CN112011055B - Functional organic silicon resin for adsorbing and light-operated desorption of protein and preparation method thereof - Google Patents
Functional organic silicon resin for adsorbing and light-operated desorption of protein and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Abstract
The invention belongs to the technical field of functional high polymer materials and biology, and particularly relates to a functional organic silicon resin for adsorbing and light-operated desorption of protein and a preparation method thereof. According to the invention, quaternary ammonium groups and photosensitive coumarin groups are introduced into organic silicon resin, protein molecules with isoelectric points less than 7.4 are adsorbed on the surface of functional organic silicon resin through electrostatic interaction, the coumarin photosensitive groups are dissociated after the irradiation of a 410nm light source, the surface charge property of the organic silicon resin is reversed, and the protein molecules are in a desorption state. The preparation method of the functional organic silicon resin has the advantages of simple synthesis process, mild reaction conditions and strong operability, and the obtained functional organic silicon resin has good biocompatibility, photoresponse and light-operated protein molecule desorption capability, can accurately regulate and control the desorption behavior of protein molecules by regulating the illumination position and the illumination time, and has important application value.
Description
Technical Field
The invention relates to a functional organic silicon resin capable of adsorbing and photo-controlling desorbed protein and a preparation method thereof, belonging to the field of functional high polymer materials and biotechnology.
Background
The fixing and releasing technology of the biological macromolecules has very important application value in the fields of separating and purifying biological molecules, screening antibody and antigen molecules, protein chips and the like. Biomacromolecules are complex in structure, prone to qualitative changes and prone to loss of biological activity, and therefore designing and preparing suitable carrier materials is one of the important challenges in this field.
The organosilicon material which takes Si-O-Si as a main chain structure and has silicon atoms connected with organic groups has excellent high and low temperature resistance, weather resistance, aging resistance and physiological inertia and is a good carrier of biological macromolecules. Meanwhile, the organic silicon material has stronger designability, and can obtain functional organic silicon materials with different structures and performances.
At present, one of the technical approaches for fixing and separating protein molecules by using an organosilicon material is to fix protein molecules by a chemical reaction based on active groups, such as amino and carboxyl, on the surface of the material (adv. mater. (2010)22, 1242-. Adsorption and desorption by utilizing the charge of biomolecules is another technical way for fixing and separating protein molecules, for example, the adsorption and desorption of proteins are regulated and controlled by ultraviolet light irradiation by utilizing polyvinylpyrrolidone hydrogel containing photosensitive groups (adv.funct.mater. (2017)27, 1-9); polyacrylamide hydrogel (Biomacromolecules (2013)14, 1587-. However, the hydrogel is a micro-crosslinked water-containing polymer swelling system, and the physical properties of the hydrogel greatly change with environmental conditions, so that the hydrogel is not suitable for being used as a solid-phase adsorption material.
In addition, CN106700080A discloses a modified silicone oil containing a carboxylic betaine zwitterionic precursor, a preparation method thereof, and an organosilicon material. The structural formula of the modified silicone oil is shown as formula I (x is more than 0 and less than or equal to 800), and the organic silicon material prepared by the modified silicone oil through a cross-linking film-forming reaction has good protein non-specific adsorption resistance and water resistance. The organic silicon material has no functions of selectively adsorbing protein molecules and desorbing the protein molecules in a light response mode. US8568594B2 discloses methods of separation of peptides and proteins and articles, devices, methods and apparatus for performing liquid chromatography, chromatographic adsorbents having one or more pentafluorophenyl groups wherein the one or more pentafluorophenyl groups are a bonded phase on an adsorbent selected from the group consisting of silica, an organic polymer, or a hybrid organosilane material, and the pentafluorophenyl groups are in monodentate, bidentate and tridentate forms. The invention uses inorganic silicon dioxide, carbon series organic polymer or hybrid organic silane as a stationary phase, uses pentafluorophenyl as an adsorption functional group, and realizes the separation of protein by utilizing a liquid chromatography technology.
At present, the light-operated adsorption and desorption of protein molecules based on organic silicon resin is rarely involved in the prior art, and therefore the invention is provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a functional organic silicon resin for adsorbing and photo-controlling desorption protein molecules and a preparation method thereof. According to the invention, a quaternary ammonium group and a photosensitive coumarin group are introduced into the organic silicon resin, protein molecules are adsorbed on the surface of the organic silicon resin before illumination, and the coumarin photosensitive group is dissociated after illumination, so that light-operated desorption of the protein molecules is realized.
The functional organic silicon resin for adsorbing and light-operated desorption of protein molecules has good light responsiveness and light-operated accuracy, and the surface charge of the resin material is converted from positive to negative under the irradiation of 410nm light. Before illumination, the functional organic silicon resin containing quaternary ammonium groups adsorbs protein molecules through electrostatic action, and after illumination, coumarin groups are dissociated, so that carboxyl is exposed on the surface of the material, the charge property of the surface of the material is reversed, and the desorption of the protein molecules is realized.
