CN105079027B - A kind of porous Se SiO2Nano-particle and its preparation method and application - Google Patents

A kind of porous Se SiO2Nano-particle and its preparation method and application Download PDF

Info

Publication number
CN105079027B
CN105079027B CN201510496173.1A CN201510496173A CN105079027B CN 105079027 B CN105079027 B CN 105079027B CN 201510496173 A CN201510496173 A CN 201510496173A CN 105079027 B CN105079027 B CN 105079027B
Authority
CN
China
Prior art keywords
sio
nano
particle
porous
hexane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510496173.1A
Other languages
Chinese (zh)
Other versions
CN105079027A (en
Inventor
刘锡建
陆杰
孙彦刚
张丽娟
张红
徐菁利
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai University of Engineering Science
Original Assignee
Shanghai University of Engineering Science
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai University of Engineering Science filed Critical Shanghai University of Engineering Science
Priority to CN201510496173.1A priority Critical patent/CN105079027B/en
Publication of CN105079027A publication Critical patent/CN105079027A/en
Application granted granted Critical
Publication of CN105079027B publication Critical patent/CN105079027B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Silicon Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The present invention relates to a kind of porous Se SiO2Nano-particle and preparation method thereof and its application, described Se SiO2Nano-particle includes simple substance Se, cladding simple substance Se SiO2And it is coated on SiO2The polyvinylpyrrolidone on surface, first by preparing Cu2‑xSe n-hexane dispersion liquids, then toward Cu2‑xDeionized water, n-hexyl alcohol, Triton X-100, n-hexane, tetraethyl orthosilicate and ammoniacal liquor are added in Se n-hexane dispersion liquids, reaction product is scattered in deionized water and obtains a nanometer Se SiO2Dispersion liquid, then toward nanometer Se SiO2Polyvinylpyrrolidone is added in dispersion liquid, and hydrothermal processes are for a period of time, that is, porous Se SiO are made2Nano-particle, obtained porous Se SiO2Application of the nano-particle in the load of cancer therapy drug thing, transhipment or sustained release.Compared with prior art, the present invention has the advantages that good biocompatibility, nanometer Se release performances are good, cancer therapy drug load factor is high.

