CN112442190A - Preparation method of silk nano material - Google Patents
Preparation method of silk nano material Download PDFInfo
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- CN112442190A CN112442190A CN201910805365.4A CN201910805365A CN112442190A CN 112442190 A CN112442190 A CN 112442190A CN 201910805365 A CN201910805365 A CN 201910805365A CN 112442190 A CN112442190 A CN 112442190A
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Abstract
The invention discloses a preparation method of a silk nano material. Rapidly stirring degummed silk in a solvent composition containing potassium hydroxide, urea, water and the like at normal temperature to uniformly disperse the silk in the solution, and then separating and ultrasonically treating the silk to obtain uniformly dispersed silk nano fibers/particles. The invention has simple process, higher yield of the silk nano-fiber/particle, and good stability of the silk nano-fiber/particle solution, and is convenient for storage and transportation. The silk nano-fiber/particle has wide application prospect in various fields such as textile, biomedical materials and the like.
Description
Technical Field
The invention relates to a preparation method of a silk nano material, belonging to the technical field of natural polymer nano material preparation.
Background
The silk is one of the earliest utilized proteins of human beings, has good hygroscopicity and excellent luster, and is popular among people. With the continuous and intensive research on the method, the utilization field of the method is also continuously widened and gradually extends to the fields of food fermentation, biological pharmacy, energy utilization and the like. To utilize silk fibroin, it is first necessary to reduce the size of silk fibroin to the micrometer or nanometer level. The silk nano material can be prepared in two modes of top-down and bottom-up. The bottom-up method comprises the steps of using a fibroin solution, combining ultrasonic treatment, shearing treatment and other external mechanical treatment, and self-assembling to form the protein nanofiber, wherein the typical width of the protein nanofiber is 3-70 nm, and the thickness of the protein nanofiber is more than 1 nm. In this method, degummed silk is first dissolved by different solvents, breaking the hydrogen bonds between the fibroin molecules, such as inorganic salt solutions (lithium bromide aqueous solution (adv. mater.2017,29,1702769.), and calcium chloride/ethanol/aqueous solution (sci. rep.2017,7,2107)), concentrated acids (adv. sci.2017,4,1700191.), and ionic liquids (j.phys. chem.b 2017,121, 6108-. The structure of the regenerated silk nanofiber is different from that of natural silk along with the damage of the original fiber structure in the silk dissolving process. Thus, the properties of materials made from silk nanofibers are often inferior to natural silk. Furthermore, achieving well dispersed silk nanofiber solutions remains a challenge. On the other hand, the top-down approach involves the incomplete dissolution of silk using weaker solvents such as hydrochloric acid/formic acid (mater. sci. eng., C2015, 48, 444-. For example, silk nanofibers from formic acid-calcium chloride solvent systems cannot be kept in solution in an all water environment. Silk nanofiber suspensions obtained from formic acid-lithium bromide solvent systems must be stored at 4 ℃ before use to avoid gelation, while hexafluoroisopropanol is a toxic solvent and harmful to the ecological environment. 3g of degummed Silk is added into sodium hydroxide/urea solution precooled to-12 ℃ in Single Molecular Layer of Silk Nano Basic Building Block of Silk Materials (ACS Nano 2018,12, 11860-containing 11870), and dialyzed to be neutral after multiple times of freezing and thawing, and then ultrasonic treatment is carried out to obtain a Silk nanofiber solution with uniform dispersion, but the prepared Silk nanofiber does not exceed 55 percent of the total amount of the added Silk at most. Moreover, such freezing-thawing to peel the silk fibers is time-consuming and energy-consuming, and is not suitable for mass production, and thus is difficult to be practically applied.
