CN108704133A - A kind of Janus particles of chemotherapy/light heat synergetic action and preparation method thereof - Google Patents
A kind of Janus particles of chemotherapy/light heat synergetic action and preparation method thereof Download PDFInfo
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Abstract
A kind of Janus particles of chemotherapy/light heat synergetic action and preparation method thereof, belong to biomedicine technical field, it can solve the technical issues of other materials are not easy to realize a variety of method combination therapy cancers, the particle is gold-silica/mesoporous silicon oxide Janus nanostructures, by Pickering emulsion methods by gold nanoparticle in-situ reducing in amination mesoporous silicon oxide hemisphere surface, both ends load different drugs respectively.The amination mesoporous silicon oxide Janus particles of gold nanoparticle modification are prepared by Pickering emulsion methods, Janus particles of the present invention can load two kinds of drugs simultaneously, the ratio of two kinds of drugs can be accurately controlled, two kinds of drugs can be stimulated by external signals such as pH, redox to respond drug release, solve the technical issues of existing medicament nano carrier leads to burst drug release.
Description
Technical field
The invention belongs to biomedicine technical fields, and in particular to a kind of Janus particles of chemotherapy/light heat synergetic action and
Preparation method.
Background technology
It is chemotherapy for the main therapeutic modality of most of cancer, but there are still poor specificities for chemotherapeutics traditional at present
The big problem with toxic side effect.In recent years, based on the drug delivery system of nano material due to its good effect, toxic side effect it is low and
It is concerned.However, in order to further increase therapeutic efficiency in actual therapeutic, it usually needs a variety of drug synergistic treatments.But
It is that isotropic particle is difficult to realize load and discharge while different physicochemical property drugs, is not easy to a variety of diagnosis and treatment methods
Synergistic effect.
Janus particle surfaces are respectively provided with different patterns or chemical functional group, to have different physical chemistry
Matter, and do not interfered with each other between each function, such as hydrophilic/hydrophobic, polar/non-polar, positive/negative charge, magnetism/non magnetic
Deng.The different drug of two kinds of physicochemical properties can be loaded on the both sides of single particle respectively by Janus particles, realize two kinds of drugs
While load and can individually control release, the synergistic effect of a variety of diagnosis and treatment methods can be also realized on single particle.However mesh
Preceding this new material of Janus particles is seldom in pharmaceutical carrier application aspect pertinent literature report.Photo-thermal therapy(PTT)It is to utilize
Optical-thermal conversion material converts light energy into the technology that thermal energy kills cancer cell under near infrared light induction.It is combined with nano material
Afterwards, the sensibility, targeting and biocompatibility etc. of chemotherapeutics can be improved.Just there is an urgent need to develop can deliver two kinds simultaneously for this
Drug is used for the carrier of chemotherapy/photo-thermal synergistic treatment.
Invention content
It is an object of the invention to solve the technical issues of other materials are not easy to realize a variety of method combination therapy cancers, carry
For a kind of Janus particles of chemotherapy/light heat synergetic action and preparation method thereof.
The present invention adopts the following technical scheme that:
A kind of Janus particles of chemotherapy/light heat synergetic action are gold-silica/mesoporous silicon oxide Janus nanostructures,
By Pickering emulsion methods by gold nanoparticle in-situ reducing in amination mesoporous silicon oxide hemisphere surface, both ends difference
Load different drugs.