Description

A kind of porous Se-SiO2Nano-particle and its preparation method and application
Technical field
The present invention relates to a kind of nano-particle and its preparation method and application, more particularly, to a kind of porous Se-SiO2Receive Rice corpuscles and its preparation method and application.
Background technology
Selenium is one of the essential trace elements of the human body, and research has shown that, selenium is lacked in human body can be easily caused more than 40 and plant disease, Such as cancer, heart disease, diabetes, hypertension metabolism disease and hepatitis.Appropriate intake selenium, has enhancing immunity of organism, delays to give birth to Thing aging and other effects.But margin of safety of the selenium between optium concentration and intoxicating concentration is very narrow, therefore develop low toxicity efficiently Selenium source be very important to the health of the mankind.Relative to the selenium of other states, the small-size effect of Nanometer Se~0 particle and make It has the photoelectric characteristic that conventional bulk selenium material does not possess, and has caused the concern of material educational circles.In addition, nanometer selenium has low toxicity Effect, and can be absorbed and utilized by human body, also with effects such as antitumor, anti-oxidant, enhancing immunity of organisms. Therefore, the synthesis of R and D nanometer selenium is the focus of relevant selenium research.
At present, there is the study on the synthesis much on nanometer selenium.As patent CN200510050295 reports a kind of bear Porous mineral materials are ground to by load type nanometer selenium preparation method, porous mineral materials carrier as miniature nano-reactor More than 300 mesh, the suspension slurry for being made 1%~10% adds selenium salt, adjusts pH=4~6, reacts 2~10 hours, and centrifugation is dried It is dry, it is ground to more than 300 mesh, the nanometer selenium powder of support type is made.Li Zhilin etc. is template using lauryl sodium sulfate, instead It is 0.01mol/L to answer system sulfite concentration, ascorbic acid concentrations 0.07mol/L, lauryl sodium sulfate mass fraction For 1.0%, 7min is reacted under normal temperature, can obtain spherical red nanometer selenium, and average grain diameter 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 10mg Na2SeO3, 50mg vitamin Es are then added, control pH Between 5~6,9h is stood, condensed emulsified, dry the selenium capsule of solidification.Chinese patent ZL201310482174.1 is disclosed Kind copper selenide/meso-porous silica core-shell nano-particle and its preparation method and application, copper selenide/mesoporous silicon oxide Core-shell nano is Cu2-xSe/mSiO2- PEG core-shell nanos, wherein x are 0-1, and m is mesoporous.Preparation method:Prepare Cu2-xSe is nanocrystalline, by CTAB by hydrophobic Cu2-xSe is nanocrystalline to be transferred in aqueous phase, then by sol-gal process with CTAB is template polyethylene glycol on one layer of mesoporous silicon oxide of its superficial growth, last surface modification coupling, is produced, can be in light Applied in heat cure and medicament slow release.But the nanometer selenium product of the preparation method synthesis of existing nanometer selenium can not reach effective The release of selenium is controlled, and function is relatively simple, it is therefore desirable to continue the synthesis of nano-scale selenium product, can really realize Nanometer selenium control release and multifunction.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of porous Se-SiO2Receive Rice corpuscles and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of porous Se-SiO2The preparation method of nano-particle, comprises the following steps:
(1) by Cu2-xSe nano-particles are scattered in n-hexane, obtain Cu2-xSe n-hexane dispersion liquids;;
(2)Se-SiO2Synthesis:Toward Cu2-xIt is pungent that deionized water, n-hexyl alcohol, polyethylene glycol are added in Se n-hexane dispersion liquids Base phenyl ether and n-hexane, stirring, tetraethyl orthosilicate is added dropwise, is sufficiently mixed, ammoniacal liquor is added dropwise after 1~60min again, stirring is anti- Should, add acetone and centrifuge, be scattered in after separation product washing in deionized water, that is, nanometer Se-SiO is made2Dispersion liquid;
(3) polyvinylpyrrolidone is added into nanometer Se-SiO2In dispersion liquid, after being stirred, stop stirring and heating Hydrothermal processes are carried out, room temperature is subsequently cooled to, centrifuge washing, that is, porous Se-SiO is made2Nano-particle.
Step (1) Cu2-xThe concentration of Se n-hexane dispersion liquids is 0.1~500mg/mL.
Cu described in step (1)2-xSe nano-particles are prepared by following steps:
Oleic acid is added into stannous chloride, obtains the solution A that concentration is 4.9mg/mL, it is 1 that volume ratio is added into selenium powder: 1 oleic acid and oleyl amine, obtain the B solution that concentration is 7.9mg/mL;Nitrogen will be passed through in solution A, B solution respectively, stirred, heating To 110~120 DEG C, 20~30min is incubated, B solution is then heated to 250~280 DEG C, 30-35min is incubated, is cooled to 200-220 DEG C, meanwhile, solution A is warming up to 200~220 DEG C, B solution is then drawn, is added in solution A, wherein, draw B solution and solution A volume ratio be 1:2,5~10min is reacted, room temperature is cooled to, centrifuge washing, that is, Cu is made2-xSe nanometers Particle.
Cu described in step (2)2-xSe n-hexane dispersion liquids:Deionized water:N-hexyl alcohol:Triton X-100: N-hexane:Tetraethyl orthosilicate:The volume ratio of ammoniacal liquor is 10:0.01~2:1~10:1~10:5~100:1~0.001:1~ 0.005, the mass concentration of described ammoniacal liquor is 25%~28%.
Cu in step (2)2-xIn Se n-hexane dispersion liquids add deionized water, n-hexyl alcohol, Triton X-100 and Mixing time after n-hexane is 1~20min, and the stirring reaction time being added dropwise after ammoniacal liquor is 24h;
The rotating speed of centrifugation is 12000rpm, and separation product washing is to be washed three times with absolute ethyl alcohol.
Nanometer Se-SiO obtained by step (2)2As long as the concentration of dispersion liquid does not influence follow-up polyvinylpyrrolidone bag Silica is covered, is operated for convenience, it is 0.1~500mg/mL to be often made into concentration.
Polyvinylpyrrolidone and nanometer Se-SiO described in step (3)2The addition of dispersion liquid is compared for 1g:5~ 200mL。
Polyvinylpyrrolidone and nanometer Se-SiO in step (3)2The mixing time of the mixed liquor of dispersion liquid be 0.2~ 3h。
The temperature of hydrothermal processes is 75~99 DEG C in step (3), and processing time is 0.2~5h.
The Se-SiO that above-mentioned preparation method is prepared2Nano-particle, including simple substance Se, cladding simple substance Se SiO2And It is coated on SiO2The polyvinylpyrrolidone on surface.
A kind of porous Se-SiO2Application of the nano-particle in the load of cancer therapy drug, transhipment or sustained release.
This patent is in building-up process, in deionized water, n-hexyl alcohol, Triton X-100 and n-hexane reactant In system, after ammoniacal liquor is added dropwise, Cu2-xSe nano-particles are oxidized, and generate Se simple substance, at the same time, teos hydrolysis generation SiO2It is coated on Se quantum dots, forms Se-SiO2Nano-particle, and a Se-SiO2Nano-particle has coated many Se quantum dots (referring to Fig. 2).Compared with patent CN 201310482174.1, coated with silica of the invention is nonpolar Carried out in solvent, Cu2-xSe is aoxidized in reaction system, generates Se simple substance, while carried out SiO2Cladding, passes through That XRD can prove synthesis is Se-SiO2Nano-particle (referring to Fig. 1).And dioxy in patent CN 201310482174.1 SiClx cladding is carried out in polar system, and silica has directly coated Cu2-xSe nano particles, generate Cu2-xSe- mSiO2Nano-particle, in building-up process, Cu2-xSe, which does not react, generates other materials.
