CN105079027A - Porous Se-SiO2 nanoparticle as well as preparation method and application thereof - Google Patents

Porous Se-SiO2 nanoparticle as well as preparation method and application thereof Download PDF

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CN105079027A
CN105079027A CN201510496173.1A CN201510496173A CN105079027A CN 105079027 A CN105079027 A CN 105079027A CN 201510496173 A CN201510496173 A CN 201510496173A CN 105079027 A CN105079027 A CN 105079027A
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porous
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CN105079027B (en
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刘锡建
陆杰
孙彦刚
张丽娟
张红
徐菁利
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Shanghai University of Engineering Science
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Abstract

The invention relates to a porous Se-SiO2 nanoparticle as well as a preparation method and application thereof. The porous Se-SiO2 nanoparticle consists of elementary Se, SiO2 covering the elementary Se and polyvinylpyrrolidone covering the surface of the SiO2; the preparation method comprises the following steps: firstly preparing a Cu2-xSe normal hexane dispersion liquid, and then adding de-ionized water, n-hexanol, polyethylene glycol octylphenol ether, n-hexane, tetraethyl orthosilicate and ammonia water to the Cu2-xSe normal hexane dispersion liquid; dispersing a reaction product in the de-ionized water so as to obtain a nano Se-SiO2 dispersion liquid, then adding polyvinylpyrrolidone to the nano Se-SiO2 dispersion liquid and conducting hydrothermal treatment for a certain duration so as to obtain the porous Se-SiO2 nanoparticle; and the prepared porous Se-SiO2 nanoparticle can be applied to the loading, transfer or slow release of anti-cancer drugs. Compared with the prior art, the porous Se-SiO2 nanoparticle disclosed by the invention has the advantages of good biocompatibility, good nano Se release performance, high anti-cancer drug loading rate and the like.

Description

A kind of porous Se-SiO 2nanoparticle and its preparation method and application
Technical field
The present invention relates to a kind of nanoparticle and its preparation method and application, especially relate to a kind of porous Se-SiO 2nanoparticle and its preparation method and application.
Background technology
Selenium is one of trace element of needed by human, and research proves, lacking selenium in human body can easily cause more than 40 to plant disease, as cancer, heart disease, diabetes, hypertension metabolism disease and hepatitis etc.Appropriate absorption selenium, has enhancing human body immunity, delays the effects such as biological decay.But the margin of safety of selenium between optium concentration and intoxicating concentration is very narrow, it is very important for therefore developing the health of the efficient selenium source of low toxicity to the mankind.Relative to the selenium of other states, the small-size effect of Nanometer Se~0 particle and make it have the photoelectric characteristic that conventional bulk selenium material do not possess, has caused the concern of material educational circles.In addition, nanometer selenium has low toxic action, and can absorb by human body and utilize, also there is the effects such as antitumor, antioxidation, enhancing human body immunity power.Therefore, the synthesis of R and D nanometer selenium is the focus of relevant selenium research.