A kind of preparation method of the Janus particles of chemotherapy/light heat synergetic action, includes the following steps:
The first step prepares amination mesoporous silicon dioxide nano particle:0.25 g cetyl trimethylammonium bromides(CTAB)Add
Enter in 120 mL water, be warming up to 80 DEG C, the sodium hydroxide solution of 0.875 mL, 2 mol/L is added, by the orthosilicic acid of 1.25 mL
Tetra-ethyl ester(TEOS)It is added in above-mentioned solution, is centrifuged after 80 DEG C of 2 h of stirring, remove supernatant, bottom precipitation is redispersed in 6.0
80 DEG C of 8 h of reflux remove CTAB in the hydrochloric acid-methanol solution of %, are dried in vacuo bottom precipitation after centrifugation, obtain the mesoporous of drying
Dry 1.0 g of mesoporous silicon dioxide nano particle are scattered in 50 mL methanol by Nano particles of silicon dioxide, are added 1.0
ML 3- aminopropyl triethoxysilanes(APTES)Flow back 8 h in 80 DEG C, after centrifugation, is dried in vacuo after bottom precipitation is washed,
Obtain amination mesoporous silicon dioxide nano particle;
Second step prepares the Pickering lotions of amination mesoporous silicon dioxide nano particle:20-100mg aminations is mesoporous
Nano particles of silicon dioxide is scattered in 6-10mL lauryl sodium sulfate(SDS)Solution, with the 0.6-1.0 for being heated to 70-90 DEG C
G solid paraffins mix, and the temperature is maintained to stir 0.5-1.5 h under the rotating speed of 500-3000rpm, and cooled and filtered obtains
The Pickering lotions of amination mesoporous silicon dioxide nano particle;
Third walks, and the Janus particles of gold nanoparticle modification are obtained by local reduction way:Amination mesoporous silicon oxide is received
The chlorauric acid solution 0.5-3mL of 10-100mmol/L is added in 20mL water in the Pickering emulsion dispersions of rice corpuscles, stirring
After filtering, solid filtrate is redispersed in 20mL water, adds the sodium borohydride solution of 10-200mmol/L by 0.5-2h,
10-60min is reacted, after filtering, solid filtrate is dissolved in chloroform, after release, obtains gold-silica/mesoporous silicon oxide
Janus particles;
The both ends of gold-silica/mesoporous silicon oxide Janus particles are loaded different drugs by the 4th step respectively.
The both ends of the gold-silica/mesoporous silicon oxide Janus particles load different drugs respectively, including such as
Lower step:
Gold-silica/mesoporous silicon oxide Janus particles load the first drug, by gold-silica/meso-porous titanium dioxide
After silicon Janus particles are mixed with the first drug, directly it is adsorbed in mesoporous, or by gold-silica/mesoporous silicon oxide
Janus particles side is keyed after carboxylated or sulfhydrylation or amidation modification, with the first drug with chemistry, to reach loud
The purpose of answering property release;
Gold-silica/mesoporous silicon oxide Janus the particles for loading the first drug load second of drug, by load regulation
A kind of gold-silica/mesoporous silicon oxide Janus particles of drug are connect with second of drug or gold-silica/and it is mesoporous
Silica Janus particles are connect by golden sulfide linkage with the mercapto derivatives of second of drug or gold-silica/mesoporous two
Silica Janus particles are connect with mercapto group-beta-cyclodextrin makes it form complex compound with second of drug, to reach response release
Purpose.
Beneficial effects of the present invention are as follows:
Gold-silica of the present invention/mesoporous silicon oxide Janus particles are made of silica and gold, gold nanoparticle
By in-situ synthesis tight distribution in the hemisphere of Nano particles of silicon dioxide, make the pharmaceutical carrier that there is photo-thermal effect, and increase
The drug loading of gold nanoparticle side is added.
Gold-silica of the present invention/mesoporous silicon oxide Janus particles can load two kinds of drugs, Ke Yijing simultaneously
The really ratio of two kinds of drugs of control, and two kinds of drugs can be stimulated by external signals such as pH, redox to respond drug release, solved
The technical issues of existing medicament nano carrier leads to burst drug release.
Gold-silica of the present invention/mesoporous silicon oxide Janus particles overcome single methods of chemotherapy in cancer
Limitation in treatment can be used for chemotherapy/photo-thermal synergistic treatment of tumour cell.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of amination silica dioxide nano particle/paraffin emulsion droplet different amplification.
Fig. 2 is the scanning electron microscope diagram of amination mesoporous silicon dioxide nano particle/paraffin emulsion droplet different amplification.
Fig. 3 is the transmission electron microscope photo of gold-silica/mesoporous silicon oxide Janus particles.
Fig. 4 is that the photo-thermal effect of gold-silica/mesoporous silicon oxide Janus particles is investigated, and A is amination mesoporous two
Silicon oxide nanoparticle(MSN)With gold-amination mesoporous silicon dioxide nano particle(MSN-Au)Photo-thermal effect investigate, B is
Photo-thermal effect before and after different capacity near infrared light MSN-Au is investigated.
Gold-silica/mesoporous silicon oxide Janus particles carry adriamycin in the phosphate buffer that Fig. 5 is different pH
Release profiles.
Fig. 6 is the release profiles of taxol under conditions of being shone with and without near infrared light.
