CN108030926B - Salen-type manganese complex-chitosan composite material with high SOD enzyme activity and preparation method thereof - Google Patents
Salen-type manganese complex-chitosan composite material with high SOD enzyme activity and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Salen-type manganese complex-chitosan composite material with high SOD enzyme activity and a preparation method thereof, wherein the Salen-type complex is a complex formed by a product obtained by condensing 2, 6-diformylphenol and ethylenediamine and manganese ions, and is formed by combining aldehyde groups in the Salen-type complex with amino groups on chitosan through C ═ N bonds. The Salen-type manganese complex with high SOD activity is combined with chitosan by a covalent bond, so that active sites are uniformly dispersed on a chitosan carrier, and SOD activity detection and reproducibility experiments show that the composite material has the characteristics of high stability, good activity and good biocompatibility, and is expected to be applied to related application fields related to removal of superoxide anion free radicals.
Description
Technical Field
The invention relates to a superoxide dismutase (SOD) simulant, in particular to a preparation method of an SOD simulant with Salen type manganese complex which takes chitosan as a carrier as an active site.
Background
Superoxide dismutase is an important antioxidant enzyme in a biological system, can convert superoxide anion free radicals in a biological body into hydrogen peroxide and water, and can be used for treating various diseases in medicine. Because natural SOD enzyme has the problems of difficult extraction and storage, difficult permeation of cell membranes due to large molecular weight and the like, the use of the natural SOD enzyme is limited, and related treatment is generally carried out by replacing the natural SOD enzyme with a mimic with SOD activity. In order to overcome the inherent defects of small molecule mimics, such as poor recycling rate, difficult recycling, toxicity caused by the interaction with macromolecules in organisms and the like, the study of the mimics has been shifted from small molecules to systematic simulation combining the macromolecule environment and an active center: such as simulation study of SOD using nanoparticles, polymers and natural materials as carriers. However, the nano particles have poor dispersibility, are uneven and are easy to agglomerate; the synthetic polymer has a plurality of problems in degradation rate, toxicity and discharge of degraded products, and natural materials which have good biocompatibility and are biodegradable and the degraded products are nontoxic, such as carboxymethyl cellulose and chitosan, attract attention. Due to its injectability, good permeability, high water content and mechanical properties similar to those of tissue, it is the material of choice. The Salen-type manganese complex is a micromolecular complex which is proved to have high SOD activity, the Salen-type manganese complex modified chitosan composite material is synthesized by reacting amino on chitosan with aldehyde group in Salen-type manganese complex molecules, and SOD activity tests show that the material not only has high SOD activity, but also has the characteristics of recycling, good stability and biocompatibility.
Disclosure of Invention
Based on the defects of the prior art, the invention solves the technical problem that small molecules with high active SOD enzyme activity are combined with chitosan gel through covalent bonds to form an organic-inorganic hybrid material with SOD active sites and stable performance.
In order to solve the technical problems, the invention provides a preparation method of a Salen-type manganese complex-chitosan composite material with high SOD enzyme activity, which comprises the following steps:
step one, preparing chitosan gel: dissolving chitosan with the deacetylation degree of 95% in an acetic acid solution, mixing with a sodium tripolyphosphate solution after stabilization, violently stirring to form ivory white suspension, standing, performing centrifugal separation, and washing with ultrapure water to obtain a product, namely the chitosan gel;
step two, preparing the Salen type manganese complex modified chitosan composite material: stirring and dissolving the Salen-Mn complex in anhydrous DMF to obtain a mixed solution A, taking wet chitosan gel, ultrasonically dispersing the wet chitosan gel in the anhydrous DMF to obtain a mixed solution B, pouring the mixed solution B into the mixed solution A, stirring and reacting at room temperature, centrifugally separating gel precipitate, washing the flocculent gel precipitate with water and ethanol for 4-6 times at intervals of more than 1.5 hours each time, and soaking the gel precipitate in the ethanol; and after washing, centrifugally separating, drying for more than 24 hours at 40-50 ℃ in vacuum, and carefully grinding the obtained yellow-green solid to obtain the Salen-type manganese complex-chitosan composite material with high SOD enzyme activity. The synthetic route diagram, the photoelectron spectrum, the infrared spectrum and the scanning electron microscope diagram are respectively shown in the figures 1-4.
Preferably, the preparation method of the Salen-type manganese complex-chitosan composite material with high SOD enzyme activity provided by the invention further comprises part or all of the following technical characteristics:
as an improvement of the technical scheme, in the first step, the ratio of the deacetylation degree chitosan to the acetic acid solution to the sodium tripolyphosphate solution is 1.2-1.8 g: 500 mL: 450-600 mL; the deacetylation degree chitosan is 95% deacetylation degree chitosan; the solubility of the acetic acid solution is 1% m/v; the solubility of the sodium tripolyphosphate solution is 0.5mg/mL, and in the step one, the ratio of the deacetylation degree chitosan to the acetic acid solution to the sodium tripolyphosphate solution is 1.2-1.8 g: 500 mL: 450-600 mL; the deacetylation degree chitosan is 95% deacetylation degree chitosan; the solubility of the acetic acid solution is 1% m/v; the solubility of the sodium tripolyphosphate solution is 0.5 mg/mL. The specific preparation method is that 1.2-1.8g of chitosan with 95% deacetylation degree is dissolved in 500mL of 1% (m/v) acetic acid solution, stirred until the chitosan is completely dissolved, and then kept stand for one hour to stabilize the chitosan. Then pumping the chitosan solution into 450-600mL of 0.5mg/mL TPP (sodium tripolyphosphate) solution at the speed of 100 mL/min through a peristaltic pump.
As an improvement of the technical scheme, in the first step, the standing time is 12-36 hours.
As an improvement of the technical scheme, the chitosan gel obtained in the first step is stored in water for later use.
As an improvement of the technical scheme, in the second step, the Salen type complex is obtained by reacting the Salen type ligand with 2, 6-diformylphenol and ethylenediamine in a molar ratio of 2-2.5:1 in an ethanol solvent. The preparation method of the Salen type ligand comprises the steps of dissolving 2-2.5mmol of 2, 6-diformylphenol in 20-30mL of ethanol solution, stirring for about 1 hour, dropwise adding a mixed solution of ethylenediamine (1-1.2mmol) and 10-15mL of ethanol, continuing stirring for 2 hours after dropwise adding to generate yellow precipitates, filtering, washing with ethanol, and drying to obtain the Salen type ligand. Taking a Salen type ligand as a raw material to react with manganese acetate in an ethanol solution according to the molar ratio of 1:1-1.2, washing the generated precipitate with ethanol, and drying to obtain the Salen type complex.
As an improvement of the technical scheme, in the second step, the ratio of the Salen-Mn complex to the anhydrous DMF used for preparing the mixed solution A is 0.09-0.2 g: 35-50 mL:
as an improvement of the above technical scheme, in the second step, the ratio of the wet chitosan gel and the anhydrous DMF used in preparing the mixed solution B is 0.4-0.6 g: 20-30 mL.
As an improvement of the technical scheme, in the second step, the reaction is carried out for 12 to 48 hours under stirring at room temperature; the centrifugation conditions for centrifuging the gel precipitate were 8000rpm, 15 min.
The Salen-type manganese complex-chitosan composite material with high SOD enzyme activity is prepared by any method.
Detection of SOD activity of Chitosan-DOTA-Mn (II) by using tetrazolium blue photoluminescence method
Riboflavin is sensitive to light, and under the action of methionine, the irradiated riboflavin can be reduced to produce O2 -.And oxygen. Nitrotetrazolium blue chloride (NBT) as an index substance can react with O2 -.React to obtainFormazan that had reached blue color was measured to have a wavelength of 560nm when its absorbance was maximized. When a catalyst having SOD enzyme activity is added to the reaction system, O2 -.Is reduced into oxygen and hydrogen peroxide under the catalytic action of the catalyst, so that the generation of formazan is inhibited, and the absorbance at 560nm is obviously reduced. Therefore, the darker the blue color of the reaction solution, the lower the superoxide dismutase activity. Wherein the SOD activity unit is an enzyme activity unit (IC50) based on the amount of enzyme required to inhibit NBT photoreduction by 50%. In order to reduce the systematic error in the test, a blank experiment was carried out, and the measured values were the average of three measurements.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the Salen-Mn-Chitosan composite material (Salen type manganese complex-Chitosan composite material) synthesized by the method has good biocompatibility and can be applied to the related field related to removal of super-anion free radicals.
The Salen type complex is a complex formed by a product obtained by condensing 2, 6-diformylphenol and ethylenediamine and manganese ions, and is formed by combining aldehyde groups in the Salen type complex and amino groups on chitosan through C ═ N bonds. The Salen-type manganese complex with high SOD activity is combined with chitosan by a covalent bond, so that active sites are uniformly dispersed on a chitosan carrier, and SOD activity detection and reproducibility experiments show that the composite material has the characteristics of high stability, good activity and good biocompatibility, and is expected to be applied to related application fields related to removal of superoxide anion free radicals.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a scheme for the synthesis of the Salen-type manganese complex modified chitosan of the present invention;
FIG. 2 is an XPS spectrum of a Salen-Mn-Chitosan composite of the present invention;
FIG. 3 is an infrared spectrum of FTIR of Salen-Mn-Chitosan ligand (L1) of the present invention;
FIG. 4 is a drawing of a dried and ground chitosan gel of the present invention (a) dried and ground Salen-Mn-Chitosan (b);
FIG. 5 is a SOD assay curve of Salen-Mn-Chitosan of the present invention.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example 1
The synthetic route of the invention is as follows: the complex is formed by firstly condensing 2, 6-diformylphenol and ethylenediamine, forming a complex by manganese ions, and then combining aldehyde groups in the complex with amino groups on chitosan by C ═ N bonds. The specific synthetic route is as follows:
1) preparation of chitosan gel
1.5g of chitosan with a degree of deacetylation of 95% was dissolved in 500mL of a 1% (m/v) acetic acid solution, stirred until completely dissolved, and then allowed to stand for one hour to stabilize it. The chitosan solution was then pumped via a peristaltic pump at 100 mL/min into 500mL of a 0.5mg/mL TPP (sodium tripolyphosphate) solution and vigorously stirred magnetically. And the pH was adjusted to 4 with 10% (m/v) acetic acid solution. After completion of the dropwise addition, vigorous stirring was continued for 1 hour, and the obtained ivory white suspension was allowed to stand for 24 hours, separated by high-speed centrifugation (9000rpm, 15min), washed 5 times with ultrapure water, and stored in water for use.
2) Preparation of Salen-type manganese complex modified Chitosan (Salen-Mn-Chitosan) composite material
0.118g of L1-Mn (II) complex was weighed out and dissolved in 30mL of anhydrous DMF by magnetic stirring, 0.5g of wet chitosan gel was weighed out and dispersed in 20mL of anhydrous DMF by ultrasonic dispersion, and the resulting suspension was poured into L1-Mn (II) solution and reacted at room temperature for 24 hours. After the reaction is finished, the gel precipitate is separated by high-speed centrifugation (8000rpm, 15min), the flocculent gel precipitate is washed by water and ethanol for at least 5 times, each washing interval is at least 2 hours, and the gel precipitate is soaked in ethanol. After washing, centrifugal separation, vacuum drying at 40 deg.c for 24 hr, and grinding the yellow-green solid.
3) SOD Activity detection and evaluation
Firstly, weighing a certain amount of Cu/Zn-MNPs to be added into 8mL of PBS buffer solution, wherein the concentration of the Cu/Zn-MNPs is 0.05 mol.L-1Methionine, 1.16X 10-3mol L-1NBT,8.50×10-5mol·L-1Riboflavin and 2.55X 10-6 mol. L-1EDTA. EDTA was added to the reaction solution to remove the interference of trace metal ions on the experimental results. Before the reaction, air was introduced into the reaction solution and the mixture was stirred in the dark for 5 minutes. Then the reaction was carried out for 10 minutes under light. And measuring the absorbance of the reaction solution at 560nm before (Aa) and after (Ab) illumination by an ultraviolet-visible spectrometer. As shown in FIG. 5, which calculates the inhibition ratio according to the formula (2-1) and plots the inhibition ratio against the sample concentration, it is understood from FIG. 5 that the IC50 of Salen-Mn-Chitosan is 0.0025 mg/mL.
