CN100554306C - A kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) - Google Patents
A kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) Download PDFInfo
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- CN100554306C CN100554306C CNB2007100554568A CN200710055456A CN100554306C CN 100554306 C CN100554306 C CN 100554306C CN B2007100554568 A CNB2007100554568 A CN B2007100554568A CN 200710055456 A CN200710055456 A CN 200710055456A CN 100554306 C CN100554306 C CN 100554306C
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Abstract
The present invention relates to a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone), belong to polymer chemistry and biological technical field.Be under condition of normal pressure, the monomer 6-caprolactone is mixed with organic solvent, add the zymin catalyzed reaction, under 60～100 ℃ of temperature, react 24～120h, after reaction finishes, in reaction system, add methylene dichloride, remove by filter enzyme, filtrate is carried out vacuum concentration remove organic solvent, add ice cold methanol in the resistates, precipitate under the low temperature, centrifugal collecting precipitation, precipitation gets polymerisate through vacuum-drying.Selected zymin is the super thermophilic esterase AFEST that derives from super hyperthermophilic archaeon strain Archaeoglobus fulgidus.The present invention has overcome harsh reaction conditions such as decompression, protection of inert gas, and syntheticly implements with aftertreatment technology with sophisticated, thus have that production technique is simple, safety, energy consumption is low, output is high characteristics.
Description
Technical field
The present invention relates to a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone), belong to polymer chemistry and biological technical field.
Background technology
Poly-(6-caprolactone) is a kind of synthesizing polyester with good biocompatibility and biological degradability, at aspects such as controlled release drug delivery system, bone reparation and organizational projects extensive studies and application arranged as bio-medical material.In addition, it is lower that poly-(6-caprolactone) and most of traditional hot plastic materials have under good consistency and the molten state viscosity, thereby be widely used in plastic working, thermoplastic adhesive, molding etc.Lower molecular weight poly-(6-caprolactone) is widely used as the soft section part and the pharmaceutical carrier of synthesis of polyurethane.
At present, the synthetic of poly-(6-caprolactone) mainly is by metal catalyst, and as stannous iso caprylate, aluminum isopropylate etc., the catalysis ring-opening polymerization is realized under body or solution condition.But harsh reaction conditions (high temperature, high pressure etc.), long reaction times (nearly tens hours) and complicated last handling process (power consumption, time-consuming and a large amount of solvent consumption) have brought difficulty to production.Simultaneously, the trace residue of heavy metal catalyst and genotoxic potential have limited its widespread use in biomedical materials field.
In recent years, enzymatic polymerization since the high advantage of reaction conditions gentleness, nontoxic, stereoselectivity and locational choice height, catalytic efficiency aspect poly-(6-caprolactone) synthetic, play an important role.1993, Knani and Kobayashi reported at first and have utilized the enzymatic ring-opening polymerization to synthesize poly-(6-caprolactone) that molecular weight of product reaches 7700.At present, multiple commercially available lipase all is used to the polyreaction of catalysis 6-caprolactone as porcine pancreatic lipase, antarctic candidia lipase, fluorescent pseudomonas lipase etc.Yet super thermophilic esterase catalyzed 6-caprolactone polyreaction is not appeared in the newspapers as yet.
Esterase (Esterase, EC 3.1.1.1) is the serine hydrolase class that a class is distributed widely in tissue and organ, can many endogenous and the exogenous materials that contain ester bond, thioester bond, amido linkage of hydrolysis.Its major function is the integrity that participates in lipid metabolism, signal conduction and keep biofilm structure, can also finish numerous reactions such as transesterification, esterification and transesterify in organic phase.In recent years, people's separation from the ancient bacterium of the thermophilic of oceanic heat flow has obtained super thermophilic esterase, for modern enzyme engineering technology has represented new application prospect.Super thermophilic esterase has overcome not only that the chemical catalyst catalytic efficiency is low, the inferior position of specificity difference, and compares with middle temperature enzyme, has very high stability.This will greatly promote the development of biotechnology industry, thus the raising of the level of motivating technical transformation of the factory with financial strength and quality of life.Utilize super thermophilic esterase as biological catalyst following advantage to be arranged: (1) enzyme preparation cost reduces.Enzyme stable higher can carry out separation and purification and packed and transported under the room temperature.(2) reaction rate accelerates.Along with the raising of temperature of reaction, the enzyme catalysis ability strengthens.(3) standard that requires of reactor cooling system reduces, and energy consumption reduces.(4) product purity improves.Under catalytic condition, assorted bacterium existence is seldom arranged, thereby reduced the pollution of bacterium metabolite product.Because the pyroreaction activity of super thermophilic esterase, and to the strong resistance of organic solvent, stain remover and denaturing agent, its potentiality that all are widely used at aspects such as food, medicine, process hides, functional materials, oil production and waste treatment.