Description of terms:
a compound of formula I: functional organic silicon resin (I) in the structural formula, R1Is methyl or ethyl; r2Is methyl or ethyl; x is 0, 1; y is 0, 1 or 2;
a compound of formula II: 7-N, N-diethylamino-4-methylcoumarin (II);
a compound of formula III: 7-N, N-diethylamino-4-hydroxymethylcoumarin (III);
a compound of formula IV: 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin (IV);
a compound of formula V: an amino group-containing siloxane (V) in which R is1Is methyl or ethyl; r2Is methyl or ethyl; x is 0, 1; y is 0, 1 or 2;
a compound of formula VI: coumarin siloxane (VI) of the formula R1Is methyl or ethyl; r2Is methyl or ethyl; x is 0, 1; y is 0, 1 or 2. .
In the specification, the compound numbers are completely consistent with the structural formula numbers, have the same reference relationship, and are based on the structural formula of the compound.
Room temperature: means 25 ℃ plus or minus 5 ℃.
The technical scheme of the invention is as follows:
a functional organic silicon resin for adsorbing and photo-controlling desorption protein molecules has a molecular structure general formula shown in a formula I:
in the formula I, R1Is methyl or ethyl, R2Is methyl or ethyl; x is 0 or 1 and y is 0, 1 or 2.
According to the invention, it is preferred that in formula I, R1Is methyl, R2Is methyl or ethyl; x is 0 or 1 and y is 0, 1 or 2.
According to the present invention, preferably, the functional silicone resin for adsorbing and photo-desorbing protein molecules has the following molecular structure:
x is 0 or 1.
According to the present invention, preferably, the functional silicone resin can effectively adsorb protein molecules with isoelectric points less than 7.4;
preferably, the surface charge of the functional organic silicon resin for adsorbing and photo-desorbing protein molecules is changed from positive to negative under the irradiation of light at 410 nm.
According to the invention, the preparation method of the functional organic silicon resin for adsorbing and photo-desorbing protein molecules comprises the following steps:
(1) carrying out oxidation reaction on the compound of the formula II to obtain an intermediate 1, and carrying out reduction reaction on the intermediate 1 to obtain a compound of a formula III;
(2) carrying out acylation reaction on the compound of the formula III and chloroacetyl chloride to obtain a compound of a formula IV;
(3) carrying out substitution reaction on a compound shown in the formula IV and a compound shown in the formula V to obtain a compound shown in the formula VI;
(4) carrying out condensation polymerization reaction on a compound shown in a formula VI in the dark under the action of an alkaline catalyst to obtain a compound shown in a formula I, namely functional organic silicon resin for adsorbing and light-operated desorption of protein molecules;
according to the invention, preferably, in the step (1), the compound shown in the formula II is dissolved in 1, 4-dioxane, an oxidant selenium dioxide is added, and after oxidation reaction, filtration and reduced pressure concentration are carried out to obtain an intermediate 1; dissolving the intermediate 1 in methanol, adding reducing agent sodium borohydride in batches in ice water bath, heating the reaction system to room temperature, carrying out reduction reaction on the intermediate 1, and separating and purifying the product to obtain a compound shown in the formula III;
preferably, the preparation conditions of step (1) are one or more of the following:
A. the molar ratio of the compound shown in the formula II to the selenium dioxide is 1: 1.5-2;
B. the molar ratio of the compound shown in the formula II to the sodium borohydride is 1: 2;
C. the separation and purification process comprises the following steps: adding 0.1mol/L diluted hydrochloric acid into the obtained reaction solution, extracting with dichloromethane for three times, washing the organic phase with deionized water, saturated sodium bicarbonate solution and deionized water for three times respectively, drying with anhydrous magnesium sulfate, performing suction filtration, evaporating the solvent, concentrating, and purifying by column chromatography to obtain a compound shown in the formula III; further preferably, in the column chromatography purification method, the stationary phase is silica gel, the eluent is a mixed solvent of dichloromethane and acetone, and the volume ratio of dichloromethane to acetone in the mixed solvent is 5: 1;
D. the temperature of the oxidation reaction is 105-115 ℃, and the time of the oxidation reaction is 20-30 h.
According to the invention, preferably, in the step (2), the compound of the formula III obtained in the step (1) is dissolved in tetrahydrofuran, triethylamine is added, chloroacetyl chloride is added dropwise in an ice water bath, then the reaction system is heated to room temperature for reaction, and the compound of the formula IV is obtained through acylation reaction and product separation and purification;
preferably, the preparation conditions of step (2) are one or more of the following:
A. the molar ratio of the compound shown in the formula III to the chloroacetyl chloride is 1: 1.5;
B. the molar ratio of the chloracetyl chloride to the triethylamine is 1: 1;
C. the separation and purification process comprises the following steps: filtering to remove triethylamine salt, removing the solvent by rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, evaporating the solvent, concentrating, and performing column chromatography purification to obtain a compound shown in the formula IV; further preferably, in the column chromatography purification method, the stationary phase is silica gel, the eluent is a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of dichloromethane to ethyl acetate in the mixed solvent is 6: 1;
D. the acylation reaction time is 3-6 h.
According to the invention, preferably, in the step (3), the compound of the formula IV obtained in the step (2) is dissolved in tetrahydrofuran under nitrogen atmosphere, and is subjected to substitution reaction with the compound of the formula V at room temperature to obtain a compound of the formula VI;
preferably, the molar ratio of the compound shown in the formula IV to the compound shown in the formula V is 1: 1;
preferably, the substitution reaction time is 40-50 h. Wherein in the structural formula of the compounds of the formulas V and VI, R1Is methyl or ethyl; r2Is methyl or ethyl; x is 0 or 1; y is 0, 1 or 2.
