CN106832344B - Polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel preparation method and applications - Google Patents
Polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel preparation method and applications Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel, this method is first in surface of graphene oxide grafted polystyrene sulfonic acid, again by the static monitor of polypyrrole in conjunction with the compound phase of polystyrolsulfon acid graft grapheme, target product polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel is obtained.There are a variety of effects such as zwitterion interaction, π-πconjugation, hydrogen bond between polystyrolsulfon acid graft grapheme and polypyrrole in the composite hydrogel, make it have good mechanical strength, graphene and the good chemical property of polypyrrole make it also have electroresponsive simultaneously, can be realized the control release of drug under electro photoluminescence.
Description
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of drug controlled release material with Electro-stimulate response
Material --- polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel preparation method.
Background technique
As people are to the pay attention to day by day of health, ground for what the system with good drug controlled release performance was carried out
Study carefully more and more deep.By good controlled drug delivery system, drug can be made to realize the control on time or space in organism
System release, optium concentration needed for keeping drug to maintain disease treatment in vivo, so that drug is dense during avoiding conventional administration
Treatment invalid problem when poisoning, drug concentration are low when spending higher, achievees the purpose that controllable therapeutic.More drug is studied at present
Controlled release material is hydrogel material.Hydrogel is a kind of hydrophily but the macromolecule network for being not dissolved in water, with micro-
The advantages that view hole diameter and mechanical strength are adjustable, especially sensitive aqueous gel have perception environment slight change, and pass through itself
The swelling and contraction of volume responds these abilities from environmental stimuli.
It is more currently for the hydrogel research with stimulating responsives such as temperature, pH, ionic strengths, and for having electricity
The hydrogel research of the drug controlled release performance of stimuli responsive is less.This, which is primarily due to common hydrogel material, does not have
Electro-chemical activity, for electro photoluminescence almost without response；It on the other hand is by the more difficult reality of the conductive hydrogel reported at present
Existing conductive component being uniformly distributed in hydrogel body, and resulting conductive hydrogel mechanical strength is poor, limits in fact
Border application.
Summary of the invention
It is an object of the invention to overcome existing drug controlled release hydrogel material above shortcomings, one kind is provided
Polystyrolsulfon acid graft grapheme/polypyrrole compound hydrogel material preparation method with Electro-stimulate response.The present invention
Grafted polystyrene sulfonic acid on the surface of graphene first, then by the static monitor of polypyrrole and polystyrolsulfon acid graft grapheme
Compound phase combine, prepared the polystyrolsulfon acid graft grapheme with excellent mechanical property and electric property/poly-
Pyrroles's composite hydrogel.Preparation method of the present invention is simple, is not necessarily to complex device, the composite hydrogel being prepared is in electric field action
Under, can effectively Drug controlled release time and dosage.To achieve the above object, the technical solution adopted in the present invention is such as
Under:
Polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel preparation method, comprising the following steps: (1) will
Graphene oxide, 2- bromine isobutyl acylbromide, triethylamine dispersion in organic solvent, are obtained after the reaction was completed containing the oxygen for causing group
Graphite alkene；(2) water-dispersible containing the graphene oxide for causing group, catalyst, anti-activator, connection are added under protective atmosphere
Two pyridines and sodium styrene sulfonate are reacted, and the graphene oxide of polystyrolsulfon acid grafting is obtained；(3) water-dispersible poly-
The graphene oxide of styrene sulfonic acid grafting is added reducing agent and is reacted, obtains polystyrolsulfon acid graft grapheme；(4)
Water-dispersible polystyrolsulfon acid graft grapheme, is added pyrroles and oxidant reacts, and obtains polystyrolsulfon acid grafting
Graphene/polypyrrole composite hydrogel.
According to above scheme, graphene oxide in step (1), 2- bromine isobutyl acylbromide, triethylamine amount ratio be 1g:20-
100mL:10-40mL。
According to above scheme, step (1) organic solvent is chloroform or n,N-Dimethylformamide, reaction condition
For ice-water bath, reaction time 24-48h, after the reaction was completed through centrifugation, washing, so dry that contain the graphite oxide for causing group
Alkene.
According to above scheme, contain graphene oxide, catalyst, anti-activator, the bipyridine for causing group in step (2)
And the mass ratio of sodium styrene sulfonate is 8-200:2.5-12:1:19-95:206-825.
According to above scheme, the catalyst is stannous chloride or cuprous bromide, and the anti-activator is copper chloride or bromination
Copper.
According to above scheme, reaction temperature is 10-30 DEG C, reaction time 6-12h in step (2), and protection gas is argon gas,
Graphene oxide of the product through centrifugation, washing, the grafting of dry polystyrolsulfon acid.
