CN104928741B - How sensitive chitosan gel rubber of brick mud structure and its preparation method and application - Google Patents
How sensitive chitosan gel rubber of brick mud structure and its preparation method and application Download PDFInfo
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- CN104928741B CN104928741B CN201510262241.8A CN201510262241A CN104928741B CN 104928741 B CN104928741 B CN 104928741B CN 201510262241 A CN201510262241 A CN 201510262241A CN 104928741 B CN104928741 B CN 104928741B
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Abstract
The invention discloses a kind of how sensitive chitosan gel rubber of brick mud structure and its preparation method and application.The method in a kind of protein load to inorganic nano material-layered double hydroxide, then with electrochemistry is first mixed co-deposition with chitosan solution, the sandwich construction plural gel that layered double hydroxide and chitosan are alternateed is obtained.Pass through the release to chitosan LDH plural gels insulin in the solution respectively containing different ions, different pH value and the different voltages of application, showing the gel has ion, pH value, the characteristic of electrically susceptible sense, shows that it can carry out accurately can control release by ion, pH value and different voltages to medicine.Reaction condition of the present invention is gentle, to chitosan without destruction, on the one hand the mechanical property of chitosan gel rubber can be improved, electric field response ability of the protein in chitosan gel rubber on the other hand can be greatly improved, the fields such as the controlled release of gene, antibody and medicine are can be applied to.
Description
Technical field
The invention belongs to material science, and in particular to the how sensitive chitosan gel rubber and its system of a kind of brick-mud structure
Preparation Method and application.
Background technology
Chitosan (chitosan) is also known as chitosan, is chitin (chitin) warp being widely present by nature
Cross what deacetylation was obtained, chemical name is β (1-4) -2- aminoglucans.Chitosan is the straight-chain polysaccharide for having amino, raw
Thing compatibility is good, biodegradable, is widely used in the carrier of pharmaceutical grade protein.Responded using the film forming and pH of chitosan
Property, can be in electrode surface in-situ preparation chitosan gel rubber, this special nature of chitosan is used as albumen controlled release chip for it
Carrier provides unique advantage.
Electrode surface generation gel is acted on using the co-deposition of chitosan and protein, electric signal controlled release egg is then used
In vain.The problem of existing is that in release initial stage violent release occurs for protein, and the electric field response performance of gel also needs further raising.
The content of the invention
It is an object of the invention to provide how sensitive chitosan gel rubber of a kind of brick-mud structure and its preparation method and application.
Reaction condition of the present invention is gentle, and preparation process is simple and quick, environment-friendly, to chitosan without destruction.
The technical scheme that the present invention is provided is specific as follows：
A kind of preparation method of the how sensitive chitosan gel rubber of brick-mud structure, comprises the following steps：
(1) under normal temperature, Chitosan powder is added in deionized water, pH value of solution is adjusted to 3 with concentrated hydrochloric acid while stirring,
PH value of solution is adjusted to 5 after chitosan is completely dissolved, then with NaOH solution, continues to stir to solution to become to clarify, then to solution
Middle addition H2O2And NaCl, stir and be completely dissolved to solid, obtain solution A；
(2) layered double hydroxide that flake nano is loaded with protein is added into solution A, is well mixed, obtains
To solution B；
(3) constant current mode of operation is used, adds 0.0015-0.0025A electric current to carry out solution B between anode and negative electrode
The co-deposition of chitosan and the layered double hydroxide for being loaded with protein, then exists the co-deposition product of cathode surface
Dried at 60 DEG C, obtain the sandwich construction plural gel that layered double hydroxide and chitosan are alternateed, i.e. brick-mud knot
The how sensitive chitosan gel rubber of structure.
In described solution A, the concentration of chitosan is 0.01g/mL, H2O2Volume fraction be 0.25%, NaCl quality
Fraction is 0.25%.
The concentration of described NaOH solution is 1mol/L.
Described anode is platinum filament, and described negative electrode is titanium sheet.
The molecular formula of described layered double hydroxide is Mg2Al(OH)6Cl·xH2O。
Described protein is insulin.
The preparation method of the described layered double hydroxide for being loaded with protein, comprises the following steps：By 4 mass
The layered double hydroxide of part and the protein of 1 mass parts are added in the glycine-NaOH cushioning liquid that pH is 8.6,
5h is stirred under normal temperature, with 16000rpm centrifugation 5min, with buffer solution for cleaning twice, freezes and grinds, that is, loaded
There is the layered double hydroxide of protein.
