CN114805917A - Preparation method of three-stage porous material based on fibrin fiber bridging - Google Patents
Preparation method of three-stage porous material based on fibrin fiber bridging Download PDFInfo
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Abstract
The invention discloses a preparation method of a three-stage porous material based on fibrin fiber bridging. Placing macroscopic porous materials MAs into a container, adding fibrinogen Fg, extruding to mix uniformly, adding thrombin Thr, mixing uniformly, and standing to react to generate a fibrin @ MAs complex; and (3) loading the nano-porous material NMs on the fibrin @ MAs complex, and washing with water to obtain a three-stage porous complex. The novel three-stage porous structure constructed based on the fibrin fiber bridged macropore and the nano porous material realizes the compatibility of high mass transfer and high specific surface area in the same material, the obtained complex shows good harmful substance adsorption characteristic, the NMs is greatly and stably loaded in the complex, and the complex is compatible with high mass transfer efficiency, large specific surface area and active sites.
Description
Technical Field
The invention belongs to a preparation method of a novel multistage porous structure complex in the technical field of preparation of macroscopic materials, and particularly relates to a technical method for preparing a fibrin fiber bridging-based three-stage porous material.
Background
Over the last decades, porous materials have attracted extensive research interest in the fields of energy, environment, catalysis, sensing, etc. On the one hand, macro-porous Materials (MAs) with micron-sized diameter pores (1-1000 μm), such as sponges, foams and water/aerogels, exhibit high mass transfer efficiency, excellent mechanical stability and macro-operability. But are generally chemically inert and too large a pore volume often results in a small surface area per unit volume of material (i.e., low space utilization). On the other hand, Nanoporous Materials (NMs) with pore diameters on the (sub) nanometer scale, such as metal organic framework Materials (MOFs), mesoporous silica, activated carbon and the like, have high specific surface area and abundant active sites, but are easy to agglomerate, difficult to process and inconvenient to operate. The two materials are organically combined to exert the characteristics of the porous material to the maximum extent, namely the compatibility of high mass transfer efficiency and high specific surface area in one material is realized, and the method has scientific research value and wide application prospect.
Current binding strategies can be largely divided into two categories, one is to construct MAs with NMs as the basic unit, and the other is to modify NMs to pre-prepared MAs by in situ growth, polymer cross-linking, etc. The former is used for preparing various macro materials with high specific surface area, but the problems of unclear pore structure, low mass transfer efficiency and mechanical strength and the like exist. The latter can maintain a large porosity of the MAs, but the space utilization is still low, usually by modifying NMs to the MAs framework. In overview, the above preparation strategy achieved the combination of MAs and NMs by constructing a secondary porous structure, but still did not achieve good compatibility of high mass transfer efficiency with high space utilization, mainly because of the large gap in the pore size of MAs and NMs. Meanwhile, most of the combined preparation processes are complicated, long in time consumption, and inflexible and adjustable in material components, structures and the like, so that a new preparation method and a more exquisite structure are urgently needed to break through the gap and realize compatibility.
Disclosure of Invention
In order to solve the current situation and the difficult problem in the background, the invention aims to construct a novel three-stage porous composite material based on fibrin bridging and realize the compatibility of high specific surface area and high mass transfer efficiency in the same macroscopic material.
The technical scheme and the specific preparation steps adopted by the invention are as follows:
1) cutting macro porous materials MAs into a certain size and shape, cleaning, drying and storing for later use; meanwhile, preparing a nano porous material NMs into a suspension with a certain concentration, and uniformly dispersing for later use by ultrasonic;
2) placing a macro-porous material MAs into a container, such as a hole of a 96-hole plate, adding fibrinogen Fg with a certain volume into the macro-porous material MAs, properly extruding to mix uniformly, adding thrombin Thr, mixing uniformly, standing for a period of time to wait for in-situ polymerization of fibrin inside the macro-porous material MAs, and generating a fibrin @ MAs complex;
the fibrinogen Fg reacts with the thrombin Thr to generate fibrin which is directly generated in the internal pores of the macroscopic porous material MAs.
3) After reacting for a period of time, loading the nano-porous material NMs on the fibrin @ MAs complex in a certain way, and finally washing with a large amount of water to remove the loosely loaded nano-porous material NMs, so as to prepare a three-stage porous complex for storage and standby.
