CN100434517C - Method for reversiblely assembling enzyme using nano sheet-like TiO2 - Google Patents
Method for reversiblely assembling enzyme using nano sheet-like TiO2 Download PDFInfo
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- CN100434517C CN100434517C CNB2006100287420A CN200610028742A CN100434517C CN 100434517 C CN100434517 C CN 100434517C CN B2006100287420 A CNB2006100287420 A CN B2006100287420A CN 200610028742 A CN200610028742 A CN 200610028742A CN 100434517 C CN100434517 C CN 100434517C
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Abstract
The present invention relates to a method for reversibly assembling enzyme with lamellar nanometer titanium oxide. The method is characterized in that firstly, organic amine is used to strip layered titanate into single-sheet nanometer colloidal sol, and then by controlling the surface charge of enzymes, alternate assembly is realized between the single-sheet nanometer colloidal sol and a single layer of titanium oxide with negative charge so as to realize the fixing of enzymes and reversibly release and reclaim carriers. In the present invention, titanium oxide with high thermal stability and chemical stability is used as carriers for fixing enzymes to improve the biological performance of enzymes. According to demand, products of the present invention can be prepared in the forms of particle, gel, membrane, etc., which are favorable to preservation. In the self-assembly method of the present invention, because of the sufficient contact between enzyme molecules and titanium oxide layers, 1 gram of carriers have the maximum charge number of 5.9 grams of hemoglobin. The fixed enzymes can reserve about 80% of free enzymatic activity, and meanwhile, the thermal stability and the stability of organic solvent are both greatly improved.
Description
Technical field
The present invention is the universal method of the inorganic laminated titanium oxide immobilized enzyme of a kind of usefulness, or rather, relates to a kind of method of reversiblely assembling enzyme using nano sheet-like TiO 2, belongs to inorganic chemistry and nano material correlative technology field.
Background technology
Enzyme be a class efficiently, highly single-minded biological catalyst.Enzyme has obtained application very early on human history, and uses increasingly extensive.But the deadly defect of enzyme in application is that stability is low, and extremely responsive for high temperature, organic solvent or extreme PH.This gives separation, preparation, the application of enzyme and reclaims and all bring certain difficulty.The appearance of immobilized enzyme has partly overcome these shortcomings, for the large-scale industrial application of enzyme has been opened up new prospect.
The process for fixation of enzyme is a lot, roughly can be divided into two big classes such as physical method (as absorption, embedding etc.) and chemical process (crosslinked as covalent bonding, enzyme).The performance of immobilized enzyme often depends on fixing means and used solid substrate.The material that is commonly used to immobilized enzyme at present is the polymer or the protein material of natural or synthetic mostly.And common inorganic materials such as glass, alumina, diatomite, metal, metal oxide and various collosol and gel, though have the destructiveness of better mechanical strength, thermally-stabilised and organic solvent-resistant, they seldom are used in bio-active substance aspects such as enzyme except that the part sol gel film.This mainly is because these materials be difficult to form the structure of large specific surface, and the surface also is difficult to functionalization with in conjunction with biomacromolecule.
Known to the people, inorganic lamellar material is owing to having adjustable interlamellar spacing feature, so be the macromolecular carrier of a class potential fixed biologically.The principle of its immobilized enzyme be the layer that is based upon inorganic lamellar material with layer between can come interactionally by weak static or hydrogen bond, so just might destroy original structure and that biomolecules is introduced layer is middle.Kanzaki the earliest, (Bull.Chem.Soc.Jpn.1991,64:2292) and Ding, (Chem.Mater.1995 7:562) has attempted the biological enzyme molecule directly is inserted into the metal phosphate interlayer Y. etc. Y. etc.But for realizing direct intercalation, often need extreme reaction conditionss such as more than 10 day reaction times and strong acid and strong base, these are the active structure of destructive enzyme itself very easily all.The stripping technology of inorganic lamellar material is greatly developed recently.By the effect of quaternary ammonium hydroxide, a series of inorganic lamellar material can both be peeled off into nano-sheet, and the thickness of material is individual layer or which floor basic aspect.By the self-assembly effect of this nano-sheet material and guest molecule, a series of functional molecular can both enter under the condition of milder in the middle of the inorganic layer.2000, Kumar, C.V. (J.Am.Chem.Soc.2000,122:830) wait reported with the method for above-mentioned indirect intercalation with myohaemoglobin, oxyphorase, lysozyme, Quimotrase and glucose oxidase all intercalation go in the middle of the alpha zirconium phosphate layer.The present inventor also once assembled myohaemoglobin and haemoglobin molecule with the nano-sheet manganese oxide, and obtained different patterns by its volatilization process of control.But the formed product of Bao Dao assemble method was single collosol and gel in the past, was difficult to make particle or other form, and the combination of enzyme and inorganic laminate can not regulate and control, and made enzyme and carrier be difficult to recycle.
Summary of the invention
The invention provides a kind of method with the reversible assembling enzyme of nano-sheet titanium oxide large vol.Enzyme after fixing can keep most of free enzymatic activity, improves its thermotolerance and anti-organic solvent simultaneously.
A kind of method with the reversible assembling enzyme of nano-sheet titanium oxide large vol of the present invention is characterized in that: with having high heat stability, chemically stable, eco-friendly titanium oxide as the solid fixed carrier of enzyme.At first prepare flaky Nano sol from synthetic alkali metal containing ionic layered titanate at high temperature, the surface charge by control enzyme molecule allows it and electronegative titanium oxide individual layer realize the reversible assembling then.
The described nano-sheet titanium oxide sol that is used for fixing enzyme is by following method preparation: at first use the proton in the proton (example hydrochloric acid, nitric acid or sulfuric acid) in the excessive inorganic acid, the alkalimetal ion of exchange layered titanate interlayer generates the solid metatitanic acid, use quaternary ammonium hydroxide with reference to 1 then: the soda acid comparison solid metatitanic acid of 0.2-1 carries out swelling property and peels off, to colloidal sol centrifugation disgorging under 5000-10000rpm of gained, use organic monoacid (as acetic acid or citric acid etc.) to regulate colloidal sol at last near neutral.
Described surface charge by the control enzyme realizes that reversible packaging technology is that enzyme molecule with 1-10 times of quality mixes in stirring at room with neutral titanium oxide sol, add organic monoacid then till causing precipitation, General Result is that the pH value of solution is near its iso-electric point.Adding quaternary ammonium hydroxide then in the mixture precipitation of gained makes its pH be higher than enzyme molecule iso-electric point 2-3 to allow the mixture that forms peel off into colloid admixture again.
The present invention specifically implements as follows: earlier enzyme and nano-sheet titanium oxide sol are mixed, and then the organic monoacid that adds dilution adds TBAH at last again and peels off the reduction glue compound up to the initiation precipitation in product.Specific embodiment such as Fig. 1:
A. basic metal stratiform titanate is synthetic
Reactant is alkaline carbonate and nano-sheet titanium dioxide, mixes the synthetic chemistry metering-type according to accurate proportioning and is respectively Cs
0.7Ti
1.825 0.175O
4(represents the room) and A
xTi
2-x/3Li
X/3O
4Series (x=0.8, A=K; X=0.70, product A=Cs).Reaction conditions: 800-1200 ℃ of following roasting 20 hours is cooled to room temperature and grinds, and repeats pyroreaction more once, and grinding at room temperature once more.
B. the preparation of nano-sheet titanium oxide sol
A kind of ratio according to 1g/100ml is reacted in the basic metal stratiform titanate of top gained and 3mol/l hydrochloric acid, nitric acid or the sulfuric acid, and time 1-24 hour, repeat above-mentioned reaction after the filtration several times, clean with excessive water and obtain the solid metatitanic acid.Gained solid metatitanic acid and quaternary ammonium hydroxide are with reference to 0.2-1: 1 soda acid mixed in molar ratio stirs, and reacts after 1-8 days, with colloidal sol centrifugation under 5000-10000rpm of gained.
C. reversiblely assembling enzyme using nano sheet-like TiO 2
The neutral nano-sheet titanium oxide sol of enzyme molecule and top gained is with 1-10: 1 mass ratio mixes in stirring at room, and the organic acid that dropwise adds concentration and be 1mol/l generates the stratiform biological composite up to causing precipitation.Dropwise adding quaternary ammonium hydroxide makes the mixture precipitation peel off into the colloid admixture of enzyme molecule and nano-sheet titanium oxide again.
The processing method characteristics of the reversible assembling enzyme of nano-sheet titanium oxide large vol provided by the invention are:
A. reaction conditions gentleness, the activity that can at utmost keep enzyme reaches about 80%;
B. reaction process is controlled, just can realize that by simple adjusting potential of hydrogen enzyme fixes and discharge, thereby the circulation that realizes carrier reduces cost in actual applications;
C. the specific surface energy that the nano-sheet titanium oxide is big reaches the charge capacity raising carrier utilising efficiency of 1 gram carrier in conjunction with 5.9 gram enzymes;
D. used titanium dioxide carrier has high heat stability, chemically stable and eco-friendly characteristic, the impact that energy protective layer glucose-6-phosphate dehydrogenase resists thermal shocking and other organic molecule, and on demand, product can be made the form of particle, jelly or film, is beneficial to preservation.
Description of drawings
Fig. 1 is for being example with the oxyphorase, the schema of whole technological process.
Fig. 2 is for being the simulation peroxidase of selecting with the oxyphorase among the embodiment 1, and the reaction mass ratio of oxyphorase and titanium oxide is 4: 1 gained stratiform biological composites, the colloid admixture after peeling off with tetra-alkyl ammonium hydroxide and the x-ray diffraction pattern of the mixture of assembling once more.
Fig. 3 is for being the simulation peroxidase of selecting with the oxyphorase among the embodiment 2, and the reaction mass ratio of oxyphorase and titanium oxide is the x-ray diffraction pattern of 6: 1 gained stratiform biological composites.
Fig. 4 is for being the bio-active substance of selecting with the bovine serum albumin among the embodiment 3, and the reaction mass ratio of bovine serum albumin and titanium oxide is the x-ray diffraction pattern of 4: 1 gained stratiform biological composites.
Embodiment
After taking by weighing accurately that cesium carbonate 5g and titanium dioxide 6.5g mix and grinding evenly, 800 ℃ of reactions 20 hours down, reaction repeated once, intercooling also grinds.Get the layered titanate Cs of gained
0.7Ti
1.825 0.175O
4(represents the hole) 10g, putting into concentration is the 1000ml hydrochloric acid soln of 3mol/l, stirring at room 24 hours, the centre is changed hydrochloric acid soln and is repeated 3 times, filters and wash remained on surface acid.Get 2g solid metatitanic acid adding 200ml and contain in the aqueous solution of 3ml 40% TBAH, stirring at room is after 8 days, and is standby after the centrifugation under 8000rpm.The colloid 100ml that gets titanium oxide content and be 1mg/ml mixes with the 400mg oxyphorase, and regulating pH with 1mol/l acetic acid is about 6.0, causes the generation of self-assembly, generates the magneta colour precipitation, and content of hemoglobin is less than 0.01mg/ml in the upper solution.Again be suspended in being deposited to pH8-9 and can forming colloid admixture again in the water with the titration of 0.005mol/l TBAH.As the simulation peroxidase, the reaction of using hydrogen peroxide catalysis methyl catechol is as characteristic reaction with oxyphorase, and the oxyphorase under the same reaction conditions after the immobilization can keep 71% of free oxyphorase initial velocity of reaction.Thermo qualitative improves a lot, and handles at 0.1mol/l pH 7.0 phosphate buffered saline buffers under 90 ℃ of the immobilization oxyphorases still to keep former active 25% in 20 minutes, and free oxyphorase was handled the back in 5 minutes and just only has been less than 5% activity simultaneously.The immobilization oxyphorase can keep higher activity in the mixed solvent that contains acetonitrile and water, and free enzyme does not have activity substantially at this solvent.
Fig. 2 is experiment gained mixture sedimentary x-ray diffraction pattern, and the variation of the different steps product X-x ray diffration pattern x of reversible intercalation in the whole presentation graphs 1.The interlamellar spacing of the laminated composites of calculating by the diffraction peak position is that 7.12nm just in time is in the scope that mono-layer oxidized titanium thickness 0.75nm adds haemoglobin molecule size (5.3-6.5nm).Layer structure disappears after regulating pH with TBAH, adds acetic acid then and can re-assembly nano-sheet titanium oxide and haemoglobin molecule to together.
Accurately take by weighing after cesium carbonate 20g and titanium dioxide 26g grind evenly, 800 ℃ of reactions 20 hours down, reaction repeated once, intercooling also grinds.Get the layered titanate Cs of gained
0.7Ti
1.825 0.175O
4(represents the hole) 20g puts into 2l hydrochloric acid soln (3mol/l), stirring at room 24 hours, and the centre is changed hydrochloric acid soln and is repeated 3 times, filters and wash remained on surface acid.Get the solid metatitanic acid adding of 2g 200ml and contain in the aqueous solution of 4ml 40% TBAH, stirring at room is after 4 days, and is standby after the centrifugation under 8000rpm.Getting titanium oxide content is that 1mg/ml colloid 100ml mixes with the 600mg oxyphorase, and regulating pH with 1mol/l acetic acid is about 5.5, causes the generation of self-assembly, generates the magneta colour precipitation, and content of hemoglobin is less than 0.10mg/ml in the upper solution.The laggard row element analysis of the sample lyophilize of this maximal absorptive capacity is found that ultimate load is 5.9g oxyphorase/g titanium dioxide carrier.As the simulation peroxidase, the reaction of using hydrogen peroxide catalysis methyl catechol is as characteristic reaction with oxyphorase, and the oxyphorase under the same reaction conditions after the immobilization can keep 63% of free oxyphorase initial velocity of reaction.
Fig. 3 is the sedimentary x-ray diffraction pattern of experiment gained stratiform biological composite.The interlamellar spacing of the laminated composites of calculating by the diffraction peak position is 8.35nm, greater than the structure of oxyphorase monolayer alignment, should form jagged bilayer structure.This swollen structure is the major cause of a large amount of absorption of lamellar titanium oxide.
Accurately take by weighing salt of wormwood 5.6g, Quilonum Retard 1.0g and titanium dioxide 14.0g and grind evenly, 1000 ℃ of reactions 20 hours down, reaction repeated once, the intermediate demand cooling is also ground evenly.Get the layered titanate K of gained
xTi
2-x/3Li
X/3O
4(x=0.8) 20g, putting into concentration is the sulphuric acid soln 500ml of 3mol/l, stirring at room 24 hours is filtered and is washed with 0.5mol/l, removes the sulfuric acid of remained on surface at last with massive laundering.Get the solid metatitanic acid of 2g and add 200ml and contain in the aqueous solution of 4.0ml 40% TBAH and stir, room temperature reaction is after 5 days, and centrifugation is standby under 8000rpm.Getting titanium oxide content is that 1mg/ml colloid 100ml mixes with the 400mg bovine serum albumin, is about 5.0 with 1mol/l acetic acid or lemon acid for adjusting pH, generates the product white precipitate of self-assembly, and protein content is less than 0.05mg/ml in the upper solution.
Fig. 4 is the sedimentary x-ray diffraction pattern of experiment gained stratiform biological composite.The interlamellar spacing of the laminated composites of calculating by the diffraction peak position is that 6.78nm just in time is in the scope that mono-layer oxidized titanium thickness 0.75nm adds haemoglobin molecule size (5.3-6.5nm).
Claims (7)
1, a kind of method with reversiblely assembling enzyme using nano sheet-like TiO 2, it is characterized in that: use titanium dioxide as enzyme fixed carrier, at first prepare flaky Nano sol from high temperature synthetic alkali metal containing ionic layered titanate, the surface charge by control enzyme molecule allows it and electronegative titanium oxide individual layer realize the reversible assembling then; Concrete steps are:
A. basic metal stratiform titanate is synthetic
Reactant is alkaline carbonate and nano-sheet titanium dioxide, mixes the synthetic chemistry metering-type according to proportioning and is respectively Cs
0.7Ti
1.825 0.175O
4, K
0.8Ti
2-0.8/3Li
0.8/3O
4Or CS
0.7Ti
2-0.7/3Li
0.7/3O
4Product, reaction conditions is 800-1200 ℃ of following roasting 20 hours, is cooled to room temperature and grinds, and repeats pyroreaction more once, and grinding at room temperature once more, wherein represents the room;
B. the preparation of nano-sheet titanium oxide sol
The basic metal stratiform titanate and the 3mol/l inorganic acid of step (a) gained react according to the ratio of 1g/100ml, repeat above-mentioned reaction after the reaction after filtration, obtain the solid metatitanic acid with excessive water cleaning, with the solid metatitanic acid of gained and quaternary ammonium hydroxide with reference to 0.2-1: 1 soda acid mixed in molar ratio stirs, react after 1-8 days, the colloidal sol centrifugation of gained;
C. reversiblely assembling enzyme using nano sheet-like TiO 2
The neutral nano-sheet titanium oxide sol of enzyme molecule and step (b) gained is with 1-10: 1 mass ratio mixes in stirring at room, the organic acid that dropwise adds concentration and be 1mol/l generates the stratiform biological composite up to causing precipitation, dropwise adds quaternary ammonium hydroxide and makes the mixture precipitation peel off into the colloid admixture of enzyme molecule and nano-sheet titanium oxide again.
2, by the described method with reversiblely assembling enzyme using nano sheet-like TiO 2 of claim 1, it is characterized in that described inorganic acid is a hydrochloric acid, a kind of in nitric acid or the sulfuric acid.
3, by the described method of claim 1, it is characterized in that colloidal sol centrifugation under 5000-10000rpm of gained with reversiblely assembling enzyme using nano sheet-like TiO 2.
4, by the described method of claim 1, it is characterized in that used organic acid is acetic acid or citric acid with reversiblely assembling enzyme using nano sheet-like TiO 2.
5, by the described method of claim 1, it is characterized in that alkalimetal ion layered titanate and the inorganic acid reaction time in the step (b) is 1-24 hour with reversiblely assembling enzyme using nano sheet-like TiO 2.
6, by the described method with reversiblely assembling enzyme using nano sheet-like TiO 2 of claim 1, the pH value that it is characterized in that the described neutral nano-titanium oxide colloidal sol of step (c) adds quaternary ammonium hydroxide and makes its PH be higher than enzyme molecule iso-electric point 2-3 near its iso-electric point.
7, by the described method with reversiblely assembling enzyme using nano sheet-like TiO 2 of claim 1, the product that it is characterized in that gained is particle, jelly or film.
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| CN101857638B (en) * | 2010-05-25 | 2012-06-20 | 北京化工大学 | Method for preparing bovine hemoglobin/titanium-based titanium dioxide hybrid material |
| CN102153289A (en) * | 2010-12-02 | 2011-08-17 | 中国科学院上海硅酸盐研究所 | Laminar titanium dioxide array film and preparation method thereof |
| CN103317786A (en) * | 2012-03-22 | 2013-09-25 | 中国科学院海洋研究所 | Titanium dioxide nano-sheet/lysozyme multilayer composite film, preparation method and applications thereof |
| CN107418947A (en) * | 2017-07-19 | 2017-12-01 | 苏州凯邦生物技术有限公司 | A kind of preparation method of high activity immobilization desizing enzyme |
| CN109133162A (en) * | 2018-07-30 | 2019-01-04 | 大连理工大学 | A kind of Large ratio surface ultra-thin two-dimension TiOx nano sheet material and preparation method |
| WO2021117568A1 (en) * | 2019-12-12 | 2021-06-17 | 昭和電工株式会社 | Highly heat-resistant anatarse-type titanium oxide and method for producing same |
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