CN101974507B - Method for preparing immobilized laccase - Google Patents
Method for preparing immobilized laccase Download PDFInfo
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- CN101974507B CN101974507B CN201010505175XA CN201010505175A CN101974507B CN 101974507 B CN101974507 B CN 101974507B CN 201010505175X A CN201010505175X A CN 201010505175XA CN 201010505175 A CN201010505175 A CN 201010505175A CN 101974507 B CN101974507 B CN 101974507B
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Abstract
The invention discloses a method for preparing immobilized laccase, comprising the following steps of: taking CuBr2 as a catalyst, taking 2,2'-bipyridine as a ligand, taking ethyl 2-bromopropanoate as a free initiator, and taking a porous sintering glass ring as a vector to prepare a porous sintering glass ring with the function of glycidyl methacrylate graft polymerization; and adding the porous sintering glass ring into a laccase solution, shaking or stirring for 16-24h, then adding a glutaraldehyde solution to crosslink for 1h, filtering, washing by pure water, removing unadsorbed free enzyme, and then centrifugally removing surface moisture to obtain the immobilized laccase adsorbed and crosslinked on the porous sintering glass ring. The invention combines a physical adsorption method and a covalence-crosslinking method, draws the strong points to offset the weakness and optimizes coordination. The prepared immobilized laccase is suitable for synthesis of a resveratrol dimer and solves the post-turbidity problem caused by slow juice clarification and long-time storage in beverage processing.
Description
Technical field
The invention belongs to the immobilized enzyme preparing technical field, be specifically related to the preparation method of immobilization laccase.
Background technology
Japan scholar Tian Yanliu youth finds to make " Rhus lacquer " oxidation hardened enzyme in lacquer tree resin, Bei Telande (G.E.Bertrand, 1894) had at length studied South East Asia and produced the enzyme in the lacquer, called after laccase afterwards.Laccase (Laccases) is phenol oxidase a kind of who Resorcinol (quinhydrones) is oxidized to para benzoquinone by oxygen, also is called the hydroquinone oxidation enzyme.Laccase is the protein that is combined with a plurality of cupric ions, belongs to the covellite oxydase, and molecular weight is about 120,000, contains 4 atom copper, can be suppressed by CN-.Laccase survives in the air, and the unique product in back that reacts is exactly a water, is a kind of environment-friendly type enzyme in essence.In recent years, along with the reinforcement gradually of environmental consciousness, laccase has become numerous scholars' research object.
Laccase is distributed widely in fungi, plant and the insect.In fungi, laccase is present in the aspergillus tubigensis bacterial classifications such as (Aspergillus) of pore fungus (Poly-porus) and imperfect fungi of neurospora (Neurospora) and Podospora (Podospora), Basidiomycetes of Ascomycetes.Find that at present laccase also extensively is present in the bacterium, as giving birth to fat azospirillum (Azospirlllum lipoferum) etc.The similarity of its aminoacid sequence of laccase of different sources is not high, so the laccase molecular weight is widely different.
Various phenols dyestuffs, chlorophenol, substituted phenol, thiophenol, aromatic amine, dihydroxyphenyl propane etc. are decomposed in the oxygen direct oxidation of laccase in can catalytic air; In the presence of laccase amboceptor (HBT, ABTS etc.), laccase can also replace phenyl diamines, ditan, organo phosphorous compounds (agricultural chemicals) and Dioxins etc. by the catalyzed degradation N-relevant with xylogen.Because it has Substratspezifitaet and stability quite widely preferably, so laccase has great application prospect at improvement phenolic wastewater, textile printing and dyeing wastewater and aspects such as paper-making industrial waste water and biosensor.
Recent study finds that the unique catalysis characteristics of laccase has a wide range of applications it in biological detection, becomes the effective tool and the means of composition analyses such as substrate, coenzyme, suppressor factor as biosensors efficiently.The biosensors that laccase constitutes mainly contains two kinds: laccase electrode and laccase enzyme mark.
Enzyme is as protein; Have proteinic common characteristics (as: can not reuse, to the high susceptibility of denaturing agent and toxicological effect), when running into high temperature, strong acid, highly basic, can lose activity, have no catalysis and can say; Effective use that these have all limited laccase has improved use cost; And more purified laccase price is very high, has also limited the use of laccase.A kind of new technology that occurs in recent years just can partly address these problems---enzyme immobilization technology.