At present, had much about the study on the synthesis of nanometer selenium.As patent CN200510050295 reports a kind of load type nano selenium preparation method, porous mineral materials carrier is as miniature nano-reactor, porous mineral materials is ground to and is greater than 300 orders, the suspension slurry making 1% ~ 10% adds selenium salt, adjustment pH=4 ~ 6, react 2 ~ 10 hours, centrifugal oven dry, be ground to and be greater than 300 orders, the nanometer selenium powder of obtained support type.Li Zhilin etc. use sodium lauryl sulphate to be template, reaction system sulfite concentration is 0.01mol/L, ascorbic acid concentrations is 0.07mol/L, sodium lauryl sulphate mass fraction is 1.0%, react 7min under room temperature, can obtain spherical red nanometer selenium, mean diameter is about 35nm (inorganic chemicals industry, 2009,41 (7): 32 ~ 34).Patent CN02153282 reports a kind of preparation method of red active nano elemental selenium gelatin-microcapsule, in 50 DEG C of water-baths, with 1 liter of deionized water dissolving 40g gelatin and 10mgNa 2seO 3, then add 50mg vitamin E, control pH, between 5 ~ 6, leaves standstill 9h, condensed emulsified, solidifies dry selenium capsule.Chinese patent ZL201310482174.1 discloses kind copper selenide/meso-porous silica core-shell nanoparticle and its preparation method and application, and copper selenide/meso-porous silica core-shell nanoparticle is Cu 2-xse/mSiO 2-PEG core-shell nano, wherein x is 0-1, m is mesoporous.Preparation method: preparation Cu 2-xse is nanocrystalline, by CTAB by hydrophobic Cu 2-xse is nanocrystalline to be transferred in aqueous phase, then by sol-gal process with CTAB be template at its superficial growth one deck mesoporous silicon oxide, Polyethylene Glycol in last finishing coupling, to obtain final product, and can apply in photo-thermal therapy and medicament slow release.But the nanometer selenium product of the preparation method of existing nanometer selenium synthesis can not reach the effective release controlling selenium, and function ratio is more single, therefore need the synthesis continuing nano-scale selenium product, the nanometer selenium Co ntrolled release of realization that can be real and multifunction.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of porous Se-SiO is provided 2nanoparticle and its preparation method and application.
Object of the present invention can be achieved through the following technical solutions:
A kind of porous Se-SiO 2the preparation method of nanoparticle, comprises the following steps:
(1) by Cu 2-xse nanoparticle dispersion, in normal hexane, obtains Cu 2-xse normal hexane dispersion liquid; ;
(2) Se-SiO 2synthesis: toward Cu 2-xdeionized water, hexanol, Triton X-100 and normal hexane is added in Se normal hexane dispersion liquid, stir, drip tetraethyl orthosilicate, abundant mixing, drip ammonia again after 1 ~ 60min, stirring reaction, add acetone and centrifugalize, be scattered in deionized water after separated product washing, i.e. obtained nanometer Se-SiO 2dispersion liquid;
(3) polyvinylpyrrolidone is added nanometer Se-SiO 2in dispersion liquid, after being uniformly mixed, stopping stirring and heating carrying out hydrothermal processes, be then cooled to room temperature, centrifuge washing, be i.e. obtained porous Se-SiO 2nanoparticle.
Step (1) Cu 2-xthe concentration of Se normal hexane dispersion liquid is 0.1 ~ 500mg/mL.
Cu described in step (1) 2-xse nanoparticle is prepared by following steps:
In Cu-lyt., add oleic acid, obtain the solution A that concentration is 4.9mg/mL, in selenium powder, add oleic acid and oleyl amine that volume ratio is 1:1, obtain the B solution that concentration is 7.9mg/mL; Pass into nitrogen by solution A, B solution respectively, stir, be heated to 110 ~ 120 DEG C, insulation 20 ~ 30min, is then heated to 250 ~ 280 DEG C by B solution, insulation 30-35min, be cooled to 200-220 DEG C again, meanwhile, solution A be warming up to 200 ~ 220 DEG C, then draw B solution, join in solution A, wherein, the B solution drawn and the volume ratio of solution A are 1:2, and reaction 5 ~ 10min, is cooled to room temperature, centrifuge washing, i.e. obtained Cu 2-xse nanoparticle.
Cu described in step (2) 2-xse normal hexane dispersion liquid: deionized water: hexanol: Triton X-100: normal hexane: tetraethyl orthosilicate: the volume ratio of ammonia is 10:0.01 ~ 2:1 ~ 10:1 ~ 10:5 ~ 100:1 ~ 0.001:1 ~ 0.005, the mass concentration of described ammonia is 25% ~ 28%.
Cu in step (2) 2-xthe mixing time added in Se normal hexane dispersion liquid after deionized water, hexanol, Triton X-100 and normal hexane is 1 ~ 20min, and the stirring reaction time dripped after ammonia is 24h;
The rotating speed of centrifugalize is 12000rpm, and separated product washing is for using absolute ethanol washing three times.