The pore diameter of the macro porous material MAs is in the range of 1-1000 μm, the material form can be various three-dimensional porous materials such as sponge, foam, aerogel and the like, and the material types include but are not limited to Melamine (MS), Polyurethane (PS), Nickel (NF), graphene and the like;
the pore size of the nano-porous material NMs is on the nano-scale, and includes but is not limited to nano-porous materials with micro-porous and mesoporous structures, and the species include but are not limited to metal organic frameworks, covalent organic frameworks, mesoporous silicon, and the like.
A combination of one or more of NMs above is loaded in the same complex.
In the step 1), the concentration of the nano porous material NMs solution is 20 mug mL -1 -15mg mL -1 。
The fibrinogen Fg and the thrombin Thr in the step 2) are both prepared by phosphate buffer solution PBS, and the formula of the phosphate buffer solution PBS comprises 0.01M NaH 2 PO 4 -Na 2 HPO 4 0.15M NaCl and pH 7.0.
In the step 2), the concentration of the fibrinogen Fg in the solution prepared by the fibrinogen Fg in phosphate buffered saline PBS is 0.75-2.5mg mL -1 (ii) a The concentration of the thrombin Thr in the solution prepared by phosphate buffer solution PBS is 100-200U mL -1 The volume of the solution prepared from fibrinogen Fg and thrombin Thr in phosphate buffered saline PBS is determined according to the capacity of the macroscopic porous material MAs.
In the step 2), the standing reaction time of the fibrinogen Fg and the thrombin Thr is 10s-7 min.
In the step 3), an in-situ embedding method or an adsorption method is specifically adopted in a certain mode.
The in-situ embedding method is characterized in that a certain amount of nano-porous material NMs is directly added into the fibrin @ MAs complex obtained in the step 2), and then the mixture is subjected to standing reaction for 10s-7min, cross-linking by Glutaraldehyde (GA) and water washing to obtain the fibrin @ MAs complex.
The adsorption method is that the fibrin @ MAs complex obtained in the step 2) is washed by water to remove raw materials and products such as fibrinogen Fg, thrombin Thr and the like, then the fibrin @ MAs complex is soaked in a solution of the nano porous material NMs, the complex is taken out after oscillation for 3h-12h, and the fibrin @ MAs complex is washed by water to obtain the fibrin @ MAs complex.
All the reactions of the invention are carried out at normal temperature of 25 ℃.
The application range of various complexes prepared by the method includes but is not limited to water body purification, catalysis, sensing and the like.
The innovation of the invention is that the macro porous material Mas and the nano porous material NMs with different pore relations are combined, fibrin is generated by in-situ polymerization inside the macro porous material MAs to form a composite body, and then the composite body and the nano porous material NMs are loaded to generate, so that the novel three-stage porous material with macro porous, fibrin and nano porous is obtained.
The novel three-stage porous structure is constructed on the basis of the fibrin fiber bridged macropore and the microporous material, the compatibility of high mass transfer and high specific surface area in the same material is realized, and the obtained complex exhibits good harmful substance adsorption property.
Compared with the prior art, the invention has the following advantages:
the complex has a special three-stage porous structure, not only ensures a sufficient mass transfer path in application, but also realizes large and stable load of NMs in the complex, and the complex is compatible with high mass transfer efficiency, large specific surface area and active sites.
The method benefits from an efficient biological polymerization reaction mechanism, and is simple and rapid to operate and universal.
Drawings
FIG. 1 is a scanning electron micrograph of Zr-LMOFs-fibrin-melamine sponge (Zr-F @ MS) of example 1;
FIG. 2 is a graph showing a fluorescence emission spectrum, an X-ray diffraction spectrum and a Fourier transform infrared spectrum of Zr-F @ MS in example 1;
FIG. 3 is a graph showing the results of the stability characterization of Zr-F @ MS in example 1;
FIG. 4 is a graph showing the results of adsorption of Methylene Blue (MB) by Zr-F @ MS in example 1;
FIG. 5 is a scanning mirror image of Zr-LMOFs-fibrin-polyurethane sponge (Zr-F @ PS) in example 2;
FIG. 6 is a scanning electron micrograph of Zr-LMOFs-fibrin-nickel foam (Zr-F @ NF) of example 3;
Detailed Description
In order to make the technical solutions of the present invention better understood, the method provided by the present invention is described in detail below with reference to the accompanying drawings and examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The embodiment of the invention is as follows:
EXAMPLE 1 preparation of Zr-F @ MS by embedding method
Cutting Melamine Sponge (MS) into cylinders with height of 5mm and diameter of 2mm by a puncher, completely cleaning with deionized water and absolute ethyl alcohol, drying in an oven at 80 ℃, and storing at normal temperature for later use. The Zr-LMOFs particles are ultrasonically dispersed in water to prepare 1mg mL -1 And (3) suspension. MS was placed in the well of a clear 96-well plate, and 40. mu.L of 0.75mg mL was added thereto -1 Fg, pressing MS to make Fg and MS fully contact. Then 5. mu.L of 100U mL of -1 Thr and mixed well to trigger in situ polymerization in fibrin MS to give F @ MS. After 7min of reaction, 20. mu.L of 1mg mL was added -1 The Zr-LMOFs suspension is mixed evenly. After 8min, 200. mu.L of 0.1% GA solution was added for covalent crosslinking of fibrin, and finally, Zr-F @ MS was obtained after multiple washes with deionized water.
