CN103290085A - Silk protein powder and preparation method thereof - Google Patents

Silk protein powder and preparation method thereof Download PDF

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Publication number
CN103290085A
CN103290085A CN2013101744777A CN201310174477A CN103290085A CN 103290085 A CN103290085 A CN 103290085A CN 2013101744777 A CN2013101744777 A CN 2013101744777A CN 201310174477 A CN201310174477 A CN 201310174477A CN 103290085 A CN103290085 A CN 103290085A
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silk
fibroin
liquid
solid content
sericin
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徐国文
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HUZHOU XINTIANSI BIO-TECH Co Ltd
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HUZHOU XINTIANSI BIO-TECH Co Ltd
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Abstract

The invention discloses silk protein powder and a preparation method thereof. The preparation method comprises the following steps of: (1) degumming silks; (2) performing enzymolysis on silk fibroins and sericin; (3) separating and purifying silk proteins; and (4) pre-concentrating and drying a silk protein liquid. The silk protein powder disclosed by the invention comprises sericin proteins and silk fibroin proteins, has the advantages of high purity, high biological activity, proper molecular weight, white color, zero foreign smell and the like and can be used for making biological and medical materials, health protection food and the like, and the aims of pure nature, high activity, high functionality, rich nutrition and the like are fulfilled.

Description

A kind of silk fibroin powder and preparation method thereof
Technical field
The present invention relates to a kind of silk fibroin powder and preparation method thereof.
Background technology
Fibroin comprises and contains silk fibroin and sericin, be rich in 18 seed amino acids, wherein the glycine of silk fibroin, L-Ala, Serine account for more than 70%, the polarity side group amino acid of sericin accounts for more than 73%, be functional outstanding natural nutrient substance, be widely used in biology, medicine, food, makeup, electronic material, leather and fabric etc.
China's silk resource is very abundant, for decades, many insighted scholars are engaged in silk development of resources research, and the time have research theory, article to deliver, but the fibroin product of domestic production so far is mainly fibroin powder, sericin powder and silk amino acid, because fibroin powder poorly water-soluble, sericin powder impurity height and silk amino acid molecular amount are too little, removing of smell substance and pigment is not thorough, biological activity is destroyed serious, and these product heavy metals, ash content height have hindered it greatly in Application for Field such as biology, medicine, food.
Summary of the invention
The objective of the invention is to overcome the deficiency of domestic silk fibroin powder on qualities such as purity, color and luster, peculiar smell and biological activity, a kind of better water-soluble and biological activity that has is provided, the silk fibroin powder of moderate molecular weight and sericin powder are captured the bottleneck that hinders the fibroin Application Areas.Utilize nutrition and the abundant biological activity of natural silk uniqueness, manufacturing has high nutrition, high reactivity and can generally be applied to field high quality raw material such as biology, medicine, food.
Another object of the present invention is to provide the preparation method of this silk fibroin powder.
For achieving the above object, the present invention has taked following technical scheme:
A kind of preparation method of silk fibroin powder comprises the steps:
(1) degumming technology of silk:
Figure 2013101744777100002DEST_PATH_IMAGE001
Soak silk more than 12 hours with tap water, pure water cleans 3-5 time, and except the assorted matter of dust, centrifuge dehydration detects water content, is convenient to the next procedure prescription;
Figure 385342DEST_PATH_IMAGE002
Press silk: the weight bath raio of water=1:6-10, silk and pure water are added high pressure come unstuck in the still, high-temperature steam is heated to and boils, and keeps 0.15-0.20 MPa vapor pressure, comes unstuck 0.5-1 hour, emits the silk gum aqueous solution.Sloughed 80% above silk gum this moment.Measure solid content.Pull fibroin out, water content is measured in centrifuge dehydration;
(2) enzymolysis of fibroin:
Press the weight ratio of shredded dried bean curd element or silk gum: pure water=1:20-30, pure water is added in fibroin or the silk gum, regulate solid-to-liquid ratio, and heat to 45-55 ℃, transfer pH value to 7.2 ± 2; Add Alcalase enzyme, constant temperature 45-60 minute, inactivation in the 0.30-0.5g/L ratio; Add Flavourzyme enzyme, constant temperature 45-60 minute, inactivation in the 0.1-0.3g/L ratio again;
(3) separation of fibroin, purifying:
Select for use Japan to produce fiber-reactive carbon decoloring method, press the 8-15% part by weight of solid content in the liquid, add the fiber-reactive charcoal, heat to 60-80 ℃, stirred 30-60 minute, filter; With PVDF or Ps hollow fiber ultrafiltration membrane, operation pressure is lower than 0.2MPa, and the ultrafiltration solid content is lower than 5%.Large molecular weight protein returns enzymolysis process after the ultrafiltration.