Disclosure of Invention
The invention aims to solve the problems in the prior art and aims to provide a method for preparing silk nano fibers/particles. The scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of silk nano-fiber/particle comprises the following steps:
(1) preparing a potassium hydroxide/urea/thiourea aqueous solution, wherein the concentration of the potassium hydroxide is 5 wt% -50 wt%, and more preferably 5 wt% -30 wt%; the concentration of urea is 0 wt% -40 wt%, more preferably 4 wt% -30 wt%; the concentration of the thiourea is 0 wt% -the maximum concentration of the thiourea which can be dissolved, and more preferably 0-10%;
(2) cooling the mixed solution prepared in the step (1) to below 30 ℃, adding degummed silk, and quickly stirring to uniformly disperse the silk;
(3) replacing the solvent in the uniformly dispersed mixed solution obtained in the step (2) with deionized water until the pH value of the dispersed silk is neutral;
(4) and (4) performing ultrasonic treatment on the silk solution with the neutral pH value in the step (3) to uniformly disperse the silk solution to obtain light blue silk nanofiber/particle solution.
Preferably, the ratio of potassium hydroxide in step (1): the mass concentration ratio of the urea is 1: 2-2: 1, and the total concentration of the potassium hydroxide and the urea is more than 20%, and more preferably more than 30%.
Preferably, the stirring time in the step (2) is 1min to 48h, more preferably 10min to 12 h.
Preferably, the separation method in step (2) includes dialysis, filtration, ultracentrifugation, and the like.
Preferably, in the step (4), a cell disruptor is adopted for ultrasonic treatment, and the power is 100-1200w, preferably 100-600 w; the ultrasonic treatment time is not more than 6h, and more preferably 10 min-2 h.
Preferably, the silk nanofiber/particle solution obtained in step (4) is stored at 4 ℃.
Preferably, the mass of the silk added in the step (2) is 1-12% of the mass of the mixed solution, and more preferably 1-8%.
Preferably, the conversion rate of the nano fibers/particles in the finally obtained silk nano/particle fiber solution is 50-100%.
Compared with the prior art, the preparation method of the silk nanofiber provided by the invention has the beneficial effects that:
the invention adopts a potassium hydroxide/urea/thiourea solvent system, silk is dispersed in the solution at normal temperature through mechanical stirring, the uniformly dispersed silk nano fiber/particle solution is prepared through separation and ultrasound, the ultrasound power is increased to a certain range, and the silk nano fiber can be further dispersed into a nano particle form.
2 the method used by the invention is simple, safe, environment-friendly, low in investment and low in cost, and the prepared silk nanofiber/particle has high conversion rate, and is suitable for mass production.
Drawings
FIG. 1 is a light test of the silk nanofiber solution obtained in example 8, wherein the Tyndall effect can be clearly seen;
FIG. 2 is an atomic force microscope image of the silk nanofiber solution obtained in example 8 diluted to a concentration of ten-thousandth, and obvious silk nanofibers can be seen;
FIG. 3 is an atomic force microscope image of the silk nanoparticle solution obtained in example 23 diluted to a concentration of ten-thousandth, showing that silk nanoparticles having a relatively uniform size are observed.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1:
adding 1g of silk raw material into a 2 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring for 24h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 600w for 30min to give a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers in the obtained solution to be five per thousand by using a weighing method. The total mass of the silk nanofibers therein was calculated from the total mass of the solution after sonication, and then the conversion of the nanofibers was calculated as 53% by dividing the total mass of the silk nanofibers by the mass of the initially added silk.
Example 2:
adding 1g of silk raw material into a 4 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring for 24h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 600w for 30min to give a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be five per thousand by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 58%.
Example 3:
adding 1g of silk raw material into 100g of 8 wt% potassium hydroxide/20 wt% urea solution, quickly stirring at room temperature for 24h to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 600w for 30min to give a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be eight thousandths of the total weight by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 66%.
Example 4:
adding 3g of silk raw material into 100g of 8 wt% potassium hydroxide/10 wt% urea/10 wt% thiourea solution, rapidly stirring at room temperature for 12h to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 400w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be eight thousandths of the total weight by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 56%.
Example 5:
adding 3g of silk raw material into 100g of 8 wt% potassium hydroxide/20 wt% urea solution, rapidly stirring at room temperature for 12h to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to neutrality. Then transferred to a beaker and sonicated in a cell disruptor at 400w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the obtained silk nanofiber by a weighing method to be one percent. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 65%.
Example 6:
adding 3g of silk raw material into a 15 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring for 3h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the obtained silk nanofiber by a weighing method to be one percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 82%.
Example 7:
adding 4g of silk raw material into a 20 wt% potassium hydroxide/10 wt% urea/10 wt% thiourea solution with the total mass of 100g, rapidly stirring for 2h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be twelve thousandths by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 75%.
Example 8:
adding 4g of silk raw material into a 20 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring for 1h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing the silk fiber solution with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be fifteen thousandths by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 80%.
Example 9:
adding 5g of silk raw material into a 25 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring for 0.5h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 85%.
Example 10:
adding 5g of silk raw material into a 35 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring at room temperature for 20min to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 90%.
Example 11:
adding 8g of silk raw material into 40 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring at room temperature for 10min to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be three percent by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 90%.
Example 12:
adding 5g of silk raw material into a 20 wt% potassium hydroxide/30 wt% urea solution with the total mass of 100g, rapidly stirring at room temperature for 10min to obtain a uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 95%.
Example 13:
adding 4g of silk raw material into a 20 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring at room temperature for 30min to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 75%.
Example 14:
adding 4g of silk raw material into 20 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring at room temperature for 10min to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be fifteen thousandths by using a weighing method. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 68%.
Example 15:
adding 3g of silk raw material into 20 wt% potassium hydroxide/15 wt% urea solution with the total mass of 100g, rapidly stirring for 1h at room temperature to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be fifteen thousandths by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 80%.
Example 16:
adding 3g of silk raw material into a 20 wt% potassium hydroxide/10 wt% urea solution with the total mass of 100g, rapidly stirring for 1h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing the silk fiber solution with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be eight thousandths of the total weight by using a weighing method. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 70%.
Example 17:
adding 3g of silk raw material into 20 wt% potassium hydroxide/5 wt% urea solution with the total mass of 100g, rapidly stirring for 1h at room temperature to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be five per thousand by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 60%.
Example 18:
adding 3g of silk raw material into a 15 wt% potassium hydroxide/15 wt% urea solution with the total mass of 100g, rapidly stirring at room temperature for 30min to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be fifteen thousandths by using a weighing method. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 78%.
Example 19:
adding 4g of silk raw material into a 15 wt% potassium hydroxide/20 wt% urea solution with the total mass of 100g, rapidly stirring for 1h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing the silk fiber solution with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be seventeen thousandth by using a weighing method. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 86%.
Example 20:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 1h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be seventeen thousandth by using a weighing method. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 81%.
Example 21:
adding 6g of silk raw material into 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 2h at room temperature to obtain uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. The total mass of the silk in the silk nanofiber solution was calculated according to the total volume, and then the conversion rate of the nanofibers was calculated to be 89%.
Example 22:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 100%.
Example 23:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 600w for 30min to give a light blue silk nanoparticle solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the obtained silk nanoparticles to be two percent by using a weighing method. And calculating the total mass of the silk in the silk nanoparticle solution according to the total volume, and then calculating the conversion rate of the nanoparticles to be 100%.
Example 24:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred into a beaker and sonicated in a cell disruptor at a power of 800w for 30min to obtain a light blue silk nanoparticle solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the obtained silk nanoparticles to be two percent by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nano particles to be 100%.
Example 25:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred into a beaker and sonicated in a cell disruptor at 1000w power for 30min to obtain a light blue silk nanoparticle solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the obtained silk nanoparticles to be two percent by using a weighing method. And calculating the total mass of the silk in the silk nanoparticle solution according to the total volume, and then calculating the conversion rate of the nanoparticles to be 100%.
Example 26:
adding 10g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring the silk fiber solution into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred into a beaker and sonicated in a cell disruptor at 1000w power for 30min to obtain a light blue silk nanoparticle solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the obtained silk nanoparticles to be two percent by using a weighing method. And calculating the total mass of the silk in the silk nanoparticle solution according to the total volume, and then calculating the conversion rate of the nanoparticles to be 100%.
Example 27:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, and washing by an ultracentrifugation method until the dispersed silk fiber solution is neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 100%.
Example 28:
adding 6g of silk raw material into a 15 wt% potassium hydroxide/25 wt% urea solution with the total mass of 100g, rapidly stirring for 6h at room temperature to obtain a uniformly dispersed silk fiber solution, and washing by using a filtering method until the dispersed silk fiber solution is neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers by using a weighing method to be two percent. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 100%.
Example 29:
adding 4g of silk raw material into a 20 wt% potassium hydroxide/5 wt% thiourea solution with the total mass of 100g, rapidly stirring for 2h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be twelve thousandths by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 56%.
Example 30:
adding 4g of silk raw material into a 20 wt% potassium hydroxide/8 wt% thiourea solution with the total mass of 100g, rapidly stirring for 2h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be twelve thousandths by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 63%.
Example 31:
adding 4g of silk raw material into a 20 wt% potassium hydroxide/10 wt% thiourea solution with the total mass of 100g, rapidly stirring for 2h at room temperature to obtain a uniformly dispersed silk fiber solution, transferring into a dialysis bag, and dialyzing with deionized water to be neutral. Then transferred to a beaker and sonicated in a cell disruptor at 300w power for 30min to obtain a light blue silk nanofiber solution. The resulting solution was centrifuged at 8000r/min, and the supernatant liquid was poured into a jar and stored in a refrigerator at 4 ℃ under sealed conditions. And (3) taking part of the solution for freeze-drying, and calculating the content of the silk nano-fibers to be twelve thousandths by using a weighing method. And calculating the total mass of the silk in the silk nanofiber solution according to the total volume, and then calculating the conversion rate of the nanofiber to be 72%.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (6)
1. A preparation method of a silk nano material is characterized by comprising the following steps:
(1) preparing a potassium hydroxide/urea/thiourea aqueous solution, wherein the concentration of potassium hydroxide is 5-50 wt%, the concentration of urea is 0-40 wt%, and the concentration of thiourea is 0-10 wt%;
(2) cooling the mixed solution prepared in the step (1) to below 30 ℃, adding degummed silk, and quickly stirring to uniformly disperse the silk;
(3) replacing the solvent in the uniformly dispersed mixed solution obtained in the step (2) with deionized water until the pH value of the dispersed silk is neutral;
(4) and (4) performing ultrasonic treatment on the silk solution with the neutral pH value in the step (3) to uniformly disperse the silk solution to obtain light blue silk nanofiber/particle solution.
2. The method according to claim 1, wherein in the step (1), the ratio of potassium hydroxide: the concentration ratio of the urea is 1: 2-2: 1, and the total concentration of the potassium hydroxide and the urea is more than 20%.
3. The method according to claim 1, wherein the stirring time in step (2) is 1min to 48 hours.
4. The preparation method as claimed in claim 1, wherein the step (4) is carried out by using a cell disruptor with a power of 100 and 1200w and a sonication time of not more than 6 h.
5. The method according to claim 1, wherein the silk added in the step (2) accounts for 1-12% of the mixed solution.
6. The method according to claim 1, wherein the nanofiber/particle conversion rate of the finally obtained silk nanofiber solution is 50-100%.
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| JPS6455191A (en) * | 1987-08-27 | 1989-03-02 | Norinsuisansho Sanshi Shikenjo | Production of ultrafine powder of silk protein |
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