Summary of the invention
Super hyperthermophilic archaeon strain Archaeoglobus fulgidus is a class thermophilic microorganism that grows in crater, oil field settling and the hot spring, and optimum growth temperature is 83 ℃.This bacterium is a kind of known bacterial classification, and (Deutsche Sammlung von Mikroorganismen Zellkulturen, DSMZ www.dsmz.de), preserve and are numbered DSM 4304 to be stored in German microbial strains preservation center.1997, Klenk has reported genome sequence (The complete genome sequence of thehyperthermophilic, the sulphate-reducing archaeon Archaeoglobus fulgidus.Nature 1997 of this super hyperthermophilic archaeon strain; 390:364-370).Document (Stress-induced production of biofilm in thehyperthermophile Archaeoglobus fulgidus.Applied and EnvironmentalMicrobiology 1997; 63:3158-3163) describe characteristics such as this bacteria growing situation in detail.Any researchist of this area can fully understand Archaeoglobus fulgidus bacterial classification by document, because this bacterial classification has been a kind of generally acknowledged product, and anyone can buy from German microbial strains preservation center with the form of commodity.
2000, Manco utilizes polymerase chain reaction (Polymerization chain reaction, PCR) technology is angled the gene A F1716 that has got super thermophilic esterase AFEST from Archaeoglobus fulgidus genome, utilize pT7-SCll to be expression vector, with recombinant plasmid clone in e. coli bl21, obtain a strain engineering bacteria (Cloning, overexpression, and properties of a newthermophilic and thermostable esterase with sequence similarity tohormone-sensitive lipase subfamily from the archaeon Archaeoglobus fulgidus.Archives of Biochemistry and Biophysics 2000; 373:182-192).This project bacterium not only culture condition is simple, and can breed and efficiently express super thermophilic esterase AFEST fast.The method that the document has introduced at length that angling of super thermophilic esterase AFEST gene got, used carrier and engineering bacteria make up.Anyone of this area can fully understand structure and the characteristic of this project bacterium by the document, and utilizes identical or corresponding techniques to angle from Archaeoglobus fulgidus genome and get the super structure of having a liking for the gene of esterase AFEST and carrying out engineering bacteria.
The objective of the invention is to utilize the super thermophilic esterase preparation of super thermophilic esterase engineering bacterium fermentation, purifying preparation to be catalyzer, catalyzed polymerization 6-caprolactone in non-aqueous media is set up and is reached aftertreatment technology a kind of synthesizing of poly-(6-caprolactone) without metal catalyst, mild condition.Main contents of the present invention comprise the preparation of super thermophilic esterase preparation and the synthetic and aftertreatment of poly-(6-caprolactone).
Novel super thermophilic esterase catalyzed preparation of poly (6-caprolactone), it is under condition of normal pressure, and the monomer 6-caprolactone is mixed with organic solvent, adds super thermophilic esterase preparation catalyzed reaction, reactant can obtain product poly-(6-caprolactone) through separation and purification.
