CN1230548A - Catalytic circular preparation of fibroin peptide - Google Patents
Catalytic circular preparation of fibroin peptide Download PDFInfo
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- CN1230548A CN1230548A CN 98125855 CN98125855A CN1230548A CN 1230548 A CN1230548 A CN 1230548A CN 98125855 CN98125855 CN 98125855 CN 98125855 A CN98125855 A CN 98125855A CN 1230548 A CN1230548 A CN 1230548A
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Abstract
The present invention relates to the preparation of peptide. The catalytic circular preparation includes degreasing waste silk at 80-100 deg.c in reactor for 2-4 hr, degumming with 2-8% concentration Na2CO3 or NaHCO3 solution and catalytic hydrolysis of fibroin at 80-100 deg.c by adding catalyst liquid to obtain fibroin peptide. The catalyst liquid is compounded with 0.1-30% concentration acid solution and/or 0.1-55% concentration salt solution. Through regulating the ratio of acid to salt in catalyst liquid, the decomposition speed of fibroin and the molecular weight of fibroin peptide may be controlled. The preparation process has low cost and high product quality.
Description
The present invention is a kind of catalytic cycle preparation method of silk peptide, belongs to the amino acid whose manufacturing technology field of contracting more.
Silk peptide (peptide) is a kind of amino acid that contracts more.Silk peptide is a kind of new high-tech material of producing with silk as raw material.Pharmaceutically, can make artificial skin, reducing cholesterol and hangover medicine; In the weaving, can make vinylon-albumen blend fiber, textile finish; In the glasses industry, can make contact lens; In the electron trade, can make Biomimic sensor; In the daily chemical industry, can make nutritional type makeup, the foodstuff additive of antiultraviolet.
The preparation method of silk peptide can be classified as three types in the world: 1. acid-soluble method-with sulfuric acid or dissolving with hydrochloric acid fibroin; 2. inorganic salt such as salt-solution method-usefulness lithiumbromide, calcium chloride dissolve fibroins; 3. enzyme decomposition method-usefulness proteolytic enzyme catalytic decomposition fibroin.The acid-soluble method shortcoming is that product molecular weight distribution is too wide, wayward molecular weight.The salt-solution method shortcoming is too slow, the wayward quality product of speed of response.Enzyme decomposition method shortcoming is that difficulty is isolated proteolytic enzyme itself in the reaction product, is difficult to obtain pure product silk peptide.
The objective of the invention is to overcome general in the world silk peptide preparation method's shortcoming, provide a kind of new silk peptide preparation method, i.e. silk peptide catalytic cycle preparation method.
Silk peptide catalytic cycle preparation method of the present invention is:
Useless silk → removal of impurities (removal of impurities of carding form) → degreasing (high-temperature boiling) → (alkali the comes unstuck) → catalytic liquid of coming unstuck hydrolysis → filtration under diminished pressure → infiltration (from bag) → sedimentation → ion-exchange → silk peptide
The reaction formula of silk peptide preparation by catalytic circulation of the present invention is:
Below silk peptide preparation by catalytic circulation of the present invention is described in detail:
1, will put into reactor that clear water is housed through the useless silk of removal of impurities and boil degreasing in 2～4 hours through 80～100 ℃, then the water turned letter be dried the useless silk after the degreasing;
2, the useless silk after the above-mentioned degreasing is put into reactor again, adding concentration is 2～8% Na
2CO
3Or NaHCO
3Degumming agent came unstuck through 2～4 hours, removed described alkali lye then, and the drying of the silk after will coming unstuck, and at this moment useless silk becomes fibroin after degreasing is come unstuck;
3, in reactor, pour catalytic liquid into by 1: 10～50 bath raioes, described fibroin is put into reactor, obtain silk peptide with catalytic liquid hydrolysis fibroin after 5 minutes～70 hours, the catalytic hydrolysis reaction temperature is 80～100 ℃, described catalytic liquid is that one or both mixed preparing in the saline solution of 0.5～30% acid and 20～55% form by concentration, the ratio of mixture of acid and saline solution is determined that by the pH value of mixing solutions the variation range of pH value is PH1～6.Described acid is HCl or H
2SO
4, described salt is LiBr or CaCl
2Ratio, the decomposition rate of may command fibroin and the molecular weight of silk peptide by acid and salt in the adjusting catalytic liquid.
For example, when the catalytic hydrolysis reaction temperature is 80～100 ℃, during with 30%HCl hydrolysis fibroin, can finish hydrolysis reaction in 2～3 minutes, molecular weight be about 1000～2000 silk peptide; Use saturated CaCl
2During the hydrolysis fibroin, finish reaction in 50～70 hours, molecular weight be about 10000～30000 silk peptide.
By regulating in the above-mentioned catalytic liquid ratio of acid and saline solution, prepare various catalytic liquid.Catalytic liquid can be controlled the decomposition rate of fibroin and the molecular weight of silk peptide, and the preparation of catalytic liquid is core characteristics of the present invention.
Above-mentioned make the head product silk peptide by fibroin after, separate silk peptide through filtration under diminished pressure, infiltration, sedimentation, ion exchange method circulation again.The hole fineness difference of permeable membrane is the osmotic effect difference then, and the detailed rules and regulations separating effect is good more more for infiltration fenestra fineness (is 1000 as molecular weight), and productive rate is high more, and the thick more then separating effect of infiltration fenestra fineness (is 10000 as molecular weight) is poor more, and productive rate is low more.
The present invention adopts homemade osmotic bag, and described osmotic bag is prepared from pyroxylin (e) cement, and its volume is 50～5000ml (milliliter), and the infiltration temperature is 15～25 ℃, and penetration mode is a flowing-type.
Membrane separation technique is not good enough to small molecular weight object separating effect at present.In order to improve productive rate, the present invention partly is collected in macromolecule in the osmotic bag after permeation sepn, and partly uses molecular weight in effusive high post bottle settlement separate; Again molecular weight in the lower floor in the high post bottle partly is collected in infiltration again in the osmotic bag, at last small molecular weight part in upper strata in the high post bottle is obtained silk peptide with the ion exchange method separation.
The used ion-exchanger of described ion exchange method is cationic, as macropore weakly acidic resin D113-III, macropore strong acid resin D001MB etc.
The silk peptide total amount that makes through above-mentioned infiltration, sedimentation, ion exchange method is its product volume.Used catalytic liquid when separating silk peptide through distillation, concentrate and ion exchange method and be separated into water, salt, continues to recycle again.Thisly recycle the cycle characteristics that water, salt promptly are circulation methods of the present invention.
Embodiment 1:
Take by weighing the useless silk 250g that produce in Dongtai area, through put into after the removal of impurities reactor that clear water is housed through 90～100 ℃ boil 2 hours after, the water turned letter is dried the useless silk after the degreasing; Useless silk after the above-mentioned degreasing is put into reactor again, and adding concentration is 6% Na
2CO
3Degumming agent removes described alkali lye after coming unstuck in 3 hours, and the drying of the silk after will coming unstuck, and described useless silk becomes fibroin after degreasing is come unstuck; By 1: 15 bath raio, get the 3750ml catalytic liquid then, described catalytic liquid is 55%CaCl by concentration
2Form with 5%HCl, the pH value of its mixing solutions is PH3.Described catalytic liquid is poured in the 5000ml reactor, then above-mentioned fibroin is put into reactor, the catalytic hydrolysis reaction temperature is 95 ℃, reacts to obtain the head product silk peptide after 30 hours; Described silk peptide is put in the osmotic bag of making of pyroxylin (e) cement and is separated behind filtration under diminished pressure, and the osmotic bag volume is 4000ml, and the infiltration temperature is 20 ℃, and penetration mode is a flowing-type; Settlement separate through described high post bottle again, carry out ion-exchange with macropore weakly acidic resin D113-III and separate, obtain the elaboration silk peptide at last, its productive rate is 46.4%.
Use the said products as main raw material, add other subsidiary, can make multi-functional fleece fabrics finishing composition, it is respond well.
Embodiment 2:
Take by weighing the useless silk 300g that produce in Ningbo, Jiangsu area, through put into after the removal of impurities reactor that clear water is housed through 90～100 ℃ boil 4 hours after, the water turned letter is dried the useless silk after the degreasing; Useless silk after the above-mentioned degreasing is put into reactor again, and adding concentration is 3% Na
2CO
3Degumming agent removes described alkali lye after coming unstuck in 2.5 hours, and the drying of the silk after will coming unstuck, and described useless silk becomes fibroin after degreasing is come unstuck; By 1: 15 bath raio, get the 4500ml catalytic liquid then, described catalytic liquid is 55%CaCl by concentration
2Form with 5%HCl, the pH value of its mixing solutions is PH6.Described catalytic liquid is poured in the 10000ml reactor, then above-mentioned fibroin is put into reactor, the catalytic hydrolysis reaction temperature is 95 ℃, reacts to obtain the head product silk peptide after 60 hours; Described silk peptide is put into behind filtration under diminished pressure in the osmotic bag of making of pyroxylin (e) cement and is separated, and the infiltration temperature is 20 ℃, and penetration mode is a flowing-type; Settlement separate through described high post bottle again, carry out ion-exchange with macropore weakly acidic resin D113-III and separate, obtain the elaboration silk peptide at last, its productive rate is 80%.
Use the said products as main raw material, add other auxiliary material, can make a mao eyeball fabric antipilling finishing agent, it is respond well.
Embodiment 3:
Take by weighing the useless silk 100g that produce in Yantai, Shandong area, through put into after the removal of impurities reactor that clear water is housed through 90～100 ℃ boil 4 hours after, the water turned letter is dried the useless silk after the degreasing; Useless silk after the above-mentioned degreasing is put into reactor again, and adding concentration is 5% NaHCO
3Degumming agent removes described alkali lye after coming unstuck in 3.5 hours, and the drying of the silk after will coming unstuck, and described useless silk becomes fibroin after degreasing is come unstuck; By 1: 15 bath raio, get the 1500ml catalytic liquid and pour in the 2000ml reactor then, described catalytic liquid is 55%CaCl by concentration
2Form with 5%HCl, the pH value of its mixing solutions is PH4; Then above-mentioned fibroin is put into reactor, the catalytic hydrolysis reaction temperature is 98 ℃, reacts to obtain the head product silk peptide after 50 hours; Described silk peptide is put into behind filtration under diminished pressure in the osmotic bag of making of pyroxylin (e) cement and is separated, the infiltration temperature is 20 ℃, penetration mode is a flowing-type, settlement separate through described high post bottle again, carrying out ion-exchange with macropore strong acid resin D001MB separates, obtain the elaboration silk peptide at last, its productive rate is 60%.
Use the said products as main raw material, add other subsidiary, can make, its refractive index reaches about about 1.7.
Preparation by catalytic circulation of the present invention becomes useful thing to the waste material of Silk Industry. Catalysis of the present invention Round-robin method is compared with above-mentioned other method, and production cost is low, good product quality, good economical benefit. Should Produce the silk peptide non-environmental-pollution with this method, obtain green product, and the reusable edible resource. With The multi-functional fleece fabrics finishing agent that the elaboration silk peptide that this method makes is made as main material, hair eyeball are knitted Thing antipilling finishing agent and contact lenses material are all obtained good result.
Claims (5)
1, a kind of catalytic cycle preparation method of silk peptide is characterized in that described method is:
(1), will put into reactor that clear water is housed through the useless silk of removal of impurities and boil degreasing in 2～4 hours through 80～100 ℃, then the water turned letter is dried the useless silk after the degreasing;
(2), the useless silk after the above-mentioned degreasing is put into reactor again, adding concentration is 2～8% Na
2CO
3Or NaHCO
3Degumming agent came unstuck through 2～4 hours, removed described alkali lye then, and the drying of the silk after will coming unstuck, and at this moment useless silk becomes fibroin after degreasing is come unstuck;
(3), in reactor, pour catalytic liquid into by 1: 10～50 bath raioes, described fibroin is put into reactor, obtain silk peptide with catalytic liquid hydrolysis fibroin after 5 minutes～70 hours, the catalytic hydrolysis reaction temperature is 80～100 ℃, described catalytic liquid is that one or both mixed preparing in the saline solution of 0.5～30% acid and 20～55% form by concentration, the ratio of mixture of acid and saline solution is determined that by the pH value of mixing solutions the variation range of pH value is PH1～6; Described acid is HCl or H
2SO
4, described salt is LiBr or CaCl
2By the ratio of acid and salt in the adjusting catalytic liquid, control the decomposition rate of fibroin and the molecular weight of silk peptide.
2, by the described method of claim 1, it is characterized in that described silk peptide again through the separation that circulates of filtration under diminished pressure, infiltration, sedimentation, ion exchange method, the osmotic bag of described infiltration usefulness is prepared from pyroxylin (e) cement, its volume is 50～5000ml, the infiltration temperature is 15～25 ℃, and penetration mode is a flowing-type.
3, by the described method of claim 2, it is characterized in that after permeation sepn, partly be collected in macromolecule in the osmotic bag, and partly use high post bottle settlement separate molecular weight in effusive, again molecular weight in the lower floor in the high post bottle partly is collected in infiltration again in the osmotic bag, at last small molecular weight part in upper strata in the high post bottle is obtained silk peptide with the ion exchange method separation.
4, by the described method of claim 3, it is characterized in that the used ion-exchanger of described ion exchange method is cationic, as macropore weakly acidic resin D113-III, macropore strong acid resin D001MB etc.
5, by claim 2 or 3 or 4 described methods, used catalytic liquid when it is characterized in that separating silk peptide through distillation, concentrate and ion exchange method and be separated into water, salt, continues to recycle again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125855A CN1099424C (en) | 1998-12-22 | 1998-12-22 | Catalytic circular preparation of fibroin peptide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125855A CN1099424C (en) | 1998-12-22 | 1998-12-22 | Catalytic circular preparation of fibroin peptide |
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| CN1230548A true CN1230548A (en) | 1999-10-06 |
| CN1099424C CN1099424C (en) | 2003-01-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98125855A Expired - Fee Related CN1099424C (en) | 1998-12-22 | 1998-12-22 | Catalytic circular preparation of fibroin peptide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002076487A1 (en) * | 2001-03-21 | 2002-10-03 | Aminogen Co., Ltd. | Anticancer agents containing antigenotoxic and immunostimulative peptides produced from the hydrolysate of silkworm cocoon |
| CN107216376A (en) * | 2017-07-28 | 2017-09-29 | 浙江理工大学 | A kind of extracting method of tussah silk fibroin |
| CN112409469A (en) * | 2020-11-04 | 2021-02-26 | 付俊 | Extraction method of silk peptide |
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| RU2013153535A (en) | 2011-05-04 | 2015-06-10 | Орбит Элюминэ Инк. | METHODS FOR RARE EARTH EXTRACTION FROM VARIOUS ORE |
| JP2014519468A (en) | 2011-06-03 | 2014-08-14 | オーバイト アルミナ インコーポレイテッド | Method for preparing hematite |
| EP2755918A4 (en) | 2011-09-16 | 2015-07-01 | Orbite Aluminae Inc | Processes for preparing alumina and various other products |
| CN104302791B (en) | 2012-01-10 | 2017-03-15 | 奥佰特氧化铝有限公司 | Method for processing red mud |
| JP2015518414A (en) | 2012-03-29 | 2015-07-02 | オーバイト アルミナ インコーポレイテッドＯｒｂｉｔｅ Ａｌｕｍｉｎａｅ Ｉｎｃ． | Fly ash treatment process |
| MY175471A (en) | 2012-07-12 | 2020-06-29 | Orbite Tech Inc | Processes for preparing titanium oxide and various other products |
| JP2015535886A (en) | 2012-09-26 | 2015-12-17 | オーバイト アルミナ インコーポレイテッドＯｒｂｉｔｅ Ａｌｕｍｉｎａｅ Ｉｎｃ． | Process for preparing alumina and magnesium chloride by HCl leaching of various materials |
| AU2013344721A1 (en) | 2012-11-14 | 2015-07-02 | Orbite Aluminae Inc. | Methods for purifying aluminium ions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019808B (en) * | 1990-10-31 | 1992-12-30 | 上海丝织地毯厂 | Extract the method for silk-protein from carpet leftover bits and pieces waste silk |
| JP2615440B2 (en) * | 1995-01-27 | 1997-05-28 | 農林水産省蚕糸・昆虫農業技術研究所長 | Method for producing fine powder of silk fibroin |
| CN1061685C (en) * | 1995-05-24 | 2001-02-07 | 复旦大学 | Regenerated silk protein and complex material thereof for fixation of enzyme and bio-active substance |
-
1998
- 1998-12-22 CN CN98125855A patent/CN1099424C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002076487A1 (en) * | 2001-03-21 | 2002-10-03 | Aminogen Co., Ltd. | Anticancer agents containing antigenotoxic and immunostimulative peptides produced from the hydrolysate of silkworm cocoon |
| CN107216376A (en) * | 2017-07-28 | 2017-09-29 | 浙江理工大学 | A kind of extracting method of tussah silk fibroin |
| CN112409469A (en) * | 2020-11-04 | 2021-02-26 | 付俊 | Extraction method of silk peptide |
| CN112409469B (en) * | 2020-11-04 | 2023-09-26 | 付俊 | Extraction method of silk peptide |
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| CN1099424C (en) | 2003-01-22 |
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