CN114717277A - Nano cellulose and preparation method and application thereof - Google Patents
Nano cellulose and preparation method and application thereof Download PDFInfo
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- 229920001046 Nanocellulose Polymers 0.000 title claims description 45
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000001913 cellulose Substances 0.000 claims abstract description 68
- 229920002678 cellulose Polymers 0.000 claims abstract description 67
- BJRNKVDFDLYUGJ-RMPHRYRLSA-N hydroquinone O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-RMPHRYRLSA-N 0.000 claims abstract description 34
- 229960000271 arbutin Drugs 0.000 claims abstract description 17
- BJRNKVDFDLYUGJ-UHFFFAOYSA-N p-hydroxyphenyl beta-D-alloside Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
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- 239000008107 starch Substances 0.000 claims abstract description 13
- 235000019698 starch Nutrition 0.000 claims abstract description 13
- 102000004190 Enzymes Human genes 0.000 claims abstract description 11
- 108090000790 Enzymes Proteins 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 4
- 108010077004 Cellodextrin phosphorylase Proteins 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- HXXFSFRBOHSIMQ-VFUOTHLCSA-N alpha-D-glucose 1-phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(O)=O)[C@H](O)[C@@H](O)[C@@H]1O HXXFSFRBOHSIMQ-VFUOTHLCSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
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- 102000009097 Phosphorylases Human genes 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- 150000004676 glycans Chemical class 0.000 claims description 8
- 229920001282 polysaccharide Polymers 0.000 claims description 8
- 239000005017 polysaccharide Substances 0.000 claims description 8
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- DBLXOVFQHHSKRC-UHFFFAOYSA-N ethanesulfonic acid;2-piperazin-1-ylethanol Chemical compound CCS(O)(=O)=O.OCCN1CCNCC1 DBLXOVFQHHSKRC-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008135 α-glycosides Chemical class 0.000 claims description 4
- 229920000945 Amylopectin Polymers 0.000 claims description 3
- 229920000856 Amylose Polymers 0.000 claims description 3
- 150000008494 α-glucosides Chemical class 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 125000000600 disaccharide group Chemical group 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- -1 phosphate radical ions Chemical class 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000000338 in vitro Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 25
- 239000000839 emulsion Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000003275 alpha amino acid group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006911 enzymatic reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 150000002338 glycosides Chemical class 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 108050004944 Alpha-glucan phosphorylases Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000188 beta-D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
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Abstract
The invention provides a nano-cellulose and a preparation method and application thereof, wherein the nano-cellulose has a new function, is a novel nano-cellulose with functional groups and can be used as an emulsifier; the preparation method adopts arbutin with functional groups as a primer and starch as a substrate, prepares the novel nano-cellulose under the catalysis of in vitro enzyme, has simple preparation process of enzyme-synthesized cellulose and environment-friendly reaction conditions, and better solves the defects of high energy consumption, environmental pollution and the like in the existing preparation process of nano-cellulose.
Description
Technical Field
The invention relates to the field of enzyme engineering, in particular to nano-cellulose and a preparation method and application thereof.
Background
As a novel nano material, nanocellulose not only has the characteristic of high specific surface area of a common nano material, but also has the advantages of low density, low cost, high strength, reproducibility, biodegradability and the like, and is widely applied to coatings, electronic equipment and composite materials. The traditional method for preparing the nano-cellulose is to mechanically crush natural cellulose by high power and treat the natural cellulose with strong acid and alkali, but the nano-cellulose obtained by the method does not have any functional group except hydroxyl.