Fig. 7 is that the gold-mesoporous silicon oxide, gold-mesoporous silicon oxide/adriamycin and taxol/gold-of various concentration are mesoporous
The cytotoxicity of silica/adriamycin Janus particles.
Fig. 8 is adriamycin, gold-mesoporous silicon oxide, gold-mesoporous silicon oxide/adriamycin and taxol/gold-mesoporous two
Silica/cytotoxicity of adriamycin Janus particles under the conditions of being shone in the presence/absence of infrared light.
Specific implementation mode
Embodiment 1
The first step prepares amination mesoporous silicon dioxide nano particle:0.25 g cetyl trimethylammonium bromides(CTAB)Add
Enter in 120 mL water, be warming up to 80 DEG C, the sodium hydroxide solution of 0.875 mL, 2 mol/L is added, by the orthosilicic acid of 1.25 mL
Tetra-ethyl ester(TEOS)It is added in above-mentioned solution, is centrifuged after 80 DEG C of 2 h of stirring, remove supernatant, bottom precipitation is redispersed in
80 DEG C of reflux 8h remove CTAB in 6.0% hydrochloric acid-methanol solution, are dried in vacuo bottom precipitation after centrifugation, obtain dry Jie
Dry 1.0 g of mesoporous silicon dioxide nano particle are scattered in 50 mL methanol by hole Nano particles of silicon dioxide, are added 1.0
ML 3- aminopropyl triethoxysilanes(APTES)Flow back 8 h in 80 DEG C, is dried in vacuo, obtains after washing bottom precipitation after centrifugation
To amination mesoporous silicon dioxide nano particle;
Second step prepares the Pickering lotions of amination mesoporous silicon dioxide nano particle:By 20 mg amination titanium dioxides
Silicon nano is scattered in 10 mL lauryl sodium sulfate(SDS)Solution is mixed with the 1.0 g solid paraffins for being heated to 80 DEG C,
And the temperature is maintained to stir 1 h, cooled and filtered under the rotating speed of 2000rpm;
Third walks, and the Janus particles of gold nanoparticle modification are obtained by local reduction way:By Pickering emulsion dispersions in
In 20 mL water, the 0.5 mL chlorauric acid solutions of 10 mmol/L are added, 0.5 h are stirred, after filtering, by solid filtrate redisperse
In 20 mL water, the sodium borohydride solution of 10 mmol/L is added, reacts 10 min, after filtering, solid filtrate is dissolved in chlorine
It is imitative, after release, obtain gold-silica/mesoporous silicon oxide Janus particles;
4th step prepares and loads a kind of Janus particles of drug:By gold-silica/mesoporous silicon oxide Janus particles point
It dissipates in 25 mL N,N-dimethylformamides(DMF)In, 100 mg succinic anhydrides are added, is protected from light 24 h, after centrifugation, takes bottom
Portion's precipitation is redispersed in 50 mL Doxorubicin solutions, is protected from light 24 h.
Embodiment 2
The first step prepares amination mesoporous silicon dioxide nano particle:0.25 g cetyl trimethylammonium bromides(CTAB)Add
Enter in 120 mL water, be warming up to 80 DEG C, the sodium hydroxide solution of 0.875 mL, 2 mol/L is added, by the orthosilicic acid of 1.25 mL
Tetra-ethyl ester(TEOS)It is added in above-mentioned solution, is centrifuged after 80 DEG C of 2 h of stirring, remove supernatant, bottom precipitation is redispersed in
80 DEG C of reflux 8h remove CTAB in 6.0% hydrochloric acid-methanol solution, are dried in vacuo bottom precipitation after centrifugation, obtain dry Jie
Dry 1.0 g of mesoporous silicon dioxide nano particle are scattered in 50 mL methanol by hole Nano particles of silicon dioxide, are added 1.0
ML 3- aminopropyl triethoxysilanes(APTES)Flow back 8 h in 80 DEG C, is dried in vacuo, obtains after washing bottom precipitation after centrifugation
To amination mesoporous silicon dioxide nano particle;
Second step prepares the Pickering lotions of amination mesoporous silicon dioxide nano particle:By 50 mg amination titanium dioxides
Silicon nano is scattered in 8.0 mL lauryl sodium sulfate(SDS)Solution is mixed with the 0.8 g paraffin for being heated to 80 DEG C, and
The temperature is maintained to stir 1h, cooled and filtered under the rotating speed of 3000pm;
Third walks, and the Janus particles of gold nanoparticle modification are obtained by local reduction way:By Pickering emulsion dispersions in
In 20 mL water, the 1.0 mL chlorauric acid solutions of 50mmol/L are added, 1.0 h are stirred, after filtering, by solid filtrate redisperse
In 20 mL water, the sodium borohydride solution of 100 mmol/L is added, reacts 30 min, after filtering, solid filtrate is dissolved in chlorine
It is imitative, after release, obtain gold-silica/mesoporous silicon oxide Janus particles;
4th step prepares and loads a kind of Janus particles of drug:Janus particles are scattered in 25 mL N, N- dimethyl methyls
Amide(DMF)In, 100 mg succinic anhydrides are added, is protected from light 24 h, is redispersed in after centrifugation in 50 mL Doxorubicin solutions,
It is protected from light 24 h.
Embodiment 3
The first step prepares amination mesoporous silicon dioxide nano particle:0.25 g cetyl trimethylammonium bromides(CTAB)Add
Enter in 120 mL water, be warming up to 80 DEG C, the sodium hydroxide solution of 0.875 mL, 2 mol/L is added, by the orthosilicic acid of 1.25 mL
Tetra-ethyl ester(TEOS)It is added in above-mentioned solution, is centrifuged after 80 DEG C of 2 h of stirring, remove last time clear liquid, bottom precipitation is redispersed in
80 DEG C of reflux 8h remove CTAB in 6.0% hydrochloric acid-methanol solution, are dried in vacuo bottom precipitation after centrifugation, obtain dry Jie
Dry 1.0 g of mesoporous silicon dioxide nano particle are scattered in 50 mL methanol by hole Nano particles of silicon dioxide, are added 1.0
ML 3- aminopropyl triethoxysilanes(APTES)Flow back 8 h in 80 DEG C, is dried in vacuo, obtains after washing bottom precipitation after centrifugation
To amination mesoporous silicon dioxide nano particle;
Second step prepares the Pickering lotions of amination mesoporous silicon dioxide nano particle:By 50 mg amination titanium dioxides
Silicon nano is scattered in 10 mL lauryl sodium sulfate(SDS)Solution is mixed with the 1.0 g solid paraffins for being heated to 80 DEG C,
And the temperature is maintained to stir 1 h, cooled and filtered (Fig. 2) under the rotating speed of 2500pm.
Third walks, and the Janus particles of gold nanoparticle modification are obtained by local reduction way:By Pickering lotions point
It dissipates in 20 mL water, the 1.0 mL chlorauric acid solutions of 50mmol/L is added, stir 0.5 h, after filtering, again by solid filtrate
It is scattered in 20 mL water, 100 mmol/L sodium borohydride solutions is added, react 10 min, after filtering, solid filtrate is dissolved in
Chloroform after release, obtains gold-silica/mesoporous silicon oxide Janus particles (Fig. 3);
4th step prepares and loads a kind of Janus particles of drug:Janus nano-particles are scattered in 25 mL DMF, are added
Enter 100 mg succinic anhydrides, be protected from light 24 h, is redispersed in after centrifugation in 50 mL Doxorubicin solutions, is protected from light 24 h;
5th step has photo-thermal effect (Fig. 4) by Janus particles prepared by the 4th step due to the presence of gold nanoparticle.Ah
The amino of mycin is connect with the carboxyl of Janus nanoparticles, and drug is made not discharge under the conditions of normal pH in vivo, in cancer cell
(Fig. 5) is released the drug under acid condition;
6th step prepares the Janus particles of second of drug of load:A kind of Janus of drug of load prepared by the 4th step
Particle is scattered in 10 mg 6- mercapto group-beta-cyclodextrin solution, reacts 24 h, and the dimethyl that taxol is redispersed in after centrifugation is sub-
In sulfolane solution, 24 h are reacted.Obtained Janus particles are discharged since PTX is modified in gold nanoparticle side by photo-thermal
Effects (Fig. 6).
7th step, the Janus particles prepared by the 6th step can discharge two kinds of drugs (Fig. 7) simultaneously in cancer cell, and have
There is photo-thermal therapy to act on (Fig. 8).
