A method for preparing a controllable topography multi-dimensional polymer nanostructure

Abstract

The application relates to the technical field of nanostructure preparation, in particular to a preparation method of multi-dimensional polymer nanostructures with controllable morphology. The application discloses a preparation method of multi-dimensional polymer nanostructures with controllable morphology, which comprises the following steps: step one, dissolving block polymers in an organic solvent, and adding auxiliary special structure preparation and functional units to the organic solvent to prepare a growth solution; step two, dissolving a certain amount of surfactants in water as a growth environment; step three, placing a growth substrate with adjustable area into the growth environment of step two, and applying the growth solution of step one to the growth substrate; and step four, applying external stimulation induction to step three, and through a solvent volatilization and self-assembly process, the growth solution grows into nanostructures on the growth substrate. The method is simple, easy to mass-produce, suitable for various substrate materials, and has strong controllability; through simple regulation, multi-dimensional polymer nanostructures with different structural lengths, different structural sizes, uniform structures and various functions can be prepared.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nanostructure preparation, and particularly relates to a preparation method of a multi-dimensional polymer nanostructure with controllable morphology. BACKGROUND

[0002] In recent decades, nanostructures have attracted extensive research interest due to their large specific surface area, unique surface nanostructure, wide material selection, and other characteristics, and have been widely applied in the fields of battery nanostructures, catalyst loading, biomolecule delivery, cell regulation and cell capture.

[0003] At present, the methods for preparing nanostructures mainly include template method, chemical deposition method, etching method, self-assembly method and the like. Although the nanostructure surface morphology prepared by the template method is regular and controllable, the preparation and removal processes of the nano template are relatively complex, and there are disadvantages such as long preparation process and difficulty in large-scale preparation. The nanostructure prepared by the etching method can be prepared with controllable nanostructure morphology spacing, but the etching process uses ion gas or corrosive acid, and the preparation conditions are relatively harsh, and the selected materials are relatively limited. Although the nanostructure prepared by the chemical deposition method simplifies the process to a certain extent, and can prepare nanostructures with regular and controllable morphology, the selected materials by the chemical deposition method are mostly inorganic materials, and the selectivity of the substrate is limited.

[0004] Block copolymers can form regular and ordered structures through microphase separation, and based on this, nanostructures can be prepared by using the method of polymer self-assembly, so as to produce membranes with uniform pore size and pore size distribution. Specifically, the formation of different microphase separation structures of block copolymers can be controlled through solvent vapor treatment, external electric field induction, non-solvent induced phase separation and the like, among which the solvent vapor treatment and the external electric field induction are still in the laboratory preparation stage, and it is difficult to mass-produce. The existing non-solvent induced phase separation treatment method requires that the block copolymer be self-assembled on a support layer with a specific structure, and then be combined with the support layer to obtain a surface burr structure nanostructure, and the use of the substrate material is limited.

[0005] Therefore, the present application provides a preparation method of a multi-dimensional polymer nanostructure with controllable morphology. SUMMARY

[0006] In order to make up for the shortcomings of the prior art and solve the technical problems in the background art, the present application provides a preparation method of a multi-dimensional polymer nanostructure with controllable morphology.

[0007] The present application is realized by the following technical scheme:

[0008] The present application provides a preparation method of a multi-dimensional polymer nanostructure with controllable morphology.

[0009] Step one: dissolve the block polymer in an organic solvent and add auxiliary special structure preparation and functional units to the solvent to prepare a growth solution;

[0010] Step two: dissolve a certain amount of surfactant in water as a growth environment;

[0011] Step three: place the growth substrate with adjustable area into the growth environment of step two and apply the growth solution of step one to it;

[0012] Step four: apply external stimulus induction to step three and go through the solvent evaporation and self-assembly process to make the growth solution grow into nanostructures on the growth substrate.

[0013] The dimension of the nanostructure mainly describes the dimension of the growth substrate, including but not limited to one or more of one-dimensional tube, one-dimensional line, two-dimensional plane, three-dimensional inner sphere, and three-dimensional mesh.

[0014] Preferably, the block polymer includes a two-segment, three-segment, and three or more segmented polymer or multi-arm block polymer or hyperbranched polymer, and the block polymer has hydrophobic segments and hydrophilic segments, and the weight ratio of the hydrophobic segments to the hydrophilic segments is (0.5-100): 1.

[0015] The molecular weight of the hydrophobic segment is 10KDa-200KDa, and the molecular weight of the hydrophilic segment is 1KDa-100KDa.

[0016] The self-assembly on the interface can be triggered by using the above hydrophilic and hydrophobic segments, so that the nanostructure is prepared in one step.

[0017] In theory, the hydrophilic polymer tends to enrich on the oil-water interface, and then under the combined action of a certain external stimulus and the elastic force of the hydrophobic segment, the interface controlled deformation obtains more space outward, so that the nanostructure is prepared in one step.

[0018] In this process, the length, ratio, type, and external stimulus of the hydrophilic and hydrophobic ends will affect the growth rate and structure of the nanostructure.

[0019] In general, the smaller the rigidity of the hydrophobic segment, the more abundant the structure, the lower the length of the hydrophobic segment, the more abundant the structure; the more hydrophilic the hydrophilic segment, the more abundant the structure, the longer the hydrophilic segment, the more abundant the structure.