4) Salen-Mn-Chitosan stability evaluation
Since Mn (II) ions themselves have strong SOD activity, the following test was conducted in order to eliminate the influence of free manganese ions possibly existing in the test on the results. Respectively taking 2mg of composite material Salen-Mn-Chitosan, dispersing the composite material Salen-Mn-Chitosan in 10mL of PBS solution by ultrasonic wave for 45s, standing the obtained suspension for 24 hours, then centrifuging the suspension at 9000rpm for 15min for three times in total, and taking the obtained supernatant as 0.2mg/mL solution. The supernatant was carefully removed, diluted to 20g/mL, 10g/mL and 1g/mL, and tested for SOD activity as described above, and no SOD activity was detected. It can be shown that the composite material has no free metal ions, and the SOD activity of the composite material is derived from the composite material.
The chitosan gel has good biocompatibility, can stably exist in a solution after being bonded with an active component Salen-Mn, has high SOD activity, and is expected to be applied to clinical medicine, medicaments and related application fields related to the problem of removing superoxide anion free radicals.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (9)
1. A preparation method of a Salen-type manganese complex-chitosan composite material with high SOD enzyme activity is characterized by comprising the following steps:
step one, preparing chitosan gel: dissolving chitosan with deacetylation degree in acetic acid solution, mixing with sodium tripolyphosphate solution after stabilization, violently stirring to form ivory white suspension, standing, centrifugally separating, and washing with ultrapure water to obtain the chitosan gel;
step two, preparing the Salen type manganese complex modified chitosan composite material: stirring and dissolving the Salen-Mn complex in anhydrous DMF to obtain a mixed solution A, taking wet chitosan gel, ultrasonically dispersing the wet chitosan gel in the anhydrous DMF to obtain a mixed solution B, pouring the mixed solution B into the mixed solution A, stirring and reacting at room temperature, centrifugally separating gel precipitate, washing the flocculent gel precipitate with water and ethanol for 4-6 times at an interval of more than 1.5 hours each time, and soaking the gel precipitate in the ethanol; after washing, centrifugally separating, drying for more than 24 hours in vacuum at 40-50 ℃, and carefully grinding the obtained yellow-green solid to obtain the Salen-type manganese complex-chitosan composite material with high SOD enzyme activity;
the Salen-type manganese complex is a complex formed by a product obtained by condensing 2, 6-diformylphenol and ethylenediamine and manganese ions, and is formed by combining aldehyde groups in the Salen-type manganese complex and amino groups on chitosan through a C = N bond.
2. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: in the first step, the ratio of deacetylation degree chitosan to acetic acid solution to sodium tripolyphosphate solution is 1.2-1.8 g: 500 mL: 450-600 mL; the deacetylation degree chitosan is 95% deacetylation degree chitosan; the concentration of the acetic acid solution is 1% m/v; the concentration of the sodium tripolyphosphate solution is 0.5 mg/mL.
3. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: in the first step, the standing time is 12-36 hours.
4. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: and (3) storing the chitosan gel obtained in the first step in water for later use.
5. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: in the second step, the Salen type complex is obtained by reacting 2, 6-diformylphenol and ethylenediamine in a molar ratio of 2.0-3.0:1 in an ethanol solvent at room temperature to obtain a Salen ligand, washing and drying the Salen ligand, then reacting the Salen ligand with manganese acetate in an ethanol solution in a molar ratio of 1:1-1.2, and washing and drying the generated precipitate with ethanol to obtain the Salen type complex.
6. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: in the second step, the ratio of the Salen-Mn complex to the anhydrous DMF used in the preparation of the mixed solution A is 0.09-0.2 g: 35-50 mL.
7. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: in the second step, the ratio of the wet chitosan gel to the anhydrous DMF used in the preparation of the mixed solution B is 0.4-0.6 g: 20-30 mL.
8. The method for preparing the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity as claimed in claim 1, wherein: in the second step, stirring and reacting at room temperature for 12-48 hours; the centrifugation conditions for centrifuging the gel precipitate were 8000rpm, 15 min.
9. A Salen-type manganese complex-chitosan composite material with high SOD enzyme activity is characterized in that: the Salen-type manganese complex-chitosan composite material having high SOD enzyme activity is prepared by the method of any one of claims 1 to 8.
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