A kind of how sensitive chitosan gel rubber of brick-mud structure, is prepared by above-mentioned preparation method.
The how sensitive chitosan gel rubber of above-mentioned brick-mud structure is in the controlled release field of gene, antibody and medicine
Using.
The preparation principle of the present invention is as follows：
First in a kind of protein load to inorganic nano material-layered double hydroxide (LDHs), then gather with shell
Sugar juice mixing is co-deposited.LDHs is a kind of inorganic laminated nano material, and general structure is [M1-x 2+Mx 3+(OH)2]x+
[Xn- x/n]·mH2O, M are Mg2+, Al3+, Zn2+Deng metal ion, Xn-For under alkalescence condition can stable existence anion.With it is exhausted
Most of negatively charged differences of mineral, its sheet surfaces are positively charged, and interlayer has balance anion.LDHs have it is very strong from
Sub- exchange capacity, good biocompatibility as the cell reservoirs of polypeptide, protein, nucleic acid and gene, and can improve biological point
The stability of son, is a kind of great future " green " carrier material.
The mode of this Organic-inorganic materials hybrid improves electric field response performance and the electric field control of electro-deposition chitosan gel rubber
Ability is released, and LDHs also has response to electric signal, and under electric field action, positively charged nanoscale twins can be in negative pole table
Orientation transition occurs for face, generates sandwich construction.Positively charged flake nano material mixes shape with positively charged glycosaminoglycan
Into uniform solution；Using electrochemical co-deposition pattern, the Organic-inorganic composite gel of multilayer is generated in cathode surface；The gel
With ion, pH value, the characteristic of electrically susceptible sense, the release to containing medicine can be controlled by ion, pH value and different voltages.
The present invention has advantages below and beneficial effect：
(1) reaction condition of the present invention is gentle, and preparation process is simple and quick, to chitosan without destruction；
(2) brick-mud structure of chitosan-LDH plural gels formation of the present invention is similar with the structure of nature shell, a side
Face can improve the mechanical property of chitosan gel rubber, and electric field response of the protein in chitosan gel rubber on the other hand can be greatly improved
Ability；
(3) the Organic-inorganic composite gel has the characteristic of ion, pH, electrically susceptible sense etc., is combined with microelectronics, can
The fields such as the controllable release applied to gene, antibody and medicine, break traditions the mode being passively administered, and realizes their essence
True controlled release.
Brief description of the drawings
Fig. 1 is the ESEM comparison diagram of pure chitosan gel and chitosan-LDH plural gels in embodiment 2；Wherein,
Fig. 1 (A) is the scanning electron microscope (SEM) photograph of pure chitosan gel, and Fig. 1 (B) is the scanning electron microscope (SEM) photograph of chitosan-LDH plural gels.
Fig. 2 is insulin in the cushioning liquid releasing curve diagram containing different anions, different pH value.
Fig. 3 is releasing curve diagram of the insulin under the conditions of added electric field.
Embodiment
Embodiment 1：It is prepared by the layered double hydroxide for being loaded with insulin
(1) layered double hydroxide Mg2Al(OH)6Cl·xH2O preparation：Configuration 80mL contains MgCl2
(24mmol) and AlCl3The solution of (8.0mmol), under conditions of logical nitrogen, is quickly poured into 320mL NaOH within 5s
In (0.15M) solution, completely cut off air stirring 15min.By mixed solution with 9000rpm centrifugation 5min, deionized water is used
Twice of cleaning, then be well mixed with 140mL deionized waters, pour into reactor, react 18h at 100 DEG C in an oven.LDH is tied
After crystalline substance, with 16000rpm centrifugation 5min, freeze, grind into powder, that is, obtain molecular formula for Mg2Al(OH)6Cl·xH2O
Layered double hydroxide.
(2) insulin load：Weigh the sweet ammonia that the ready LDHs and 62.5mg insulin of 0.25g adds 50mL pH8.6
In acid-NaOH cushioning liquid, 5h is stirred under normal temperature, with 16000rpm centrifugation 5min, with buffer solution for cleaning twice, is freezed
And grind, that is, it is loaded with the layered double hydroxide of insulin.
Embodiment 2
1g chitosans are added in 99mL deionized waters, pH value of solution is adjusted to 3 with dense HCl while stirring, treats chitosan
After being completely dissolved, then with 1mol/L NaOH solution regulation pH to 5, obtain the chitosan solution that concentration is 0.01g/mL, Xiang Rong
200uL H are added in liquid2O2With 0.25g NaCl (H2O2The generation of bubble in deposition process can be reduced, NaCl, which can increase solution, to be led
Electrically), stirring obtains solution A to being completely dissolved.