The nanocellulose prepared by the in vitro enzyme method has precise molecular chain structure and has obvious advantages compared with Chemical synthesis (Chemical Reviews 2016,116, 2307-2413). The whole enzyme catalysis reaction process is completed in one step in aqueous solution, the reaction condition is mild, and no protection or deprotection process is needed. Cellodextrin phosphorylase (CDP) can specifically recognize hydroxyl at the 4 th position on a beta-D-glucose primer, and has no recognition on hydroxyl at other positions on the beta-D-glucose primer, so that functional groups on the surface of the nano-cellulose can be controlled by designing the beta-D-glucose primer to meet different application requirements. Functional group groups can be introduced to the surface of the nano-cellulose by regulating the type of the substituent group at the 1 st position of the beta-D-glucose primer. The novel green nano-cellulose preparation method with low energy consumption effectively overcomes the defects of the traditional cellulose preparation method, is a novel nano-cellulose preparation method which is expected to realize large-scale production, and has wide application prospect in modern industry.
Disclosure of Invention
The invention aims to provide a nano-cellulose.
Another technical problem to be solved by the present invention is to provide a method for preparing the above nanocellulose.
Another technical problem to be solved by the present invention is to provide the application of the above nanocellulose.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a nano-cellulose is a chain cellulose composed of beta- (1,4) -D-glucoside bonds, the crystal form of the nano-cellulose is a cellulose II type with better thermal stability, namely, cellulose molecular chains are arranged in an antiparallel manner, and phenol groups are aggregated on the upper and lower surfaces of the nano-cellulose.
Preferably, the nanocellulose is in a two-dimensional sheet shape, the length is between 1 and 2 μm, the width is less than 1 μm, the thickness is between 5 and 6nm, and the degree of polymerization is about 10.
A method for preparing nanometer cellulose comprises taking starch as substrate, arbutin as primer, adding alpha-glycoside phosphorylase (alpha-GP) and cellodextrin phosphorylase (CDP), adding inorganic phosphate radical ion and magnesium ion (Mg)2+) Carrying out enzyme catalytic reaction in a 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) buffer solution to produce and obtain nano-cellulose; wherein the alpha-glucoside phosphorylase takes starch as a substrateThe method comprises the steps of catalyzing starch to be phosphorized in the presence of inorganic phosphorus to generate alpha-D-Glucose-1-phosphate (alpha-G1P), then connecting Glucose units on the alpha-D-Glucose-1-phosphate to arbutin in the presence of catalysis of cellodextrin phosphorylase to form new Glucose non-reducing ends and release inorganic phosphate radical ions, and then continuously connecting the Glucose units on the alpha-D-Glucose-1-phosphate to the newly formed non-reducing ends by the cellodextrin phosphorylase to form the nano cellulose with arbutin at one end.
Preferably, in the preparation method of the nanocellulose, the target product nanocellulose is obtained by purification and freeze drying, and the concentration of phosphate ions is kept unchanged after the reaction is finished.
Preferably, in the preparation method of the nano-cellulose, the 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) solution used for purifying the nano-cellulose is the same as the HEPES used in the reaction, and the cycle number of washing and centrifuging is in the range of 2-10.
In the preparation method of the nano-cellulose, the enzyme catalysis process is completed by the combined action of alpha GP and CDP in a buffer solution, the alpha GP catalyzes inorganic phosphorus and starch to generate a monomer alpha G1P, then a phosphate group on the 1 site of a G1P monomer and a hydroxyl group on the 4 site of a glucose unit of arbutin are condensed under the action of CDP, inorganic phosphoric acid is released at the same time, and finally chain cellulose consisting of beta- (1,4) -D-glucoside bonds is formed. The crystal form of the obtained nano-cellulose is a cellulose II type with better thermal stability, namely, the molecular chains of the cellulose are arranged in an antiparallel manner, so that the phenol groups are gathered on the upper and lower surfaces of the nano-cellulose, and the nano-cellulose is endowed with a new function.
Preferably, in the method for preparing nanocellulose, the substrate is disaccharide containing D-glucose unit, polysaccharide or any mixture thereof, and the substrate and the phosphate are catalyzed by enzyme capable of converting the substrate and the phosphate into alpha G1P.
Preferably, in the preparation method of the nanocellulose, the polysaccharide containing the D-glucose unit is soluble starch, soluble amylose or soluble amylopectin, and the polysaccharide and the phosphate are converted into the alpha G1P by using glycoside phosphorylase (alpha-glucan phosphorylase, EC 2.4.1.1, alpha GP) catalysis.