According to above scheme, the mass ratio of polystyrolsulfon acid is grafted in step (3) graphene oxide and reducing agent is
1:2.5-8, reaction temperature are 90 DEG C, reaction time 18-24h, and product is through centrifugation, washing, dry that polystyrolsulfon acid connects
Branch graphene.
According to above scheme, the reducing agent is one of ascorbic acid or tea polyphenols.
According to above scheme, the amount ratio of polystyrolsulfon acid graft grapheme, pyrroles and oxidant is in step (4)
30- is stirred after pyrroles is added into polystyrolsulfon acid graft grapheme dispersion liquid before 0.25-4g:1mL:0.8-48g reaction
60min, adds oxidant stirring 2-5min, reacts 24-36h in 10-20 DEG C of standing, is washed with deionized water to obtain the final product.
According to above scheme, the oxidant is one of iron chloride, ferric nitrate, ferric sulfate or ammonium persulfate.
Above-mentioned polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel obtained is as drug controlled release material
Application.
Compared with prior art, the invention has the following advantages: polystyrolsulfon acid is grafted to graphene table by (1)
Face improves the solubility property of graphene, and introduces the functional group for largely having negative electrical charge on the surface of graphene, is conducive to it
With the doping of polypyrrole；(2) polystyrolsulfon acid is connected on the surface of graphene by covalent bond, and grafting density is high；(3) polyphenyl second
There are a variety of effects such as zwitterion interaction, π-πconjugation, hydrogen bonds between alkene Sulphonic Acid Functionalized graphene and polypyrrole,
So that composite hydrogel has good mechanical strength；(4) graphene and the good chemical property of polypyrrole make Compound Water
Gel has electroresponsive, and the control release of drug can be achieved under electro photoluminescence.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.It should be understood that following embodiment is only better embodiment of the present invention, do not constitute to this hair
Bright restriction, on this basis the present invention can also there are many other embodiments, equally fall into protection scope of the present invention it
It is interior.
Reagent used in the present invention be it is common commercially available, analyze pure, deionized water is self-control.
Embodiment 1
1) 0.5g graphene oxide, 25mL 2- bromine isobutyl acylbromide, 10mL triethylamine are dispersed in 50mL chloroform,
It is transferred in ice-water bath and reacts 24 hours, obtain after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.02g graphene oxide for containing initiation group is dispersed in 4mL deionized water, under the conditions of argon atmosphere
It is separately added into 3mg stannous chloride, 0.5mg copper chloride, 0.15mmol bipyridine, 1.2mmol sodium styrene sulfonate, is uniformly mixed
It is reacted 6 hours at 20 DEG C afterwards, obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.1g polystyrolsulfon acid is grafted is dispersed in 30mL water, 0.5g ascorbic acid is added,
It is reacted 18 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.05g polystyrolsulfon acid graft grapheme is dispersed in 10mL water, 50 μ L pyrroles is added, stirred 30 minutes
Afterwards, the ferric nitrate of 1mmol is added.After being again stirring for 2 minutes, reaction 24 hours are stood at 10 DEG C, is washed with deionized, obtains
To polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel.
Embodiment 2
1) 0.6g graphene oxide, 30mL 2- bromine isobutyl acylbromide, 10mL triethylamine are dispersed in 60mLN, N- dimethyl methyl
It in amide, is transferred in ice-water bath and reacts 30 hours, obtain after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.05g graphene oxide for containing initiation group is dispersed in the deionized water of 6mL, in argon atmosphere condition
Under be separately added into 4mg cuprous bromide, 0.6mg copper bromide, 0.2mmol bipyridine, 1.5mmol sodium styrene sulfonate, at 20 DEG C
Lower reaction 8 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.12g polystyrolsulfon acid is grafted is dispersed in 35mL water, 0.6g tea polyphenols is added,
It is reacted 20 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.08g polystyrolsulfon acid graft grapheme is dispersed in 15mL water, the pyrroles of 75 μ L, stirring 45 is added
After minute, the ferric sulfate of 1.5mmol is added.After being again stirring for 3 minutes, reaction 24 hours are stood at 20 DEG C, use deionized water
Washing, obtains polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel.
