CN109180963A - A kind of selfreparing supramolecular hydrogel and its preparation method and application - Google Patents
A kind of selfreparing supramolecular hydrogel and its preparation method and application Download PDFInfo
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- CN109180963A CN109180963A CN201810931194.5A CN201810931194A CN109180963A CN 109180963 A CN109180963 A CN 109180963A CN 201810931194 A CN201810931194 A CN 201810931194A CN 109180963 A CN109180963 A CN 109180963A
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The present invention provides a kind of selfreparing supramolecular hydrogels and its preparation method and application, specifically, the supramolecular hydrogel is to be prepared by the following method: L-type guanosine being taken to be dissolved in Klorvess Liquid, it is heated to boiling, after L-type guanosine is completely dissolved, it is cooled to form supramolecular hydrogel in room temperature.The results show, the supramolecular hydrogel provided by the invention being self-assembly of by L-type guanosine not only overcomes the defect of D type guanosine hydrogel, good self-reparing capability and biocompatibility are also shown simultaneously, therefore there is good application prospect in biomedicine field.
Description
Technical field
The present invention relates to a kind of selfreparing supramolecular hydrogels and its preparation method and application.
Background technique
Hydrogel is the hydrophily and not soluble in water and can absorb large quantity of moisture and (usually contain using water as decentralized medium
Water is greater than the 50% of gross mass) macromolecule polymer material with cross-linked structure.Because of the physical crosslinking between polymer chain
It acts on chemical crosslinking without being dissolved in the water, can only be swollen and keep certain shape, meanwhile, also there is good water to seep
Permeability, biocompatibility can reduce adverse reaction as body implant.Thus hydrogel is as excellent bio-medical material
Material is used widely.
2 kinds of water-setting glue gel point: chemical gel and physical gel；Chemical gel (is called molecular gel): gel molecular is logical
It crosses covalent bond to be connected, no thermal reversibility；Physical gel (also known as supermolecular gel): gel molecular by intermolecular force,
Hydrogen bond, electrostatic interaction, pi-pi bond, hydrophobic effect, coordinate bond etc. are connected, and have thermal reversibility.Supermolecular gel has 3 big advantages:
It is invertibity, degradable, multi-functional, so being widely used in biologic medical field.
It is D type, including 2 kinds of purine nucleosides, adenosine and guanosine there are mainly five types of nucleosides in human body, 3
Kind pyrimidine, including cytidine, thymidine, uridine.Wherein D type guanosine has 2 hydrogen bond donors,
2 hydrogen bond receptors, it means that guanosine can not only be combined with other molecules, can be combined with oneself and oneself, with its uniqueness
Structure show big advantage in supramolecular hydrogel field.Since Ivar Bang discovery D type guanylic acid in 1910 can
Since at gel, D type guanosine is just always the research hotspot in supermolecular gel field.But what guanosine was formed
There are two main disadvantages for supermolecular gel: needing very high K+ concentration and be easy to crystallize in a short time to lead to stability very
Difference (in for 24 hours), this just significantly limits its application.
Summary of the invention
The purpose of the present invention is to provide a kind of novel selfreparing macromolecule hydrogels and its preparation method and application.
Present invention firstly provides a kind of selfreparing supramolecular hydrogels, it is to be prepared by the following method: taking L-type bird
Purine nucleosides is dissolved in Klorvess Liquid, is heated to boiling, at room temperature cooling 5 minutes to get supramolecular hydrogel.
Further, the molar ratio of the L-type guanosine and potassium chloride is 0.1~4:1.
Further, the molar ratio of the L-type guanosine and potassium chloride is 0.25~4:1.
Further, the molar ratio of the L-type guanosine and potassium chloride is 4:1.
The present invention also provides the preparation methods of above-mentioned hydrogel, it is the following steps are included: take L-type guanosine to be dissolved in
It in Klorvess Liquid, is heated to boiling, after L-type guanosine is completely dissolved, is cooled to form supramolecular hydrogel in room temperature
Glue.
Further, the molar ratio of the L-type guanosine and potassium chloride is 0.1~4:1.
Further, the molar ratio of the L-type guanosine and potassium chloride is 0.25~4:1.
Further, the molar ratio of the L-type guanosine and potassium chloride is 4:1.
The present invention also provides above-mentioned supramolecular hydrogels to prepare self-repair material, coating material, in sustained release preparation
Purposes.
The results show, the present invention construct a kind of novel supramolecular hydrogel using LG for the first time, and the gel is not only
It overcomes D type guanosine hydrogel and easily crystallizes unstable defect, while also showing good self-reparing capability and life
Object compatibility, therefore be expected to be used for preparing self-repair material, coating material and sustained release preparation, have very in biomedicine field
Good application prospect.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is that the stability of gel compares figure.
Fig. 2 is the surface topography map of gel.
Fig. 3 is the self-reparing capability phenogram of gel.