Take 0.15mg to be loaded with the layered double hydroxide of insulin to be added in 15mL solution As, stirring mixes it
Close uniform, obtain solution B.
By the use of platinum filament as anode, the titanium sheet of 4cm × 2cm × 100 μm is negative electrode, using constant current mode of operation, is set
Electric current is 0.0025A, and chitosan and LDH co-deposition are carried out to solution B, and deposition process is carried out 30 minutes.Then by negative electrode table
The co-deposition product in face is dried at 60 DEG C, is obtained the sandwich construction that layered double hydroxide and chitosan alternate and is answered
Gel is closed, the dry state gel finally given is 1 μm or so.The chitosan gel rubber for being not added with LDH simultaneously is deposited under identical condition
30 minutes, it is used as control.
By containing Cl respectively to chitosan-LDH plural gels-、PO4 3-、NO3 -Plasma, pH4,7,9 and application
The release of insulin in 5V, 0V, the solution of -5V voltages, showing the gel has ion, pH value, the characteristic of electrically susceptible sense (such as
Shown in Fig. 2 and Fig. 3), show that it can carry out accurately can control release by ion, pH value and different voltages to medicine.
Dried gel, passes through field emission microscopy observation under the conditions of 60 DEG C, it may be clearly seen which form multi-level
Ordered structure, i.e. brick-mud structure.
Embodiment 3
1g chitosans are added in 99mL deionized waters, pH value of solution is adjusted to 3 with dense HCl while stirring, treats chitosan
After being completely dissolved, then with 1mol/L NaOH solution regulation pH to 5, obtain the chitosan solution that concentration is 0.01g/mL, Xiang Rong
200uL H are added in liquid2O2With 0.25g NaCl, stir to being completely dissolved, obtain solution A.
Take 0.15mg to be loaded with the layered double hydroxide of insulin to be added in 15mL solution As, stirring mixes it
Close uniform, obtain solution B.
By the use of platinum filament as anode, the titanium sheet of 4cm × 2cm × 100 μm is negative electrode, using constant current mode of operation, is set
Electric current is 0.002A, and chitosan and LDH co-deposition are carried out to solution B, and deposition process is carried out 30 minutes.Then by cathode surface
Co-deposition product dried at 60 DEG C, obtain the sandwich construction that layered double hydroxide and chitosan alternate and be combined
Gel, the dry state gel finally given is 0.8 μm or so.The chitosan gel rubber for being not added with LDH simultaneously is deposited under identical condition
30 minutes, it is used as control.
By containing Cl respectively to chitosan-LDH plural gels-、PO4 3-、NO3 -Plasma, pH4,7,9 and application
The release of insulin in 5V, 0V, the solution of -5V voltages, showing the gel has ion, pH value, the characteristic of electrically susceptible sense, table
Bright its can carry out accurately can control release by ion, pH value and different voltages to medicine.Dried under the conditions of 60 DEG C
Gel afterwards, passes through field emission microscopy observation, it may be clearly seen which form multi-level ordered structure, i.e. brick-mud
Structure.
Embodiment 4
1g chitosans are added in 99mL deionized waters, pH value of solution is adjusted to 3 with dense HCl while stirring, treats chitosan
After being completely dissolved, then with 1mol/L NaOH solution regulation pH to 5, obtain the chitosan solution that concentration is 0.01g/mL, Xiang Rong
200uL H are added in liquid2O2With 0.25g NaCl, stir to being completely dissolved, obtain solution A.
Take 0.15mg to be loaded with the layered double hydroxide of insulin to be added in 15mL solution As, stirring mixes it
Close uniform, obtain solution B.
By the use of platinum filament as anode, the titanium sheet of 4cm × 2cm × 100 μm is negative electrode, using constant current mode of operation, is set
Electric current is 0.0015A, and chitosan and LDH co-deposition are carried out to solution B, and deposition process is carried out 30 minutes.Then by negative electrode table
The co-deposition product in face is dried at 60 DEG C, is obtained the sandwich construction that layered double hydroxide and chitosan alternate and is answered
Gel is closed, the dry state gel finally given is 0.5 μm or so.The chitosan gel rubber for being not added with LDH simultaneously sinks under identical condition
Product 30 minutes, is used as control.
