CN1306092A - Process for preparing levoamino acid by splitting racemic amino acid by immobilized amino acylase - Google Patents
Process for preparing levoamino acid by splitting racemic amino acid by immobilized amino acylase Download PDFInfo
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- CN1306092A CN1306092A CN 00113235 CN00113235A CN1306092A CN 1306092 A CN1306092 A CN 1306092A CN 00113235 CN00113235 CN 00113235 CN 00113235 A CN00113235 A CN 00113235A CN 1306092 A CN1306092 A CN 1306092A
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Abstract
A process for preparing levoamino acid by splitting recemic amino acid with immobilized amino acylase includes immobilizing the free-state amino acylase by weekly acidic anionic exchange resin to prepare immobilized enzyme column, N-acytylating recemic amino acid by civegar anhydride to obtain D,L-N-acetylamino acid, preparing its solution, enzymolytic splitting by passing it through said immobilized enzyme column at 42-45 deg.C and 0.01-0.05 mL/min.g of speed, vacuum concentrating, cooling, crystallizing, separating levoamino acide from D-N-acetylamino acid which can be used to prepare D-L-N-acetylamino acid for cyclic application.
Description
The present invention relates to a kind of production method of biochemical product; it is the method that the amino acidylate lytic enzyme of immobilization splitting racemic amino acid is produced Aminosteril KE; D, the producing of L-N-acetylamino acid, fixation support and curing, the racemic method of D-N-acetylamino acid.
Amino acid is meant in the molecule and not only contains amino but also contain the general name of a compounds of carboxyl.It is to constitute the proteic base substance of organism.Along with development of modern science and technology, amino acid has been widely used in fields such as medicine, biochemical pesticide, food-flavoring comps and enriched nutrient, plant-growth regulator, leather, daily cosmetics, health care, and range of application is expanded day by day.
Nature is composed the amino acid of depositing and is generally levo form, is present in the animal and plant body, and be a class of biologically active.From the bioprotein that constitutes with peptide chain form bonded multiple amino acids, extract Aminosteril KE, one side component complexity, separation and purification becomes single crystalline amino acid, the numerous length of technology, yield is extremely low; On the other hand, environmental pollution is very serious, thereby is that modern society progressively eliminates.
Synthetic amino acid, output is big, the yield height, but except that glycine, be the mixture of levo form and dextrorotatory form.Dextrorotatory form amino acid often produces toxic side effect or does not possess biological activity biological function, so, often to carry out left and right fractionation of revolving body to the amino acid of synthetic, to reach certain optical purity.
Left and right difference of revolving body amino acid owing to space structure, make the deflection of plane polarized light generation equal angular, different directions, show different biological property, but because molecular structure is the same, so its physical properties does not have evident difference, and chemical property is just the same, separates that left and right to revolve body very difficult.
The purpose of this invention is to provide the method that the efficient splitting racemic amino acid of the amino acidylate lytic enzyme of a kind of immobilization is produced Aminosteril KE.
Principle of the present invention is: 1, D, the producing of L-N-acetylamino acid
2, D, L-N-acetylamino acid enzyme splits
CO
2 -CO
2 -OH
3N-C-H
++ H-C-N-C-CH
3R R HL-amino acid D-N-acetylamino acid 3, D-N-acetylamino acid racemize
The method steps of the amino acidylate lytic enzyme of the immobilization that the present invention releases splitting racemic amino acid is as follows:
(1) the acidulous anion exchange resin is adorned post after balance.Amino acidylate lytic enzyme (commercially available product) is made the water-soluble enzyme of 1000～1500 μ/ml, at the uniform velocity pass through the carrier post, carry out the immobilization of enzyme at 42～45 ℃ of flow velocitys with 0.01～0.05mL/ming carrier.When the immobilized enzyme vigor reaches 500～700 μ/g carrier, Gu enzyme finishes.Then with the washing of 0.15M sodium acetate soln.
(2) with D, the acid of L-N-acetylamino is made into 5～10% (w/w) aqueous solution, uses Na
2CO
3Or NH
3H
2It is 6.5～10.0 that O adjusts solution PH.
(3) with D, L-N-acetylamino acid substrate solution, splits at the uniform velocity by the enzyme post with the flow velocity of 0.01～0.05mL/ming carrier under 42～45 ℃ of keeping warm modes.