Fig. 4 is the biocompatibility phenogram of gel, and a indicates that DG forms the K+ range of needs of gel, and it is solidifying that b indicates that LG is formed
The K+ range of needs of glue, c indicate the cytotoxicity of DG, and d indicates the cytotoxicity of LG.
Specific embodiment
The preparation of embodiment 1, subject hydrogel
The L-type guanosine of 2.8mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, the L-type guanosine supramolecular hydrogel (abbreviation LG) of 1.4wt% is cooled into room temperature.
The preparation of embodiment 2, subject hydrogel
The L-type guanosine of 5.6mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, L-type guanosine supramolecular hydrogel (abbreviation LG) is cooled into room temperature.
The preparation of embodiment 3, subject hydrogel
The L-type guanosine of 8.4mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, L-type guanosine supramolecular hydrogel (abbreviation LG) is cooled into room temperature.
The preparation of embodiment 4, subject hydrogel
The L-type guanosine of 11.2mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, L-type guanosine supramolecular hydrogel (abbreviation LG) is cooled into room temperature.
The preparation of embodiment 5, subject hydrogel
The L-type guanosine of 22.4mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, L-type guanosine supramolecular hydrogel (abbreviation LG) is cooled into room temperature.
The preparation of embodiment 6, subject hydrogel
The L-type guanosine of 33.6mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, L-type guanosine supramolecular hydrogel (abbreviation LG) is cooled into room temperature.
The preparation of embodiment 7, subject hydrogel
The L-type guanosine of 44.8mg is dissolved in the KCl solution of the 0.2M of 200 μ l, is heated to 100 DEG C, to L-type bird
After purine nucleosides is completely dissolved, L-type guanosine supramolecular hydrogel (abbreviation LG) is cooled into room temperature.
Illustrate beneficial effects of the present invention below by way of test example.
The nature examination of test example 1, hydrogel
1 detection material
L-type guanosine forms supramolecular hydrogel in embodiment 7
Comparative example 1: the D type guanosine of 44.8mg is dissolved in the 0.2MKCl solution of 200ul, is heated to 100 DEG C of boilings
It rises, after being completely dissolved, in the cooling 5 minutes hydrogels (abbreviation DG) formed to get D type guanosine of room temperature.
2 Detection of Stability
The gel being prepared is placed in vial and is inverted, its stability is visually observed.Testing result is shown in Fig. 1, from Fig. 1
As can be seen that D type guanosine is unstable, just crystallized after 1h.And L-type guanosine of the present invention forms supermolecule
Hydrogel has good stability (> 1 month).
3 show pattern
Hydrogel material to be detected is lyophilized, with the pattern of scanning electron microscopic observation hydrogel.
The surface topography of gel is shown in Fig. 2, figure it is seen that D type and L-type gel are capable of forming porous structure, DG
Laminated structure (see Fig. 2 a, 2c) easily is formed, is easy crystallization；And LG easily forms membrane structure (see Fig. 2 b, 2d), belongs to stable knot
Structure, and be easy to smear, the potential medicaments coating material that is developed into is applied to clinic.
The self-reparing capability of 4LG
The L-type guanosine of 5.6mg is dissolved in the 0.2M KCl solution of 200ul, is heated to 100 DEG C of boilings, completely
After dissolution, methyl blue and thioflavin colour developing is added, it is 5 minutes cooling in room temperature, the performance of its selfreparing is tested after gel-forming.
From figure 3, it can be seen that LG hydrogel has good self-reparing capability, it can be made various shape, can also use
It writes, can also be finally injected directly into PBS solution with dropper, and can completely sucks out.I.e. the present invention is prepared
LG not only there is self-healing property, the stabilization of structure can also be kept under conditions of injection, shows fabulous self-healing properties,
It lays the foundation for clinical research.
The biocompatibility of 5LG
Cells survival rate by detecting oral cavity normal epithelium cell NOK-SI evaluates L-type guanosine hydrogel in body
Outside to the cytotoxicity of normal cell.Well-grown cell is collected respectively, is configured to cell suspension, while it is close to adjust its cell
Degree be inoculated in 96 orifice plates, wait 4~6h cell it is adherent after be added 100 μ l various concentrations gel rubber material (0,0.125,0.25,
0.5、1、2mg·ml-1), 20 μ l MTT are added in 37 DEG C of incubations afterwards for 24 hours, are incubated for 4h, and DMSO (dimethyl sulfoxide) 150 μ l, inspection is added
Survey the absorbance value of 570nm wavelength.Detection gel rubber material is to the toxicity of cell in vitro, and as a result see Fig. 4: L-type bird of the present invention is fast
Purine nucleosides hydrogel has good biocompatibility to the toxicity very little of normal cell NOK-SI cell, however same
Under the conditions of, D type guanosine hydrogel shows biggish toxicity.
To sum up, the present invention constructs a kind of novel supramolecular hydrogel using LG for the first time, which not only overcomes D type
Guanosine hydrogel easily crystallizes unstable defect, while also showing good self-reparing capability and biocompatibility,
Therefore it is expected to be used for preparing self-repair material, coating material and sustained release preparation, before biomedicine field has application very well
Scape.
Claims (9)
1. a kind of selfreparing supramolecular hydrogel, it is characterised in that: it is to be prepared by the following method: taking L-type guanosint
Glycosides is dissolved in Klorvess Liquid, is heated to boiling, and after L-type guanosine is completely dissolved, is cooled to form oversubscription in room temperature
Sub- hydrogel.
2. hydrogel according to claim 1, it is characterised in that: the molar ratio of the L-type guanosine and potassium chloride
For 0.1~4:1.
3. hydrogel according to claim 2, it is characterised in that: the molar ratio of the L-type guanosine and potassium chloride
For 0.25~4:1.
4. hydrogel according to claim 3, it is characterised in that: the molar ratio of the L-type guanosine and potassium chloride
For 4:1.
5. the preparation method of any one of Claims 1 to 4 hydrogel, it is characterised in that: it is the following steps are included: take L-type
Guanosine is dissolved in Klorvess Liquid, is heated to boiling, and after L-type guanosine is completely dissolved, is cooled in room temperature
Form supramolecular hydrogel.
6. preparation method according to claim 5, it is characterised in that: mole of the L-type guanosine and potassium chloride
Than for 0.1~4:1.
7. preparation method according to claim 6, it is characterised in that: mole of the L-type guanosine and potassium chloride
Than for 0.25~4:1.
8. according to preparation method described in right 5, it is characterised in that: the molar ratio of the L-type guanosine and potassium chloride is
4:1.
9. the described in any item supramolecular hydrogels of Claims 1 to 4 are preparing self-repair material, coating material, sustained release preparation
In purposes.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533926A (en) * | 2020-05-18 | 2020-08-14 | 四川大学 | Chiral supramolecular nucleoside hydrogel based on boron ester bond and preparation method and application thereof |
| CN111617311A (en) * | 2020-06-17 | 2020-09-04 | 湖北大学 | Preparation method and application of strong-toughness self-repairing tissue adhesion hydrogel material based on base self-assembly |
| CN111647164A (en) * | 2020-06-23 | 2020-09-11 | 河南工业大学 | Guanosine supramolecular metal organogel/MOF composite material and preparation method and application thereof |
| CN112002562A (en) * | 2020-09-22 | 2020-11-27 | 青岛科技大学 | Preparation of self-healing hydrogel electrolyte with ion channel and application of self-healing hydrogel electrolyte in all-solid-state supercapacitor |
| CN113058076A (en) * | 2021-03-29 | 2021-07-02 | 四川大学 | Supermolecule nucleoside hydrogel and preparation method and application thereof |
| CN115177581A (en) * | 2022-05-11 | 2022-10-14 | 四川大学 | Injectable hydrogel for immunotherapy and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533926A (en) * | 2020-05-18 | 2020-08-14 | 四川大学 | Chiral supramolecular nucleoside hydrogel based on boron ester bond and preparation method and application thereof |
| CN111533926B (en) * | 2020-05-18 | 2022-12-02 | 四川大学 | Chiral supramolecular nucleoside hydrogel based on boron ester bond and preparation method and application thereof |
| CN111617311A (en) * | 2020-06-17 | 2020-09-04 | 湖北大学 | Preparation method and application of strong-toughness self-repairing tissue adhesion hydrogel material based on base self-assembly |
| CN111617311B (en) * | 2020-06-17 | 2022-04-15 | 湖北大学 | Preparation method and application of strong-toughness self-repairing tissue adhesion hydrogel material based on base self-assembly |
| CN111647164A (en) * | 2020-06-23 | 2020-09-11 | 河南工业大学 | Guanosine supramolecular metal organogel/MOF composite material and preparation method and application thereof |
| CN112002562A (en) * | 2020-09-22 | 2020-11-27 | 青岛科技大学 | Preparation of self-healing hydrogel electrolyte with ion channel and application of self-healing hydrogel electrolyte in all-solid-state supercapacitor |
| CN112002562B (en) * | 2020-09-22 | 2022-01-28 | 青岛科技大学 | Preparation of self-healing hydrogel electrolyte with ion channel and application of self-healing hydrogel electrolyte in all-solid-state supercapacitor |
| CN113058076A (en) * | 2021-03-29 | 2021-07-02 | 四川大学 | Supermolecule nucleoside hydrogel and preparation method and application thereof |
| CN113058076B (en) * | 2021-03-29 | 2022-03-11 | 四川大学 | Supermolecule nucleoside hydrogel and preparation method and application thereof |
| CN115177581A (en) * | 2022-05-11 | 2022-10-14 | 四川大学 | Injectable hydrogel for immunotherapy and preparation method and application thereof |
| CN115177581B (en) * | 2022-05-11 | 2023-08-04 | 四川大学 | Injectable hydrogel for immunotherapy and preparation method and application thereof |
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