CN109721744A - A kind of selfreparing anti-bacterial hydrogel based on boric acid ester bond - Google Patents
A kind of selfreparing anti-bacterial hydrogel based on boric acid ester bond Download PDFInfo
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- 241000305071 Enterobacterales Species 0.000 description 1
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Abstract
The invention discloses a kind of selfreparing anti-bacterial hydrogels based on boric acid ester bond.The selfreparing anti-bacterial hydrogel is prepared by PEG derivative with polyvinyl alcohol, and PEG derivative is prepared according to the method included the following steps: PEG-COOH, the boronic acid compounds containing aldehyde radical, the organic amine containing hydroxyl and isonitrile are reacted through Ugi to obtain the final product；PEG-COOH is the polyethylene glycol of both ends carboxy blocking.The present invention is prepared for the polyethyleneglycol derivative (PEG-Ugi) containing boric acid base group and phenol structure by Ugi reaction.After the aqueous solution of PEG-Ugi is mixed with PVA aqueous solution, the two, which is reacted by boric acid base group with the hydroxyl in PVA structure, generates boric acid ester bond, quickly forms hydrogel.Since boric acid ester bond belongs to dynamic chemical key, it is a kind of novel antibiotic property self-healing property hydrogel that phenol structure, which has antibacterial functions, therefore obtained hydrogel with self-reparing capability and has antibiotic property.The method of the present invention prepares hydrogel using the secure and cheap raw material being easy to get, and preparation method is simple, and Gelation Conditions are mild, has preferable application value.
Description
Technical field
The present invention relates to a kind of selfreparing anti-bacterial hydrogels based on boric acid ester bond, belong to Material Field.
Background technique
Selfreparing hydrogel is a kind of novel intelligent material, in multiple necks such as food, biological medicine, agricultural, industrial coating
Domain has huge potential using value, there is certain demand in these fields to the antibiotic property of material, therefore have antibacterial ability
Selfreparing hydrogel have better added value and application prospect.Conventional method prepares anti-bacterial hydrogel mainly for antibacterial
It closes object (small-molecule drug, metal salt/nanoparticle etc.) to be embedded in hydrogel, be realized by the sustained release of antimicrobial compound anti-
Bacterium.However, easily leading to environmental hazard after antimicrobial compound release, antibacterial functions are realized to discharge heavy metallic salt/nano particle
Hydrogel more faces stringent environmental management requirement.Therefore, Development of Novel antibiotic property self-healing property hydrogel has centainly urgent
Property.
Summary of the invention
The object of the present invention is to provide a kind of selfreparing anti-bacterial hydrogel based on boric acid ester bond, the present invention using safety and
Raw material cheap and easy to get prepares hydrogel, and preparation method is simple, and Gelation Conditions are mild, has preferable application value.
Present invention firstly provides a kind of preparation methods of PEG derivative (PEG-Ugi), include the following steps:
PEG-COOH, the boronic acid compounds containing aldehyde radical, the organic amine containing hydroxyl and isonitrile obtain institute through Ugi reaction
State PEG derivative；
The PEG-COOH is the polyethylene glycol of both ends carboxy blocking.
In above-mentioned preparation method, the PEG-COOH is reacted to obtain by acid anhydrides with polyethylene glycol；
The PEG (polyethylene glycol) of different segments is suitable for the present invention, specifically, the molecule of the polyethylene glycol (PEG)
Amount can be 1000~4000, such as PEG1000, PEG2000, PEG3000, PEG4000.
In above-mentioned preparation method, the acid anhydrides can be phthalic anhydride, succinic anhydride or maleic anhydride etc..
In above-mentioned preparation method, the boronic acid compounds containing aldehyde radical can be the phenyl boric acid containing aldehyde radical；Specifically may be used
For 4- aldehyde radical phenyl boric acid.
In above-mentioned preparation method, the organic amine containing hydroxyl can be the phenol containing amino；Concretely 4- ammonia
Base -2- metoxyphenol.
The isonitrile can be isocyanide hexamethylene.
In above-mentioned preparation method, the temperature of the Ugi reaction can be 25~60 DEG C, and the time can be 6~24 hours, such as exist
It is reacted 10 hours under conditions of 60 DEG C；
Methanol can be used as solvent in the Ugi reaction；It is derivative using the PEG is collected after ether precipitating after reaction
Object.
