CN113121831A - Preparation method of chitosan modified cyclodextrin compound based on porous material catalysis - Google Patents
Preparation method of chitosan modified cyclodextrin compound based on porous material catalysis Download PDFInfo
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- CN113121831A CN113121831A CN202110458071.6A CN202110458071A CN113121831A CN 113121831 A CN113121831 A CN 113121831A CN 202110458071 A CN202110458071 A CN 202110458071A CN 113121831 A CN113121831 A CN 113121831A
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
The invention discloses a high-efficiency preparation method of a cyclodextrin grafted chitosan compound, which takes porous materials subjected to acidification treatment as a catalyst, wherein the porous materials are selected from zeolite molecular sieves or silicon dioxide particles and react for 4-6h at 35-50 ℃ and under the pressure of 0.1-0.2 MPa; the CD-CS complex is obtained.
Description
Technical Field
The invention relates to a synthesis method of a high polymer material compound, in particular to a preparation method of chitosan cross-linked cyclodextrin, belonging to the field of organic synthesis.
Background
It is well known in the art that in ophthalmic materials, especially eye drops, polysaccharide molecules such as chitosan, in combination with cyclodextrin and its derivatives (usually carboxyl or amino modified derivatives) through crosslinking, have the effects of controlling the release rate, reducing the metabolic rate, improving the stability, etc. Especially, the method improves the residence time of the ocular surface of the medicine and increases the slow release performance, and is a very beneficial technical effect.
The natural polysaccharide polymer has good biocompatibility and biodegradability, and can be used as an effective medicament or carrier. However, natural polysaccharides have a problem of poor water solubility.
Among the polysaccharide molecules, the most common is chitosan (chitosan, CS, chemical name polyglucosamine (1-4) -2-amino-B-D-glucose), which is the deacetylated product shell of chitin (chitin, poly-2-acetyl-amino- β (1, 4) -D-glucose). Chitosan is a high molecular amino polysaccharide, has the characteristics of good biocompatibility, biodegradability and the like, also has the functions of broad-spectrum antibacterial activity, inflammation diminishing and the like, is widely applied in the medical field, and is commonly used as a thickening agent in eye drops. The molecular chain of the compound has abundant hydroxyl and amino, and chemical reaction is easy to occur. Is widely used in biomacromolecule drug delivery systems.
However, chitosan is insoluble in water and general organic reagents, and can be dissolved only in acidic solutions such as acetic acid. Although chitosan has good biocompatibility and can be biodegraded, and is suitable for being used as a controlled-release carrier of drugs, the chitosan is difficult to be directly used in the field of ophthalmology, and generally needs to be modified to form a complex, such as a complex forming a covalent bond. Since chitosan has a cationically charged amino group, it can be crosslinked with other molecules by means of amidation reactions.
Natural Cyclodextrin (CD) is a cyclic oligosaccharide whose glucosyl group is connected by alpha-1, 4 glycosidic bonds to form a funnel-like structure, hydroxyl groups are connected at the narrow opening and the wide opening of the funnel, and CH groups from C-3 and C-5 carbon atoms and oxygen atoms in glycosidic bonds are arranged inside the hollow cavity of the funnel. Cyclodextrin can be separated under the action of amylase, has wide sources, non-toxicity, biodegradability and other properties, and is widely applied to pharmaceutical preparations, such as alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD) and gamma-cyclodextrin (gamma-CD), wherein the most widely applied beta-cyclodextrin is beta-cyclodextrin. The cyclodextrin and its derivatives can increase water solubility, stability and bioavailability of the medicine, and promote absorption of the medicine. Both CS and CD are FDA-approved drug materials.
This structure allows the cyclodextrin to entrap guest molecules and form complexes because of the hydrophobic inner cavity and hydrophilic outer cavity properties of cyclodextrin. Therefore, in the prior art, chitosan and cyclodextrin or derivatives thereof are subjected to crosslinking modification to obtain a compound which is applied to the ophthalmic preparation.
However, since the crosslinking of cyclodextrin with chitosan belongs to the amidation reaction, it is known in the art that the amidation reaction is extremely inefficient at higher water content, and the reaction is usually required for more than 24 hours even in the presence of reaction promoters such as EDC and/or NHS. Therefore, there is a need to provide a highly efficient method for cross-linking cyclodextrin with chitosan.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-efficiency preparation method of a cyclodextrin grafted chitosan compound.
