CN114717277B - Nanocellulose and preparation method and application thereof - Google Patents
Nanocellulose and preparation method and application thereof Download PDFInfo
- Publication number
- CN114717277B CN114717277B CN202210372511.0A CN202210372511A CN114717277B CN 114717277 B CN114717277 B CN 114717277B CN 202210372511 A CN202210372511 A CN 202210372511A CN 114717277 B CN114717277 B CN 114717277B
- Authority
- CN
- China
- Prior art keywords
- nanocellulose
- concentration
- alpha
- glucose
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 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 38
- 229920002678 cellulose Polymers 0.000 claims abstract description 27
- 239000001913 cellulose Substances 0.000 claims abstract description 27
- 229960000271 arbutin Drugs 0.000 claims abstract description 19
- 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 19
- 102000004190 Enzymes Human genes 0.000 claims abstract description 16
- 108090000790 Enzymes Proteins 0.000 claims abstract description 16
- 229920002472 Starch Polymers 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 239000008107 starch Substances 0.000 claims abstract description 16
- 235000019698 starch Nutrition 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 108010077004 Cellodextrin phosphorylase Proteins 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 17
- 108010073135 Phosphorylases Proteins 0.000 claims description 11
- 102000009097 Phosphorylases Human genes 0.000 claims description 11
- 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 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 150000004676 glycans Chemical class 0.000 claims description 9
- 229920001282 polysaccharide Polymers 0.000 claims description 9
- 239000005017 polysaccharide Substances 0.000 claims description 9
- 150000008135 α-glycosides Chemical class 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 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
- 229910019142 PO4 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 7
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 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 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229920000856 Amylose Polymers 0.000 claims description 3
- 229920000945 Amylopectin Polymers 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 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
- 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
- 229940085991 phosphate ion Drugs 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
- 125000000600 disaccharide group Chemical group 0.000 claims 1
- 229930182470 glycoside Natural products 0.000 claims 1
- 150000002338 glycosides 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
- 239000000839 emulsion Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 238000003786 synthesis reaction 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
- 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
- 108050004944 Alpha-glucan phosphorylases Proteins 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011734 sodium Substances 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
- 102000005744 Glycoside Hydrolases Human genes 0.000 description 1
- 108010031186 Glycoside Hydrolases Proteins 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000002016 disaccharides Chemical class 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
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- 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
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a nano-cellulose, a preparation method and application thereof, wherein the nano-cellulose endows the nano-cellulose with a new function, is a novel nano-cellulose with functional groups, and can be used as an emulsifier; the preparation method selects arbutin with functional groups as a primer and starch as a substrate, and prepares the novel nanocellulose under the catalysis of in-vitro enzyme, so that the preparation process of the enzyme synthesized cellulose is simple, the reaction conditions are environment-friendly, and the defects of high energy consumption, environmental pollution and the like in the existing nanocellulose preparation process are well overcome.
Description
Technical Field
The invention relates to the field of enzyme engineering, in particular to nanocellulose and a preparation method and application thereof.
Background
The nanocellulose serving as a novel nanomaterial not only has the characteristic of high specific surface area of common nanomaterial, 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 nano-cellulose preparation method is to crush natural cellulose by a high-power machine and treat the natural cellulose with strong acid and alkali, but the nano-cellulose obtained by the method has no functional group except hydroxyl.
The nanocellulose molecular chain prepared by an in vitro enzyme method has an accurate structure and obvious advantages compared with Chemical synthesis (Chemical Reviews 2016,116,2307-2413). The whole enzyme catalytic reaction process is completed in one step in an aqueous solution, the reaction condition is mild, and no protection or deprotection process is needed. The cellodextrin phosphorylase (Cellodextrin phosphorylase, CDP) can specifically identify the hydroxyl group at the 4 th position on the beta-D-glucose primer, and has no identification on the hydroxyl groups at other positions on the beta-D-glucose primer, so that the functional groups on the surface of the nanocellulose can be controlled by designing the beta-D-glucose primer so as to meet different application requirements. The functional group can be introduced into the surface of the nanocellulose by regulating and controlling the type of the substituent at the No. 1 position of the beta-D-glucose primer. The green low-energy-consumption novel nano-cellulose preparation method effectively solves 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 the modern industry.
Disclosure of Invention
The invention aims to provide nanocellulose.
Another technical problem to be solved by the present invention is to provide a method for preparing the nanocellulose.
