GB2220946A - Method of producing free epsilon-polylysine - Google Patents
Method of producing free epsilon-polylysine Download PDFInfo
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- GB2220946A GB2220946A GB8915565A GB8915565A GB2220946A GB 2220946 A GB2220946 A GB 2220946A GB 8915565 A GB8915565 A GB 8915565A GB 8915565 A GB8915565 A GB 8915565A GB 2220946 A GB2220946 A GB 2220946A
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- United Kingdom
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- solution
- polylysine
- cpolylysine
- exchange resin
- producing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Polyamides (AREA)
- Peptides Or Proteins (AREA)
Description
2220946 1 METHOD OF PRODUCING FREE E-POLYLYSINE The present invention
relates to a method of producing free c-polylysine.
It is known that E-polylysine is obtained, e. g., by cultivating Streptomyces albulus subsE. lysinopolymerus No. 346 as described in Japanese Laid-Open Patent Publication No. 53- 72896/1978.
As represented by the following formula, the above substance is a polymer of L-lysine and a high-molecular weight compound in which amino groups of c-position of L- lysine fc.-m peptide bonds to adjacent carboxyl groups of L-lysine on its straight chain.
H NH-(CH) -CH-CO OH 2 4 1 t NH 2 tn As the substance is a polymer of L-lysine which is an essential amino acid, it is usable in safety and it has a particular property of matter because it has many amino groups. By using these properties, the application of the substance to toiletries, cosmeticsi feed additives, agricultural chemicals, food additives, electronic materials and the like is progressed.
A conventional method of producing c-polylysine is as follows. Namely, after separating micro-organisms from a 25 culture broth of E-polylysine, the pH value of the cul- 2 tur broth is adjusted to 8.5 by adding an alkaline solution, the mixed solution is passed through a weakly acidic cation exchange resin, and e- polylysine is ad-sorbed to the resin. The resin is washed with water, and c-polylysine is eluted from the resin with 0.1 N hydrochloric acid. The collected eluate is concentrated and decolorized by active carbon, and then e-polylysine is precipitated by adding a solvent such as methanol, acetone, etc.. e-Polylysine prepared by the above method from the culture broth is the salt of hydrochloride of c-polylysine.
However, it is also required to supply free e-polylysine to the fields of pharmaceutical, food additives, agricultural chemicals, etc.
Hitherto, a method of producing free e-polylysine from an e-polylysine culture broth, an acidic salt (ex. sulfate, hydrochloride, nitrate or phosphate) of epolylysine or a solution thereof is unknown. An object of the present invention is to efficiently produce this free c-polylysine on an industrial scale.
Further, when c-polylysine is eluted from a cation exchange resin in the above conventional method, the elution should be conducted with an acidic water solution. As a result, e-polylysine is obtained as acidic salt by a precipitation with a solvent, freezedrying or spray drying. The acidic salt of e-polylysine has no problem when it is used as a water solution. However, owing to the poor solubility in an organic solvent, the acidic salt can not be used as alcohol preparations for preserving food by dissolving in ethyl alcohol. For increasing the solubility in ethyl alcohol, e-polylysine should be free c- polylysine.
The object of the present invention is to overcome these problems by using a basic anion exchange resin or an acidic cation exchange resin and provides a method of 3 producing free C-polylysine on an industrial scale, efficiently.
The present invention provides a method of producing free E-polylysine, comprising passing an e-polylysine solution, preferably a solution of acidic salt of epolylysine or a solution obtained by removing microorganisms from a culture broth of E-polylysine through a basic anion exchange resin, and treating the collected solution in a process selected from the group consisting of precipitation in an organic solvent, freeze-drying and spray drying to obtain free c-polylysine.
Further, the present invention provides a method of producing free cpolylysine, comprising passing an epolylysine solution through an acidic cation exchange resin to adsorb c-polylysine to the resin, eluting epolylysine with an alkaline solution from the resin, removing excess alkali in the solution with an ultrafiltration membrane, and treating the solution in a process selected from the group consisting of precipitation in an organic solvent, freeze-drying and spray drying to obtain free cpolylysine.
The solution of acidic salt of e-polylysine which is used in the present invention is preferably a purified culture broth of C-polylysine which is treated with a cation exchange resin, an ultrafiltration membrane or the like. Acidic salts such as sulfate, hydrochloride, nitrate, phosphate, etc. can be exemplified. Further, the culture broth of e-polylysine can be used as it is.
Either weakly or strongly basic anion exchange resin can be used, and the strongly basic anion exchange resin is preferred. Either weakly or strongly acidic cation exchange resin can be used, and the weakly acidic cation exchange resin is preferred. 35 As an alkaline solution, a solution contains cation 4 which can be exchanged with E-polylysine and has a hydroxyl group derived from sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide and the like. 5 An ultrafiltration membrane which penetrates an alkaline solution and does not penetrate C-polylysine can be used, and it preferably is a membrane of cut-off molecular weight about 1000. In the process for preparing free E-polylysine, by using the quantity of the basic anion exchange resin able to exchange anion of equivalent weight or above for cpolylysine, in an c-polylysine solution such as an cpolylysine acidic solution or an E-polylysine culture broth, anion is exchanged by reacting with the resin of a column type or a batch type. The produced free cpolylysine is precipitated in an organic solvent, freeze-dried or spray dried.
In the process for preparing free E-polylysine, by using the quantity of the acidic cation exchange resin able to exchange cation of equivalent weight or above for c-polylysine, an E-polylysine solution is reacted with the resin of a column type or a batch type and cpolylysine is adsorbed on the resin. Then, c-polylysine is eluted from the resin with an alkaline solution, the eluted solution is treated with an ultrafiltration membrane to remove excess alkali. c-Polylysine is then obtained by precipitation in an organic solventr freezedrying or spray drying.
The merit of the invention is that free c-polylysine can be industrially and efficiently produced by a simple operation at a low cost and provided in fields of food additives, agricultural chemicals, phermaceutical and the like.
The following examples illustrate this invention more specifically, but these will not always be precise in M&C FOLIO: 230P58979 WANGDOC: 0868i practical applications. Example I One liter of wet basic anion exchange resin of Amber-lite@ IRA-402 (a trimethyl ammonium groupcontaining resin, OH_ Lype) was charged in a column, 1000 ml of 5% c-polylysine hydrochloride solution was passed through the column at a: flow rate of SV=0.2. Then, 1000 ml of distilled water was passed through the column at the same flow rate. 2000 ml of the passed liquid was collected and freeze-dried and 35.0 g of free c- polylysine was obtained. The chlorine content of the producL was less than 0.1%. Example 2 SLreptomyces albulus was cultured in a mini jarfermenter for 96 hours, the broth was filtered and 2.0 liters of the filtrate was obtained. The c- polylysine concentration of the filtrate was 8.07 g/l.
1.0 liter of the filtrate was adjusted to the pH value of 8.5 and filtered. The filtrate was passed through the column containing 200 ml of a weakly acidic cation exchange resin of Amberlite(D (a carboxy groupcontaining resin) (H type) at a flow rate of SV=I, and c=polylysine was adsorbed to the cation exchange resin. The resin was washed with 800 ml of 0.2 N acetic acid solution, and then with 800 ml of distilled water (the both flow rates were SV=2). Then, 1000 ml of 0.1 N hydrochloric acid solution was passed through the cation exchange resin at a flow rate of SV=1 and c-polylysine was eluted. The amount of eluted solution,with the extracted solution was 1000 ml. The content of cpolylysine in the solution was 6.06 g/1 and the recovery of c-polylysine was 75%.
The eluted soluLion 100 ml was dialyzed with an ultrafiltration membrane of cut-off molecular weight 1000 produced by Fuji Filter Industry Company in Japan (trade name: FilLron NOVA lK, surface area 700cm 2). The ultrafiltration conditions are as follows:
6 Circulation flow rate: 700 ml/min Inlet pressure: 1.0 kg/cm 2 Outlet pressure: 0.6 kg/cm2 In the process of ultrafiltration, 1.0 liter of eluted solution from the cation exchange resin was concentrated to 400 ml, 600 ml of distilled water was mixed with the concentrated solution, and then the mixed solution was dialyzed with an ultrafiltration membrane to obtain 400 ml of concentrated solution. The dialysis was repeated three times and 400 ml of concentrated solution was obtained. The e-polylysine concentration of the obtained solution was 14.1 g/1 and the recovery of epolylysine was 93%.
The concentrated solution 400 ml was passed through a basic anion exchange resin of Amberlite 0 IRA-402 (OH_ type) 200 ml at a flow rate of SV=0.2 and distilled water 500 ml was passed through the resin. The amount of the collected solution was 900 ml. The E-polylysine concentration of the collected solution was 5.99 g/l and the recovery of c-polylysine was 95.6%.
The obtained solution was freeze-dried. The weight of the dried product was 5.60 g, the color was white and the purity was 96.0%. The chlorine content of the product was less than 0.1%.
Example 3
Streptomyces albulus was cultured in a mini jar fermenter for 96 hours, the broth was filtered and 2.0 liters of the filtrate was obtained. The e-polylysine concentration of the filtrate was 8.07 g/l.
1000 ml of the filtrate was dialyzed with an ultra filtration membrane of cut-off molecular weight 3000 produced by Fuji Filter Industry Company (trade name Filtron NOVA 3K, surface area: 700cm 2). The ultafil tra tion conditions are the same as those of the ultrafiltra- tion membrane of cut-off molecular weight 1000 in Example 7 1 5 2. 1.8 liters of the dialyzed liquid which was passed through the ultrafiltration membrane of cut-off molecular weight 3000 was obtained. The C-polylysine concentration of the obtained liquid was 4.17 g/l and the recovery of C-polylysine was 93%.
The obtained liquid 1.8 liters was dialyzed with an ultrafiltration membrane of cut-off molecular weight 1000 produced by Fuji Filter Industry Company (trade name: Filtron NOVA 1K, surface area: 700cm 2). The ultrafiltration conditions are the same as those of the ultrafiltration membrane of cut-off molecular weight 1000 in Example 2. This dialyzed liquid 1.8 liters which was passed through the ultrafiltration membrane of cut-off molecular weight 3000 was concentrated to 250 ml. The e-polylysine concentration of the concentrated solution was 26.88 g/l and the recovery of c-polylysine was 93%.
The concentrated solution 250 ml was passed through a basic anion exchange resin of Amberiite e IRA-402'(OHtype) 200 ml at a flow rate of SV=0.2 and distilled water 500 ml was passed through the resin. The amount of the collected solution was 700 ml. The e-polylysine concentration of the collected solution was 8.56 g/l and the recovery of e-polylysine was 95.6%.
The obtained solution was freeze-dried. The weight of the dried product was 6.70 9, the color was white and the purity was 96. 0%. Example 4 One liter of wet weakly acidic cation exchange resin of Amberlite e IRC(NH 4 + type) was charged in a column, 1000 ml of 5% e-polylysine hydrochloride solution (containing 40 9/1 of free e-polylysine) at pH 8.5 was passed through the column at a flow rate of SV=1 to adsorb cpolylysine to the resin. 3000 ml of distilled water was passed through the column at the same flow rate to wash the column. After washing the column, 3000 ml of 0.1 N of 8 sodium hydroxide solution was passed through the cation exchange resin at a flow rate of SV=1 and c-polylysine was elued. The amount of eluted solution with the extracted solution was 3000 ml. The content of e- polylysine 5 in the solution was 10.39 g/1 and the recovery of epolylysine was 77.9%. The eluted solution 3000 ml was dialyzed with an ultrafiltration membrane of cut-off molecular weight 1000 produced by Fuji Industry Company in Japan (trade name:
Filtron NOVA 1K, surface area: 700cm 2). The ultrafiltra tion conditions are as follows:
Circulation flow rate: 700 ml/min Inlet pressure: 1.0 kg/cm 2 Outlet pressure: 0.6 kg/cm 2 In the process of ultrafiltration, 3000 ml of eluted solution from the cation exchange resin was concentrated to 1500 ml,, 1500 ml of distilled water was mixed with the concentrated solution, and then the mixed solution was dialyzed with an ultrafiltration membrane to obtain 1500 ml of concentrated solution. The dialysis was repeated five times and 1500 ml of concentrated solution was obtained. The e-polylysine concentration of the obtained solution was 19.3 9/1 and the recovery of epolylysine was 93%.
The concentrated solution 1500 ml was freeze-dried and free c-polylysine 28.9 9 was obtained. The sodium content of the product was less than 0.1%.
Example 5
Streptomyces albulus was cultured in a mini Jar fermenter for 96 hours, the broth was filtered and 2.0 liters of the filtrate was obtained. The c-polylysine concentration of the filtrate was 8.07 9/1.
1000 ml of the filtrate was adjusted to the pH 8.5 and filterd. The filtrate was passed through the column containing 200 ml of a weakly acidic cation exchange 9 resin of Amberlite e IRC-50 (NH4+ type) at a flow rate of SV=l, and C- polylysine was adsorbed to the cation exchange resin. The resin was washed With 800 ml of distilled water (SV=2). After washing, 1000 ml of 0. 1 N of sodium hydroxide solution was passed through the cation exchange resin at SV=1 and C-polylysine was eluted. The amount of eluted solution with the extracted solution was 1000 ml. The content of C-polylysine in the solution was 6.06 9/1 and the recovery of e-polylysine was 75%.
The eluted solution 1000 ml was dialyzed with an ultrafiltration membrane of cut-off molecular weight 1000 produced by Fuji Industry Company in Japan (trade name: Filtron NOVA 1K, surface area: 700cm 2). The ultrafiltra- tion conditions are the same as those in Example 4.
In the process of ultrafiltration, 1.0 liter of eluted solution from the cation exchange resin was concentrated to 400 ml, 600 ml of distilled water was mixed with the concentrated solution, and then the mixed solution was dialyzed with an ultrafiltration membrane to obtain 400 ml of concentrated solution. The dialysis was repeated five times and 400 ml of concentrated solution was obtained. The c-polylysine concentration of the obtained solution was 14.1 9/1 and the recovery of e- polylysine was 93%.
The obtained solution 400 ml was freeze-dried. The weight of the dried product was 5.60 g, the color was white and the purity was 99.0%. The sodium content of the product was less than 0.1 %.
Example 6
A concentrated solution 400 ml was obtained by the same process as in Example 5. 6.0 g of Dextrin was added to the concentrated solution 400 ml, and the mixture was spray dried. The weight of the obtained powder was 11.0 9, the color of the powder was white and the content of C-polylysine was 45% by weight. Example 7 A concentrated solution 400 ml was obtained by the same process as in Example S. Acetone 1600 ml was added to the solution and a precipitate was produced. The precipitate was collected by centrifugation and dried in vacuo. The weight of the obtained powder was 4.76 9, the color was white and the purity was 98.3%.
11
Claims (13)
1. A method of producing tree c-polylysine which comprises passing an cpolylysine Solution through a basic anion exchange resin, collecting the passed solution, and treating the collected solution process by precipitation in an organic solvent. freeze-drying or by spray drying to obtain free c-polylysine.
2. A method as claimed in claim 1, wherein cpolylysine obtained by cultivating a micro-organism having the ability of producing c-polylysine is used.
3. A method as claimed in claim 2, wherein the microorganism is SLreptomyces albulus.
4. A method as claimed in claim 1, wherein the cpolylysine solution is a solution obtained by removing micro-organisms from an c-polylysine culture broth, or a solution of acidic salt of c-polylysine.
5. A method as claimed'in claim 4, wherein the solution of acidic salt of c-polylysine is a solution obtained by eluting c-polylysine with an acidic solution from a cation exchange resin after a filtrate of a culture broth obtained by cultivating a micro-organism having the ability of producing c-polylysine has been adsorbed on the cation exchange resin.
6. A method as claimed in claim 1, wherein the cpolylysine solution is a solution obtained by treating a solution, which is obtained by separating microorganisms from a culture broth obtained by cultivating a microorganism having the ability of producing cpolylysine with an ultrafiltration membrane of CUL-Off 12 molecular weight 1000 or less. and by collecting fractions which do not permeate the ultrafiltration membrane.
7. A method as claimed in claim 1. wherein the cpolylysine Solution is a solution obtained by treating a solution, which is obtained by separating microorganisms from a culture broth obtained by cultivating the microorganisms having the ability of producing cpolylysine, with an ultrafiltration membrane of cut-off molecular weight at least 3000, then by treating the penetrated solution containing c-polylysine with an ultratiltration membrane of cut-off molecular weight 1000 or less, and by collecting fractions which do not permeate the ultrafiltration membrane.
8. A method as claimed in claim 1, the basic anion exchange resin is one having trimethyl ammonium basic groups.
9. A method of producing free c-polylysine which comprises passing an cpolylysine solution through an acidic cation exchange resin to adsorb cpolylysine onto the resin, eluting c-polylysine with an alkaline solution from the resin, removing excess alkali in the solution with an ultrafiltration membrane, and treating the solution by precipitation in an organic solvent, freeze-drying or by spray drying to obtain free cpolylysine.
10. A method as claimed in claim 9, wherein cpolylysine obtained by cultivating a micro-organism having the ability of producing c-polylysine is used.
11. A method as claimed in claim 9, wherein the acidic cation exchange resin is one having carboxyl groups.
v 13
12. A method as claimed in claim 9, wherein the micro-organism is Streptomyces albulus.
13. A method as claimed in claim 9, wherein the cpolylysine solution is an c-polylysine culture broth or a solution of acidic salt of c- polylysine.
1, i Published 1990 at T4e Patent Office. State House.66'71 High Holborn, London WCIR4T?.FVrther copies maybe obtainedfrom The Patent Office. Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 187
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16882688A JPH0220295A (en) | 1988-07-08 | 1988-07-08 | Production of free epsilon-polylysine |
| JP24425188A JPH0292927A (en) | 1988-09-30 | 1988-09-30 | Production of free epsilon-polylysine |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8915565D0 GB8915565D0 (en) | 1989-08-23 |
| GB2220946A true GB2220946A (en) | 1990-01-24 |
| GB2220946B GB2220946B (en) | 1991-09-18 |
Family
ID=26492369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8915565A Expired - Fee Related GB2220946B (en) | 1988-07-08 | 1989-07-07 | Method of producing free epsilon-polylysine |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE3922278C2 (en) |
| FR (1) | FR2633931A1 (en) |
| GB (1) | GB2220946B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0557954A2 (en) * | 1992-02-26 | 1993-09-01 | Chisso Corporation | A process for producing epsilon-poly-L-lysine |
| CN108484901A (en) * | 2018-04-10 | 2018-09-04 | 中国科学院长春应用化学研究所 | A kind of method that thermal polycondensation prepares the polylysine of the linear epsilon-polylysine of high-content |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0220271A (en) * | 1988-07-07 | 1990-01-23 | Chisso Corp | Ethanol preparation for food preservation |
| DE19753630B4 (en) * | 1997-12-03 | 2005-09-01 | Michael Stehle | Use of a composition for the subsequent sealing of tires |
| CN113003898B (en) * | 2021-04-24 | 2023-02-03 | 诸城市浩天药业有限公司 | Corn soaking water treatment method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0254419A2 (en) * | 1986-06-24 | 1988-01-27 | Chisso Corporation | An agent for preventing plant virus diseases |
-
1989
- 1989-07-06 DE DE19893922278 patent/DE3922278C2/en not_active Expired - Fee Related
- 1989-07-07 FR FR8909206A patent/FR2633931A1/en active Granted
- 1989-07-07 GB GB8915565A patent/GB2220946B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0254419A2 (en) * | 1986-06-24 | 1988-01-27 | Chisso Corporation | An agent for preventing plant virus diseases |
Non-Patent Citations (1)
| Title |
|---|
| JP 62058975 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0557954A2 (en) * | 1992-02-26 | 1993-09-01 | Chisso Corporation | A process for producing epsilon-poly-L-lysine |
| EP0557954A3 (en) * | 1992-02-26 | 1994-10-26 | Chisso Corp | A process for producing epsilon-poly-l-lysine |
| CN108484901A (en) * | 2018-04-10 | 2018-09-04 | 中国科学院长春应用化学研究所 | A kind of method that thermal polycondensation prepares the polylysine of the linear epsilon-polylysine of high-content |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2220946B (en) | 1991-09-18 |
| FR2633931A1 (en) | 1990-01-12 |
| DE3922278A1 (en) | 1990-01-11 |
| FR2633931B1 (en) | 1994-04-22 |
| GB8915565D0 (en) | 1989-08-23 |
| DE3922278C2 (en) | 1993-11-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20080707 |