It is the PEG-COOH, the boronic acid compounds containing aldehyde radical, described containing hydroxyl in above-mentioned preparation method
The molar ratio of organic amine and the isonitrile can be 1:1.5~3:1.5~3:2~5, such as 1:3:3:5.
Multifunctional polymer is usually prepared to need through multistep reaction, not only step is various, but also separating-purifying process compared with
For complexity, yield is lower and higher cost.Multi-component reaction is quickly obtained using more than two reaction substrates by single step reaction
Multi-functional compounds, the step of having significantly simplified synthesis multi-functional compounds and cost.The present invention is reacted using Ugi, by boric acid
Group is connected to PEG end group by single step reaction with phenol structure, is quickly prepared for multi-functional PEG derivative (PEG-Ugi).
On the basis of PEG derivative (PEG-Ugi), invention further provides one kind to have self-reparing capability
Anti-bacterial hydrogel, be prepared by the PEG derivative and polyvinyl alcohol (PVA), be to utilize the base in the PEG derivative
Group reacts with the hydroxyl in the PVA generates the realization connection of boric acid ester bond；
Specifically, the degree of polymerization of the PVA can be 500~1700, alcoholysis degree be 88~99%, as PVA1788,
PVA1799, PVA0588 etc. are used in plastic.
Specifically, the solution of the PEG derivative is mixed with the solution of the polyvinyl alcohol, is obtained after shaking described
Hydrogel, gelation time can be 10~60 seconds；
PBS solution can be used and prepare the solution of the PEG derivative and the solution of the polyvinyl alcohol；
The pH value of the PBS solution is 7~8；
The mass concentration of the solution of the PEG derivative can be 5~12%, such as 8~12%, 8~10%, 10~12%,
8%, 10% or 12%；
The mass concentration of the solution of the polyvinyl alcohol can be 5~10%, such as 8%；
The volume ratio of the solution of the solution and polyvinyl alcohol of the PEG derivative can be 1:0.5~2, such as 1:1.
The present invention quickly prepares hydrogel using material cheap and easy to get.Polyvinyl alcohol (PVA) is that one kind is widely used in
The water-soluble material of the industries such as weaving, food, medicine, building, papermaking, agricultural, macromolecule chemical industry, it is cheap and easy to get and have preferable
Biological safety.Hydroxyl in PVA structure can generate boric acid ester bond in conjunction with boric acid, and the present invention will using this reaction
PVA is mixed with the multi-functional PEG-Ugi of preparation, reacts life with the hydroxyl in PVA structure by the borate in PEG-Ugi structure
At borate, to realize two kinds of polymer crosslinkings and obtain hydrogel.Borate is dynamic chemical key and forms speed
Comparatively fast, therefore the hydrogel of this reaction preparation is utilized to have self-reparing capability and faster plastic speed (when by environmental damage
Meeting self-regeneration is to restore original function and structure).
The anti-bacterial hydrogel with self-reparing capability of the above-mentioned offer of the present invention, as a kind of reviewing one's lessons by oneself with antibacterial functions
Rehydration gel rubber material provides a kind of new approaches for anti-bacterial hydrogel.Traditional anti-bacterial hydrogel is by wrapping in hydrogel mostly
It buries antimicrobial compound and obtains antibacterial functions, easily cause unknown environmental hazard after antimicrobial compound release.Meanwhile antimicrobial compound
After release, the antibacterial ability of hydrogel can be also remarkably decreased.In comparison, the present invention uses macromolecular anti-biotic material (PEG-
Ugi it) is used as the plastic factor, antibacterial group is connected directly between in hydrogel backbone, therefore this hydrogel peace property is preferable and has
Continual and steady antibacterial ability.
The present invention is prepared for polyethylene glycol (PEG) derivative (PEG- containing boric acid base group and phenol structure by Ugi reaction
Ugi).After the aqueous solution of PEG-Ugi is mixed with polyvinyl alcohol (PVA) aqueous solution, the two passes through in boric acid base group and PVA structure
Hydroxyl reaction generate boric acid ester bond, quickly form hydrogel.Since boric acid ester bond belongs to dynamic chemical key, phenol structure has anti-
Bacterium function, therefore obtained hydrogel with self-reparing capability and has antibiotic property, is a kind of novel antibiotic property self-healing property water
Gel.The method of the present invention prepares hydrogel using the secure and cheap raw material being easy to get, and preparation method is simple, and Gelation Conditions are mild,
With preferable application value.