Another technical problem to be solved by the present invention is to provide an application of the nanocellulose.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a nano-cellulose is chain cellulose composed of beta- (1, 4) -D-glucoside bonds, and the crystal form is cellulose II type with better thermal stability, namely cellulose molecular chains are arranged in antiparallel, and phenol groups are gathered on the upper surface and the lower surface of the nano-cellulose.
Preferably, the nanocellulose is in a two-dimensional sheet shape, has a length of 1-2 μm, a width of less than 1 μm, a thickness of 5-6nm, and a degree of polymerization of about 10.
A method for preparing nanocellulose comprises using starch as substrate, arbutin as primer, adding alpha-glycoside phosphorylase (alpha-glucan phosphorylase, alpha GP) and cellodextrin phosphorylase (cellodextrin phosphorylase, CDP), and adding inorganic phosphate ion and magnesium ion (Mg) 2+ ) Performing enzyme catalytic reaction in a 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES) buffer solution to produce and obtain nanocellulose; the alpha-glycoside phosphorylase takes starch as a substrate, catalyzes the starch to be phosphorylated in the presence of inorganic phosphorus to generate alpha-D-Glucose-1-phosphate (alpha G1P), then under the catalysis of the cellodextrin phosphorylase, glucose units on the alpha-D-Glucose-1-phosphate are connected to arbutin to form a new Glucose non-reducing end, inorganic phosphate ions are released, and then the cellodextrin phosphorylase continuously connects the Glucose units on the alpha-D-Glucose-1-phosphate to the newly formed non-reducing end, so that nanocellulose with the arbutin at one end can be formed.
Preferably, according to the preparation method of the nanocellulose, the target product nanocellulose is obtained through purification and freeze drying, and the concentration of phosphate ions is kept unchanged after the reaction is finished.
Preferably, in the above method for preparing nanocellulose, the 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES) solution used for purifying nanocellulose is consistent with HEPES used in the reaction, and the cycle number of washing and centrifugation ranges from 2 times to 10 times.
According to the preparation method of the nanocellulose, the enzyme catalysis process is completed in a buffer solution through the combined action of alpha GP and CDP, the alpha GP catalyzes inorganic phosphorus and starch to generate a monomer alpha G1P, then a phosphate group on the 1 st position of the G1P monomer and a hydroxyl group on the 4 th position of a glucose unit of arbutin are condensed under the action of the CDP, and inorganic phosphoric acid is released at the same time, so that the chain cellulose consisting of beta- (1, 4) -D-glucoside bonds is finally formed. The crystal form of the obtained nanocellulose is cellulose II type with better thermal stability, namely cellulose molecular chains are arranged in an antiparallel manner, so that phenol groups are gathered on the upper surface and the lower surface of the nanocellulose, and a novel function is given to the nanocellulose.
Preferably, the above nanocellulose is prepared by a method wherein the substrate is a disaccharide comprising D-glucose units, a polysaccharide or any mixture thereof, catalyzed by an enzyme capable of converting the substrate and phosphate to αg1p.
Preferably, in the above-mentioned method for preparing nanocellulose, the polysaccharide containing D-glucose units is soluble starch, soluble amylose or soluble amylopectin, and the glucoside phosphorylase (α -glucan phosphorylase, EC 2.4.1.1, αgp) is used to catalyze and convert the polysaccharide and phosphate into αg1p.
Preferably, in the above-mentioned nanocellulose preparation method, the concentration of the polysaccharide containing D-glucose units is 10-200g/L, more preferably 50g/L.
Preferably, in the above nanocellulose preparation method, 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 above nanocellulose preparation method, the concentration of the alpha-glycoside phosphorylase is 1-10g/L, more preferably 2g/L.
Preferably, in the preparation method of the nanocellulose, the concentration of the arbutin is 1-100mM. More preferably 10mM.
Preferably, in the above method for preparing nanocellulose, the concentration of the 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES) solution is 10-1000mM, more preferably 200mM.
Preferably, in the above method for producing nanocellulose, the concentration of magnesium ions is 1 to 100mM, more preferably 10mM.
Preferably, in the above method for preparing nanocellulose, the concentration of the phosphate is 1-100mM, more preferably 20mM.
Preferably, in the above-mentioned method for producing nanocellulose, the concentration of the cellodextrin phosphorylase (CDP) is 0.1-10g/L, more preferably 2g/L.
Preferably, the reaction temperature of the above nanocellulose preparation method is 30-80 ℃, more preferably 40-50 ℃.
Preferably, in the above method for preparing nanocellulose, the amino acid sequence NCBI of the glycosidase is wp_011250357.1.