Compared with prior art, the present invention is coated nanometer selenium by silica, forms Se-SiO2Nano-particle, so Afterwards by polyvinylpyrrolidone (PVP) and Se-SiO2Nanoparticle dispersion liquid mixes, and hydrothermal processes, PVP is coated on titanium dioxide Silicon face, silica and PVP are respectively provided with good biocompatibility, are advantageous to Se-SiO2Nano-particle in vivo should With, and hydrothermal processes are by Se-SiO2Nano-particle forms loose structure, is advantageous to nanometer Se release, and the hole formed Road can be used for loading cancer therapy drug, it is possible to achieve multifunction.
Brief description of the drawings
Fig. 1 is Se-SiO prepared by the present invention2X-ray diffraction (XRD) figure of nano-particle;
Fig. 2 is Se-SiO prepared by the present invention2Transmission electron microscope (TEM) figure of nano-particle;
Fig. 3 is hydrothermal processes 1.5h prepared by present invention Se-SiO2Transmission electron microscope (TEM) figure of nano-particle;
Fig. 4 is hydrothermal processes 2h prepared by present invention Se-SiO2Transmission electron microscope (TEM) figure of nano-particle.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to Following embodiments.
Embodiment 1
(1)Cu2-xSe synthesis:49mg stannous chlorides are placed in there-necked flask, add 10mL oleic acid, form solution A, will 79mg selenium powders are placed in another there-necked flask, add 5mL oleic acid and 5mL oleyl amines, form B solution.Two there-necked flasks are put into heating In set, nitrogen is passed through, is stirred, after being heated to 120 DEG C, 20 minutes are incubated, with the moisture and oxygen in removing device.Then by B Solution is heated to 280 DEG C, is incubated half an hour, then be cooled to 220 DEG C.Meanwhile solution A is warming up to 220 DEG C.Use syringe 5mL B solutions are drawn, are expelled in 10mL solution As, after reacting 5 minutes, are cooled to room temperature.Appropriate absolute ethyl alcohol is added to exist Centrifuged 12 minutes under 12000r/min.After being washed three times with ethanol, 10mL n-hexanes are added, obtain Cu2-xSe n-hexane dispersion liquids, it is standby With;
(2) Cu made from 5mL steps (1) is taken2-xSe n-hexane dispersion liquids are added in reaction bulb, add 0.9mL go from Sub- water, 3mL n-hexyl alcohols and 3mL Triton X-100 (Triton X-100), 30mL n-hexanes are then added, stirred, 0.05mL TEOS (tetraethyl orthosilicate) are added dropwise after 5min, fully mix, 0.1mL ammoniacal liquor is added dropwise after 5min, the quality of ammoniacal liquor is dense Spend for 25%.After stirring 24h, add acetone and centrifuged in 12000rpm, centrifugation product is washed three times with absolute ethyl alcohol, is finally divided Dissipate in 20mL deionized waters, nanometer Se-SiO is made2Dispersion liquid, obtain Se-SiO2Nano-particle, its XRD and TEM figures point Not as depicted in figs. 1 and 2, it can be seen that SiO2Multiple Se simple substance quantum dots are coated, form Se-SiO2Nano-particle.
(3) Se-SiO obtained by step (2) is taken2Dispersion liquid 20mL, ultrasonic disperse 5min, add in reaction bulb, then add Enter 0.2g PVP (polyvinylpyrrolidone) stirrings 1h.Stop stirring, be warming up to 95 DEG C, be held at 95 DEG C and keep 1.5h.So After cool down, 12000rpm centrifuge, with absolute ethyl alcohol will centrifuge product wash 3 times, with remove remain surfactant (PVP).Last ultrasonic disperse preserves with standby in deionized water, obtains porous Se-SiO2Nano-particle, its TEM figures are as schemed Shown in 3.
Embodiment 2
(1)Cu2-xSe synthesis:49mg stannous chlorides are placed in there-necked flask, add 10mL oleic acid, form solution A, will 79mg selenium powders are placed in another there-necked flask, add 5mL oleic acid and 5mL oleyl amines, form B solution.Two there-necked flasks are put into heating In set, nitrogen is passed through, is stirred, after being heated to 120 DEG C, 20 minutes are incubated, with the moisture and oxygen in removing device.Then by B Solution is heated to 280 DEG C, is incubated half an hour, then be cooled to 220 DEG C.Meanwhile solution A is warming up to 220 DEG C.Use syringe 5mL B solutions are drawn, are expelled in 10mL solution As, after reacting 5 minutes, are cooled to room temperature.Appropriate absolute ethyl alcohol is added to exist Centrifuged 12 minutes under 12000r/min.After being washed three times with ethanol, 10mL n-hexanes are added, obtain Cu2-xSe n-hexane dispersion liquids, it is standby With;