Selected super thermophilic esterase preparation is the super thermophilic esterase AFEST preparation that derives from super hyperthermophilic archaeon strain Archaeoglobus fulgidus.Super thermophilic esterase AFEST preparation is prepared through fermentation, purifying by the super thermophilic esterase engineering bacteria, the substratum of super thermophilic esterase engineering bacteria is 1～2% yeast powder, 1.5～2.0% peptones, 0.5～1.0% sodium-chlor, pH is 7.0～7.5,115～121 ℃ of sterilization 15～20min down; Seed liquor is amplified step by step, and inoculum size is that 1～2%, 37 ℃ of growth turbidity that are cultured to culture are at OD
600Reach 1.5～2.0; Then, add sec.-propyl-β-D-sulfo-glycopyranoside and induce, final concentration is 1mM, and 37 ℃ are continued to cultivate 3～4h down; Centrifugal 20～the 30min of fermented liquid 5000～8000r/min is collected thalline; Thalline in subzero 20 ℃～subzero 40 ℃ with room temperature under multigelation 2～3 times, add the 50mmol/L phosphoric acid buffer according to 1: 6～8 (w/v), pH value 8.0 mixes the 20～30min of ultrasonication afterwards; Cytoclasis liquid is incubated 20～30min in 80～90 ℃, with sex change precipitation intestinal bacteria foreign protein; After the cooling, collect supernatant behind the centrifugal 15～20min of 7000～8000r/min, obtain crude enzyme liquid; Crude enzyme liquid carries out ultrafiltration through 20kD film bag, and liquid carries out freeze-drying after the ultrafiltration, obtains super thermophilic esterase AFEST preparation.
Organic solvent is toluene, normal hexane or hexanaphthene.The volume ratio of organic solvent and 6-caprolactone is 2.0～5.0: 1.The mass ratio of super thermophilic esterase AFEST preparation and 6-caprolactone is 1: 4～20.Catalyzed reaction is in the capping system, reacts 24～120h under 60～100 ℃ of temperature.Separation and purification is to add methylene dichloride in reaction system, removes by filter enzyme, filtrate is carried out vacuum concentration remove organic solvent, adds ice cold methanol in the resistates, precipitate under the low temperature, and centrifugal collecting precipitation, precipitation gets polymerisate through vacuum-drying.The volume ratio of methylene dichloride and 6-caprolactone is 25～50: 1.The low-temperature sludge temperature is subzero 20 ℃～subzero 40 ℃, and the vacuum-drying time is 16～24h.
Through nucleus magnetic resonance (
1H NMR) characterizes the structure that product has poly-(6-caprolactone) (accompanying drawing 1).Product is analyzed through gel permeation chromatography (GPC), and number-average molecular weight is 1200～2300g/mol, and polymolecularity 1.1～1.5 can be widely used as soft segment of polyurethane part and pharmaceutical carrier.
The present invention has the following advantages:
1. the present invention uses super thermophilic esterase as catalyzer, owing to set up the engineering bacterium fermentation of comparative maturity and the preparation technology of zymin, thereby reduced production cost greatly;
2. to adopt the super thermophilic esterase with high heat stability be catalyzer in the present invention, carries out polyreaction in hot conditions, greatly improved speed of reaction, shortened the production cycle, provides favourable condition for production-scale expansion when reducing cost;
3. the product of the present invention's employing extracts and aftertreatment technology, and is simple to operate, and the organic solvent of Shi Yonging reclaims and recycling easily simultaneously, when reducing production costs, can not pollute environment, meets the requirement of present green chemical industry.
Description of drawings
Fig. 1: by embodiment 2 method synthetic products
1H NMR collection of illustrative plates;
As shown in Figure 1, among the figure, 0ppm is the division of internal standard substance tetramethylsilane (TMS) methyl hydrogen; 7.28ppm be solvent deuterochloroform (CDCl
3) in residual chloroform (CHCl
3) in the division peak of hydrogen.Produce 1.38ppm the triplet of locating is two the hydrogen divisions in c place, the multiplet at 1.65ppm place is b and the hydrogen atom splitted result of d place, and the triplet at 2.31ppm place is that two the hydrogen divisions in a place produce, and 4.06ppm then is the hydrogen atom splitted result of e place.In addition, 3.65 places feature division peak that little triplet is last two hydrogen atoms of end group f.