Preferably, in the above preparation method of nanocellulose, the amino acid sequence NCBI of the cellodextrin phosphorylase is wp_020457986.1.
The nanocellulose is applied as an emulsifier.
The beneficial effects are that:
the nanocellulose endows the nanocellulose with a new function, and is novel nanocellulose with functional groups; the preparation method selects arbutin with functional groups as a primer and starch as a substrate, and prepares the novel nanocellulose under the catalysis of in-vitro enzyme, so that the preparation process of the enzyme synthesized cellulose is simple, the reaction conditions are environment-friendly, and the defects of high energy consumption, environmental pollution and the like in the existing nanocellulose preparation process are well overcome.
The enzyme catalytic reaction process is completed in one step in the aqueous solution, so that arbutin with functional groups can be successfully introduced to the surface of nanocellulose, 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, green and safe, solves the problems of high energy consumption, environmental pollution and lack of functional groups in the cellulose in the existing nanocellulose preparation process, has low cost and wide application prospect in industrial production, and is easy to industrialize.
The nanocellulose has wide application prospects in the directions of nanocomposite materials, perking emulsion, hydrogel, textile engineering, medical tissue engineering and the like.
Drawings
FIG. 1 is a representation of a novel nanocellulose synthesized using enzymatic catalysis: (a) 1 H NMR; (b) a wide angle X-ray diffraction pattern; (c) Transmission Electron Microscopy (TEM).
FIG. 2 shows the catalytic reaction pathway.
FIG. 3 is a graph of an emulsion of 1.0wt% nanocellulose stabilized n-undecane described in example 1 with corresponding digital photographs (inset).
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
Example 1
As shown in fig. 2, a preparation method of nanocellulose specifically comprises the following steps:
(1) In the whole reaction system, 50g/L of soluble starch, 10mM arbutin primer, 20mM inorganic phosphorus (KH 2 PO 4 And K 2 HPO 4 Formulated), 10mM magnesium ion, 2g/L αGP (amino acid sequence NCBI accession number WP_ 011250357.1) and 2g/L CDP (amino acid sequence NCBI accession number WP_ 020457986.1), 200mM HEPES (pH 7.5) buffer solution, and the whole system was placed in a water bath at 45℃to perform nanocellulose synthesis;
(2) The nanocellulose obtained in step (1) was washed with HEPES solution (consistent with that in step (1)) and centrifuged for 10 times, followed by freeze-drying.
The characterization of the novel nanocellulose synthesized by the enzyme catalysis method in the examples is shown in fig. 1. FIG. (a) is a novel nanocellulose 1 H NMR data. 4.35ppm Hydrogen (H) at position 1 in the glucose structural unit expressed as novel nanocellulose 1 ) Displacement of (2); 4.35ppm Hydrogen (H) at positions 2-6 in glucose structural unit of novel nanocellulose 2 ～H 6 ) Displacement of (2); 5.21ppm of hydrogen (H) bonded to phenol 7 ) Displacement of (2); 6.42 and 6.81ppm as hydrogen (H) in the benzene ring 8 And H 9 ) Is a displacement of (a). Panel (b) is X-ray diffraction (WAXD) data for novel nanocellulose. The three diffraction peaks of 12.1 DEG, 19.9 DEG and 22.1 DEG are respectively attributed to cellulose II crystal form (monoclinic)(110) And (020) diffraction plane, with interplanar spacings of 0.72, 0.44, and 0.4nm, respectively. Fig. (c) is a Transmission Electron Microscope (TEM) image of the novel nanocellulose. The novel nanocellulose is in a sheet shape, the average length is about 300nm, and the length-diameter ratio is 4.6. The characterization result fully shows that the novel nanocellulose with the tail end containing phenol groups is successfully synthesized by an in vitro enzymatic method.
An emulsification experiment was performed on nanocellulose synthesized by the enzyme catalysis method in example 1. The nanocellulose obtained was prepared into a 1.0wt% suspension with distilled water by centrifugation, and then homogenized for 1min at room temperature using a disperser at a speed of 10000 rpm. 12.00g of the nanocellulose suspension is mixed with 3ml of n-undecane (oil-water ratio is 1:4v/W), the mixture is homogenized again at the speed of 15000rpm for 3 minutes at room temperature to obtain a coarse emulsion, and finally the coarse emulsion is subjected to ultrasonic emulsification in an ice bath for 2 minutes at the power of 360W, so that the oil-in-water (O/W) emulsion is obtained.
The emulsion prepared with nanocellulose in example 1 was characterized. As shown in FIG. 3, the emulsion pattern and the droplet size distribution test showed that the droplet size of the emulsion was about 8 μm as compared with Jun. This experiment demonstrates that the nanocellulose of the invention can be used as an emulsifier for preparing emulsions.
Example 2
The preparation method of the nanocellulose comprises the following specific steps:
(1) To the whole reaction system, 100g/L of soluble amylose, 50mM arbutin primer, 40mM inorganic phosphorus (from NaH were added 2 PO 4 And Na (Na) 2 HPO 4 Formulated), 10mM magnesium ion, 5g/L αGP and 2g/L CDP,600mM HEPES (pH 7.5) buffer solution, and the whole system was placed in a water bath at 40℃to perform nanocellulose synthesis;
(2) The nanocellulose obtained in step (1) was washed with HEPES solution (consistent with that in step (1)) and centrifuged for 10 times, followed by freeze-drying.
Example 3
The preparation method of the nanocellulose comprises the following specific steps:
(1) In the whole reaction system, 10g/L of soluble starch, 1mM arbutin primer, 1mM inorganic phosphorus (KH 2 PO 4 Formulated), 10mM magnesium ion, 1g/L αGP and 0.1g/L CDP,10mM HEPES (pH 7.5) buffer solution, and the whole system was placed in a water bath at 45℃to perform nanocellulose synthesis;
(2) The nanocellulose obtained in step (1) was washed with HEPES solution (consistent with that in step (1)) and centrifuged for 10 times, followed by freeze-drying.
Example 4
The preparation method of the nanocellulose comprises the following specific steps:
(1) 200g/L of soluble pullulan, 100mM arbutin primer, 100mM inorganic phosphorus (from K) 2 HPO 4 Formulated), 10mM magnesium ion, 10g/L αGP and 10g/L CDP,1000mM HEPES (pH 7.5) buffer solution, and the whole system was placed in a water bath at 50℃to perform nanocellulose synthesis;
(2) The nanocellulose obtained in step (1) was washed with HEPES solution (consistent with that in step (1)) and centrifuged for 10 times, followed by freeze-drying.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (12)
1. A nanocellulose, characterized in that: is thatβThe crystal form of chain cellulose consisting of- (1, 4) -D-glucosidic bonds is cellulose II type with better thermal stability, namely cellulose molecular chains are arranged in anti-parallel, phenol groups are gathered on the upper surface and the lower surface of nano cellulose, and the chain cellulose is prepared by the following method: starch is taken as a substrate, arbutin is taken as a primer, alpha-glycoside phosphorylase and cellodextrin phosphorylase are added, and enzyme catalytic reaction is carried out in 4-hydroxyethyl piperazine ethane sulfonic acid buffer solution containing inorganic phosphate ions and magnesium ions, so that nanocellulose is produced; the alpha-glycoside phosphorylase takes starch as a substrate, catalyzes the starch to be subjected to phospholysis in the presence of inorganic phosphorus to generate alpha-D-glucose-1-phosphate, then connects glucose units on the alpha-D-glucose-1-phosphate to arbutin under the catalysis of the cellodextrin phosphorylase to form a new glucose non-reducing end, releases inorganic phosphate ions, and continuously connects the glucose units on the alpha-D-glucose-1-phosphate to the newly formed non-reducing end.
2. Nanocellulose as claimed in claim 1 wherein: the two-dimensional sheet is in the shape of 1-2 μm in length, less than 1 μm in width, 5-6nm in thickness and 10 in polymerization degree.
3. The method for preparing nanocellulose as claimed in claim 1, wherein: starch is taken as a substrate, arbutin is taken as a primer, alpha-glycoside phosphorylase and cellodextrin phosphorylase are added, and enzyme catalytic reaction is carried out in 4-hydroxyethyl piperazine ethane sulfonic acid buffer solution containing inorganic phosphate ions and magnesium ions, so that nanocellulose is produced; the alpha-glycoside phosphorylase takes starch as a substrate, catalyzes the starch to be subjected to phospholysis in the presence of inorganic phosphorus to generate alpha-D-glucose-1-phosphoric acid, then under the catalysis of the cellodextrin phosphorylase, the glucose unit on the alpha-D-glucose-1-phosphoric acid is connected to arbutin to form a new glucose non-reducing end, inorganic phosphate ions are released, and then the cellodextrin phosphorylase continuously connects the glucose unit on the alpha-D-glucose-1-phosphoric acid to the newly formed non-reducing end, so that nanocellulose with the arbutin at one end can be formed.
4. A method of preparing nanocellulose as claimed in claim 3 wherein: the target product nanocellulose is obtained through purification and freeze drying, and the concentration of phosphate ions is kept unchanged after the reaction is finished.
5. A method of preparing nanocellulose as claimed in claim 3 wherein: the substrate is disaccharide containing D-glucose unit, polysaccharide or any mixture thereof, and is catalyzed by enzyme capable of converting the substrate and phosphate into alpha G1P; the polysaccharide containing the D-glucose unit is soluble starch, soluble amylose or soluble amylopectin, and the polysaccharide and phosphate are converted into alpha G1P by adopting the catalysis of glycoside phosphorylase.
6. The method for producing nanocellulose as claimed in claim 5 wherein: the polysaccharide comprising D-glucose units has a concentration of 10-200g/L.
7. The method for producing nanocellulose as claimed in claim 5 or 6 wherein: the concentration of the polysaccharide comprising D-glucose units is 50g/L.
8. The method for producing nanocellulose as claimed in claim 5 wherein: 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. A method of preparing nanocellulose as claimed in claim 3 wherein: the concentration of the alpha-glycoside phosphorylase is 1-10g/L; the concentration of the arbutin is 1-100mM; the concentration of the 4-hydroxyethyl piperazine ethane sulfonic acid solution is 10-1000mM; the concentration of the magnesium ions is 1-100mM; the concentration of the phosphate ions is 1-100mM; the concentration of the cellodextrin phosphorylase is 0.1-10g/L.
10. The method for producing nanocellulose as claimed in claim 3 or 9 wherein: the concentration of the alpha-glycoside phosphorylase is 2g/L; the concentration of arbutin is 10 mM; the concentration of the 4-hydroxyethyl piperazine ethane sulfonic acid solution is 200 mM; the concentration of magnesium ions is 10 mM; the concentration of the phosphate ion is 20 mM; the concentration of the cellodextrin phosphorylase is 2g/L.
11. A method of preparing nanocellulose as claimed in claim 3 wherein: the reaction temperature is 30-80 ℃.
12. Use of nanocellulose as claimed in claim 1 as an emulsifier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210372511.0A CN114717277B (en) | 2022-04-11 | 2022-04-11 | Nanocellulose and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210372511.0A CN114717277B (en) | 2022-04-11 | 2022-04-11 | Nanocellulose and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114717277A CN114717277A (en) | 2022-07-08 |
| CN114717277B true CN114717277B (en) | 2024-03-12 |
Family
ID=82241733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210372511.0A Active CN114717277B (en) | 2022-04-11 | 2022-04-11 | Nanocellulose and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114717277B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926431A (en) * | 2004-01-09 | 2007-03-07 | 诺维信股份有限公司 | Bacillus licheniformis chromosome |
| CN101010083A (en) * | 2004-06-30 | 2007-08-01 | 康宾纳特克斯公司 | Methods and reagents for the treatment of metabolic disorders |
| CN106456479A (en) * | 2014-05-21 | 2017-02-22 | 罗地亚经营管理公司 | Sulfate-free personal care compositions |
| WO2019125011A2 (en) * | 2017-12-21 | 2019-06-27 | 주식회사 에이치엔에이파마켐 | Transdermal delivery complex using metal-organic framework and nanocellulose |
| WO2020004604A1 (en) * | 2018-06-29 | 2020-01-02 | 日揮触媒化成株式会社 | Porous cellulose particles and production method thereof, and cosmetic |
| CN110819667A (en) * | 2018-08-08 | 2020-02-21 | 中国科学院天津工业生物技术研究所 | Method for preparing laminaribiose by starch conversion |
| CN110857443A (en) * | 2018-08-24 | 2020-03-03 | 中国科学院天津工业生物技术研究所 | Method for producing inositol by complete phosphorization of cellulose |
| CN110857444A (en) * | 2018-08-24 | 2020-03-03 | 中国科学院天津工业生物技术研究所 | Preparation method of scyllo-inositol |
| JP2021042271A (en) * | 2019-09-06 | 2021-03-18 | 凸版印刷株式会社 | Composite particle, manufacturing method of composite particle, and personal care product including composite particle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7431172B2 (en) * | 2018-04-23 | 2024-02-14 | ダニスコ・ユーエス・インク | Synthesis of glucans containing β-1,3 glycosidic bonds using phosphorylase enzymes |
-
2022
- 2022-04-11 CN CN202210372511.0A patent/CN114717277B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1926431A (en) * | 2004-01-09 | 2007-03-07 | 诺维信股份有限公司 | Bacillus licheniformis chromosome |
| CN101010083A (en) * | 2004-06-30 | 2007-08-01 | 康宾纳特克斯公司 | Methods and reagents for the treatment of metabolic disorders |
| CN106456479A (en) * | 2014-05-21 | 2017-02-22 | 罗地亚经营管理公司 | Sulfate-free personal care compositions |
| WO2019125011A2 (en) * | 2017-12-21 | 2019-06-27 | 주식회사 에이치엔에이파마켐 | Transdermal delivery complex using metal-organic framework and nanocellulose |
| WO2020004604A1 (en) * | 2018-06-29 | 2020-01-02 | 日揮触媒化成株式会社 | Porous cellulose particles and production method thereof, and cosmetic |
| CN110819667A (en) * | 2018-08-08 | 2020-02-21 | 中国科学院天津工业生物技术研究所 | Method for preparing laminaribiose by starch conversion |
| CN110857443A (en) * | 2018-08-24 | 2020-03-03 | 中国科学院天津工业生物技术研究所 | Method for producing inositol by complete phosphorization of cellulose |
| CN110857444A (en) * | 2018-08-24 | 2020-03-03 | 中国科学院天津工业生物技术研究所 | Preparation method of scyllo-inositol |
| JP2021042271A (en) * | 2019-09-06 | 2021-03-18 | 凸版印刷株式会社 | Composite particle, manufacturing method of composite particle, and personal care product including composite particle |
Non-Patent Citations (1)
| Title |
|---|
| Facile biosynthesis of synthetic crystalline cellulose nanoribbon from maltodextrin through a minimized two-enzyme phosphorylase cascade and its application in emulsion;Qiangzi Li et al;《Journal of Biotechnology》;第332卷;第54-60页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114717277A (en) | 2022-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11739165B2 (en) | Phosphoric acid-esterified fine cellulose fiber and method for producing the same | |
| US11932706B2 (en) | Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom | |
| Phanthong et al. | Nanocellulose: Extraction and application | |
| Wang et al. | Preparation of nanocellulose in high yield via chemi-mechanical synergy | |
| Kumari et al. | Cellulose nanofibers from lignocellulosic biomass of lemongrass using enzymatic hydrolysis: characterization and cytotoxicity assessment. | |
| CN105839440B (en) | A kind of preparation method of bagasse nano-cellulose | |
| CN107602709B (en) | Clean preparation method of carboxymethyl nano-cellulose material | |
| Sun et al. | Cellulose pretreatment with inorganic salt hydrate: Dissolution, regeneration, structure and morphology | |
| CN109295785B (en) | Preparation method of cellulose nano-fibrils | |
| Rai et al. | Biomedical engineering aspects of nanocellulose: A review | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| Dias et al. | Xylanase increases the selectivity of the enzymatic hydrolysis with endoglucanase to produce cellulose nanocrystals with improved properties | |
| CN114717277B (en) | Nanocellulose and preparation method and application thereof | |
| Dias et al. | High-yield production of rod-like and spherical nanocellulose by controlled enzymatic hydrolysis of mechanically pretreated cellulose | |
| US12018432B2 (en) | Processes and systems for producing nanocellulose from old corrugated containers | |
| Buruaga-Ramiro et al. | Lytic polysaccharide monooxygenases and cellulases on the production of bacterial cellulose nanocrystals | |
| Li et al. | Facile biosynthesis of synthetic crystalline cellulose nanoribbon from maltodextrin through a minimized two-enzyme phosphorylase cascade and its application in emulsion | |
| de Souza et al. | Eucalyptus spp. cellulose nanocrystals obtained by acid hydrolysis and ultrasound processing for structural strengthening in paper packaging | |
| Trisanti et al. | The degradation of cellulose in ionic mixture solutions under the high pressure of carbon dioxide | |
| Venkateshaiah et al. | Nanocellulose: Sustainability and Preparation | |
| Venkateshaiah et al. | Sustainability and Preparation | |
| Hildebrandt et al. | Presentation 13 Production of plasticised fibre composites (PLAFCO) with a paper machine via partial dissolution of paper | |
| Zhang | 2D NMR Characterization of Cellobiose Sulfate Hydrolyzed from Cellulose Nanocrystals | |
| CH715261A2 (en) | Process for the production of cellulose nanocrystals (CNC). |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |