CN102776256A - Method for catalytic synthesis of fructose lauric acid monoester by using immobilized phospholipase A1 - Google Patents
Method for catalytic synthesis of fructose lauric acid monoester by using immobilized phospholipase A1 Download PDFInfo
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- CN102776256A CN102776256A CN2012102293120A CN201210229312A CN102776256A CN 102776256 A CN102776256 A CN 102776256A CN 2012102293120 A CN2012102293120 A CN 2012102293120A CN 201210229312 A CN201210229312 A CN 201210229312A CN 102776256 A CN102776256 A CN 102776256A
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Abstract
The invention discloses a method for catalytic synthesis of the fructose lauric acid monoester by using the immobilized phospholipase A1. According to the method, lauric acid and fructose are subjected to catalytic reaction through enzymes to synthesize the fructose lauric acid monoester. The preparation method includes the steps of immobilizing the phospholipase A1, preparing a dehydration organic solvent, and subjecting the immobilized phospholipase A1 to catalytic synthesis to produce the fructose lauric acid monoester. According to the method for catalytic synthesis of the fructose lauric acid monoester by using the immobilized phospholipase A1, the used phospholipase A1 is cheap in price and only 5% to 10% of the price of lipase, and the price of resin D-201 used for immobilizing the phospholipase is low. The immobilized phospholipase A1 has good catalytic effect, the conversion rate of the fructose lauric acid monoester is high, the product separation is simple, and the immobilized phospholipase A1 can be recycled. Accordingly, products prepared through the method are low in cost and have good application prospect in industry.
Description
Technical field
The present invention relates to a kind of immobilized phospholipase A1 catalysis, synthetic surgar ester surfactant---fructose LAURIC ACID 99 MIN monoesters belongs to the organic synthesis field.
Background technology
Sugar ester generally is to be formed by connecting through ester bond longer chain fatty acid and sugar.Therefore the sugar ester molecule has nonpolar longer chain fatty acid and polar poly-hydroxy sugar simultaneously, thereby has Action of Surfactant.The sugar ester molecule does not have the ionize functional group, is typical nonionogenic tenside.It has important use as the typical non-ionic type green bio tensio-active agent of one type of excellent property in industry such as food, makeup, medicine, washing composition, fiber.The fructose ester has wide application field equally as one type of nonionogenic tenside.
The compound method of sugar ester has chemical method and enzyme process; Chemical method carries out under high temperature, noxious solvent and basic catalyst often; This makes that product color is dark, monoester content is not high; Production energy consumption is high and have potential safety hazard, and the esterification position and the Zhi Huadu of product are wayward, for product separation and use have brought inconvenience.Therefore see from Product Safety and environmental angle that Applied Biotechnology substitutes traditional chemical route of synthesis production compound and meets the International Development trend.Enzyme process is synthetic to have characteristics such as high efficiency and specificity, reaction conditions gentleness, by product be less, and development in recent years is very fast.
At present, it mainly is lypase that enzyme process prepares fructose LAURIC ACID 99 MIN monoesters method, and like NOVO435, but business-like lypase costs an arm and a leg, and has therefore just limited it and has used.
Phospholipase A1 is a kind of microbe-derived Phospholipid hydrolase that Novozymes Company releases, and is usually used in greasy coming unstuck, and this enzyme is a kind of carboxylic ester hydrolase, has lipase activity and phospholipase activity simultaneously.In certain reaction system, its meeting precedence table reveals wherein a kind of specific enzyme lives, such as lipase activity.Do not see at present about adopting immobilized phospholipase A1 catalysis fructose and LAURIC ACID 99 MIN to prepare the report of fructose LAURIC ACID 99 MIN monoesters.
