CN116813806A - Preparation method of monodisperse cellooligosaccharide - Google Patents
Preparation method of monodisperse cellooligosaccharide Download PDFInfo
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- CN116813806A CN116813806A CN202310863083.6A CN202310863083A CN116813806A CN 116813806 A CN116813806 A CN 116813806A CN 202310863083 A CN202310863083 A CN 202310863083A CN 116813806 A CN116813806 A CN 116813806A
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- FYGDTMLNYKFZSV-ZWSAEMDYSA-N cellotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](OC(O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-ZWSAEMDYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- 239000001913 cellulose Substances 0.000 claims abstract description 53
- 239000002244 precipitate Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 230000008929 regeneration Effects 0.000 claims abstract description 15
- 238000011069 regeneration method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 1-ethyl-3-methylimidazole cyanide salt Chemical compound 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 3
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 2
- HCCUDHUHQPPUFU-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole-2-carboxylic acid Chemical compound CCCCN1C=CN(C)C1C(O)=O HCCUDHUHQPPUFU-UHFFFAOYSA-N 0.000 claims description 2
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 2
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 2
- 101710130006 Beta-glucanase Proteins 0.000 claims description 2
- 102000005575 Cellulases Human genes 0.000 claims description 2
- 108010084185 Cellulases Proteins 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 108010001817 Endo-1,4-beta Xylanases Proteins 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000005016 bacterial cellulose Substances 0.000 claims description 2
- 102000006995 beta-Glucosidase Human genes 0.000 claims description 2
- 108010047754 beta-Glucosidase Proteins 0.000 claims description 2
- 108010055059 beta-Mannosidase Proteins 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000008104 plant cellulose Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 230000002378 acidificating effect Effects 0.000 claims 2
- 239000012467 final product Substances 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 235000010980 cellulose Nutrition 0.000 description 32
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 6
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 6
- 239000008108 microcrystalline cellulose Substances 0.000 description 5
- 229940016286 microcrystalline cellulose Drugs 0.000 description 5
- 229920001542 oligosaccharide Polymers 0.000 description 5
- 150000002482 oligosaccharides Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The application discloses a preparation method of monodisperse cellooligosaccharide, which comprises the steps of mixing a cellulose raw material with a solvent, and stirring at a certain temperature until the cellulose raw material is dissolved to prepare a cellulose solution; hydrolyzing the cellulose solution for a period of time at a certain hydrolysis temperature to obtain a hydrolyzed cellulose solution; mixing the hydrolyzed cellulose solution with the regeneration reagent a, storing for a certain time at a certain temperature to obtain a precipitate A, separating the precipitate A from supernatant, mixing the supernatant with the regeneration reagent B, and storing for a certain time at a certain temperature to obtain a precipitate B, wherein the precipitate A and the precipitate B are the monodisperse cellooligosaccharides. The application solves the problems of complicated preparation process, time consumption, low yield, high cost, difficulty in realizing large-scale production and the like of the monodisperse cellooligosaccharide, and is a preparation method with high efficiency, convenience, low cost and controllable molecular weight at present.
Description
Technical Field
The application belongs to the field of biomass materials, and relates to a preparation method of a cellooligosaccharide material, in particular to a preparation method of cellooligosaccharide with extremely narrow molecular weight distribution.
Background
Cellulose is one of the most abundant polysaccharides in nature, has the advantages of low cost, complete biodegradation, no toxicity, no pollution, good biocompatibility, reproducibility, good mechanical properties, high stability and the like, and is widely used as a bracket material in the fields of biological medicine, electronic devices, sensors and the like. The monodisperse cellooligosaccharide is easy to dissolve in a solvent, has a short molecular chain, and can effectively solve the problem that high molecular weight cellulose is difficult to crystallize and regulate; because of the narrow molecular weight distribution, the assembly body with a regular structure is easy to form, and the method has numerous advantages in the aspect of designing the self-defined structural material, and various literature reports on self-assembly research of monodisperse cellooligosaccharide at present to obtain crystals with various forms such as lamellar, spherical, needle-shaped, ribbon-shaped and the like; in addition, the cellooligosaccharide not only maintains various advantages of cellulose, but also has more reducing ends, namely higher chemical reactivity than high-molecular-weight cellulose, and various functional groups are introduced through a chemical grafting method, so that the cellooligosaccharide has more possibility in structure, property and function.
However, the preparation method of the monodisperse cellulose oligosaccharide is generally a combination of a degradation method and a synthesis method, and the methods have complicated procedures, time consumption, low yield and high cost, and are difficult to realize large-scale production, so that the monodisperse cellulose oligosaccharide which is currently commercially available is quite expensive and has a price of hundreds or even tens of thousands of yuan per gram, and therefore, research and application of the monodisperse cellulose oligosaccharide have resulted in a flexible index.