Detailed description of the invention
Fig. 1 is the reaction route that phthalic anhydride synthesizes PEG-COOH with PEG.
Fig. 2 is the synthetic reaction route (Fig. 2 a) of PEG-Ugi) and PEG-Ugi1H-NMR and11B-NMR spectrogram (figure
2b))。
Fig. 3 is the formation schematic diagram of hydrogel.
Fig. 4 be hydrogel rheological analysis and SEM figure, wherein Fig. 4 a) be hydrogel rheological analysis, Fig. 4 b) be water-setting
The SEM of glue schemes.
Fig. 5 is the selfreparing picture of hydrogel.
Fig. 6 is the analysis of hydrogel self-reparing capability, wherein Fig. 6 a) be hydrogel linear viscoelastic region range scans, Fig. 6 b)
For the modulus change figure of hydrogel under alternate strain.
Fig. 7 is that plastic factor PEG-Ugi analyzes the minimal inhibitory concentration of Escherichia coli.
Fig. 8 is that plastic factor PEG-Ugi analyzes the minimal inhibitory concentration of Staphylococcus aureus.
Fig. 9 is the antibacterial activity of hydrogel, wherein Fig. 9 a) be Escherichia coli antibiogram, Fig. 9 b) it is golden yellow grape ball
Bacterium antibacterial picture；Control group is gelatin.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
The preparation of embodiment 1, PEG-Ugi
1, the preparation of PEG-COOH
Synthetic route is as shown in Figure 1.
PEG3000 is dissolved in toluene back spin, toluene is evaporated off, so in triplicate, removes the moisture in PEG.
Above-mentioned anhydrous PEG is dissolved in super dry tetrahydrofuran, adds the phthalic anhydride of doubling dose, three second of monovalent
Amine.Drying tube is connect on reaction flask, is reacted at room temperature 3 hours or so.Reaction solution is poured into ether and is precipitated, collected by suction obtains white
Color solid.White solid is placed in vacuum desiccator drying to constant weight, can be obtained PEG-COOH.
2, the preparation of PEG-Ugi
Synthetic route chart such as Fig. 2 a) shown in.
PEG-COOH is dissolved in methanol, sequentially adds 3 equivalent 4- aldehyde radical phenyl boric acids, 3 equivalent 4- amino 2- methoxybenzenes
Phenol, 5 equivalent isocyanide hexamethylenes.Reaction solution is kept for 10 hours at 45 DEG C.Ether is added in reaction solution and generates precipitating, centrifugation
(6000 revs/min, 4 minutes) collect solid precipitating afterwards.Obtained solid is deposited in vacuum desiccator and dries to constant weight, obtains
PEG-Ugi。
As shown in Fig. 2 b)1H-NMR and11B-NMR (interior illustration) spectrogram is it is found that the present embodiment has obtained target PEG derivative
Object PEG-Ugi.
The preparation of embodiment 2, hydrogel
1, the preparation of PVA solution
PBS solution (pH value 7.4) is heated to 90 DEG C or so, a certain amount of PVA powder is added, is stirred overnight, obtains
To the PBS solution of PVA, mass concentration 8%.
2, the preparation of PEG-Ugi solution
A certain amount of PEG-Ugi is added in PBS solution, concussion makes it completely dissolved, the PBS solution of PEG-Ugi is obtained,
Mass concentration is 8%.
3, the preparation of hydrogel
The PBS solution of the PVA of same volume and the PBS solution of PEG-Ugi are taken, acutely concussion about 2 rapidly after the two mixing
~5s, as shown in Figure 3.
The concentration of PEG-Ugi in the PBS solution of PEG-Ugi is adjusted to 10% and 12% according to the method described above and prepares water-setting
Glue.
Embodiment 3, hydrogel properties test
1, hydrogel glue is tested by force
It prepares round pie hydrogel sample (diameter~20mm, room temperature~25 DEG C), is placed it in after standing about 1 hour parallel
On the lower plate testboard of plate, modifies its shape and be allowed to coincide with test parallel-plate.Data (shearing mould is acquired under the conditions of setting
Amount-frequency scanning test pattern；Strain 1%；Frequency sweeping ranges: 0.1rad/s to 100rad/s).As a result as shown in Fig. 4 a),
With the increase of PEG-Ugi solid content, the glue of hydrogel shows by force the trend of growth, illustrates hydrogel glue by force and has and is adjustable
Property.