Immobilized enzyme (immobilized enzyme) is the enzyme with physics or chemical process treatment of water-soluble, make it to become water insoluble or be fixed in solid phase carrier but still enzyme derivative with enzymic activity.Immobilized enzyme has tangible advantage than loose enzyme: 1. certain mechanical strength and good stability are arranged; Can make different shape (like particulate state, tubulose, membranaceous) is contained in the reactive tank; Be convenient to take out, can be continuously, use repeatedly, can reduce production costs greatly; Also can make catalyzer and system's phase-splitting, the later stage of being convenient to product separates.2. but thorough washing is not before use brought impurity into, and is little to the reaction influence.3. stability improves, and is difficult for losing activity, and prolong work-ing life, but life-time service and storage, and can regenerate.4. be convenient to automated operation, simultaneously also for realizing that canalization, serialization and the robotization of producing provide possibility, are convenient to the continuous production with computer control.
Usually, the process for fixation of enzyme is divided into physical method and chemical process, and wherein, physical method mainly contains three kinds of absorption method, entrapping method and ionic adsorption methods.Chemical process mainly contains two kinds of covalent attachment method and crosslinkings.The process for fixation of enzyme is no doubt a lot, but its relative merits are respectively arranged, and sums up like following table.
Obviously, the physisorphtion preparation is easy, enzyme activity keeps high, but a little less than the bonding force; And the covalent cross-linking method bonding force is strong, and it is moderate that enzyme activity keeps, but the preparation difficulty.The inventor finds that these two kinds of methods have complementarity, makes it to combine, and is the research direction of immobilization laccase preparation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of immobilization laccase; In conjunction with physisorphtion and covalent cross-linking method; Learn from other's strong points to offset one's weaknesses, optimize cooperation; Prepared immobilization laccase is applicable to the synthetic of Pallidol, and in beverage processing the polymerization oxidation aldehydes matter, solve juice clarification slowly with the long-time back muddy problem that is produced that stores.
In order to achieve the above object, the present invention adopts following technical scheme to be achieved.
A kind of preparation method of immobilization laccase, adopting has porous sintered glass ring, it is characterized in that, may further comprise the steps:
Step 1, with CuBr
2Be catalyzer, 2,2 '-dipyridyl is a part, and the 2 bromopropionic acid ethyl ester is free initiator, is carrier with porous sintered glass ring, and preparation has the porous sintered glass ring of glycidyl methacrylate graft polymerizable functional;
Step 2, in laccase solution, add porous sintered glass ring, after concussion under 30 ℃ of conditions or stirring 16～24 hours with glycidyl methacrylate graft polymerizable functional; Add glutaraldehyde solution, making the final mass concentration of LUTARALDEHYDE is 1%, under the room temperature crosslinked 1 hour; Filter back pure water washing; Remove the not resolvase of absorption, centrifugal again removal surface-moisture promptly obtains adsorbing crosslinked immobilization laccase on porous sintered glass ring.
The mass concentration of said laccase solution is 2～3% laccase solution.
The further optimization and the characteristics of technique scheme also are:
Described preparation with porous sintered glass ring of glycidyl methacrylate graft polymerizable functional specifically comprises: get porous sintered glass ring earlier and add in the dichloromethane solvent; After stirring also vacuum outgas; Added triethylamine and initiator 2-bromo isobutyryl bromine reaction 24 hours; Reaction finishes the back spinning and goes out solid; Wash successively with methylene dichloride, THF and acetone solvent, and vacuum-drying under normal temperature, the porous sintered glass ring that bonding has initiator 2-bromo isobutyl acylbromide got; Should add in the cyclohexanone solvent by porous sintered glass ring again, after stirring and the vacuum outgas, add SY-Monomer G, 2,2 '-dipyridyl, CuBr
2, and free initiator 2 bromopropionic acid ethyl ester; Then, feed nitrogen flooding and remove the air in the reaction system, after in-5 ℃～5 ℃ ice baths, vacuumizing, rise to room temperature and feed nitrogen again, remove air so repeatedly; At last, under nitrogen protection and stirring, 30 ℃ are carried out the constant temperature graft polymerization reaction, and reaction is cooled to normal temperature with reaction system after finishing, and the spinning reaction product promptly gets the porous sintered glass ring with glycidyl methacrylate graft polymerizable functional.