In order to achieve the above object, the present invention provides a method for preparing a cyclodextrin-grafted chitosan complex under a porous material catalytic system, the method comprising the steps of:
(1) preparing an acidified porous material as a catalyst, the porous material being selected from zeolite molecular sieves or silica particles;
(2) dissolving the carboxylated or carboxymethylated cyclodextrin derivative in deionized water in a reactor equipped with a magnetic stirring rod, adding EDC and a condensation accelerator (preferably selected from PyBOP or HBTU), and stirring at room temperature for 15-60min to activate the carboxyl group of the cyclodextrin;
dissolving chitosan with acetic acid solution to obtain chitosan solution, mixing with the above activated cyclodextrin solution, and adding appropriate amount of glacial acetic acid under stirring to adjust pH (preferably pH 3-4); then adding a porous material subjected to surface acidification treatment as a catalyst, and performing ultrasonic pretreatment for 30-60min at room temperature; sealing the reaction kettle after ultrasonic treatment, replacing the reaction atmosphere with nitrogen, heating to 35-50 ℃, adjusting the pressure to 0.1-0.2MPa, and continuously stirring for reaction for 4-6 h; and after the reaction is finished, filtering to remove solids, concentrating and dialyzing the product solution, centrifuging, and carrying out vacuum freeze drying to obtain the CD-CS compound.
Wherein, during the reaction period, a sample can be taken for chromatographic monitoring, and the reaction is finished when the content of the product is stable.
Wherein EDC can also be replaced by other activators such as 1, 3-dicyclohexylcarbodiimide or N, N' -diisopropylcarbodiimide, etc.
Among these, carboxylated or carboxymethylated cyclodextrin derivatives are commercially available or can be prepared using methods known in the art, for example, carboxylated cyclodextrins can be prepared according to the procedure in CN 2016105814842: firstly, preparing cyclodextrin and sodium hydroxide into a solution with a proper concentration; then adding sodium chloroacetate, and reacting for 5h at 50 ℃; then adjusting the pH of the system to 7 by using hydrochloric acid, adding excessive methanol for precipitation, filtering the precipitate, and drying the precipitate overnight at 40 ℃ by using a vacuum drier, thereby preparing the carboxylated cyclodextrin with the yield of more than 90%.
Or preparing carboxymethylated cyclodextrin according to the method in CN 201810920493: weighing chloroacetic acid, and dissolving the chloroacetic acid in deionized water; weighing beta-cyclodextrin, dissolving the beta-cyclodextrin in a NaOH solution with the mass fraction of 25%, dropwise adding the beta-cyclodextrin into a prepared chloroacetic acid solution, reacting at room temperature, adjusting the pH to 7 by using glacial acetic acid, standing at 4 ℃ for 16h, then adding methanol until no precipitate is generated, standing for 12h, filtering, continuously adding water for dissolving, adding methanol until no precipitate is generated, filtering, repeatedly washing the obtained product with sufficient ethanol water solution, and drying to obtain a white product, namely carboxymethyl-beta-cyclodextrin.
Wherein, the mass ratio of the chitosan to the cyclodextrin (preferably alpha-or beta-cyclodextrin) is 3-5: 1.
Wherein, the molar ratio of EDC to cyclodextrin is preferably 1: 1.
Wherein the molar ratio of EDC to condensation accelerator is preferably 1-2: 1.
In the present invention, the amount of the solvent used in the reaction is not particularly limited, and the deionized water is preferably used in a mass-to-volume ratio of 1g to 5 to 10mL based on the chitosan, and for example, 5 to 10mL of the solvent can be used for 1g of chitosan.
In the method of the present invention, the preparation process of the porous material catalyst subjected to surface acidification treatment is as follows: soaking porous silica or zeolite molecular sieve particle catalyst with particle size of 0.5-2mm in acetic acid aqueous solution with acetic acid content not less than 50% by volume at room temperature for 6-12h, and heating and refluxing for 1-2 h; and filtering after the reflux is finished, and drying in vacuum to obtain acidified catalyst particles.
Wherein the mass amount of the catalyst is 10-50wt%, preferably 20-30wt% of the solution.