A small amount of hydrogel is taken, its microstructure is observed by SEM after freeze-drying.As shown in Fig. 4 b), hydrogel dehydration collapse
Afterwards, surface, which still can see, hole residual, illustrates that hydrogel has reticular structure.
2, the test of hydrogel self-healing properties
Qualitative characterization: by hydrogel prepared by embodiment 2, (PEG-Ugi mass concentration is that 12%, PVA mass concentration is
8%) it is prepared into about 3 centimetres of diameter of cake, therebetween punching (simulation damage, aperture~1 centimetre).Hydrogel is stood,
The variation of beaten circular hole is observed at regular intervals.As a result as shown in Figure 5, it is seen that circular hole is gradually reduced until completely disappearing, card
The real hydrogel has self-reparing capability.
Quantitatively characterizing: whether hydrogel there is shear shinning property to be whether it has the basis of self-reparing capability.This hair
The bright shear shinning property using the rheometer quantitatively characterizing hydrogel, test process are as follows: it is broken to apply big strain to hydrogel
Its bad three-dimensional net structure, then whether restored using the three-dimensional network of small strain observation hydrogel.It is answered by alternate change
The size of change, tests destruction-recovery process of hydrogel three-dimensional network, and the three-dimensional crosslinked network structure for verifying hydrogel is being broken
Reversible recovery characteristics after bad.
The linear-viscoelastic range of the hydrogel is tested first.To hydrogel carry out modulus of shearing-range of strain (1~
1000%) it scans, when elastic modulus G ' declines, and G ' value is less than viscous modulus G ", has been determined as the network structure of hydrogel
It destroys.As shown in Fig. 6 a), hydrogel gel network structure under 400% strain has been destroyed.As reference, select to water
The network structure of gel has big strain (400%) and the small strain (1%) in linear viscoelastic region of destruction, and alternating is applied to water
It on gel sample, carries out continuous time scanning (frequency 1Hz), the variation of test observation modulus of shearing.As a result as shown in Fig. 6 b),
The three-dimensional network of hydrogel is destroyed under big strained condition, and damaged three-dimensional network is able to structure again under the conditions of small strain
It builds, the intensity of hydrogel is fully returned to prerupture level, it was demonstrated that the hydrogel has preferable self-reparing capability.
Embodiment 4, antibiotic property test
1, the minimal inhibitory concentration test of PEG-Ugi
8mg/mL, 4mg/mL, 2mg/mL, 1mg/mL, 0.5mg/mL is respectively configured using PEG-Ugi prepared by embodiment 1
Nutrient broth solution.Escherichia coli or Staphylococcus aureus bacterium solution are taken, with broth dilution to about 106CFU/mL.By PEG-Ugi
1:1 is mixed solution by volume with bacterium solution, and the ultraviolet absorptivity of solution is tested at 620nm.It after 24 hours, measures again, root
Increase according to ultraviolet light absorption angle value and calculates minimal inhibitory concentration.As a result such as Fig. 7 (Escherichia coli) and Fig. 8 (Staphylococcus aureus) institute
Show, it can be seen that PEG-Ugi concentration is respectively in 2mg/mL and 8mg/mL, the growth of Escherichia coli and Staphylococcus aureus
Inhibited, shows that polymer P EG-Ugi has certain antibacterial ability.
2, the antibiotic property test of hydrogel
According to the method in embodiment 2, above-mentioned self-healing property hydrogel (PEG-Ugi mass is prepared respectively in circular die
Concentration be 12%, PVA mass concentration be 8%) with gelatin hydrogel (control group).Two kinds of hydrogels are individually placed to solid culture
A fritter agar is placed at the top of hydrogel, and takes 2uL bacterium solution (~10 in the both ends of base6CFU/mL it) is added on agar, later will
Culture medium is placed in 37 DEG C of incubators.Every culture is taken pictures for 24 hours, observes bacterium colony growing state.As a result (Fig. 9 a) is big as shown in Figure 9
Enterobacteria；Fig. 9 b) be Staphylococcus aureus), gelatin hydrogel is after adding bacterium solution 24 hours, Escherichia coli and Staphylococcus aureus
Hydrogel is crossed on solid medium to outgrowth, and the hydrogel that PEG-Ugi and PVA is mixed to form is adding bacterium solution 48 small
When after could see there is bacterium growth on solid medium, show the selfreparing hydrogel have certain antibacterial ability.
