CN110256705A - A kind of pH response type polymer film and preparation method thereof - Google Patents
A kind of pH response type polymer film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of pH response type polymer films and preparation method thereof, use tannic acid, chitosan and dextran aldehyde for raw material, synthesize target product, i.e. dextran aldehyde-tannic acid/chitosan polymer film by covalent bond LBL self-assembly method；Wherein, the mass ratio of tannic acid, chitosan and dextran aldehyde is 0.3-1:0.3-1:1.Polymer film prepared by the present invention, which can change pH, to be made a response, and control release embedding molecule improves the utilization efficiency of drug molecule.Resulting polymers film has the characteristics that synthesis step is easy to operate, low in cost, has broad application prospects in antifouling and antibiosis field.
Description
Technical field
The invention belongs to anti-soil technology fields more particularly to a kind of pH response type polymer film and preparation method thereof.
Background technique
Marine fouling organism is attached to oceanographic equipment surface and causes equipment damage, influences marine economy development.The whole world is every
Year because caused by marine biofouling economic loss reach hundreds billion of dollars (Biofouling, 2011,27,87-98).Marine organisms
The focus that the prevention and treatment being stained always is studied both at home and abroad.In numerous antifouling strategies, coating marine anti-pollution coating be still it is most succinct,
Economically and efficiently method (Adv.Funct.Mater., 2013,23,5706-5718).Currently, it is excellent, anti-to develop anti-pollution
Lasting and environmentally friendly anti-fouling system of dirty period has become the dominant direction of marine anti-pollution coating development
(Adv.Funct.Mater.2013,23,3307-3314)。
In recent years, the intelligent anti-fouling system constructed using stimuli responsive type high molecular polymer, can be dirty by induction biology
The variation of site environment information, such as the reduction of microenvironment pH caused by microorganism attachment are damaged, to adjust releasing for biocide
Put, biocide made to release required effective dose in necessary time and privileged site, realize the fixed point of biocide, timing,
Quantitative control release.
However, the high molecular material for preparing antifouling film layer is usually artificial synthesized macromolecule, these high molecular synthesis steps
Rapid cumbersome, higher cost, it is often more important that these organic polymers have environmental toxicity more, and it is antifouling in intelligence seriously to limit it
The application of coatings art.In contrast, natural polymer has environment friendly and biodegradability, and is able to maintain that packet
It is embedded in the stability of drug therein, enhances anti-fouling effect, these characteristics make it be well suited as the green material of anti-fouling system
Material.Currently, poly- based on natural polysaecharides polymer chitosan, dextran aldehyde and natural poly- polyphenol tannin acid construct pH response type
There is not been reported for compound film layer.
Summary of the invention
The object of the invention is that providing a kind of pH response type polymer film and its preparation to solve the above-mentioned problems
Method.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of pH response type polymer film, uses tannic acid, chitosan and dextran aldehyde for raw material, leads to
Cross covalent bond LBL self-assembly method synthesis target product, i.e. dextran aldehyde-tannic acid/chitosan polymer film；Wherein, tannin
The mass ratio of acid, chitosan and dextran aldehyde is 0.3-1:0.3-1:1.
Further:
1) cetyl trimethylammonium bromide is dissolved in deionized water and forms micellar solution；
2) acetic acid aqueous solution containing tannic acid is added into above-mentioned acquisition micellar solution, obtains tannic acid capsule after mixing evenly
Solution；The acetic acid aqueous solution of chitosan-containing is then added, after mixing evenly as tannic acid/chitosan nano capsule solution；
3) sodium metaperiodate is dissolved in the aqueous solution for forming sodium metaperiodate in deionized water, glucan stirring is then added, obtains
Obtain dextran aldehyde aqueous solution；
4) trishydroxymethylaminomethane is dissolved in deionized water, adjusting solution ph is 8-8.5, obtains trihydroxy methyl amino
Aminomethane buffer；It then adds Dopamine hydrochloride and forms Dopamine hydrochloride-trishydroxymethylaminomethane buffering after mixing
Liquid；
5) matrix is immersed in above-mentioned Dopamine hydrochloride-TRIS buffer, enables matrix surface
Modification forms the matrix of poly-dopamine modification；The matrix that poly-dopamine is modified is added to the resulting dextran aldehyde of step 3)
In aqueous solution, matrix is then dipped in tannic acid/chitosan nano capsule solution obtained by step 2) by deposition processes again, and
After take out matrix, then deposit immersion in different solutions according to this step repeatedly, i.e., matrix surface deposits to form dextran aldehyde-
Tannic acid/chitosan polymer film.
Matrix can be sheet glass, dimethyl silicone polymer piece or sheet metal (aluminium flake, copper sheet).
Cetyl trimethylammonium bromide and water stir 10-15min at 40-50 DEG C after mixing in the step 1), to
With.
The final concentration of 1-3mg/mL of tannic acid in acetic acid aqueous solution of the step 2) containing tannic acid；Wherein, acetic acid aqueous solution
The additional amount of middle acetic acid is 1-3 μ L/mL；
The final concentration of 1-3mg/mL of chitosan in the acetic acid aqueous solution of the chitosan-containing, wherein in acetic acid aqueous solution
The additional amount of acetic acid is 1-3 μ L/mL.
The final concentration of 32mg/mL of the aqueous solution meso-periodic acid sodium of the step 3) sodium metaperiodate, glucan additional amount are
25mg/mL；
Glucan is added in the aqueous solution of the sodium metaperiodate, is stirred overnight, then dialysis obtains dextran aldehyde water
Solution.
Step 4) the trishydroxymethylaminomethane is dissolved in the final concentration of of trishydroxymethylaminomethane in deionized water
12.1mg/mL, Dopamine hydrochloride additional amount are 2mg/mL；
Described matrix immerses in Dopamine hydrochloride-TRIS buffer, and soaking time is for 24 hours, to repair it
Decorations form the matrix of poly-dopamine modification；
The matrix of step 5) the poly-dopamine modification is added into the aqueous solution of the resulting dextran aldehyde of step 3), soaks
The bubble time is 15min, and matrix is then dipped to tannic acid/chitosan nano capsule solution obtained by step 2) again by deposition processes
In, soaking time 15min, deposition processes, i.e. matrix surface deposit to form dextran aldehyde-tannic acid/chitosan polymer
Film.
A kind of pH response type polymer film of claim 1 the method preparation, it is characterised in that: press claim 1 institute
State dextran aldehyde-tannic acid/chitosan polymer film of method preparation gained pH response type bilayer.
A kind of pH response type polymer film prepares the dextran aldehyde-of gained pH response type bilayer according to the method
Tannic acid/chitosan polymer film.
A kind of application of pH response type polymer film, the dextran aldehyde-tannic acid/chitosan polymer film is as medicine
Object package carrier.
The polymer film discharges the drug of embedding under pH response.
The drug is triclosan, Bravo or the carbendazim of hydrophobicity wide-spectrum bactericide.
The additional amount of the drug accounts for the 1.03-1.74% of capsule quality.
The beneficial effects of the present invention are:
The present invention has many advantages, such as easy to operate, and preparing technique process simplicity and manufacturing cost are cheap.It is used herein
Raw material be natural green macromolecule, have wide applicability.Polymer film prepared by the present invention has pH sensibility,
It is advantageously implemented fixed point, the timing, quantitative control release of fungicide.There is good research in terms of marime fouling protection and open
Application prospect is sent out, therefore, which has good potentiality of economical exploit.
Inventive polymers film can further embed wide-spectrum bactericide, such as triclosan, specifically used surfactant ten
Six alkyl trimethyl ammonium bromides enter hydrophobicity triclosan molecule embedding in tannic acid/chitosan nano capsule, are prepared
Medicament-carried nano capsule efficiently solves the hydrophobic defect of triclosan；The Nano capsule of preparation and dextran aldehyde are passed through
Drug-carrying polymer film is prepared in LBL self-assembly method, which has the stability of high-efficient and lasting, and can be to pH
Variation makes a response release embedding molecule, avoids the loss of effective component triclosan, improves the utilization efficiency of triclosan.
