CN108030926A - A kind of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity and preparation method thereof - Google Patents
A kind of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity and preparation method thereof Download PDFInfo
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- CN108030926A CN108030926A CN201711352389.6A CN201711352389A CN108030926A CN 108030926 A CN108030926 A CN 108030926A CN 201711352389 A CN201711352389 A CN 201711352389A CN 108030926 A CN108030926 A CN 108030926A
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- chitosan
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- enzyme activity
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/555—Heterocyclic compounds containing heavy metals, e.g. hemin, hematin, melarsoprol
Abstract
The invention discloses a kind of Salen type manganese complex Chitosan Composites with high SOD enzyme activity and preparation method thereof; the Salen type complexs are 2; the complex that 6 diformyl phenol and the product of ethylenediamine condensation are formed with manganese ion, the complex are combined into by the amino on the aldehyde radical and chitosan in Salen type complexs with C=N keys.The present invention is by the Salen types manganese complex with high SOD activity and chitosan with Covalent bonding together, avtive spot is set to be dispersed on chitin carrier, SOD Activity determinations and reappearance experiment show that the composite material has stability height, activity is good, the characteristics of good biocompatibility, be expected to be applied in the related application field for being related to removing ultra-oxygen anion free radical.
Description
Technical field
The present invention relates to the analogies of superoxide dismutase (SOD) a kind of, and in particular to one kind is using chitosan as carrier
Salen types manganese complex for avtive spot SOD analogies preparation.
Background technology
Superoxide dismutase is a kind of important antioxidase in biosystem, can be by the superoxide anion in organism
Radical conversion is hydrogen peroxide and water, and the antioxidant with SOD medically can be used for the treatment of a variety of diseases.By
Its use, general apparatus are limited the problems such as natural SOD enzymes are not easy greatly in the presence of extraction, storage difficulty, molecular weight and pass through cell membrane
The analogies for having SOD activity replace natural SOD enzymes into related treatment.The defects of in order to overcome small molecule mimetics intrinsic, such as
Recycling rate of waterused is poor, it is difficult to which the problems such as recycling, with the effect of biological internal macromolecular it being made to produce toxicity, analogies are ground
Study carefully the system simulation for turning to from small molecule and being combined with macromolecular environment with activated centre：Such as with nano particle, polymer and
Natural material is the analog study of the SOD of carrier.But nano particle is there are bad dispersibility, uneven easily to reunite；The polymerization of synthesis
The thing toxicity of product and discharge after degradation rate, degraded is and good biocompatibility, biodegradable and drop there are problems
Solution product nontoxic natural material such as carboxymethyl cellulose, chitosan cause the concern of people.Because of its syringeability, good infiltration
Property, water content is high and the mechanical performance similar with tissue and become preferred material.Salen type manganese complexes are the tools to be proved to
There is the small molecule partner of high SOD activity, the present invention is by the amino on chitosan and Salen type manganese complex molecules
Aldehyde radical reaction synthesized Salen types manganese complex modification Chitosan Composites, show that the material removes through SOD active testings
It is outer with high SOD activity, also have that reusable edible, stability is good and biocompatibility feature concurrently.
The content of the invention
Based on above the deficiencies in the prior art, technical problem solved by the invention is by with high activity SOD enzyme activity
Small molecule and chitosan gel rubber by Covalent bonding together, it is miscellaneous to form the organic-inorganic stablized with SOD avtive spots and performance
Change material, which adds the catalytic active center in molecule on chitosan gel rubber, reaches and improves its bio-compatible and enzyme
The dual purpose of activity.
In order to solve the above technical problem, the present invention provides a kind of Salen types manganese cooperation with high SOD enzyme activity
The preparation method of thing-Chitosan Composites, comprises the following steps：
Step 1: prepared by chitosan gel rubber：95% deacetylation chitosan is dissolved in acetic acid solution, stablize after with trimerization
Sodium radio-phosphate,P-32 solution mixes, and is vigorously stirred, forms ivory white suspension, stands, and centrifuges, and be with milli-Q water, product
For the chitosan gel rubber；
Step 2: the preparation of Salen types manganese complex modification Chitosan Composites：Salen-Mn complexs are stirred
It is dissolved in anhydrous DMF and obtains mixed liquor A, separately takes the chitosan gel rubber of moistening, ultrasonic disperse obtains mixed liquid B in anhydrous DMF,
Mixed liquid B is poured into mixed liquor A, reaction is stirred at room temperature, gel precipitation is centrifuged, by the cotton-shaped gel precipitation water of gained
Washed 4-6 times with ethanol, each washroom when at least 1.5 is small more than, and gel precipitation is soaked in ethanol；Wash
Cheng Hou, centrifuges, when 40-50 DEG C of vacuum drying 24 is small more than, gained greenish yellow solid is carefully ground, and is described to have
Salen types manganese complex-Chitosan Composites of high SOD enzyme activity.Its synthetic route chart, photoelectron spectroscopy, infrared figure
Spectrum and scanning electron microscope (SEM) photograph are shown in Fig. 1-4 respectively.
As the preferred of above-mentioned technical proposal, the Salen types manganese provided by the invention with high SOD enzyme activity coordinates
The preparation method of thing-Chitosan Composites further comprises the part or all of of following technical characteristic：
As the improvement of above-mentioned technical proposal, in the step 1, deacetylation chitosan, acetic acid solution and tripolyphosphate
The ratio of sodium solution is 1.2-1.8g：500mL：450-600 mL；The deacetylation chitosan gathers for 95% deacetylation shell
Sugar；The solubility of the acetic acid solution is 1%m/v；The solubility of the sodium tripolyphosphate solution is in step 1 described in 0.5mg/mL,
The ratio of deacetylation chitosan, acetic acid solution and sodium tripolyphosphate solution is 1.2- 1.8g：500mL：450-600mL；It is described
Deacetylation chitosan is 95% deacetylation chitosan；The solubility of the acetic acid solution is 1%m/v；The sodium tripolyphosphate
The solubility of solution is 0.5mg/mL.Specific collocation method is as follows, and 95% deacetylation chitosans of 1.2-1.8g are dissolved in
In 500mL 1% (m/v) acetic acid solution, stirring stands one hour to after being completely dissolved and makes it stable.By by peristaltic pump with
Chitosan solution is pumped into 450-600mL 0.5mg/mL TPP (sodium tripolyphosphate) solution by 100mL/ points of speed to be formed.
As the improvement of above-mentioned technical proposal, in the step 1, when time of repose is 12-36 small.
As the improvement of above-mentioned technical proposal, the chitosan gel rubber obtained by the step 1 preserves spare in water.
As the improvement of above-mentioned technical proposal, in the step 2, Salen type complexs be by Salen types ligand and 2,
6- diformyls phenol and ethylenediamine molar ratio are 2-2.5:1 reacts in alcohol solvent and obtains.The preparation tool of Salen type ligands
Body method is that 2,6- diformyl phenol 2-2.5mmol is dissolved in 20-30mL ethanol solutions, when stir about 1 is small after, be added dropwise
The mixed liquor of ethylenediamine (1-1.2mmol) and ethanol 10-15mL, continue after dripping off stirring 2 it is small when, produce yellow mercury oxide, filtering
It is dry after being washed with ethanol, up to Salen type ligands.Using Salen types ligand as raw material and manganese acetate in molar ratio 1:1-1.2
Reacted in ethanol solution, the precipitation of generation washed with ethanol, it is dry after up to Salen type complexs.
As the improvement of above-mentioned technical proposal, in the step 2, the Salen-Mn complexs used during mixed liquor A are prepared
It is 0.09-0.2g with anhydrous DMF ratio：35-50mL：
As the improvement of above-mentioned technical proposal, in the step 2, chitosan used during mixed liquid B and moistening is prepared
The ratio of gel and anhydrous DMF is 0.4-0.6g：20-30 mL.
As the improvement of above-mentioned technical proposal, in the step 2, be stirred at room temperature reaction 12- 48 it is small when；Centrifuge solidifying
The centrifugal condition of glue precipitation is 8000rpm, 15min.
A kind of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity, described having are high
Salen types manganese complex-Chitosan Composites of SOD enzyme activity are prepared by the preceding any means.
Utilize the SOD activity of tetrazole indigo plant photoluminescence method detection Chitosan-DOTA-Mn (II)
Riboflavin is very sensitive to light, and under methionine effect, the riboflavin through illumination can be reduced and produce O2 -.And oxygen
Gas.Nitroblue tetrazolium chloride (NBT) is used as index substance energy and O2 -.Reaction obtains the first a ceremonial jade-ladle, used in libation of blueness, its suction is understood by measurement
Light value wavelength corresponding when maximum is 560nm.When being added in reaction system containing the catalyst with SOD enzyme activity, O2 -.
Oxygen and hydrogen peroxide are reduced under its catalytic action, so as to inhibit the generation of first a ceremonial jade-ladle, used in libation so that its extinction at 560nm
Value is decreased obviously.Therefore reaction solution blueness is deeper, illustrates that superoxide dismutase activity is lower.Wherein SOD active units are to press down
Enzyme amount needed for NBT photo-reductions 50% processed is as an enzyme activity unit (IC50).In testing to reduce systematic error, carry out
Blank assay, institute's measured value are the average value measured three times.
Compared with prior art, technical scheme has the advantages that：The Salen- synthesized in the present invention
Mn-Chitosan composite materials (Salen types manganese complex-Chitosan Composites) have good biocompatibility, can be
It is related in the association area for removing super radical anion and is applied.
Salen types complex of the present invention is 2,6- diformyls phenol and the product and manganese ion of ethylenediamine condensation
The complex of formation, the complex by the amino on the aldehyde radical and chitosan in Salen type complexs with C=N be bonded close and
Into.Salen types manganese complex with high SOD activity and chitosan with Covalent bonding together, are made avtive spot equal by the present invention
Even to be scattered on chitin carrier, SOD Activity determinations and reappearance experiment show that the composite material has stability height, activity
Well, the characteristics of good biocompatibility, it is expected to be applied in the related application field for being related to removing ultra-oxygen anion free radical.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the present invention can
Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, will simply it be situated between to the attached drawing of embodiment below
Continue.
Fig. 1 is the synthetic route of the chitosan of Salen- types manganese complex modification of the present invention；
Fig. 2 is the XPS collection of illustrative plates of Salen-Mn-Chitosan composite materials of the present invention；
Fig. 3 is the infrared spectrogram of its ligand (L1) of FTIR of Salen-Mn-Chitosan of the present invention；
Fig. 4 is present invention drying and chitosan gel rubber (a) drying ground and the Salen-Mn-Chitosan ground
(b)；
Fig. 5 is the SOD measure curves of Salen-Mn-Chitosan of the present invention.
Embodiment
The following detailed description of the present invention embodiment, its as part of this specification, by embodiment come
Illustrate the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Embodiment 1
The synthetic route of the present invention：The present invention first with 2,6- diformyls phenol and product and the manganese of ethylenediamine condensation from
The complex that son is formed, is then combined into the amino on the aldehyde radical and chitosan in the complex with C=N keys again.Specifically
Synthetic route is as follows：
1) prepared by chitosan gel rubber
95% deacetylation chitosans of 1.5g are dissolved in 500mL 1% (m/v) acetic acid solution, are stirred to after being completely dissolved
One hour is stood to make it stable.Chitosan solution is pumped into by 500mL 0.5mg/ with 100mL/ points of speed by by peristaltic pump
In mL TPP (sodium tripolyphosphate) solution, and vigorous magnetic stirs.And adjust pH to 4 with 10% (m/v) acetic acid solution.Drop
Continue to be vigorously stirred after adding into 1 it is small when, the ivory white suspension of gained stand 24 it is small when after, via high speed centrifugation (9000rpm,
15min) separate, and it is spare in water with milli-Q water 5 times, preservation.
2) preparation of Salen types manganese complex modification chitosan (Salen-Mn-Chitosan) composite material
Weigh L1-Mn (II) complex 0.118g magnetic agitations to be dissolved in 30mL anhydrous DMFs, the shell for separately weighing moistening gathers
Sugared gel 0.5g, ultrasonic disperse pour into gained suspension in L1-Mn (II) solution, room temperature is anti-in 20mL anhydrous DMFs
Answer 24 it is small when.After reaction, be centrifuged at a high speed gel precipitation (8000rpm, 15min), the cotton-shaped gel precipitation water of gained
Washed at least 5 times with ethanol, gel precipitation when at least 2 is small and is soaked in ethanol by each washroom.Washing is completed
Afterwards, centrifuge, when 40 DEG C of vacuum drying 24 are small, gained greenish yellow solid is carefully ground, spare.
3) SOD Activity determinations and evaluation
A certain amount of Cu/Zn-MNPs is weighed first to be added in the PBS buffer solutions of 8mL, including 0.05molL-1Egg
Propylhomoserin, 1.16 × 10-3mol L-1NBT,8.50×10-5 mol·L-1Riboflavin and 2.55 × 10-6molL-1EDTA.Instead
It is the interference in order to remove trace metal ion to experimental result to answer and EDTA is added in liquid.Before starting the reaction, first to reaction solution
In be passed through air, and stirred 5 minutes under dark condition.Reacted 10 minutes under illumination condition afterwards.And use ultraviolet-visible
Spectrometer measurement is before illumination after (Aa) and illumination (Ab), absorbance of the reaction solution at 560nm.Calculated and pressed down according to formula (2-1)
Rate processed is simultaneously drawn shown in the curve map 5 between sample concentration and inhibiting rate, as shown in Figure 5 the IC50 of Salen- Mn-Chitosan
For 0.0025mg/mL.
4) Salen-Mn-Chitosan estimation of stability
Because Mn (II) ion inherently has very strong SOD activity, in order to exclude in experiment free manganese that may be present from
Son impacts result, is tested as follows.2mg composite material Salen-Mn-Chitosan are taken respectively, by its ultrasound 45s
It is scattered in the PBS solution of 10mL, when gained suspension standing 24 is small, then 9000rpm centrifuges 15min and amounts to three times, institute
Obtain supernatant and be considered as 0.2mg/mL solution.Careful taking-up supernatant, is diluted to 20g/mL, 10g/mL and 1g/mL, according to
Previously described method carries out SOD active testings to it, does not as a result detect SOD activity.Do not swum in explainable composite material
From metal ion, the SOD activity of composite material derives from composite material in itself.
Since chitosan gel rubber has good biocompatibility, and in solution after being bonded with active constituent Salen- Mn
In can be stabilized, SOD activity it is very high, be expected in clinical medicine, medicine and be related to and remove ultra-oxygen anion free radical problem
Related application is applied in field.
Each raw material cited by the present invention, and bound, the section value of each raw material of the present invention, and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is the preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
Enclose, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity, its feature
It is, comprises the following steps：
Step 1: prepared by chitosan gel rubber：Deacetylation chitosan is dissolved in acetic acid solution, it is molten with sodium tripolyphosphate after stablizing
Liquid mixes, and is vigorously stirred, forms ivory white suspension, stands, and centrifuges, and is described with milli-Q water, product
Chitosan gel rubber；
Step 2: the preparation of Salen types manganese complex modification Chitosan Composites：The stirring of Salen-Mn complexs is dissolved in nothing
Mixed liquor A is obtained in water DMF, separately takes the chitosan gel rubber of moistening, ultrasonic disperse obtains mixed liquid B in anhydrous DMF, will mix
Liquid B is poured into mixed liquor A, and reaction is stirred at room temperature, and gel precipitation is centrifuged, by the cotton-shaped gel precipitation water of gained and ethanol
Washing 4-6 times, each washroom when at least 1.5 is small more than, and gel precipitation is soaked in ethanol；After the completion of washing,
Centrifuge, when 40-50 DEG C of vacuum drying 24 is small more than, gained greenish yellow solid is carefully ground, be it is described have it is high
Salen types manganese complex-Chitosan Composites of SOD enzyme activity.
2. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：In the step 1, the ratio of deacetylation chitosan, acetic acid solution and sodium tripolyphosphate solution
For 1.2-1.8g：500 mL：450-600mL；The deacetylation chitosan is 95% deacetylation chitosan；The acetic acid is molten
The solubility of liquid is 1%m/v；The solubility of the sodium tripolyphosphate solution is 0.5mg/mL.
3. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：In the step 1, when time of repose is 12-36 small.
4. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：Chitosan gel rubber obtained by the step 1 preserves spare in water.
5. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：In the step 2, Salen type complexs are 2,6- diformyls phenol and ethylenediamine molar ratio
For 2.0-3.0:1 in alcohol solvent room temperature reaction obtain Salen ligands, particularly after the washed drying of Salen ligands again
With manganese acetate in molar ratio 1:1-1.2 reacts in ethanol solution, the precipitation of generation washed with ethanol, it is dry after up to Salen
Type complex.
6. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：In the step 2, the Salen-Mn complexs used during mixed liquor A and anhydrous DMF ratio are prepared
For 0.09-0.2g：35-50mL.
7. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：In the step 2, chitosan gel rubber and anhydrous DMF used during mixed liquid B and moistening are prepared
Ratio be 0.4-0.6g：20-30mL.
8. the system of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity as claimed in claim 1
Preparation Method, it is characterised in that：In the step 2, be stirred at room temperature reaction 12-48 it is small when；Centrifuge the centrifugation bar of gel precipitation
Part is 8000rpm, 15min.
A kind of 9. Salen types manganese complex-Chitosan Composites with high SOD enzyme activity, it is characterised in that：Described
Salen types manganese complex-Chitosan Composites with high SOD enzyme activity are as the method system described in claim 1-8
It is standby and obtain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108498790A (en) * | 2018-07-04 | 2018-09-07 | 烟台凯多海洋生物研究院有限公司 | It is to wrap up protectant SOD Compositional types cancer rehabilitation agent with chitosan |
| CN109453809A (en) * | 2018-11-22 | 2019-03-12 | 长春工业大学 | A kind of CS-Salen-Mn type composite catalyst and preparation method based on natural polymer chitosan |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108498790A (en) * | 2018-07-04 | 2018-09-07 | 烟台凯多海洋生物研究院有限公司 | It is to wrap up protectant SOD Compositional types cancer rehabilitation agent with chitosan |
| CN109453809A (en) * | 2018-11-22 | 2019-03-12 | 长春工业大学 | A kind of CS-Salen-Mn type composite catalyst and preparation method based on natural polymer chitosan |
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