(2) Cu made from 5mL (1) is taken2-xSe n-hexane dispersion liquids are added in reaction bulb, add 0.9mL deionizations Water, 3mL n-hexyl alcohols and 3mL Triton X-100,30mL n-hexanes are then added, stirred, 0.05mL TEOS are added dropwise after 5min (tetraethyl orthosilicate), fully mix, 0.1mL ammoniacal liquor is added dropwise after 5min.Stir 24h after, add acetone in 12000rpm from The heart, centrifugation product are washed three times with absolute ethyl alcohol, are finally scattered in 20mL deionized waters, and nanometer Se-SiO is made2It is scattered Liquid, obtain Se-SiO2Nano-particle.
(3) Se-SiO obtained by step (2) is taken2Dispersion liquid 20mL, ultrasonic disperse 5min, add in reaction bulb, then add Enter 0.2g PVP (polyvinylpyrrolidone) stirrings 1h.Stop stirring, be warming up to 95 DEG C, be held at 95 DEG C and keep 2h.Then Cooling, 12000rpm are centrifuged, and will centrifuge product with absolute ethyl alcohol washs 3 times, to remove the surfactant of residual (PVP).Last ultrasonic disperse preserves with standby in deionized water, obtains porous Se-SiO2Nano-particle, its TEM figures are as schemed Shown in 4.
(4) the porous Se-SiO for taking 5mg steps (3) to prepare2Nano-particle sample, it is 0.5mg/mL to add 2.5mL concentration Doxorubicin hydrochloride (DOX) solution, ultrasonic disperse, lucifuge stirring 24h.It is then centrifuged for separating, is washed with deionized to removing and does not have There is the medicine of absorption, the load factor for calculating adriamycin is up to 10.4%.
Embodiment 3
A kind of porous Se-SiO2Nano-particle, including simple substance Se, cladding simple substance Se SiO2And it is coated on SiO2Surface Polyvinylpyrrolidone, its preparation method comprises the following steps:
(1) nanometer Cu2-xSe synthesis:49mg stannous chlorides are placed in there-necked flask, add 10mL oleic acid, it is molten to form A Liquid, 79mg selenium powders are placed in another there-necked flask, add 5mL oleic acid and 5mL oleyl amines, form B solution.Two there-necked flasks are put Enter in heating mantle, be passed through nitrogen, stir, after being heated to 120 DEG C, be incubated 20 minutes, B solution is then heated to 280 DEG C, protect Warm half an hour, then 220 DEG C are cooled to, meanwhile, solution A is warming up to 220 DEG C.Draw 5mL solution Bs and add 10mL solution As In, 5min is reacted, room temperature is subsequently cooled to, adds appropriate absolute ethyl alcohol and centrifuged 12 minutes under 12000r/min, centrifugation is produced After thing is washed three times with ethanol, n-hexane is added, obtains the Cu that concentration is 0.1mg/mL2-xSe n-hexane dispersion liquids;
(2)Se-SiO2Synthesis:Take Cu made from 10mL steps (1)2-xSe n-hexane dispersion liquids are added in reaction bulb, Then 2mL deionized waters, 10mL n-hexyl alcohols and 10mL Triton X-100,100mL n-hexanes are added, is stirred, is dripped after 20min Add 1mL TEOS, then be sufficiently mixed, the ammoniacal liquor that 1mL mass concentrations are 25% is added dropwise after 10min, after stirring 24h, add acetone in Centrifuged under 12000rpm, centrifugation product is washed three times with absolute ethyl alcohol, is finally scattered in deionized water, obtained concentration is 0.1mg/mL Se-SiO2Dispersion liquid;
(3) Se-SiO obtained by step (2) is taken2Dispersion liquid 20mL, ultrasonic disperse 5min, add in reaction bulb, then add Enter 0.1g PVP stirring 0.2h, stop stirring, be warming up to 75 DEG C and be incubated 0.2h, then cool down, the centrifugation point under 12000rpm From centrifugation product is washed 3 times with absolute ethyl alcohol, that is, porous Se-SiO is made2Nano-particle.
Embodiment 4
A kind of porous Se-SiO2Nano-particle, including simple substance Se, cladding simple substance Se SiO2And it is coated on SiO2Surface Polyvinylpyrrolidone, its preparation method comprises the following steps:
