CN106278371B - A kind of three-dimensional porous silica-base film preparation method of functionality hierarchical and its biologic applications - Google Patents
A kind of three-dimensional porous silica-base film preparation method of functionality hierarchical and its biologic applications Download PDFInfo
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Abstract
The present invention relates to a kind of functional hierarchical three-dimensional meso-hole silica-base film preparation method and its biologic applications.Preparation method is: hierarchical porous silicon film is prepared by means of soft template and hard template method, main technique includes three steps: (1) synthesis of hard template polystyrene particle, (2) preparation of the silicon performed polymer containing Pluronic F127, (3) filling colloidal sol, (4) remove the polystyrene particle and Pluronic F127 in hard template；Film prepared by the present invention is for extracting different fragments biomarker DNA.The invention reside in: hierarchical porous silicon preparation process is simple, large scale preparation can be achieved, compared with conventional two-dimentional silica-base film, extraction for the biomarker of high concentration, the extraction efficiency of hierarchical porous silicon greatly improves, and provides a kind of new strategy for the early diagnosis of clinical sample.
Description
Technical field
The present invention relates to a kind of functional hierarchical three-dimensional meso-hole silica-base film preparation method and its biologic applications.Specifically relate to
And a kind of preparation method based on the three-dimensional porous silica membrane of hierarchical and its for the detection of biomarker, to realize
The early diagnosis of clinical sample belongs to the in-vitro diagnosis field of biomarker.
Background technique
Biomarker not only can from molecular level inquire into pathogenesis, but also accurately, sensitively evaluation early stage, low water
There is unique advantage in terms of flat damage, it is possible to provide early warning largely provides auxiliary diagnosis for clinician
Foundation.Free nucleic acid in patients serum/blood plasma is as some novel clinical detection biomarkers, especially in early carcinoma
Play the part of critically important role in disease detection.Therefore efficient nucleic acid isolation technics is prediction, and monitoring and treating cancer patient provide
The excellent means of one quantitative analysis, due to patient the case where different and otherness process for separation and purification, it is isolated
Nucleic acid, specific proteins concentration be often repeatability it is poor as a result, this separation and extraction technology there is an urgent need to be a kind of
Inexpensive, quick, efficient and reliable method.The nucleic acid of Current commercial isolates and purifies in column, and Qiagen splitter is a kind of
Most typical DNA separation and Extraction kit, it can from blood plasma, serum and other cell-free body fluid efficiently purifying free nucleic acid,
It is repeated preferable, but its price is higher, and the cost of single experiment expense is too big, at least needs to spend 150 yuan, and the DNA obtained
Yield is relatively low.There is an urgent need to be a kind of inexpensive, quick, high efficient and reliable method for this separation and extraction technology.
The extraction efficiency height of the biomarker of clinical sample relies on the specific surface area of material and the flux volume in duct.
Medium hole nano particles and 2 D mesopore silica-base material due to their specific surface area, lead to during extracting biomarker
It is smaller to measure volume, it is easy to duct be blocked by protein abundant in serum/plasma and lipid, can inhibit to adsorb so significantly
Efficiency.The mesoporous silica-base material preparation process of current conventional three-dimensional is relative complex, in clinical detection application process, practical operation
Flexibility is slightly relatively low.
Therefore a kind of preparation method based on the three-dimensional porous silica-base film of functional hierarchical is provided and its for clinical sample
The early stage of product, accurate in-vitro diagnosis was of great significance.
Summary of the invention
The object of the present invention is to provide a kind of functional hierarchical porous silicon preparation method and its biologic applications, this
Method can overcome the above problem of conventional method, and adopting said method easy can prepare on a large scale the three-dimensional porous silicon substrate of hierarchical
Film, the film will carry out unmarked technical research using nucleic acid as target detection thing, provide for the early diagnosis of clinical sample
A kind of new strategy.
A kind of first purpose to realize the present invention: the three-dimensional porous silicon substrate of functional hierarchical of technical solution of the present invention
Method for manufacturing thin film, characterized by the following steps:
(1) synthesis of hard template polystyrene particle:
A, styrene, polyetherimide and ethyl alcohol are added in flask and are stirred, nitrogen is then led into flask, to remove
Oxygen inside reaction vessel；
B, azodiisobutyronitrile is added thereto and is polymerize to 75 DEG C for heating reaction system；
C, by centrifuge washing, to remove remaining styrene and polyetherimide in dereaction, finally by freeze-drying
Mode obtain polystyrene particle；
D, the ethanol solution of polystyrene particle is deposited to by way of spin coating on silicon wafer, spin coating number 3-5 times, so
The silicon wafer is placed in baking oven afterwards and is solidified in 80 DEG C of constant temperature 6h, hard template polystyrene particle is obtained；
(2) preparation of the silicon performed polymer containing Pluronic F127:
The ethanol solution, ethyl orthosilicate, hydrochloric acid solution of Pluronic F127 are added in vial and are stirred, silicon is obtained
Performed polymer；
(3) filling colloidal sol
Silicon performed polymer is infiltrated into full wafer hard template by way of spin coating, spin coating number 2-5 times, room temperature is dried；
(4) polystyrene particle and Pluronic F127 in hard template are removed
Using the polystyrene particle and Pluronic F127 in Muffle furnace high-temperature calcination removal hard template, 2 DEG C/min
Speed be warming up to 500 DEG C, and constant temperature 4h, room temperature is then cooled to the speed of 2 DEG C/min, stays in porous orderly knot on substrate
Structure is three-dimensional porous silica-base film.