In the present technique step, can realize purpose of the present invention with common filtration unit and filtration process, those of ordinary skills can grasp this technology, and this point is not creation point of the present invention place yet.
But as preferred, related filtrate can be adopted the ultra-filtration membrane gas-vapor mix, the antipollution novel ultrafiltration membrane device of technology such as membrane element symmetry assembling back flushing, and mentioned ultra-filtration membrane gas-vapor mix, the antipollution novel ultrafiltration membrane device of technology such as membrane element symmetry assembling back flushing and the content of ultrafiltration membrane technique, be 200920122593.3 in the patent No., patent name is " ultra-filtration membrane self-stripping unit ultra-filtration membrane self-stripping unit ", the patent No. is 200920125178.3, patent name is " ultra-filtration membrane gas-vapor mix washing unit ", the patent No. is 200920191683.8, patent name is 200920125179.8 for " membrane element ultrasonic cleaning equipment " patent No., and patent name is at length open for having in " hollow fiber ultrafiltration membrane element ".
(4) pre-concentration of fibroin liquid and drying:
Target protein sees through liquid and carries out nanofiltration pre-concentration and desalination, and the nanofiltration membrane material adopts aromatic polyamide compound, molecular weight cut-off: 150---200KD; The nanofiltration membrane working pressure is 1 MPa--2.5 MPa, 4 times of concentration rates, and solid content is controlled at 12-15%;
Concentrated solution adopts spray drying technology, has selected hig h-speed centrifugal spray drying equipment for use.The control of liquid solid content at 12-15%, inlet temperature 180-210 ℃, temperature out 80-95 ℃, is namely made silk fibroin powder; The aluminium foil bag of packing into.
In this step, described hig h-speed centrifugal spray drying equipment is common equipment, the non-inventor's proprietary design.
The molecular weight 500-5000Da of the preparation-obtained silk fibroin powder of aforesaid method accounts for more than 85%, protein 〉=95%, moisture≤4%, ash content≤3%, lead≤0.5ppm, arsenic 0.3ppm, mercury 0.3ppm.
Compared with prior art, the present invention has following beneficial effect:
1. silk fibroin powder of the present invention has advantages such as purity height, biological activity height, molecular weight are moderate, white free from extraneous odour.Can be used for producing bioelectronics, medical material, protective foods etc., realize pure natural, active strong, functional excellence, purpose such as nutritious.
2, the present invention adopts enzymolysis production process science uniqueness.Compare with the conventional acid alkali hydrolysis method, have reaction temperature and easy to control, effective constituent is destroyed advantages such as few, environment friendly and pollution-free.
3. preparation technology of the present invention is simple, easy to operate, and applied range is effective;
4. separation, the purifying process advanced person of the present invention's employing are easy to control.Compare with technology such as used ion-exchange, separation efficiency height, time are short, the operation easy control of conforming to the principle of simplicity.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the related scope of embodiment.
Embodiment 1
A kind of preparation method of silk fibroin powder comprises the steps:
1, coming unstuck of silk:
(1) claims 100 kilograms of silks, with tap water silk was soaked 13 hours, clean 5 times with pure water again, dry with whizzer;
(2) press silk: the bath raio of water=1:6 (weight ratio), 100kg silk and 600kg pure water are added high pressure come unstuck in the still, high-temperature steam is heated to and boils, and keeps 0.15 MPa vapor pressure, emits silk gum liquid 522kg in 1 hour.Record solid content 4.99%, must do solid 26.05kg.The natural silk oven dry of taking out, claim dried solid 71kg.
2, the enzymolysis of fibroin:
Respectively silk gum liquid and fibroin are carried out enzymolysis:
Silk gum liquid 420kg puts into the enzymolysis still and heats to 45 ℃, transfers pH value to 7.2, and solid 0.3% by doing, ratio adds Flavourzyme enzyme (being enzyme-added 7.8g), constant temperature 45 minutes, inactivation.Add Alcalase enzyme (being enzyme-added 5.2g), constant temperature 45 minutes, inactivation by shredded dried bean curd fibroin 0.2% part by weight again; Claim sericin liquid 408kg.Sampling 100g is put the thermostat container oven dry, records solid content 6.1%, the actual about 24.9kg of sericin that contains.