Claims (12)
1. a kind of preparation method of PEG derivative, includes the following steps:
PEG-COOH, the boronic acid compounds containing aldehyde radical, the organic amine containing hydroxyl and isonitrile obtain described through Ugi reaction
PEG derivative；
The PEG-COOH is the polyethylene glycol of both ends carboxy blocking.
2. preparation method according to claim 1, it is characterised in that: the PEG-COOH is reacted by acid anhydrides with polyethylene glycol
It obtains.
3. preparation method according to claim 2, it is characterised in that: the acid anhydrides is phthalic anhydride, succinic anhydride
Or maleic anhydride.
4. preparation method according to any one of claim 1-3, it is characterised in that: the boric acid chemical combination containing aldehyde radical
Object is the phenyl boric acid containing aldehyde radical.
5. preparation method described in any one of -4 according to claim 1, it is characterised in that: the organic amine containing hydroxyl is
Phenol containing amino；
The isonitrile is isocyanide hexamethylene.
6. preparation method according to any one of claims 1-5, it is characterised in that: the temperature of the Ugi reaction is 25
~60 DEG C, the time is 6~24 hours.
7. the PEG derivative of any one of claim 1-6 the method preparation.
8. PEG derivative is in preparing anti-bacterial hydrogel or the anti-bacterial hydrogel for having self-reparing capability described in claim 7
Using.
9. a kind of hydrogel, the PEG derivative as described in claim 7 is prepared with polyvinyl alcohol.
10. hydrogel according to claim 9, it is characterised in that: the solution and the polyvinyl alcohol of the PEG derivative
Solution mixing, the hydrogel is obtained after shaking.
11. hydrogel according to claim 10, it is characterised in that: prepare the molten of the PEG derivative using PBS solution
The solution of liquid and the polyvinyl alcohol；
The mass concentration of the solution of the PEG derivative is 8~12%；
The mass concentration of the solution of the polyvinyl alcohol is 8~12%；
The volume ratio of the solution of the solution and polyvinyl alcohol of the PEG derivative is 1:0.5~2.
12. hydrogel described in any one of PEG derivative or claim 9-11 described in claim 7 is in antibacterial or preparation antibacterial
Application in product.
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| CN110628044A (en) * | 2019-08-30 | 2019-12-31 | 厦门大学 | Ternary crosslinked hydrogel electrolyte, preparation method and application thereof |
| CN110746616A (en) * | 2019-10-25 | 2020-02-04 | 南京大学 | Cellulose hydrogel containing phenylboronic acid and preparation method and application thereof |
| CN113045771A (en) * | 2019-12-27 | 2021-06-29 | 河北大学 | Aspartic acid-based self-repairing antibacterial hydrogel and preparation method and application thereof |
| WO2022092043A1 (en) * | 2020-10-29 | 2022-05-05 | 国立大学法人 東京大学 | Associative polymer material |
| CN116253905A (en) * | 2023-02-18 | 2023-06-13 | 四川大学 | Stable and intelligent anti-infective hydrogel, and preparation method and application thereof |
| WO2023214550A1 (en) * | 2022-05-03 | 2023-11-09 | 国立大学法人 東京大学 | Polymer material having phase separation structure obtained by controlling number of branches |
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| CN113045771A (en) * | 2019-12-27 | 2021-06-29 | 河北大学 | Aspartic acid-based self-repairing antibacterial hydrogel and preparation method and application thereof |
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| WO2023214550A1 (en) * | 2022-05-03 | 2023-11-09 | 国立大学法人 東京大学 | Polymer material having phase separation structure obtained by controlling number of branches |
| WO2023214551A1 (en) * | 2022-05-03 | 2023-11-09 | 国立大学法人 東京大学 | Polymer material having phase separation structure |
| CN116253905A (en) * | 2023-02-18 | 2023-06-13 | 四川大学 | Stable and intelligent anti-infective hydrogel, and preparation method and application thereof |
| CN116253905B (en) * | 2023-02-18 | 2024-03-01 | 四川大学 | Stable and intelligent anti-infective hydrogel, and preparation method and application thereof |
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