Compared with the prior art, the method adopts a porous catalytic material with higher content and a specific condensing agent system, and effectively enriches the molecules of the reaction raw material in the aqueous solution by means of the stronger adsorption effect of the porous catalytic material and the intermolecular effect of hydrogen bonds formed by a large amount of groups such as hydroxyl and the like contained on the surface and the hydroxyl, amino and the like in cyclodextrin and chitosan molecules, so that the amidation grafting/crosslinking reaction can form an excellent reaction interface on the surface of the catalytic material, the amidation reaction is promoted to be carried out, the reaction efficiency is obviously improved, the reaction time is greatly shortened, and the yield is correspondingly improved.
Drawings
FIG. 1 is an IR spectrum of a product of example 1 of the present invention, the upper curve representing the uncrosslinked chitosan product and the lower curve representing the crosslinked chitosan.
Detailed Description
The following detailed description of preferred embodiments of the invention and the examples included therein will make it easier to understand the context of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
Example 1
1) Weighing 18g of purified chitosan, slowly dropwise adding 3wt% acetic acid solution at room temperature under stirring to dissolve the chitosan, and fully stirring to swell the chitosan to obtain a semitransparent chitosan solution.
2) Soaking porous silica particle catalyst with the particle size of about 1mm in 50% acetic acid water solution at room temperature for 8h, and heating and refluxing for 1 h; and filtering after the reflux is finished, and drying in vacuum to obtain acidified catalyst particles.
3) 4g of carboxylated beta-cyclodextrin (ca. 3.5mmol) with a purity above 95% was dissolved in 35ml of deionized water, 3.5mmol of EDC and 2mmol of PyBOP condensing agent were added and reacted at room temperature with stirring for 45min to activate the carboxyl groups of the cyclodextrin.
4) Adding the activated cyclodextrin solution into a chitosan solution under stirring, adjusting the pH value to about 4 by using glacial acetic acid, adding 62g of the acidified catalyst particles (accounting for about 30% of the solution by mass), and performing ultrasonic pretreatment at room temperature by 80-100KHz for 30min to fully perform surface adsorption on the catalyst particles and the raw materials;
5) after ultrasonic treatment, the reaction kettle is sealed, the reaction atmosphere is replaced by nitrogen, the temperature is raised to 40 ℃, the pressure is adjusted to 0.2MPa, the reaction is finished after continuously stirring and reacting for 4 hours, the solid is removed by filtration, the filtrate is neutralized to be neutral by sodium hydroxide, the filtrate is filtered again, the filtrate is concentrated and dialyzed (the molecular weight cut-off of a dialysis bag is 5000), the solid is frozen and dried in vacuum after centrifugal separation, and thus the chitosan grafted cyclodextrin compound is obtained, wherein the crude yield is about 92% based on the cyclodextrin raw material. Its infrared spectrum is shown in the attached figure, 2930 cm-1And 1740 cm-1Nearby peaks (characteristic absorption peaks for CS and CD) were present in the composite, indicating successful graft crosslinking.
Example 2
1) Weighing 16g of purified chitosan, slowly dropwise adding 2wt% acetic acid solution at room temperature under stirring to dissolve the chitosan, and fully stirring to swell the chitosan to obtain a semitransparent chitosan solution.
2) Soaking a zeolite molecular sieve ZSM-5 catalyst with the particle size of about 1mm in an acetic acid aqueous solution with the volume of acetic acid of 60% at room temperature, and heating and refluxing for 1h after soaking for 6 h; and filtering after the reflux is finished, and drying in vacuum to obtain acidified catalyst particles.
3) Dissolving 19g of alpha-cyclodextrin and 15 g of sodium hydroxide in 100 mL of deionized water, adding 2.5g of sodium chloroacetate, and reacting in a water bath at 50 ℃ for 4 hours; neutralizing the pH value of the system to be neutral by hydrochloric acid, pouring into a large amount of methanol for precipitation, filtering, and vacuum-drying the obtained solid to obtain powdery carboxylated cyclodextrin; 4g of the above carboxylated α -cyclodextrin was dissolved in 40ml of deionized water, 3.5mmol of EDC and 2mmol of PyBOP condensing agent were added and reacted at room temperature with stirring for 30min to activate the carboxyl group of the cyclodextrin.