Embodiment 3
1) triethylamine of 0.8g graphene oxide, the 2- bromine isobutyl acylbromide of 40mL, 18mL are dispersed in the N of 70mL, N- bis-
It in methylformamide, is transferred in ice-water bath and reacts 24 hours, obtain after centrifugation, washing, drying containing the oxidation stone for causing group
Black alkene；
2) the 0.06g graphene oxide for containing initiation group is dispersed in the deionized water of 8mL, in argon atmosphere condition
Under be separately added into 5mg stannous chloride, 1mg copper chloride, 0.25mmol bipyridine, 1.6mmol sodium styrene sulfonate, at 25 DEG C
Reaction 6-12 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.1g polystyrolsulfon acid is grafted is dispersed in 35mL water, 0.7g ascorbic acid is added,
It is reacted 18-24 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.1g polystyrolsulfon acid graft grapheme is dispersed in 15mL water, the pyrroles of 100 μ L, stirring 40 is added
After minute, the ammonium persulfate of 2mmol is added.After being again stirring for 4 minutes, reaction 30 hours are stood at 15 DEG C, use deionized water
Washing, obtains polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel.
Embodiment 4
1) triethylamine of 0.75g graphene oxide, the 2- bromine isobutyl acylbromide of 45mL, 20mL are dispersed in three chloromethanes of 80mL
It in alkane, is transferred in ice-water bath and reacts 48 hours, obtain after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.08g graphene oxide for containing initiation group is dispersed in the deionized water of 8mL, in argon atmosphere condition
Under be separately added into 5mg cuprous bromide, 0.9mg copper bromide, 0.25mmol bipyridine, 1.6mmol sodium styrene sulfonate, at 30 DEG C
Lower reaction 10 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.1-0.2g polystyrolsulfon acid is grafted is dispersed in 30-50mL water, 0.5- is added
0.8g tea polyphenols react 18-24 hours at 90 DEG C, obtain polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.15g polystyrolsulfon acid graft grapheme is dispersed in 20mL water, the pyrroles of 150 μ L, stirring 50 is added
After minute, the iron chloride of 6mmol is added.It is again stirring for after five minutes, reaction 30 hours is stood at 20 DEG C, are washed with deionized water
It washs, obtains polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel.
Embodiment 5
1) triethylamine of 1g graphene oxide, the 2- bromine isobutyl acylbromide of 50mL, 20mL are dispersed in the N of 90mL, N- diformazan
It in base formamide, is transferred in ice-water bath and reacts 40 hours, obtain after centrifugation, washing, drying containing the graphite oxide for causing group
Alkene；
2) the 0.1g graphene oxide for containing initiation group is dispersed in the deionized water of 10mL, in argon atmosphere condition
Under be separately added into 6mg cuprous bromide, 1.2mg copper bromide, 0.3mmol bipyridine, 2mmol sodium styrene sulfonate, at 25 DEG C
Reaction 12 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.2g polystyrolsulfon acid is grafted is dispersed in 50mL water, 0.8g ascorbic acid is added,
It is reacted 24 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.2g polystyrolsulfon acid graft grapheme is dispersed in 20mL water, the pyrroles of 200 μ L, stirring 60 is added
After minute, the ferric nitrate of 5mmol is added.It is again stirring for after five minutes, reaction 36 hours is stood at 20 DEG C, are washed with deionized water
It washs, obtains polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel.
Embodiment 6
1) triethylamine of 0.6g graphene oxide, the 2- bromine isobutyl acylbromide of 35mL, 16mL are dispersed in three chloromethanes of 80mL
It in alkane, is transferred in ice-water bath and reacts 24 hours, obtain after centrifugation, washing, drying containing the graphene oxide for causing group；
2) the 0.04g graphene oxide for containing initiation group is dispersed in the deionized water of 7mL, in argon atmosphere condition
Under be separately added into 4mg cuprous bromide, 0.8mg copper bromide, 0.2mmol bipyridine, 1.4mmol sodium styrene sulfonate, at 15 DEG C
Lower reaction 12 hours obtains the graphene oxide of polystyrolsulfon acid grafting after centrifugation, washing, drying；
3) graphene oxide that 0.16g polystyrolsulfon acid is grafted is dispersed in 40mL water, 0.7g ascorbic acid is added,
It is reacted 18 hours at 90 DEG C, obtains polystyrolsulfon acid graft grapheme after centrifugation, washing, drying；
4) 0.1g polystyrolsulfon acid graft grapheme is dispersed in 10-20mL water, the pyrroles of 100 μ L, stirring is added
After forty minutes, the ammonium persulfate of 4mmol is added.After being again stirring for 2 minutes, reaction 24 hours are stood at 10 DEG C, use deionization
Water washing obtains polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel.
