CN1459502A - Anionic type laminated material immobilized enzyme and its preparation method - Google Patents

Anionic type laminated material immobilized enzyme and its preparation method Download PDF

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CN1459502A
CN1459502A CN02117919A CN02117919A CN1459502A CN 1459502 A CN1459502 A CN 1459502A CN 02117919 A CN02117919 A CN 02117919A CN 02117919 A CN02117919 A CN 02117919A CN 1459502 A CN1459502 A CN 1459502A
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enzyme
houghite
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immobilized enzyme
molecule
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段雪
任玲玲
何静
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Beijing University of Chemical Technology
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier

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Abstract

A anionic laminated material immobilized enzyme is prepared through intercalating the moleculae of object containing carboxy and amino groups between the layers of quasi-hydrotalcite as anionic laminated material, adding cross-linking agent and enzyme, and forming covalent bond between the amino groups on object and enzyme moleculae under the action of cross-linking agent to immobilize the enzyme moleculae between layers of quasi-hydrotalcite, so obtain layer column. Its advantage is high stability of enzyme moleculae.

Description

A kind of anionic type laminated material immobilized enzyme and preparation method thereof
Affiliated field:
The present invention relates to a kind of anionic type laminated material immobilized enzyme and preparation method thereof.
Background technology:
Enzyme as green catalyst have catalysis high efficiency, catalyzed reaction wide ranges, very high catalysis specificity, with many advantages such as high affinity, catalytic reaction condition gentleness, the energy consumption of substrate is low, renewable.Therefore enzyme is at medicine and chemical industry, and especially heavy chemical engineering industry is more and more used.Because resolvase (FreeEnzyme) generally is present in the aqueous solution with low concentration, the temperature of survival, pH value scope are narrower, easy sex change and inactivation, and poor stability, this is very limited its application.
In order to overcome the shortcoming of resolvase, people expect selecting appropriate carriers with enzyme immobilization, the enzyme molecule is because the change of microenvironment on every side like this, its thermostability and chemical stability are improved, can make prolong hundreds of times the work-ing life of enzyme, and immobilized enzyme is easy to separate with liquid phase reaction thing, product, therefore can use repeatedly.At present, immobilized enzyme (Immobilized Enzyme is abbreviated as IME) is used widely at commercial catalysts, and the development of immobilized enzyme is also benefited from other field such as bioseparation and purification in addition, diagnosis, bioprocess and disease treatment aspect.
The carrier of immobilized enzyme divides inorganic carrier and organic carrier.Because enzyme easily combines with organic polymer in the mode of chemistry, make it to use more and more widely, but the subject matter that exists is: the polymer carrier wetting ability is poor, the enzyme charge capacity is little, chemical stability is low.
The investigator transfers to inorganic carrier again to the interest of fixed enzyme vector at present.This is not only for economically consideration, also be because inorganic carrier has superiority more than organic carrier aspect physical properties, for example inorganic carrier physical strength height, Heat stability is good, anti-organic solvent, antimicrobial erosion, easy to operate, shelf-life long, easily regenerate by thermo-cracking.Many inorganic carriers also have the advantage that does not change its structure in wideer pH value, temperature and pressure scope.
Document Challa V.Kumar and George L.Mclendon, Nanoencapsulation ofCytochrome c and Horseradish Peroxidase at the Galleries of α-ZirconiumPhosphate, Chem.Mater.1997,9, introduced among the 863-870 directly cytopigment enzyme and peroxidation horseradish enzyme have been fixed between the alpha zirconium phosphate laminate, it is 3.3nm that interlamellar spacing increases, the functional group of enzyme and carrier interactions and alpha zirconium phosphate laminate has direct relation, and the avidity of carrier pair cell pigment c is far longer than the avidity of carrier to peroxidation horseradish enzyme.Its weak point is because the alpha zirconium phosphate laminate shows strongly-acid, the method of this direct immobilized enzyme only is suitable for a spot of enzyme that can survive in this pH value scope, and because enzyme and carrier interact by ionic linkage, reactive force relatively a little less than, make the thermostability of immobilized enzyme relatively poor, with resolvase much at one.The operational stability of immobilized enzyme is not discussed in the document.