4) Adding the activated cyclodextrin solution into a chitosan solution under stirring, adjusting the pH value to 3 by using glacial acetic acid, adding 60g of the acidified catalyst particles, and carrying out ultrasonic pretreatment at room temperature for 30min at 80-100KHz to fully carry out surface adsorption on the catalyst particles and the raw materials;
5) after ultrasonic treatment, the reaction kettle is sealed, the reaction atmosphere is replaced by nitrogen, the temperature is raised to 45 ℃, the pressure is 0.1MPa, the reaction is finished after continuously stirring and reacting for 5 hours, the solid is removed by filtration, the filtrate is neutralized to be neutral by sodium hydroxide, the filtrate is filtered again, the filtrate is concentrated and dialyzed (the cut-off molecular weight of a dialysis bag is 5000), the solid is frozen and dried in vacuum after centrifugal separation, and therefore the chitosan grafted cyclodextrin compound is obtained, and the crude yield is about 88% based on cyclodextrin raw materials.
Comparative example 1
The conditions were the same as in example 1 except that no catalyst was contained. The yield after 24h of reaction was 86%.
Comparative example 2
Example 1 was changed to the same conditions except that the temperature and pressure in step (5) of example 1 were adjusted to room temperature and normal pressure, respectively. The yield after 12h of reaction was about 85%.
In conclusion, the invention provides a method for preparing a chitosan grafted cyclodextrin compound, and in the method, the reaction time is effectively shortened and the reaction efficiency is improved by selecting/combining a specific mesoporous material catalyst and an accelerant.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes, modifications and/or alterations to the present invention may be made by those skilled in the art after reading the technical disclosure of the present invention, and all such equivalents may fall within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A method for preparing cyclodextrin grafted chitosan compound under a porous material catalytic system is characterized by comprising the following steps:
(1) preparing an acidified porous material as a catalyst, the porous material being selected from zeolite molecular sieves or silica particles;
(2) dissolving carboxylated or carboxymethylated cyclodextrin derivatives in deionized water in a reactor equipped with a magnetic stirring rod, adding EDC and a condensation accelerator, and stirring and reacting at room temperature for 15-60min to activate the carboxyl of cyclodextrin;
(3) dissolving chitosan with acetic acid solution to obtain chitosan solution, mixing with the activated cyclodextrin solution, and adding appropriate amount of glacial acetic acid under stirring to adjust pH; then adding a porous material subjected to surface acidification treatment as a catalyst, and performing ultrasonic pretreatment for 30-60min at room temperature; sealing the reaction kettle after ultrasonic treatment, replacing the reaction atmosphere with nitrogen, heating to 35-50 ℃, adjusting the pressure to 0.1-0.2MPa, and continuously stirring for reaction for 4-6 h; and after the reaction is finished, filtering to remove solids, concentrating and dialyzing the product solution, centrifuging, and carrying out vacuum freeze drying to obtain the cyclodextrin grafted chitosan compound.
2. The process of claim 1, wherein the condensation accelerator is selected from PyBOP or HBTU.
3. The method of claim 1, wherein the cyclodextrin derivative is a carboxylated cyclodextrin prepared by the process comprising: firstly, preparing cyclodextrin and sodium hydroxide into a solution with a proper concentration; then adding sodium chloroacetate, and reacting for 5h at 50 ℃; then adjusting the pH of the system to 7 by using hydrochloric acid, adding excessive methanol for precipitation, filtering precipitates, and drying in vacuum to prepare the carboxylated cyclodextrin with the yield of more than 90%.
4. The method of claim 1, wherein the mass ratio of chitosan to cyclodextrin is 3-5: 1; preferably, the cyclodextrin is alpha-cyclodextrin or beta-cyclodextrin.
5. The method of claim 1, wherein the molar ratio of EDC to cyclodextrin is 1: 1.
6. The process of claim 1 wherein the molar ratio of EDC to condensation promoter is 1-2: 1.
7. The method of claim 1, wherein the surface-acidized porous material catalyst is prepared by the following steps: soaking porous silica or zeolite molecular sieve particle catalyst with particle size of 0.5-2mm in acetic acid aqueous solution with acetic acid content not less than 50% by volume at room temperature for 6-12h, and heating and refluxing for 1-2 h; and filtering after the reflux is finished, and drying in vacuum to obtain acidified catalyst particles.
8. The process of claim 7 wherein the catalyst is present in an amount of from 10 to 50wt% of the solution.
9. A cyclodextrin grafted chitosan complex obtained by the process of any one of claims 1 to 8.
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| CN114702682A (en) * | 2022-04-24 | 2022-07-05 | 齐鲁工业大学 | Preparation method of bifunctional dextrin with high embedding rate and fast absorption |
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