CN103304733A - Preparation method of degradable environmental sensitive polymer nano hydrogel and application - Google Patents
Preparation method of degradable environmental sensitive polymer nano hydrogel and application Download PDFInfo
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Abstract
The invention belongs to the technical field of high molecular materials, and in particular relates to preparation of a degradable environmental sensitive polymer nano hydrogel and an application. According to the invention, the degradable multiple environmental sensitive polymer nano hydrogel is obtained through precipitation polymerization by taking N-vinyl caprolactam as a main monomer, N, N'-di(acrylyl) cystamine as a crosslinking agent as well as hydrophilic monomers such as methylacrylic acid, hydroxymethyl acrylamide, polyethylene glycol monomethyl ether metacrylic acid ester (Mw=2000) as comonomers. According to the invention, the raw materials are easily-available, and the preparation method is simple. According to the method, water is used as the solvent, so that the method is environment-friendly. The polymer nano hydrogel prepared is good in dispersibility, uniform in size, and good in stability and biocompatibility. The phase inversion temperature of the polymer can be adjusted by controlling the use levels of methylacrylic acid, N-hydroxymethyl acrylamide and polyethylene glycol monomethyl ether metacrylic acid ester and the pH value of the environment. Therefore, the hydrogel can be applied to release of medicines in fixed points and is used as a carrier for targeted release of medicines.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the preparation method and application that a kind of environment correspondence for medicine control release is gathered (N-caprolactam) nanogel.
Background technology
Polyalcohol hydrogel be can be in water swelling but undissolved tridimensional network system, compare with hydrophobic polymer and to have lot of advantages, big or small controlled such as particle, good colloidal stability and biocompatibility.In addition, polyalcohol hydrogel can adsorb medicine or bioactive molecules, and can make the material that is fixed keep for a long time active, so hydrogel has a wide range of applications in fields such as medicine control releases.
In recent years, the environment sensitive nano-hydrogel has caused widely as medicine controlled release carrier to be paid close attention to, it can respond to the variation of external environment information (such as temperature, pH value, ionic strength, reduction potential, light etc.), and the physicochemical property of self are changed, thereby the control that can realize medicine discharges.Wherein, the temperature sensitivity nano-hydrogel has attracted numerous researchists, because the temperature of cancerous tumours cell is usually above normal cell, temperature sensitive polymer just can be realized at high temperature fast release anti-cancer medicine, slowly discharge the function of medicine under the low temperature, thereby effectively reduce medicine to Normocellular infringement.The most classical temperature sensitive polymer is NIPA, but has limited its application as pharmaceutical carrier owing to having certain cytotoxicity.In recent years, another kind of temperature sensing polymer---poly-(N-caprolactam) received numerous researchists' concern.Its good biocompatibility, phase transition temperature is 30 ~ 32
oC can regulate phase transition temperature by adding other comonomer, so the useful as drug carrier, realizes that the control of medicine discharges.
Yet the nano-hydrogel based on poly-(N-caprolactam) of report mostly is nondegradable at present, thereby can't realize the abundant release to medicine.Can realize the degraded of polymer nano hydrogel by introducing functional linking agent.Researchist's discovery, the concentration of intracellular reducing substance gsh is about 2-10 mM, and much larger than the extracellular (2-20 μ M), this is so that the inside and outside reduction potential difference of cell.Based on this point, we have introduced a kind of linking agent that contains disulfide linkage---N, N '-two (acryloyl) cystamine, formed polymer nano hydrogel inner disulfide linkage in the cell reducing environment is reduced into the sulfydryl fracture take it as linking agent, whole polymer network is untied become micromolecular linear polymer, medicine is by fully, discharge rapidly then.
With regard to degradable environment-responsive polymer nano hydrogel, the most of more complicated of the synthetic method of present bibliographical information, step is many, and how to carry out in organic phase.Adopt pertinent literature that the aqueous phase precipitation polymerization prepares degradable poly (N-caprolactam) nano-hydrogel seldom, this preparation method is simple, environmental protection, efficient are higher, and the particle,colloid good stability, the good biocompatibility that make, can realize that by the response to environment the control of medicine discharges, thereby be a kind of desirable pharmaceutical carrier.