Summary of the invention:
The objective of the invention is: the guest molecule that selection has reactive groups, by the intercalation method, be assembled into the stratified material interlayer by the interlayer orientation force, construct " molecular reactor " that can further react, obtain pillared material.Be carrier with this material again, the enzyme molecule be fixed in " molecular reactor " being fixed enzyme pillared material.This immobilized enzyme is because of being subjected to the restriction of geometry in the laminate, and substrate and product are changed on the reaction platform of being constructed by laminate in order during reaction, and the enzyme molecule can not run off.
Houghite (Layered Double Hydroxides is abbreviated as LDHs) is a kind of anionic type laminated material, and its typical structure is by MgO 6(ZnO 6) octahedra shared prismatic becomes unit layer, the divalent ion that is positioned on the laminate can be within the specific limits by the Al of similar radius 3+Replace etc. the isomorphous, make laminate positively charged, the tradable CO of interlayer 3 2-Positive charge balance on negatively charged ion and the laminate makes this structure be electric neutrality.Layer is strutted by other molecules easily with layer, and veneer structure is unaffected, but this constructional feature makes lamellar compound have intercalation and assembling performance.Therefore select the main body stratified material of houghite as immobilized enzyme.
Guest molecule selects to contain carboxyl and amino group and its carboxyl quantity molecule more than or equal to amino quantity, by the intercalation method, object carboxyl and main body laminate are interacted by the interlayer orientation force, be assembled between the laminate of houghite, and amino is retained between the laminate as active group, for subsequent reactions provides specific reaction platform.This houghite pillared material of having assembled guest molecule is being claimed " molecular reactor " visually.Amino group and enzyme molecule that " molecular reactor " provided form covalent linkage by linking agent, the enzyme molecule are fixed in " molecular reactor ", being fixed enzyme pillared material.
Preparation were established is: the houghite of desired structure is made into suspension, the guest molecule intercalation that contains carboxyl and amino group simultaneously is assembled into interlayer, add linking agent and enzyme molecule then, amino group forms covalent linkage as the active group in " molecular reactor " by linking agent and enzyme molecule, thereby form the immobilized enzyme pillared material, being fixed enzyme.
The concrete operations step is as follows:
A: preparation laminate divalence, trivalent metal cation mol ratio are 1.6-4.5: 1 houghite (preparation method sees patent application 00132146), get a certain amount of this houghite and join that compound concentration is the suspension of 0.2-2M in the container that fills deionized water, the room temperature lower magnetic force stirs, add excessive guest molecule by houghite and guest molecule complete reaction, by turbid solution become settled solution in the container this moment, standby;
With concentration is the NaOH dilute solution of 0.01-0.5M, add in the reactor of band condensation and stirring, stir on one side, drip above-mentioned standby settled solution on one side, keep dropping process pH＞9, after dropping finishes, the about 6h of condensing reflux, filter, use the hot water thorough washing to pH＜8, dry in about 85 ℃, obtaining interlayer anion is the houghite pillared material of guest molecule.
B: the weight ratio in " molecular reactor " and water is 1: the ratio of 50-80 adds in the reactor of band magnetic agitation, weight ratio in " molecular reactor " and linking agent is 1: the ratio of 1-3, in reactor, add 5%wt concentration linking agent, about magnetic agitation 1 hour, filter, fully washing;