Summary of the invention
The method that the purpose of this invention is to provide a kind of immobilized phospholipase A1 catalysis acrose LAURIC ACID 99 MIN monoesters.This method reaction solvent is nontoxic, and enzyme dosage is few and can recycle, and the equal separate easily of reaction product and reaction solvent and lypase helps serialization production.The method of employing immobilized phospholipase A1 catalysis acrose LAURIC ACID 99 MIN monoesters provided by the present invention comprises following content:
(1) immobilization of phospholipase A1: the DA-201 macroporous adsorbent resin of getting 5 ~ 10 parts of activated processing of quality; The phosphate buffered saline buffer of 10 ~ 25 parts of quality, 0.5 ~ 2 part of free phospholipase A1 of quality mixes, at 25 ~ 35 ℃ of following whip attachment 2 ~ 6h; Filter then; Get the macroporous adsorbent resin immobilized phospholipase, with the immobilized enzyme vacuum-drying that makes, subsequent use;
(2) preparation dehydrated organic solvent: 3 or 4 molecular sieves are placed activation 5～10h in 95～105 ℃ of baking ovens, place the moisture eliminator internal cooling again to room temperature, subsequent use; Afterwards, 3 after activation or 4 molecular sieves are joined in the organic solvent as reaction medium for use according to the amount that every liter of solvent adds 50～80 parts of quality, 24～72h is placed in sealing, removes by filter molecular sieve, gets dehydrated organic solvent again;
(3) immobilized phospholipase A1 catalysis acrose LAURIC ACID 99 MIN monoesters: get 10～40.6 parts of Quality Month cinnamic acids and 1.8～36.5 parts of quality fructose place above-mentioned dehydrated organic solvent to mix; Wherein LAURIC ACID 99 MIN concentration is 5～24wt%, and the immobilized phospholipase A1 that adds again with respect to LAURIC ACID 99 MIN quality 8～25wt% begins reaction; Behind reaction 0～2h according to adding 3 or 4 molecular sieves after the activation with respect to LAURIC ACID 99 MIN quality 0.5-2 amount doubly to remove the water that generates in the dereaction; Hunting speed 150 ~ 185r/min vibrate or stirring reaction 8～96h down at 35 ℃～45 ℃; After reaction finishes, adopt filter method that immobilized phospholipase A1, molecular sieve and unreacted sugar are removed; Gained filtrating is removed organic solvent through rotary evaporation, obtains product fructose LAURIC ACID 99 MIN monoesters after the purification.
The DA-201 macroporous adsorbent resin of activated processing and phosphate buffered saline buffer mass ratio are 1:2 in the said step (1); The consumption of phospholipase A1 is the 20wt% of macroporous adsorbent resin quality.
Reaction medium organic solvent kind is any one in propyl carbinol, the trimethyl carbinol, tertiary amyl alcohol, chloroform, butanone, acetone or the acetonitrile in the said step (2), or two or more mixtures; And described reaction medium organic solvent polarity scope promptly
Log?P=3.0～7.0。
The consumption of immobilized phospholipase A1 is LAURIC ACID 99 MIN quality 20wt% in the said step (3).
The consumption and the LAURIC ACID 99 MIN mass ratio of activatory 3 or 4 molecular sieves are 1:1 in the said step (3).
Advantage of the present invention is following
(1), compares with traditional chemical synthesis process and have eco-friendly characteristics owing to adopt enzymatic synthesis method; Add molecular sieve in the reaction process and help removing the moisture that produces in the dereaction, esterification is carried out to positive dirction; Reaction solvent belongs to organic solvent commonly used, and toxicity is little, and boiling point is low, is easy to separate with product.
(2) detecting the proof catalysate through HPLC-MS (LC-MS) is fructose LAURIC ACID 99 MIN monoesters; Detect through RP-HPLC-ELSD (RPLC-light scattering detector), the transformation efficiency of immobilized phospholipase A1 catalysis fructose LAURIC ACID 99 MIN monoesters reaches 68.05%.
(3) compare with the fixed lipase catalyzed synthetic sugar ester of the employing of having reported; The price of the immobilized phospholipase A1 that the present invention adopted has only the 10%-15% of commercialization immobilized lipase; Therefore adopt phospholipase A1 to have cost advantage as catalyzer, industrial applications has good prospects.
Description of drawings
Fig. 1 is the esterification equation of immobilized phospholipase A1 catalysis fructose LAURIC ACID 99 MIN monoesters of the present invention.
Fig. 2 is the LC-MS collection of illustrative plates that reacts the fructose LAURIC ACID 99 MIN monoesters that obtains.
Embodiment
Below in conjunction with concrete instance and accompanying drawing the present invention is done further detailed narration, but implementation method of the present invention is flexible, is not limited only to this routine described concrete operations mode.
Material therefor in below implementing: commercialization phospholipase A1 (Lecitase
Ultra, Denmark Novozymes Company), to measure through tributyrin pH-stat method, enzyme activity unit is 3326 U/g; Macroporous adsorbent resin DA-201, Tianjin sea light chemical industry ltd; D-fructose, Shanghai uncle bio tech ltd difficult to understand; LAURIC ACID 99 MIN, Tianjin Da Mao chemical reagent factory; 3 or 4 molecular sieves, Tianjin good fortune Chen Huaxueshijichang; Various reaction mediums are the AR level.
Through LC-MS catalysate fructose LAURIC ACID 99 MIN monoesters is identified; Through high performance liquid chromatograph-light scattering detector to product in the content of fructose LAURIC ACID 99 MIN monoesters detect, to confirm the transformation efficiency of fructose LAURIC ACID 99 MIN monoesters.
Embodiment 1:
A. take by weighing the DA-201 macroporous adsorbent resin of the activated processing of 5 g, the 10g phosphate buffered saline buffer, the free phospholipase A1 of 1g mixes, and at 25 ℃ of following whip attachment 2h, filters then, gets the macroporous adsorbent resin immobilized phospholipase, and its enzyme work is 1850 U/g.Vacuum-drying, subsequent use;
B. 4 molecular sieves are placed activation 10h in 105 ℃ of baking ovens, place the moisture eliminator internal cooling again to room temperature, subsequent use; Afterwards, 4 molecular sieves after the activation are joined in the trimethyl carbinol as reaction medium according to the amount that every liter of solvent adds 80g, 72h is placed in sealing, removes by filter molecular sieve again, gets dehydrated organic solvent;
C. enzymatic esterification: getting 10g LAURIC ACID 99 MIN and 1.8g fructose is to mix in the above-mentioned dehydrated organic solvent of 42ml at volume, and the immobilized phospholipase A1 that adds 2g again begins reaction; Activation 4 molecular sieves that add 10g behind the reaction 2h are to remove the water that generates in the dereaction; Hunting speed 160r/min vibrate or stirring reaction 48h down at 45 ℃; After reaction finishes, adopt filter method that immobilized phospholipase A1, molecular sieve and unreacted sugar are removed, get gained filtrating, identify through LC-MS and can know that synthetic product is a fructose LAURIC ACID 99 MIN monoesters; Measure through high performance liquid chromatograph, the transformation efficiency of fructose LAURIC ACID 99 MIN monoesters is 68.05%.
Embodiment 2:
A. take by weighing the DA-201 macroporous adsorbent resin of the activated processing of 5 g, the 20g phosphate buffered saline buffer, the free phospholipase A1 of 1g mixes, and at 30 ℃ of following whip attachment 4h, filters then, gets the macroporous adsorbent resin immobilized phospholipase, and its enzyme work is 1462 U/g.Vacuum-drying, subsequent use;
B. 4 molecular sieves are placed activation 8h in 100 ℃ of baking ovens, place the moisture eliminator internal cooling again to room temperature, subsequent use; Afterwards, 4 molecular sieves after the activation are joined in the tertiary amyl alcohol as reaction medium according to the amount that every liter of solvent adds 60g, 24h is placed in sealing, removes by filter molecular sieve again, gets dehydrated organic solvent;
C. enzymatic esterification: getting 10g LAURIC ACID 99 MIN and 2.3g fructose is to mix in the above-mentioned dehydrated organic solvent of 100ml at volume, and the immobilized phospholipase A1 that adds 2g again begins reaction; Activation 4 molecular sieves that add 10g behind the reaction 1h are to remove the water that generates in the dereaction; Hunting speed 160r/min vibrate or stirring reaction 48h down at 40 ℃; After reaction finishes, adopt filter method that immobilized phospholipase A1, molecular sieve and unreacted sugar are removed, get gained filtrating, identify through LC-MS and can know that synthetic product is a fructose LAURIC ACID 99 MIN monoesters; Measure through high performance liquid chromatograph, the transformation efficiency of fructose LAURIC ACID 99 MIN monoesters is 64.68%.
Embodiment 3:
A. take by weighing the DA-201 macroporous adsorbent resin of the activated processing of 5 g, the 20g phosphate buffered saline buffer, the free phospholipase A1 of 1g mixes, and at 35 ℃ of following whip attachment 3h, filters then, gets the macroporous adsorbent resin immobilized phospholipase, and its enzyme work is 1344 U/g.Vacuum-drying, subsequent use;
B. 3 molecular sieves are placed activation 5h in 95 ℃ of baking ovens, place the moisture eliminator internal cooling again to room temperature, subsequent use; Afterwards, 3 molecular sieves after the activation are joined in the acetone as reaction medium according to the amount that every liter of solvent adds 50g, 72h is placed in sealing, removes by filter molecular sieve again, gets dehydrated organic solvent;
C. enzymatic esterification: getting 40.6g LAURIC ACID 99 MIN and 36.5 fructose is to mix in the above-mentioned dehydrated organic solvent of 812ml at volume, and the immobilized phospholipase A1 that adds 8.12g again begins reaction; Activation 3 molecular sieves that add 40.6g behind the reaction 1h are to remove the water that generates in the dereaction; Hunting speed 170r/min vibrate or stirring reaction 72h down at 40 ℃; After reaction finishes, adopt filter method that immobilized phospholipase A1, molecular sieve and unreacted sugar are removed, get gained filtrating, identify through LC-MS and can know that synthetic product is a fructose LAURIC ACID 99 MIN monoesters; Measure through high performance liquid chromatograph, the transformation efficiency of fructose LAURIC ACID 99 MIN monoesters is 61.35%.
Fig. 2 is the LC-MS collection of illustrative plates that reacts the fructose LAURIC ACID 99 MIN monoesters that obtains, and the molecular weight of fructose LAURIC ACID 99 MIN monoesters is 362, and 385.3 peaks that occur in the spectrogram are [M+Na] mass signal, so catalysis synthetic product is for being fructose LAURIC ACID 99 MIN monoesters.
Claims (3)
1. method of utilizing immobilized phospholipase A1 catalytic preparation fructose LAURIC ACID 99 MIN monoesters is characterized in that LAURIC ACID 99 MIN and fructose may further comprise the steps through enzymic catalytic reaction acrose LAURIC ACID 99 MIN monoesters:
(1) immobilization of phospholipase A1: the DA-201 macroporous adsorbent resin of getting 5 ~ 10 parts of activated processing of quality; The phosphate buffered saline buffer of 10 ~ 25 parts of quality, 0.5 ~ 2 part of free phospholipase A1 of quality mixes, at 25 ~ 35 ℃ of following whip attachment 2 ~ 6h; Filter then; Get the macroporous adsorbent resin immobilized phospholipase, with the immobilized enzyme vacuum-drying that makes, subsequent use;
(2) preparation dehydrated organic solvent: 3 or 4 molecular sieves are placed activation 5～10h in 95～105 ℃ of baking ovens, place the moisture eliminator internal cooling again to room temperature, subsequent use; Afterwards, 3 after activation or 4 molecular sieves are joined in the organic solvent as reaction medium for use according to the amount that every liter of solvent adds 50～80 parts of quality, 24～72h is placed in sealing, removes by filter molecular sieve, gets dehydrated organic solvent again;
(3) immobilized phospholipase A1 catalysis acrose LAURIC ACID 99 MIN monoesters: get 10～40.6 parts of Quality Month cinnamic acids and 1.8～36.5 parts of quality fructose place above-mentioned dehydrated organic solvent to mix; Wherein LAURIC ACID 99 MIN concentration is 5～24wt%, and the immobilized phospholipase A1 that adds again with respect to LAURIC ACID 99 MIN quality 8～25wt% begins reaction; Behind reaction 0～2h according to adding 3 or 4 molecular sieves after the activation with respect to LAURIC ACID 99 MIN quality 0.5-2 amount doubly to remove the water that generates in the dereaction; Hunting speed 150 ~ 185r/min vibrate or stirring reaction 8～96h down at 35 ℃～45 ℃; After reaction finishes, adopt filter method that immobilized phospholipase A1, molecular sieve and unreacted sugar are removed; Gained filtrating is removed organic solvent through rotary evaporation, obtains product fructose LAURIC ACID 99 MIN monoesters after the purification.
2. method according to claim 1 is characterized in that, phospholipase A1 is a kind of microbe-derived Phospholipid hydrolase of Novozymes Company in the said step (1), and commodity are called Lecitase Ultra; Its consumption is 5 ~ 20wt% of macroporous adsorbent resin quality.
3. method according to claim 1 and 2 is characterized in that: reaction medium organic solvent kind is any one in propyl carbinol, the trimethyl carbinol, tertiary amyl alcohol, chloroform, butanone, acetone or the methylethylketone in the said step (2), or two or more mixtures; And described reaction medium organic solvent polarity scope is Log P=3.0～7.0.
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| CN104293764A (en) * | 2013-07-19 | 2015-01-21 | 丰益(上海)生物技术研发中心有限公司 | Phosphatidase A1 immobilization method |
| CN105462952A (en) * | 2015-12-31 | 2016-04-06 | 内蒙古金达威药业有限公司 | Method for immobilizing lipase B from candida antarctica fermented supernatant fluid |
| CN106727025A (en) * | 2017-01-13 | 2017-05-31 | 华南理工大学 | A kind of camellia skin cream and preparation method thereof |
| CN106880521A (en) * | 2017-01-13 | 2017-06-23 | 华南理工大学 | A kind of camellia bath foam and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293764A (en) * | 2013-07-19 | 2015-01-21 | 丰益(上海)生物技术研发中心有限公司 | Phosphatidase A1 immobilization method |
| CN105462952A (en) * | 2015-12-31 | 2016-04-06 | 内蒙古金达威药业有限公司 | Method for immobilizing lipase B from candida antarctica fermented supernatant fluid |
| CN105462952B (en) * | 2015-12-31 | 2018-06-29 | 内蒙古金达威药业有限公司 | A kind of method of fixed fat enzyme B in fermented supernatant fluid from antarctic candida |
| CN106727025A (en) * | 2017-01-13 | 2017-05-31 | 华南理工大学 | A kind of camellia skin cream and preparation method thereof |
| CN106880521A (en) * | 2017-01-13 | 2017-06-23 | 华南理工大学 | A kind of camellia bath foam and preparation method thereof |
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