The preparation method of immobilization laccase of the present invention; In conjunction with physisorphtion and covalent cross-linking method; Learn from other's strong points to offset one's weaknesses, optimize cooperation, the immobilization laccase of preparation is applicable to the synthetic of Pallidol; And in beverage processing, make the polymerization of oxidation aldehydes matter, solve the back muddy problem that fruit juice is clarified slowly and long-time storage is produced in the course of processing.
Embodiment
Further specify the effect of technical scheme of the present invention and products therefrom below in conjunction with specific embodiment and checking example.Porous sintered glass ring wherein is that bigization of Yixing City filler ltd produces.
Embodiment 1,
Step 1, with CuBr
2Be catalyzer, 2,2 '-dipyridyl is a part, and the 2 bromopropionic acid ethyl ester is free initiator, is carrier with porous sintered glass ring, and preparation has the porous sintered glass ring of glycidyl methacrylate graft polymerizable functional, and detailed process is following:
The porous sintered glass ring of getting 5Kg earlier adds the 15L dichloromethane solvent; Stir also vacuum outgas then after 15 minutes, add the triethylamine of 0.5Kg and the initiator 2-bromo isobutyl acylbromide of 1Kg, normal-temperature reaction 24 hours; Reaction finishes the back spinning and goes out solid; Wash successively with methylene dichloride, THF and acetone solvent, and vacuum-drying under normal temperature, the porous sintered glass ring that chemically bonded has initiator 2-bromo isobutyl acylbromide promptly got.This porous sintered glass ring of getting 2Kg again adds in the 5L cyclohexanone solvent, stirs also vacuum outgas after 15 minutes, adds the SY-Monomer G of 1.5Kg, the part 2 of 0.75Kg, the Catalysts Cu Br of 2 '-dipyridyl, 60g
2, and the free initiator 2 bromopropionic acid ethyl ester of 0.1Kg; Then, feed high pure nitrogen and drove away air in 30 minutes, in salt ice bath (5 ℃～5 ℃), vacuumize 15 minutes again after, be warming up to room temperature and feed high pure nitrogen again, three times so repeatedly, thoroughly to remove air; At last, under nitrogen protection and stirring, 30 ℃ are carried out the constant temperature graft polymerization reaction; After reaction finishes; With ice-water bath reaction system is cooled to normal temperature, the spinning reaction product promptly gets the porous sintered glass ring with glycidyl methacrylate graft polymerizable functional.
Step 2, to get the 25L mass concentration be 2% fungal laccase solution (the L10 laccase of enlightening industry development ltd is worn in Shanghai), adds the porous sintered glass ring of the above-mentioned preparation of 1Kg, after stirring 16 hours under 30 ℃ of conditions; Adding concentration is 25% glutaraldehyde solution; Making the final mass concentration of LUTARALDEHYDE is 1%, under the room temperature crosslinked 1 hour, filters back pure water washing; Remove the not resolvase of absorption; Centrifugal again removal surface-moisture promptly obtains adsorbing crosslinked immobilization laccase on porous sintered glass ring, and records the enzyme 0.9696u/g of being alive.
Wherein, the measuring method of laccase vigor is: methyl catechol is dissolved in 5mmol/L sodium succinate damping fluid (pH4.5), and making methyl catechol concentration is 4mmol/L; In the 10mL reaction solution, contain the sodium succinate damping fluid that 2mL laccase solution and 8mL are dissolved with methyl catechol; 30 ℃ of reactions are after 30 minutes; Measuring absorbancy in the 465nm wavelength, is contrast with water, is 1 enzyme unit (u) that lives with the enzyme amount of catalyzed oxidation 1nmol methyl catechol in 1 minute.The measuring method of immobilization laccase vigor is: methyl catechol is dissolved in 5mmol/L sodium succinate damping fluid (pH4.5), and making methyl catechol concentration is 4mmol/L; In the 10mL reaction solution, contain the sodium succinate damping fluid that 2mL water and 8mL are dissolved with methyl catechol; Add the 0.2g immobilization laccase again; 30 ℃ of concussion reactions are after 30 minutes, and the centrifuging and taking supernatant is measured absorbancy in the 465nm wavelength; With the mixed solution that does not add immobilization laccase is contrast, is 1 enzyme unit (u) that lives with the enzyme amount of catalyzed oxidation 1nmol methyl catechol in 1 minute.