Based on the above, the application aims to provide a preparation method of monodisperse cellooligosaccharide, which is short in time consumption, simple in working procedure and suitable for realizing industrial production.
Disclosure of Invention
The application aims to overcome the defects of the prior art, and provides a preparation method of monodisperse cellooligosaccharide, which solves a plurality of problems of the current preparation method and achieves the aims of high efficiency, convenience and controllable molecular weight.
The above purpose is achieved by the following technical scheme:
a method for preparing monodisperse cellooligosaccharide, comprising the following steps:
1) Mixing cellulose raw material with solvent, stirring at a certain temperature until the cellulose raw material is dissolved, and preparing cellulose solution;
further, step 1) the cellulosic feedstock is selected from the group consisting of: any one of plant cellulose, animal cellulose and bacterial cellulose.
Further, the concentration of the cellulose in the step 1) in the solvent is 1-30wt%.
Further, the solvent of step 1) includes, but is not limited to: sulfuric acid, phosphoric acid, sodium hydroxide/urea, lithium hydroxide/urea, hydrofluoric acid, cuprous chloride/ammonia water, zinc chloride, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole cyanide salt, 1-butyl-3-methylimidazole cyanide salt, N-dimethylacetamide-N-magnesium chloride, 1-butyl-3-methylimidazole-2-carboxylate, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole chloride, cuprammonium solution, N-methylmorpholine-N-oxide.
Further, the temperature in the step 1) is-80-100 ℃.
2) If the solvent used in the step 1) does not belong to an acidic reagent, mixing the cellulose solution in the step 1) with a hydrolysis reagent, and then hydrolyzing for a period of time at a certain hydrolysis temperature; if the solvent used in the step 1) belongs to an acidic reagent, no hydrolysis reagent is added; then hydrolyzing for a period of time at a certain hydrolysis temperature to obtain a hydrolyzed cellulose solution;
further, step 2) the hydrolysis reagents include, but are not limited to: hydrochloric acid, sulfuric acid, phosphoric acid, beta-glucanase, beta-glucosidase, brewer's enzyme, exocellulase, beta-xylanase, beta-mannanase.
Further, the hydrolysis temperature in the step 2) is 0-100 ℃.
Further, the hydrolysis time in the step 2) is 1 hour to 8 weeks.
3) Mixing the hydrolyzed cellulose solution obtained in the step 2) with a regeneration reagent a, storing for a certain time at a certain temperature to obtain a precipitate A, separating the precipitate A from supernatant, mixing the supernatant with a regeneration reagent B, and storing for a certain time at a certain temperature to obtain a precipitate B, wherein the precipitate A and the precipitate B are the monodisperse cellooligosaccharides.
Further, step 3) the regeneration reagent a includes, but is not limited to: water, methanol, ethanol, isopropanol, tetrahydrofuran, acetone.
Further, the volume ratio of the hydrolyzed cellulose solution to the regeneration agent a in the step 3) is 1:0.5-20.
Further, step 3) the rejuvenating agent b includes, but is not limited to: water, methanol, ethanol, isopropanol, tetrahydrofuran, acetone.
Further, the volume ratio of the hydrolyzed cellulose solution to the regeneration agent b in the step 3) is 1:0.5-20.
Further, the certain temperature in the step 3) is between-20 and 100 ℃.
Further, the certain time in the step 3) is 0 to 168 hours.
The application also discloses the monodisperse cellooligosaccharide prepared by any one of the preparation methods.
Compared with the prior art, the application has the following beneficial effects:
the application can prepare the monodisperse cellooligosaccharide with narrower molecular weight distribution without column chromatography, thereby shortening the preparation process, cost and time.
Drawings
FIG. 1 is a schematic diagram of the mechanism of the present application for preparing monodisperse cellooligosaccharides.
FIG. 2 is a graph showing the polymerization degree distribution of microcrystalline cellulose (MCC, starting material) and monodisperse cellooligosaccharide (P76 h) obtained by hydrolyzing for 76 hours in example 1.
FIG. 3 shows the molecular weight distribution of precipitate B of example 3, as measured by mass spectrometry, and the number average polymerization degree was 6 as calculated from the peak intensities thereof.
FIG. 4 is a liquid nuclear magnetic resonance spectrum of precipitate B of example 3.