In above scheme, the three-dimensional porous silica-base film macropore diameter size is 1 μm, and mesoporous size is 6nm.
In above scheme, the mass ratio of the Pluronic F127 and ethyl alcohol is 1:10-3:10, and the concentration of hydrochloric acid is
The volume ratio of 1M, ethyl orthosilicate and hydrochloric acid is 1:1.
In above scheme, the spin speed that the polystyrene particle deposits on silicon wafer is 350rpm, and spin-coating time is
120 seconds.
In above scheme, the spin speed that the silicon performed polymer deposits on silicon wafer is 2000rpm, spin-coating time 20
Second.
In above scheme, the mass ratio of the polyetherimide and ethyl alcohol is 1:100-5:100, azodiisobutyronitrile with
The mass ratio of styrene is 1:100-4:100.
In above scheme, the hard template polystyrene particle partial size is 1 μm.Polystyrene particle is to pass through dispersin polymerization
Synthesis: polyetherimide is made as monomer, azodiisobutyronitrile as initiator, dehydrated alcohol as dispersing agent, styrene
For dispersion solvent.
In above scheme, contain the preparation of the silicon performed polymer of Pluronic F127: ethyl orthosilicate and hydrochloric acid are as reaction
Agent, soft template of the F127 as pore, reaction dissolvent is ethyl alcohol.
Second purpose to realize the present invention: the three-dimensional porous silica-base film of technical solution of the present invention functionality hierarchical
The application of film made from preparation method, it is characterised in that: the three-dimensional porous silica-base film is used for mentioning for the DNA of different fragments
It takes.
In above scheme, different DNA fragments are respectively 206bp, 507bp, 1100bp.
In above scheme, the solvent of biomarker dispersion is phosphate physiological buffered solution.
The beneficial effect of present aspect is that the hierarchical porous silicon macropore partial size is 1 μm, and mesoporous partial size is 6nm, thin
Film preparation simple process is, it can be achieved that large scale preparation, compared with conventional two-dimentional silica-base film, for the biomarker of high concentration
The extraction efficiency of the extraction of object, hierarchical porous silicon greatly improves, and provides one kind for the early diagnosis of clinical sample
New strategy.
The present invention is described further with specific embodiment with reference to the accompanying drawings of the specification.
Detailed description of the invention
Fig. 1 is the SEM figure and DLS map of hard template polystyrene particle；
Fig. 2 is the preparation technology flow chart of the three-dimensional porous silica-base film of hierarchical；
Fig. 3 is that SEM, TEM and AFM of the three-dimensional porous silica-base film of hierarchical scheme；
Fig. 4 is extraction of the three-dimensional porous silica-base film of hierarchical to the nucleic acid of different fragments.
Specific embodiment
The present invention is specifically described below by embodiment, is served only for that invention is further explained, no
It can be interpreted as limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention
Make some nonessential modifications and adaptations.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
As shown in Fig. 2, the invention discloses a kind of three-dimensional porous silica-base film preparation methods of functional hierarchical, including such as
Lower step:
(1) synthesis of hard template polystyrene particle:
A, by the styrene of 13mL, the ethyl alcohol of the polyetherimide of 2.5g, 120g is added in the three-necked flask of 250mL,
The mixing speed of 500rpm leads to nitrogen 30min to three-necked flask, to remove the oxygen inside reaction vessel；
B, the azodiisobutyronitrile of 0.12g is added thereto, then polymerize for 24 hours to 75 DEG C for heating reaction system；
C, for several times by centrifuge washing, to remove remaining monomer styrene and dispersing agent polyetherimide in dereaction, from
The heart speed 7500rpm, centrifugation time 10min, obtain polystyrene particle finally by the mode of freeze-drying；
D, the ethanol solution of 2% polystyrene particle is deposited to by way of spin coating on silicon wafer, spin coating number 3-5
Secondary, with the volatilization of ethyl alcohol, polystyrene particle will be assembled on silicon wafer automatically, then place the silicon wafer in baking oven in 80 DEG C
Constant temperature 6h is solidified, and hard template polystyrene particle is obtained；
As shown in Figure 1, polystyrene size is than more uniform, about 1 μm of the size of particle.