(1) nanometer Cu2-xSe synthesis:Stannous chloride will be taken to be placed in there-necked flask, and add oleic acid, forming concentration is 4.9mg/mL solution A, then selenium powder is placed in another there-necked flask, it is 1 to add volume ratio:1 oleic acid and oleyl amine, form concentration For 7.9mg/mL solution B.Two there-necked flasks are put into heating mantle, are passed through nitrogen, are stirred, after being heated to 110 DEG C, insulation 30 Minute, B solution is then heated to 250 DEG C, is incubated 35min, then 200 DEG C are cooled to, meanwhile, solution A is warming up to 200 ℃.Draw solution B is added in solution A, and the volume ratio of solution B and solution A is 1:2,10min is reacted, room temperature is subsequently cooled to, adds Enter appropriate absolute ethyl alcohol to centrifuge 12 minutes under 12000r/min, after centrifugation product is washed three times with ethanol, add n-hexane, obtain To the Cu that concentration is 500mg/mL2-xSe n-hexane dispersion liquids;
(2)Se-SiO2Synthesis:Take Cu made from 10mL steps (1)2-xSe n-hexane dispersion liquids are added in reaction bulb, Then 1mL deionized waters, 5mL n-hexyl alcohols and 5mL Triton X-100,50mL n-hexanes are added, is stirred, is added dropwise after 1min 0.05mL TEOS, then be sufficiently mixed, the ammoniacal liquor that 0.2mL mass concentrations are 28% is added dropwise after 60min, after stirring 24h, adds third Ketone is centrifuged in 12000rpm, and centrifugation product is washed three times with absolute ethyl alcohol, is finally scattered in deionized water, obtained concentration is 200mg/mL Se-SiO2Dispersion liquid;
(3) Se-SiO obtained by step (2) is taken2Dispersion liquid 50mL, ultrasonic disperse 5min, add in reaction bulb, then add Enter 10g PVP stirring 3h, stop stirring, be warming up to 99 DEG C and be incubated 5h, then cool down, centrifuged under 12000rpm, from Heart product is washed 3 times with absolute ethyl alcohol, that is, porous Se-SiO is made2Nano-particle.
Embodiment 5
A kind of porous Se-SiO2Nano-particle, including simple substance Se, cladding simple substance Se SiO2And it is coated on SiO2Surface Polyvinylpyrrolidone, its preparation method comprises the following steps:
(1) nanometer Cu2-xSe synthesis:Stannous chloride will be taken to be placed in there-necked flask, and add oleic acid, forming concentration is 4.9mg/mL solution A, then selenium powder is placed in another there-necked flask, it is 1 to add volume ratio:1 oleic acid and oleyl amine, form concentration For 7.9mg/mL solution B.Two there-necked flasks are put into heating mantle, are passed through nitrogen, are stirred, after being heated to 115 DEG C, insulation 25 Minute, B solution is then heated to 270 DEG C, is incubated 32min, then 210 DEG C are cooled to, meanwhile, solution A is warming up to 210 ℃.Draw solution B is added in solution A, and the volume ratio of solution B and solution A is 1:2,8min is reacted, room temperature is subsequently cooled to, adds Enter appropriate absolute ethyl alcohol to centrifuge 12 minutes under 12000r/min, after centrifugation product is washed three times with ethanol, add n-hexane, obtain To the Cu that concentration is 10mg/mL2-xSe n-hexane dispersion liquids;
(2)Se-SiO2Synthesis:Take Cu made from 1000mL steps (1)2-xSe n-hexane dispersion liquids are added to reaction bulb In, then add 1mL deionized waters, 100mL n-hexyl alcohols and 100mL Triton X-100,500mL n-hexanes, stirring, 10min 0.1mL TEOS are added dropwise afterwards, then are sufficiently mixed, the ammoniacal liquor that 0.5mL mass concentrations are 26% is added dropwise after 10min, after stirring 24h, Add acetone to centrifuge in 12000rpm, centrifugation product is washed three times with absolute ethyl alcohol, is finally scattered in deionized water, is made dense Spend the Se-SiO for 500mg/mL2Dispersion liquid;
(3) Se-SiO obtained by step (2) is taken2Dispersion liquid 20mL, ultrasonic disperse 5min, add in reaction bulb, then add Enter 1g PVP stirring 2h, stop stirring, be warming up to 85 DEG C and be incubated 3h, then cool down, centrifuged under 12000rpm, from Heart product is washed 3 times with absolute ethyl alcohol, that is, porous Se-SiO is made2Nano-particle.