Embodiment 2,
Step 1 is with CuBr
2Be catalyzer, 2,2 '-dipyridyl is a part, and the 2 bromopropionic acid ethyl ester is free initiator, is carrier with porous sintered glass ring, and preparation has the porous sintered glass ring of glycidyl methacrylate graft polymerizable functional, and detailed process is following:
The porous sintered glass ring of getting 10Kg earlier adds the 20L dichloromethane solvent; Stir also vacuum outgas then after 15 minutes, add the 2-bromo isobutyl acylbromide of 1.6Kg and the triethylamine of 1Kg, normal-temperature reaction 24 hours; Reaction finishes the back spinning and goes out solid; Wash successively with methylene dichloride, THF and acetone solvent, and vacuum-drying under normal temperature, the porous sintered glass ring that chemically bonded has initiator 2-bromo isobutyl acylbromide promptly got.This porous sintered glass ring of getting 5Kg again adds in the 10L cyclohexanone solvent; Stir also vacuum outgas after 15 minutes; Add the SY-Monomer G of 3Kg, the part 2 of 1.5Kg, the Catalysts Cu Br2 of 2 '-dipyridyl and 120g, and the free initiator 2 bromopropionic acid ethyl ester of 0.5Kg; Then, feed high pure nitrogen and drove away air in 30 minutes, in salt ice bath (5 ℃～5 ℃), vacuumize 15 minutes again after, rise to room temperature and feed high pure nitrogen again, three times so repeatedly, to remove the air in the solution; At last, under nitrogen protection and stirring, 30 ℃ are carried out the constant temperature graft polymerization reaction; After reaction finishes; With ice-water bath reaction system is cooled to normal temperature, the spinning reaction product promptly gets the porous sintered glass ring with glycidyl methacrylate graft polymerizable functional.
Step 2 is got the 50L mass concentration and is 3% laccase solution (Guangzhou sea promise biotechnology ltd produces), adds the porous sintered glass ring of the above-mentioned preparation of 3Kg; After 24 hours, add 25% glutaraldehyde solution in concussion under 30 ℃ of conditions, making the final mass concentration of LUTARALDEHYDE is 1%; Under the room temperature crosslinked 1 hour; Filter back pure water washing, remove the not resolvase of absorption, centrifugal again removal surface-moisture; Promptly obtain adsorbing crosslinked immobilization laccase on porous sintered glass ring, and record the enzyme 0.9696u/g of being alive.
Checking example 1,
Get the immobilization laccase 300g (containing porous sintered glass ring weight) and the trans-resveratrol 100g of instance 1 preparation, react behind the adding 300g acetic acid ethyl dissolution trans-resveratrol, reacted 2 hours down, generate Pallidol in 30～40 ℃; After reaction finishes, can add new reaction substrate (trans-resveratrol) again and continue to generate Pallidol with the immobilization laccase reaction; Reaction times can reach 8～10 times.After 8 batches successive reaction, the immobilization laccase enzyme is lived and is kept 28～32%, and the laccase service efficiency improves greatly.Not immobilized laccase reacts once only, explains that immobilization laccase enzyme reservation amount alive is high.
Checking example 2,
Get the immobilization laccase 3Kg (containing porous sintered glass ring weight) and the trans-resveratrol 1Kg of instance 1 preparation; React after adding 4Kg acetic acid ethyl dissolution trans-resveratrol; Reacted 3 hours down in 30～40 ℃, the product amount of assaying reaction generation Pallidol is reacted first and is reached 38.2%; After 8 batches successive reaction, the product amount that generates Pallidol still reaches 28%, and the single product amount of immobilization laccase is not up to 33.5%.Explain and adopt the reaction efficiency of immobilization laccase to improve greatly.
Checking example 3,
Get the immobilization laccase 3Kg (containing porous sintered glass ring weight) and the trans-resveratrol 1Kg of instance 2 preparations; React after adding 5Kg acetic acid ethyl dissolution trans-resveratrol; Reacted 4 hours down in 30～40 ℃; Pallidol and by product that assaying reaction generates, amount of by-products is up to 0.82%, and the amount of by-products of immobilization laccase is not up to 8.9%.Explain and adopt immobilization laccase that amount of by-products is reduced greatly.
Checking example 4,
In the beverage processing process, utilize the laccase can the oxidation aldehydes matter; Make its polymerization; This both can make fruit juice clarification fast in the course of processing; Solved the back muddy problem that the long-time storage of fruit juice is produced again, and without Vinylpyrrolidone polymer (PVP), activated carbon or sorbent treatment, pollution problem is few.
Get the immobilization laccase 0.5Kg (containing porous sintered glass ring weight) of instance 2 preparations; Add to and be used for clarification in the 50Kg Sucus Mali pumilae; Act on after 12 hours, phenols, Flavonol and colored compound have reduced by 48.6%, 47% and 43% respectively in the mensuration Sucus Mali pumilae, and the clearance of catechuic acid reaches 75%; After reaction finished, the porous sintered glass ring that only will have immobilization laccase took out and gets final product, and it is reusable; And adopt not immobilization laccase, then can't effectively remove.
Although above combination embodiment is described technical scheme of the present invention and invention effect with the checking example, the present invention is not limited to above-mentioned specific examples, and above-mentioned specific embodiment only is schematic, guiding, rather than restrictive.Those of ordinary skill in the art under the situation that does not break away from claim of the present invention institute protection domain, can also make a variety of forms under the enlightenment of this specification sheets, these all belong to the row of the present invention's protection.
Claims (2)
1. the preparation method of an immobilization laccase, adopting has porous sintered glass ring, it is characterized in that, may further comprise the steps:
Step 1, with CuBr
2Be catalyzer, 2,2 '-dipyridyl is a part, and the 2 bromopropionic acid ethyl ester is free initiator, is carrier with porous sintered glass ring, and preparation has the porous sintered glass ring of glycidyl methacrylate graft polymerizable functional;
Step 2, in laccase solution; Add the porous sintered glass ring with glycidyl methacrylate graft polymerizable functional, after concussion under 30 ℃ of conditions or stirring 16～24 hours, adding glutaraldehyde solution to final mass concentration is 1%; Under the room temperature crosslinked 1 hour; Filter back pure water washing, centrifugal again removal surface-moisture promptly obtains adsorbing crosslinked immobilization laccase on porous sintered glass ring;
Wherein, The described preparation with porous sintered glass ring of glycidyl methacrylate graft polymerizable functional of step 1 specifically comprises: get porous sintered glass ring earlier and add in the dichloromethane solvent; After stirring also vacuum outgas; Added triethylamine and initiator 2-bromo isobutyryl bromine reaction 24 hours, reaction finishes the back spinning and goes out solid, washs successively with methylene dichloride, THF and acetone solvent; And vacuum-drying under normal temperature, get the porous sintered glass ring that bonding has initiator 2-bromo isobutyl acylbromide; Should add in the cyclohexanone solvent by porous sintered glass ring again, after stirring and the vacuum outgas, add SY-Monomer G, 2,2 '-dipyridyl, CuBr
2, and free initiator 2 bromopropionic acid ethyl ester; Then, feed nitrogen flooding and remove the air in the reaction system, after in-5 ℃～5 ℃ ice baths, vacuumizing, rise to room temperature and feed nitrogen again, remove air so repeatedly; At last, under nitrogen protection and stirring, 30 ℃ are carried out the constant temperature graft polymerization reaction, and reaction is cooled to normal temperature with reaction system after finishing, and the spinning reaction product promptly gets the porous sintered glass ring with glycidyl methacrylate graft polymerizable functional.
2. immobilization laccase preparation method according to claim 1 is characterized in that, the mass concentration of said laccase solution is 2～3%.
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| CN106866762B (en) * | 2016-12-22 | 2019-10-18 | 北京化工大学 | A kind of bionical laccase of nucleotidyl metal |
| CN110438116B (en) * | 2019-09-02 | 2021-09-21 | 成都信息工程大学 | Laccase immobilization method |
| CN114317614B (en) * | 2022-01-11 | 2024-01-30 | 安徽农业大学 | Method for preparing humic acid-like by using lignin precursor and application of humic acid-like by using lignin precursor |
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| CN101294157B (en) * | 2008-07-01 | 2012-07-04 | 北京师范大学 | Method for fixing laccase on stephanoporate silica gel |
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