(2) preparation of the silicon performed polymer containing Pluronic F127:
By the ethanol solution of the 10% of 5mL Pluronic F127, the ethyl orthosilicate of 1mL, the hydrochloric acid solution of the 1M of 1ml
It is added in the vial of 20mL and stirs, mixing speed 500rpm, mixing time 5h obtain silicon performed polymer；
(3) filling colloidal sol
Silicon performed polymer is infiltrated into full wafer hard template by way of spin coating, spin coating number 2-5 times, room temperature is dried；
(4) polystyrene particle and Pluronic F127 in hard template are removed
Using the polystyrene particle and Pluronic F127 in Muffle furnace high-temperature calcination removal hard template, 2 DEG C/min
Speed be warming up to 500 DEG C, and constant temperature 4h, room temperature is then cooled to the speed of 2 DEG C/min, stays in porous orderly knot on substrate
Structure is three-dimensional porous silica-base film.
In above scheme, the three-dimensional porous silica-base film macropore diameter size is 1 μm, and mesoporous size is 6nm.
In above scheme, the mass ratio of the Pluronic F127 and ethyl alcohol is 1:10-3:10, and the concentration of hydrochloric acid is
The volume ratio of 1M, ethyl orthosilicate and hydrochloric acid is 1:1.
In above scheme, the spin speed that the polystyrene particle deposits on silicon wafer is 350rpm, and spin-coating time is
120 seconds.
In above scheme, the spin speed that the silicon performed polymer deposits on silicon wafer is 2000rpm, spin-coating time 20
Second.
In above scheme, the mass ratio of the polyetherimide and ethyl alcohol is 1:100-5:100, azodiisobutyronitrile with
The mass ratio of styrene is 1:100-4:100.
In above scheme, the hard template polystyrene particle partial size is 1 μm.Polystyrene particle is to pass through dispersin polymerization
Synthesis: polyetherimide is made as monomer, azodiisobutyronitrile as initiator, dehydrated alcohol as dispersing agent, styrene
For dispersion solvent.
In above scheme, contain the preparation of the silicon performed polymer of Pluronic F127: ethyl orthosilicate and hydrochloric acid are as reaction
Agent, soft template of the F127 as pore, reaction dissolvent is ethyl alcohol.
Wherein, the applicant also by prepare 2 D mesopore silica-base film come with the resulting 3-D ordered multiporous silicon of the present invention
Base film compares, wherein the preparation process of 2 D mesopore silica-base film and 3-D ordered multiporous silica-base film preparation process phase
It is other all the same than eliminating hard template technique.
As shown in figure 3, silica-base film has the micro-nano porous structure of high-sequential, there is the big channel being connected knot
Structure.Mesoporous pore size size is about 6nm, and AFM data illustrate that the film only has the deformation of 14.1nm, illustrates the 3-D ordered multiporous silicon
The surface of base film is relatively more firm.
And the invention also discloses utilize film made from the three-dimensional porous silica-base film preparation method of functional hierarchical
The DNA applied to different fragments extraction.
The extraction for DNA of following three-dimensional porous silica-base films of hierarchical, DNA extract flow chart (see Fig. 4):
1. the silica gel culture dish (height of 3mm diameter and 1mm) comprising 60 The Small Well holes is placed in the top of film.Blood
Sample is launched into culture dish, and is incubated for 40 minutes, it is expected farthest to improve the adsorbance of DNA.Culture dish clear water
It rinses five times, to remove the DNA or inhibitor that dissociate in blood sample.The DNA useful load of each Jing Dong be it is flexible, this be according to
Rely the diameter in Jing Dong.
2. there is very big adsorption effect in order to illustrate the high interior pore volume of three-dimensional porous silica-base film and to DNA, I
Comparison dna in silicon wafer, 2 D mesopore silica-base film, the absorption on three-dimensional porous silica-base film, film is modified through APTES,
Just there are many sites of positive charge on its surface.Under DNA any concentration, the adsorption efficiency of the modified silicon wafer film of APTES is less than 10%.
The adsorption efficiency of DNA is almost nil, when DNA concentration is lower than 20ng/mL, 2 D mesopore film (2D_F127) and three porous thin
Film (3D micro) has a similar adsorption efficiency.However, when DNA reaches 2000ng/mL or more, three-dimensional porous silicon substrate
Film has been higher by 50% than 2 D mesopore film to DNA adsorption efficiency.The hexagon porous structure of F127 is not exclusively mutually
Connection, such 2 D mesopore film can be such that the diffusion area of fluid sample substantially reduces, therefore its adsorption efficiency is relatively low.So
And three-dimensional porous silica-base film have interconnect a large amount of channels, micropore and it is mesoporous run through mutually, liquid can be on six sides
The infiltration of shape nanometer and free diffusing (see Fig. 3 c-d), so its adsorption efficiency is relatively high.In addition, we have also investigated different lengths
DNA fragmentation adsorption efficiency, with test three-dimensional porous silica-base film to DNA separate.Three-dimensional porous silica-base film adsorbs DNA
High-efficient 60%-85% (see Fig. 4 b).This means that our three-dimensional porous silica-base film not only can be to low to DNA separation
The DNA separation of section, and the DNA of the high segment in cell or serum can be separated.
Claims (7)
1. a kind of three-dimensional porous silica-base film preparation method of functionality hierarchical, characterized by the following steps:
(1) synthesis of hard template polystyrene particle:
A, styrene, polyetherimide and ethyl alcohol are added in flask and are stirred, nitrogen is then led into flask, to remove dereaction
The oxygen of receptacle；
B, azodiisobutyronitrile is added thereto and is polymerize to 75 DEG C for heating reaction system；
C, by centrifuge washing, to remove remaining styrene and polyetherimide in dereaction, finally by the side of freeze-drying
Formula obtains polystyrene particle；
D, the ethanol solution of polystyrene particle is deposited to by way of spin coating on silicon wafer, spin coating number 3-5 times, then will
The silicon wafer is put into baking oven to be solidified in 80 DEG C of constant temperature 6h, obtains hard template polystyrene particle；
(2) preparation of the silicon performed polymer containing Pluronic F127:
The ethanol solution, ethyl orthosilicate, hydrochloric acid solution of Pluronic F127 are added in vial and are stirred, silicon pre-polymerization is obtained
Body；
(3) by hard template spin coating silicon performed polymer
Silicon performed polymer is infiltrated into full wafer hard template by way of spin coating, spin coating number 2-5 times, room temperature is dried；
(4) polystyrene particle and Pluronic F127 in hard template are removed
Using the polystyrene particle and Pluronic F127 in Muffle furnace high-temperature calcination removal hard template, the speed of 2 DEG C/min
Degree is warming up to 500 DEG C, and constant temperature 4h, is then cooled to room temperature with the speed of 2 DEG C/min, stays on substrate porous and hierarchical structure i.e.
For three-dimensional porous silica-base film.
2. the three-dimensional porous silica-base film preparation method of functionality hierarchical according to claim 1, it is characterised in that: described
Three-dimensional porous silica-base film macropore diameter size be 1 μm, mesoporous size be 6nm.
3. the three-dimensional porous silica-base film preparation method of functionality hierarchical according to claim 1, it is characterised in that: step
(2) mass ratio of Pluronic F127 and ethyl alcohol described in are 1:10-3:10, and the concentration of hydrochloric acid is 1M, ethyl orthosilicate and salt
The volume ratio of acid is 1:1.
4. the three-dimensional porous silica-base film preparation method of functionality hierarchical according to claim 1, it is characterised in that: described
The spin speed that polystyrene particle deposits on silicon wafer is 350rpm, and spin-coating time is 120 seconds.
5. the three-dimensional porous silica-base film preparation method of functionality hierarchical according to claim 1, it is characterised in that: described
The spin speed that silicon performed polymer deposits on silicon wafer is 2000rpm, and spin-coating time is 20 seconds.
6. the three-dimensional porous silica-base film preparation method of functionality hierarchical according to claim 1, it is characterised in that: step
(1) mass ratio of polyetherimide described in and ethyl alcohol is 1:100-5:100, the mass ratio of azodiisobutyronitrile and styrene
For 1:100-4:100.
7. made from the functional three-dimensional porous silica-base film preparation method of hierarchical as described in claim 1-6 any one
The application of film, it is characterised in that: extraction of the three-dimensional porous silica-base film for the DNA of different fragments.
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| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
| CN102701224A (en) * | 2012-06-11 | 2012-10-03 | 华东理工大学 | Method for preparing three-dimensional ordered macroporous material |
| CN102730705A (en) * | 2012-07-10 | 2012-10-17 | 苏州大学 | Preparation method for array hole low dielectric material |
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| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
| CN102701224A (en) * | 2012-06-11 | 2012-10-03 | 华东理工大学 | Method for preparing three-dimensional ordered macroporous material |
| CN102730705A (en) * | 2012-07-10 | 2012-10-17 | 苏州大学 | Preparation method for array hole low dielectric material |
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