The characterization results were as follows:
the structure and morphology of the Zr-F @ MS prepared in example 1 was characterized by observation with a field emission scanning electron microscope. MS is a framework structure, and contains 40-200 μm macropores (primary framework, FIG. 1 (A)). After fibrin is formed and accumulated in the MS, a large number of fibers with the diameter of about 20nm appear on the MS framework and the pore walls, and the fibers are interwoven into a fiber grid to form a secondary framework (figure 1 (B)). After loading of Zr-LMOFs, the primary and secondary framework structures were retained, and at the same time, a large number of spherical particles having a particle size of 100-400nm (tertiary structure) appeared in the sample, and the particles were uniformly dispersed on the fiber mesh, mostly entangled with fibers of about 20nm (FIG. 1(C)), thereby confirming the tertiary porous structure of Zr-F @ MS. The wound fibers are expected to improve the stability of the Zr-LMOFs in the composite body, and compared with the conventional wrapping and complete sealing, the structure is more favorable for retaining active sites and porous characteristics on the structure.
The load condition and the interaction of each component in the Zr-F @ MS are characterized by various spectral means. . As shown in FIG. 2(A), under the excitation of ultraviolet light, neither MS nor F @ MS has a fluorescence characteristic peak in the 350-500nm waveband. In contrast, Zr-F @ MS shows a clear fluorescence emission peak near 400nm, which indicates the successful loading of Zr-LMOFs and the maintenance of the fluorescence characteristics thereof; the phase structure of each component in Zr — F @ MS was characterized and analyzed by X-ray diffraction spectroscopy, and the result is shown in fig. 2 (B). Compared with F @ MS, the Zr-F @ MS has obvious diffraction peaks at 2 theta of 4.94 degrees, 7.38 degrees, 8.86 degrees, 10.22 degrees, 11.65 degrees and the like, and belongs to characteristic peaks of Zr-LMOFs through retrieval, so that the successful load and the invariable matter-phase structure of the Zr-LMOFs are proved; the Fourier transform infrared spectrum characterization result is shown in FIG. 2 (C). MS at 812cm -1 Has a sharp characteristic peak, which is derived from the bending vibration of triazine ring in melamine. In contrast to MS, F @ MS not only retained the MS at 812cm -1 Characteristic peaks at (E), also at 1539 and 1658cm -1 Two new absorption peaks appear nearby, corresponding to the telescopic vibration of the amides I and II respectively, and the existence of the fibrin is proved. The Zr-LMOFs granules have obvious absorption peaks at 661, 787, 867, 1418, 1604, 1547 and the like, which respectively correspond to Zr-O bond vibration, benzene ring C-H vibration, carboxyl symmetrical and asymmetrical stretching peak, and benzene ring C-C bond vibration 1655cm -1 The sharp peak at this point is due to the C ═ O bond vibration of DMF remaining in Zr — LMOFs. Zr-F @ MS samples are found at 667, 714 and 782, 812, 1542 and 1652cm -1 Characteristic peaks belonging to Zr-LMOFs, MS and fibrin are displayed nearby, so that the simultaneous existence of Zr-LMOFs, MS and fibrin in Zr-F @ MS is proved.