For the Electro-stimulate response for understanding polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel prepared by the present invention
And drug controlled release performance, We conducted relevant experiments.The polystyrolsulfon acid grafting stone for taking 50mg embodiment 5 to prepare
Black alkene/polypyrrole composite hydrogel is placed it in containing impregnating one hour in salicylic phosphate buffer solution, then by its
Taking-up is placed in not salicylated phosphate buffer solution, carries out electro photoluminescence release.Adjusting applied voltage is 0V or 1.0V, often
2mL solution was drawn from solution every 0.5 hour, measured salicylic content, while supplementing the PBS of same volume.It is salicylic
Content is measured at 298nm using ultraviolet spectrophotometry, and the accumulation of different time is calculated according to the salicylic acid content of measurement
Release the drug percentage.The result shows that salicylic cumulative release percentage is 11% in 0V after 6 hours；In 1.0V,
After 6 hours, salicylic cumulative release percentage is 57%, shows apparent electroresponsive release behavior.
This is because polypyrrole strand shows the state more expanded under high electric field, be conducive to the release of small-molecule drug.It will
Salicylic acid is changed to dexamethasone or quadracycline and has also obtained same conclusion.
Claims (8)
1. polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel preparation method, which is characterized in that including following step
It is rapid:
(1) in organic solvent by graphene oxide, 2- bromine isobutyl acylbromide, triethylamine dispersion, it is obtained after the reaction was completed containing drawing
Send out the graphene oxide of group；
(2) water-dispersible containing the graphene oxide for causing group, catalyst, anti-activator, union II pyrrole are added under protective atmosphere
Pyridine and sodium styrene sulfonate are reacted, and the graphene oxide of polystyrolsulfon acid grafting is obtained；
(3) graphene oxide of water-dispersible polystyrolsulfon acid grafting, is added reducing agent and is reacted, obtain polystyrene sulphur
Sour graft grapheme；
(4) water-dispersible polystyrolsulfon acid graft grapheme, is added pyrroles and oxidant reacts, and obtains polystyrene sulphur
Sour graft grapheme/polypyrrole composite hydrogel；
The amount ratio of polystyrolsulfon acid graft grapheme, pyrroles and oxidant is 0.25-4g:1mL:0.8- in step (4)
Pyrrolo- is added into polystyrolsulfon acid graft grapheme dispersion liquid and stirs 30-60min, adds oxidant by 48g before reaction
Stir 2-5min, react 24-36h in 10-20 DEG C of standing, washed to obtain the final product with deionized water, the oxidant be iron chloride,
One of ferric nitrate, ferric sulfate or ammonium persulfate.
2. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel as described in claim 1, special
Sign is: graphene oxide in step (1), 2- bromine isobutyl acylbromide, triethylamine amount ratio be 1g:20-100mL:10-40mL.
3. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel as described in claim 1, special
Sign is: step (1) organic solvent is chloroform or n,N-Dimethylformamide, and reaction condition is ice-water bath, reaction
Time is 24-48h, after the reaction was completed through centrifugation, washing, dry contain the graphene oxide for causing group.
4. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel as described in claim 1, special
Sign is: containing graphene oxide, catalyst, anti-activator, bipyridine and the styrene sulfonic acid for causing group in step (2)
The mass ratio of sodium is 8-200:2.5-12:1:19-95:206-825.
5. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel as described in claim 1, special
Sign is: reaction temperature is 10-30 DEG C, reaction time 6-12h in step (2), and protection gas is argon gas, and product is centrifuged, is washed
Wash, dry polystyrolsulfon acid grafting graphene oxide.
6. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel as described in claim 1, special
Sign is: the mass ratio of polystyrolsulfon acid is grafted in step (3) graphene oxide and reducing agent is 1:2.5-8, reaction temperature
Degree is 90 DEG C, reaction time 18-24h, and product is through centrifugation, washing, dry polystyrolsulfon acid graft grapheme.
7. the preparation method of polystyrolsulfon acid graft grapheme/polypyrrole composite hydrogel as described in claim 1, special
Sign is: step (2) catalyst is stannous chloride or cuprous bromide, and the anti-activator is copper chloride or copper bromide, step
(3) reducing agent is one of ascorbic acid or tea polyphenols.
8. polystyrolsulfon acid graft grapheme/polypyrrole Compound Water that any one of -7 methods are prepared according to claim 1
Application of the gel as drug controlled release material.
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| CN102543463A (en) * | 2011-12-13 | 2012-07-04 | 武汉工程大学 | Water-soluble graphene used for super capacitor electrode material and preparation method thereof |
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
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| CN102543463A (en) * | 2011-12-13 | 2012-07-04 | 武汉工程大学 | Water-soluble graphene used for super capacitor electrode material and preparation method thereof |
| CN105733260A (en) * | 2016-03-02 | 2016-07-06 | 廖彩芬 | Graphene/conducive macromolecular polymer aerogel and preparation method thereof |
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| Title |
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| Polymer Brushes via Controlled, Surface-Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide;Sun Hwa Lee et al.;《Macromolecular Rapid Communications》;20100202;第31卷(第3期);第281-288页 |
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