Detailed description of the invention
Fig. 1 is (a) poly-dopamine prepared by embodiment 3, (b) triclosan@tannic acid/chitosan nano capsule, (c) dextrorotation
Sugared acid anhydride aldehyde, (d) dextran aldehyde-triclosan@tannic acid/chitosan polymer film infrared spectroscopy (FTIR) spectrogram；
Fig. 2 is that triclosan@tannic acid/chitosan nano capsule scanning electron microscope (SEM) prepared by embodiment 3 is shone
Piece；
Fig. 3 is that dextran aldehyde-triclosan@tannic acid/chitosan polymer film section SEM prepared by embodiment 3 is shone
Piece；
Fig. 4 is that dextran aldehyde-triclosan@tannic acid/chitosan polymer film surface SEM prepared by embodiment 3 is shone
Piece；
Fig. 5 is dextran aldehyde-triclosan@tannic acid/chitosan polymer film of the preparation of embodiment 3 different pH's
Triclosan release profiles in PBS buffer solution.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
Embodiment 1
(1) 0.15g cetyl trimethylammonium bromide is weighed, is dissolved in 40mL deionized water, is stirred at 50 DEG C of water-bath
15min obtains the cetyl trimethylammonium bromide micellar solution that concentration is 3.75mg/mL.
(2) it weighs 50mg tannic acid to be dissolved in 50mL aqueous solution and (contain 50 μ L acetic acid in aqueous solution), obtaining concentration is
The acetic acid aqueous solution containing tannic acid of 1mg/mL；Similarly, compound concentration is the acetic acid aqueous solution of the chitosan-containing of 1mg/mL.Amount
It takes acetic acid aqueous solution of the 5mL containing tannic acid to be added in 5mL cetyl trimethylammonium bromide micellar solution, stirs 20min, make
It obtains micellar surface and coats cyst wall tannic acid；Then, the acetic acid aqueous solution for measuring 5mL chitosan-containing is added in the above solution, is stirred
20min is mixed, so that tannin acid surfaces coat chitosan again, obtains tannic acid/chitosan nano capsule of core-shell structure.
(3) it weighs 3.2g sodium metaperiodate and is dissolved in 100mL deionized water, obtain the water for the sodium metaperiodate that concentration is 32mg/mL
Solution；It weighs 2.5g glucan to be added in the above sodium metaperiodate aqueous solution, is protected from light and is stirred overnight, dialysis removes extra reaction
Object obtains dextran aldehyde after freeze-drying.
(4) it weighs 1.21g trishydroxymethylaminomethane and is dissolved in 100mL deionized water, obtain the three hydroxyl first that concentration is 100mM
The aqueous solution of base aminomethane is 8.5 using hydrochloric acid conditioning solution pH value, obtains TRIS buffer；It weighs
0.2g Dopamine hydrochloride is dissolved in the above TRIS buffer, obtains the Dopamine hydrochloride-that concentration is 2mg/mL
TRIS buffer.
(5) sheet glass is cut into 1 × 2.5cm, uses acetone, ethyl alcohol respectively, deionized water washing is dried with nitrogen spare；
Sheet glass is placed in Dopamine hydrochloride-TRIS buffer, be protected from light deposition for 24 hours, and after washed through deionized water
It washs, obtains the sheet glass of poly-dopamine modification；The sheet glass that poly-dopamine is modified is immersed in above-mentioned concentration 1mg/mL as the right side again
Revolve glucosides aldehyde solution in 15min, and after washed through deionized water, obtain deposition dextran aldehyde sheet glass.It then will deposition
The sheet glass of upper dextran aldehyde immerses 15min in tannic acid/chitosan nano capsule solution again, and after washed through deionized water
It washs, obtains dextran aldehyde and tannic acid/chitosan nano capsule bi-layer membrane.It repeats above step 20 times, obtains the right side
Glucosides aldehyde-tannic acid/chitosan polymer film is revolved, is dried with nitrogen.
Embodiment 2
(1) 0.15g cetyl trimethylammonium bromide is weighed, is dissolved in 40mL deionized water, is stirred at 50 DEG C of water-bath
15min obtains the cetyl trimethylammonium bromide micellar solution that concentration is 3.75mg/mL.
(2) it weighs 150mg tannic acid to be dissolved in 50mL aqueous solution and (contain 150 μ L acetic acid in aqueous solution), obtaining concentration is
The acetic acid aqueous solution containing tannic acid of 3mg/mL；Similarly, compound concentration is the acetic acid aqueous solution of the chitosan-containing of 3mg/mL.Amount
It takes acetic acid aqueous solution of the 5mL containing tannic acid to be added in 5mL cetyl trimethylammonium bromide micellar solution, stirs 20min, make
It obtains micellar surface and coats cyst wall tannic acid；Then, the acetic acid aqueous solution for measuring 5mL chitosan-containing is added in the above solution, is stirred
20min is mixed, so that tannin acid surfaces coat chitosan again, obtains tannic acid/chitosan nano capsule of core-shell structure.
(3) it weighs 3.2g sodium metaperiodate and is dissolved in 100mL deionized water, obtain the water for the sodium metaperiodate that concentration is 32mg/mL
Solution；It weighs 2.5g glucan to be added in the above sodium metaperiodate aqueous solution, is protected from light and is stirred overnight, dialysis removes extra reaction
Object obtains dextran aldehyde after freeze-drying.
(4) it weighs 1.21g trishydroxymethylaminomethane and is dissolved in 100mL deionized water, obtain the three hydroxyl first that concentration is 100mM
The aqueous solution of base aminomethane is 8.5 using hydrochloric acid conditioning solution pH value, obtains TRIS buffer；It weighs
0.2g Dopamine hydrochloride is dissolved in the above TRIS buffer, obtains the Dopamine hydrochloride-that concentration is 2mg/mL
TRIS buffer.
(5) sheet glass is cut into 1 × 2.5cm, uses acetone, ethyl alcohol respectively, deionized water washing is dried with nitrogen spare；
Sheet glass is placed in Dopamine hydrochloride-TRIS buffer, be protected from light deposition for 24 hours, and after washed through deionized water
It washs, obtains the sheet glass of poly-dopamine modification；The sheet glass that poly-dopamine is modified is immersed in above-mentioned concentration 1mg/mL as the right side again
Revolve glucosides aldehyde solution in 15min, and after washed through deionized water, obtain deposition dextran aldehyde sheet glass.It then will deposition
The sheet glass of upper dextran aldehyde immerses 15min in tannic acid/chitosan nano capsule solution again, and after washed through deionized water
It washs, obtains dextran aldehyde and tannic acid/chitosan nano capsule bi-layer membrane.It repeats above step 20 times, obtains the right side
Glucosides aldehyde-tannic acid/chitosan polymer film is revolved, is dried with nitrogen.
Embodiment 3
By taking triclosan as an example, the polymer film of embedding medicinal is prepared:
(1) 0.15g cetyl trimethylammonium bromide is weighed, is dissolved in 40mL deionized water, is stirred at 50 DEG C of water-bath
15min obtains the cetyl trimethylammonium bromide micellar solution that concentration is 3.75mg/mL.
(2) 4g triclosan is weighed, is dissolved in 50mL methylene chloride, the mother liquor of 20mg/mL is configured to, 200 μ L mother liquors is taken to add
Enter into 40mL cetyl trimethylammonium bromide micellar solution, ultrasonic 60min is stirred overnight, methylene chloride is made to volatilize, obtains
Embed the cetyl trimethylammonium bromide micellar solution of triclosan.
(3) it weighs 50mg tannic acid to be dissolved in 50mL aqueous solution and (contain 50 μ L acetic acid in aqueous solution), obtaining concentration is
The acetic acid aqueous solution containing tannic acid of 1mg/mL；Similarly, compound concentration is the acetic acid aqueous solution of the chitosan-containing of 1mg/mL.Amount
Acetic acid aqueous solution of the 5mL containing tannic acid is taken to be added in the cetyl trimethylammonium bromide micellar solution of 5mL embedding triclosan,
20min is stirred, so that micellar surface coats cyst wall tannic acid；Then, measure 5mL chitosan-containing acetic acid aqueous solution be added to
In upper solution, 20min is stirred so that tannin acid surfaces coat chitosan again and is embedded tannic acid/chitosan of triclosan
Nano capsule is denoted as triclosan@tannic acid/chitosan nano capsule (referring to Fig. 1 and Fig. 2).
