CN106636055A - Preparation method and application of cellulose-SiO2 composite carrier - Google Patents
Preparation method and application of cellulose-SiO2 composite carrier Download PDFInfo
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Abstract
The invention provides a preparation method and application of a cellulose-SiO2 composite carrier. The preparation method comprises the following steps: adding an ion solution into dialdehyde cellulose-SiO2 powder; stirring until the powder is dissolved, and centrifuging and de-foaming the solution to prepare a first fixed solution; cooling the first fixed solution to be 20 DEG C to 40 DEG C to prepare a second mixed solution, wherein the cooling time is 60 minutes to 120 minutes; preparing the second mixed solution into a liquid film with the thickness of 0.2mm to 1.0mm or micro-spheres with the diameter of 0.4mm to 1.2mm; putting the liquid film or the micro-spheres into an ethanol-water solution with the volume percent concentration of 15 percent and condensing; washing the condensed and molded thin film or micro-spheres with de-ionized water. The composite carrier provided by the invention has a self-cleaning function; after the composite carrier is used for a solidified enzyme, a lot of enzyme activity of free enzymes can be remained; the enzymes solidified on the composite carrier can be recycled and repeatedly utilized; the temperature sensitivity is greatly reduced when being compared with that of the free enzymes, and the composite carrier has the properties of stability and uneasiness of deactivating.
Description
Technical field
The present invention relates to immobilized enzyme carrier technique field, the cellulose-SiO of more particularly to a kind of immobilized enzyme2Complex carrier
Preparation method and cellulose-SiO2Application of the complex carrier in terms of immobilized enzyme.
Background technology
Enzyme belongs to biocatalyst, and compared with common chemical reaction catalyst, enzyme can be more gentle in normal temperature, normal pressure etc.
Under conditions of carry out the catalytic reaction of high selectivity.But because enzyme is usually water soluble protein, therefore often have the disadvantage that:
1. it is unstable, easy in inactivation；2. it is difficult to reclaim and Reusability；3. continuous operation can not be realized.
Enzyme immobilization technology can improve disadvantages mentioned above.In enzyme immobilization technology, the most key is the selection of carrier material
Or process.At present typical carrier material has natural macromolecular material, synthesis macromolecular material, inorganic material etc..Wherein, it is based on
, due to possessing nontoxicity, mass-transfer performance is good, raw material is easy to get for the fixed enzyme vector of natural biomass materials, cheap etc. excellent
Point, receives significant attention.And cellulose has only as the maximum biological material of yield in the world as fixed enzyme vector
Special advantage.In recent years occur in that transforming the hydroxyl of cellulose as aldehyde radical prepares dialdehyde cellulose, take this directly with protein
Amino produces covalently cross-linked, the method so as to realize enzyme immobilizatio.The method avoids and add in conventional method aldehydes,
The drawbacks of such as formaldehyde easily causes pollution with glutaraldehyde.
But cellulose still comes with some shortcomings as a kind of natural macromolecular material as fixed enzyme vector, mainly
It is embodied in following two aspect：1. hydrophily is too strong, easily adsorbs other impurity when using and is contaminated；2. organic matter rigidity not
By force, durability is to be improved.
The content of the invention
For this reason, it may be necessary to provide a kind of solidification zymophore preparation method, the cellulose-SiO prepared by the method2Complex carrier
With hydrophobicity, it is difficult to adsorb pollutant, while itself has rigidity, durability can be applicable to the fixation of various enzymes.
The present invention provides a kind of cellulose-SiO for immobilized enzyme2The preparation method of complex carrier, comprises the following steps：
S1：By dialdehyde cellulose-SiO2Powder add solion, stir to powder after being completely dissolved by solution carry out from
Heart deaeration, makes the first mixed solution；
S2：First mixed solution is cooled into temperature for 20～40 DEG C, cool time is 60～120 minutes, is made
Second mixed solution；
S3：Second mixed solution prepared by S2 steps is made into the 0.4～1.2mm of liquid film or diameter of 0.2～1.0mm of thickness
Microballoon；
S4：By liquid film or microballoon obtained in S3 steps, it is placed in the ethanol-water solution that concentration of volume percent is 15% and coagulates
Gu；
S5：The liquid film or microballoon of coagulation forming in deionized water cleaning S4 steps.
Further, in the S1 steps, the solion is 1- pi-allyl -3- methylimidazole villaumites, 1- ethyl -3-
Any one in methylimidazole acetate or 1- ethyl-3-methylimidazole bromides.
Further, in the S1 steps, the dialdehyde cellulose-SiO2Powder is 1 with the weight ratio of ionic liquid:10
～30.
Further, in the S1 steps, control solution temperature is maintained at 60～120 DEG C, and mixing time is controlled 2～6
Hour, the evacuation and centrifugal degassing time is 10 minutes, and centrifugal speed is 8000～12000r/min.
Further, in the S4 steps, concentration of volume percent is that 15% ethanol-water solution was changed every 30 minutes
1 time, it is 2～5 times to change total degree.
Further, the dialdehyde cellulose-SiO in step S12Powder is prepared by the following method and obtains：
A1：Put into dialdehyde cellulose and SiO successively in ethanol-water solution2-NH2, it is well mixed, obtain the 3rd mixing molten
Liquid；
A2：3rd mixed solution is stirred and heated to 63～67 DEG C, and reacts 17～19 hours at 63～67 DEG C,
Obtain the first suspension；
A3：First suspension carries out suction filtration, washing, vacuum drying, grinding, obtains the dialdehyde cellulose-SiO2
Powder.
Further, dialdehyde cellulose and SiO in step A12-NH2Weight ratio be 20.0～60.0；
Further, the SiO in step A12-NH2It is prepared by the following method and obtains：
B1：Tetraethyl orthosilicate or butyl silicate add ethanol water, are well mixed, and obtain the 4th mixed solution；
B2：4th mixed solution adds and 70～80 DEG C is warming up to after glacial acetic acid, reacts 10～20 minutes, obtains the 5th
Mixed solution；
B3：5th mixed solution is added dropwise over N- aminoethyls-γ-aminopropyltrimethoxysilane, until occurring solidifying
Glue；
B4：Gel vacuum drying prepared by B3 steps, obtains SiO2-NH2。
Further, the dialdehyde cellulose in step A1 is prepared by the following method and obtains：
C1：Microcrystalline cellulose or pulp are added in hydrochloric acid solution, are stirred, and reaction is centrifuged taking precipitate after 12 hours
Matter；
C2：Deposit prepared by C1 steps is washed with deionized, is soaked, the second suspension is obtained；
C3：Sodium metaperiodate is added in second suspension, until deposit is uniformly dispersed, the 3rd suspension is obtained,
During control suspension pH value be maintained at 3～5, temperature is maintained at 35～50 DEG C, and this step is carried out under the conditions of lucifuge.
C4：The tert-butyl alcohol is added in 3rd suspension, the dialdehyde cellulose is centrifugally separating to obtain.
Meanwhile, inventor provide a kind of cellulose-SiO2Application of the complex carrier in terms of immobilized enzyme.Cellulose-SiO2
In complex carrier, dialdehyde cellulose is the main body for fixing zymophore, and side chain carries a large amount of aldehyde radicals, can produce crosslinking with zymoprotein,
Stable covalent bond is formed, plays a part of stable immobilized enzyme；And SiO2Particle, can simultaneously play two aspect effects：One side
Face, SiO2Particle carries out inorganic hybridization to cellulose, can make property of the carrier with part inorganic material, is effectively improved cellulose
The weatherability of material, durability and stability；On the other hand, SiO2Particle has certain hydrophobicity, and carrier can be avoided to use
When adsorb pollutant, i.e., with certain automatically cleaning effect.
Complex carrier is used to solidify after enzyme, can retain the most enzyme activity of resolvase, compares other solidification zymophore materials
With obvious advantage.Meanwhile, the enzyme being solidificated on complex carrier can be recycled and Reusability, and realize continuous behaviour
Make.Solidification enzyme on this carrier is compared resolvase and is greatly reduced to the sensitiveness of temperature, the characteristic with stable not easy in inactivation.
Prior art is different from, above-mentioned technical proposal has the advantage that：Cellulose-SiO provided by the present invention2It is compound
Carrier, introduces SiO2-NH2, it is allowed to that covalent cross-linking occurs with the part aldehyde radical of dialdehyde cellulose, make inorganic matter SiO2With organic matter
Cellulose hydridization, can simultaneously play reinforcing fiber element gel carrier mechanical strength and hydrophobic effect.Cellulose-SiO2It is compound
The hydrophobic improvement of carrier, can avoid fixing when zymophore is used and adsorb pollutant, with certain automatically cleaning effect.It is simultaneously multiple
Closing carrier is used to solidify after enzyme, can retain the most enzyme activity of resolvase, and the enzyme being solidificated on complex carrier can be recycled
And Reusability, resolvase is compared to the sensitiveness of temperature and is greatly reduced, the characteristic with stable not easy in inactivation.
Specific embodiment
Microcrystalline cellulose described in present embodiment is a kind of purifying, the cellulose of part depolymerization, white, odorless, nothing
Taste, the crystalline powder being made up of small porous particle, its main component is the straight chain formula polysaccharide combined with β-Isosorbide-5-Nitrae-glucoside bond
Material.
Pulp described in present embodiment is provided for Qingshan Paper limited company.Alpha-cellulose content is more than in pulp
91%, dynamic viscosity is 9.0mPaS, and whiteness is more than 85%ISO, and iron ion content is less than 15mg/kg, and hemi-cellulose content is less than
3.0%, content of ashes is less than 0.15%, and resin content is less than 0.3%.
Pi-allyl -3- the methylimidazole villaumites of ionic liquid 1- described in present embodiment, 1- ethyl-3-methylimidazole acetic acid
Salt and 1- ethyl-3-methylimidazoles bromide are provided for Lanzhou Chemical Physics research institute of the Chinese Academy of Sciences.Ionic liquid purity is all higher than
98.5%, moisture is less than 1.0%, and imidazoles is less than 0.5% with acid ion content.
A kind of cellulose-the SiO of embodiment 12The preparation method of complex carrier
(1) weigh 6g microcrystalline celluloses to be dissolved in the hydrochloric acid solution that 100mL concentration is 5mol/L, stirring, hydrolysis 12
Precipitation is taken after being centrifuged after hour.Deposit is washed with deionized, soaks, and precipitation is suspended in deionized water；In stirring
It is lower to add sodium metaperiodate in solution, until deposit is uniformly dispersed.Reaction carry out in light protected environment, during pH value of solution
Value remains 4, and temperature is 35 DEG C.The tert-butyl alcohol, centrifugation is added to obtain dialdehyde cellulose after reaction in solution.
(2) 10mL tetraethyls siloxanes is added in 50mL ethanol-water solutions (percent by volume is 50%), mixing is equal
It is even, 0.1mL glacial acetic acids are added, 75 DEG C, after 10 minutes are warming up to, it is added dropwise over N- aminoethyl-γ-aminopropyl trimethoxy silicon
Alkane, until there is gel.Gel is vacuum dried, SiO is obtained2-NH2。
(3) gained dialdehyde cellulose takes gained SiO in 6g, step (2) in step (1)2-NH20.1g is taken, 50mL second is added
In alcohol-water solution (percent by volume is 50%), mixing is reacted 8 hours, suction filtration at 75 DEG C, washing, vacuum drying, grinding,
Obtain the dialdehyde cellulose-SiO of powder2。
(4) the powder dialdehyde cellulose-SiO of gained in 1g steps (3) is taken2It is dissolved in the 1- ethyl -3- methyl of 20g
In imidazole acetate ionic liquid, solution processes fluid temperature is controlled at 60 DEG C, and is stirred 120 minutes, is completely dissolved powder,
Obtain containing cellulose-SiO2Solion, solion supercentrifuge evacuation and centrifugal degassing under 8000r/min rotating speeds
After 10min, cool down 60 minutes to 20 DEG C in running water, increase solution viscosity.Solution after cooling is poured on into knifing machine
On knifing panel, start scraper, solution is bulldozed, so as to make the liquid film that thickness is 0.2mm, liquid film is placed in into percent by volume
Concentration be 15% ethanol-water solution in solidified, liquid 2 times is changed during solidification, liquid is changed every time at intervals of 30 minutes.Jing go from
Dialdehyde cellulose-SiO is obtained after sub- water cleaning2Plural gel film.
The solidity test of the glucose oxidase of embodiment 2.
Dialdehyde cellulose-the SiO of the gained of embodiment 12Plural gel film carries out the solidification of glucose oxidase, solidification
Step is as follows：Compound concentration for 1mg/mL glucose oxidase-phosphate solution (pH=6.5), by dialdehyde cellulose-
SiO2Plural gel film immerses solution, after being placed in shaking table 33 DEG C of oscillating reactions 4 hours, takes out gel film, uses phosphate
Respectively washing 3 times of buffer solution and deionized water, glucose oxidase of being fixed on carrier.
The glucose oxidase of the solidification is carried out into series of tests, it is as a result as follows：The solidification grape being immobilized onto on carrier
Carbohydrate oxidase can retain the activity of free glucose oxidase up to 72.3%；Reuse the enzyme of the glucose oxidase after 5 times
The rate of recovery living is 78.0%；Glucose oxidase enzyme activity of the constant temperature after 60 minutes compares the water-bath at 30 DEG C under 40 DEG C of water-bath
Glucose oxidase enzyme activity of the lower constant temperature after 60 minutes only declines 6.1%, and free glucose oxidase under equal conditions enzyme
It is living to decline up to 75.3%.
Meanwhile, the glucose oxidase of the solidification stands 15 days in PBS and does not observe long bacterium phenomenon.
A kind of cellulose-the SiO of embodiment 32The preparation method of complex carrier
(1) weigh 4g pulps to be dissolved in the hydrochloric acid solution that 100mL concentration is 5mol/L, stirring, hydrolysis is after 12 hours
Precipitation is taken after centrifugation.Deposit is washed with deionized, soaks, and precipitation is suspended in deionized water；Under agitation to molten
Sodium metaperiodate is added in liquid, until deposit is uniformly dispersed.Reaction carry out in light protected environment, during solution ph keep
For 3, temperature is 50 DEG C.The tert-butyl alcohol, centrifugation is added to obtain dialdehyde cellulose after reaction in solution.
(2) 20mL butyl silicates are added in 60mL ethanol-water solutions (percent by volume is 50%), are well mixed,
0.5mL glacial acetic acids are added, 85 DEG C, after 15 minutes are warming up to, N- aminoethyls-γ-aminopropyltrimethoxysilane is added dropwise over,
Until there is gel.Gel is vacuum dried, SiO is obtained2-NH2。
(3) gained dialdehyde cellulose takes gained SiO in 4g, step (2) in step (1)2-NH20.1g is taken, 50mL second is added
In alcohol-water solution (percent by volume is 50%), mixing is reacted 24 hours, suction filtration at 65 DEG C, washing, and vacuum drying is ground
Mill, obtains the dialdehyde cellulose-SiO of powder2。
(4) the powder dialdehyde cellulose-SiO of gained in 3g steps (3) is taken2It is dissolved in 30g1- pi-allyl -3- methyl
In imidazoles chloride salt ions liquid, temperature control at 120 DEG C, stirring be completely dissolved powder within 40 minutes, obtain containing dialdehyde cellulose-
SiO2Solion, while hot with supercentrifuge under 10000r/min rotating speeds evacuation and centrifugal degassing 10 minutes, it is natural in atmosphere
Cooling 100 minutes to 30 DEG C, increases solution viscosity.By the solution extrusion extrusion graininess drop of 1.2 millimeters of diameter, put
Solidified in ethanol-water solution (percent by volume is 15%), liquid 3 times is changed during solidification, every time at intervals of 30 minutes.Jing
Dialdehyde cellulose-SiO is obtained after deionized water cleaning2Composite gel microsphere.
The solidity test of the cellulase of embodiment 4.
Dialdehyde cellulose-the SiO of the gained of embodiment 32Plural gel film carries out the solidification of cellulase, curing schedule
It is as follows：Compound concentration is the cellulase-phosphate solution (pH=7.2) of 1.5mg/mL, by dialdehyde cellulose-SiO2It is compound
In gel micro-ball immersion solution, it is placed in shaking table and vibrates, after reacting 6 hours at 40 DEG C gel micro-ball is taken out, final gel is micro-
Respectively washing 3 times of ball phosphate buffer and deionized water, cellulase of being fixed on microsphere supported.
The cellulase of the solidification is carried out into series of tests, it is as a result as follows：The cured fiber element enzyme being immobilized onto on carrier
The activity of free cellulose enzyme can be retained up to 81.5%；The enzyme activity rate of recovery for reusing cellulase after 5 times is 76.7%；
The enzyme activity of cellulase compares the enzyme activity of the cellulase after 60 DEG C of water-baths 90 minutes after 70 DEG C of water-bath 90 minutes, only declines
3.4%, and the enzyme activity of free cellulose enzyme under equal conditions declines up to 36.9%.
Meanwhile, the cellulase of the solidification stands 15 days in PBS and does not observe long bacterium phenomenon.
A kind of cellulose-the SiO of embodiment 52The preparation method of complex carrier
(1) weigh 3g microcrystalline celluloses to be dissolved in the hydrochloric acid solution that 100mL concentration is 5mol/L, uniform stirring, hydrolysis is anti-
Precipitation is taken after being centrifuged after answering 12 hours.Deposit is washed with deionized, soaks, and precipitation is suspended in deionized water；
Sodium metaperiodate is added in solution under stirring, until deposit is uniformly dispersed.Reaction carry out in light protected environment, during it is molten
Liquid pH value remains 5, and temperature is 45 DEG C.The tert-butyl alcohol, centrifugation is added to obtain dialdehyde cellulose after reaction in solution.
(2) 15mL butyl silicates are added in 40mL ethanol-water solutions (percent by volume is 50%), are well mixed,
0.3mL glacial acetic acids are added, 80 DEG C, after 20 minutes are warming up to, N- aminoethyls-γ-aminopropyltrimethoxysilane is added dropwise over,
Until there is gel.Gel is vacuum dried, SiO is obtained2-NH2。
(3) gained dialdehyde cellulose takes gained SiO in 2g, step (2) in step (1)2-NH20.1g is taken, 50mL second is added
In alcohol-water solution (percent by volume is 50%), mixing is reacted 16 hours, suction filtration at 70 DEG C, washing, and vacuum drying is ground
Mill, obtains the dialdehyde cellulose-SiO of powder2。
(4) the powder dialdehyde cellulose-SiO of gained in 1g steps (3) is taken2It is dissolved in 30g 1- ethyl -3- methyl miaows
In azoles bromide ionic liquid, at 90 DEG C, stirring is completely dissolved powder in 80 minutes to temperature control, obtains containing dialdehyde cellulose-SiO2
Solion, while hot by solution supercentrifuge after evacuation and centrifugal degassing 10min under 12000r/min rotating speeds, by solution in sky
Natural cooling 60 minutes to 40 DEG C in gas, increase solution viscosity.By the solution extrusion extrusion graininess of 0.4 millimeter of diameter
Drop, is placed in ethanol-water solution (percent by volume is 15%) and is solidified, and liquid 5 times is changed during solidification, every time at intervals of 30
Minute.Dialdehyde cellulose-SiO is obtained Jing after deionized water cleaning2Composite gel microsphere.
The solidity test of the beta galactosidase of embodiment 6.
Dialdehyde cellulose-the SiO of the gained of embodiment 52Plural gel film carries out the solidification of cellulase, curing schedule
It is as follows：Compound concentration is the beta galactosidase-phosphate solution (pH=7) of 2.5mg/mL, by dialdehyde cellulose-SiO2It is multiple
In closing gel micro-ball immersion solution, it is placed in shaking table and vibrates, reacts 3 hours at 20 DEG C, with phosphate buffer and deionization
Water respectively washing 3 times, beta galactosidase of being fixed on microsphere supported.
The beta galactosidase of the solidification is carried out into series of tests, it is as a result as follows：The beta galactose being immobilized onto on carrier
Glycosides enzyme can retain the activity of free beta galactosidase up to 74.8%；The enzyme activity for reusing beta galactosidase after 5 times is reclaimed
Rate is 71.2%；The enzyme activity of beta galactosidase compares β-gala after 30 DEG C of water-baths 60 minutes after 45 DEG C of water-bath 60 minutes
The enzyme activity of glycosidase declines 12.5%, and free beta galactosidase under equal conditions enzyme activity declines up to 42.9%.
Meanwhile, it is immobilized onto the beta galactosidase on carrier and 15 days is stood in PBS and is not observed and grows
Bacterium phenomenon.
Test by more than, show a kind of cellulose-SiO for immobilized enzyme of product of the present invention2Complex carrier is in solidification
After enzyme, the enzyme activity of resolvase more than 70% can be retained, compare other solidification zymophore materials and there is obvious advantage.Meanwhile, Gu
Changing enzyme activity of the enzyme on this complex carrier after reusing 5 times still has using front more than 70%, it was demonstrated that be solidificated in this multiple
The enzyme closed on carrier can be recycled and Reusability, and realize continuous operation.And bathtub test explanation solidification in embodiment
Enzyme on this carrier is compared resolvase and is greatly reduced to the sensitiveness of temperature, solidifies enzyme on this carrier and has and is stably difficult
The characteristic of inactivation.Finally, be solidified on the enzyme on the carrier 15 days are stood in PBS do not observe long bacterium phenomenon,
Illustrate that the carrier has certain automatically cleaning effect.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposit between operating
In any this actual relation or order.And, term " including ", "comprising" or its any other variant are intended to
Nonexcludability is included, so that a series of process, method, article or terminal device including key elements not only includes those
Key element, but also including other key elements being not expressly set out, or also include for this process, method, article or end
The intrinsic key element of end equipment.In the absence of more restrictions, limited by sentence " including ... " or " including ... "
Key element, it is not excluded that also there is other key element in the process including the key element, method, article or terminal device.This
Outward, herein, " it is more than ", " being less than ", " exceeding " etc. are interpreted as not including this number；" more than ", " below ", " within " etc. understand
It is to include this number.
Although being described to the various embodiments described above, those skilled in the art once know basic wound
The property made concept, then can make other change and modification to these embodiments, so embodiments of the invention are the foregoing is only,
Not thereby the scope of patent protection of the present invention, equivalent structure or equivalent process that every utilization description of the invention is made are limited
Conversion, or is directly or indirectly used in other related technical fields, be included in the same manner the present invention scope of patent protection it
It is interior.
Claims (10)
1. a kind of cellulose-SiO for immobilized enzyme2The preparation method of complex carrier, it is characterised in that comprise the following steps：
S1：By dialdehyde cellulose-SiO2Powder adds solion, stirs to powder that solution is carried out into centrifugation after being completely dissolved is de-
Bubble, makes the first mixed solution；
S2：First mixed solution is cooled into solution temperature for 20～40 DEG C, cool time is 60～120 minutes, is made
Second mixed solution；
S3：By S2 steps prepare the second mixed solution make 0.2～1.0mm of thickness 0.4～1.2mm of liquid film or diameter it is micro-
Ball；
S4：By liquid film or microballoon obtained in S3 steps, it is placed in the ethanol-water solution that concentration of volume percent is 15% and solidifies；
S5：The liquid film or microballoon of coagulation forming in deionized water cleaning S4 steps.
2. preparation method according to claim 1, it is characterised in that in the S1 steps, the solion is 1- alkene
Any one in propyl group -3- methylimidazole villaumites, 1- ethyl-3-methylimidazoles acetate or 1- ethyl-3-methylimidazole bromides.
3. preparation method according to claim 1, it is characterised in that in the S1 steps, the dialdehyde cellulose-SiO2
Powder is 1 with the weight ratio of ionic liquid:10～30.
4. preparation method according to claim 1, it is characterised in that in the S1 steps, control solution temperature is maintained at
60～120 DEG C, mixing time was controlled at 2～6 hours；The evacuation and centrifugal degassing time is 10 minutes, and centrifugal speed is 8000～12000r/
min。
5. preparation method according to claim 1, it is characterised in that in the S4 steps, concentration of volume percent is
15% ethanol-water solution was changed 1 time every 30 minutes, and it is 2～5 times to change total degree.
6. preparation method according to claim 1, it is characterised in that the dialdehyde cellulose-SiO in step S12Powder passes through
Following methods are prepared：
A1：Put into dialdehyde cellulose and SiO successively in ethanol-water solution2-NH2, it is well mixed, obtain the 3rd mixed solution；
A2：3rd mixed solution is stirred and heated to 63～67 DEG C, and reacts 17～19 hours at 63～67 DEG C, obtains
First suspension；
A3：First suspension carries out suction filtration, washing, vacuum drying, grinding, obtains the dialdehyde cellulose-SiO2Powder.
7. preparation method according to claim 6, it is characterised in that dialdehyde cellulose and SiO in step A12-NH2Weight
Amount ratio is 20.0～60.0.
8. preparation method according to claim 6, it is characterised in that the SiO in step A12-NH2Make by the following method
It is standby and obtain：
B1：Tetraethyl orthosilicate or butyl silicate add ethanol water, are well mixed, and obtain the 4th mixed solution；
B2：4th mixed solution adds and 70～80 DEG C is warming up to after glacial acetic acid, reacts 10～20 minutes, obtains the 5th mixing
Solution；
B3：5th mixed solution is added dropwise over N- aminoethyls-γ-aminopropyltrimethoxysilane, until there is gel；
B4：Gel vacuum drying prepared by B3 steps, obtains SiO2-NH2。
9. preparation method according to claim 6, it is characterised in that the dialdehyde cellulose in step A1 is by the following method
It is prepared：
C1：Microcrystalline cellulose or pulp are added in hydrochloric acid solution, is stirred, centrifuging and taking deposit after reacting 12 hours；
C2：Deposit prepared by C1 steps is washed with deionized, is soaked, the second suspension is obtained；
C3：Sodium metaperiodate is added in second suspension, until deposit is uniformly dispersed, the 3rd suspension, process is obtained
Middle control suspension pH value is maintained at 3～5, and temperature is maintained at 35～50 DEG C, and this step is carried out under the conditions of lucifuge.
C4：The tert-butyl alcohol is added in 3rd suspension, the dialdehyde cellulose is centrifugally separating to obtain.
10. a kind of cellulose-SiO2Application of the complex carrier in terms of immobilized enzyme.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092265A (en) * | 2018-09-10 | 2018-12-28 | 陕西科技大学 | A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified |
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| CN109092265B (en) * | 2018-09-10 | 2021-02-19 | 陕西科技大学 | Cellulose-based adsorbent modified by polyimidazole ionic liquid and preparation method and application thereof |
| CN109721760A (en) * | 2018-12-27 | 2019-05-07 | 南京工业大学 | A kind of preparation method of polymeric aerogels |
| CN113138220A (en) * | 2021-04-23 | 2021-07-20 | 广州万孚生物技术股份有限公司 | Electrochemical biosensor and preparation method thereof |
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