Embodiment
Examples of implementation given below are that the invention will be further described, so that those skilled in the art is more fully understood the present invention.But given embodiment can not be interpreted as limiting the scope of the invention, thereby nonessential improvement and adjustment that this technical professional is made according to the foregoing invention content also should belong to protection domain of the present invention.
Embodiment 1:
The preparation of super thermophilic esterase AFEST preparation
The substratum of super thermophilic esterase engineering bacteria is as follows: 1% yeast powder, 1.6% peptone, 0.5% sodium-chlor, pH are 7.0,115 ℃ of sterilization 20min down.Seed liquor is amplified step by step, and inoculum size is 1%, and volume of culture is 10 liters.37 ℃ of growth turbidity that are cultured to culture are at OD
600Reach 1.8.Then, add IPTG and induce (final concentration is 1mM), 37 ℃ are continued to cultivate 3h down.The centrifugal 20min of fermented liquid 5000r/min is collected thalline.Thalline in-20 ℃ with room temperature under multigelation 2 times, add 50mmol/L phosphoric acid buffer (pH 8.0) according to 1: 6 (w/v), mix back ultrasonication 20min.Cytoclasis liquid is incubated 30min in 80 ℃, with sex change precipitation intestinal bacteria foreign protein.After the cooling, collect supernatant behind the centrifugal 15min of 8000r/min, obtain crude enzyme liquid.Crude enzyme liquid carries out ultrafiltration through 20kD film bag, and liquid carries out freeze-drying after the ultrafiltration, obtains super thermophilic esterase AFEST preparation.
Embodiment 2:
200 μ L (215mg) 6-caprolactones (purity 〉=99%) are mixed with 600 μ L toluene, add 20mg super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 72h, with 10mL methylene dichloride lysate, remove by filter enzyme, it is 99.97% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate is carried out vacuum concentration, adds ice cold methanol precipitation under subzero 20 ℃ in the resistates, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 1768g/mol, and polymolecularity is 1.21.
Embodiment 3:
200 μ L (215mg) 6-caprolactones (purity 〉=99%) are mixed with 600 μ L hexanaphthenes, add 20mg super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 72h, with 10mL methylene dichloride lysate, remove by filter enzyme, it is 95.29% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate is carried out vacuum concentration, adds ice cold methanol in the resistates in subzero 20 ℃ of precipitations, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 2238g/mol, and polymolecularity is 1.46.
Embodiment 4:
200 μ L (215mg) 6-caprolactones (purity 〉=99%) are mixed with 600 μ L normal hexanes, add 20mg super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 72h, with 10mL methylene dichloride lysate, remove by filter enzyme, it is 100% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate is carried out vacuum concentration, adds ice cold methanol in the resistates in subzero 20 ℃ of precipitations, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 2073g/mol, and polymolecularity is 1.31.
Embodiment 5:
200 μ L (215mg) 6-caprolactones (purity 〉=99%) are mixed with 600 μ L toluene, add 20mg super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 60h, with 10mL methylene dichloride lysate, remove by filter enzyme, it is 99.38% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate is carried out vacuum concentration, adds ice cold methanol in the resistates in subzero 20 ℃ of precipitations, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 1268g/mol, and polymolecularity is 1.26.
Embodiment 6:
200 μ L (215mg) 6-caprolactones (purity 〉=99%) are mixed with 600 μ L toluene, add 30mg super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 72h, with 10mL methylene dichloride lysate, remove by filter enzyme, it is 99.65% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate is carried out vacuum concentration, adds ice cold methanol in the resistates in subzero 20 ℃ of precipitations, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 1262g/mol, and polymolecularity is 1.29.
Embodiment 7:
5mL (5.38g) 6-caprolactone (purity 〉=99%) is mixed with 15mL toluene, add 500mg super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 72h, with 250mL methylene dichloride lysate, remove by filter enzyme, it is 100% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate is carried out vacuum concentration, adds ice cold methanol in the resistates in subzero 20 ℃ of precipitations, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 1215g/mol, and polymolecularity is 1.19.