(4) it weighs 3.2g sodium metaperiodate and is dissolved in 100mL deionized water, obtain the water for the sodium metaperiodate that concentration is 32mg/mL
Solution；It weighs 2.5g glucan to be added in the above sodium metaperiodate aqueous solution, is protected from light and is stirred overnight, dialysis removes extra reaction
Object obtains dextran aldehyde after freeze-drying.
(5) it weighs 1.21g trishydroxymethylaminomethane and is dissolved in 100mL deionized water, obtain the three hydroxyl first that concentration is 100mM
The aqueous solution of base aminomethane is 8.5 using hydrochloric acid conditioning solution pH value, obtains TRIS buffer；It weighs
0.2g Dopamine hydrochloride is dissolved in the above TRIS buffer, obtains the Dopamine hydrochloride-that concentration is 2mg/mL
TRIS buffer.
(6) sheet glass is cut into 1 × 2.5cm, uses acetone, ethyl alcohol respectively, deionized water washing is dried with nitrogen spare；
Sheet glass is placed in Dopamine hydrochloride-TRIS buffer, is protected from light deposition for 24 hours, deionized water washing obtains
The sheet glass of poly-dopamine modification；It is in dextran aldehyde solution that the sheet glass that poly-dopamine is modified, which is immersed in concentration 1mg/mL,
15min, deionized water washing, obtains the sheet glass of deposition dextran aldehyde.The sheet glass of upper dextran aldehyde will then be deposited
15min in triclosan@tannic acid/chitosan nano capsule solution is immersed, deionized water washing obtains dextran aldehyde and trichlorine
The bi-layer membrane of raw@tannic acid/chitosan nano capsule.It repeats above step 20 times, obtains dextran aldehyde-triclosan@
Tannic acid/chitosan polymer film (referring to Fig. 1, Fig. 3 and Fig. 4), is dried with nitrogen.
Embodiment 4
By taking triclosan as an example, the polymer film of embedding medicinal is prepared:
(1) 0.15g cetyl trimethylammonium bromide is weighed, is dissolved in 40mL deionized water, is stirred at 50 DEG C of water-bath
15min obtains the cetyl trimethylammonium bromide micellar solution that concentration is 3.75mg/mL.
(2) 4g triclosan is weighed, is dissolved in 50mL methylene chloride, the mother liquor of 20mg/mL is configured to, 200 μ L mother liquors is taken to add
Enter into 40mL cetyl trimethylammonium bromide micellar solution, ultrasonic 60min is stirred overnight, methylene chloride is made to volatilize, obtains
Embed the cetyl trimethylammonium bromide micellar solution of triclosan.
(3) it weighs 150mg tannic acid to be dissolved in 50mL aqueous solution and (contain 150 μ L acetic acid in aqueous solution), obtaining concentration is
The acetic acid aqueous solution containing tannic acid of 3mg/mL；Similarly, compound concentration is the acetic acid aqueous solution of the chitosan-containing of 3mg/mL.Amount
Acetic acid aqueous solution of the 5mL containing tannic acid is taken to be added in the cetyl trimethylammonium bromide micellar solution of 5mL embedding triclosan,
20min is stirred, so that micellar surface coats cyst wall tannic acid；Then, measure 5mL chitosan-containing acetic acid aqueous solution be added to
In upper solution, 20min is stirred so that tannin acid surfaces coat chitosan again and is embedded tannic acid/chitosan of triclosan
Nano capsule is denoted as triclosan@tannic acid/chitosan nano capsule.