Detailed Description
The application is further illustrated below in conjunction with specific examples. These examples are only for illustrating the present application and are not intended to limit the scope of the present application. Further, after reading the teachings of the present application, those skilled in the art may make various changes or modifications to the present application, which equivalent forms also fall within the scope of the present application as defined in the appended claims.
Example 1
A method for preparing monodisperse cellooligosaccharide, comprising the following steps:
1) 3wt% microcrystalline cellulose is mixed with 83wt% phosphoric acid, and magnetically stirred at room temperature for 12 hours until the solution becomes clear and transparent;
2) Hydrolyzing for 76 hours in a baking oven at 40 ℃ to obtain hydrolyzed cellulose solution;
3) Mixing the hydrolyzed cellulose phosphate solution with water of equal mass, storing at 4deg.C for 24 hr, centrifuging to obtain precipitate A, mixing the supernatant with three times of isopropanol, storing at 4deg.C for 24 hr, and centrifuging to obtain precipitate B.
The yields of the obtained precipitates A and B were about 49% and 19%, respectively, the weight average polymerization degrees thereof were 18 and 7, respectively, and the molecular weight polydispersity coefficients thereof were 1.29 and 1.07, respectively.
Example 2
A method for preparing monodisperse cellooligosaccharide, comprising the following steps:
4) 3wt% microcrystalline cellulose was mixed with 83wt% phosphoric acid and magnetically stirred at room temperature for about 12 hours until the solution became clear and transparent;
5) Hydrolyzing in a baking oven at 23 ℃ for 6 weeks to obtain hydrolyzed cellulose solution;
6) Mixing the hydrolyzed cellulose phosphate solution with water of equal mass, storing at 4deg.C for 24 hr, centrifuging to obtain precipitate A, mixing the supernatant with three times of isopropanol, storing at 4deg.C for 24 hr, and centrifuging to obtain precipitate B.
The yields of the obtained precipitates A and B were about 40% and 19%, respectively, the weight average polymerization degrees thereof were 15 and 7, respectively, and the molecular weight polydispersity coefficients thereof were 1.22 and 1.10, respectively.
Example 3
A method for preparing monodisperse cellooligosaccharide, comprising the following steps:
1) Mixing 5wt% of cotton cellulose with 83wt% of phosphoric acid, placing in a 60 ℃ oven for 2-3 hours, and magnetically stirring at room temperature until the solution becomes clear and transparent;
2) Hydrolyzing for 8 hours in a baking oven at 60 ℃ to obtain a hydrolyzed cellulose solution;
3) Mixing the hydrolyzed cellulose phosphate solution with water of equal mass, storing at 4deg.C for 24 hr, centrifuging to obtain precipitate A, mixing the supernatant with three times of isopropanol, storing at 4deg.C for 24 hr, and centrifuging to obtain precipitate B.
The yields of the obtained precipitates A and B were about 25% and 10%, respectively, the weight average polymerization degrees thereof were 15 and 6, respectively, and the molecular weight polydispersity coefficients thereof were 1.15 and 1.07, respectively.
Example 4
A method for preparing monodisperse cellooligosaccharide, comprising the following steps:
1) 5% by weight of microcrystalline cellulose was mixed with 98% by weight of 1-butyl-3-methylimidazole chloride salt and after stirring at 100℃for 3 hours, the solution became clear and transparent;
2) Adding 0.5wt%1.66mol/L hydrochloric acid solution into the cellulose solution in the step 1), and hydrolyzing for 48 hours in a baking oven at 40 ℃ to obtain hydrolyzed cellulose solution;
3) Mixing the hydrolyzed cellulose solution with water of equal mass, storing at 4deg.C for 24 hr, centrifuging to obtain precipitate A, mixing the supernatant with three times of isopropanol, storing at 4deg.C for 24 hr, and centrifuging to obtain precipitate B.
The yields of the obtained precipitates A and B were about 35% and 10%, respectively, the weight average polymerization degrees thereof were 16 and 7, respectively, and the molecular weight polydispersity coefficients thereof were 1.20 and 1.09, respectively.
According to the mechanism diagram shown in fig. 1, as the cellulose molecules are continuously hydrolyzed by phosphoric acid after dissolution, the molecular weight of the cellulose molecules is continuously reduced and approaches to the critical value of the soluble molecular weight in the regeneration environment, and when the molecular weight of most cellulose molecules is near the critical value, cellulose can be separated in the regeneration process, and two monodisperse cellooligosaccharides are obtained.
