CN104876230A - Monodispersed ordered hydrophobic silica nanoparticle preparation method - Google Patents
Monodispersed ordered hydrophobic silica nanoparticle preparation method Download PDFInfo
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Abstract
The invention relates to a monodispersed ordered hydrophobic silica nanoparticle preparation method and belongs to the field of preparation of inorganic materials. The method includes: firstly, preparing a mixed solution from surfactant, a pre-polymer, water and ethanol prior to putting the mixed solution in a beaker, and stirring for 6 hours at the temperature of 30 DEG C; secondly, pouring the mixed solution into the beaker, adding a certain amount of benzene to form micro emulsion, and stirring for 1 hour at the temperature of 69 DEG C; thirdly, regulating the temperature to 105 DEG C till the water and ethanol are distillated out completely; fourthly, drying residual solution to obtain powder samples prior to adding mixed cleaning solution, centrifuging at high speed, and taking precipitate at the bottom of a centrifuge tube prior to drying at the temperature of 60 DEG C; fifthly, collecting dried products to obtain the monodispersed uniform-size nanoporous hydrophobic silica. The prepared monodispersed nanoporous hydrophobic silica is less than 50nm in size, both particle size and pore diameter can be adjusted, pore canals are ordered in height, and the technique process is simple. The prepared monodispersed nanoporous hydrophobic silica can be used for wrapping and transmitting anticarcinogen, and can prolong release time of drugs.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, relate to the preparation method of the orderly hydrophobic titanium dioxide nano silicon particles of a kind of single dispersing.
Background technology
After Kresge etc. synthesizes MCM-41 Series Molecules sieve first, people start to pay close attention to the research of the mesoporous silicon oxide with regular pore canal.Because mesoporous silica particles has, specific surface area is large, aperture can regulate, surface can by features such as other base group modification, good biocompatibilities, therefore mesoporously catalyzer, sensor, optical material, drug loading, material of construction, rubber, electric parts, precise materials, medical treatment product, waterproof, anti-pollution, the field such as antireflection, gas delivery can be widely used in, particularly in drug loading and drug controlled release field.Nanotechnology thoroughly can change the Diagnosis and Treat of cancer.Having thousands of patient in the world dies from cancer every year.Physicians have developed a variety of cancer therapy drug, but most cancer therapy drug has problems in biocompatibility, stability, bioavailability etc.The wetting ability of medicine and hydrophobicity not only determine the processes such as the absorption of medicine in human body, distribution, metabolism, excretion, also directly have influence on the value of medicine simultaneously.The physico-chemical property of medicine can be changed by the hydrophilic and hydrophobic changing medicine, the bioavailability etc. of medicine can be promoted.A lot of medicines all has higher cytotoxicity, while killing virocyte, and also can major injury human normal cell.The medicine of this class needs to be delivered to patient part by carrier loaded, and slow releasing kills virocyte.Desirable drug delivery system needs the biocompatibility had, huge drug loading and higher encapsulation rate, and cell-specific---targeting; Do not discharge medicine before also needing to ensure not arrive patient part, after arriving patient part, slowly release medicine.
Method mainly vapor phase process and the hydrolysis methods of current production nano silicon, product can be reunited when process, and this can affect the application in its later stage.In the middle of laboratory, use many methods to be sol-gel processing and micro emulsion method.The performance of products obtained therefrom is better than first two method.But the most of condition of these methods is relatively stricter, operating process is complicated, and some raw material ratio costly.This just makes to be difficult to by the excellent water drain silica of a large amount of processability of these methods.The preparation of current water drain silica mainly utilizes precursor (TEOS) hydrolysis to prepare monodisperse silica, and silica sphere is now hydrophilic.Then add organism (MTES, VTES, TMCS) modification in addition with hydrophobic grouping, the product of acquisition is hydrophobic.The raw material added in general this preparation method is excessive, containing multiple excess raw material, and post-processed more complicated.Zhang Sulin etc. (Advanced Materials, 2009,21:419-424.) are relevant with the size of particle by the amount of research discovery active somatic cell Phagocytic granules, and the particle that particle size is no more than 50 nm is more prone to by cytophagy.By research, Tang Qunli etc. (Journal of controlled release, 2006,114:41-46.) find that the mesoporous material after front three alkyl Si modification can time of releasing of prolong drug greatly.G. by research, V. R. Rao etc. (Advanced Materials, 2002,14,1301-1304.) find that the monodispersity of mesoporous material can control the release rate of medicine.The size of the hydrophobic titanium dioxide silicon grain of current preparation is all greater than 50 nm substantially, and bad dispersibility, and surperficial duct order is not high.In sum, if one-step synthesis single dispersing dewatering nano hole silicon-dioxide becomes current primary study direction.
Single dispersing prepared by the present invention orderly dewatering nano hole silicon-dioxide, size is less than 50 nm, and particle diameter and aperture can regulate, and duct high-sequential, technological process is simple.The single dispersing dewatering nano hole silicon-dioxide of preparation can be used for parcel and transmit cancer therapy drug, and can time of releasing of prolong drug.
