CN102943069A - Co-immobilization glucose oxidase/catalase microspheres and application thereof in production of gluconic acid or gluconic salt - Google Patents
Co-immobilization glucose oxidase/catalase microspheres and application thereof in production of gluconic acid or gluconic salt Download PDFInfo
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Abstract
The invention discloses co-immobilization glucose oxidase/catalase microspheres and application thereof in preparation of gluconic acid (salt) for catalytic oxidation of glucose. The co-immobilization glucose oxidase/the catalase microspheres can effectively promote covalent linkage of carriers and enzyme molecules, immobilization efficiency is improved greatly, service life of immobilization glucose oxidase (GOD)/catalase (CAT) is prolonged remarkably, the co-immobilization glucose oxidase/the catalase microspheres can be used repeatedly, are low in production cost, and facilitate sustainable development. Gluconic acid (salt) prepared by the co-immobilization glucose oxidase/the catalase microspheres is high in yield, reaction condition is temperate, a device is simple and easy to obtain, and the production method is environment-friendly.
Description
Technical field
The present invention relates to the production method of gluconic acid or its salt, particularly mixed immobilized glucose oxidase/catalase microspheres and the application in catalytic oxidation of glucose production gluconic acid or its salt thereof.
Background technology
Gluconic acid is the glucose oxidase product, after derivative, can obtain serial gluconic acid product, it comprises calglucon, the products such as Potassium Gluconate, Sunmorl N 60S, Menesia, Zinc Gluconate, Ferrous Gluconate, manganese gluconate, copper gluconate, gluconic acid barium and Gluconolactone.Gluconate series product and Gluconolactone, at home and abroad demand reaches ten thousand tons of 70-80, and output constantly enlarges.
The production method of calglucon has electrolytic oxidation, bromination method, metal catalytic synthesis method, fermentation method etc.In industrialized production, mainly adopt at present metal catalytic method and fermentation method.
The electrolytic oxidation preparation of gluconic acid is existing suitability for industrialized production abroad, and it is still under test at home, the people such as Shandong in 2000 war light are plated in ruthenium on the titanium as working electrode, and current efficiency (generating the theoretical consumes power of unit mole gluconic acid/generation unit mole gluconic acid actual consumption electric weight) can reach 76.50%.
The people such as Wang Zumo and Gao Shutong adopts respectively hydrogen peroxide, clorox as oxygenant with the eletrooxidation method, and productive rate is respectively 70% and 90%, has realized the industrialization pilot scale.But the eletrooxidation method needs the content of strict control catalyzer effective constituent in reaction solution, and temperature, pH are had dependency, and intermediate steps is many, and by product is many, and product is difficult to separate, and is difficult to regeneration as the salt of catalyzer, and productive rate is lower.Reaction times is longer, and environment is had larger pollution.
China adopts the fermentative Production calglucon more at present, then with the ion-exchange of calglucon process, evaporation concentration, the acid of crystallization synthesis of glucose.Biological fermentation process need to be cultivated many processes such as bacterial classification, strain screening and sterilization, and comparatively strict to temperature requirement, by product is many, cycle is longer, and in the gluconic acid process of producing because adding the impurity such as thalline, the product purity of affecting glucose acid, thereby its development is badly in need of solving a lot of technical problems.
In recent years, Enzymes Industry is accompanied by the fast development of downstream industry and develops, and all is greatly improved on kind and quality.Enzyme method technique utilizes zymin directly conversion of glucose to be become gluconic acid exactly, passes through the neutralizing effect of alkali again, converts it into the gluconate series product.Compare with fermentation method, the outstanding feature of enzyme process is exactly not need seed culture, has removed the raw and auxiliary materials such as microorganism and substratum to the interference of reaction system, has improved the purity of reaction product, brings convenience to purifying.Do not had seed culture, thereby reaction is more prone to control, produces and also can become more steady.For the producer, enzyme method technique is easy, and equipment is simple, easy to operate, does not have the danger of microbiological contamination, and product is single, and purity is high, is easy to separate and make with extra care, and quality product and yield significantly improve, and product hierarchy reaches food grade and injection stage standard fully.For newly founding the factory, can save seeding tank and extracting section equipment, reduced facility investment.Compare with the metal catalytic method, enzyme process also has safe characteristics.
With being fixed of enzyme, can significantly improve Enzymic stability.Be not subject to the impact of external environment and inactivation.Immobilized enzyme is easy to and product separation, owing to only have substrate in the reaction system, product, with immobilized enzyme Separation and Recovery from reaction system, only there is product in immobilized enzyme after reaction finishes in the system, be easy to carry out the refining of product, and product purity is high.Immobilized enzyme can repeat to recycle, and greatly reduces the cost of enzyme.
The existing technique of utilizing immobilized enzyme method to prepare gluconate, for example civilian disclosed method is " chemistry and biotechnology " the 2nd phase in 2008 " research of Immobilization of Glucose Oxidase by Calcium Alginate Gel Capsules " one: utilize calcium alginate gel particle fixing glucose oxidase (GOD), the method is easy to operation, reaction conditions is gentle, but this method has only been fixed an enzyme, the H that produces in the catalytic process
2O
2Can't in time decompose, accelerate the inactivation of GOD and CAT; In addition, the immobilized enzyme less stable is reused number of times few.And for example civilian disclosed method is " food and pharmaceutical " the 9th phase in 2011 " immobilized enzyme method prepares the research of calglucon " one: glucose oxidase and catalase covalency are fixed on the pretreated chitosan of glutaraldehyde, are calglucon with gained immobilized enzyme catalysis conversion of glucose.On September 28th, 2011, disclosed publication number was " a kind of method for preparing mixed immobilized glucose oxidase/catalase microspheres " patent of CN102199592 for another example, disclosed method is: take chitosan-arginine negatively charged ion microballoon as carrier, add GOD and CAT mixing solutions and glutaraldehyde, through crosslinking reaction, filtration, washing, lyophilize, prepare co-immobilization GOD and CAT microballoon.The advantage of the method is to take full advantage of arginine as " flexible arm ", has realized glucose oxidase and catalatic co-immobilization on " flexible arm ", has reduced the space steric effect of immobilized enzyme.Yet still there are some shortcomings in these methods, and are limited such as the carrier microballoons surface-area, can't the too much zymoprotein of load, and make enzymatic activity recovery lower.In addition, since the impact of resistance to mass transfer, the H that generates in the reaction process
2O
2Can not decompose rapidly, thereby cause GOD and CAT inactivation, immobilized enzyme is very fast after using continuously just to lose most enzymic activity.It is fixation support that the present invention adopts the polymethacrylic acid macroporous resin, cost is low, aperture, particle diameter and epoxy group(ing) density are all controlled, studies show that, the parameters such as the aperture of resin, particle diameter are very large on the charge capacity impact of enzyme, so the polymethacrylic acid macroporous resin can be applicable to greatest extent according to real needs the immobilization of GOD/CAT.The present invention's employing is assembled zymoprotein crosslinked, makes the limited more zymoprotein of carrier surface area energy load.Because carrier has suitable aperture, can overcome the impact of resistance to mass transfer in addition, immobilized enzyme diffusion mass transfer resistance is very little, and speed of reaction is close to using resolvase.
Summary of the invention
Its main purpose of the present invention provides and a kind ofly overcomes that the immobilization cost was high in the past, complex process, the shortcomings such as the enzyme rate of recovery alive is low provide a kind of mixed immobilized glucose oxidase/catalase (GOD/CAT) microballoon, it is higher that microballoon of the present invention has an enzymatic activity recovery, the advantages such as immobilized enzyme is stable, and is reusable.The gluconic acid that a kind of production process is simple, pollutent is few, product purity is high, energy consumption is low (salt) production method is provided in addition, and namely immobilized enzyme method is made gluconic acid (salt).Use the immobilized enzyme catalysis of the present invention's preparation to produce gluconic acid (salt), immobilized enzyme internal divergence resistance to mass transfer is very little, and speed of reaction is close to using resolvase, and transformation efficiency can reach 100%, and the no coupling product generation, sees accompanying drawing 1.
In order to realize purpose of the present invention, intend adopting following technical scheme:
One aspect of the present invention relates to a kind of mixed immobilized glucose oxidase/catalase microspheres, and it forms by the method that comprises the steps is prepared:
(1) to have macroporous structure PGMA microballoon as carrier, the mean pore size of described microballoon is between 100-200nm, take 1-5%(v/v) ethylenediamine solution is amination reagent, by the carrier quality: amination reagent volume 1:40 is scattered in carrier in the amination reagent, at pH7-9,40-80 ℃ of lower oscillatory reaction 1-6h collects the amination carrier;
(2) according to glucose oxidase: catalatic vigor is dissolved in GOD and CAT in the phosphoric acid buffer of pH5-8 than being the ratio of 1:1-6; In the enzyme lysate, add carbodiimide and N-hydroxy-succinamide, then 0-8 ℃ of lower reaction 15-60min be scattered in the amination carrier in the enzyme liquid 25-35 ℃ of lower stirring reaction 1-10h;
(3) acetone and the 0.1-2.0%(v/v of 1-5 times of reaction solution volume of adding in step (2) reaction solution) linking agent, continue reaction 0.5-1.5h, above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, with phosphoric acid buffer or water washing 3-5 time, drying obtains mixed immobilized glucose oxidase/catalase microspheres.
In a preferred embodiment of the present invention, described linking agent is selected from the twain-aldehyde compound linking agents such as glutaraldehyde, Vanillin.
In a preferred embodiment of the present invention, described macroporous structure PGMA microballoon is to obtain by the following method, described method comprises the steps: that the resin for immobilized enzyme is macropore GMA resin, can obtain by suspension polymerization, control the size in microballoon aperture by the consumption of control pore-creating agent and linking agent, the size of resin microsphere particle diameter is regulated by rotating speed.Preferably, function monomer glycidyl methacrylate (GMA), cross-linking monomer Ethylene glycol dimethacrylate (EDMA), triallyl isocyanide uraturia ester (TAIC), pore-creating agent toluene are mixed, disperse phase is for being suspension stabilizer polyvinyl alcohol (PVA) aqueous solution, then use Diisopropyl azodicarboxylate (AIBN) to carry out polyreaction as initiator, the microballoon that generates is through vacuumizing filtration, and embathe vacuum-drying with deionized water and ethanol.
The present invention also relates to the application of above-mentioned mixed immobilized glucose oxidase/catalase microspheres on the other hand, and described being applied as for the immobilized enzyme catalysis oxidizing glucose produced gluconic acid or its salt.
In a preferred embodiment of the present invention, described catalytic oxidation process comprises the steps: glucose solution, in salt-forming reagent and the reaction vessel of mixed immobilized glucose oxidase/catalase microspheres adding with whipping device, temperature of reaction 32-40 ℃, pH 5.5～7.5, ventilation 1:0.14～0.15(v/v/h) (whose volume on whose volume ratio); Oxidization time 12～20 hours, termination reaction when residual sugar is lower than 0.3%.
In a preferred embodiment of the present invention, described step also is included in and reclaims mixed immobilized glucose oxidase/catalase microspheres after oxidizing reaction finishes, reuse, preferably, mixed immobilized glucose oxidase/catalase microspheres reuses number of times between 15-20 time.
In a preferred embodiment of the present invention, described salt-forming reagent is selected from calcium carbonate, magnesiumcarbonate, zinc hydroxide.
Mixed immobilized glucose oxidase/catalase microspheres of the present invention can effectively promote the covalently bound of carrier and enzyme molecule, greatly improved immobilization efficiency, and significant prolongation the work-ing life of co-immobilization GOD/CAT, but Reusability, production cost is low, is conducive to Sustainable development, adopt mixed immobilized glucose oxidase/catalase microspheres of the present invention to prepare the gluconate yield high, reaction conditions is gentle, and equipment is simple and easy to, and is a kind of production method of environmental protection.
Description of drawings
Fig. 1: enzyme catalysis method is produced the calglucon reaction process.
Embodiment
The resin that is used for immobilized enzyme is macropore GMA resin, can obtain by suspension polymerization, and suspension polymerization is carried out in the 250ml there-necked flask, and the size of resin microsphere particle diameter is regulated by rotating speed, is rotating speed 500rpm herein.External phase is by function monomer GMA(0.05mol) cross-linking monomer EDMA(0.0125mol), TAIC(0.0125mol), pore-creating agent toluene (0.084 mol) forms.AIBN is as initiator, and its quality is 2% of three kinds of monomer masses.Disperse phase is 1% suspension stabilizer polyvinyl alcohol (PVA).Temperature is controlled at 75 ℃ of 2h, 85 ℃ of 2h.After reaction stopped, microballoon was through vacuumizing filtration, and embathed with deionized water and ethanol, vacuum-drying and get final product.Control the size in microballoon aperture by the consumption of control pore-creating agent and linking agent, the size of resin microsphere particle diameter is regulated by rotating speed.After reaction stopped, microballoon passed through vacuumizing filtration, and embathed vacuum-drying with deionized water and ethanol.This resin surface contains abundant epoxide group, and the PGMA surface itself has the epoxy group(ing) of high reaction activity, need not just can directly react with amino, hydroxyl, sulfydryl through overactivation.Maximum benefit is to select the suitable carrier of suitable immobilized enzyme by the size of control aperture, particle diameter.
Embodiment 1:
A kind of method for preparing mixed immobilized glucose oxidase/catalase microspheres, the concrete grammar step is as follows:
Take 2%(v/v) bovine serum albumen solution is amination reagent, the carrier mean pore size is 100-200nm, and by the carrier quality: amination reagent volume 1:40 is scattered in 2%(v/v with carrier) in the amination reagent, at pH8.0,60 ℃ of lower 200rpm oscillatory reaction 2h collect the amination carrier., GOD and CAT are dissolved in the phosphoric acid buffer of 0.5mol/l of pH6 than being the ratio of 1:2 according to the vigor of GOD:CAT.The amination carrier is scattered in the enzyme liquid, and 30 ℃ are reacted 2h under mixing speed 200rpm, add acetone and the 0.5%(v/v of 2 times of reaction solution volumes in reaction solution) glutaraldehyde, continue reaction 1h.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, use the 0.01mol/l phosphoric acid buffer of pH7.0 to wash 3 times, 4 ℃ of dryings are just prepared Resins, epoxy co-immobilization GOD/CAT microballoon, and the GOD enzyme activity is 106.8U/g.
Embodiment 2:
Take 2%(v/v) ethylenediamine solution is amination reagent, the carrier mean pore size is 100-200nm, and by the carrier quality: amination reagent volume 1:40 is scattered in 2%(v/v with carrier) in the amination reagent, at pH8.0,60 ℃ of lower 200rpm oscillatory reaction 2h collect the amination carrier., GOD and CAT are dissolved in the phosphoric acid buffer of 0.1mol/l of pH6 than being the ratio of 1:2 according to the vigor of GOD:CAT.The amination carrier is scattered in the enzyme liquid, and 30 ℃ are reacted 2h under mixing speed 200rpm, add acetone and the 0.5%(v/v of 2 times of reaction solution volumes in reaction solution) glutaraldehyde, continue reaction 1h.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, use the 0.01mol/l phosphoric acid buffer of pH7.0 to wash 3 times, 4 ℃ of dryings are just prepared Resins, epoxy co-immobilization GOD/CAT microballoon, and enzyme activity is 111.9U/g.
Embodiment 3:
Take 2%(v/v) ethylenediamine solution is amination reagent, the carrier mean pore size is 400-500nm, and by the carrier quality: amination reagent volume 1:40 is scattered in 2%(v/v with carrier) in the amination reagent, at pH8.0,60 ℃ of lower 200rpm oscillatory reaction 2h collect the amination carrier., GOD and CAT are dissolved in the phosphoric acid buffer of 0.1mol/l of pH6 than being the ratio of 1:2 according to the vigor of GOD:CAT.The amination carrier is scattered in the enzyme liquid, and 30 ℃ are reacted 2h under mixing speed 200rpm, add acetone and the 0.5%(v/v of 2 times of reaction solution volumes in reaction solution) glutaraldehyde, continue reaction 1h.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, use the 0.01mol/l phosphoric acid buffer of pH7.0 to wash 3 times, 4 ℃ of dryings are just prepared Resins, epoxy co-immobilization GOD/CAT microballoon, and enzyme activity is 35.9U/g.
Embodiment 4:
Take 2%(v/v) ethylenediamine solution is amination reagent, the carrier mean pore size is 100-200nm, and by the carrier quality: amination reagent volume 1:40 is scattered in 2%(v/v with carrier) in the amination reagent, at pH8.0,60 ℃ of lower 200rpm oscillatory reaction 2h collect the amination carrier., GOD and CAT are dissolved in the phosphoric acid buffer of 0.8mol/l of pH6 than being the ratio of 1:2 according to the vigor of GOD:CAT.In the enzyme lysate, add 0.2%(w/v) carbodiimide and 0.2%(w/v) N-hydroxy-succinamide, 4 ℃ the reaction 30min.The amination carrier is scattered in the enzyme liquid, and 30 ℃ are reacted 2h under mixing speed 200rpm, add acetone and the 1.5%(v/v of 2 times of reaction solution volumes in reaction solution) glutaraldehyde, continue reaction 1h.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, use the 0.01mol/l phosphoric acid buffer of pH7.0 to wash 3 times, 4 ℃ of dryings are just prepared Resins, epoxy co-immobilization GOD/CAT microballoon, and enzyme activity is 263U/g.
Embodiment 5:
According to mass percent 20% preparation glucose solution, in the there-necked flask of stirring rake is housed, add glucose solution, calcium carbonate, the enzyme amount adds immobilized glucose oxidase and catalase according to 0.6%～1% of glucose amount, carry out oxidation and carry out simultaneously in gluconic acid and the calcium carbonate and the reaction that produces calglucon, oxidizing temperature 32-40 ℃.Ventilation 1:0.14～0.15(v/v/h); Oxidization time 12～20 hours, pH 5.5～7.5, and oxidation finished when residual sugar was lower than 0.3%, after oxidation finishes, reclaimed immobilized enzyme, reused 20 batches of enzyme activities and still had more than 80%.
Immobilized enzyme is compared with resolvase, because external diffusion in existing, initial reaction rate is slightly low, along with reaction is carried out, owing to using the immobilized enzyme reaction to be subjected to the impact of product or other condition elements less, speed of reaction finally all finishes (as shown in Figure 1) a little more than using resolvase after reaction proceeds to 15h.
The above be the specific embodiment of the present invention only, but protection scope of the present invention is not limited to this, and any variation or replacement of expecting without creative work all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (7)
1. mixed immobilized glucose oxidase/catalase microspheres, it forms by the method that comprises the steps is prepared:
(1) to have macroporous structure PGMA microballoon as carrier, the mean pore size of described microballoon is between 100-200nm, take 1-5%(v/v) ethylenediamine solution is amination reagent, by the carrier quality: amination reagent volume 1:40 is scattered in carrier in the amination reagent, at pH7-9,40-80 ℃ of lower oscillatory reaction 1-6h collects the amination carrier;
(2) according to glucose oxidase: catalatic vigor is dissolved in GOD and CAT in the phosphoric acid buffer of pH5-8 than being the ratio of 1:1-6; In the enzyme lysate, add carbodiimide and N-hydroxy-succinamide, then 0-8 ℃ of lower reaction 15-60min be scattered in the amination carrier in the enzyme liquid 25-35 ℃ of lower stirring reaction 1-10h;
(3) acetone and the 0.1-2.0%(v/v of 1-5 times of reaction solution volume of adding in step (2) reaction solution) linking agent, continue reaction 0.5-1.5h, above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, with phosphoric acid buffer or water washing 3-5 time, drying obtains mixed immobilized glucose oxidase/catalase microspheres.
2. mixed immobilized glucose oxidase/catalase microspheres according to claim 1, described linking agent is selected from the twain-aldehyde compound linking agents such as glutaraldehyde, Vanillin.
3. mixed immobilized glucose oxidase/catalase microspheres according to claim 1, described macroporous structure PGMA microballoon is to obtain by the following method, described method comprises the steps: that the resin for immobilized enzyme is macropore GMA resin, can obtain by suspension polymerization, control the size in microballoon aperture by the consumption of control pore-creating agent and linking agent, the size of resin microsphere particle diameter is regulated by rotating speed.
4. the application of the described mixed immobilized glucose oxidase/catalase microspheres of claim 1-3 any one, described being applied as for the immobilized enzyme catalysis oxidizing glucose produced gluconic acid or its salt.
5. application according to claim 4, described catalytic oxidation process comprises the steps: glucose solution, in salt-forming reagent and the reaction vessel of mixed immobilized glucose oxidase/catalase microspheres adding with whipping device, temperature of reaction 32-40 ℃, pH 5.5～7.5, ventilation 1:0.14～0.15(v/v/h) (whose volume on whose volume ratio); Oxidization time 12～20 hours,, termination reaction when residual sugar is lower than 0.3%.
6. application according to claim 4, described step also is included in and reclaims mixed immobilized glucose oxidase/catalase microspheres after oxidizing reaction finishes, reuse, preferred, mixed immobilized glucose oxidase/catalase microspheres reuse number of times more than 15 times.
7. application according to claim 5, described salt-forming reagent is selected from calcium carbonate, magnesiumcarbonate, zinc hydroxide.
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| CN103173770A (en) * | 2013-04-01 | 2013-06-26 | 滁州旭中化工有限公司 | Aluminum alloy corrosion inhibitor |
| CN103332796A (en) * | 2013-04-01 | 2013-10-02 | 滁州旭中化工有限公司 | Degradable phosphorus-free composite corrosion and scale inhibitor |
| CN103524569A (en) * | 2013-10-23 | 2014-01-22 | 河北工业大学 | Technological method for removing glucose in isomaltooligosaccharide product by using multiple immobilized enzymes |
| CN104099317A (en) * | 2014-07-18 | 2014-10-15 | 江南大学 | Method for fixing pullulanase with chitosan magnetic nanoparticles |
| CN106497910A (en) * | 2016-11-18 | 2017-03-15 | 青岛啤酒股份有限公司 | A kind of pair of enzyme common immobilization method and the immobilized enzyme prepared by the method |
| CN106754856A (en) * | 2016-11-30 | 2017-05-31 | 温县兴发生物科技有限公司 | A kind of method that co-immobilization glucose oxidase and catalase prepare ferrous gluconate |
| CN106754857A (en) * | 2016-11-30 | 2017-05-31 | 温县兴发生物科技有限公司 | A kind of method that co-immobilization glucose oxidase and catalase prepare zinc gluconate |
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| CN103147080A (en) * | 2013-04-01 | 2013-06-12 | 滁州旭中化工有限公司 | Corrosion inhibitor |
| CN103173770A (en) * | 2013-04-01 | 2013-06-26 | 滁州旭中化工有限公司 | Aluminum alloy corrosion inhibitor |
| CN103332796A (en) * | 2013-04-01 | 2013-10-02 | 滁州旭中化工有限公司 | Degradable phosphorus-free composite corrosion and scale inhibitor |
| CN103524569A (en) * | 2013-10-23 | 2014-01-22 | 河北工业大学 | Technological method for removing glucose in isomaltooligosaccharide product by using multiple immobilized enzymes |
| CN103524569B (en) * | 2013-10-23 | 2015-06-10 | 河北工业大学 | Technological method for removing glucose in isomaltooligosaccharide product by using multiple immobilized enzymes |
| CN104099317A (en) * | 2014-07-18 | 2014-10-15 | 江南大学 | Method for fixing pullulanase with chitosan magnetic nanoparticles |
| CN106497910A (en) * | 2016-11-18 | 2017-03-15 | 青岛啤酒股份有限公司 | A kind of pair of enzyme common immobilization method and the immobilized enzyme prepared by the method |
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| CN107475050A (en) * | 2017-07-27 | 2017-12-15 | 东华大学 | A kind of method that Sugared beverages sugariness is reduced using biology enzyme |
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| CN111419825A (en) * | 2020-06-03 | 2020-07-17 | 烟台大学 | Intelligent response type sustained and controlled release microsphere and preparation method thereof |
| CN114452821A (en) * | 2022-01-26 | 2022-05-10 | 中国科学技术大学 | Bipolar membrane electrodialysis device, method for preparing regenerated alkali by using bipolar membrane electrodialysis device and application of bipolar membrane electrodialysis device |
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