Washed filter cake is put into container; add deionized water and phosphoric acid buffer catalysis activity with the protective enzyme molecule; solid-to-liquid ratio in houghite pillared material and liquid enzymes is 1: the ratio of 6-12 adds needs the fixed enzyme; fixing at a certain temperature about 20h in shaking table; through centrifugation; fully washing, being fixed enzyme.
The laminate divalent metal M of used houghite 2+For the used houghite of A is main body laminate divalent metal M 2+Be Mg 2+, Cu 2+, Ni 2+, Zn 2+, Fe 2+, Mn 2+,, Ca 2+Any, preferred Mg 2+Or Zn 2+, trivalent metal cation M 3+Be Al 3+, Ga 3+, Co 3+, Fe 3+, Cr 3+, V 3+, Ti 3+Any, preferred Al 3+And Fe 3+The preferred M of its mol ratio 2+: M 3+=2-4: 1; Interlayer anion is Cl -, CO 2-, NO 3 -, OH -, SO 4 2-, ClO 3-Any or several combinations.
Used guest molecule is to contain the acid more than or equal to amino quantity of carboxyl and amino group and carboxyl quantity simultaneously, preferred L-glutamic acid, aspartic acid, 6-aminocaprolc acid.More preferably L-glutamic acid.
Used enzyme is the enzyme that can survive under various pH values, as penicillin acylase, lipase, peroxidation horseradish enzyme etc., and preferred penicillin acylase.
Used linking agent is anyly to contain two aldehyde groups, and can be simultaneously under less than 40 ℃ temperature with the enzyme molecule in the material of amino generation chemical reaction in the amino and guest molecule, as glutaraldehyde, tri-chlorination piperazine etc., preferred glutaraldehyde.
Effect: will carry out the stable operation Journal of Sex Research by the immobilized enzyme that above method is prepared to obtain, its periodical operation under 37 ℃, concentration of substrate 8% condition, but operate continuously nearly about 60 times, the immobilized enzyme vigor has kept the 80-90% of its initial vigor.The THERMAL STABILITY of this immobilized enzyme shows, when the resolvase vigor when sharply descending for 45 ℃, the immobilized enzyme vigor can still remain unchanged about 57 ℃.And this immobilized enzyme is easy to separate with liquid phase reaction thing, product
Description of drawings:
Fig. 1 is an immobilized enzyme structural models synoptic diagram.
The structure of immobilized enzyme as shown in Figure 1, between the main body laminate of houghite, the carboxyl function group 2 of guest molecule forms ionic linkage with positively charged laminate 1, guest molecule with the amino functional group and linking agent with aldehyde radical reaction generate schiff alkali group 3, enzyme molecule 4 combines with covalent linkage 5 with linking agent.
Embodiment:
Embodiment 1
A: preparation Mg 2+: Al 3+=2: 1 Mg-Al hydrotalcite is got 4.0g and is joined in the container that fills the 100ml deionized water, and the room temperature lower magnetic force stirs, and adds excessive L-glutamic acid 7.5g, and by turbid solution become settled solution in the container this moment, standby.
Compound concentration is the NaOH solution of 0.05M, pour in the reactor that has condensation and whipping appts, stir on one side, drip above-mentioned standby settled solution on one side, keep dropping process pH＞9, after dropping finishes, condensing reflux 6h, filter, use the hot water thorough washing to pH＜8, in 85 ℃ of dry 24h, obtaining interlayer anion is the Mg-Al type houghite pillared material of L-glutamic acid.
B: get the pillared LDHs of above-mentioned 0.5g L-glutamic acid in the beaker that the 30ml deionized water is housed, add the 10ml5% glutaraldehyde, magnetic agitation 1 hour is filtered, fully washing.The phosphoric acid buffer that adds 80ml deionized water and 1.25mlpH=7.93 adds 4.5ml (167U/ml) penicillin acylase, fixes 20 hours for 30 ℃ in shaking table, centrifugation, fully washing, being fixed penicillin acylase.
By the X-ray diffractogram of steps A sample as can be known, its characteristic diffraction peak moves to Small angle, and ° locating to occur interlamellar spacing in 2 θ=7.6 is d 003=1.2nm is (greater than the houghite sample d that does not insert guest molecule 003=0.76nm) characteristic diffraction peak; The IR spectrogram shows, its 1377cm -1The CO of place 3 2-The peak disappears, generation respectively at 1594cm -1The N-H flexural vibration appear in the place, 1405,1356cm -1Asymmetric and the symmetrical absorption band of carboxylic acid ion appears in the place, illustrates that L-glutamic acid is assembled into the LDHs interlayer.
By the X-ray diffractogram of the sample of step B preparation as can be known, locating to occur interlamellar spacing littler angle 2 θ=1.8 ° is the more weak characteristic peak of d=4.4nm; By the IR spectrogram as can be seen, except that the key band of pillared material, at 1639cm -1The vibrational band of schiff alkali C=N appears in the place, proves that penicillin acylase exists between the laminate.
The operational stability of immobilized enzyme studies show that, after the operate continuously 50 times, the immobilized enzyme vigor has kept 90% of its initial vigor in batch reactor; The THERMAL STABILITY of immobilized enzyme shows, when the resolvase vigor when sharply descending for 45 ℃, the immobilized enzyme vigor still remains unchanged at 55 ℃.
Embodiment 2
Preparation Mg 2+: Al 3+=3: 1 Mg-Al hydrotalcite, getting 4.0g joins in the container that fills the 100ml deionized water, the room temperature lower magnetic force stirs, and adds excessive L-glutamic acid 8.0g, prepares the Mg-Al type houghite pillared material that interlayer anion is a L-glutamic acid by the method for embodiment 1.
B: the method by embodiment 1 prepares immobilized penicillin acylated enzyme.
The sample X-ray diffractogram of step B preparation and IR characterization result and example 1 are similar, prove that the penicillin acylase molecule successfully is fixed between the laminate.
The operational stability of immobilized enzyme studies show that, after the operate continuously 60 times, the immobilized enzyme vigor has kept 80% of its initial vigor in batch reactor; The THERMAL STABILITY of immobilized enzyme shows, when the resolvase vigor when sharply descending for 45 ℃, the immobilized enzyme vigor still remains unchanged at 55 ℃.
Embodiment 3
A: preparation Mg 2+: Al 3+=4: 1 Mg-Al houghite, getting 4.0g joins in the container that fills the 100ml deionized water, the room temperature lower magnetic force stirs, and adds excessive L-glutamic acid 9.0g, prepares the Mg-Al type houghite pillared material that interlayer anion is a L-glutamic acid by the method for embodiment 1.
B: the method by embodiment 1 prepares immobilized penicillin acylated enzyme.
The sample X-ray diffraction of step B preparation and IR characterization result and example 1 are similar, prove that the penicillin acylase molecule successfully is fixed between the laminate.
The operational stability of immobilized enzyme studies show that, after the operate continuously 40 times, the immobilized enzyme vigor has kept 80% of its initial vigor in batch reactor; The THERMAL STABILITY of immobilized enzyme shows, when the resolvase vigor when sharply descending for 45 ℃, the immobilized enzyme vigor still remains unchanged at 55 ℃.Embodiment 4
A: preparation Zn 2+: Al 3+=1.6: 1 Zn-Al houghite, this houghite 4.0g is joined in the container that fills the 100ml deionized water, the room temperature lower magnetic force stirs, and adds excessive L-glutamic acid 7.5g, prepares the Zn-Al type houghite pillared material that interlayer anion is a L-glutamic acid by the method for embodiment 1.
B:: the method by embodiment 1 prepares immobilized penicillin acylated enzyme.
The sample X-ray diffraction of step B preparation and IR characterization result and example 1 are similar, prove that the penicillin acylase molecule successfully is fixed between the laminate.
The operational stability of immobilized enzyme studies show that, after the operate continuously 30 times, the immobilized enzyme vigor has kept 82% of its initial vigor in batch reactor; The THERMAL STABILITY of immobilized enzyme shows, when the resolvase vigor when sharply descending for 45 ℃, the immobilized enzyme vigor still remains unchanged at 52 ℃.
Embodiment 5
Preparation Zn 2+: Al 3+=2: 1 Zn-Al houghite, this houghite 4.0g is joined in the container that fills the 100ml deionized water, the room temperature lower magnetic force stirs, and adds excessive L-glutamic acid 8.5g, prepares the Zn-Al type houghite pillared material that interlayer anion is a L-glutamic acid by the method for steps A among the embodiment 1.
B: the method by step B among the embodiment 1 prepares immobilized penicillin acylated enzyme.
The sample X-ray diffraction of step B preparation and IR characterization result and example 1 are similar, prove that the penicillin acylase molecule successfully is fixed between the laminate.
The operational stability of immobilized enzyme studies show that, after the operate continuously 50 times, the immobilized enzyme vigor has kept 85% of its initial vigor in batch reactor; The THERMAL STABILITY of immobilized enzyme shows, when the resolvase vigor when sharply descending for 45 ℃, the immobilized enzyme vigor still remains unchanged at 52 ℃.