Claims (8)

  1. A kind of 1. porous Se-SiO2The preparation method of nano-particle, it is characterised in that comprise the following steps:
    (1) by Cu2-xSe nano-particles are scattered in n-hexane, obtain Cu2-xSe n-hexane dispersion liquids;
    (2) toward Cu2-xDeionized water, n-hexyl alcohol, Triton X-100 and n-hexane are added in Se n-hexane dispersion liquids, Stirring, tetraethyl orthosilicate is added dropwise, is sufficiently mixed, ammoniacal liquor is added dropwise after 1~60min again, stirring reaction, adds acetone and centrifuges and divide From separation product is scattered in deionized water after washing, and nanometer Se-SiO is made2Dispersion liquid;
    (3) polyvinylpyrrolidone is added into nanometer Se-SiO2In dispersion liquid, after being stirred, stop stirring and heating progress heat Liquid processing, room temperature is subsequently cooled to, centrifuge washing, that is, porous Se-SiO is made2Nano-particle;
    Cu described in step (2)2-xSe n-hexane dispersion liquids:Deionized water:N-hexyl alcohol:Triton X-100:Just oneself Alkane:Tetraethyl orthosilicate:The volume ratio of ammoniacal liquor is 10:0.01~2:1~10:1~10:5~100:1~0.001:1~ 0.005, the mass concentration of described ammoniacal liquor is 25%~28%.
  2. A kind of 2. porous Se-SiO according to claim 12The preparation method of nano-particle, it is characterised in that step (1) Middle Cu2-xThe concentration of Se n-hexane dispersion liquids is 0.1~500mg/mL.
  3. A kind of 3. porous Se-SiO according to claim 12The preparation method of nano-particle, it is characterised in that step (2) Middle Cu2-xThe stirring added in Se n-hexane dispersion liquids after deionized water, n-hexyl alcohol, Triton X-100 and n-hexane Time is 1~20min, and the stirring reaction time being added dropwise after ammoniacal liquor is 24h;
    The rotating speed of centrifugation is 12000rpm, and separation product washing is to be washed three times with absolute ethyl alcohol.
  4. A kind of 4. porous Se-SiO according to claim 12The preparation method of nano-particle, it is characterised in that step (3) Described in polyvinylpyrrolidone and nanometer Se-SiO2The addition of dispersion liquid is compared for 1g:5~200mL.
  5. A kind of 5. porous Se-SiO according to claim 12The preparation method of nano-particle, it is characterised in that step (3) Middle polyvinylpyrrolidone and nanometer Se-SiO2The mixing time of the mixed liquor of dispersion liquid is 0.2~3h.
  6. A kind of 6. porous Se-SiO according to claim 12The preparation method of nano-particle, it is characterised in that step (3) The temperature of middle hydrothermal processes is 75~99 DEG C, and processing time is 0.2~5h.
  7. 7. the porous Se-SiO that the preparation method as described in claim 1~6 is any is prepared2Nano-particle, its feature exist In described Se-SiO2Nano-particle includes simple substance Se, cladding simple substance Se SiO2And it is coated on SiO2The polyethylene on surface Pyrrolidones.
  8. A kind of 8. porous Se-SiO as claimed in claim 72Nano-particle is in the load of cancer therapy drug, transhipment or sustained release Using.
CN201510496173.1A 2015-08-13 2015-08-13 A kind of porous Se SiO2Nano-particle and its preparation method and application Active CN105079027B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510496173.1A CN105079027B (en) 2015-08-13 2015-08-13 A kind of porous Se SiO2Nano-particle and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510496173.1A CN105079027B (en) 2015-08-13 2015-08-13 A kind of porous Se SiO2Nano-particle and its preparation method and application

