CN109908349A - A kind of preparation method and applications of glutathione response type barium oxide nanoparticle - Google Patents
A kind of preparation method and applications of glutathione response type barium oxide nanoparticle Download PDFInfo
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- CN109908349A CN109908349A CN201910241300.1A CN201910241300A CN109908349A CN 109908349 A CN109908349 A CN 109908349A CN 201910241300 A CN201910241300 A CN 201910241300A CN 109908349 A CN109908349 A CN 109908349A
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Abstract
The present invention discloses a kind of preparation method and applications of glutathione response type barium oxide nanoparticle, which is by ammonium metavanadate, hyaluronic acid by one-step synthesis method.Preparation method of the invention is simple, and raw material is cheap and easily-available.Have the characteristics that good biocompatibility by the barium oxide nanoparticle after hyaluronic acid decorated, there is good dispersion in aqueous solution.Moreover, having good absorption in the near infrared region after glutathione is incubated for, near infrared light can be converted to thermal energy, can be used for photo-thermal therapy.Barium oxide nanoparticle prepared by the present invention can be used for tumor microenvironment GSH-PX activity response type photo-thermal therapy, have broad application prospects in photo-thermal therapy of cancer field.
Description
Technical field
The present invention relates to biological medicine Material Field, specifically a kind of glutathione response type barium oxide nanoparticle
Preparation method and applications.
Background technique
In recent years, intrinsic physiology microenvironment feature (such as redox state, pH, the enzyme, ion) triggering of tumor tissues
Diagnosis and treatment cause the extensive concern of people.This treatment method can reduce the damage of anticancer drug normal tissue simultaneously, mention
Its high therapeutic effect.In various physiological parameters, redox state is in a variety of pathological states such as chronic inflammation, apoplexy, cancer
In play an important role (Rubartelli, A.; Lotze, M. T.Trends Immunol. 2007.).Research shows that paddy
The sweet peptide of Guang (GSH) is the reducing agent that content is most in tumour, and the content of tumor tissues GSH-PX activity is apparently higher than normal tissue,
Increase also can seriously effect of the restricted part drug to tumor thermal therapy for glutathione level simultaneously.Therefore, exploitation has
Preparation is simple, good biocompatibility, it is cheap while be easy to get, there is glutathione response reagent for consuming glutathione into one
Step improve photo-thermal therapy effect novel nano-material be numerous researchers research hotspot, this is to developing novel nanometer
Material has great meaning.
Currently, existing document report Transition Metals V compounds of group can be applied to bio-sensing in animal body, drug is passed
It send, imaging and photo-thermal therapy (Chen Y, Cheng L, Dong Z, et al.Angew. Chem. Int. Ed.
2017.).Vanadium is a kind of metallic element with multivalent state, and wherein the different valence state of vanadium corresponds to different colors, so increasingly
More researchers is applied to the research for the treatment of of cancer using this feature.Gold can be obtained in ammonium metavanadate solution under heating conditions
The high price barium oxide solution of yellow, the high price barium oxide have glutathione response, are gone back under the incubation of glutathione
Original at near infrared region absorb and solution colour be in black low price barium oxide.But high price barium oxide has very
Big toxicity, which limits its applications in vivo.
Summary of the invention
The present invention provides a kind of preparation method and applications of glutathione response type barium oxide nanoparticle, it is intended to
Further widen the function of existing photo-thermal therapy reagent.
Firstly, a kind of preparation method of glutathione response type barium oxide nanoparticle provided by the invention, with inclined vanadium
Sour ammonium, hyaluronic acid are raw material, and this method includes the following steps:
1) it weighs a certain amount of ammonium metavanadate and hyaluronic acid is dissolved in distilled water respectively, stir evenly, it is spare；
2) heating stirring ammonium metavanadate solution, reaction obtain golden solution, i.e. barium oxide solution A；
3) barium oxide solution A is added dropwise in hyaluronic acid solution, is transferred in high-temperature high-pressure reaction kettle after mixing evenly
Reaction, obtains the aqueous solution B of hyaluronic acid decorated barium oxide nanoparticle；
4) isometric ethyl alcohol is added into aqueous solution B, is centrifuged, obtains yellow solid C；
5) it by solid C with ethanol washing 3 times, then is centrifuged, obtains solid D；
6) solid D is dried in vacuo to get glutathione response type barium oxide nanoparticle is arrived.
In preparation method step 1) of the present invention, the mass ratio of ammonium metavanadate and hyaluronic acid is 1:1；Ammonium metavanadate and distillation
Water quality ratio is 1:40；Hyaluronic acid and distilled water mass ratio are 1:100.
In preparation method step 2 of the present invention, heating temperature is 60 ~ 100 DEG C, and the reaction time is 10 ~ 60 min.
In preparation method step 3) of the present invention, temperature of reaction kettle is 60 ~ 100 DEG C, reacts 5 ~ 6 h.
It is a kind of with glutathione sound it is a further object to provide being prepared by the process described above
The barium oxide nanoparticle answered is used for photo-thermal therapy.
Invention further provides glutathione response type barium oxide nanoparticles in tumor microenvironment glutathione
In the presence of realize photo-thermal therapy application.The glutathione response type barium oxide nanoparticle is as the suitable of prodrug
Answering disease is the high tumour cell of glutathione concentrations content.
Further, when the drug is liquid preparation, glutathione response type barium oxide nanoparticle concentration is 200
~500 μg/ml。
The high cancer cell of the glutathione concentrations content includes mouse mastopathy cell, mouse melanin cancer cell, reality
Light application time when border is applied is 1 ~ 10 min.
Barium oxide nanoparticle of the present invention passes through one-step synthesis method with ammonium metavanadate, hyaluronic acid.Hyaluronic acid is one
Kind acid mucopolysaccharide itself has good CD44 receptor target, and most cancer cell is CD44 overexpression.Institute
With the property that not only there is the barium oxide nanoparticle after hyaluronic acid decorated barium oxide nanoparticle itself to have,
Also there is good targeting and biocompatibility, make hyaluronic acid decorated barium oxide nanoparticle in photo-thermal therapy cancer
Aspect has very big application prospect.
The invention has the advantages that the barium oxide nanoparticle that (1) is prepared by means of the present invention has well
Biocompatibility, show good absorption in the near infrared region after the incubation of glutathione, under laser irradiation can will
Luminous energy is converted to thermal energy；(2) present invention modifies barium oxide nanoparticle with hyaluronic acid, can improve barium oxide and receive
The biocompatibility of rice corpuscles increases its targeting, this will further expand barium oxide nanoparticle in tumor microenvironment
The application range in photo-thermal therapy field；(3) raw material of the nanoparticle of this method preparation is easy to get, and simple, convenient；(4)
Glutathione response photo-thermal therapy may be implemented in barium oxide nanoparticle prepared by the present invention, has in field of cancer treatment wide
Wealthy application prospect.
Detailed description of the invention
Fig. 1 is the UV absorption variation diagram that glutathione of the present invention is incubated for barium oxide nanoparticle.
Specific embodiment
The content of present invention is further described below with reference to embodiment and attached drawing, but is not limitation of the invention.
Embodiment 1
Glutathione response type barium oxide nanoparticle is prepared, is included the following steps:
1) it weighs that 0.5 g ammonium metavanadate is dissolved in 20 mL distilled water, 0.5 g hyaluronic acid is dissolved in 50 mL distilled water, stirs evenly,
It is spare；
2) heating ammonium metavanadate reacts 20 min, obtains golden solution, i.e. barium oxide solution A to 80 DEG C；
3) barium oxide solution A is added dropwise in hyaluronic acid solution, is transferred in high-temperature high-pressure reaction kettle after mixing evenly,
Stop heating after reacting 6 h under the conditions of 90 DEG C, obtains hyaluronic acid decorated barium oxide solution B；
4) isometric ethyl alcohol is added into the resulting aqueous solution B of previous step, is centrifuged, obtains yellow solid C；
5) it by solid C with ethanol washing 3 times, then is centrifuged, obtains solid D；
6) solid D is dried in vacuo to get glutathione response type barium oxide nanoparticle is arrived.
Embodiment 2
Glutathione response type barium oxide nanoparticle is prepared, is included the following steps:
1) it weighs that 0.5 g ammonium metavanadate is dissolved in 20 mL distilled water, 0.5 g hyaluronic acid is dissolved in 50 mL distilled water, stirs evenly,
It is spare；
2) heating ammonium metavanadate reacts 20 min, obtains golden solution, i.e. barium oxide solution A to 80 DEG C；
3) after barium oxide solution A being added dropwise in hyaluronic acid solution, it is transferred to high-temperature high-voltage reaction afterwards after mixing evenly
In kettle, stops heating after 6 h are reacted under the conditions of 90 DEG C, obtain hyaluronic acid decorated barium oxide solution B；
4) isometric ethyl alcohol is added into the resulting aqueous solution B of previous step, is centrifuged, obtains yellow solid C；
5) it by solid C with ethanol washing 3 times, then is centrifuged, obtains solid D；
6) solid D is dried in vacuo to get glutathione response type barium oxide nanoparticle is arrived.