The structural stability of Zr-F @ MS is characterized in detail by adopting a fluorescence means. As shown in FIG. 3(A), via vortexAfter 60min, repeated extrusion for 100 times, soaking in water for 64 days and ultrasonic treatment for 360min, the Zr-F @ MS stability reaches (98.72 +/-0.22)%, (95.65 +/-0.23)%, (99.55 +/-0.13)% and (99.91 +/-0.05)%. All the test results prove the structural integrity and the load stability of the Zr-F @ MS, and show the application potential of the Zr-F @ MS in an actual scene. In addition, the fluorescence quantitative analysis result also proves the high load efficiency and capacity of the Zr-LMOFs in the Zr-F @ MS. As shown in FIG. 3(B), the solutions were prepared from Zr-LMOFs suspensions (0.1, 1, 2.5, 5, 7.5 and 10mg mL) at different concentrations -1 ) Prepared Zr-F @ MS, the fluorescence intensity values of the clear liquid at 400nm are 7, 174, 396, 859, 1086 and 1350 respectively. The corresponding load ratios were calculated to be 99.9%, 99.3%, 99.6%, 99.7% and 99.8%, respectively.
The application performance verification of this example 1 is as follows:
the performance of Zr-F @ MS in adsorbing the dye MB in water was first evaluated, as shown in FIG. 4 (A). The same amount of Zr-LMOFs particles are loaded in Zr-F @ MS or directly dispersed in MB solution, the adsorption rates of the Zr-LMOFs particles and the Zr-F @ MS are equivalent, and the equilibrium adsorption capacities of the Zr-LMOFs particles and the MB solution are respectively 614mg g -1 And 482.9mg g -1 Due to the three-stage porous structure of Zr-F @ MS, a sufficient mass transfer path is ensured, and the dispersed loading of the Zr-LMOFs is realized. More importantly, it is also highlighted that the structure of the fibrin fibres entanglement avoids as much as possible the blocking/covering of the Zr — LMOFs pores and of the specific surface area. As shown in FIG. 4(B), Zr-F @ MS was used for 150mg L -1 The removal rate of MB can reach 95.7 percent at most. In addition to static adsorption, Zr — F @ MS also exhibited excellent adsorption performance in the filtration test (see fig. 4 (C)). 400 uL of 10mg L -1 The light blue MB solution became completely colorless by syringe pumping through the Zr-F @ MS, and the removal rate was measured to be close to 100% (defined as 1 cycle). After 20 cycles, the Zr-F @ MS still had a 91% removal rate for the same amount of MB, while the Zr-F @ MS itself remained intact except for the blue color of MB, indicating that it had excellent adsorption and stability in practical filtration applications.
EXAMPLE 2 preparation of Zr-F @ PS by embedding
Cutting PS into pieces with a height of 5mm and a diameter of 2mmCompletely cleaning a cylinder with the diameter of mm by using deionized water and absolute ethyl alcohol, drying in an oven at the temperature of 80 ℃, and storing at normal temperature for later use. PS was placed in the wells of a clear 96-well plate, and 40. mu.L of 0.75mg mL was added thereto -1 Fg, pressing PS to make them fully contact. Then 5. mu.L of 100U mL of -1 Thr (PBS 2) and mixed well. After 7min, 20. mu.L of 1mg mL was added -1 The Zr-LMOFs suspension is mixed evenly. And reacting for 8min, adding 200 mu L of 0.1 percent GA solution for crosslinking, and washing for multiple times by deionized water after 5min to obtain Zr-F @ PS.
The characterization results were as follows:
the structure and the micro-morphology of the Zr-F @ PS are characterized by SEM. As shown in FIG. 5(A), Zr-F @ PS is in a three-stage porous structure: the macropores of the PS are reserved, the PS framework is coated on the fibrin fiber grid and extends in the axial hole by taking the framework as the axis, and the spherical Zr-LMOFs particles are uniformly distributed on the fibrin grid and are wound by small fibers.
EXAMPLE 3 preparation of Zr-F @ NF by embedding
Cutting NF into cylinders with height of 5mm and diameter of 2mm, cleaning with deionized water and anhydrous ethanol, drying in an oven at 80 deg.C, and storing at room temperature. NF was placed in the well of a clear 96-well plate, and 40. mu.L of 0.75mg mL was added thereto -1 Fg, pressing NF to make them contact. Then 5. mu.L of 100U mL of -1 Thr (PBS 2) and mixed well. After 7min, 20. mu.L of 1mg mL was added -1 Suspending the Zr-LMOFs and mixing evenly. And reacting for 8min, adding 200 mu L of 0.1 percent GA solution for crosslinking, and washing for multiple times by deionized water after 5min to obtain Zr-F @ NF.
The characterization results were as follows:
the structure and the micro-morphology of the Zr-F @ NF were characterized by SEM. As shown in FIG. 5(B), Zr-F @ NF was in a tertiary porous structure: the large pores of NF are reserved, the fibrous protein fiber grid is coated with an NF framework and extends in the axial holes by taking the framework as an axial hole, and the spherical Zr-LMOFs particles are uniformly distributed on the fibrous protein grid and are wound by small fibers. Examples 2 and 3 above demonstrate the general applicability of the method to various types of macroporous macrocomposites.
EXAMPLE 4 preparation of Cr-F @ MS by embedding
Cutting MS into pieces with height of 5mm and diameter of 2mAnd completely cleaning the cylinder m by using deionized water and absolute ethyl alcohol, drying the cylinder m in an oven at the temperature of 80 ℃, and storing the cylinder m at normal temperature for later use. MS was placed in the well of a clear 96-well plate, and 40. mu.L of 0.75mg mL was added thereto -1 Fg, pressing MS to make them contact fully. Then 5. mu.L of 100U mL of -1 Thr (PBS 2) and mixed well. After 7min, 20. mu.L of 1mg mL was added -1 MIL-100(Cr) suspension and mixed well. And reacting for 8min, adding 200 mu L of 0.1 percent GA solution for crosslinking, and washing for multiple times by deionized water after 5min to obtain Cr-F @ MS.
The characterization results were as follows:
the structure and the micro-morphology of Cr-F @ MS are characterized by SEM. As shown in FIG. 5(C), Cr-F @ MS has a three-stage porous structure: the macro-pores of MS are reserved, fibrin fiber grids are coated on an MS framework or extend in axial holes by taking the framework as an axial hole, octahedron MIL-100(Cr) is uniformly distributed on the fibrin grids, and small fibers are wound, so that the method is proved to have universality for other types of NMs.
EXAMPLE 5 preparation of Zr/F @ MS by adsorption
MS was placed in the well of a clear 96-well plate, and 40. mu.L of 0.75mg mL was added thereto -1 Fg, pressing MS to make Fg and MS fully contact. Then 5. mu.L of 200U mL was added to the MS in the squeezed state -1 Thr (PBS 2), and rapidly squeezed again to mix Fg and Thr well and trigger fibrin formation. Adding 200 μ L of 0.1% GA aqueous solution after 5min, repeatedly sucking the solution with a pipette to accelerate the exchange of the internal and external solutions of MS, soaking for 5min, carefully taking out the sponge, soaking in a large amount of water to remove PBS, cleaning, and storing in a wet state for later use. Taking Zr-LMOFs to be ultrasonically dispersed in water to form 50 mu g mL -1 And (3) solution. The sponge was immersed in 200. mu.L of 50. mu.g mL -1 And oscillating the Zr-LMOFs solution in the dark and turning over the centrifugal tube to ensure that the Zr-LMOFs are fully contacted with the sponge. After 3h, the oscillation is finished, clear liquid is discarded, 400 mu L of water is added into the solution for two times respectively, the solution is fully washed to remove the Zr-LMOFs which are not firmly adsorbed, and the obtained Zr/F @ MS is stored in a wet state and is kept away from light for standby.
The characterization results were as follows:
the structure and the appearance of Zr/F @ MS are characterized by SEM. As shown in FIG. 6(A), Zr/F @ MS has a three-stage porous structure: and (3) reserving the macropores of the MS, coating an MS framework with a fibrin fiber grid, taking the framework as an axial direction and extending in the pores, and adsorbing spherical Zr-LMOFs particles in the pores and on fibrin fibers of the MS framework.
The application performance verification of this example 5 is as follows:
under the optimized condition (10min is the optimal incubation time), the performance of Zr/F @ MS fluorescence detection m-PT is evaluated, and the result is shown in FIG. 6 (B). It can be seen that the fluorescence intensity value of Zr/F @ MS at 405nm is reduced along with the increase of the concentration of m-PT, and the linear relation y between the quenching rate (QR, y) and the logarithm (lgc) of the concentration of m-PT is 0.36lgc-0.46(r is lgc-0.46) 2 0.9781), linear detection range 50-2500 μ g L -1 The detection limit is 4.95 mu g L -1 (S/N is 3), the performance is comparable with that of the similar sensor.
Claims (10)
1. A preparation method of a three-stage porous material based on fibrin fiber bridging is characterized by comprising the following steps:
1) cutting macro porous materials MAs, cleaning, drying and storing for later use; meanwhile, preparing a nano porous material NMs into a suspension with a certain concentration, and uniformly dispersing for later use by ultrasonic;
2) placing a macroscopic porous material MAs in a container, adding fibrinogen Fg into the macroscopic porous material MAs, extruding to mix uniformly, adding thrombin Thr, mixing uniformly, standing for a period of time to wait for in-situ polymerization of fibrin in the macroscopic porous material MAs to generate a fibrin @ MAs complex;
3) after the reaction, the nano-porous material NMs is loaded on the fibrin @ MAs complex in a certain way, and finally the nano-porous material NMs which is not firmly loaded is removed by washing with water, so that a three-stage porous complex is prepared.
2. The preparation method of the fibrin fiber bridging-based three-stage porous material as claimed in claim 1, wherein: the pore diameter of the macro porous material MAs is in the range of 1-1000 μm; the pore size of the nanoporous material NMs is on the nanometer scale.
3. The preparation method of the fibrin fiber bridging-based three-stage porous material as claimed in claim 1, wherein: a combination of one or more of NMs above is loaded in the same complex.
4. The preparation method of the fibrin fiber bridging-based three-stage porous material as claimed in claim 1, wherein: in the step 1), the concentration of the nano porous material NMs solution is 20 mug mL -1 -15mg mL -1 。
5. The preparation method of the fibrin fiber bridging-based three-stage porous material as claimed in claim 1, wherein: the fibrinogen Fg and the thrombin Thr in the step 2) are both prepared by phosphate buffer solution PBS, and the formula of the phosphate buffer solution PBS comprises 0.01M NaH 2 PO 4 -Na 2 HPO 4 0.15M NaCl and pH 7.0.
6. The preparation method of the fibrin fiber bridging-based three-stage porous material according to claim 5, wherein: in the step 2), the concentration of the fibrinogen Fg in the solution prepared by the phosphate buffered saline PBS is 0.75-2.5mg mL -1 (ii) a The concentration of thrombin Thr in the solution prepared by phosphate buffer solution PBS is 100-200U mL -1 。
7. The preparation method of the fibrin fiber bridging-based three-stage porous material as claimed in claim 1, wherein: in the step 2), the standing reaction time of the fibrinogen Fg and the thrombin Thr is 10s-7 min.
8. The preparation method of the fibrin fiber bridging-based three-stage porous material as claimed in claim 1, wherein: in the step 3), an in-situ embedding method or an adsorption method is specifically adopted in a certain mode.
9. The preparation method of the fibrin fiber bridging-based three-stage porous material according to claim 8, wherein: the in-situ embedding method is characterized in that the nano-porous material NMs is directly added into the fibrin @ MAs complex obtained in the step 2), and then the mixture is subjected to standing reaction for 10s-7min, cross-linking by Glutaraldehyde (GA) and water washing to obtain the fibrin @ MAs complex.
10. The preparation method of the fibrin fiber bridging-based three-stage porous material according to claim 8, wherein: the adsorption method is that the fibrin @ MAs complex obtained in the step 2) is washed by water to remove raw materials and products such as fibrinogen Fg, thrombin Thr and the like, then the fibrin @ MAs complex is soaked in a solution of a nano porous material NMs, the complex is taken out after shaking for 3h-12h, and the fibrin @ MAs complex is washed by water to obtain the fibrin @ MAs complex.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053679A (en) * | 2007-04-17 | 2007-10-17 | 浙江大学 | Method for preparing polymer multiporous holder filled with fiber protein gel |
| CN101062430A (en) * | 2007-04-25 | 2007-10-31 | 韩春茂 | Collagen-chitosan / fibrin glue asymmetric bracket and the preparing method and the application thereof |
| CN107051398A (en) * | 2017-04-26 | 2017-08-18 | 浙江大学 | A kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film |
| WO2019025070A1 (en) * | 2017-07-31 | 2019-02-07 | Università Degli Studi Di Genova | A three-dimensional hydrogel scaffold for cell culturing and a method for the production thereof |
-
2022
- 2022-03-30 CN CN202210330385.2A patent/CN114805917B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053679A (en) * | 2007-04-17 | 2007-10-17 | 浙江大学 | Method for preparing polymer multiporous holder filled with fiber protein gel |
| CN101062430A (en) * | 2007-04-25 | 2007-10-31 | 韩春茂 | Collagen-chitosan / fibrin glue asymmetric bracket and the preparing method and the application thereof |
| CN107051398A (en) * | 2017-04-26 | 2017-08-18 | 浙江大学 | A kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film |
| WO2019025070A1 (en) * | 2017-07-31 | 2019-02-07 | Università Degli Studi Di Genova | A three-dimensional hydrogel scaffold for cell culturing and a method for the production thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王心如: "《中华医学百科全书.毒理学》", 31 March 2019, 中国协和医科大学出版社 * |
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