Summary of the invention
The object of the invention is to propose a kind of degradable environment-responsive polymer nano hydrogel and its preparation method and application.
The degradable environment-responsive polymer nano hydrogel that the present invention proposes is by adopting precipitation polymerization to prepare at aqueous phase.The introducing of comonomer methacrylic acid, N hydroxymethyl acrylamide, polyethylene glycol monomethyl ethermethacrylic acid esters etc. not only can change the phase transition temperature of polymkeric substance, and makes it have pH susceptibility; Equally, being introduced in of polyethylene glycol monomethyl ethermethacrylic acid esters also improved its biocompatibility when changing the polymer phase transition temperature.In addition, in preparation process, introduce dexterously the linking agent contain disulfide linkage, make the polymer nano hydrogel for preparing can be degradable in reducing environment, thereby the fixed point that can realize medicine discharges.Its preparation process is as follows:
(1) take water as solvent, 950 ~ 980mg N-caprolactam, 20 ~ 40 mg methacrylic acids or N hydroxymethyl acrylamide, 20 ~ 100 mg sodium lauryl sulphate and 10 ~ 100 mg sodium bicarbonates are dissolved in the 100 mL water;
(2) with 20 ~ 200 mg linking agent N, N '-two (acryloyl) cystamine is dissolved in 1 ~ 10 mL dimethyl sulfoxide (DMSO), and is transferred in the reaction system of step (1) gained; Under mechanical stirring, in the nitrogen atmosphere, temperature of reaction risen to 60 ~ 80 ℃ after, add fast 10 ~ 100 mg Potassium Persulphates, add 0 ~ 100 mg polyethylene glycol monomethyl ethermethacrylic acid esters behind the polyreaction 0.25-1 h, stopped reaction behind the 4-8 h slowly is cooled to room temperature in nitrogen atmosphere; After reaction finished, unreacted monomer was removed in dialysis, and linear polymer and other impurity can obtain degradable environment-responsive polymer nano hydrogel after the freeze-drying.Wherein unreacted monomer refers to the N-caprolactam, methacrylic acid, N hydroxymethyl acrylamide and polyethylene glycol monomethyl ethermethacrylic acid esters; Linear polymer is the linear polymer that several monomer copolymerizations form; Other impurity are ammonium lauryl sulfates, sodium bicarbonate and Potassium Persulphate etc.
Among the present invention, mechanical stirring speed is 100 ~ 400 rpm in the step (2).
Among the present invention, the Mw of polyethylene glycol monomethyl ethermethacrylic acid esters=2000.
The degradable environment-responsive polymer nano hydrogel that utilizes preparation method of the present invention to obtain is controlled the application of the carrier that discharges as medicine.
Raw material of the present invention is easy to get, and the preparation method is simple, take water as solvent, and environmental sound.The polymer nano hydrogel good dispersity for preparing, big or small homogeneous has satisfactory stability and biocompatibility.Can regulate the phase transition temperature of polymer nano hydrogel by the consumption of controlling methacrylic acid or N hydroxymethyl acrylamide, polyethylene glycol monomethyl ethermethacrylic acid esters, the fixed point that can be applicable to medicine discharges, as the carrier of drug targeting release.Owing to containing the introducing of disulfide bond crosslinking agent so that polymer nano hydrogel has degradability in reducing environment, thus medicine can be fully, discharge rapidly.Because polymer nano hydrogel has the multiple environment-responsives such as temperature, reduction, pH, the product that the inventive method obtains has great application prospect in medicine control release field.
The method for preparing degradable environment correspondence polymer nano hydrogel both at home and abroad at present mainly adopts conversed phase micro emulsion copolymerization and active free radical polymerization method, and these methods uses a large amount of organic solvent or tensio-active agent, and step is many, complicated operation.Comparatively speaking, the present invention has following characteristics:
(1) polymerization process adopts precipitation polymerization, and is harmless to human and environment take water as solvent, makes simultaneously the preparation method become simple to operation;
(2) prepared polymer nano hydrogel size homogeneous, good stability has good biocompatibility;
(3) phase transition temperature of polymer nano hydrogel is controlled;
(4) introduce cleverly the disulfide bond crosslinking agent, make the polymer nano hydrogel can be degradable in the cell reducing environment, thereby discharge medicine fast, fully, improved the utilization ratio of medicine.