(4) it weighs 3.2g sodium metaperiodate and is dissolved in 100mL deionized water, obtain the water for the sodium metaperiodate that concentration is 32mg/mL
Solution；It weighs 2.5g glucan to be added in the above sodium metaperiodate aqueous solution, is protected from light and is stirred overnight, dialysis removes extra reaction
Object obtains dextran aldehyde after freeze-drying.
(5) it weighs 1.21g trishydroxymethylaminomethane and is dissolved in 100mL deionized water, obtain the three hydroxyl first that concentration is 100mM
The aqueous solution of base aminomethane is 8.5 using hydrochloric acid conditioning solution pH value, obtains TRIS buffer；It weighs
0.2g Dopamine hydrochloride is dissolved in the above TRIS buffer, obtains the Dopamine hydrochloride-that concentration is 2mg/mL
TRIS buffer.
(6) sheet glass is cut into 1 × 2.5cm, uses acetone, ethyl alcohol respectively, deionized water washing is dried with nitrogen spare；
Sheet glass is placed in Dopamine hydrochloride-TRIS buffer, is protected from light deposition for 24 hours, deionized water washing obtains
The sheet glass of poly-dopamine modification；It is in dextran aldehyde solution that the sheet glass that poly-dopamine is modified, which is immersed in concentration 1mg/mL,
15min, deionized water washing, obtains the sheet glass of deposition dextran aldehyde.The sheet glass of upper dextran aldehyde will then be deposited
15min in triclosan@tannic acid/chitosan nano capsule solution is immersed, deionized water washing obtains dextran aldehyde and trichlorine
The bi-layer membrane of raw@tannic acid/chitosan nano capsule.It repeats above step 20 times, obtains dextran aldehyde-triclosan@
Tannic acid/chitosan polymer film, is dried with nitrogen.
Performance survey is carried out to dextran aldehyde-triclosan tannic acid/chitosan polymer film of above-mentioned acquisition embedding medicinal
Examination:
(1) to the dextran aldehyde of embedding medicinal-triclosan@tannic acid/chitosan polymer film carry out respectively FTIR and
SEM test.
By Fig. 1 (a) poly-dopamine, (b) triclosan@tannic acid/chitosan nano capsule, (c) dextran aldehyde is (d) right
Sugared acid anhydride aldehyde-triclosan@tannic acid/chitosan polymer film FTIR spectrogram is revolved as it can be seen that for (a) spectrogram, in 2941cm-1Place
Absorption peak is attributed to C-H stretching vibration, in 1630cm-1The absorption peak at place is attributed to the stretching vibration and N-H bending vibration of aromatic rings
It is dynamic, in 1512 and 1293cm-1C-O-the H of N-H scissoring vibration and phenol that the absorption peak that place observes is attributed to amide groups respectively stretches
Contracting vibration, in 1461cm-1The absorption peak at place is attributed to C=C stretching vibration in indoles, and this feature peak is in the FTIR spectrogram of (d)
Also it is observed, shows poly-dopamine deposition on the glass substrate.For the FTIR spectrogram of (b), 2918,2850,1722,
1604cm-1The absorption peak that place observes is attributed to-CH in cetyl trimethylammonium bromide respectively2And-CH3The flexible vibration of C-H
C=O and C=C-C stretching vibration in dynamic and tannic acid.(d) C-H stretching vibration absworption peak is transferred to 2922 Hes in FTIR spectrogram
2851cm-1Place, shows triclosan@tannic acid/chitosan nano capsule deposition among polymer film.For the FTIR spectrum of (c)
Figure, in 1720 and 1153cm-1The absorption peak at place is attributed to the stretching vibration and C-H stretching vibration of carbonyl respectively.For (d)
FTIR spectrogram, in 1639cm-1The absorption peak at place is attributed to C=N stretching vibration, this is because the carbonyl and nanometer of dextran aldehyde
The amino of chitosan occurs caused by Aldehyde-ammonia Condensation reaction generation imine linkage in capsule.In addition, in 1720 and 1158cm-1The weak suction at place
It receives peak to be also observed, shows that dextran aldehyde is deposited on polymer film.The above result shows that dextran aldehyde-trichlorine
Raw@tannic acid/chitosan polymer film is successfully prepared.
It can significantly observe triclosan@tannic acid/chitosan nano capsule shape close to ball by Fig. 2 SEM photograph
Shape, compact structure, no significant defect, average diameter are about 500nm；Fig. 3 SEM cross-section photograph can measure dextran aldehyde-
Triclosan@tannic acid/chitosan polymer film thickness is 3.91 μm；Fig. 4 SEM pattern photo can see triclosan@tannic acid/
Chitosan nano capsule distribution is in polymer film surface.
(2) pH response release is carried out to the dextran aldehyde of embedding medicinal-triclosan@tannic acid/chitosan polymer film
Triclosan detection:
Buffer is PBS buffer solution, and adjusting pH of buffer using hydrochloric acid and sodium hydroxide is respectively 4,5,6,7,8.Experiment
In, upper dextran aldehyde-triclosan tannic acid/chitosan polymer film glass substrate will be deposited and be placed in 10mL difference pH value
PBS buffer solution in, per pipetting 2mL buffer at regular intervals, using Hitachi U-2900 spectrophotometer λ=
281nm measures absorbance.Combined standard curve, the relation curve of the triclosan concentration and time that are released (referring to Fig. 5).
As a result as shown in figure 5, within release time for 24 hours, dextran aldehyde-triclosan@tannic acid/chitosan polymer
Film release efficiency in the PBS buffer solution of pH=6 is maximum, and the triclosan concentration of release reaches 4.01mg/L；In the PBS of pH=5
Release efficiency takes second place in buffer, and the triclosan concentration of release is 3.03mg/L；It is discharged in pH=4,7,8 PBS buffer solution
Efficiency is lower, and the triclosan concentration of release is respectively 2.05mg/L, 1.82mg/L, 1.27mg/L.The result shows that dextran aldehyde-
Triclosan@tannic acid/chitosan polymer film discharges triclosan efficiency highest under mildly acidic conditions, and in highly acid, neutrality
And there is lower triclosan release efficiency under weak basic condition.
It is recorded according to above-described embodiment and is replaced triclosan by other hydrophobicity biocide molecules, that is, obtain thickness about
For 3.9 μm of drug-carrying polymer film, released since dextran aldehyde-triclosan@tannic acid/chitosan polymer film drug controls
It is only related with the pH response property of imine linkage to put performance, i.e. tannic acid/chitosan nano capsule and dextran aldehyde is to pass through Asia
Amine key connects the polymer film to be formed, and imine linkage is broken under conditions of pH=5.0-6.5, leads to dextran aldehyde-trichlorine
The destruction of raw@tannic acid/chitosan polymer film, so that the drug molecule release of embedding.Therefore, all to be introduced into surface
The drug molecule of lammonium bromide hydrophobic side can be embedded into polymer film, while drug point
Son is able to achieve identical pH response releasing effect.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of preparation method of pH response type polymer film, it is characterised in that: use tannic acid, chitosan and dextran aldehyde
For raw material, target product, i.e. dextran aldehyde-tannic acid/chitosan polymer film are synthesized by covalent bond LBL self-assembly method；
Wherein, the mass ratio of tannic acid, chitosan and dextran aldehyde is 0.3-1:0.3-1:1.
2. the preparation method of pH response type polymer film according to claim 1, it is characterised in that:
1) cetyl trimethylammonium bromide is dissolved in deionized water and forms micellar solution；
2) acetic acid aqueous solution containing tannic acid is added into above-mentioned acquisition micellar solution, it is molten to obtain tannic acid capsule after mixing evenly
Liquid；The acetic acid aqueous solution of chitosan-containing is then added, after mixing evenly as tannic acid/chitosan nano capsule solution；
3) sodium metaperiodate is dissolved in the aqueous solution for forming sodium metaperiodate in deionized water, glucan stirring is then added, is obtained right
Revolve sugared acid anhydride aldehyde aqueous solution；
4) trishydroxymethylaminomethane is dissolved in deionized water, adjusting solution ph is 8-8.5, obtains trishydroxymethylaminomethane
Buffer；It then adds Dopamine hydrochloride and forms Dopamine hydrochloride-TRIS buffer after mixing；
5) matrix is immersed in above-mentioned Dopamine hydrochloride-TRIS buffer, matrix surface is enable to modify
Form the matrix of poly-dopamine modification；The matrix that poly-dopamine is modified is added water-soluble to the resulting dextran aldehyde of step 3)
In liquid, matrix is then dipped in tannic acid/chitosan nano capsule solution obtained by step 2) again, then takes by deposition processes
Matrix out, then deposit immersion in different solutions according to this step repeatedly, i.e., matrix surface deposits to form dextran aldehyde-tannin
Acid/chitosan polymer film.
3. pH response type polymer film as described in claim 2 and preparation method thereof, it is characterised in that: ten in the step 1)
Six alkyl trimethyl ammonium bromides and water stir 10-15min after mixing at 40-50 DEG C, for use.
4. pH response type polymer film as described in claim 2 and preparation method thereof, it is characterised in that: the step 2) is containing single
The final concentration of 1-3mg/mL of tannic acid in the acetic acid aqueous solution of peaceful acid；Wherein, the additional amount of acetic acid is 1-3 in acetic acid aqueous solution
μL/mL；
The final concentration of 1-3mg/mL of chitosan in the acetic acid aqueous solution of the chitosan-containing, wherein acetic acid in acetic acid aqueous solution
Additional amount be 1-3 μ L/mL.
5. pH response type polymer film as described in claim 2 and preparation method thereof, it is characterised in that: the high iodine of step 3)
The final concentration of 32mg/mL of the aqueous solution meso-periodic acid sodium of sour sodium, glucan additional amount are 25mg/mL；
Glucan is added in the aqueous solution of the sodium metaperiodate, is stirred overnight, then dialysis obtains dextran aldehyde aqueous solution.
6. pH response type polymer film as described in claim 2 and preparation method thereof, it is characterised in that: three hydroxyl of step 4)
Aminomethane is dissolved in the final concentration of 12.1mg/mL of trishydroxymethylaminomethane in deionized water, and Dopamine hydrochloride is added
Amount is 2mg/mL；
7. pH response type polymer film as described in claim 2 and preparation method thereof, it is characterised in that: the step 4) is described
Matrix immerses in Dopamine hydrochloride-TRIS buffer, and soaking time is for 24 hours, its modification to be made to form poly- DOPA
Amine-modified matrix；The matrix of poly-dopamine modification is added into the aqueous solution of the resulting dextran aldehyde of step 3), when immersion
Between be 15min, matrix is then dipped in tannic acid/chitosan nano capsule solution obtained by step 2) by deposition processes again, leaching
The bubble time is 15min, and deposition processes, i.e. matrix surface deposit to form dextran aldehyde-tannic acid/chitosan polymer film.
8. a kind of pH response type polymer film of claim 1 the method preparation, it is characterised in that: by described in claim 1
Dextran aldehyde-tannic acid/chitosan polymer film of method preparation gained pH response type bilayer.
9. a kind of application of pH response type polymer film according to any one of claims 8, it is characterised in that: the dextran aldehyde-is mono-
Peaceful acid/chitosan polymer film is as drug encapsulation body.
10. the application of pH response type polymer film according to claim 9, it is characterised in that: the drug is that hydrophobicity is wide
Compose triclosan, Bravo or the carbendazim of fungicide.
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| CN110734655A (en) * | 2019-10-08 | 2020-01-31 | 齐鲁工业大学 | pH-responsive super-hydrophobic coating material, and preparation method and application thereof |
| CN112262850A (en) * | 2020-10-27 | 2021-01-26 | 扬州大学 | PH-responsive pyraclostrobin controlled-release agent and preparation method and application thereof |
| CN113462000A (en) * | 2021-06-21 | 2021-10-01 | 武汉大学 | Surface antibacterial treatment method of absorbable surgical material |
| CN116570733B (en) * | 2023-07-13 | 2023-10-13 | 四川大学华西医院 | Multifunctional core-shell structured drug micelle and preparation method thereof |
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