According to the invention, preferably, in the step (4), the compound of formula VI obtained in the step (3) is dissolved in a solvent A, an alkaline catalyst solution is added, and polycondensation reaction is carried out under the condition of keeping out of the sun, so as to obtain a functional organic silicon resin solution;
preferably, the preparation conditions of step (4) are one or more of the following:
A. the solvent A is dichloromethane, trichloromethane, methanol, ethanol or tetrahydrofuran, and is further preferable to be dichloromethane or tetrahydrofuran; the concentration of the compound shown in the formula VI is 10-50 mg/mL;
B. the alkaline catalyst is one or more of alkali metal hydroxide, ammonia water, carbonate compounds and fluoride salt compounds; the concentration of the alkaline catalyst aqueous solution is 0.1-1 mmol/L; the volume mass ratio of the alkaline catalyst aqueous solution to the compound shown in the formula VI is 0.02-0.1 muL: 1mg, and more preferably 0.05-0.1 muL: 1 mg;
C. the condensation reaction time is 1-4 h, and preferably 2-3 h.
According to the present invention, a preferred embodiment of the method for preparing a functional silicone resin for the adsorption and photoabsorption of protein molecules comprises the steps of:
(1) dissolving a compound shown in a formula II in 1, 4-dioxane, adding an oxidant selenium dioxide, carrying out oxidation reaction for 24 hours at 110 ℃, filtering, and carrying out reduced pressure concentration to obtain an intermediate 1; dissolving the intermediate 1 in methanol, slowly adding a reducing agent sodium borohydride in batches at 0-4 ℃ in an ice water bath, heating a reaction system to room temperature, carrying out reduction reaction on the intermediate 1 for 4 hours, adding 0.1mol/L diluted hydrochloric acid into the obtained reaction solution, extracting with dichloromethane for three times, washing the organic phase with deionized water, a saturated sodium bicarbonate solution and deionized water for three times respectively, drying the organic phase with anhydrous magnesium sulfate, carrying out suction filtration, concentrating an evaporation solvent, and purifying by column chromatography to obtain a compound shown in the formula III;
(2) dissolving the compound of the formula III obtained in the step (1) in tetrahydrofuran, adding triethylamine, slowly dropwise adding chloroacetyl chloride in an ice water bath at 0-4 ℃, and then heating a reaction system to room temperature for reaction; performing acylation reaction for 4h, filtering to remove triethylamine salt, performing rotary evaporation to remove a solvent, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, evaporating the solvent, concentrating, and performing column chromatography purification to obtain a compound shown in the formula IV;
(3) dissolving the compound of formula IV obtained in the step (2) in tetrahydrofuran under nitrogen atmosphere, and carrying out substitution reaction with the compound of formula V for 48h at room temperature to obtain a compound of formula VI;
(4) and (3) dissolving the compound of the formula VI obtained in the step (3) in a solvent A, adding an alkaline catalyst solution into the solvent A, and carrying out polycondensation reaction in the dark to obtain the functional organic silicon resin solution.
According to the invention, the activated carrier material is placed in the prepared functional organic silicon resin solution to be soaked for a certain time to obtain the material dipped with the functional organic silicon resin, and the material is placed at room temperature for aging, then is washed by solvent A and deionized water, and is used for adsorption and light-operated desorption protein molecule tests after being dried.
According to the present invention, preferably, the carrier material is a glass sheet, a silicon sheet or a quartz sheet;
the carrier material activation process comprises the following steps: soaking a 2cm multiplied by 2cm carrier material in a newly prepared Piranha solution (the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 7:3) for 12 hours, then washing with deionized water and drying for 1 hour at 90 ℃ under a vacuum environment;
preferably, the soaking time is 6-12 h, and further preferably 8-12 h;
preferably, the reaction time at room temperature is 3-6 h, and more preferably 4-6 h.
According to the invention, the protein molecule adsorption process of the functional organic silicon resin comprises the following steps: and (3) soaking the obtained functional organic silicon resin coating material in a phosphoric acid buffer solution of protein molecules, taking out, washing with the phosphoric acid buffer solution and deionized water, and drying to obtain the functional organic silicon resin for adsorbing the protein molecules.