Press the weight ratio of shredded dried bean curd element: pure water=1:30, the 71kg natural silk adds pure water 2130kg, heats to 45 ℃, transfers pH value to 7.2, and solid 0.3% by doing, ratio adds Flavourzyme enzyme (being enzyme-added 21.3g), constant temperature 45 minutes, inactivation.Add Alcalase enzyme (being enzyme-added 14.2), constant temperature 45 minutes, inactivation by plain 0.2% part by weight of shredded dried bean curd again; Claim silk protein liquid 2080kg.Sampling 100g is put the thermostat container oven dry, records solid content 3.25%, the actual about 67.6kg of silk fibroin that contains.
3, the separation of fibroin liquid, purifying:
The separation of sericin liquid, purifying:
Select for use Japan to produce the fiber-reactive charcoal.In the ratio of solid content 12%, add fiber-reactive charcoal 3kg, heat to 65 ℃, stirred 30 minutes, leach.Claim light yellow transparent liquid 354kg.Sampling 100g is put the thermostat container oven dry, records solid content 6.2%.Estimate sericin content 21.9kg.Use hollow fiber ultrafiltration membrane, intersection accuracy 10000Da; Destainer carried out circulating filtration 1.5 hours.The macromole sericin that does not see through is on a small quantity returned the enzymolysis operation carry out secondary enzymolysis.
The separation of silk protein liquid, purifying:
Select for use Japan to produce the fiber-reactive charcoal.In the ratio of solid content 12%, add fiber-reactive charcoal 8.1kg, heat to 65 ℃, stirred 30 minutes, leach.Claim light yellow transparent liquid 2016kg.Sampling 100g is put the thermostat container oven dry, records solid content 2.97%.Estimate silk fibroin content 59.9kg.Adopt the antipollution novel ultrafiltration membrane device of technology such as ultra-filtration membrane gas-vapor mix, membrane element symmetry assembling back flushing, use hollow fiber ultrafiltration membrane, intersection accuracy 10000 DaDestainer carried out circulating filtration 1.5 hours.The macromole silk fibroin that does not see through is on a small quantity returned the enzymolysis operation carry out secondary enzymolysis.
4, the pre-concentration of fibroin and drying:
Sericin liquid and silk protein liquid are carried out nanofiltration pre-concentration and desalination respectively, adopt the aromatic polyamide composite nanometer filtering film, molecular weight cut-off: 150--200KD; The nanofiltration membrane working pressure is 1.5 MPa, circulates 2 hours, gets solid content and be 14.5% sericin liquid 151kg.Solid content is 13.9% silk protein liquid 430kg.
Adopt spray drying technology, selected hig h-speed centrifugal spray drying equipment for use.Respectively sericin liquid and silk protein liquid are imported the spraying drying opening for feed by 304 stainless steel pipes, 190 ℃ of inlet temperatures, 95 ℃ of temperature outs, the real sericin powder 21.2kg that gets.Silk fibroin powder 56.4kg.Be respectively charged into aluminium foil bag.
Embodiment 2:
A kind of preparation method of silk fibroin powder comprises the steps:
1, coming unstuck of silk:
(1) claims 100 kilograms of silks, with tap water silk was soaked 14 hours, clean 5 times with pure water again, dry with whizzer;
(2) press silk: the bath raio of water=1:8 (weight ratio), 100kg silk and 800kg pure water are added high pressure come unstuck in the still, high-temperature steam is heated to and boils, and keeps 0.17 MPa vapor pressure, emits liquid in 0.6 hour, takes out silk gum liquid 518kg.Record solid content 4.94%, must do solid 25.6kg.The natural silk oven dry of taking out, claim dried solid 73kg.
2, the enzymolysis of fibroin:
Respectively silk gum liquid and fibroin are carried out enzymolysis:
Silk gum liquid 418kg puts into the enzymolysis still and heats to 45 ℃, transfers pH value to 7.2, and solid 0.4% by doing, ratio adds Flavourzyme enzyme (being enzyme-added 10.2g), constant temperature 45 minutes, inactivation.Add Alcalase enzyme (being enzyme-added 6.2g), constant temperature 45 minutes, inactivation by shredded dried bean curd fibroin 0.25% part by weight again; Claim sericin liquid 407kg.Sampling 100g is put the thermostat container oven dry, records solid content 5.9%, the actual about 24kg of sericin that contains.
Press the weight ratio of shredded dried bean curd element: pure water=1:30, the 73kg natural silk adds pure water 2190kg, heats to 50 ℃, transfers pH value to 7.3, and solid 0.4% by doing, ratio adds Flavourzyme enzyme (being enzyme-added 29.2g), constant temperature 50 minutes, inactivation.Add Alcalase enzyme (being enzyme-added 18.3g), constant temperature 55 minutes, inactivation by plain 0.25% part by weight of shredded dried bean curd again; Claim silk protein liquid 2155kg.Sampling 100g is put the thermostat container oven dry, records solid content 3.14%, the actual about 67.7kg of silk fibroin that contains.
3, the separation of fibroin liquid, purifying:
The separation of sericin liquid, purifying:
Select for use Japan to produce the fiber-reactive charcoal.In the ratio of solid content 10%, add fiber-reactive charcoal 3kg, heat to 65 ℃, stirred 30 minutes, leach.Claim light yellow transparent liquid 350kg.Sampling 100g is put the thermostat container oven dry, records solid content 6.18%.Estimate sericin content 21.6kg.Adopt the antipollution novel ultrafiltration membrane device of technology such as ultra-filtration membrane gas-vapor mix, membrane element symmetry assembling back flushing, use hollow fiber ultrafiltration membrane, intersection accuracy 10000 DaDestainer carried out circulating filtration 1.5 hours.The macromole sericin that does not see through is on a small quantity returned the enzymolysis operation carry out secondary enzymolysis.
The separation of silk protein liquid, purifying:
Select for use Japan to produce the fiber-reactive charcoal.In the ratio of solid content 10%, add fiber-reactive charcoal 6kg, heat to 70 ℃, stirred 40 minutes, leach.Claim light yellow transparent liquid 2070kg.Sampling 100g is put the thermostat container oven dry, records solid content 3%.Estimate shredded dried bean curd fibroin 61.2kg.Adopt the antipollution novel ultrafiltration membrane device of technology such as ultra-filtration membrane gas-vapor mix, membrane element symmetry assembling back flushing, use hollow fiber ultrafiltration membrane, intersection accuracy 10000 DaWhen destainer carries out circulating filtration 1.8.The macromole silk fibroin that does not see through is on a small quantity returned the enzymolysis operation carry out secondary enzymolysis.
4, the pre-concentration of fibroin and drying:
Sericin liquid and silk protein liquid are carried out nanofiltration pre-concentration and desalination respectively, adopt the aromatic polyamide composite nanometer filtering film, molecular weight cut-off: 150--200KD; The nanofiltration membrane working pressure is 1.5 MPa, circulates 2 hours, claims to such an extent that solid content is 14% sericin liquid 159kg.Solid content is 12.9% silk protein liquid 490kg.
Adopt spray drying technology, selected hig h-speed centrifugal spray drying equipment for use.Respectively sericin liquid and silk protein liquid are imported the spraying drying opening for feed by 304 stainless steel pipes, 190 ℃ of inlet temperatures, 95 ℃ of temperature outs, the real sericin powder 21.7kg that gets.Silk fibroin powder 58.0kg.Be respectively charged into aluminium foil bag.
Embodiment 3
A kind of preparation method of silk fibroin powder comprises the steps:
1, coming unstuck of silk:
(1) claims 100 kilograms of silks, with tap water silk was soaked 15 hours, clean 5 times with pure water again, dry with whizzer;
(2) press silk: the bath raio of water=1:9 (weight ratio), 100kg silk and 900kg pure water are added high pressure come unstuck in the still, high-temperature steam is heated to and boils, and keeps 0.19 MPa vapor pressure, emits liquid in 0.5 hour, takes out silk gum liquid 522kg.Record solid content 4.85%, must do solid 25.3kg.The natural silk oven dry of taking out, claim dried solid 70kg.
2, the enzymolysis of fibroin:
Respectively silk gum liquid and fibroin are carried out enzymolysis:
Silk gum liquid 422kg puts into the enzymolysis still and heats to 45 ℃, transfers pH value to 7.2, and solid 0.35% by doing, ratio adds Flavourzyme enzyme (being enzyme-added 8.6g), constant temperature 45 minutes, inactivation.Add Alcalase enzyme (being enzyme-added 7.6g), constant temperature 45 minutes, inactivation by shredded dried bean curd fibroin 0.3% part by weight again; Claim sericin liquid 405kg.Sampling 100g is put the thermostat container oven dry, records solid content 5.95%, the actual about 24.1kg of sericin that contains.
Press the weight ratio of shredded dried bean curd element: pure water=1:30, the 75kg natural silk adds pure water 2250kg, heats to 42 ℃, transfers pH value to 7.1, and solid 0.35% by doing, ratio adds Flavourzyme enzyme (being enzyme-added 26.3g), constant temperature 55 minutes, inactivation.Add Alcalase enzyme (being enzyme-added 22.5g), constant temperature 50 minutes, inactivation by plain 0.3% part by weight of shredded dried bean curd again; Claim silk protein liquid 2168kg.Sampling 100g is put the thermostat container oven dry, records solid content 3.0%, the actual about 65.0kg of silk fibroin that contains.
3, the separation of fibroin liquid, purifying:
The separation of sericin liquid, purifying:
Select for use Japan to produce the fiber-reactive charcoal.In the ratio of solid content 9%, add fiber-reactive charcoal 3.2kg, heat to 65 ℃, stirred 30 minutes, leach.Claim light yellow transparent liquid 363kg.Sampling 100g is put the thermostat container oven dry, records solid content 6.11%.Estimate sericin content 22.2kg.Adopt the antipollution novel ultrafiltration membrane device of technology such as ultra-filtration membrane gas-vapor mix, membrane element symmetry assembling back flushing, use hollow fiber ultrafiltration membrane, intersection accuracy 10000 DaDestainer carried out circulating filtration 1.5 hours.The macromole sericin that does not see through is on a small quantity returned the enzymolysis operation carry out secondary enzymolysis.
The separation of silk protein liquid, purifying:
Select for use Japan to produce the fiber-reactive charcoal.In the ratio of solid content 9%, add fiber-reactive charcoal 5.85kg, heat to 75 ℃, stirred 50 minutes, leach.Claim light yellow transparent liquid 2033kg.Sampling 100g is put the thermostat container oven dry, records solid content 2.84%.Estimate shredded dried bean curd fibroin 57.7kg.Adopt the antipollution novel ultrafiltration membrane device of technology such as ultra-filtration membrane gas-vapor mix, membrane element symmetry assembling back flushing, use hollow fiber ultrafiltration membrane, the hurdle cuts precision 10000 DaWhen destainer carries out circulating filtration 2.The macromole silk fibroin that does not see through is on a small quantity returned the enzymolysis operation carry out secondary enzymolysis.
4, the pre-concentration of fibroin and drying:
Sericin liquid and silk protein liquid are carried out nanofiltration pre-concentration and desalination respectively, adopt the aromatic polyamide composite nanometer filtering film, molecular weight cut-off: 150--200KD; The nanofiltration membrane working pressure is 1.5 MPa, circulates 2 hours, gets solid content and be 14.8% sericin liquid 150kg.Solid content is 12.9% silk protein liquid 490kg.
Adopt spray drying technology, selected hig h-speed centrifugal spray drying equipment for use.Respectively sericin liquid and silk protein liquid are imported the spraying drying opening for feed by 304 stainless steel pipes, 190 ℃ of inlet temperatures, 95 ℃ of temperature outs, the real sericin powder 21.6kg that gets.Silk fibroin powder 57.4kg.Be respectively charged into aluminium foil bag.

Claims (3)

1. the preparation method of a silk fibroin powder is characterized in that, comprises the steps:
(1) coming unstuck of silk:
Figure 792002DEST_PATH_IMAGE001
Soak silk more than 12 hours with tap water, pure water cleans 3-5 time, and except the assorted matter of dust, centrifuge dehydration detects water content, is convenient to the next procedure prescription;
Figure 990902DEST_PATH_IMAGE002
Press silk: the weight bath raio of water=1:6-10, silk and pure water are added high pressure come unstuck in the still, high-temperature steam is heated to and boils, keep the 0.15-0.20mPa vapor pressure, came unstuck 0.5-1 hour, emit the silk gum aqueous solution, slough 80% above silk gum this moment, measured solid content; Pull fibroin out, water content is measured in centrifuge dehydration;
(2) enzymolysis of fibroin:
Press the weight ratio of shredded dried bean curd element or silk gum: pure water=1:20-30, pure water is added in fibroin or the silk gum, regulate solid-to-liquid ratio, and heat to 45-55 ℃, transfer pH value to 7.2 ± 2; Add Alcalase enzyme, constant temperature 45-60 minute, inactivation in the 0.30-0.5g/L ratio; Add Flavourzyme enzyme, constant temperature 45-60 minute, inactivation in the 0.1-0.3g/L ratio again;
(3) separation of fibroin, purifying:
Select for use Japan to produce fiber-reactive carbon decoloring method, press the 8-15% part by weight of solid content in the liquid, add the fiber-reactive charcoal, heat to 60-80 ℃, stirred 30-60 minute, filter; With PVDF or Ps hollow fiber ultrafiltration membrane, operation pressure is lower than 0.2MPa, and the ultrafiltration solid content is lower than 5%; Large molecular weight protein returns enzymolysis process after the ultrafiltration;
(4) pre-concentration of fibroin and drying:
Target protein sees through liquid and carries out nanofiltration pre-concentration and desalination, and the nanofiltration membrane material adopts aromatic polyamide compound, molecular weight cut-off: 150--200KD; The nanofiltration membrane working pressure is 1 MPa--2.5 MPa, 4 times of concentration rates, and solid content is controlled at 12-15%;
Concentrated solution adopts spray drying technology, has selected hig h-speed centrifugal spray drying equipment for use; The control of liquid solid content at 12-15%, inlet temperature 180-210 ℃, temperature out 80-95 ℃, is namely made silk fibroin powder; The aluminium foil bag of packing into.
2. the preparation-obtained silk fibroin powder of the preparation method of the described silk fibroin powder of claim 1.
3. silk fibroin powder according to claim 2, it is characterized in that, described silk fibroin powder is silk fibroin or sericin powder, and the molecular weight 500-5000Da of silk fibroin or sericin accounts for more than 85%, protein 〉=95%, moisture≤4%, ash content≤3%, lead≤0.5ppm, arsenic 0.3ppm, mercury 0.3ppm.
CN2013101744777A 2013-05-13 2013-05-13 Silk protein powder and preparation method thereof Pending CN103290085A (en)

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CN105385728A (en) * 2015-12-21 2016-03-09 湖州新天丝生物技术有限公司 Co-production even-molecular-weight-distribution fibroin-polypeptide and sericin-polypeptide powder and preparing method thereof
CN105648008A (en) * 2016-01-04 2016-06-08 山东润牧生物科技有限公司 Feeding silk antibacterial peptide preparation and preparation method thereof
CN106632637A (en) * 2017-01-03 2017-05-10 王玲燕 Mulberry silk protein extraction method
CN106831939A (en) * 2017-01-03 2017-06-13 王玲燕 A kind of tussah silk protein extracting method
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CN110373889A (en) * 2019-06-25 2019-10-25 浙江理工大学 A kind of Degumming method of silk knitted fabric
CN110551192A (en) * 2019-09-16 2019-12-10 姚建林 extraction method of silk peptide protein
CN112042947A (en) * 2020-09-18 2020-12-08 广西绢麻纺织科学研究所有限公司 Silkworm cocoon silk fibroin-containing dietary fiber and preparation method and application thereof
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Publication number Priority date Publication date Assignee Title
CN104532365A (en) * 2015-01-15 2015-04-22 武汉纺织大学 Silk nanofiber manufacturing method
CN104532365B (en) * 2015-01-15 2016-04-27 武汉纺织大学 A kind of preparation method of silk nanofiber
CN105385728A (en) * 2015-12-21 2016-03-09 湖州新天丝生物技术有限公司 Co-production even-molecular-weight-distribution fibroin-polypeptide and sericin-polypeptide powder and preparing method thereof
CN105648008A (en) * 2016-01-04 2016-06-08 山东润牧生物科技有限公司 Feeding silk antibacterial peptide preparation and preparation method thereof
CN106632637A (en) * 2017-01-03 2017-05-10 王玲燕 Mulberry silk protein extraction method
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Application publication date: 20130911