Summary of the invention
The present invention mainly provides a kind of brand-new single stage method to prepare the method for single dispersing ordered nano hole water drain silica.The silicon-dioxide uniform particle sizes that this method prepares, good dispersity, particle size and aperture can regulate, and can be used for wrapping up and transmitting cancer therapy drug.
In order to reach effect above, the present invention takes following technical scheme: single stage method prepares the method for single dispersing ordered nano hole water drain silica, carries out according to following step:
A) first front aggressiveness, tensio-active agent, water, ethanol (mol ratio=1:2.75:422.94:315.65) are mixed with mixing solutions;
B) mixing solutions is placed in beaker, stirs 6 h, now solution clear below 30 ° of C, is homogeneous phase solution.
C) mixing solutions is poured in flask, add a certain amount of organic solvent (front aggressiveness and organic solvent mol ratio=1:832.96) and form micro emulsion, 105 ° of C are adjusted the temperature to, until water and the complete azeotropic distillation of ethanol are out stir 1h below 69 ° of C after.
D) surplus solution dry obtain powdered sample, after add mixing, washing liquid (V
virahol: V
water=1:1), carry out high speed centrifugation, get throw out below centrifuge tube and dry under 60 ° of C.
E) collect the product of drying, obtain single dispersing, nanoporous water drain silica of uniform size.
Wherein by regulating the ratio between water, precursor, tensio-active agent to regulate the size of hydrophobic titanium dioxide silicon grain and the size in aperture.
In above-mentioned technical scheme, the organic solvent selected in the technical scheme of prioritizing selection can be benzene, toluene, hexanaphthene etc.
In technical scheme, the tensio-active agent of prioritizing selection is CTAB or CTAC, and precursor is MTES or MTMS.(CTAB is cetyl trimethylammonium bromide; CTAC is palmityl trimethyl ammonium chloride; MTES is Union carbide A-162; MTMS is methyltrimethoxy silane).
The temperature range that in step c), azeotropic distillation is selected is 69-115 ° of C; Step d) medium speed is 7500 r/min-9000 r/min.The scope prioritizing selection 20-200 nm of nanoporous silica granular size; Optimum range is 30-50 nm; The pore diameter range of water drain silica is 1-5 nm; At the uniform velocity stir when in technique scheme, preferred technical scheme is azeotropic.
Present method prepares single dispersing ordered nano hole water drain silica by azeotropic distillation self-assembly, the size of the water drain silica of preparation can be regulated by the proportioning changing tensio-active agent, water and precursor, and the amount that aperture can change tensio-active agent regulates.Present method design is unique, and the nanoporous water drain silica size of preparation is even, and monodispersity is good, duct high-sequential.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 is prepared into single hydrophobic titanium dioxide silicon grain electron microscope image;
Fig. 2 is that embodiment 1 is prepared into single water drain silica Particle Contact Angle test pattern;
Fig. 3 is that embodiment 2 is prepared into single dispersing water drain silica electron microscope image.
Embodiment
Below by embodiment, the present invention will be further elaborated.
Embodiment 1
First weigh 1 g CTAB to pour in 100 ml beakers, add 0.2 ml MTES, 7.6 ml deionized waters and 18.4 ml ethanol.Add rotor, under 30 ° of C, stir 6 h.After mixed solution is poured in 250 ml there-necked flasks, and add 74 ml benzene, be warming up to 69 ° of C azeotropic distillation 1h.After adjust the temperature to 105 ° of C, steam residual moisture.Reaction product is dried under 60 ° of C, after add mixing, washing liquid (V
virahol: V
water=1:1), put into whizzer, centrifugal below 9000 r/min.Get throw out below centrifuge tube to dry under 60 ° of C, obtain water drain silica.The particle diameter of single dispersing water drain silica is 30 nm, and aperture is 1.12 nm.Azeotropic distillation prepares the electron microscope image of single dispersing water drain silica as shown in Figure 1.The contact angle test pattern of the water drain silica obtained as shown in Figure 2.
Embodiment 2
Weigh 1 g CTAB to pour in 100 ml beakers, add 1 ml MTES, 7.6 ml deionized waters and 18.4 ml ethanol, put into rotor, under 30 ° of C, stir 6 h.After mixed solution is poured in 250 ml there-necked flasks, and add 74 ml benzene, be warming up to 69 ° of C azeotropic distillation 1 h.After adjust the temperature to 105 ° of C, steam residual moisture.Reaction product is dried under 60 ° of C, after add mixing, washing liquid (V
virahol: V
water=1:1), put into whizzer, centrifugal below 9000 r/min.Get throw out below centrifuge tube to dry under 60 ° of C, obtain monodispersed water drain silica.The particle diameter of single dispersing water drain silica is 125 nm, and aperture is 3.1 nm.Azeotropic distillation prepares the electron microscope image of single dispersing water drain silica as shown in Figure 3.