Description of drawings
The transmission electron microscope photo of Fig. 1, degradable environment-responsive polymer nano hydrogel (* 2W), background dyes with phospho-wolframic acid.
The transmission electron microscope photo of Fig. 2, degradable environment-responsive polymer nano hydrogel (* 5W), background dyes with phospho-wolframic acid.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1: with 980 mg N-caprolactams, and 20 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.Stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 37.6 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 2: with 970 mg N-caprolactams, and 30 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.Stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 40.0 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 3: with 960 mg N-caprolactams, and 40 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.Stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 44.2 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 4: with 970 mg N-caprolactams, and 30 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.After half an hour, add 10 mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 41.0 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 5: with 970 mg N-caprolactams, and 30 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.After half an hour, add 30 mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 43.2 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 6: with 970 mg N-caprolactams, and 30 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.After half an hour, add 50 mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 44.5 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 7: with 970 mg N-caprolactams, and 30 mg methacrylic acids, 20 mg sodium lauryl sulphate and 25 mg sodium bicarbonates are dissolved in the 100 mL water.With linking agent 40 mg N, N '-two (acryloyl) cystamine is dissolved in the 2 mL dimethyl sulfoxide (DMSO), fully is transferred in the reaction system after the dissolving.Keep stirring velocity 200 rpm and nitrogen atmosphere, temperature of reaction is risen to 60 ~ 80 ℃ after, add fast Potassium Persulphate 25 mg, polyreaction is initiated immediately.After half an hour, add 100 mg polyethylene glycol monomethyl ethermethacrylic acid esters, stopped reaction behind 6 h slowly is cooled to room temperature in nitrogen atmosphere.After reaction finishes, remove unreacted monomer with the method for dialysing, other impurity such as linear polymer can obtain after the freeze-drying that (pH 7.4,0.15 M NaCl) phase transition temperature is 47.5 under the physiological condition
oThe degradable environment-responsive polymer nano hydrogel of C.
Embodiment 8: preparation 1mg mL
-1The Zorubicin aqueous solution.Get a certain amount of Zorubicin solution and mix with the dispersion liquid that contains the polymer nano hydrogel carrier, the mass ratio of medicine and carrier is 0.3, stirs 12～24h under the room temperature, and centrifugation is washed 3 times repeatedly with deionized water, obtains the nano-hydrogel of medicine carrying.The supernatant liquor of collecting is used for the uv-absorbing test, and drawing carrying drug ratio is 14%, and encapsulation rate is 62%.
Claims (4)
1. the preparation method of a degradable environment-responsive polymer nano hydrogel is characterized in that concrete steps are as follows:
(1) take water as solvent, 950 ~ 980mg N-caprolactam, 20 ~ 40 mg methacrylic acids or N hydroxymethyl acrylamide, 20 ~ 100 mg sodium lauryl sulphate and 10 ~ 100 mg sodium bicarbonates are dissolved in the 100 mL water;
(2) with 20 ~ 200 mg linking agent N, N '-two (acryloyl) cystamine is dissolved in 1 ~ 10 mL dimethyl sulfoxide (DMSO), and is transferred in the reaction system of step (1) gained; Under mechanical stirring, in the nitrogen atmosphere, temperature of reaction risen to 60 ~ 80 ℃ after, add fast 10 ~ 100 mg Potassium Persulphates, add 0 ~ 100 mg polyethylene glycol monomethyl ethermethacrylic acid esters behind the polyreaction 0.25-1 h, stopped reaction behind the 4-8 h slowly is cooled to room temperature in nitrogen atmosphere; After reaction finished, unreacted monomer, linear polymer and other impurity were removed in dialysis, can obtain degradable environment-responsive polymer nano hydrogel after the freeze-drying.
2. the preparation method of degradable environment-responsive polymer nano hydrogel according to claim 1 is characterized in that mechanical stirring speed is 100 ~ 400 rpm in the step (2).
3. the preparation method of degradable environment-responsive polymer nano hydrogel according to claim 1 is characterized in that the Mw of polyethylene glycol monomethyl ethermethacrylic acid esters=2000.
4. as claimed in claim 1 application of the degradable environment-responsive polymer nano hydrogel that obtains of the preparation method carrier that control discharges as medicine.
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