Preferably, in the method for preparing nanocellulose, the concentration of the polysaccharide containing D-glucose units is 10 to 200g/L, and more preferably 50 g/L.
Preferably, in the method for preparing nanocellulose, the phosphate is one or a mixture of two or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.
Preferably, in the method for preparing nanocellulose, the concentration of the alpha-glycoside phosphorylase is 1 to 10g/L, and more preferably 2 g/L.
Preferably, in the preparation method of the nano-cellulose, the concentration of arbutin is 1-100 mM. More preferably 10 mM.
Preferably, in the method for preparing the nano-cellulose, the concentration of the 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) solution is 10-1000mM, and more preferably 200 mM.
Preferably, in the method for preparing nanocellulose, the concentration of magnesium ions is 1 to 100mM, more preferably 10 mM.
Preferably, in the method for preparing nanocellulose, the concentration of the phosphate is 1 to 100mM, and more preferably 20 mM.
Preferably, in the method for preparing nanocellulose, the concentration of cellodextrin phosphorylase (CDP) is 0.1-10g/L, and more preferably 2 g/L.
Preferably, the reaction temperature of the method for preparing the nano-cellulose is 30-80 ℃, and more preferably 40-50 ℃.
Preferably, in the method for producing nanocellulose, the glycoside phosphorylase amino acid sequence NCBI accession No. WP — 011250357.1.
Preferably, in the method for preparing nanocellulose, the cellodextrin phosphorylase amino acid sequence NCBI accession number is WP — 020457986.1.
The application of the nano-cellulose as an emulsifier.
Has the beneficial effects that:
the nano-cellulose is endowed with a new function and is novel nano-cellulose with functional groups; the preparation method adopts arbutin with functional groups as a primer and starch as a substrate, prepares the novel nano-cellulose under the catalysis of in vitro enzyme, has simple preparation process of enzyme-synthesized cellulose and environment-friendly reaction conditions, and better solves the defects of high energy consumption, environmental pollution and the like in the existing preparation process of nano-cellulose.
The enzymatic reaction process is completed in one step in aqueous solution, arbutin with functional groups can be successfully introduced to the surface of the nano-cellulose, the reaction condition is mild, the substrate is cheap, and any protection or deprotection process is not needed; the method has the advantages of simple and convenient process, low cost, greenness and safety, solves the problems of high energy consumption, environmental pollution and lack of functional groups in the existing preparation process of the nano-cellulose, has low cost, is easy to industrialize, and has wide application prospect in industrial production.
The nano-cellulose has wide application prospect in the directions of nano-composite materials, Perking emulsion, hydrogel, textile engineering, medical tissue engineering and the like.
Drawings
FIG. 1 is a representation of the novel nanocellulose synthesized by enzymatic catalysis: (a)1h NMR; (b) a wide angle X-ray diffraction pattern; (c) transmission Electron Microscopy (TEM).
FIG. 2 is a catalytic reaction pathway.
FIG. 3 is a photograph of a 1.0 wt% nanocellulose-stabilized n-undecane emulsion and the corresponding digital photograph (inset).
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
As shown in fig. 2, a method for preparing nanocellulose comprises the following specific steps:
(1) in the whole reaction system, the reaction solution is mixed,adding 50g/L soluble starch, 10mM arbutin primer, 20mM inorganic phosphorus (from KH)2PO4And K2HPO4Prepared) 10mM magnesium ions, 2g/L alpha GP (amino acid sequence NCBI accession number WP _011250357.1), 2g/L CDP (amino acid sequence NCBI accession number WP _020457986.1) and 200mM HEPES (pH 7.5) buffer solution, and the whole system is placed at 45 ℃ in a water bath for nano-cellulose synthesis;
(2) and (3) washing, centrifuging and purifying the nano-cellulose obtained in the step (1) for 10 times by using a HEPES solution (consistent with the step (1)), and then freezing and drying.
The characterization of the novel nanocellulose synthesized by the enzymatic method in the examples is shown in fig. 1. The diagram (a) is that of the novel nanocellulose1H NMR data. 4.35ppm hydrogen (H) in position 1 of the glucose building block expressed as novel nanocellulose1) Displacement of (2); 4.35ppm is the hydrogen (H) at position 2-6 in the glucose structural unit of the novel nano-cellulose2～H6) Displacement of (2); 5.21ppm are hydrogen (H) bound to phenol7) Displacement of (2); 6.42 and 6.81ppm are hydrogen (H) in the benzene ring8And H9) Displacement of (2). Panel (b) is X-ray diffraction (WAXD) data for the novel nanocellulose. The three diffraction peaks of 12.1 degrees, 19.9 degrees and 22.1 degrees are respectively attributed to the cellulose II crystal form (monoclinic crystal)
(110) And (020) diffraction planes with interplanar spacings of 0.72, 0.44 and 0.4nm, respectively. Fig. (c) is a Transmission Electron Micrograph (TEM) of the novel nanocellulose. The novel nano-cellulose is in a flaky shape, the average length is about 300nm, and the length-diameter ratio is 4.6. The above characterization results fully demonstrate that the novel nanocellulose containing the phenol group at the terminal is successfully synthesized by the in vitro enzyme method.
The nanocellulose synthesized by the enzymatic method in example 1 was subjected to an emulsification experiment. The obtained nanocellulose was prepared into a 1.0 wt% suspension with distilled water by centrifugation, and then homogenized at room temperature for 1min at 10000rpm using a disperser. 12.00g of the nanocellulose suspension was mixed with 3ml of n-undecane (oil-water ratio 1: 4v/W), the mixture was homogenized again at 15000rpm for 3 minutes at room temperature to obtain a crude emulsion, and finally ultrasonic emulsification was performed in an ice bath at a power of 360W for 2 minutes to obtain an oil-in-water (O/W) type emulsion.
The emulsion prepared with the nanocellulose of example 1 was characterized. As shown in FIG. 3, the emulsion plot and droplet size distribution tests show that the emulsion has a droplet size of about 8 μm, compared to Jun-I. The experiment can prove that the nano-cellulose can be used as an emulsifier for preparing emulsion.
Example 2
A preparation method of nano-cellulose comprises the following specific steps:
(1) in the whole reaction system, 100g/L soluble amylose, 50mM arbutin primer and 40mM inorganic phosphorus (prepared from NaH) are added2PO4And Na2HPO4Prepared) 10mM magnesium ion, 5g/L alpha GP, 2g/L CDP and 600mM HEPES (pH 7.5) buffer solution, and the whole system is put in a water bath at 40 ℃ for the synthesis of nano-cellulose;
(2) and (2) washing, centrifuging and purifying the nano-cellulose obtained in the step (1) for 10 times by using a HEPES solution (which is consistent with the step (1)), and then freezing and drying.
Example 3
A preparation method of nano-cellulose comprises the following specific steps:
(1) in the whole reaction system, 10g/L soluble starch, 1mM arbutin primer and 1mM inorganic phosphorus (KH from)2PO4Prepared) 10mM magnesium ions, 1g/L alpha GP, 0.1g/L CDP and 10mM HEPES (pH 7.5) buffer solution, and the whole system is put in a water bath at 45 ℃ for the synthesis of nano-cellulose;
(2) and (3) washing, centrifuging and purifying the nano-cellulose obtained in the step (1) for 10 times by using a HEPES solution (consistent with the step (1)), and then freezing and drying.
Example 4
A preparation method of nano-cellulose comprises the following specific steps:
(1) in the whole reaction system, 200g/L soluble amylopectin, 100mM arbutin primer and 100mM inorganic phosphorus (from K)2HPO4Prepared) 10mM magnesium ion, 10g/L alpha GP, 10g/L CDP and 1000mM HEPES (pH 7.5) buffer solution, and the whole system is put in a water bath at 50 ℃ for the synthesis of nano-cellulose;
(2) and (3) washing, centrifuging and purifying the nano-cellulose obtained in the step (1) for 10 times by using a HEPES solution (consistent with the step (1)), and then freezing and drying.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. A nanocellulose, characterized by: the cellulose is chain cellulose consisting of beta- (1,4) -D-glucoside bonds, the crystal form of the cellulose is cellulose type II with better thermal stability, namely, the molecular chains of the cellulose are arranged in an antiparallel manner, and the phenol groups are aggregated on the upper and lower surfaces of the nanocellulose.
2. The nanocellulose of claim 1, characterized in that: it is in two-dimensional sheet shape, with length of 1-2 μm, width less than 1 μm, thickness of 5-6nm, and polymerization degree of about 10.
3. The method for producing nanocellulose according to claim 1, wherein: taking starch as a substrate and arbutin as a primer, adding alpha-glucoside phosphorylase and cellodextrin phosphorylase, and carrying out enzyme catalytic reaction in a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution containing inorganic phosphate ions and magnesium ions to produce and obtain nano-cellulose; the alpha-glucoside phosphorylase takes starch as a substrate, the starch is catalyzed to carry out phosphorolysis in the presence of inorganic phosphorus to generate alpha-D-glucose-1-phosphate, then a glucose unit on the alpha-D-glucose-1-phosphate is connected to arbutin under the catalysis of cellodextrin phosphorylase to form a new glucose non-reducing end and release inorganic phosphate ions, and then the cellodextrin phosphorylase continuously connects the glucose unit on the alpha-D-glucose-1-phosphate to the formed non-reducing end to form the nano cellulose with new arbutin at one end.
4. The method for producing nanocellulose according to claim 3, characterized in that: the target product nano-cellulose is obtained through purification and freeze drying, and the concentration of phosphate radical ions is kept unchanged after the reaction is finished.
5. The method for producing nanocellulose according to claim 3, characterized in that: the substrate is disaccharide, polysaccharide or any mixture thereof containing D-glucose unit, and is catalyzed by enzyme capable of converting the substrate and phosphate into alpha G1P; the polysaccharide containing D-glucose units is soluble starch, soluble amylose or soluble amylopectin, and is converted into alpha G1P by using glycosidic phosphorylase for catalyzing with phosphate.
6. The method for producing nanocellulose according to claim 5, characterized in that: the concentration of the polysaccharide containing D-glucose units is 10-200 g/L.
7. The method for producing nanocellulose according to claim 5 or 6, characterized in that: the concentration of the polysaccharide comprising D-glucose units was 50 g/L.
8. The method for producing nanocellulose according to claim 5, characterized in that: the phosphate is one or a mixture of two or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.
9. The method for producing nanocellulose according to claim 3, characterized in that: the concentration of the alpha-glycoside phosphorylase is 1-10 g/L; the concentration of the arbutin is 1-100 mM; the concentration of the 4-hydroxyethyl piperazine ethanesulfonic acid solution is 10-1000 mM; the concentration of the magnesium ions is 1-100 mM; the concentration of the phosphate is 1-100 mM; the concentration of the cellodextrin phosphorylase is 0.1-10 g/L.
10. The method for producing nanocellulose according to claim 3 or 9, characterized in that: the concentration of the alpha-glycoside phosphorylase is 2 g/L; the concentration of the arbutin is 10 mM; the concentration of the 4-hydroxyethyl piperazine ethanesulfonic acid solution is 200 mM; the concentration of the magnesium ions is 10 mM; the concentration of the phosphate is 20 mM; the concentration of the cellodextrin phosphorylase is 2 g/L.
11. The method for producing nanocellulose according to claim 3, characterized in that: the reaction temperature is 30-80 ℃.
12. Use of nanocellulose as claimed in claim 1 as an emulsifier.
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