Embodiment 3
Weigh 1 g CTAB to pour in 100 ml beakers, add 2 ml MTMS, 7.6 ml deionized waters and 18.4 ml ethanol, put into rotor, under 30 ° of C, stir 6 h.After mixed solution is poured in 250 ml there-necked flasks, and add 74 ml benzene, be warming up to 69 ° of C azeotropic distillation 1 h.After adjust the temperature to 105 ° of C, steam residual moisture.Reaction product is dried under 60 ° of C, after add mixing, washing liquid (V
virahol: V
water=1:1), put into whizzer, centrifugal below 9000 r/min.Get throw out below centrifuge tube to dry under 60 ° of C, obtain monodispersed water drain silica.
Embodiment 4
Weigh 1 g CTAB to pour in 100 ml beakers, add 3 ml MTMS, 7.6 ml deionized waters and 18.4 ml ethanol, put into rotor, under 30 ° of C, stir 6 h.After mixed solution is poured in 250 ml there-necked flasks, and add 74 ml benzene, be warming up to 69 ° of C azeotropic distillation 1h.After adjust the temperature to 105 ° of C, steam residual moisture.Reaction product is dried under 60 ° of C, after add mixing, washing liquid (V
virahol: V
water=1:1), put into whizzer, centrifugal below 9000 r/min.Get throw out below centrifuge tube to dry under 60 ° of C, obtain monodispersed water drain silica.
Embodiment 5
Weigh 1 g CTAB to pour in 100 ml beakers, add 4 ml PTMS, 7.6 ml deionized waters and 18.4 ml ethanol, put into rotor, under 30 ° of C, stir 6 h.After mixed solution is poured in 250 ml there-necked flasks, and add 74 ml benzene, be warming up to 69 ° of C azeotropic distillation 1 h.After adjust the temperature to 105 ° of C, steam residual moisture.Reaction product is dried under 60 ° of C, after add mixing, washing liquid (V
virahol: V
water=1:1), put into whizzer, centrifugal below 9000 r/min.Get throw out below centrifuge tube to dry under 60 ° of C, obtain monodispersed water drain silica.
Embodiment 6
Weigh 1.5 g CTAB to pour in 100 ml beakers, add 1 ml PTES, 7.6 ml deionized waters and 18.4 ml ethanol, put into rotor, under 30 ° of C, stir 6 h.After mixed solution is poured in 250 ml there-necked flasks, and add 74 ml benzene, be warming up to 69 ° of C azeotropic distillation 1 h.After adjust the temperature to 105 ° of C, steam residual moisture.Reaction product is dried under 60 ° of C, after add mixing, washing liquid (V
virahol: V
water=1:1), put into whizzer, centrifugal below 9000 r/min.Get throw out below centrifuge tube to dry under 60 ° of C, obtain monodispersed water drain silica.
Claims (5)
1. a preparation method for the orderly water drain silica of single dispersing, is characterized in that carrying out according to following step:
A) first front aggressiveness, tensio-active agent, water, ethanol (mol ratio=1:2.75:422.94:315.65) are mixed with mixing solutions;
B) mixing solutions is placed in beaker, stirs 6 h, now solution clear below 30 ° of C, is homogeneous phase solution;
C) mixing solutions is poured in flask, add a certain amount of organic solvent (front aggressiveness and organic solvent mol ratio=1:832.96) and form micro emulsion, 105 ° of C are adjusted the temperature to, until water and the complete azeotropic distillation of ethanol are out stir 1h below 69 ° of C after;
D) surplus solution dry obtain powdered sample, after add mixing, washing liquid (V
virahol: V
water=1:1), carry out high speed centrifugation, get throw out below centrifuge tube and dry under 60 ° of C;
E) collect the product of drying, obtain single dispersing, nanoporous water drain silica of uniform size.
2. the preparation method of the orderly water drain silica of a kind of single dispersing according to claim 1, is characterized in that wherein by regulating the ratio between water, precursor, tensio-active agent to regulate the size of hydrophobic titanium dioxide silicon grain and the size in aperture.
3. the preparation method of the orderly water drain silica of a kind of single dispersing according to claim 1, is characterized in that organic solvent can be benzene, toluene, hexanaphthene etc.
4. the preparation method of the orderly water drain silica of a kind of single dispersing according to claim 1, is characterized in that tensio-active agent is CTAB or CTAC, and precursor is MTES or MTMS; (CTAB is cetyl trimethylammonium bromide; CTAC is palmityl trimethyl ammonium chloride; MTES is Union carbide A-162; MTMS is methyltrimethoxy silane).
5. the preparation method of the orderly water drain silica of a kind of single dispersing according to claim 1, is characterized in that the temperature range that in step c), azeotropic distillation is selected is 69-115 ° of C; Step d) medium speed is 7500 r/min-9000 r/min;
The scope prioritizing selection 20-200 nm of nanoporous silica granular size; Optimum range is 30-50 nm; The pore diameter range of water drain silica is 1-5 nm; At the uniform velocity stir when in technique scheme, preferred technical scheme is azeotropic.
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Effective date of registration: 20170217 Address after: 213023 Changzhou Economic Development Zone, Jiangsu bell tower Economic Development Zone, No. 213 ERON Road, Changzhou bell tower high tech service center building, No. 8812 Applicant after: Changzhou Yingzhong Nano Technology Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Applicant before: Changzhou University |
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