Claims (3)
1. a kind of Janus particles of chemotherapy/light heat synergetic action, it is characterised in that:The Janus particles are gold-silica/Jie
Hole silica Janus nanostructures, by Pickering emulsion methods by gold nanoparticle in-situ reducing in amination mesoporous two
Silica hemisphere surface, both ends load different drugs respectively.
2. a kind of preparation method of the Janus particles of chemotherapy/light heat synergetic action as described in claim 1, it is characterised in that:
Include the following steps:
The first step prepares amination mesoporous silicon dioxide nano particle:0.25 g cetyl trimethylammonium bromides are added 120
In mL water, 80 DEG C are warming up to, the sodium hydroxide solution of 0.875 mL, 2 mol/L is added, by the tetraethyl orthosilicate of 1.25 mL
It is added in above-mentioned solution, is centrifuged after 80 DEG C of 2 h of stirring, remove supernatant, bottom precipitation is redispersed in the hydrochloric acid-methanol of 6.0 %
80 DEG C of 8 h of reflux remove CTAB in solution, are dried in vacuo bottom precipitation after centrifugation, obtain dry mesoporous silicon dioxide nano
Dry 1.0 g of mesoporous silicon dioxide nano particle are scattered in 50 mL methanol by particle, and 1.0 mL 3- aminopropyls three are added
Ethoxysilane after centrifugation, is dried in vacuo after bottom precipitation is washed in 80 DEG C of 8 h of reflux, obtains amination meso-porous titanium dioxide
Silicon nano;
Second step prepares the Pickering lotions of amination mesoporous silicon dioxide nano particle:20-100mg aminations is mesoporous
Nano particles of silicon dioxide is scattered in 6-10mL sodium dodecyl sulfate solutions, with the 0.6-1.0 g solids for being heated to 70-90 DEG C
Paraffin mixes, and the temperature is maintained to stir 0.5-1.5 h under the rotating speed of 500-3000rpm, and cooled and filtered obtains amination
The Pickering lotions of mesoporous silicon dioxide nano particle;
Third walks, and the Janus particles of gold nanoparticle modification are obtained by local reduction way:Amination mesoporous silicon oxide is received
The chlorauric acid solution 0.5-3mL of 10-100mmol/L is added in 20mL water in the Pickering emulsion dispersions of rice corpuscles, stirring
After filtering, solid filtrate is redispersed in 20mL water, adds the sodium borohydride solution of 10-200mmol/L by 0.5-2h,
10-60min is reacted, after filtering, solid filtrate is dissolved in chloroform, after release, obtains gold-silica/mesoporous silicon oxide
Janus particles;
The both ends of gold-silica/mesoporous silicon oxide Janus particles are loaded different drugs by the 4th step respectively.
3. the preparation method of the Janus particles of chemotherapy/light heat synergetic action according to claim 2, it is characterised in that:Institute
The both ends for stating gold-silica/mesoporous silicon oxide Janus particles load different drugs respectively, include the following steps:
Gold-silica/mesoporous silicon oxide Janus particles load the first drug, by gold-silica/meso-porous titanium dioxide
After silicon Janus particles are mixed with the first drug, directly it is adsorbed in mesoporous, or by gold-silica/mesoporous silicon oxide
Janus particles side is keyed after carboxylated or sulfhydrylation or amidation modification, with the first drug with chemistry, to reach loud
The purpose of answering property release;
Gold-silica/mesoporous silicon oxide Janus the particles for loading the first drug load second of drug, by load regulation
A kind of gold-silica/mesoporous silicon oxide Janus particles of drug are connect with second of drug or gold-silica/and it is mesoporous
Silica Janus particles are connect by golden sulfide linkage with the mercapto derivatives of second of drug or gold-silica/mesoporous two
Silica Janus particles are connect with mercapto group-beta-cyclodextrin makes it form complex compound with second of drug, to reach response release
Purpose.
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CN113480744A (en) * | 2021-06-04 | 2021-10-08 | 上海应用技术大学 | Multifunctional Pickering emulsion and preparation method thereof |
CN114767871A (en) * | 2022-04-19 | 2022-07-22 | 中国工程物理研究院机械制造工艺研究所 | Mesoporous silicon drug-loaded system, preparation method thereof and mesoporous silicon drug-loaded system |
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REYNALDO VILLALONGA等: ""Enzyme-Controlled Sensing–Actuating Nanomachine Based on Janus Au–Mesoporous Silica Nanoparticles"", 《CHEM. EUR. J.》 * |
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