[0020] Preferably, the hydrophobic segment includes one or more of polystyrene, polymethyl methacrylate, polylactic acid, polylactide, poly(lactic-co-glycolic acid), polydimethylsiloxane, and polyisobutylene.

[0021] Preferably, the hydrophilic segment comprises one or more of poly-4-vinylpyridine, polyacrylic acid, polyethylene glycol, poly(polyethylene glycol methyl ether methacrylate), poly N,N-dimethylacrylamide.

[0022] Preferably, the organic solvent comprises one or more of ethyl acetate, dimethyl carbonate, ethylene glycol dimethyl ether, dioxane, benzene, toluene, xylene, dichloromethane, trichloromethane, 1,2-dichloroethane, trichloroethane, carbon tetrachloride, tetrahydrofuran, N,N-dimethylformamide, acetone; and the concentration of the growth solution in step one is 0.1-500 mg / ml.

[0023] Preferably, the functional unit comprises one or more of ferroferric oxide nanoparticles, gold nanoparticles, silver nanoparticles, graphene nanosheets, quantum dots, doxorubicin, paclitaxel, quaternary ammonium salt, gene transfection molecules.

[0024] For example: ferroferric oxide nanoparticles affect its structure, gold heating, silver antibacterial, graphene heating, doxorubicin anticancer.

[0025] Preferably, the surfactant comprises one or more of sodium dodecyl sulfate, cetyltrimethylammonium bromide, polyvinyl alcohol; and the concentration of the surfactant in the growth environment in step two is 0-100 mg / ml.

[0026] Preferably, the growth substrate comprises one or more of hollow tubes, solid wires, flat sheets, rough sheets, water-in-oil emulsions, hollow grids;

[0027] and the surface of the growth substrate has a specific structure or is made of multiple materials; the specific structure comprises topological structure micropillars, conical arrays, microfluidic channels or porous grids;

[0028] The multiple materials comprise glass, iron, copper, aluminum oxide, polydimethylsiloxane, polyethylene, polyimide or cross-linked polyurethane.

[0029] Preferably, the external stimulus comprises a physical method of heat, magnetism, electricity, light, and the time of external stimulus is 0-24 h;

[0030] The thermal physical method comprises thermal stimulation, which is used to adjust the growth environment temperature at 0-80℃;

[0031] The magnetic physical method comprises applying a magnetic field, and the magnetic field comprises a parallel magnetic field, a uniform magnetic field, and the magnetic field strength ranges from 0 to 50 mT, and the frequency of the uniform magnetic field ranges from 0 to 200 Hz;

[0032] The electrical physical method comprises electrical stimulation, and the electrical stimulation comprises applying a voltage of a certain intensity, and the electrical stimulation power ranges from 0 to 36 W;

[0033] The photophysical method includes light stimulation, and the light stimulation includes applying light waves of a certain wave band, and the light wave wavelength is 450nm, 532nm, 808nm, 1064nm.

[0034] Preferably, the morphology of the nanostructure includes one or more of a nano-burr structure, a nano-dot structure, a nano-wire structure, a nano-pore structure, and a nano-grid structure.

[0035] The beneficial effects of the present application are:

[0036] 1. The present application uses block polymers as raw materials, dissolves them in organic solvents, then slowly adds the block copolymer solution to the hydrophobic surface of the target substrate of deionized water, and injects the surfactant aqueous solution, and through the solvent evaporation block polymer self-assembly process, a morphology-controllable multi-dimensional polymer nanostructure is obtained.

[0037] 2. The multi-dimensional polymer nanostructure prepared by the present application has a morphology, size and function of the multi-dimensional surface that can be adjusted, and by adjusting the types of chain segment polymers, the number of blocks, the molecular weight of the block polymer, the concentration, the reaction temperature and the functional units, different morphologies, different surface properties and different functional multi-dimensional polymer nanostructures can be realized.

[0038] 3. The present application has the advantages of controllable surface morphology, adjustable chemical properties, easy large-scale preparation, optional substrates, and wide industrial application prospect, and the prepared morphology-controllable multi-dimensional polymer nanostructure has a huge application prospect in the fields of liquid biopsy, tumor diagnosis, drug release, catalytic nanostructure, oil-water separation, and other chemical, biological and industrial fields. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 The scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 1 of the present application is shown in the figure;

[0040] Figure 2 The scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 2 of the present application is shown in the figure;

[0041] Figure 3 The scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 3 of the present application is shown in the figure;

[0042] Figure 4 The scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 4 of the present application is shown in the figure;

[0043] Figure 5 The scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 6 of the present application is shown in the figure;

[0044] Figure 6A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 7 of the present application;

[0045] Figure 7 A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 9 of the present application;

[0046] Figure 8 A phase diagram of the multi-dimensional polymer nanostructure obtained by changing the ratio of the hydrophilic and hydrophobic polymers in the present application;

[0047] Figure 9 A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 10 of the present application;

[0048] Figure 10 A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 11 of the present application;

[0049] Figure 11 A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 12 of the present application;

[0050] Figure 12 A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 14 of the present application;

[0051] Figure 13 A scanning electron microscope photograph of the multi-dimensional polymer nanostructure prepared in Example 15 of the present application;

[0052] Figure 14 A graph showing the relationship between the number of burrs and the ratio of the chain segments in Examples 1 to 3 of the present application;

[0053] Figure 15 A graph showing the relationship between the pore size and the ratio of the chain segments in Examples 4 to 6 of the present application;

[0054] Figure 16 A graph showing the relationship between the thickness of the burrs and the ratio of the chain segments in Examples 1 to 3 of the present application. DETAILED DESCRIPTION

[0055] The present application will be further described with reference to the following examples. It should be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods in the following examples, unless otherwise specified, were generally conducted under conventional conditions or under the conditions recommended by the manufacturers.