According to the present invention, preferably, the protein is a protein having an isoelectric point of less than 7.4; the concentration of the protein solution is 0.1-1 mg/mL; the pH value of the phosphoric acid buffer solution is 7.4;
preferably, the soaking time is 0.5-2 hours, and further preferably 1-2 hours;
preferably, the functional silicone resin prepared under the conditions of soaking time of 12h and aging at room temperature for 6h is placed in 50mL phosphoric acid buffer solution of bovine serum albumin (1.0mg/mL) to be soaked for 2h, and the adsorption capacity of the functional silicone resin to the bovine serum albumin is 36.1 mg.
According to the invention, the molecular process of the light-operated desorption protein of the functional organic silicon resin is as follows: after the obtained functional organic silicon resin for adsorbing protein molecules is irradiated by 410nm light, the protein molecules can be desorbed, and the desorbed protein molecules are washed by phosphoric acid buffer solution. By the photomask technology, the amount of protein molecule desorption and the region of the functional organic silicon resin surface for desorbing the protein molecule can be controlled.
According to the present invention, it is preferable that the size of the photomask is 2cm × 2cm, the stripe width is 100 μm, the black portion is an opaque portion, and the transparent portion is a transparent portion; the distance between the functional organic silicon resin material and the striped photomask is 5-10 cm;
preferably, the intensity of the 410nm light source is 60-160 mW/cm2(ii) a The irradiation time is 0.5-2 h.
The reaction route of the invention is as follows:
the invention has the beneficial effects that:
1. the organic silicon resin for adsorbing and photo-controlling desorption protein molecules disclosed by the invention has excellent high and low temperature resistance, weather resistance, aging resistance and physiological inertia, and is a good carrier of biological macromolecules.
2. The functional organic silicon resin disclosed by the invention can effectively adsorb protein molecules with isoelectric points less than 7.4, can realize light-operated desorption of the protein molecules after being irradiated by 410nm visible light, and has good light responsiveness and light-operated desorption of the protein molecules.
3. The preparation method of the functional organic silicon resin disclosed by the invention is simple in synthesis process, mild in reaction condition and strong in operability.
4. The functional organic silicon resin for adsorbing and optically controlling the desorption of the protein molecules can regulate and control the desorption behavior of the protein molecules by regulating the illumination position and the illumination time, and has important application value.
Drawings
FIG. 1 is a chart showing an infrared absorption spectrum of a functional silicone resin obtained in example 1 of the present invention.
Fig. 2 is a schematic view of photo-desorption of protein molecules twice by using a photomask after the functional silicone resin adsorbs the protein molecules in example 1 of the present invention.
Fig. 3 is a micro pattern of protein adsorbed on the surface of the functional silicone resin obtained in example 1 of the present invention, which is obtained by performing photo-controlled desorption of protein molecules through a photomask twice.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are conventional methods unless otherwise specified, and the reagents and materials described therein are commercially available without otherwise specified.
Example 1
A method for preparing functional organic silicon resin for adsorbing and photo-desorbing protein molecules comprises the following steps:
(1) 7-N, N-diethylamino-4-methylcoumarin (4.63g,20mmol) was dissolved in 1, 4-dioxane (120mL), and selenium dioxide (3.33g,30mmol) was added to the solution. The reaction mixture was heated to reflux with stirring for 24 h. After filtration, concentration under reduced pressure gave a brown oil, which was dissolved in methanol (130mL) and sodium borohydride (380mg,10mmol) was added. The solution was stirred at room temperature for 4 h. The resulting suspension was carefully hydrolyzed with 1M HCl solution (20mL), diluted with water and the resulting solution extracted three times with dichloromethane (20 mL). The organic phase was washed three times with water (30mL), saturated sodium bicarbonate solution (30mL) and water (30mL), respectively, and dried over anhydrous magnesium sulfate. After suction filtration and concentration by evaporation of the solvent, the crude product was purified by column chromatography (eluent: dichloromethane/acetone 5: 1) to give 7-N, N-diethylamino-4-hydroxymethylcoumarin as a yellow solid in a yield of 52%.
(2) Dissolving the 7-N, N-diethylamino-4-hydroxymethyl coumarin (0.67g, 2.71mmol) obtained in the step (1) in anhydrous tetrahydrofuran (20mL), adding triethylamine (0.38mL), slowly dropwise adding chloroacetyl chloride (0.31g, 2.71mmol) in an ice water bath, after the reaction is finished, removing triethylamine salt through suction filtration, removing the solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, and purifying by column chromatography (eluent: dichloromethane/ethyl acetate 6:1) to obtain the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin with the yield of 86%.
(3) Dissolving the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin (0.25g, 0.79mmol) obtained in the step (2) in anhydrous dichloromethane (20mL), adding alpha-aminopropyltriethoxysilane (0.17g, 0.79mmol), and reacting at 25 ℃ under nitrogen atmosphere for 48h to obtain coumarin siloxane.
(4) And (3) dissolving the coumarin siloxane obtained in the step (3) in 50mL of dichloromethane to prepare a solution of 50mg/mL, adding 500 mu L of sodium hydroxide aqueous solution (1.0mmol/L), and carrying out pre-polycondensation reaction for 3h in the dark condition to obtain a functional organic silicon resin solution. The infrared absorption spectrum of the obtained functional silicone resin is shown in fig. 1.
(5) And (3) placing the activated quartz plate in the prepared functional organic silicon resin solution for soaking for 12h, taking out the quartz plate, and continuing to react for 6h at room temperature. Washing with dichloromethane and deionized water, and drying to obtain the functional organic silicon resin coating material.
(6) Adsorption of protein molecules: and (3) placing the functional organic silicon resin coating material obtained in the step (4) into 50mL phosphoric acid buffer solution (1.0mg/mL) of bovine serum albumin, soaking for 2h, taking out, washing with phosphoric acid buffer solution and deionized water, and drying to obtain the functional organic silicon resin coating material for adsorbing protein molecules.
(7) Photo-desorption of proteinsA step of: placing the functional silicone resin adsorbing protein molecules obtained in step (5) on a photomask (with a distance of 5cm), and using a 410nm light source (160 mW/cm)2) After 2h of irradiation, washing with phosphoric acid buffer solution and deionized water, and drying to obtain the first light-operated functional organic silicon resin for desorbing protein molecules. Rotating the photomask horizontally by 90 deg., placing above the first photo-desorption functional silicone resin (5 cm apart), and using 410nm light source (160 mW/cm)2) And (3) irradiating for 2 hours, washing with phosphoric acid buffer solution and deionized water, and drying to obtain the functional organic silicon resin for the second light-operated desorption of protein.
The schematic diagrams of the functional organic silicon resin adsorbed protein molecules and the photo-desorption protein molecules by using a photomask are shown in FIG. 2; after the obtained functional organic silicon resin adsorbs protein molecules, the protein molecules are photo-desorbed twice through a photomask, and the obtained organic silicon resin surface adsorbed protein micro-pattern is shown in fig. 3. In fig. 3, the white portions (100 μm × 100 μm) in the form of squares are non-illuminated regions where proteins are adsorbed, and the black frame regions are regions where proteins are desorbed from the surface of the silicone resin by illumination with a photomask, and the desorption behavior of proteins adsorbed by the silicone resin can be controlled by illumination with light.
Example 2
A method for preparing functional organic silicon resin for adsorbing and photo-desorbing protein molecules comprises the following steps:
(1) 7-N, N-diethylamino-4-methylcoumarin (4.63g,20mmol) was dissolved in 120mL1, 4-dioxane, and selenium dioxide (2.22g,20mmol) was added to the solution. The reaction mixture was heated to reflux with stirring for 72 h. After filtration, concentration under reduced pressure gave a brown oil which was dissolved in methanol (130mL) and sodium borohydride (380mg,10mmol) was added. The solution was stirred at room temperature for 4 h. The resulting suspension was carefully hydrolyzed with 1M HCl solution (20mL), diluted with water and the resulting solution extracted three times with dichloromethane (20 mL). The organic phase was washed three times with water (30mL), saturated sodium bicarbonate solution (30mL) and water (30mL), respectively, and dried over anhydrous magnesium sulfate. After suction filtration and solvent evaporation concentration, the crude product was purified by column chromatography (eluent: dichloromethane/acetone 5: 1) to give 7-N, N-diethylamino-4-hydroxymethylcoumarin as a yellow solid in a yield of 24%.
(2) Dissolving the 7-N, N-diethylamino-4-hydroxymethyl coumarin (0.67g, 2.71mmol) obtained in the step (1) in anhydrous tetrahydrofuran (20mL), adding triethylamine (0.76mL), slowly dropwise adding chloroacetyl chloride (0.465g, 4.07mmol) in an ice water bath, after the reaction is finished, removing triethylamine salt through suction filtration, removing the solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, and purifying by column chromatography (eluent: dichloromethane/ethyl acetate 6:1) to obtain the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin with the yield of 80%.
(3) Dissolving the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin (0.53g, 1.59mmol) obtained in the step (2) in anhydrous dichloromethane (20mL), adding alpha-aminopropyltriethoxysilane (0.35g, 1.59mmol), and reacting at 25 ℃ in a nitrogen atmosphere for 78 hours to obtain the coumarinyl bridged silane.
(4) And (3) dissolving the coumarin siloxane obtained in the step (3) in 70mL of dichloromethane to prepare a solution of 20mg/mL, adding 700 mu L of sodium hydroxide aqueous solution (0.5mmol/L), and carrying out pre-polycondensation reaction for 3h in the dark condition to obtain a functional organic silicon resin solution.
(5) And (3) placing the activated glass slide into the prepared functional organic silicon resin solution to be soaked for 10h, taking out the glass slide to be aged for 5h at room temperature, washing the glass slide with dichloromethane and deionized water, and drying to obtain the functional organic silicon resin coating material.
Example 3
A method for preparing functional organic silicon resin for adsorbing and photo-desorbing protein molecules comprises the following steps:
(1) 7-N, N-diethylamino-4-methylcoumarin (4.63g,20mmol) was dissolved in 120mL1, 4-dioxane, and selenium dioxide (3.33g,30mmol) was added to the solution. The reaction mixture was heated to reflux with stirring for 48 h. After filtration, concentration under reduced pressure gave a brown oil which was dissolved in methanol (130mL) and sodium borohydride (380mg,10mmol) was added. The solution was stirred at room temperature for 4 h. The resulting suspension was carefully hydrolyzed with 1M HCl solution (20mL), diluted with water and the resulting solution extracted three times with dichloromethane (20 mL). The organic phase was washed three times with water (30mL), saturated sodium bicarbonate solution (30mL) and water (30mL), respectively, and dried over anhydrous magnesium sulfate. After suction filtration and concentration of the evaporated solvent, the crude product was purified by column chromatography (eluent: dichloromethane/acetone 5: 1) to give 7-N, N-diethylamino-4-hydroxymethylcoumarin as a yellow solid in a yield of 65%.
(2) Dissolving the 7-N, N-diethylamino-4-hydroxymethyl coumarin (0.67g, 2.7mmol) obtained in the step (1) in anhydrous tetrahydrofuran (20mL), adding triethylamine (0.76mL), slowly dropwise adding chloroacetyl chloride (0.62g, 5.4mmol) in an ice water bath, after the reaction is finished, removing triethylamine salt through suction filtration, removing the solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, and purifying by column chromatography (eluent: dichloromethane/ethyl acetate 6:1) to obtain the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin with the yield of 72%.
(3) Dissolving the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin (0.64g, 1.86mmol) obtained in the step (2) in anhydrous dichloromethane (20mL), adding alpha-aminopropyltrimethoxysilane (0.33g, 1.86mmol), and reacting at 25 ℃ in a nitrogen atmosphere for 60 hours to obtain the coumarinyl bridged silane.
(4) Dissolving the coumarin siloxane obtained in the step (3) in dichloromethane to prepare 60mL of 10mg/mL solution, adding 600 mu L of sodium hydroxide aqueous solution (0.1mmol/L), and performing pre-condensation reaction for 2h in the dark.
(5) And (3) placing the activated silicon wafer into the prepared functional organic silicon resin solution to be soaked for 8h, taking out the silicon wafer, aging at room temperature for 6h, washing with dichloromethane and deionized water, and drying to obtain the functional organic silicon resin coating material.
Example 4
A method for preparing functional organic silicon resin for adsorbing and photo-desorbing protein molecules comprises the following steps:
(1) 7-N, N-diethylamino-4-methylcoumarin (4.63g,20mmol) was dissolved in 120mL1, 4-dioxane, and selenium dioxide (3.33g,30mmol) was added to the solution. The reaction mixture was heated to reflux with stirring for 48 h. After filtration, concentration under reduced pressure gave a brown oil which was dissolved in methanol (100mL) and sodium borohydride (380mg,10mmol) was added. The solution was stirred at room temperature for 4 h. The resulting suspension was carefully hydrolyzed with 1M HCl solution (20mL), diluted with water and the resulting solution extracted three times with dichloromethane (20 mL). The organic phase was washed three times with water (30mL), saturated sodium bicarbonate solution (30mL) and water (30mL), respectively, and dried over anhydrous magnesium sulfate. After suction filtration and concentration of the evaporated solvent, the crude product was purified by column chromatography (eluent: dichloromethane/acetone 5: 1) to give 7-N, N-diethylamino-4-hydroxymethylcoumarin as a yellow solid in 67% yield.
(2) Dissolving the 7-N, N-diethylamino-4-hydroxymethyl coumarin (0.67g, 2.71mmol) obtained in the step (1) in anhydrous tetrahydrofuran (20mL), adding triethylamine (0.76mL), slowly dropwise adding chloroacetyl chloride (0.62g, 5.42mmol) in an ice water bath, after the reaction is finished, removing triethylamine salt through suction filtration, removing the solvent through rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, and purifying by column chromatography (eluent: dichloromethane/ethyl acetate 6:1) to obtain the 7-N, N-diethylamino-4-chloroacetic acid ethyl ester coumarin with the yield of 73%.
(3) Dissolving the 7-N, N-diethylamino-4-ethyl chloroacetate coumarin (0.64g, 1.86mmol) obtained in the step (2) in anhydrous dichloromethane (20mL), adding N-methyl-3-trimethoxysilyl-1-propylamine (0.36g, 1.86mmol), and reacting at 25 ℃ under nitrogen atmosphere for 60 hours to obtain the coumarinyl bridged silane.
(4) Dissolving the coumarin siloxane obtained in the step (3) in 60mL of dichloromethane to prepare 10mg/mL solution, adding 600 mu L of sodium hydroxide aqueous solution (0.1mmol/L), and performing pre-condensation reaction for 2h under dark condition.
(5) And (3) placing the activated quartz plate in the prepared functional organic silicon resin solution for soaking for 8h, taking out the quartz plate, aging for 4h at room temperature, washing with dichloromethane and deionized water, and drying to obtain the functional organic silicon resin coating material.
Comparative example 1
Adsorption of functional silicone resin to protein molecules:
coumarin siloxane is dissolved in 50mL dichloromethane to prepare 50mg/mL solution, 500 μ L sodium hydroxide aqueous solution (1.0mmol/L) is added, and pre-condensation reaction is carried out for 3h under the condition of keeping out of the light. And (3) placing the activated quartz plate in the prepared functional organic silicon resin solution for soaking for 12h, taking out the quartz plate, aging for 6h at room temperature, washing with dichloromethane and deionized water, and drying to obtain the functional organic silicon resin coating material.
Preparing a 0.1mg/mL avidin phosphate buffer solution, soaking the obtained functional organic silicon resin coating material in 50mL of the prepared avidin phosphate buffer solution for 2h, and monitoring the concentration of the avidin in the avidin phosphate buffer solution before and after adsorption by using an ultraviolet-visible spectrophotometer, wherein the result shows that the adsorption amount of the functional organic silicon resin on the avidin is 4.7mg and is far less than the adsorption amount (36.1mg) of the functional organic silicon resin on bovine serum albumin under the same condition, and the result shows that the functional organic silicon resin obtained by the invention has no functional adsorption property on the avidin (the isoelectric point is more than 7.4).
Claims (21)
1. A functional organic silicon resin for adsorbing and photo-controlling desorption protein molecules is characterized in that the molecular structural general formula of the functional organic silicon resin is shown as formula I:
Ⅰ
in the formula I, R1Is methyl or ethyl, R2Is methyl or ethyl; x is 0 or 1 and y is 0, 1 or 2.
2. The functional silicone resin for the adsorption and photodesorption of protein molecules of claim 1, wherein R in formula I is1Is methyl, R2Is methyl or ethyl; x is 0 or 1 and y is 0, 1 or 2.
3. The functional silicone resin for adsorbing and photo-desorbing protein molecules as claimed in claim 1, wherein the molecular structure of the functional silicone resin for adsorbing and photo-desorbing protein molecules is as follows:
x is 0 or 1.
4. The functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 1, wherein the functional silicone resin is capable of effectively adsorbing protein molecules having an isoelectric point of less than 7.4.
5. The functional silicone resin for the adsorption and photo-desorption of protein molecules according to claim 1, wherein the surface charge of the functional silicone resin for the adsorption and photo-desorption of protein molecules is changed from positive to negative under 410nm light irradiation.
6. The method for preparing the functional silicone resin for the adsorption and the light-operated desorption of protein molecules according to claim 1, comprising the steps of:
(1) carrying out oxidation reaction on the compound of the formula II to obtain an intermediate 1, and carrying out reduction reaction on the intermediate 1 to obtain a compound of a formula III;
(2) carrying out acylation reaction on the compound of the formula III and chloroacetyl chloride to obtain a compound of a formula IV;
(3) carrying out substitution reaction on a compound shown in the formula IV and a compound shown in the formula V to obtain a compound shown in the formula VI;
(4) carrying out condensation polymerization reaction on a compound shown in a formula VI in the dark under the action of an alkaline catalyst to obtain a compound shown in a formula I, namely functional organic silicon resin for adsorbing and light-operated desorption of protein molecules;
7. the method for preparing the functional organic silicon resin for adsorbing and photo-desorbing protein molecules according to claim 6, wherein the compound of formula II in the step (1) is dissolved in 1, 4-dioxane, an oxidant selenium dioxide is added, and after oxidation reaction, the intermediate 1 is obtained by filtering and concentrating under reduced pressure; dissolving the intermediate 1 in methanol, adding reducing agent sodium borohydride in batches in ice water bath, heating the reaction system to room temperature, carrying out reduction reaction on the intermediate 1, and separating and purifying the product to obtain the compound shown in the formula III.
8. The method for preparing a functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 7, wherein the preparation conditions of step (1) are one or more of the following conditions:
A. the molar ratio of the compound shown in the formula II to the selenium dioxide is 1: 1.5-2;
B. the molar ratio of the compound shown in the formula II to the sodium borohydride is 1: 2;
C. the separation and purification process comprises the following steps: adding 0.1mol/L diluted hydrochloric acid into the obtained reaction solution, extracting with dichloromethane for three times, washing the organic phase with deionized water, saturated sodium bicarbonate solution and deionized water for three times respectively, drying with anhydrous magnesium sulfate, performing suction filtration, evaporating the solvent, concentrating, and purifying by column chromatography to obtain a compound shown in the formula III;
D. the temperature of the oxidation reaction is 105-115 ℃, and the time of the oxidation reaction is 20-30 h.
9. The method for preparing the functional organic silicon resin for adsorbing and photo-desorbing protein molecules according to claim 8, wherein in the separation and purification process in the step (1), a stationary phase in the column chromatography purification method is silica gel, an eluent is a mixed solvent of dichloromethane and acetone, and the volume ratio of dichloromethane to acetone in the mixed solvent is 5: 1.
10. The method for preparing the functional organic silicon resin for adsorbing and photo-desorbing protein molecules according to claim 6, wherein the compound of formula III obtained in the step (1) is dissolved in tetrahydrofuran in the step (2), triethylamine is added, chloroacetyl chloride is dripped in an ice-water bath, then the reaction system is heated to room temperature for reaction, and the compound of formula IV is obtained through acylation reaction, separation and purification of the product.
11. The method for preparing a functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 10, wherein the preparation conditions of step (2) are one or more of the following conditions:
A. the molar ratio of the compound shown in the formula III to the chloroacetyl chloride is 1: 1.5;
B. the molar ratio of the chloracetyl chloride to the triethylamine is 1: 1;
C. the separation and purification process comprises the following steps: filtering to remove triethylamine salt, removing the solvent by rotary evaporation, washing with water, drying with anhydrous magnesium sulfate, performing suction filtration, evaporating the solvent, concentrating, and performing column chromatography purification to obtain a compound shown in the formula IV;
D. the acylation reaction time is 3-6 h.
12. The method for preparing the functional silicone resin for adsorbing and photo-desorbing protein molecules according to claim 11, wherein in the step (2) of the column chromatography purification process, the stationary phase is silica gel, the eluent is a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of dichloromethane to ethyl acetate in the mixed solvent is 6: 1.
13. The method for preparing the functional organic silicon resin for adsorbing and photo-desorbing protein molecules according to claim 6, wherein the compound of formula IV obtained in the step (2) is dissolved in tetrahydrofuran under nitrogen atmosphere in the step (3), and is subjected to substitution reaction with the compound of formula V at room temperature to obtain the compound of formula VI.
14. The method for preparing the functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 13, wherein the molar ratio of the compound of formula iv to the compound of formula v in step (3) is 1: 1;
the substitution reaction time is 40-50 h, wherein in the structural formula of the compounds shown in the formulas V and VI, R1Is methyl or ethyl; r2Is methyl or ethyl; x is 0 or 1; y is 0, 1 or 2.
15. The method for preparing the functional organic silicon resin for adsorbing and photo-desorbing protein molecules according to claim 6, wherein in the step (4), the compound of the formula VI obtained in the step (3) is dissolved in a solvent A, an alkaline catalyst solution is added, and polycondensation reaction is carried out under the condition of keeping out of the sun, so as to obtain a functional organic silicon resin solution, wherein the solvent A is dichloromethane, trichloromethane, methanol, ethanol or tetrahydrofuran.
16. The method for preparing a functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 15, wherein the preparation conditions of step (4) are one or more of the following conditions:
A. the solvent A is dichloromethane or tetrahydrofuran, and the concentration of the compound shown in the formula VI is 10-50 mg/mL;
B. the alkaline catalyst is one or more of alkali metal hydroxide, ammonia water, carbonate compounds and fluoride salt compounds; the concentration of the alkaline catalyst aqueous solution is 0.1-1 mmol/L; the volume mass ratio of the alkaline catalyst aqueous solution to the compound shown in the formula VI is 0.02-0.1 muL: 1 mg;
C. the condensation reaction time is 1-4 h.
17. The method for preparing a functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 16, wherein the preparation conditions of step (4) are one or more of the following conditions:
A. the solvent A is dichloromethane;
B. the volume mass ratio of the alkaline catalyst aqueous solution to the compound shown in the formula VI is 0.05-0.1 muL: 1 mg;
C. the condensation reaction time is 2-3 h.
18. Use of the functional silicone resin for the adsorption and light-dependent desorption of protein molecules according to claim 1 for the adsorption and light-dependent desorption of protein molecules.
19. The use of the functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 18, wherein the activated carrier material is soaked in the prepared functional silicone resin solution for a certain period of time to obtain a material dip-coated with functional silicone resin, and the material is left to age at room temperature, then washed with solvent a and deionized water, and dried for adsorption and photoabsorption of protein molecules, wherein the solvent a is dichloromethane, chloroform, methanol, ethanol or tetrahydrofuran.
20. The use of the functional silicone resin for the adsorption and photoabsorption of protein molecules according to claim 18, wherein the adsorption of protein molecules by the functional silicone resin comprises: and (3) soaking the functional organic silicon resin coating material in a phosphoric acid buffer solution of protein molecules, taking out, washing with the phosphoric acid buffer solution and deionized water, and drying to obtain the functional organic silicon resin for adsorbing the protein molecules.
21. The use of the functional silicone resin for the adsorption and photodesorption of protein molecules according to claim 18, wherein the functional silicone resin is characterized by the photodesorption of protein molecules by the following process: after the obtained functional organic silicon resin for adsorbing protein molecules is irradiated by 410nm light, the protein molecules can be desorbed, and the desorbed protein molecules are washed by phosphoric acid buffer solution.
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