Claims (6)

1. the present invention relates to a kind of preparation method of anionic type laminated material immobilized enzyme, it is characterized in that preparing according to the following steps this immobilized enzyme:
A: preparation laminate divalence, trivalent metal cation mol ratio are 1.6-4.5: 1 houghite, get a certain amount of this houghite and join that compound concentration is the suspension of 0.2-2M in the container that fills deionized water, the room temperature lower magnetic force stirs, add excessive guest molecule by houghite and guest molecule complete reaction, by turbid solution become settled solution in the container this moment, standby;
With concentration is the NaOH dilute solution of 0.01-0.5M, add in the reactor of band condensation and stirring, stir on one side, drip above-mentioned standby settled solution on one side, keep dropping process pH＞9, after dropping finishes, the about 6h of condensing reflux, filter, use the hot water thorough washing to pH＜8, dry in about 85 ℃, obtain the houghite pillared material that interlayer has been assembled guest molecule;
B: the weight ratio in houghite pillared material that obtains from A and water is 1: the ratio of 50-80 adds the reactor of band magnetic agitation, weight ratio in this houghite and linking agent is 1: the ratio of 1-3, in reactor, add 5%wt concentration linking agent, about magnetic agitation 1 hour, filter, fully washing;
Washed filter cake is put into container; add deionized water and phosphoric acid buffer catalysis activity with the protective enzyme molecule; solid-to-liquid ratio in houghite pillared material and liquid enzymes is 1: the ratio of 6-12 adds needs the fixed enzyme; fixing at a certain temperature about 20h in shaking table; through centrifugation; fully washing, being fixed enzyme.
2. the preparation method of anionic type laminated material immobilized enzyme according to claim 1 is characterized in that, wherein the used houghite of A is main body laminate divalent metal M 2+Be Mg 2+, Cu 2+, Ni 2+, Zn 2+, Fe 2+, Mn 2+,, Ca 2+Any, its trivalent metal cation M 3+Be Al 3+, Ga 3+, Co 3+, Fe 3+, Cr 3+, V 3+, Ti 3+Any; Interlayer anion is Cl -, CO 2-, NO 3 -, OH -, SO 4 2-, ClO 3-Any or several combinations; Said guest molecule can be L-glutamic acid, aspartic acid or 6-aminocaprolc acid;
Wherein the used enzyme of B is can be a kind of for the various enzymes of surviving under the 1-11 of pH value; Used linking agent is anyly to contain two aldehyde groups, and can be simultaneously under less than 40 ℃ temperature with the enzyme molecule in the material of amino generation chemical reaction in the amino and guest molecule.
3. the preparation method of anionic type laminated material immobilized enzyme according to claim 1 is characterized in that, the used houghite of A is the preferred Mg of main body laminate divalent metal 2+Or Zn 2+The preferred Al of trivalent metal cation 3+Or Fe 3+Preferred M 2+: M 3+Mol ratio is 2-4: 1, and the preferred CO of interlayer anion 2-With or OH -The preferred L-glutamic acid of used guest molecule;
The preferred penicillin acylase of enzyme, lipase, peroxidation horseradish enzyme that B is used; The preferred glutaraldehyde of used linking agent, tri-chlorination piperazine.
4. the preparation method of anionic type laminated material immobilized enzyme according to claim 1 is characterized in that, used enzyme is penicillin acylase more preferably.
5. the preparation method of anionic type laminated material immobilized enzyme according to claim 1 is characterized in that, used linking agent is glutaraldehyde more preferably.
6. the invention still further relates to a kind of anionic type laminated material immobilized enzyme by each described method preparation in the claim 1 to 5, it is characterized in that between the main body laminate of anionic type laminated material-houghite, inserting guest molecule, guest molecule is for containing carboxyl and amino group, and carboxyl quantity is more than or equal to the molecule of amino quantity, its with carboxyl function group and positively charged laminate form ionic linkage, its with the amino functional group under the linking agent effect with the enzyme molecule on amino group form covalent linkage, the enzyme molecule is fixed between the houghite laminate thus.
CN02117919A 2002-05-23 2002-05-23 Anionic type laminated material immobilized enzyme and its preparation method Pending CN1459502A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN101140257B (en) * 2007-10-18 2010-04-21 北京化工大学 Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same
CN101281158B (en) * 2008-05-20 2010-11-17 北京化工大学 DNA sensitivity electrode modified by hydrotalcite nanometer slice and preparation thereof
CN101531766B (en) * 2009-04-10 2012-04-11 北京化工大学 Method for preparing bovine serum albumin hybridized membrane
CN107354146A (en) * 2017-07-31 2017-11-17 苏州凯邦生物技术有限公司 Preparation method using modified hydrotalcite as the immobilization biological enzyme of carrier
CN114200126A (en) * 2021-12-09 2022-03-18 牟奕 Solid phase matrix for detecting N-type penicillin and cephalosporin antibiotic antibodies and preparation method thereof

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EP4321616A1 (en) * 2022-08-09 2024-02-14 Covestro Deutschland AG Thermally stable carboxylic ester hydrolases in layered double hydroxides for intrinsic recyclable polymers

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CN1059759A (en) * 1990-10-20 1992-03-25 河北师范学院 The preparation method of complex solidifying enzyme

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101140257B (en) * 2007-10-18 2010-04-21 北京化工大学 Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same
CN101281158B (en) * 2008-05-20 2010-11-17 北京化工大学 DNA sensitivity electrode modified by hydrotalcite nanometer slice and preparation thereof
CN101531766B (en) * 2009-04-10 2012-04-11 北京化工大学 Method for preparing bovine serum albumin hybridized membrane
CN107354146A (en) * 2017-07-31 2017-11-17 苏州凯邦生物技术有限公司 Preparation method using modified hydrotalcite as the immobilization biological enzyme of carrier
CN114200126A (en) * 2021-12-09 2022-03-18 牟奕 Solid phase matrix for detecting N-type penicillin and cephalosporin antibiotic antibodies and preparation method thereof

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