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The materials used to practice the present application, unless otherwise indicated, are commercially available from conventional sources. Unless otherwise indicated, the materials used to practice the present application are used according to conventional procedures or according to the manufacturer's instructions. In addition, any method and material similar or equivalent to those described herein can be used in the practice of the present application. The present application is further illustrated by the following description and examples with reference to the accompanying drawings and specific embodiments described herein are intended to be illustrative only and not limiting to the scope of the application.

[0057] Example 1, Adjusting polymer ratio to control nanostructure:

[0058] Preparation of growth solution: two block polymers, polystyrene-b-polyetherimide PS30K-b-PEI4K, were dissolved in ethyl acetate with a concentration of 10% w / v (mass / volume), the dissolution process was placed in a shaker with 100 r / min shaking for 60 min to ensure sufficient shaking. The subscript of the polymer PS30K-b-PEI4K indicates the molecular weight of different segments in the polymer, i.e., polystyrene-polyetherimide block copolymer, the molecular weight of polystyrene is 30 KDa, and the molecular weight of polyetherimide is 4 KDa. The same expression is used in subsequent examples. In the ethyl acetate solution, 0.1% w / v of Fe3O4 nanoparticles with an average particle size of 50 nm modified by surface oleic acid was added, and ultrasonic vibration was performed for 10 min to fully disperse, thereby completing the preparation of the growth solution;

[0059] Selection of growth substrate: a hydrophobic modified silicon wafer substrate was selected. In this example, perfluorodecyltrimethoxysilane was used for gas-phase hydrophobic modification. After modification, the contact angle was about 120°.

[0060] Growth environment: sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v. The dissolution process was carried out at 40°C with stirring at 400 r / min for half an hour to achieve sufficient dissolution.

[0061] Selection of external stimulus: an 808 nm near-infrared light source with a light intensity of 5 mW / cm 2 was selected for external stimulation. The light irradiation area was 1 cm 2 , the light irradiation distance was 3 cm, and the light irradiation time was 2 h.

[0062] Growth steps: the growth substrate was placed in the growth environment, 200 μL of growth solution was applied to the growth substrate using a dropper, the near-infrared light source was fixed at a height of 3 cm from the center of the growth substrate, the light irradiation was started, and after the growth was completed, the solution was taken out, washed, and the growth results were observed.

[0063] Growth results: as shown in the accompanying Figure 1As shown, SEM characterization shows that the multidimensional polymer nanostructure prepared by this method presents abundant nanoscale burr structures on the two-dimensional silicon substrate plane. The nanoburr structure has a diameter of about 100 nm and a length of about 500 nm. The structure size is uniform and there are no obvious defects.

[0064] Example 2: Adjusting the polymer ratio to control the nanostructure:

[0065] Prepare the growth solution: Dissolve the diblock polymer polystyrene-b-polyetherimide (PS50K-b-PEI4K) in ethyl acetate at a 10% w / v (mass / volume) concentration. Shake thoroughly on a shaker at 100 rpm for 60 minutes. Add oleic acid-modified Fe₃O₄ nanoparticles (50 nm in average diameter) to the ethyl acetate solution at a 0.1% w / v concentration. Ultrasonicate for 10 minutes to fully disperse the nanoparticles. This completes the growth solution.

[0066] Select a growth substrate: Select a hydrophobically modified silicon wafer substrate. In this embodiment, perfluorodecyltrimethoxysilane is selected for vapor phase hydrophobic modification. After modification, the contact angle is about 120°.

[0067] Prepare the growth environment: dissolve sodium dodecyl sulfate in deionized water at a concentration of 2% w / v, at 40°C, 400 rpm, and stir for half an hour to achieve full dissolution.

[0068] Select external stimulation: select light intensity of 5mW / cm 2 The 808nm near-infrared light source was used for external stimulation, and the illumination area was 1cm 2 , illumination distance is 3cm, illumination time is 2h;

[0069] Growth steps: Place the growth substrate in the growth environment, apply 200 μL of growth solution to the growth substrate using a dropper, fix the near-infrared light source 3 cm above the center of the growth substrate, start illumination, remove from the solution after growth is complete, clean, and observe the growth results;

[0070] Growth results: as attached Figure 2 As shown, SEM characterization shows that the multidimensional polymer nanostructure prepared by this method presents abundant nanoscale burr structures on the two-dimensional silicon substrate plane. The diameter of the nanoburr structure is about 100 nm and the length is about 300 nm. Compared with Example 1, the burr length and density are reduced, the structure size is uniform, and there are no obvious defects.

[0071] Example 3: Adjusting the polymer ratio to control the nanostructure:

[0072] Preparation of growth solution: two block polymers polystyrene-b-polyetherimide PS70K-b-PEI4K were dissolved in ethyl acetate at a concentration of 10% w / v (mass / volume), and the solution was shaken at 100 r / min for 60 min to ensure complete shaking. Fe3O4 nanoparticles with an average particle size of 50 nm modified with oleic acid were added to the ethyl acetate solution at a concentration of 0.1% w / v, and ultrasonic vibration was performed for 10 min to ensure complete dispersion, thereby completing the preparation of the growth solution.

[0073] Selection of growth substrate: a hydrophobic modified silicon wafer substrate was selected, and in this example, perfluorodecyltrimethoxysilane was used for gas-phase hydrophobic modification. After modification, the contact angle was about 120°.

[0074] Growth environment: sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v, and the solution was stirred at 40°C and 400 r / min for half an hour to ensure complete dissolution.

[0075] Selection of external stimulus: an 808 nm near-infrared light source with a light intensity of 5 mW / cm 2 was selected for external stimulation, the light irradiation area was 1 cm 2 , the light irradiation distance was 3 cm, and the light irradiation time was 2 h.

[0076] Growth step: the growth substrate was placed in the growth environment, 200 μL of growth solution was applied to the growth substrate using a dropper, the near-infrared light source was fixed at a height of 3 cm from the center of the growth substrate, the light irradiation was started, and after the growth was completed, the solution was removed, washed, and the growth results were observed.

[0077] Growth results: as shown in the accompanying Figure 3 SEM images, the multi-dimensional polymer nanostructures prepared by this method exhibited rich nanoscale burr structures on the two-dimensional silicon substrate plane. The diameter of the nano-burr structure was about 100 nm, and the length was about 100 nm. Compared with Example 1, the burr length decreased, the structure changed from burr structure to point structure, the structure size was uniform, and there were no obvious defects.

[0078] Examples 1-3 demonstrate that the structure can be controlled by adjusting the hydrophilic-hydrophobic block ratio of the polymer. As the hydrophobic ratio increases, the structure growth becomes difficult, and the structure length and density decrease.

[0079] Example 4: adjusting the polymer ratio to control the nanostructure

[0080] Preparation of growth solution: two block polymers polystyrene-b-polyetherimide PS30K-b-PEI10K were dissolved in ethyl acetate at a concentration of 10% w / v (mass / volume), and the solution was shaken at 100 r / min for 60 min to ensure complete dissolution. Then, 0.1% w / v of Fe3O4 nanoparticles with an average particle size of 50 nm modified by oleic acid were added to the ethyl acetate solution, and the solution was ultrasonically shaken for 10 min to ensure complete dispersion, thereby completing the preparation of the growth solution;

[0081] Selection of growth substrate: a hydrophobic modified silicon wafer substrate was selected, and in this example, perfluorodecyltrimethoxysilane was used for gas-phase hydrophobic modification. After modification, the contact angle was about 120°.

[0082] Preparation of growth environment: sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v, and the solution was stirred at 40°C and 400 r / min for 30 min to ensure complete dissolution.

[0083] Selection of external stimulus: an 808 nm near-infrared light source with a light intensity of 5 mW / cm 2 was selected for external stimulation, the light irradiation area was 1 cm 2 , the light irradiation distance was 3 cm, and the light irradiation time was 2 h.

[0084] Growth step: the growth substrate was placed in the growth environment, 200 μL of the growth solution was applied to the growth substrate using a dropper, the near-infrared light source was fixed at a height of 3 cm from the center of the growth substrate, the light irradiation was started, and after the growth was completed, the solution was removed, washed, and the growth results were observed.

[0085] Growth results: as shown in the accompanying Figure 4 SEM images, the multi-dimensional polymer nanostructures prepared by this method exhibited a rich nano-scale pore structure on the two-dimensional silicon substrate plane, and the structure was transformed from a burr structure to a pore structure. However, there were still line-like structures on the pore wall surface, which were speculated to be residual burr structures during the transformation of the burr structure to the pore structure. The structure size was uniform and had no obvious defects. Examples 1 and 4 demonstrated that the structure could be controlled by adjusting the ratio of hydrophilic and hydrophobic blocks in the polymer. As the proportion of the hydrophilic chain segment increased, the structure was more likely to grow, and the structure was transformed to a porous structure.

[0086] Example 5: adjustment of polymer ratio to control nanostructure

[0087] Preparation of growth solution: two block polymers polystyrene-b-polyetherimide PS50K-b-PEI10K were dissolved in ethyl acetate at a concentration of 10% w / v (mass / volume), and the solution was shaken at 100 r / min for 60 min to ensure complete shaking. Then, 0.1% w / v of Fe3O4 nanoparticles with an average particle size of 50 nm modified by oleic acid on the surface were added to the ethyl acetate solution, and ultrasonic oscillation was performed for 10 min to ensure complete dispersion, thereby completing the preparation of the growth solution;

[0088] Selection of growth substrate: a hydrophobic modified silicon wafer substrate was selected. In this example, perfluorodecyltrimethoxysilane was used for gas-phase hydrophobic modification, and the contact angle after modification was about 120°.

[0089] Growth environment: sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v. The solution was stirred at 40°C and 400 r / min for half an hour to achieve complete dissolution.

[0090] Selection of external stimulus: an 808 nm near-infrared light source with a light intensity of 5 mW / cm 2 was selected for external stimulation. The light irradiation area was 1 cm 2 , the light irradiation distance was 3 cm, and the light irradiation time was 2 h.

[0091] Growth step: the growth substrate was placed in the growth environment, 200 μL of the growth solution was applied to the growth substrate using a dropper, the near-infrared light source was fixed at a position 3 cm away from the center of the growth substrate, and the light irradiation was started. After the growth was completed, the solution was removed, washed, and the growth results were observed.

[0092] Growth results: SEM characterization showed that the multi-dimensional polymer nanostructure prepared by this method exhibited a rich nano-scale pore structure on the two-dimensional silicon substrate plane. Compared with Example 1, the structure was completely converted into a porous structure, and the structure size was uniform without obvious defects.

[0093] Example 6, adjusting the polymer ratio to control the nanostructure:

[0094] Preparation of growth solution: two block polymers polystyrene-b-polyetherimide PS50K-b-PEI10K were dissolved in ethyl acetate at a concentration of 10% w / v (mass / volume), and the solution was shaken at 100 r / min for 60 min to ensure complete shaking. Then, 0.1% w / v of Fe3O4 nanoparticles with an average particle size of 50 nm modified by oleic acid on the surface were added to the ethyl acetate solution, and ultrasonic oscillation was performed for 10 min to ensure complete dispersion, thereby completing the preparation of the growth solution;

[0095] Selecting growth substrate: Selecting hydrophobically modified silicon wafer substrate, in this embodiment, perfluorodecyltrimethoxysilane is used for gas-phase hydrophobic modification, and the contact angle is about 120° after modification;

[0096] Growth environment: Dissolve sodium dodecyl sulfate in deionized water at a concentration of 2% w / v, the dissolution process is 40°C, 400r / min, stirring for half an hour to achieve the purpose of complete dissolution;

[0097] Selecting external stimulus: Selecting 808nm near-infrared light source with light intensity of 5mW / cm 2 , light irradiation area 1 cm 2 , light irradiation distance 3cm, light irradiation time 2h;

[0098] Growth step: Place the growth substrate in the growth environment, use a dropper to apply 200μL of growth solution on the growth substrate, fix the near-infrared light source at a height of 3cm from the center of the growth substrate, start the light irradiation, after the growth is completed, take out the solution, wash and observe the growth result;

[0099] Growth result: As shown in the attached Figure 5 SEM characterization, the multi-dimensional polymer nanostructure prepared by this method presents a rich nano-scale pore structure on the two-dimensional silicon substrate plane, compared with example 5, the structure is completely transformed into a porous structure, the structure size is uniform, and there is no obvious defect.

[0100] Examples 4-6 embody the structure control by adjusting the hydrophilic-hydrophobic block ratio in the polymer, as the hydrophobic ratio rises, the structure growth becomes difficult, and the structure changes from porous to a composite structure of pores and burrs. Comparison of examples 1-3 and 4-6 shows that the structure is controlled by adjusting the hydrophilic segment ratio in the polymer, as the hydrophilic ratio rises, the structure growth becomes easy, and the structure changes from burr to porous.

[0101] Example 7, changing the polymer type:

[0102] Preparing growth solution: Dissolve triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide PLGA50K-b-PEO4K-b-PLGA50K in dichloromethane at a concentration of 10% w / v (mass / volume), and shake in a shaker at 100r / min for 60min to ensure thorough shaking, so as to complete the preparation of the growth solution;

[0103] Selecting growth substrate: Selecting hydrophobically modified silicon wafer substrate, in this embodiment, perfluorodecyltrimethoxysilane is used for gas-phase hydrophobic modification, and the contact angle is about 120° after modification;

[0104] Growth environment: Sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v. The dissolution process was at 40°C and 400 r / min. Stirring for half an hour was sufficient to achieve the goal of full dissolution.

[0105] Select external stimulation: select a water bath heated to 50°C, with the water bath height higher than the growth environment height, keep warm for 1 hour before starting the growth step, and the growth time is 4 hours;

[0106] Growth steps: Place the growth substrate in the growth environment, use a dropper to apply 200 μL of growth solution to the growth substrate, let it grow for 4 hours, remove it from the solution after growth, clean it, and observe the growth results;

[0107] Growth results: as attached Figure 6 As shown, SEM characterization shows that the multidimensional polymer nanostructure prepared by this method presents abundant nanoscale burr structures on the two-dimensional silicon substrate plane, with uniform structural size and no obvious defects. Compared with the nanostructure in Example 1, the burr structure in this embodiment is longer, reaching about 1 μm.

[0108] Comparison of Example 1 and Example 7 shows that similar nanostructures can be obtained by changing the appropriate number of block polymer segments, the chemical composition of the hydrophilic and hydrophobic segments, and the ratio of segment lengths; that is, when an oil-water interface exists, the hydrophilic and hydrophobic block polymers of a specific composition can form a controllable nanostructure spontaneously or under simple external stimulation.

[0109] Example 8, changing the growth environment:

[0110] Prepare the growth solution: Dissolve the triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide (PLGA50K-b-PEO4K-b-PLGA50K) in dichloromethane at a concentration of 10% w / v (mass / volume). Shake the mixture on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation.

[0111] Select a growth substrate: Select a hydrophobically modified silicon wafer substrate. In this embodiment, perfluorodecyltrimethoxysilane is selected for vapor phase hydrophobic modification. After modification, the contact angle is about 120°.

[0112] Growth environment: Dissolve polyvinyl alcohol in deionized water at a concentration of 2% w / v, at 80°C, 400 r / min, and stir for half an hour to achieve full dissolution.

[0113] Select external stimulation: select a water bath heated to 80°C, with the water bath height higher than the growth environment height, keep warm for 1 hour before starting the growth step, and the growth time is 4 hours;

[0114] Growth steps: Place the growth substrate in the growth environment, use a dropper to apply 200 μL of growth solution to the growth substrate, let it grow for 4 hours, remove it from the solution after growth, clean it, and observe the growth results;

[0115] Growth results: SEM characterization showed that the multidimensional polymer nanostructure prepared by this method showed abundant nanoscale burr structures on the two-dimensional silicon substrate plane. Compared with Example 7, the richness of the structure was reduced, and the nanowires transformed into nanodots, indicating that the increase in the preparation environment temperature limited the growth of the nanostructure, and the structure size was uniform without obvious defects.

[0116] Example 9, changing the polymer ratio:

[0117] Prepare the growth solution: Dissolve the triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide (PLGA70K-b-PEO4K-b-PLGA70K) in dichloromethane at a concentration of 20% w / v (mass / volume). Shake the mixture on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation. This completes the preparation of the growth solution.

[0118] Select a growth substrate: Select a hydrophobically modified silicon wafer substrate. In this embodiment, perfluorodecyltrimethoxysilane is selected for vapor phase hydrophobic modification. After modification, the contact angle is about 120°.

[0119] Growth environment: Dissolve polyvinyl alcohol in deionized water at a concentration of 2% w / v, at 80°C, 400 r / min, and stir for half an hour to achieve full dissolution.

[0120] Select external stimulation: select a water bath heated to 50°C, with the water bath height higher than the growth environment height, keep warm for 1 hour before starting the growth step, and the growth time is 4 hours;

[0121] Growth steps: Place the growth substrate in the growth environment, use a dropper to apply 200 μL of growth solution to the growth substrate, let it grow for 4 hours, remove it from the solution after growth, clean it, and observe the growth results;

[0122] Growth results: as attached Figure 7 As shown, SEM characterization shows that the multidimensional polymer nanostructure prepared by this method presents a rich nanoscale dot structure on the two-dimensional silicon substrate plane. Compared with Example 7, the structural richness is reduced, and the nanowires are transformed into nanodots, indicating that increasing the proportion of hydrophobic segments limits the growth of the nanostructure, and the structure size is uniform without obvious defects.

[0123] Example 10, changing the growth substrate:

[0124] Prepare the growth solution: Dissolve the triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide (PLGA50K-b-PEO4K-b-PLGA50K) in dichloromethane at a concentration of 20% w / v (mass / volume). Shake the mixture on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation. This completes the preparation of the growth solution.

[0125] Select a growth substrate: Select a rough glass substrate that has been hydrophobically modified. In this embodiment, perfluorodecyltrimethoxysilane is used for vapor phase hydrophobic modification. After modification, the contact angle is about 150°.

[0126] Growth environment: Dissolve polyvinyl alcohol in deionized water at a concentration of 2% w / v; dissolve at 80°C, 400 r / min, and stir for half an hour to achieve full dissolution;

[0127] Select external stimulation: select a water bath heated to 50°C, with the water bath height higher than the growth environment height, keep warm for 1 hour before starting the growth step, and the growth time is 4 hours;

[0128] Growth steps: Place the growth substrate in the growth environment, use a dropper to apply 200 μL of growth solution to the growth substrate, let it grow for 4 hours, remove it from the solution after growth, clean it, and observe the growth results;

[0129] Growth results: as attached Figure 9 As shown in the figure, SEM characterization shows that the multidimensional polymer nanostructures prepared by this method present abundant nanoscale burr structures on the rough glass substrate, which are combined into micro-nano conformal structures. There are both micron-level undulating structures and nanoscale burr structures, indicating that this method can obtain a variety of desired structures by changing the preparation substrate.

[0130] Example 11, changing the growth substrate to a water-in-oil emulsion:

[0131] Prepare the growth solution: Dissolve the triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide (PLGA50K-b-PEO4K-b-PLGA50K) in dichloromethane at a concentration of 20% w / v (mass / volume). Shake the mixture on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation. This completes the preparation of the growth solution.

[0132] Select a growth substrate: Select a glass substrate that has been hydrophobically modified. In this embodiment, perfluorodecyltrimethoxysilane is used for vapor phase hydrophobic modification. After modification, the contact angle is about 120°.

[0133] Growth environment: Dissolve sodium dodecyl sulfate in deionized water at a concentration of 2% w / v. Dissolve at 80°C, 400 rpm, and stir for half an hour to achieve full dissolution.

[0134] Select external stimulation: select ultrasound equipment, press 100% ultrasound power, ultrasound for 5 seconds per minute, maintain the water bath temperature at 25°C, start ultrasound after adding the growth solution, and grow for 2 hours;

[0135] Growth steps: Place the growth substrate in the growth environment, use a dropper to apply 200 μL of growth solution to the growth substrate, let it grow for 2 hours, remove it from the solution after growth, clean it, and observe the growth results;

[0136] Growth results: as attached Figure 10 As shown in FIG5 , SEM characterization shows that the multidimensional polymer nanostructure prepared by this method is a burr structure that grows inward in the polymer bulk phase. Compared with Example 7, the structure is completely similar, the structural size is uniform, and there are no obvious defects, but the growth direction is different, indicating that the method does not fix the formation mode of the oil-water interface. Regardless of the form of water-in-oil, water-oil plane or oil-in-water, as long as there is an oil-water interface, the method can grow the nanostructure.

[0137] Example 12, changing the growth substrate to a one-dimensional tube:

[0138] Prepare the growth solution: Dissolve the diblock polymer polymethyl methacrylate-b-poly-4-vinylpyridine PMMA30K-b-P4VP8K in dichloromethane at a concentration of 5% w / v (mass / volume). Shake the solution on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation.

[0139] Select a growth substrate: Select a hydrophobically modified capillary. In this embodiment, perfluorodecyltrimethoxysilane-modified silica nanoparticles are used for liquid phase modification. Simply put, a commercially available super-hydrophobic powder dispersion is used as the modification liquid. The oxygen plasma-treated capillary is immersed in the modification liquid and then removed and dried.

[0140] Growth environment: Sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v, at 80°C, 400 r / min, and stirred for half an hour to achieve full dissolution.

[0141] Select external stimulation: select ultrasound equipment, press 100% ultrasound power, ultrasound for 5 seconds per minute, maintain the water bath temperature at 25°C, start ultrasound after adding the growth solution, and grow for 2 hours;

[0142] Growth Step: Place the growth substrate in the growth environment, apply 200 μL of growth solution to the growth substrate using a dropper, let the growth sit for 2 h, after the growth is complete, remove the solution from the solution, rinse, and observe the growth results;

[0143] Growth Results: As shown in FIG. 8, the multi-dimensional polymer nanostructures prepared by this method exhibit a bristle structure growing into the tube in a one-dimensional capillary, which is completely similar to the structure of Example 7, and the structure size is uniform without obvious defects. Figure 11

[0144] Example 13, change the growth substrate to a cross-linked PDMS substrate coated with a two-dimensional copper interdigital electrode:

[0145] Prepare the growth solution: Dissolve the polymer polydimethylsiloxane-b-polyethylene glycol PDMS30K-b-PEO8K in chloroform at a concentration of 10% w / v (mass / volume). Shake the solution in a shaker at 100 r / min for 60 min to ensure thorough shaking, thereby completing the preparation of the growth solution.

[0146] Select the growth substrate: Select a cross-linked PDMS substrate coated with a two-dimensional copper interdigital electrode modified by hydrophobic modification. In this example, the two-dimensional interdigital electrode is packaged in an asymmetrically modified PDMS, and the asymmetric modification of the PDMS is achieved by using perfluorodecyltrimethoxysilane vapor modification through a mask covering method.

[0147] Growth environment: Dissolve sodium dodecyl sulfate in deionized water at a concentration of 2% w / v, and stir at 80°C and 400 r / min for half an hour to achieve complete dissolution.

[0148] Select external stimulus: Apply power to the interdigital electrode at a power parameter of 15 V / 2 A, and apply power for 30 min,

[0149] Growth Step: Place the growth substrate in the growth environment, apply 500 μL of growth solution to the growth substrate using a dropper, and apply power for 30 min. After the growth is complete, remove the solution from the solution, rinse, and observe the growth results;

[0150] Growth Results: As shown in FIG. 8, the multi-dimensional polymer nanostructures prepared by this method exhibit a bristle structure growing into the tube in a one-dimensional capillary, which is completely similar to the structure of Example 7, and the structure size is uniform without obvious defects.

[0151] Example 14, change the growth substrate to a cross-linked PDMS microfluidic channel:

[0152] ​Prepare the growth solution: Dissolve the triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide (PLGA50K-b-PEO4K-b-PLGA50K) in dichloromethane at a concentration of 20% w / v (mass / volume). Shake the mixture on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation. This completes the preparation of the growth solution.

[0153] Select a growth substrate: A cross-linked PDMS substrate with microfluidic channels is selected. In this embodiment, the PDMS is also asymmetrically modified with perfluorodecyltrimethoxysilane in the vapor phase;

[0154] Growth environment: Sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v, at 80°C, 400 r / min, and stirred for half an hour to achieve full dissolution.

[0155] Select external stimulation: select a water bath heated to 50°C, with the water bath height higher than the growth environment height, keep warm for 1 hour before starting the growth step, and the growth time is 4 hours;

[0156] Growth steps: Place the growth substrate in the growth environment, use a dropper to apply 500 μL of growth solution to the growth substrate, let it grow for 4 hours, remove it from the solution after growth, clean it, and observe the growth results;

[0157] Growth results: as attached Figure 12 As shown, SEM characterization shows that the multidimensional polymer nanostructure prepared by this method presents a burr structure growing inward in the microfluidic channel. Compared with Example 7, the structure is completely similar, the structure size is uniform, and there is no obvious defect.

[0158] Example 15, changing the growth substrate to a cross-linked polyurethane porous grid:

[0159] Prepare the growth solution: Dissolve the triblock polymer polyglycolide-co-lactide-b-polyethylene glycol-b-polyglycolide-co-lactide (PLGA50K-b-PEO4K-b-PLGA50K) in dichloromethane at a concentration of 20% w / v (mass / volume). Shake the mixture on a shaker at 100 rpm for 60 minutes to ensure sufficient agitation. This completes the preparation of the growth solution.

[0160] Selecting a growth substrate: Selecting a cross-linked polyurethane with a porous grid as the substrate. In this embodiment, since the cross-linked polyurethane itself has a high hydrophobicity level, no hydrophobic modification is required;

[0161] Growth environment: Sodium dodecyl sulfate was dissolved in deionized water at a concentration of 2% w / v, at 80°C, 400 r / min, and stirred for half an hour to achieve full dissolution.

[0162] Select external stimulus: select water bath heating 50℃, water bath height higher than the growth environment height, incubation 1h before growth step, growth time 4h;

[0163] Growth step: place the growth substrate in the growth environment, use a dropper to apply 1mL of growth solution on the growth substrate, let it grow for 4h, after the growth is completed, remove the solution and observe the growth results after cleaning;

[0164] Growth results: as shown in the SEM characterization, the multi-dimensional polymer nanostructure prepared by this method presents a burr structure growing inward in the microfluidic channel, which is completely similar to the structure of Example 7, the structure size is uniform, and there is no obvious defect. Figure 13

[0165] Examples 12-15 show that this preparation method can be prepared on a variety of hydrophobic substrates, thereby imparting a variety of nanostructures on the complex microstructure of the substrate itself, and the growth conditions are not harsh, compared with traditional methods such as photolithography and etching, it has the advantages of high preparation efficiency, rich substrate selection, etc.

[0166] Appendix Figures 14-16 Statistics of Examples 1-3 and 4-6 show that by adjusting the polymer hydrophilic / hydrophobic segment ratio, length, etc. parameters, the number of burrs, burr diameter and pore diameter are not limited to the number and size range of nanostructures.

[0167] The unmentioned part of the present application is applicable to the prior art.​

Claims

1. A method for preparing a multidimensional polymer nanostructure with controllable morphology, characterized in that: The following steps are involved: Step 1: dissolving the block polymer in an organic solvent and adding functional units that assist in the preparation of special structures and functions to prepare a growth solution; wherein the functional units include ferroferric oxide nanoparticles; Step 2: Dissolve a certain amount of surfactant in water as a growth environment; Step 3: placing the growth substrate with adjustable area into the growth environment of step 2, and applying the growth liquid of step 1 thereto; Step 4: applying external stimulation to induce the growth in step 3, and through the volatilization of the organic solvent and the self-assembly process, the growth liquid grows into a nanostructure on the growth substrate; The block polymer includes a polymer of two segments, three segments or more than three blocks or a multi-arm block polymer or a hyperbranched polymer, and the block polymer has a hydrophobic segment and a hydrophilic segment, and the weight ratio of the hydrophobic segment to the hydrophilic segment is (0.5-100):1; The hydrophobic segment includes one or more of polystyrene, polymethyl methacrylate, polylactic acid, polylactide, polylactic acid / glycolic acid copolymer, polydimethylsiloxane, and polyisobutylene; The hydrophilic segment includes one or more of poly-4-vinylpyridine, polyacrylic acid, polyethylene glycol, poly(polyethylene glycol methyl ether methacrylate), and poly-N,N-dimethylacrylamide; The surfactant includes one or more of sodium lauryl sulfate, hexadecyltrimethylammonium bromide, and polyvinyl alcohol; and the concentration of the surfactant in the growth environment in step 2 is 0-100 mg / ml; External stimulation includes physical methods such as heat, electricity, and light, and the duration of external stimulation is 0-24 hours; Among them, the thermophysical method includes thermal stimulation, which is used to adjust the growth environment temperature between 0-80°C; The electrophysical method includes electrical stimulation, and the electrical stimulation includes applying a voltage of a certain intensity, and the electrical stimulation power range is 0-36W; The photophysical method includes light stimulation, and the light stimulation includes applying light waves of a certain wavelength band, and the wavelength of the light waves is 450nm, 532nm, 808nm, and 1064nm.

2. The method for preparing a morphology-controllable multidimensional polymer nanostructure according to claim 1, characterized in that: The organic solvent includes one or more of ethyl acetate, dimethyl carbonate, ethylene glycol dimethyl ether, dioxane, benzene, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, carbon tetrachloride, tetrahydrofuran, N,N-dimethylformamide, and acetone; and the concentration of the growth solution in step 1 is 0.1-500 mg / ml.

3. The method for preparing a morphology-controllable multidimensional polymer nanostructure according to claim 1, characterized in that: The growth substrate comprises one or more of a hollow tube, a solid wire, a flat sheet, a rough sheet, a water-in-oil emulsion, and a hollow grid; The growth substrate surface has a specific structure or is made of multiple materials; the specific structure includes topological micro-pillars, cone arrays, microfluidic channels or porous grids; Materials include glass, iron, copper, aluminum oxide, polydimethylsiloxane, polyethylene, polyimide, or cross-linked polyurethane.

4. The method for preparing a morphology-controllable multidimensional polymer nanostructure according to claim 1, characterized in that: The morphology of the nanostructure includes one or more combinations of a nanoburr structure, a nanodot structure, a nanowire structure, a nanopore structure, and a nanomesh structure.

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