CN107601913A - A kind of preparation method of the micro- pattern of material surface - Google Patents
A kind of preparation method of the micro- pattern of material surface Download PDFInfo
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- CN107601913A CN107601913A CN201710907931.3A CN201710907931A CN107601913A CN 107601913 A CN107601913 A CN 107601913A CN 201710907931 A CN201710907931 A CN 201710907931A CN 107601913 A CN107601913 A CN 107601913A
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Abstract
The invention discloses a kind of preparation method of the micro- pattern of material surface, comprise the following steps：Sheet glass or silicon chip activation；Configure chitosan solution；Configure micro- pattern mixed solution；Micro- pattern printing and preservation.Hydroxyapatite, CNT have been distributed in chitosan solution by the present invention, and with Fibronectin solution, the clearly micro- pattern of CNT has successfully been printed out with microcontact printing techniques.It is of the invention then explication can have been carried out for substrate surface, so as to be prepared for a series of extracellular matrix micrographics.In terms of the growth behavior of graphical regulating cell and the experimental study of function by material surface performance, have a wide range of applications.
Description
Technical field
The present invention relates to a kind of material surface modifying processing method, specifically, be one kind in biomaterial surface system
The method of standby micro- pattern, belongs to materialogy field.
Background technology
Micro ＆ nano technology is constantly developing, and has attracted a part to be directed to the scientist of research material, has been directed in material
The different figure of surface construction, to change the performance of material.Now, scientists are micro- using photoetching technique, Soft lithograph technology etc.
Pattern technology of preparing, test in the desired pattern of the micro-nano region of material surface structure.The successful application of these technologies, is started
Utilize the upsurge of micro- patterning technique material modified surface and interface.Soft lithography most proposed earlier than 1994, obtained afterwards quick
Development, wherein outstanding is the Microcontact printing (Micro-Contact Printing) based on PDMS templates.According to
Micro- patterning technique of material modification is realized by Microcontact printing, as a kind of new technology, in the modification of biomaterial surface
It is widely used.For example, the directed differentiation of the micro-nano graph regulation and control stem cell on biomaterial surface can be made；Material surface it is micro-
Micro-nano structure can also inducing cell Nian Fu ﹑ propagation and differentiation etc. bioprocess, the formation to bone play inducing action.In addition,
Research shows the biomaterial implant of the surface than smooth surface with micro-nano structure, because the micro-nano structure of micro- pattern can
The bone contact area of implant is improved, Integrated implant can be obtained earlier on.The micro- patterning technique of chitosan is exactly in biomaterial
One great development and innovation, the micro- patterning technique of chitosan that material surface is carried out, be combine the good biological nature of chitosan with it is micro-
Patterning technique improves the cell characteristics that biomaterial shows, is desirably to obtain the functional material with biological nature.However, due to
This technology is also developing, and also exists with the micro- patterning technique of the chitosan that chitosan is raw material and is not sufficiently stable, and reappearance is low, and
The problem of method cost of manufacture is high.
Therefore, it is necessary to seek a kind of simple and easy, cost is cheap, and using chitosan as raw material, or albumen is raw material, can
The method for preparing the micro- pattern of material surface.
The content of the invention
It is an object of the invention to provide a kind of preparation method for being used to prepare the micro- pattern of material surface, this method cost are low
It is honest and clean, and the processing step implemented is simple and easy.
In order to solve the above problems, the technical scheme is that：A kind of preparation method of the micro- pattern of material surface, comprising
The following steps.
（1）Sheet glass or silicon chip activation.Take out sheet glass or silicon chip with tweezers, be put into beaker cup, take a certain amount of 0.1M ~
0.5M sodium hydroxide solution is added in beaker, is made sodium hydroxide submergence sheet glass or silicon chip, is put into electric-heated thermostatic water bath,
It is 60 DEG C ~ 90 DEG C to set temperature, heats 3h ~ 5h.Take out heating water bath finishes sheet glass or silicon chip with tweezers, be put into added with
In the culture dish of three-level deionized water, 1min is shaken, sheet glass is taken out or silicon chip is put into another added with three-level deionized water
Culture dish in, the min minutes of 15 min ~ 30 are rocked on shaking table, sheet glass or silicon chip are put into other one again after taking-up
In the individual culture dish added with three-level deionized water, the min minutes of 15 min ~ 30 are rocked on shaking table, then takes out, uses hair dryer
Dry up, be put into clean culture dish at normal temperatures, cover ware lid.Operation can repeat 2 ~ 3 times above.The parameter of this operation is
What optimum experimental was drawn.It is the optimal conditions of the present invention in 2h.3- TSL 8330s are drawn with liquid-transfering gun to drip
On above-mentioned dried sheet glass or silicon chip surface, liquid is smeared with cotton swab, liquid is uniformly sprawled whole sheet glass or silicon
The surface of piece, but cotton swab is not readily accessible to the surface of sheet glass or silicon chip, placement >=10min.Then take out sheet glass or silicon chip
It is put into another culture dish added with three-level deionized water, 15min is shaken on shaking table, suck water, shakes, sucks repeatedly
The operation of water 2 times, it is put into after gently being dried up with decompression nitrogen in culture dish.Add it is a certain amount of can submerge each sheet glass or
10% ~ 15% glutaraldehyde of silicon chip surface, 30min is stood, is then placed in another culture dish added with three-level deionized water
In, 15min is shaken on shaking table, sucks water, shakes repeatedly, suck water operation 2 times, finally gently dried up with decompression nitrogen.Will
The sheet glass or silicon chip activated, after concussion cleaning, drying, it is stored in Petri dish, is preserved in room temperature environment,
Used in 1h.The time conditions quickly used, it is the inventive point of the present invention.The present invention is used more from activation, to reach
The production effect of micro- pattern, it is the creative achievement that experiment is drawn.
（2）Configure chitosan solution.A certain amount of chitosan CS is accurately weighed, it is water-soluble with the glacial acetic acid that volume ratio is≤3%
Liquid ultrasonic dissolution 1h ~ 2h, stirring, standing and defoaming 30min, is iteratively repeated three times, is then placed into being dried in vacuo in ware,
In the range of 0.09MPa >=vacuum >=0.04MPa, deaeration >=10h, be made chitosan-containing CS mass fraction for 1.5% ~
4.5% chitosan solution.Chitosan solution sealing is put into 4 DEG C of refrigerators, used after 24h.Ensure during the abundant dissolving of chitosan
The key of the effect of the present invention, and the key point of the present invention.It is of the invention real in addition, being used after refrigerating 24h after preparing
Test the Optimal Parameters and inventive point drawn.Its principle is also to be studied.
（3）Configure micro- pattern mixed solution.The chitosan solution of step preparation is taken, takes the nano hydroxyapatite for preparing powdery
Lime stone, added in the ratio of every 100mL chitosan solutions 30mg nanometer hydroxyapatites, the min of the min of ultrasonic disperse 30 ~ 60
It is dispersed in chitosan solution, the micro- pattern mixed solution of obtained hydroxyapatite/chitosan, seals, is put into 4 DEG C of refrigerators and stands
>=10min, is used in 1h；Or the chitosan solution of step preparation is taken, it is by the scattered mass percent prepared
0.02% ~ 0.03% CNT cmc soln, CNT cmc soln by volume: shell gathers
Sugar juice=1: 4 ratio mixing, the min of the min of ultrasonic disperse 30 ~ 60, the obtained micro- pattern mixing of Carbon Nanotubes/Chitosan
Solution, sealing, is put into 4 DEG C of refrigerator standing >=10min, is used in 1h；Or the certain density fine connection albumen FN of preparation is molten
Liquid.Present invention experiment obtains three kinds of micro- pattern solution, and this is the inventive point of the present invention.
（4）Micro- pattern printing.Take out the elastomeric stamp with micro- pattern prepared, and the sheet glass or silicon activated
Piece, steeps the 30min in distilled water by elastomeric stamp first, and taking-up is gently dried up with nitrogen.This is the operation that optimum experimental comes out
Point, and the inventive point of the present invention.Then the micro- pattern mixed solution of hydroxyapatite/chitosan is taken with liquid-transfering gun；Or carbon is received
The micro- pattern mixed solution of mitron/chitosan, will be non-by being grafted to π-π strong between the carboxyl of glass surface and CNT
CNT is grafted to glass sheet surface by covalent bond effect, builds micro- patterned surfaces of CNT；Or fine connection albumen
FN solution；It is added dropwise on elastomeric stamp, and micro- pattern mixed solution is fully sprawled on the surface of elastomeric stamp, elastomeric stamp
Pattern is placed on horizontal experimental bench upward, and after standing 10min ~ 30min, the unnecessary micro- of seal surface is sucked with liquid-transfering gun
Pattern mixed solution, elastomeric stamp surface is slowly blown with nitrogen.The pattern of elastomeric stamp is placed different from generally towards decentralization upward
The printing technology put, it is the inventive point at experimental summary of the present invention.After the elastomeric stamp surface of area >=50% is dried up, at once
The sheet glass activated or silicon chip are vertically covered in above seal, ensure that both on a horizontal plane, use certain mass
Counterweight push down sheet glass or silicon chip.The degree of drying is the key point of the present invention, directly affects the formation quality of pattern.
The quality of counterweight is relevant with the elasticity of elastomeric stamp, pattern magnitude.Placement >=12h；Last careful stripping elastomeric stamp, that is, obtain
The micro- pattern in the surface of sheet glass or silicon chip.Sufficient time of contact and suitable pressurization quality, it is the key point of the present invention.
（5）Preserve.The sheet glass or silicon chip for preparing micro- pattern are put into culture dish, cover the preservation of ware lid；Elastomeric stamp
After having used, 0.5h ~ 1h is soaked with 3% acetic acid solution, clean, drying is then rinsed with tertiary effluent, being capable of Reusability.This
Invention draws the preferred plan for printing micro- pattern by Success in Experiment.
As the preferred embodiment of above-mentioned technical proposal, the solution is with water using three-level deionized water.It is every
Using this method, micro- pattern can be prepared used in other materials surface, all in the protection domain of this method.
Compared with prior art, the present invention has following beneficial effect.
（1）Hydroxyapatite, CNT have been distributed in chitosan solution by the present invention, and molten with fibronectin
Liquid, the clearly micro- pattern of CNT is successfully printed out with microcontact printing techniques.Conventional research is often chosen uncertain
Substrate surface carry out the research of cell behavior, surface topography is unable to explication, therefore for surface topography to cell
The research of behavioral implications never has big progress.And the present invention can then carry out explication for substrate surface, so as to
A series of extracellular matrix micrographics is prepared for, finds the growth behavior of the graphical regulating cell by material surface performance
With function.
（2）The reagent price that the present invention uses is not costly, moreover, the operating method used is also simple and easy, so,
The cost that invention prepares a kind of micro- pattern of material surface is low.
Brief description of the drawings
Fig. 1 is the finished product photo of the embodiment of the present invention 1.
Fig. 2 is the enlarged photograph of the finished product of the embodiment of the present invention 1.
Fig. 3 is the product microphotograph of the embodiment of the present invention 1.
Fig. 4 is the product microphotograph of the embodiment of the present invention 2.
Fig. 5 is the product microphotograph of the embodiment of the present invention 2.
Embodiment
Embodiment 1
Weigh the nanometer hydroxyapatite powder that 0.01g is prepared to be dispersed in the chitosan-acetic acid solutions of 30 ml 3%, and be placed on
The min of ultrasonic disperse 15 in supersonic wave cleaning machine.2 sheets are taken to be immersed in the plastic cup for filling 0.1M sodium hydroxide solutions,
Plastic cup is put into water-bath, it is 70 DEG C to set temperature, the h of water-bath 3 ~ 4.Sheet glass is taken out, outwells sodium hydroxide solution, it is past
Distilled water submergence sheet glass is added in cup, shaking table is placed on and shakes 30 min.Sheet glass is taken out, sheet glass is cleaned up with distilled water
Surface, then dry up glass sheet surface with hair dryer normal temperature.Hydroxyapatite/chitosan solution, covering is added dropwise with liquid-transfering gun pipette tips
In whole elastomeric stamp surface, stand after sprawling 30min, then redundant solution is suctioned out with pipette tips, dried up seal half with nitrogen.Will
2 sheets are covered on seal respectively, add 15g counterweights on each sheet glass respectively, place 16h.Sheet glass is removed, by elasticity
30 min in the acetum of seal bubble after dilution, clean seal, drying storage.
Embodiment 2
0.01g CNTs are distributed in 50ml cmc solns, the carboxymethyl cellulose containing CNT after disperseing
Plain solution takes 5ml, in be added to 20mL, mass concentration is in 3% chitosan solution, obtain the compound of CNT and chitosan
Solution.After mixed solution is added drop-wise into elastomeric stamp surface spreading 10min, unnecessary CNT liquid siphons away, then with it is above-mentioned
Modified silicon chip surface perpendicular contact, with 30g counterweights, place be more than 12h overnight, elastomeric stamp is removed, by being grafted to silicon chip
CNT is grafted to silicon chip surface by strong π-π non-covalent bond effects between the carboxyl and CNT on surface, and structure is received
Micro- patterned surfaces of rice carbon pipe.Elastomeric stamp is soaked in acetic acid solution after dilution after being finished after 30min, is rinsed again with wash bottle
It is clean.
Claims (2)
1. a kind of preparation method of the micro- pattern of material surface, it is characterised in that comprise the following steps：
（1）Sheet glass or silicon chip activation, take out sheet glass or silicon chip with tweezers, are put into beaker cup, take a certain amount of 0.1M ~ 0.5M
Sodium hydroxide solution add in beaker, make sodium hydroxide submergence sheet glass or silicon chip, put into electric-heated thermostatic water bath, set
Temperature is 60 DEG C ~ 90 DEG C, heats 3h ~ 5h；The sheet glass or silicon chip that heating water bath finishes are taken out with tweezers, is put into added with water
In culture dish, 1min is shaken, sheet glass is taken out or silicon chip is put into another culture dish added with water, 15 are shaken on shaking table
The min minutes of min ~ 30, take out, after changing water, repeat to shake the min minutes of 15 min ~ 30 on shaking table, then take out, electricity consumption
Blowing is done with normal temperature wind, is put into clean culture dish, covers ware lid；In 2h, 3- aminopropyls three are drawn with liquid-transfering gun
Methoxy silane is dropped on above-mentioned dried sheet glass or silicon chip surface, is smeared liquid with cotton swab, liquid is uniformly sprawled whole
The surface of individual sheet glass or silicon chip, but cotton swab is not readily accessible to the surface of sheet glass or silicon chip, placement >=10min；Then take out
Sheet glass or silicon chip are put into another culture dish added with water, and 15min is shaken on shaking table, after changing water, repetition concussion,
Change water to operate 2 times ~ 3 times, be put into after gently being dried up with decompression nitrogen in culture dish；Adding a certain amount of can submerge each glass
10% ~ 15% glutaraldehyde of glass piece or silicon chip surface, 30min is stood, is then placed in another culture dish added with water,
15min is shaken on shaking table, after changing water, concussion is repeated, changes water operation 2 times, finally gently dried up with decompression nitrogen；Will activation
Good sheet glass or silicon chip is stored in Petri dish, is preserved in room temperature environment, is used in 1h；
（2）Chitosan solution is configured, accurately weighs a certain amount of chitosan, with the glacial acetic acid aqueous solution ultrasound that volume ratio is≤3%
1h ~ 2h is dissolved, stirring, standing and defoaming 30min, is iteratively repeated three times, is then placed into vacuum desiccator, in vacuum
In the range of 0.04MPa ~ 0.09MPa, deaeration >=2h, the mass fraction that chitosan-containing CS is made is 1.5% ~ 4.5% shell
Glycan solution；Chitosan solution sealing is put into 4 DEG C of refrigerators, used after 24h；
（3）Micro- pattern mixed solution is configured, takes the chitosan solution of step preparation, then takes the nano-hydroxy-apatite for preparing powdery
Stone, added in the ratio of every 100mL chitosan solutions 30mg nanometer hydroxyapatites, min points of the min of ultrasonic disperse 30 ~ 60
Be dissipated in chitosan solution, the micro- pattern mixed solution of obtained hydroxyapatite/chitosan, seal, be put into 4 DEG C of refrigerators stand >=
10min, used in 1h；Or the chitosan solution of step preparation is taken, it is by the scattered mass percent prepared
0.02% ~ 0.03% CNT cmc soln, CNT cmc soln by volume: shell gathers
Sugar juice=1: 4 ratio mixing, the min of the min of ultrasonic disperse 30 ~ 60, the obtained micro- pattern mixing of Carbon Nanotubes/Chitosan
Solution, sealing, is put into 4 DEG C of refrigerator standing >=10min, is used in 1h；Or to prepare certain density fibronectin FN molten
Liquid；
（4）Micro- pattern printing, take out the elastomeric stamp with micro- pattern prepared, and the sheet glass or silicon chip activated；It is first
Elastomeric stamp is first soaked in 30min in water, taking-up is gently dried up with nitrogen；Then hydroxyapatite/shell is drawn with liquid-transfering gun
The micro- pattern mixed solution of glycan, or, the micro- pattern mixed solution of Carbon Nanotubes/Chitosan is drawn, or, draw fibronectin FN
Solution, it is added dropwise on elastomeric stamp, and micro- pattern mixed solution is fully sprawled on the surface of elastomeric stamp；By elastomeric stamp
Pattern is placed on horizontal experimental bench upward, and after standing 10min ~ 30min, the unnecessary micro- of seal surface is sucked with liquid-transfering gun
Pattern mixed solution, elastomeric stamp surface is slowly blown with nitrogen；After the elastomeric stamp surface of area >=50% is dried up, at once will
The sheet glass or silicon chip activated is vertically covered in above seal, ensures both on a horizontal plane, with certain mass
Counterweight pushes down sheet glass or silicon chip, placement >=12h；The last careful surface peeled off elastomeric stamp, that is, obtain sheet glass or silicon chip
Micro- pattern；
（5）Preserve, the sheet glass or silicon chip for preparing micro- pattern are put into culture dish, cover the preservation of ware lid；Elastomeric stamp uses
After complete, 0.5h ~ 1h is soaked with 3% acetic acid solution, clean, drying is then rinsed with water, being capable of Reusability.
A kind of 2. preparation method of the micro- pattern of material surface according to claim 1, it is characterised in that：It is described to be adopted with water
It is three-level deionized water.
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| CN201710907931.3A CN107601913A (en) | 2017-09-29 | 2017-09-29 | A kind of preparation method of the micro- pattern of material surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917352A (en) * | 2022-04-29 | 2022-08-19 | 西南交通大学 | Drug-loaded disc particle with functions of adhering and regulating macrophages as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425920A (en) * | 2002-12-26 | 2003-06-25 | 浙江大学 | Method for fixing biological macro molecule in common pattern on inorganic silicone material surface |
| CN101461965A (en) * | 2009-01-14 | 2009-06-24 | 西南交通大学 | Method for preparing chitosan/protein composite micrographics on surface of material |
| CN101491695A (en) * | 2009-03-03 | 2009-07-29 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced chitosan/silicon-containing hydroxylapatite composite material |
| KR20110129364A (en) * | 2010-05-25 | 2011-12-01 | 아주대학교산학협력단 | Method of forming pattern using carbon nano tube langmuir-blodgett film and control of growth and differentiation of stem cell using the same |
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2017
- 2017-09-29 CN CN201710907931.3A patent/CN107601913A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425920A (en) * | 2002-12-26 | 2003-06-25 | 浙江大学 | Method for fixing biological macro molecule in common pattern on inorganic silicone material surface |
| CN101461965A (en) * | 2009-01-14 | 2009-06-24 | 西南交通大学 | Method for preparing chitosan/protein composite micrographics on surface of material |
| CN101491695A (en) * | 2009-03-03 | 2009-07-29 | 陕西科技大学 | Preparation method of carbon nano-tube reinforced chitosan/silicon-containing hydroxylapatite composite material |
| KR20110129364A (en) * | 2010-05-25 | 2011-12-01 | 아주대학교산학협력단 | Method of forming pattern using carbon nano tube langmuir-blodgett film and control of growth and differentiation of stem cell using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917352A (en) * | 2022-04-29 | 2022-08-19 | 西南交通大学 | Drug-loaded disc particle with functions of adhering and regulating macrophages as well as preparation method and application thereof |
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