Nanometer Se-SiO obtained by step (2) 2only otherwise affect follow-up polyvinylpyrrolidone coated silica, conveniently operate, being often made into concentration is 0.1 ~ 500mg/mL for the concentration of dispersion liquid.
Polyvinylpyrrolidone described in step (3) and nanometer Se-SiO 2the interpolation of dispersion liquid is than being 1g:5 ~ 200mL.
Polyvinylpyrrolidone and nanometer Se-SiO in step (3) 2the mixing time of the mixed liquor of dispersion liquid is 0.2 ~ 3h.
In step (3), the temperature of hydrothermal processes is 75 ~ 99 DEG C, and the processing time is 0.2 ~ 5h.
The Se-SiO that above-mentioned preparation method prepares 2nanoparticle, comprises the SiO of simple substance Se, coated simple substance Se 2and be coated on SiO 2the polyvinylpyrrolidone on surface.
A kind of porous Se-SiO 2nanoparticle is in the application of the load of cancer therapy drug, transhipment or slow release.
This patent, in building-up process, in deionized water, hexanol, Triton X-100 and normal hexane reaction system, drips after ammonia, Cu 2-xse nanoparticle is oxidized, generates Se simple substance, and at the same time, teos hydrolysis generates SiO 2be coated on Se quantum dot, form Se-SiO 2nanoparticle, and a Se-SiO 2nanoparticle is coated a lot of individual Se quantum dot (see Fig. 2).Compared with patent CN201310482174.1, coated with silica of the present invention is carried out in non-polar solven, Cu 2-xse there occurs oxidation in reaction system, generates Se simple substance, has carried out SiO simultaneously 2coated, by XRD figure can prove synthesize be Se-SiO 2nanoparticle (see Fig. 1).And coated with silica is carried out in polar system in patent CN201310482174.1, silicon dioxide is directly coated Cu 2-xse nano-particle, generates Cu 2-xse-mSiO 2nanoparticle, in building-up process, Cu 2-xse does not react and generates other material.
Compared with prior art, the present invention is coated by nanometer selenium by silicon dioxide, forms Se-SiO 2nanoparticle, then by polyvinylpyrrolidone (PVP) and Se-SiO 2nanoparticle dispersion liquid mixes, and hydrothermal processes, PVP is coated on silica surface, and silicon dioxide and PVP all have good biocompatibility, are conducive to Se-SiO 2nanoparticle is applied in vivo, and hydrothermal processes is by Se-SiO 2nanoparticle forms loose structure, is conducive to the release of nanometer Se, and the duct formed may be used for load cancer therapy drug, can realize multifunction.
Accompanying drawing explanation
Fig. 1 is Se-SiO prepared by the present invention 2x-ray diffraction (XRD) figure of nanoparticle;
Fig. 2 is Se-SiO prepared by the present invention 2transmission electron microscope (TEM) figure of nanoparticle;
Fig. 3 is the Se-SiO of hydrothermal processes 1.5h prepared by the present invention 2transmission electron microscope (TEM) figure of nanoparticle;
Fig. 4 is the Se-SiO of hydrothermal processes 2h prepared by the present invention 2transmission electron microscope (TEM) figure of nanoparticle.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.The present embodiment is implemented premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(1) Cu 2-xthe synthesis of Se: 49mg Cu-lyt. is placed in there-necked flask, adds 10mL oleic acid, forms solution A, 79mg selenium powder is placed in another there-necked flask, adds 5mL oleic acid and 5mL oleyl amine, forms B solution.Two there-necked flasks are put into heating jacket, passes into nitrogen, stir, after being heated to 120 DEG C, be incubated 20 minutes, to remove moisture in device and oxygen.Then B solution is heated to 280 DEG C, is incubated half an hour, then is cooled to 220 DEG C.Meanwhile, solution A is warmed up to 220 DEG C.Draw 5mLB solution with syringe, be expelled in 10mLA solution, react after 5 minutes, cool to room temperature.Add appropriate dehydrated alcohol under 12000r/min centrifugal 12 minutes.After washing three times with ethanol, add 10mL normal hexane, obtain Cu 2-xse normal hexane dispersion liquid, for subsequent use;