Embodiment 8:
50mL (53.8g) 6-caprolactone (purity 〉=99%) is mixed with 150mL toluene, add 5g super thermophilic esterase AFEST preparation and make catalyzer, behind 80 ℃ of following oscillatory reaction 72h, with 2L methylene dichloride lysate, remove by filter enzyme, it is 100% that filtrate is measured monomer conversion through gas-chromatography (GC).Filtrate adds ice cold methanol in subzero 20 ℃ of precipitations through vacuum concentration in the resistates, the centrifugal 15min collecting precipitation of 8000r/min, and drying under reduced pressure 16h gets polymerisate.Product is measured through gel permeation chromatography (GPC), and number-average molecular weight is 1355g/mol, and polymolecularity is 1.24.
Claims (9)
1, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone), it is characterized in that: under condition of normal pressure, the monomer 6-caprolactone is mixed with organic solvent, add the super thermophilic esterase preparation, in the capping system, catalyzed reaction 24～120h under 60～100 ℃ of temperature, reactant can obtain product poly-(6-caprolactone) through separation and purification.
2, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 1 is characterized in that: selected super thermophilic esterase preparation is the super thermophilic esterase AFEST preparation that derives from super hyperthermophilic archaeon strain Archaeoglobus fulgidus.
3, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 2, it is characterized in that: super thermophilic esterase AFEST preparation is prepared through fermentation, purifying by the super thermophilic esterase engineering bacteria, the substratum of super thermophilic esterase engineering bacteria is 1～2% yeast powder, 1.5～2.0% peptone, 0.5～1.0% sodium-chlor, pH is 7.0～7.5,115～121 ℃ of sterilization 15～20min down; Seed liquor is amplified step by step, and inoculum size is that 1～2%, 37 ℃ of growth turbidity that are cultured to culture are at OD
600Reach 1.5～2.0; Then, add sec.-propyl-β-D-sulfo-glycopyranoside and induce, final concentration is 1mM, and 37 ℃ are continued to cultivate 3～4h down; Centrifugal 20～the 30min of fermented liquid 5000～8000r/min is collected thalline; Thalline in subzero 20 ℃～subzero 40 ℃ with room temperature under multigelation 2～3 times, add the 50mmol/L phosphoric acid buffer according to 1w:6v～8v, pH value 8.0 mixes the 20～30min of ultrasonication afterwards; Cytoclasis liquid is incubated 20～30min in 80～90 ℃, with sex change precipitation intestinal bacteria foreign protein; After the cooling, collect supernatant behind the centrifugal 15～20min of 7000～8000r/min, obtain crude enzyme liquid; Crude enzyme liquid carries out ultrafiltration through 20kD film bag, and liquid carries out freeze-drying after the ultrafiltration, obtains super thermophilic esterase AFEST preparation.
4, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 1, it is characterized in that: organic solvent is toluene, normal hexane or hexanaphthene.
5, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 4, it is characterized in that: the volume ratio of organic solvent and 6-caprolactone is 2.0～5.0: 1.
6, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 3, it is characterized in that: the mass ratio of super thermophilic esterase AFEST preparation and 6-caprolactone is 1: 4～20.
7, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 1, it is characterized in that: separation and purification is to add methylene dichloride in reaction system, remove by filter enzyme, filtrate is carried out vacuum concentration remove organic solvent, add ice cold methanol in the resistates, precipitate under the low temperature, centrifugal collecting precipitation, precipitation gets polymerisate through vacuum-drying.
8, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 7, it is characterized in that: the volume ratio of methylene dichloride and 6-caprolactone is 25～50: 1.
9, a kind of method of utilizing super thermophilic esterase for catalyst to synthesize (6-caprolactone) as claimed in claim 7, it is characterized in that: the low-temperature sludge temperature is subzero 20 ℃～subzero 40 ℃, and the vacuum-drying time is 16～24h.
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| CN102676603B (en) * | 2012-01-12 | 2015-06-17 | 河南科技大学 | Method for preparing polycaprolactone |
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