 ℃.
2. SiO as claimed in claim 12The application of urushiol ester polymer microspheres in the separation of gastrodin and derivatives thereof is characterized in that: in step S1, the radical initiator is an azo radical initiator or an organic peroxide radical initiator.
3. SiO as claimed in claim 22Application of urushiol ester polymer microspheres in separation of gastrodin and derivatives thereofCharacterized in that: the azo free radical initiator is azobisisobutyronitrile.
4. SiO as claimed in claim 22The application of urushiol ester polymer microspheres in the separation of gastrodin and derivatives thereof is characterized in that: the organic peroxide free radical initiator is benzoyl peroxide.
5. SiO as claimed in claim 12The application of urushiol ester polymer microspheres in the separation of gastrodin and derivatives thereof is characterized in that: the application method is to mix SiO2The urushiol ester high molecular microspheres are used as stationary phase filler to be filled in a chromatographic column and applied to a liquid chromatograph to separate gastrodin and derivatives thereof.
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