(2) Cu that 5mL step (1) is obtained is got 2-xse normal hexane dispersion liquid joins in reaction bulb, add 0.9mL deionized water, 3mL hexanol and 3mLTritonX-100 (Triton X-100) again, then 30mL normal hexane is added, stir, 0.05mLTEOS (tetraethyl orthosilicate) is dripped after 5min, abundant mixing, drips 0.1mL ammonia after 5min, the mass concentration of ammonia is 25%.Stir after 24h, it is centrifugal in 12000rpm to add acetone, and centrifugal product absolute ethanol washing three times, is finally scattered in 20mL deionized water, obtained nanometer Se-SiO 2dispersion liquid, obtains Se-SiO 2nanoparticle, its XRD figure and TEM figure respectively as depicted in figs. 1 and 2, can find out, SiO 2coated multiple Se simple substance quantum dot, defines Se-SiO 2nanoparticle.
(3) Se-SiO that step (2) obtains is got 2dispersion liquid 20mL, ultrasonic disperse 5min, adds in reaction bulb, then adds 0.2gPVP (polyvinylpyrrolidone) and stir 1h.Stop stirring, be warming up to 95 DEG C, at being held in 95 DEG C, keep 1.5h.Then cool, 12000rpm centrifugalize, with dehydrated alcohol, centrifugal product is washed 3 times, to remove residual surfactant (PVP).Last ultrasonic disperse, in deionized water, is preserved with for subsequent use, is obtained porous Se-SiO 2nanoparticle, its TEM schemes as shown in Figure 3.
Embodiment 2
(1) Cu 2-xthe synthesis of Se: 49mg Cu-lyt. is placed in there-necked flask, adds 10mL oleic acid, forms solution A, 79mg selenium powder is placed in another there-necked flask, adds 5mL oleic acid and 5mL oleyl amine, forms B solution.Two there-necked flasks are put into heating jacket, passes into nitrogen, stir, after being heated to 120 DEG C, be incubated 20 minutes, to remove moisture in device and oxygen.Then B solution is heated to 280 DEG C, is incubated half an hour, then is cooled to 220 DEG C.Meanwhile, solution A is warmed up to 220 DEG C.Draw 5mLB solution with syringe, be expelled in 10mLA solution, react after 5 minutes, cool to room temperature.Add appropriate dehydrated alcohol under 12000r/min centrifugal 12 minutes.After washing three times with ethanol, add 10mL normal hexane, obtain Cu 2-xse normal hexane dispersion liquid, for subsequent use;
(2) Cu that 5mL (1) is obtained is got 2-xse normal hexane dispersion liquid joins in reaction bulb, then adds 0.9mL deionized water, 3mL hexanol and 3mLTritonX-100, then adds 30mL normal hexane, stir, drip 0.05mLTEOS (tetraethyl orthosilicate) after 5min, fully mix, after 5min, drip 0.1mL ammonia.Stir after 24h, it is centrifugal in 12000rpm to add acetone, and centrifugal product absolute ethanol washing three times, is finally scattered in 20mL deionized water, obtained nanometer Se-SiO 2dispersion liquid, obtains Se-SiO 2nanoparticle.
(3) Se-SiO that step (2) obtains is got 2dispersion liquid 20mL, ultrasonic disperse 5min, adds in reaction bulb, then adds 0.2gPVP (polyvinylpyrrolidone) and stir 1h.Stop stirring, be warming up to 95 DEG C, at being held in 95 DEG C, keep 2h.Then cool, 12000rpm centrifugalize, with dehydrated alcohol, centrifugal product is washed 3 times, to remove residual surfactant (PVP).Last ultrasonic disperse, in deionized water, is preserved with for subsequent use, is obtained porous Se-SiO 2nanoparticle, its TEM schemes as shown in Figure 4.