Application Example 1
It prepares resulting final product by above-mentioned and is configured to certain density aqueous solution, it is right respectively with ultraviolet-uisible spectrophotometer
The barium oxide solution that unmodified barium oxide, hyaluronic acid decorated barium oxide and glutathione is incubated for is tested,
The ultraviolet absorption curve of different solutions is obtained, as shown in Figure 1.
Found out by Fig. 1: unmodified barium oxide, hyaluronic acid decorated barium oxide solution are in 600 ~ 1200 nm
It does not absorb, and occurs a wide absorption after being incubated for glutathione in the near infrared region, illustrate that the nanoparticle has
There is photo-thermal effect, can be used for photo-thermal therapy.
Still further, it was discovered that when glutathione concentrations are 1 ~ 8 mmol/L, with the raising of glutathione concentrations, vanadium oxidation
Characteristic absorption peak of the object nanoparticle at 600 ~ 1200 nm is gradually increasing.The experimental results showed that the barium oxide nanometer of synthesis
Particle has glutathione response.
Application Example 2
By the above-mentioned aqueous solution for preparing resulting final product and being configured to concentration as 500 μ g/ml, it is divided into two parts, portion is added 6
The glutathione of mmol/L is incubated for, another does not deal with, then with 808 nm laser (1.5 W/cm2) 10 are irradiated respectively
Min, with thermal infrared imager recording solution temperature with the variation of light application time.The experimental results showed that being added what glutathione was incubated for
The temperature of barium oxide nanoparticle aqueous solution significantly increases, and temperature increases about 30 DEG C in 10 min, without dealing with
Barium oxide nanoparticle aqueous solution and pure water same light shine under the conditions of temperature hardly increase.Confirm vanadium oxygen of the invention
Compound nanoparticle can be used for photo-thermal therapy in response to glutathione.
Claims (8)
1. a kind of preparation method of glutathione response type barium oxide nanoparticle, it is characterised in that: with ammonium metavanadate, transparent
Matter acid is raw material, and this method includes the following steps:
1) it weighs a certain amount of ammonium metavanadate and hyaluronic acid is dissolved in distilled water respectively, stir evenly, it is spare；
2) heating stirring ammonium metavanadate solution, reaction obtain golden solution, i.e. barium oxide solution A；
3) barium oxide solution A is added dropwise in hyaluronic acid solution, is transferred in high-temperature high-pressure reaction kettle after mixing evenly
Reaction, obtains the aqueous solution B of hyaluronic acid decorated barium oxide nanoparticle；
4) isometric ethyl alcohol is added into aqueous solution B, is centrifuged, obtains yellow solid C；
5) it by solid C with ethanol washing 3 times, then is centrifuged, obtains solid D；
6) solid D is dried in vacuo to get glutathione response type barium oxide nanoparticle is arrived.
2. the preparation method of glutathione response type barium oxide nanoparticle according to claim 1, it is characterised in that:
In step 1), the mass ratio of ammonium metavanadate and hyaluronic acid is 1:1；
Ammonium metavanadate and distilled water mass ratio are 1:40；
Hyaluronic acid and distilled water mass ratio are 1:100.
3. the preparation method of glutathione response type barium oxide nanoparticle according to claim 1, feature exist
In: in step 2, heating temperature is 60 ~ 100 DEG C, and the reaction time is 10 ~ 60 min.
4. the preparation method of glutathione response type barium oxide nanoparticle according to claim 1, feature exist
In: in step 3), temperature of reaction kettle is 60 ~ 100 DEG C, reacts 5 ~ 6 h.
5. the glutathione response type barium oxide nanoparticle that the described in any item preparation methods of claim 1 ~ 4 are prepared
Son.
6. glutathione response type barium oxide nanoparticle depositing in tumor microenvironment GSH-PX activity described in claim 5
In the application of lower achievable photo-thermal therapy.
7. application according to claim 6, it is characterised in that: the glutathione response type barium oxide nanoparticle is made
Indication for prodrug is the high tumour cell of glutathione concentrations content.
8. application according to claim 7, it is characterised in that: when the drug is liquid preparation, glutathione response type
Barium oxide nanoparticle concentration is 200 ~ 500 μ g/ml.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113995838A (en) * | 2021-11-09 | 2022-02-01 | 清华大学 | Glutathione response photoacoustic probe and preparation method and application thereof |
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| CN108926712A (en) * | 2017-05-27 | 2018-12-04 | 首都师范大学 | Vfanadium compound is as the application in optical-thermal conversion material |
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| CN113995838A (en) * | 2021-11-09 | 2022-02-01 | 清华大学 | Glutathione response photoacoustic probe and preparation method and application thereof |
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