(4) split liquid and be concentrated into 1/2～1/4 of original volume at 60～70 ℃ of vacuum decompressions, be cooled to 0～5 ℃, stirred crystallization is separated after ethanol or methanol wash, dry Aminosteril KE.
(5) adjustment crystalline mother solution PH1.0～5.0 are stirred the back of heating up and are adjusted PH1.5～5.0 with sulfuric acid or hydrochloric acid, leave standstill crystallisation by cooling, separate the dry D-N-acetylamino acid that gets.
(6) acid of D-N-acetylamino is dissolved with 1.5～3 weight parts waters, add 1～3 times of diacetyl oxide of its theoretical consumption, be warming up to 60～70 ℃, stirred 3-5 hour; be cooled to 0～5 ℃ then, crystallization 〉=5 hour are after the centrifuge dehydration; 40～100 ℃ of dryings, get D, the acid of L-N-acetylamino.
The D that relates in present method, the acid of L-N-acetylamino is produced as follows.
Get the D of a weight part, L-amino acid drops in the enamel reaction still; add the 1-5 weight parts water, under whipped state, drip the aceticanhydride of 1.5～2.0 times of its theoretical consumptions; the control synthesis temperature is 25～50 ℃, after dropwising, 25～50 ℃ of insulated and stirred 5～10 hours; place the lass lining crystallization kettle, be cooled to 0～5 ℃, add crystallization promoter; stirred crystallization 〉=5 hour; centrifugation gets D, the acid of L-N-acetylamino.
Fixation support and curing involved in the present invention are as follows:
(1) fixed enzyme vector adopts the acidulous anion exchange resin.
(2) resin with a weight part is soaked in the 3 weight part 0.2N NaoH solution, left standstill 30 hours, then with rinsed with deionized water to PH7～8, be soaked in again in the 3 weight part 0.2N hydrochloric acid solns, left standstill 30 hours, then with rinsed with deionized water to PH5～6.
(3) will be through the resin of above-mentioned processing dress post, constant temperature to 43 ± 1 ℃; With 1 ℃ in amino acidylate lytic enzyme constant temperature to 43 soil, at the uniform velocity upwards pass through from the carrier column bottom with the flow velocity of 0.01～0.05mL/ming carrier; Deionized water with 1 ℃ in 43 soil passes through the enzyme post, and this moment, the immobilized enzyme vigor reached 500～700 μ/g carrier, and is standby at 43 ± 1 ℃ of constant temperature.
D-N-acetylamino acid racemize involved in the present invention is carried out as follows:
(1) with D-N-acetylamino acid its moisture content of constant pressure and dry≤3% under 40～80 ℃ of conditions.
(2) weight part D-N-acetylamino acid is after drying dropped in the glassed steel reaction vessels, add the water dissolution of 1.5～3 times of weight parts.
(3) add 1～3 times of diacetyl oxide of its theoretical consumption, be warming up to 60～70 ℃, stirred 3～5 hours.
(4) under whipped state, be cooled to 0～5 ℃, crystallization 〉=5 hour.
(5) centrifuge dehydration then 40～100 ℃ of dryings, gets D, the acid of L-N-acetylamino.
Advantage of the present invention: be that carrier is cheap, capacity is big, and the immobilized enzyme vigor is up to 500～700 μ/g carrier h, and the transformation period reaches 240 days, and immobilized enzyme regeneration easily; Detachable all a-amino acids of utilization the present invention, as L-Ala, arginine, aspartic acid, Gelucystine, halfcystine, L-glutamic acid, Histidine, Isoleucine, leucine, Methionin, methionine(Met), phenylalanine, Serine, Threonine, tryptophane, tyrosine, a-amino acids such as Xie Ansuan.Simultaneously, utilization the present invention produces the purification step that Aminosteril KE can be simplified reaction product, and yield is also than the free enzyme height of solubility; The cost of enzyme descends greatly in the production process; Use production process of the present invention and can realize automatization control saving labour; Utilize the amino acidylate lytic enzyme of immobilization quantity-produced total cost be approximately utilize water-soluble enzyme method for splitting in batches 80%.
Embodiment 1:D, L-ethanoyl Serine synthetic
With 100kgD, L-ethanoyl Serine is put in the glassed steel reaction vessels, adds 100kg water; stir, be incubated to 60 ℃, drip the 130kg aceticanhydride, keeping synthetic liquid temp is 60 ± 5 ℃; dropwise,, place the lass lining crystallization kettle again 60 ℃ of insulated and stirred 8 hours; be cooled to 0～5 ℃, add crystallization promoter, left standstill crystallization 8 hours; centrifugation, drying gets D; L-ethanoyl Serine 133kg, yield 90%.
Embodiment 2:D, L-ethanoyl methionine(Met) synthetic
With 100kgD, the L-methionine(Met) is put in the glassed steel reaction vessels, adds 250kg water, stirs, and drips the 95kg aceticanhydrides at 60 ℃, dropwises, 65 ℃ of insulated and stirred 6 hours.Place the lass lining crystallization kettle again, be cooled to 0～5 ℃, add crystallization promoter, left standstill crystallization 8 hours, centrifugation, drying gets D, L-ethanoyl methionine(Met) 122kg, yield 95%.
Embodiment 3:D, the L-ethanoyl is arginic synthetic
With 100kgD, the L-arginine is put in the glassed steel reaction vessels, adds 100kg water; be stirred to moltenly entirely, drip the 85kg aceticanhydrides, dropwise at 60 ℃; 65 ℃ of insulated and stirred 10 hours, place the lass lining crystallization kettle again, be cooled to 0～5 ℃; add crystallization promoter, left standstill centrifugation 6～8 hours; dry; get D, L-ethanoyl arginine 115kg, yield 93%.
Embodiment 4: the preparation of the amino acidylate lytic enzyme of immobilization
Get 10kg acidulous anion exchange resin, place the 50L container, add 0.2N NaoH solution 30L, soaked 30 hours, then with rinsed with deionized water to PH7～8, adding 30L0.2N hydrochloric acid soln soaked 30 hours, with rinsed with deionized water to PH6.0.
Will be through the resin of the above-mentioned processing diameter 140m/m that packs into, in the laminated glass post of high 800m/m, constant temperature to 43 ± 1 ℃.
Amino acidylate lytic enzyme is made 1000～1500 μ/mL enzyme liquid; constant temperature to 43 ± 1 ℃; flow velocity with 500mL/min at the uniform velocity upwards passes through from the carrier column bottom; use 43 ± 1 ℃ of 50 liters of 0.2N sodium acetate solns and 50 liters of deionized waters by the enzyme post then; at this moment; the immobilized enzyme vigor reaches 580 μ/g, and carrier is standby at 43 ± 1 ℃ of constant temperature.
Embodiment 5: the amino acidylate lytic enzyme of immobilization splits D, and L-N-ethanoyl Serine is produced the L-Serine
With 130kgD, L-ethanoyl Serine is dissolved in the 1800L water, uses Na
2CO
3Adjust PH8.0, constant temperature to 43 ± 1 ℃ is at the uniform velocity passed through constant temperature liquid from immobilized enzyme column with the 125L/h flow velocity, effluent liquid places the vacuum concentration vaporizer, under-0.07MPa, 65 ℃, be concentrated into 30% of original volume, concentrate feed is dropped in the lass lining crystallization kettle, in 0～5 ℃ of crystallisation by cooling 8 hours, centrifugation, xln embathes with 50 liters of ethanol, and is centrifugal, and drying is 4 hours under 100 ± 5 ℃, get L-Serine product 44kg, yield 95%.
Crystalline mother solution is transferred PH1.5 with 20% concentration hydrochloric acid, in the lass lining crystallization kettle, and 0～5 ℃ of crystallisation by cooling 15 hours, centrifugation, dry D-ethanoyl Serine 61kg, yield 94%.
With the D-N-ethanoyl Serine 60kg of drying, drop in the glassed steel reaction vessels, add 120kg water and 100kg diacetyl oxide; be warming up to 60 ℃; stir after 5 hours, be cooled to 0～5 ℃, crystallization 8 hours; centrifuge dehydration; 70 ℃ of dryings 4 hours, D, L-N-ethanoyl Serine 55kg; yield 91.7% changes immobilized enzyme over to and splits.
Embodiment 6: the amino acidylate lytic enzyme of immobilization splits D, and L-N-ethanoyl methionine(Met) is produced the L-methionine(Met)
With 120kgD, L-ethanoyl methionine(Met) is dissolved in the 1200L water, uses NH
4OH adjusts PH9.2, and constant temperature to 43 ± 1 ℃ is at the uniform velocity passed through constant temperature liquid from immobilized enzyme column with the 100L/h flow velocity, effluent liquid places the vacuum concentration vaporizer, under-0.065MPa, 60 ℃, be concentrated into 35% of original volume, concentrate feed is dropped in the lass lining crystallization kettle, in 0～5 ℃ of crystallisation by cooling 8 hours, centrifugation, xln embathes with 70 liters of methyl alcohol, and was centrifugal, 100 ± 5 ℃ of dryings 6 hours, get L-methionine(Met) product 45kg, yield 96%.
Crystalline mother solution is transferred PH1.8 with 20% concentration hydrochloric acid, in the lass lining crystallization kettle, 0～5 ℃ of crystallisation by cooling 15 hours, centrifugation, 50 ℃ ± 5 ℃ dryings 8 hours D-ethanoyl methionine(Met) 58kg, yield 97%.
D-ethanoyl methionine(Met) 58kg with drying puts in the glassed steel reaction vessels, adds 130kg water and 100kg diacetyl oxide; be warming up to 65 ℃; stirred 8 hours, and cooled off 0～5 ℃ then, crystallization 12 hours; centrifuge dehydration; 60 ℃ of dryings 4 hours, D, L-N-ethanoyl methionine(Met) 54kg; yield 92% changes immobilized enzyme over to and splits.
Embodiment 7: the amino acidylate lytic enzyme of immobilization splits D, and L-N-ethanoyl arginine is produced the L-arginine
With 110kgD, L-ethanoyl arginine is dissolved in 1000 premium on currency, uses NH
4OH adjusts PH9.5, and constant temperature to 43 ± 1 ℃ is at the uniform velocity passed through constant temperature liquid from immobilized enzyme column with the 100L/h flow velocity, effluent liquid places the vacuum concentration vaporizer, under-0.07MPa, 60 ℃, be concentrated into 25% of original volume, concentrate feed is dropped in the lass lining crystallization kettle, in 0～5 ℃ of crystallisation by cooling 8 hours, centrifugation, xln embathes with 80 liters of methyl alcohol, and was centrifugal, 95 ± 5 ℃ of dryings 5 hours, get L-arginine product 42.5kg, yield 96%.
Crystalline mother solution is transferred PH2.0 with 20% concentration hydrochloric acid, in the lass lining crystallization kettle, 0～5 ℃ of crystallisation by cooling 12 hours, centrifugation, 60 ℃ ± 5 ℃ dryings 10 hours, D-ethanoyl arginine 52kg, yield 94%.
The D-ethanoyl arginine 52kg of drying is put in the glassed steel reaction vessels; add 100kg water and 100kg diacetyl oxide, be warming up to 60 ℃, stirred 6 hours; be cooled to 0～5 ℃ then; crystallization 10 hours, centrifuge dehydration was 60 ℃ of dryings 6 hours; get D; L-N-ethanoyl arginine 48kg, yield 92% changes immobilized enzyme over to and splits.
Claims (10)
1, the method for the amino acidylate lytic enzyme of a kind of immobilization splitting racemic amino acid is characterized in that:
(1) the acidulous anion exchange resin is after balance; the dress post; amino acidylate lytic enzyme (commercially available product) is made the water-soluble enzyme of 1000～1500 μ/ml at the uniform velocity pass through the carrier post at 42～45 ℃ of flow velocitys with 0.01～0.05mL/ming carrier; carry out the immobilization of enzyme; when the immobilized enzyme vigor reaches 500～700 μ/g carrier, Gu enzyme finishes.
(2) with D, the acid of L-N-acetylamino is made into 5～10% (w/w) aqueous solution, uses Na
2CO
3Or NH
3H
2It is 6.5～10.0 that O adjusts solution PH.
(3) with D, L-N-acetylamino aqueous acid, splits at the uniform velocity by the enzyme post with the flow velocity of 0.01～0.05ml/ming carrier under 42～45 ℃ of keeping warm modes.
(4) split liquid and be concentrated into 1/2～1/4 of original volume at 60～70 ℃ of vacuum decompressions and be cooled to 0～5 ℃, stirred crystallization is separated after ethanol or methanol wash, dry Aminosteril KE.
(5) adjust crystalline mother solution PH1.0～5.0, stir, crystallization separates, and drying gets the acid of D-N-acetylamino.
(6) acid of D-N-acetylamino is made D, the acid of L-N-acetylamino.
2, such as claim 1 speed, prepare the method for the amino acidylate lytic enzyme of immobilization, it is characterized in that adopting the acidulous anion exchange resin as solid enzyme carrier.
3, according to claim 1, prepare the method for the amino acidylate lytic enzyme of immobilization, it is characterized in that using amino acidylate lytic enzyme, and the vigor of being made into is 1000～1500 μ/mL enzyme liquid, use Na
2CO
3Or NH
3H
2O adjusts PH6.5～10.0, at 42～45 ℃, at the uniform velocity flows through the enzyme post with 0.01～0.05mL/min.g carrier.
4, according to claim 1, prepare the method for the amino acidylate lytic enzyme of immobilization, it is characterized in that after the immobilization of enzyme suppressed by vector, washing with 0.1～0.2M sodium acetate soln.
5, according to claim 1, it is characterized in that concentration of substrate is 5～15% (w/w), and use Na
2CO
3Or NH
4OH adjusts PH6.5～10.0.
6, according to claim 1, it is characterized in that splitting temperature and be controlled at 42～45 ℃, substrate is pressed 0.01～0.05mL/ming carrier at the uniform velocity by the amino acidylate lytic enzyme of immobilization post.
7, such as claim 1 speed, it is characterized in that splitting liquid under vacuum state, 60～70 ℃ are carried out concentrating under reduced pressure, concentration ratio is controlled at 2～4: 1.
8, D as claimed in claim 1, the acid of L-N-acetylamino produce step, be characterised in that:
Get a weight fraction D, L-amino acid places glassed steel reaction vessels; add 1～5 part of water, under whipped state, drip the aceticanhydride of 1.5～2.0 times of its theoretical consumptions; the control synthesis temperature is 25～50 ℃, after dropwising, 25～50 ℃ of insulated and stirred 5～10 hours; place the lass lining crystallization kettle, be cooled to 0～5 ℃, add crystallization promoter; stirred crystallization 〉=5 hour; centrifugation gets D, the acid of L-N-acetylamino.
9, the recovery method of the described D-N-acetylamino of claim 1 acid is characterised in that:
(1) centrifugation is gone out the amino acid whose crystalline mother solution of L-and drop in the glassed steel reaction vessels, adjust PH1.5～5, rise wet to 45 ± 5 ℃ with 10～20% concentration sulfuric acid or 25～30% concentration hydrochloric acid.
(2) will go up instant liquid and place the lass lining crystallization kettle, crystallization is left standstill in cooling, 0～5 ℃ of Tc, crystallization time 〉=5 hour.
(3) use the whizzer centrifugation, 40～100 ℃ of dryings get the acid of D-N-acetylamino.
10, the described D-N-acetylamino of claim 1 acid racemize is characterized in that connecing that following steps carry out:
(1) with D-N-acetylamino acid its moisture content of constant pressure and dry≤3% under 40～100 ℃ of conditions.
(2) weight part D-N-acetylamino acid is dissolved with 1.5～3 weight parts waters; add 1～3 times of diacetyl oxide of its theoretical consumption; be warming up to 60～70 ℃, stirred 3～5 hours, be cooled to 0～5 ℃ then; crystallization 〉=5 hour; after the centrifuge dehydration, at 40～100 ℃, drying; get D, the acid of L-N-acetylamino.
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|---|---|---|---|
| CN 00113235 CN1306092A (en) | 2000-01-18 | 2000-01-18 | Process for preparing levoamino acid by splitting racemic amino acid by immobilized amino acylase |
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| CN 00113235 CN1306092A (en) | 2000-01-18 | 2000-01-18 | Process for preparing levoamino acid by splitting racemic amino acid by immobilized amino acylase |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334222C (en) * | 2004-12-03 | 2007-08-29 | 上海化工研究院 | Enzyme method for preparing laevo-rotation and dextro-rotation tryptophane 15N by resolving racemic tryptophase 15N |
| CN101130503B (en) * | 2006-08-22 | 2011-05-11 | 上海化工研究院 | Method for preparing L-serine-15N |
-
2000
- 2000-01-18 CN CN 00113235 patent/CN1306092A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334222C (en) * | 2004-12-03 | 2007-08-29 | 上海化工研究院 | Enzyme method for preparing laevo-rotation and dextro-rotation tryptophane 15N by resolving racemic tryptophase 15N |
| CN101130503B (en) * | 2006-08-22 | 2011-05-11 | 上海化工研究院 | Method for preparing L-serine-15N |
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