Publications (2)

Publication Number Publication Date
CN105079027A CN105079027A (en) 2015-11-25
CN105079027B true CN105079027B (en) 2017-12-29

Family

ID=54560958

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510496173.1A Active CN105079027B (en) 2015-08-13 2015-08-13 A kind of porous Se SiO2Nano-particle and its preparation method and application

Country Status (1)

Country Link
CN (1) CN105079027B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107497034A (en) * 2017-09-26 2017-12-22 上海市第人民医院 A kind of band coating screw thread catheter
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103505730A (en) * 2013-10-15 2014-01-15 东华大学 Copper selenide/mesoporous silica core-shell nanoparticles and preparation method and application thereof
CN104306969A (en) * 2014-09-14 2015-01-28 天津市职业大学 Method for preparing target release-controlled inorganic selenium medicine
CN104491866A (en) * 2014-12-25 2015-04-08 东华大学 Copper sulphide/mesoporous silicon dioxide core-shell nanoparticles as well as preparation and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63278220A (en) * 1987-02-13 1988-11-15 Nec Corp Formation of single crystal film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103505730A (en) * 2013-10-15 2014-01-15 东华大学 Copper selenide/mesoporous silica core-shell nanoparticles and preparation method and application thereof
CN104306969A (en) * 2014-09-14 2015-01-28 天津市职业大学 Method for preparing target release-controlled inorganic selenium medicine
CN104491866A (en) * 2014-12-25 2015-04-08 东华大学 Copper sulphide/mesoporous silicon dioxide core-shell nanoparticles as well as preparation and application thereof

Also Published As

Publication number Publication date
CN105079027A (en) 2015-11-25

Similar Documents

Publication Publication Date Title
CN105079027B (en) A kind of porous Se SiO2Nano-particle and its preparation method and application
CN105174272B (en) Au@SiO2Composite mesoporous nano material and preparation method thereof
Carné-Sánchez et al. A spray-drying strategy for synthesis of nanoscale metal–organic frameworks and their assembly into hollow superstructures
JP5809210B2 (en) Metal oxide composite having hollow core and porous shell layer and method for producing the same
CN102602883B (en) Preparation method of silica-coated iron oxide nano-core-shell structural material
Yu et al. A facile and fast synthetic approach to create selenium nanoparticles with diverse shapes and their antioxidation ability
CN101337171B (en) Hollow microsphere containing silicon magnetism and preparation method and use thereof
CN107412195A (en) A kind of antineoplastic drug carrier material of pH responses and its preparation and application
CN111137915A (en) Composite nano material with mesoporous silica coated with nano particles and preparation method and application thereof
KR20110114058A (en) A preparing method for mono-dispersed spherical mesoporous silica impregnated nano silver particles and spherical mesoporous silica prepared by the same
Zhao et al. Dendritic silica with carbon dots and gold nanoclusters for dual nanozymes
CN104495950A (en) Preparation method of carbon encapsulated magnetic C/Fe3O4 nano composite material and application thereof
CN109535436A (en) A kind of metalloporphyrin frame material and its preparation method and application with hollow nanostructures
CN109607554A (en) The preparation method of macroporous silica nanoparticle
CN109574507A (en) A kind of nano-level sphere bioactivity glass and preparation method thereof
CN105800619A (en) Internally hydrophilic and externally hydrophobic silicon oxide nanometer bottle and preparation method and application thereof
CN104439276A (en) Method for fast preparing hollow porous silicon dioxide/silver nanoparticle composite and product
Du et al. Facile synthesis of mesoporous organosilica nanobowls with bridged silsesquioxane framework by one-pot growth and dissolution mechanism
Wu et al. Template route to chemically engineering cavities at nanoscale: a case study of Zn (OH) 2 template
CN106075470B (en) The application of gold-nano-piece synthetic method and gold-nano-piece in terms of breast cancer diagnosis and treatment
CN108610060A (en) A kind of preparation method of light sensitivity particle stabilized emulsion and thin spherical joint
Mousavi Elyerdi et al. Synthesis of ultra small nanoparticles (< 50 nm) of mesoporous MCM-48 for bio-adsorption
Chen et al. Synthesis of hollow mesoporous silica nanoparticles by silica-etching chemistry for biomedical applications
Ab Wab et al. Properties of amorphous silica nanoparticles colloid drug delivery system synthesized using the micelle formation method
CN105236417A (en) Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant