CN101709103B - Method for preparing photoresponse hydrogel containing azo monomer by utilizing light sources with different wavelengths - Google Patents

Method for preparing photoresponse hydrogel containing azo monomer by utilizing light sources with different wavelengths Download PDF

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CN101709103B
CN101709103B CN2009102362754A CN200910236275A CN101709103B CN 101709103 B CN101709103 B CN 101709103B CN 2009102362754 A CN2009102362754 A CN 2009102362754A CN 200910236275 A CN200910236275 A CN 200910236275A CN 101709103 B CN101709103 B CN 101709103B
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hema
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photoresponse
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何勇
刘建伟
聂俊
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Beijing University of Chemical Technology
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Abstract

The invention provides a method for preparing a photoresponse hydrogel containing azo monomers by utilizing light sources with different wavelengths, belonging to the field of hydrogels. The method comprises the step of: crosslinking acrylic ester and the activated azo monomers by a crosslinker through ultraviolet light or visible light to prepare the photoresponse hydrogels with different properties and release mechanisms, wherein the acrylic esters comprise hydroxy-ethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA); the structures of the activated azo monomers are shown as formula (I) and formula (II), wherein R1 and R2 are H, COOH and SO3H; and the crosslinker is N, N-methylene-bisacrylamide and water-soluble bifunctional acrylic esters and comprises polyethyleneglycol diacrylate (200, 400, 600, 800, 1000), wherein the R1 and the R2 are the H, the COOH and the SO3H. The invention has moderate condition and simple step and can be used for biomedicine aspects, i.e. drug controlled-release materials, tissue engineering, and the like.

Description

The light sources with different wavelengths preparation contains the method for the photoresponse hydrogel of azo monomer
Technical field
The present invention relates to a kind of new preparation and have the method for the photoresponse hydrogel of different performance and releasing mechanism, promptly by UV-light and two kinds of Different Light of visible light, acrylate and active ozo monomer is crosslinked with linking agent, prepare the performance photoresponse hydrogel all different with releasing mechanism.Prepared photoresponse hydrogel has the potential widespread use at biomedical aspect as fields such as drug release and organizational projects.
Background technology
Nitrogen benzide is because under the irradiation of light sources with different wavelengths, its structure and performance have corresponding variation.This outstanding feature has attracted a large amount of researchists that it is studied.Intelligent aqueous gel capable comprises temperature-sensitive hydrogel, pH sensitive aquagel, photaesthesia hydrogel, glucose-sensitive hydrogels, electric sensitive aquagel etc.Most widely used temperature-sensitive hydrogel and pH sensitive aquagel all have the shortcoming of himself: temperature-sensitive hydrogel is subject to thermodiffusion and the temperature disadvantageous effect to target molecule, and the pH sensitive aquagel is subject to hydrionic diffusion.By contrast, light stimulus can realize instantaneity and accuracy, so photoresponse hydrogel has special advantage than the above two.
Containing the monomeric photoresponse hydrogel of nitrogen benzide is most representative intelligent aqueous gel capable.Under the irradiation of Different Light, nitrogen benzide generation cis-trans isomerism, and then in its size, shape and the corresponding variation of polarity generation.Li Chen (Li Chen et al.Journal of Applied Polymer Science, 2005,96,2163-2167) people such as grade has studied pH response and the response characteristics to light that contains acrylic-amino nitrogen benzide and acrylate photoresponse hydrogel.(Yan-Li Zhao et al.Langmuir 2009 Letter) waits the people to investigate by the nitrogen benzide cis-trans isomerism and causes the gel-sol of photoresponse hydrogel and the variation of sol-gel phase transition Yan-Li Zhao.
But above photoresponse hydrogel all prepares by thermal polymerization process.Because photopolymerization process has gentle reaction conditions, fast and characteristics such as the space is adjustable, so be the technology that is well suited for preparing biomaterial.
Summary of the invention
The present invention seeks in order to provide a kind of new preparation to have the method for the photoresponse hydrogel of different performance and releasing mechanism.
The technical solution used in the present invention:
By UV-light and two kinds of Different Light of visible light, acrylate and active ozo monomer is crosslinked with linking agent, prepare the performance photoresponse hydrogel all different with releasing mechanism.Described esters of acrylic acid comprises Hydroxyethyl acrylate (HEA) or hydroxyethyl methylacrylate (HEMA); The active ozo monomer structure is suc as formula (I) and (II): R wherein 1And R 2Be H, COOH, SO 3H; Used linking agent is N, and N methylene-bisacrylamide and water-soluble dual functional esters of acrylic acid comprise polyethyleneglycol diacrylate (200,400,600,800,1000).
R wherein 1And R 2Be H, COOH, SO 3H.
The present invention adopts following reaction conditions:
With olefin(e) acid hydroxyl ethyl ester HEA or hydroxyethyl methylacrylate HEMA is water-soluble monomer, azo monomer content is 1%～5% of HEA or HEMA quality, used linking agent is that mass ratio is 1: 1 N, N methylene-bisacrylamide and polyethyleneglycol diacrylate, N, the N methylene-bisacrylamide is 5%～20% of HEA or a HEMA quality, water is HEA or HEMA quality 2～4 times, when UV-irradiation adopts light trigger is (2,4, the 6-trimethylbenzoyl) diphenyl phosphine oxide is 0.5%～5% of HEA or HEMA quality; When radiation of visible light adopts mass ratio is 1: 1 camphorquinone and right-N, the N-dimethyl ethyl aminobenzoate; Camphorquinone and right-N, N-dimethyl ethyl aminobenzoate are 0.5%～5% of HEA or HEMA quality, and the light intensity of light source is controlled at 50mw～300mw, shine 2～60 minutes;
Wherein the azo monomer structure suc as formula (I) and (II),
Figure GSB00000422258300022
R wherein 1And R 2Be H, COOH, SO 3H.
Mild condition of the present invention, step is simple.The hydrogel of preparing shows different microtextures and different swelling, releasing mechanisms, can be used for biomedical aspects such as drug release material, organizational project.
Description of drawings
Fig. 1 is the sem photograph of hydrogel (I-1); UV-light be C1～C4, visible light is T1～T4.
Fig. 2 is the swelling curve figure of hydrogel (I-1); Fig. 2 A, B are respectively ultraviolet and visible light.
Fig. 3 is the drug release figure of hydrogel (I-1); Fig. 3 A, B are respectively ultraviolet and visible light.
Embodiment
Below several examples are detailed descriptions that the present invention carries out in conjunction with application, but protection scope of the present invention is not limited in this.
Embodiment one: azo monomer is the preparation of 4-sulfonic group-4 ' acryloxy nitrogen benzide hydrogel
(1) with four parts of same amount HEA (1.5g), PEGDA-600 (0.15g), N, ultrasonic 10 minutes of the mixing solutions of N methylene-bisacrylamide (0.15g), TPO (0.075g) adds 4-sulfonic group-4 ' acryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g) and water (3g) respectively.Adopt ultraviolet lamp (50mw) to shine (2 minutes, 5 minutes, 10 minutes, 30 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
(2) with HEA (1.5g), PEGDA-600 (0.15g), the N of four parts of same amount, N methylene-bisacrylamide (0.15g), camphorquinone (CQ) and right-N, ultrasonic 10 minutes of the mixing solutions of N-dimethyl ethyl aminobenzoate (EDMAB) each (0.075g) adds 4-sulfonic group-4 ' acryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g) and water (3g) respectively.Adopt visible light (70mw) to shine (5 minutes, 10 minutes, 30 minutes, 60 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
The hydrogel that UV-irradiation obtains is C1～C4, and swelling character and drug release curve are respectively as Fig. 2 (A) and 3 (A); The hydrogel that radiation of visible light obtains is T1～T4, and swelling character and drug release curve are respectively as Fig. 2 (B) and 3 (B), and their microtexture is distinguished as shown in Figure 1.Wherein the azo monomer structural formula is shown in (I).
Figure GSB00000422258300031
Embodiment two: azo monomer is the preparation of 4-sulfonic group-4 ' methacryloxy nitrogen benzide hydrogel
(1) with four parts of same amount HEMA (1.5g), PEGDA-400 (0.075g), N, ultrasonic 10 minutes of the mixing solutions of N methylene-bisacrylamide (0.075g), TPO (0.0075g) adds 4-sulfonic group-4 ' acryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g) and water (4.5g) respectively.Adopt ultraviolet lamp (80mw) to shine (2 minutes, 5 minutes, 10 minutes, 30 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
(2) with HEA (1.5g), PEGDA-400 (0.075g), the N of four parts of same amount, N methylene-bisacrylamide (0.075g), camphorquinone (CQ) and right-N, ultrasonic 10 minutes of the mixing solutions of N-dimethyl ethyl aminobenzoate (EDMAB) each (0.0075g) adds 4-sulfonic group-4 ' methacryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g) and water (4.5g) respectively.Adopt visible light (100mw) to shine (5 minutes, 10 minutes, 30 minutes, 60 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
Wherein the azo monomer structural formula is shown in (II).
Figure GSB00000422258300041
Embodiment three: azo monomer is the preparation of 4-carboxyl-4 '-acryloxy nitrogen benzide hydrogel
(1) with five parts of same amount HEA (1.5g), PEGDA-200 (0.225g), N, ultrasonic 10 minutes of the mixing solutions of N methylene-bisacrylamide (0.225g), TPO (0.03g) adds 2-cyano group-4-sulfonic group-2 '-carboxyl-4 '-acryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g, 0.075g) and water (6g) respectively.Adopt ultraviolet lamp (120mw) to shine (2 minutes, 5 minutes, 10 minutes, 15 minutes, 30 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
(2) with HEA (1.5g), PEGDA-200 (0.225g), the N of five parts of same amount, N methylene-bisacrylamide (0.225g), camphorquinone (CQ) and right-N, ultrasonic 10 minutes of the mixing solutions of N-dimethyl ethyl aminobenzoate (EDMAB) each (0.03g) adds 4-carboxyl-4 '-acryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g, 0.075g) and water (6g) respectively.Adopt visible light (120mw) to shine (5 minutes, 10 minutes, 15 minutes, 30 minutes, 60 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
Wherein the azo monomer structural formula is shown in (III).
Figure GSB00000422258300042
Embodiment four: azo monomer is the preparation of 2-carboxyl-4-sulfonic group-4 ' methacryloxy nitrogen benzide hydrogel
(1) with four parts of same amount HEA (1.5g), PEGDA-800 (0.3g), N, ultrasonic 10 minutes of the mixing solutions of N methylene-bisacrylamide (0.3g), TPO (0.045g) adds 2-carboxyl-4-sulfonic group-4 ' methacryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g) and water (6g) respectively.Adopt ultraviolet lamp (200mw) to shine (2 minutes, 5 minutes, 10 minutes, 30 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
(2) with HEA (1.5g), PEGDA-800 (0.3g), the N of four parts of same amount, N methylene-bisacrylamide (0.3g), camphorquinone (CQ) and right-N, ultrasonic 10 minutes of the mixing solutions of N-dimethyl ethyl aminobenzoate (EDMAB) each (0.045g) adds 2-carboxyl-4-sulfonic group-4 ' methacryloxy nitrogen benzide (0.015g, 0.03g, 0.045g, 0.06g) and water (6g) respectively.Adopt visible light (180mw) to shine (5 minutes, 10 minutes, 30 minutes, 60 minutes) respectively.The colloid water of preparation is washed 5 times, put into 40 ℃ of conditions of vacuum drying oven following 24 hours.
Wherein the azo monomer structural formula is shown in (IV).
Figure GSB00000422258300051
The hydrogel that above embodiment obtains all has similar swelling and medicine-releasing performance.The foregoing description only is explanation technical conceive of the present invention and characteristics; its purpose is to allow this area personage who is familiar with this technology can recognize content of the present invention and enforcement according to this; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.

Claims (1)

1. the light sources with different wavelengths preparation contains the method for the photoresponse hydrogel of azo monomer, it is characterized in that: with olefin(e) acid hydroxyl ethyl ester HEA or hydroxyethyl methylacrylate HEMA is water-soluble monomer, azo monomer content is 1%～5% of HEA or HEMA quality, used linking agent is that mass ratio is 1: 1 N, N methylene-bisacrylamide and polyethyleneglycol diacrylate, N, N methylene-bisacrylamide are 5%～10% of HEA or HEMA quality, and water is HEA or HEMA quality 2～4 times;
When UV-irradiation adopts light trigger is (2,4, the 6-trimethylbenzoyl) diphenyl phosphine oxide, is 0.5%～5% of HEA or HEMA quality; When radiation of visible light adopts mass ratio is 1: 1 camphorquinone and right-N, the N-dimethyl ethyl aminobenzoate; Camphorquinone and right-N, N-dimethyl ethyl aminobenzoate are 0.5%～5% of HEA or HEMA quality, and the light intensity of light source is controlled at 50mw～300mw, shine 2～60 minutes;
Wherein the azo monomer structure suc as formula (I) and (II),
Figure FSB00000422258200011
R wherein 1And R 2Be H, COOH, SO 3H.
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CN101824124A (en) * 2010-04-20 2010-09-08 常州杰森化工材料科技有限公司 Preparation method of photoresponse hydrogel containing azo monomers
CN103570872B (en) * 2013-10-11 2016-02-17 天津大学 High-strength light sensitive aquagel and its preparation method and application
CN104292445B (en) * 2014-09-03 2016-11-16 山东久日化学科技有限公司 A kind of preparation method of macromole p-(dimethylamino)-benzoic acid ester type compound
CN111978463B (en) * 2020-09-01 2022-05-20 金陵科技学院 Preparation method of hydrogel drug carrier with light control characteristic
CN112480309B (en) * 2020-11-25 2021-12-28 复旦大学 Deformable intelligent hydrogel robot and preparation method thereof
CN112480308B (en) * 2020-11-25 2022-03-18 复旦大学 Intelligent hydrogel and preparation method thereof
CN117247333B (en) * 2023-09-27 2024-01-16 四川大学华西医院 Light-responsive controllable permeation cross-linked small molecular vesicles, and preparation method and application thereof

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