(4) porous Se-SiO prepared by 5mg step (3) is got 2nanoparticle sample, adding 2.5mL concentration is 0.5mg/mL doxorubicin hydrochloride (DOX) solution, ultrasonic disperse, and lucifuge stirs 24h.Then centrifugalize, does not have the medicine adsorbed to removing with deionized water wash, calculate the load factor of amycin up to 10.4%.
Embodiment 3
A kind of porous Se-SiO 2nanoparticle, comprises the SiO of simple substance Se, coated simple substance Se 2and be coated on SiO 2the polyvinylpyrrolidone on surface, its preparation method comprises the following steps:
(1) nanometer Cu 2-xthe synthesis of Se: 49mg Cu-lyt. is placed in there-necked flask, adds 10mL oleic acid, forms solution A, 79mg selenium powder is placed in another there-necked flask, adds 5mL oleic acid and 5mL oleyl amine, forms B solution.Two there-necked flasks are put into heating jacket, passes into nitrogen, stir, after being heated to 120 DEG C, being incubated 20 minutes, then B solution being heated to 280 DEG C, be incubated half an hour, then be cooled to 220 DEG C, meanwhile, solution A is warmed up to 220 DEG C.Drawing 5mL solution B adds in 10mL solution A, and reaction 5min, is then cooled to room temperature, adds appropriate dehydrated alcohol under 12000r/min centrifugal 12 minutes, after centrifugal product ethanol is washed three times, adds normal hexane, obtain the Cu that concentration is 0.1mg/mL 2-xse normal hexane dispersion liquid;
(2) Se-SiO 2synthesis: get the Cu that 10mL step (1) is obtained 2-xse normal hexane dispersion liquid joins in reaction bulb, then 2mL deionized water, 10mL hexanol and 10mLTritonX-100,100mL normal hexane is added, stir, drip 1mLTEOS after 20min, more fully mix, the ammonia that 1mL mass concentration is 25% is dripped after 10min, stir after 24h, it is centrifugal under 12000rpm to add acetone, centrifugal product absolute ethanol washing three times, finally be scattered in deionized water, obtained concentration is the Se-SiO of 0.1mg/mL 2dispersion liquid;
(3) Se-SiO that step (2) obtains is got 2dispersion liquid 20mL, ultrasonic disperse 5min, adds in reaction bulb, then adds 0.1gPVP stirring 0.2h, stop stirring, be warming up to 75 DEG C and be incubated 0.2h, then cooling, centrifugalize under 12000rpm, centrifugal product absolute ethanol washing 3 times, i.e. obtained porous Se-SiO 2nanoparticle.
Embodiment 4
A kind of porous Se-SiO 2nanoparticle, comprises the SiO of simple substance Se, coated simple substance Se 2and be coated on SiO 2the polyvinylpyrrolidone on surface, its preparation method comprises the following steps:
(1) nanometer Cu 2-xthe synthesis of Se: will get Cu-lyt. and be placed in there-necked flask, and add oleic acid, forming concentration is the solution A of 4.9mg/mL, then selenium powder is placed in another there-necked flask, adds oleic acid and oleyl amine that volume ratio is 1:1, and forming concentration is the solution B of 7.9mg/mL.Two there-necked flasks are put into heating jacket, passes into nitrogen, stir, after being heated to 110 DEG C, being incubated 30 minutes, then B solution being heated to 250 DEG C, insulation 35min, then be cooled to 200 DEG C, meanwhile, solution A is warmed up to 200 DEG C.Draw solution B adds in solution A, and the volume ratio of solution B and solution A is 1:2, reaction 10min, then be cooled to room temperature, add appropriate dehydrated alcohol under 12000r/min centrifugal 12 minutes, after centrifugal product ethanol is washed three times, add normal hexane, obtain the Cu that concentration is 500mg/mL 2-xse normal hexane dispersion liquid;
(2) Se-SiO 2synthesis: get the Cu that 10mL step (1) is obtained 2-xse normal hexane dispersion liquid joins in reaction bulb, then 1mL deionized water, 5mL hexanol and 5mLTritonX-100,50mL normal hexane is added, stir, drip 0.05mLTEOS after 1min, more fully mix, the ammonia that 0.2mL mass concentration is 28% is dripped after 60min, stir after 24h, it is centrifugal in 12000rpm to add acetone, centrifugal product absolute ethanol washing three times, finally be scattered in deionized water, obtained concentration is the Se-SiO of 200mg/mL 2dispersion liquid;
(3) Se-SiO that step (2) obtains is got 2dispersion liquid 50mL, ultrasonic disperse 5min, adds in reaction bulb, then adds 10gPVP stirring 3h, stops stirring, is warming up to 99 DEG C and is incubated 5h, then cooling, centrifugalize under 12000rpm, centrifugal product absolute ethanol washing 3 times, be i.e. obtained porous Se-SiO 2nanoparticle.
Embodiment 5
A kind of porous Se-SiO 2nanoparticle, comprises the SiO of simple substance Se, coated simple substance Se 2and be coated on SiO 2the polyvinylpyrrolidone on surface, its preparation method comprises the following steps:
(1) nanometer Cu 2-xthe synthesis of Se: will get Cu-lyt. and be placed in there-necked flask, and add oleic acid, forming concentration is the solution A of 4.9mg/mL, then selenium powder is placed in another there-necked flask, adds oleic acid and oleyl amine that volume ratio is 1:1, and forming concentration is the solution B of 7.9mg/mL.Two there-necked flasks are put into heating jacket, passes into nitrogen, stir, after being heated to 115 DEG C, being incubated 25 minutes, then B solution being heated to 270 DEG C, insulation 32min, then be cooled to 210 DEG C, meanwhile, solution A is warmed up to 210 DEG C.Draw solution B adds in solution A, and the volume ratio of solution B and solution A is 1:2, reaction 8min, then be cooled to room temperature, add appropriate dehydrated alcohol under 12000r/min centrifugal 12 minutes, after centrifugal product ethanol is washed three times, add normal hexane, obtain the Cu that concentration is 10mg/mL 2-xse normal hexane dispersion liquid;
(2) Se-SiO 2synthesis: get the Cu that 1000mL step (1) is obtained 2-xse normal hexane dispersion liquid joins in reaction bulb, then 1mL deionized water, 100mL hexanol and 100mLTritonX-100,500mL normal hexane is added, stir, drip 0.1mLTEOS after 10min, more fully mix, the ammonia that 0.5mL mass concentration is 26% is dripped after 10min, stir after 24h, it is centrifugal in 12000rpm to add acetone, centrifugal product absolute ethanol washing three times, finally be scattered in deionized water, obtained concentration is the Se-SiO of 500mg/mL 2dispersion liquid;
(3) Se-SiO that step (2) obtains is got 2dispersion liquid 20mL, ultrasonic disperse 5min, adds in reaction bulb, then adds 1gPVP stirring 2h, stops stirring, is warming up to 85 DEG C and is incubated 3h, then cooling, centrifugalize under 12000rpm, centrifugal product absolute ethanol washing 3 times, be i.e. obtained porous Se-SiO 2nanoparticle.

Claims (9)

1. a porous Se-SiO 2the preparation method of nanoparticle, is characterized in that, comprises the following steps:
(1) by Cu 2-xse nanoparticle dispersion, in normal hexane, obtains Cu 2-xse normal hexane dispersion liquid;
(2) toward Cu 2-xdeionized water, hexanol, Triton X-100 and normal hexane is added in Se normal hexane dispersion liquid, stir, drip tetraethyl orthosilicate, abundant mixing, drip ammonia again after 1 ~ 60min, stirring reaction, add acetone and centrifugalize, be scattered in deionized water after separated product washing, obtained nanometer Se-SiO 2dispersion liquid;
(3) polyvinylpyrrolidone is added nanometer Se-SiO 2in dispersion liquid, after being uniformly mixed, stopping stirring and heating carrying out hydrothermal processes, be then cooled to room temperature, centrifuge washing, be i.e. obtained porous Se-SiO 2nanoparticle.
2. a kind of porous Se-SiO according to claim 1 2the preparation method of nanoparticle, is characterized in that, Cu in step (1) 2-xthe concentration of Se normal hexane dispersion liquid is 0.1 ~ 500mg/mL.
3. a kind of porous Se-SiO according to claim 1 2the preparation method of nanoparticle, is characterized in that, the Cu described in step (2) 2-xse normal hexane dispersion liquid: deionized water: hexanol: Triton X-100: normal hexane: tetraethyl orthosilicate: the volume ratio of ammonia is 10:0.01 ~ 2:1 ~ 10:1 ~ 10:5 ~ 100:1 ~ 0.001:1 ~ 0.005, the mass concentration of described ammonia is 25% ~ 28%.
4. a kind of porous Se-SiO according to claim 1 2the preparation method of nanoparticle, is characterized in that, Cu in step (2) 2-xthe mixing time added in Se normal hexane dispersion liquid after deionized water, hexanol, Triton X-100 and normal hexane is 1 ~ 20min, and the stirring reaction time dripped after ammonia is 24h;
The rotating speed of centrifugalize is 12000rpm, and separated product washing is for using absolute ethanol washing three times.
5. a kind of porous Se-SiO according to claim 1 2the preparation method of nanoparticle, is characterized in that, the polyvinylpyrrolidone described in step (3) and nanometer Se-SiO 2the interpolation of dispersion liquid is than being 1g:5 ~ 200mL.
6. a kind of porous Se-SiO according to claim 1 2the preparation method of nanoparticle, is characterized in that, polyvinylpyrrolidone and nanometer Se-SiO in step (3) 2the mixing time of the mixed liquor of dispersion liquid is 0.2 ~ 3h.
7. a kind of porous Se-SiO according to claim 1 2the preparation method of nanoparticle, is characterized in that, in step (3), the temperature of hydrothermal processes is 75 ~ 99 DEG C, and the processing time is 0.2 ~ 5h.
8. the porous Se-SiO that the preparation method as described in as arbitrary in claim 1 ~ 7 prepares 2nanoparticle, is characterized in that, described Se-SiO 2nanoparticle comprises the SiO of simple substance Se, coated simple substance Se 2and be coated on SiO 2the polyvinylpyrrolidone on surface.
9. a porous Se-SiO as claimed in claim 8 2nanoparticle is in the application of the load of cancer therapy drug, transhipment or slow release.
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CN112656959A (en) * 2020-11-13 2021-04-16 上海工程技术大学 Se @ SiO2@MnO2-ICG nano composite and preparation method and application thereof

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CN107497034A (en) * 2017-09-26 2017-12-22 上海市第人民医院 A kind of band coating screw thread catheter
CN107648724A (en) * 2017-11-04 2018-02-02 上海市第人民医院 A kind of wound healing and the urethral catheterization device of convenient drainage
CN107648724B (en) * 2017-11-04 2023-11-03 上海市第一人民医院 Urethral catheterization device capable of promoting wound healing and facilitating drainage
CN109833329A (en) * 2019-03-22 2019-06-04 暨南大学 A kind of hyaluronic acid-porous nano selenium compound and the preparation method and application thereof
CN109833329B (en) * 2019-03-22 2021-03-19 暨南大学 Hyaluronic acid-porous nano selenium compound and preparation method and application thereof
CN112656959A (en) * 2020-11-13 2021-04-16 上海工程技术大学 Se @ SiO2@MnO2-ICG nano composite and preparation method and application thereof

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