By containing Cl respectively to chitosan-LDH plural gels-、PO4 3-、NO3 -Plasma, pH4,7,9 and application
The release of insulin in 5V, 0V, the solution of -5V voltages, showing the gel has ion, pH value, the characteristic of electrically susceptible sense, table
Bright its can carry out accurately can control release by ion, pH value and different voltages to medicine.Dried under the conditions of 60 DEG C
Gel afterwards, passes through field emission microscopy observation, it may be clearly seen which form multi-level ordered structure, i.e. brick-mud
Structure.
Claims (9)
1. the preparation method of the how sensitive chitosan gel rubber of a kind of brick-mud structure, it is characterised in that comprise the following steps：
(1) under normal temperature, Chitosan powder is added in deionized water, pH value of solution is adjusted to 3 with concentrated hydrochloric acid while stirring, treats shell
After glycan is completely dissolved, then with NaOH solution regulation pH value of solution to 5, continues to stir to solution to become to clarify, then add into solution
Enter H2O2And NaCl, stir and be completely dissolved to solid, obtain solution A；
(2) layered double hydroxide that flake nano is loaded with protein is added into solution A, is well mixed, obtains molten
Liquid B；
(3) constant current mode of operation is used, adds 0.0015-0.0025A electric current to carry out shell to solution B between anode and negative electrode and gathers
The co-deposition of sugar and the layered double hydroxide for being loaded with protein, then by the co-deposition product of cathode surface at 60 DEG C
Lower drying, obtains the sandwich construction plural gel that layered double hydroxide and chitosan are alternateed, i.e. brick-mud structure
Many sensitivity chitosan gel rubbers.
2. the preparation method of the how sensitive chitosan gel rubber of brick according to claim 1-mud structure, it is characterised in that：Institute
In the solution A stated, the concentration of chitosan is 0.01g/mL, H2O2Volume fraction be for 0.25%, NaCl mass fraction
0.25%.
3. the preparation method of the how sensitive chitosan gel rubber of brick according to claim 1-mud structure, it is characterised in that：Institute
The concentration for the NaOH solution stated is 1mol/L.
4. the preparation method of the how sensitive chitosan gel rubber of brick according to claim 1-mud structure, it is characterised in that：Institute
The anode stated is platinum filament, and described negative electrode is titanium sheet.
5. the preparation method of the how sensitive chitosan gel rubber of brick according to claim 1-mud structure, it is characterised in that：Institute
The molecular formula for the layered double hydroxide stated is Mg2Al(OH)6Cl·xH2O。
6. the preparation method of the how sensitive chitosan gel rubber of brick according to claim 5-mud structure, it is characterised in that：Institute
The protein stated is insulin.
7. the preparation method of the how sensitive chitosan gel rubber of brick according to claim 6-mud structure, it is characterised in that：Institute
That states is loaded with the preparation method of the layered double hydroxide of protein, comprises the following steps：The stratiform of 4 mass parts is double
Metal hydroxides and the protein of 1 mass parts are added in the glycine-NaOH cushioning liquid that pH is 8.6, are stirred under normal temperature
5h, with 16000rpm centrifugation 5min, with buffer solution for cleaning twice, freezes and grinds, that is, obtain being loaded with protein
Layered double hydroxide.
8. a kind of how sensitive chitosan gel rubber of brick-mud structure, it is characterised in that：As the system described in any one of claim 1~7
Preparation Method is prepared.
9. the how sensitive chitosan gel rubber of brick-mud structure described in claim 8 is in the controlled release of gene, antibody and medicine
Application in field.
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| CN101353379B (en) * | 2008-09-05 | 2011-06-01 | 北京化工大学 | Protein modified biological-inorganic nano composite material and preparation thereof |
| WO2010040047A2 (en) * | 2008-10-02 | 2010-04-08 | University Of Maryland Biotechnology Institute Off. Of Research Admin./Tech.Dev. | Chitosan-coated wires for biosensing |
| FI20095502A0 (en) * | 2009-05-04 | 2009-05-04 | Licentia Oy | New inorganic-bioorganic nanocomposite materials, their preparation and their use |
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Effective date of registration: 20210429 Address after: 430000 Room G002, Block B5, Biological Innovation Park, 666 High-tech Avenue, Donghu New Technology Development Zone, Wuhan City, Hubei Province Patentee after: Aomeibaima (Wuhan) Biotechnology Co.,Ltd. Address before: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Patentee before: WUHAN University |