As can be seen from the polymerization degree distribution chart of FIG. 2, the average polymerization degree of the microcrystalline cellulose of the starting material is about 250, the molecular weight polydispersity is 2.13, the average polymerization degree of the monodisperse cellooligosaccharide obtained according to example 1 is 18, and the molecular weight polydispersity is 1.29, which indicates that the monodisperse cellooligosaccharide having a relatively uniform molecular weight distribution and a relatively small molecular weight can be successfully obtained by using the efficient and convenient preparation process of the present application.
From the mass spectrum of fig. 3, it can be seen that distinct main peaks appear at the same charge-to-mass ratio intervals in the mass spectrum of MCOs, and the charge-to-mass ratio intervals between adjacent main peaks is 162, corresponding to one anhydroglucose unit. The charge-to-mass ratio value of the main peak is the sum of the masses of one cellulose molecule and one sodium ion, which can be represented in formula (3-1):
m (n) =162×n+18+23 formula (3-1)
Wherein n is the degree of polymerization of the cellooligosaccharide. Comparing the test results, calculating the corresponding cellooligosaccharide polymerization degree DP of each main peak charge-to-mass ratio n . We calculated the number average and weight average degrees of polymerization of MCOs according to the formula (3-2) and the formula (3-3), wherein C i Represents the cellooligosaccharide content, DP, of degree of polymerization i i The cellooligosaccharide molecular weight of degree of polymerization i:
the weight average polymerization degree of the MCOs obtained by the experiment obtained by the calculation is 6, and meanwhile, the polydispersity index of the molecular weight of the MCOs obtained by the experiment obtained by the calculation according to the formula (3-4) is 1.078, which shows that the molecular weight distribution of the oligosaccharide product is very narrow, and the molecular weight distribution of the oligosaccharide product is proved to be very narrow, so that the monodisperse cellooligosaccharide with the polymerization degree of about 6 is successfully prepared.
From the nuclear magnetic resonance hydrogen spectrum of fig. 4, the hydroxyl hydrogen (αβ -OH-1 ") at the reducing end of MCOs corresponds to two bimodals at δ=6.34 ppm and δ=6.68 ppm. Aldehyde carbonyl hydrogens at the reducing end (αβ -H-1 ") correspond to two bimodals at δ=4.41 ppm and δ=4.89 ppm. Whereas the tertiary hydrocarbon (H-1, 1') linked at the ends of the repeat units corresponds to a bimodal peak at δ=4.31 ppm. The ratio of the peak area of hydroxyl hydrogen at the reducing end to aldehyde carbonyl hydrogen in the nuclear magnetic resonance hydrogen spectrum is 1:1, and the peak area corresponds to two hydrogen environments under the isomerism of the reducing end, so that the test result is consistent with the actual distribution. The ratio of the peak area corresponding to the tertiary hydrocarbon connected with the tail end of the repeating unit to the peak area of the hydroxyl hydrogen at the reducing end is 5:1, which indicates that the ratio of the hydrogen at the tail end of the repeating unit to the hydrogen at the reducing end of the prepared MCOs is 5:1. And calculating the number average polymerization degree of the obtained product to be 6 according to the hydrogen content ratio of the terminal position of the repeating unit to the reducing end.
Claims (9)
1. A method for preparing monodisperse cellooligosaccharides, comprising:
1) Mixing cellulose raw material with solvent, stirring at a certain temperature until the cellulose raw material is dissolved, and preparing cellulose solution;
2) Hydrolyzing the cellulose solution for a period of time at a certain hydrolysis temperature to obtain a hydrolyzed cellulose solution;
3) Mixing the hydrolyzed cellulose solution with the regeneration reagent a, storing for a certain time at a certain temperature to obtain a precipitate A, separating the precipitate A from supernatant, mixing the supernatant with the regeneration reagent B, and storing for a certain time at a certain temperature to obtain a precipitate B, wherein the precipitate A and the precipitate B are the monodisperse cellooligosaccharides.
2. The method of manufacturing according to claim 1, wherein:
step 1) the cellulosic feedstock is selected from: any one of plant cellulose, animal cellulose and bacterial cellulose;
the solvent is selected from: sulfuric acid, phosphoric acid, sodium hydroxide/urea, lithium hydroxide/urea, hydrofluoric acid, cuprous chloride/ammonia water, zinc chloride, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole cyanide salt, 1-butyl-3-methylimidazole cyanide salt, N-dimethylacetamide-N-magnesium chloride, 1-butyl-3-methylimidazole-2-carboxylate, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole chloride, cuprammonium solution, N-methylmorpholine-N-oxide.
3. The method of manufacturing according to claim 1, wherein:
the temperature of the step 1) is-80-100 ℃; the concentration of the cellulose in the solvent is 1-30wt%.
4. The method of manufacturing according to claim 1, wherein:
the hydrolyzed cellulose solution of step 2) is prepared by the following method:
mixing cellulose solution prepared from acidic solvent and cellulose raw material with hydrolysis reagent, and hydrolyzing at certain hydrolysis temperature for a period of time to obtain the final product; or (b)
The cellulose solution prepared from the non-acidic solvent and the cellulose raw material is directly hydrolyzed for a period of time at a certain hydrolysis temperature, and the preparation method is obtained.
5. The method of manufacturing according to claim 4, wherein:
the hydrolysis reagent comprises: hydrochloric acid, sulfuric acid, phosphoric acid, beta-glucanase, beta-glucosidase, brewer's enzyme, exocellulase, beta-xylanase, beta-mannanase.
6. The method of manufacturing according to claim 4, wherein:
the hydrolysis temperature is 0-100 ℃, and the hydrolysis time is 1 hour-8 weeks.
7. The method of manufacturing according to claim 1, wherein:
step 3) the regeneration reagent a comprises: water, methanol, ethanol, isopropanol, tetrahydrofuran, and acetone;
the volume ratio of the hydrolyzed cellulose solution to the regeneration reagent a is 1:0.5-20;
the certain temperature is between-20 and 100 ℃; the certain time is 0-168 hours.
8. The method of manufacturing according to claim 1, wherein:
step 3) the regeneration reagent b comprises: water, methanol, ethanol, isopropanol, tetrahydrofuran, and acetone;
the volume ratio of the hydrolyzed cellulose solution to the regeneration reagent b is 1:0.5-20;
the certain temperature is between-20 and 100 ℃; the certain time is 0-168 hours.
9. A monodisperse cellooligosaccharide produced according to the production process of any one of claims 1 to 8.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040217063A1 (en) * | 2003-05-01 | 2004-11-04 | Yiheng Zhang | Cellodextrin production by mixed acid hydrolysis and chromographic separation |
| CN102690897A (en) * | 2012-05-22 | 2012-09-26 | 中国科学院宁波材料技术与工程研究所 | Two-step hydrolysis method for preparing reducing sugars with cellulose |
| CN105255966A (en) * | 2015-10-27 | 2016-01-20 | 江苏大学 | Method for raising hydrolysis yield of microcrystalline cellulose through ionic liquid pretreatment |
| CN105492619A (en) * | 2013-07-01 | 2016-04-13 | 巴斯夫欧洲公司 | Endoglucanase-induced production of cellulose oligomers |
| CN106244735A (en) * | 2016-07-29 | 2016-12-21 | 中国科学院过程工程研究所 | A kind of production technology of cell-oligosaccharide |
| US20190330378A1 (en) * | 2017-01-03 | 2019-10-31 | Institute Of Metal Research Chinese Academy Of Sciences | Cellulose ii nanocrystal particles and preparation method and use thereof |
| CN113773403A (en) * | 2021-09-27 | 2021-12-10 | 安徽农业大学 | Preparation method of cellulose oligosaccharide and cellooligosaccharide graft polymer prepared by preparation method |
-
2023
- 2023-07-14 CN CN202310863083.6A patent/CN116813806A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040217063A1 (en) * | 2003-05-01 | 2004-11-04 | Yiheng Zhang | Cellodextrin production by mixed acid hydrolysis and chromographic separation |
| CN102690897A (en) * | 2012-05-22 | 2012-09-26 | 中国科学院宁波材料技术与工程研究所 | Two-step hydrolysis method for preparing reducing sugars with cellulose |
| CN105492619A (en) * | 2013-07-01 | 2016-04-13 | 巴斯夫欧洲公司 | Endoglucanase-induced production of cellulose oligomers |
| CN105255966A (en) * | 2015-10-27 | 2016-01-20 | 江苏大学 | Method for raising hydrolysis yield of microcrystalline cellulose through ionic liquid pretreatment |
| CN106244735A (en) * | 2016-07-29 | 2016-12-21 | 中国科学院过程工程研究所 | A kind of production technology of cell-oligosaccharide |
| US20190330378A1 (en) * | 2017-01-03 | 2019-10-31 | Institute Of Metal Research Chinese Academy Of Sciences | Cellulose ii nanocrystal particles and preparation method and use thereof |
| CN113773403A (en) * | 2021-09-27 | 2021-12-10 | 安徽农业大学 | Preparation method of cellulose oligosaccharide and cellooligosaccharide graft polymer prepared by preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 娄春华，侯玉双: "《高分子科学导论》", 哈尔滨工业大学出版社, pages: 171 - 176 * |
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