CN114835833A - Rice straw xylan sulfate, preparation method and application - Google Patents
Rice straw xylan sulfate, preparation method and application Download PDFInfo
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- 229920001221 xylan Polymers 0.000 title claims abstract description 102
- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 97
- 235000009566 rice Nutrition 0.000 title claims abstract description 97
- 239000010902 straw Substances 0.000 title claims abstract description 97
- -1 xylan sulfate Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 240000007594 Oryza sativa Species 0.000 title 1
- 241000209094 Oryza Species 0.000 claims abstract description 96
- 150000004823 xylans Chemical class 0.000 claims abstract description 51
- 238000000502 dialysis Methods 0.000 claims abstract description 22
- 238000005670 sulfation reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 238000006467 substitution reaction Methods 0.000 claims abstract description 11
- 230000019635 sulfation Effects 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000002537 cosmetic Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical group CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- UDYFLDICVHJSOY-UHFFFAOYSA-N sulfur trioxide-pyridine complex Substances O=S(=O)=O.C1=CC=NC=C1 UDYFLDICVHJSOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 abstract description 13
- 230000002000 scavenging effect Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 abstract description 2
- 229930003268 Vitamin C Natural products 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 235000019154 vitamin C Nutrition 0.000 abstract description 2
- 239000011718 vitamin C Substances 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 235000013305 food Nutrition 0.000 abstract 1
- 235000013376 functional food Nutrition 0.000 abstract 1
- 238000000338 in vitro Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 9
- 229920001282 polysaccharide Polymers 0.000 description 9
- 150000004804 polysaccharides Chemical class 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 235000000023 Auricularia auricula Nutrition 0.000 description 1
- 241001149430 Auricularia auricula-judae Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000008809 cell oxidative stress Effects 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HEILIGJNYTWOHU-UHFFFAOYSA-N ethanol 2-hydroxybenzoic acid Chemical compound CCO.OC(=O)C1=CC=CC=C1O HEILIGJNYTWOHU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002519 immonomodulatory effect Effects 0.000 description 1
- 210000002865 immune cell Anatomy 0.000 description 1
- 239000002955 immunomodulating agent Substances 0.000 description 1
- 229940121354 immunomodulator Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- MGWYLLDHLQLFAI-UHFFFAOYSA-N n,n-dimethylformamide;sulfurochloridic acid Chemical compound CN(C)C=O.OS(Cl)(=O)=O MGWYLLDHLQLFAI-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 125000001805 pentosyl group Chemical group 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
Abstract
The invention discloses a rice straw xylan sulfate with antioxidant activity and a preparation method thereof, wherein the preparation method comprises the following steps: rice straw xylan is obtained by taking rice straw as a raw material and adopting an alkali extraction alcohol precipitation dialysis method, is subjected to sulfation modification, and is subjected to control of different esterification conditions to obtain rice straw xylan sulfate with the degrees of substitution of 0.233, 1.276 and 1.566 respectively. The obtained rice straw xylan sulfate is subjected to an in vitro antioxidant test, the esterified product shows better OH scavenging capacity, and the antioxidant activity of the esterified product is equivalent to the OH scavenging capacity of vitamin C under the same concentration. The preparation method has the advantages of simple operation, low cost, high yield and great popularization and application value, and the product can be applied to industries such as corresponding cosmetic raw materials, functional foods or medical formula foods and has extremely high social and economic significance and application potential.
Description
Technical Field
The invention belongs to the technical field of polysaccharide modification, and particularly relates to rice straw xylan sulfate, a preparation method and application thereof.
Background
With the development of modern science and technology and the improvement of living standard, the life of human beings is continuously prolonged, but the skin aging caused by the radiation of general electronic equipment and environmental pollution arouses more and more attention of people. Therefore, cosmetics with anti-aging, anti-oxidation, anti-radiation and other effects have become the research hotspot and development direction at present. Natural plant cosmetic raw materials are gradually receiving attention from students because of their properties of oxidation resistance, radiation resistance and small toxic and side effects.
The polysaccharide is an important biological macromolecule, is also an important component of the skin, and has an outstanding effect in the skin metabolism process. However, natural plant-derived polysaccharides have a large molecular weight, cannot be effectively utilized by the human body, and have diverse activities, so that the clinical use thereof is very limited. The current research has more applications in the aspects of anti-inflammation, radiation resistance, oxidation resistance, fatigue resistance, aging delay of immunomodulators and the like by carrying out structural modification on polysaccharide. Wang et al have studied that ganoderan sulfuric acid derivatives have good antioxidant activity, can effectively improve SOD activity and GSH content in mice, and inhibit free radicals from damaging organs such as spleen (Wang, J.G., Wang, Y.T., Liu, X.B., et al, free radial scanning and immunomodulating activities of polysaccharides and derivatives [ J ] Carbohydrate polymers.2013,91 (33-38)). Hua Zhang et al prepared black fungus neutral polysaccharide fragment sulfate by chlorosulfonic acid-N, N-dimethylformamide method and confirmed that it plays a role in protecting against injury caused by radiation-induced cell oxidative stress by directly scavenging free radicals generated by radiation, promoting immune cell proliferation, etc. (Zhang H, Wang ZY, Yang L, et al. InVitro antibacterial Activities of treated Derivatives of Polysaccharides Extracted from Auricularia auricula. International Journal of Molecular Sciences,2011,84: 3202-3287.).
Disclosure of Invention
The technical problem to be solved by the invention is to provide the rice straw xylan sulfate, the preparation method and the application thereof, the characteristics of simple and convenient operation, high substitution degree of sulfuric acid in the product, high yield and the like are realized, and the foundation can be laid for the development and application of the rice straw xylan sulfate as a novel cosmetic raw material in future.
In order to solve the technical problems, the embodiment of the invention provides rice straw xylan sulfate, which has the following structural formula:
the invention also provides a preparation method of the rice straw xylan sulfate, which comprises the following steps:
s1, extracting and preparing rice straw xylan: extracting the rice straw powder by an alkali extraction alcohol precipitation dialysis method, and dialyzing with running water to obtain rice straw xylan;
s2, preparation of rice straw xylan sulfate: and (S1) carrying out sulfation reaction on the rice straw xylan obtained in the step (S1), and dialyzing with running water to obtain the rice straw xylan sulfate.
Wherein the grain size of the rice straw powder is 80 meshes, and the preparation of the rice straw powder comprises the following steps: collecting rice straws, cleaning with clear water to remove dirt on the surface, draining water, drying, pulverizing, and sieving with 80 mesh sieve.
Wherein the step S1 includes the following steps:
s1.1, alkali extraction: pouring the rice straw powder into a NaOH solution with the mass fraction of 5% -10%, and reacting for 30 min-1 h at 50-60 ℃ and the microwave power of 300-800W to obtain an alkali extraction reaction solution;
s1.2, alcohol precipitation: cooling, standing and filtering the alkali extraction reaction solution obtained in the step S1.1, adjusting the filtrate to be neutral by using HCl, and standing overnight in 2-2.5 times of volume of absolute ethyl alcohol with the temperature of 4 ℃ to obtain a rice straw xylan crude product;
s1.3, dialysis: and (3) carrying out running water dialysis on the rice straw xylan crude product obtained in the step (S1.2) for 24-48 h through a dialysis bag, and carrying out vacuum freeze drying to obtain the rice straw xylan.
Wherein the step S2 is: slowly adding the rice straw xylan into a sulfation reagent, and carrying out sulfation reaction for 2.5-4 h under the stirring condition, wherein the reaction temperature is 45-65 ℃; and after the reaction is finished, cooling to room temperature, adding 2-2.5 times of volume of absolute ethyl alcohol, standing for 8-24 h at 4 ℃, performing suction filtration to obtain a filter cake, and performing dialysis and freeze-drying to obtain the rice straw xylan sulfate.
Wherein, during the sulfation reaction, the mass ratio of the rice straw xylan to the esterification reagent is 1: 5 to 10.
Wherein the sulfation reagent is chlorosulfonic acid/anhydrous pyridine solution, sulfur trioxide pyridine complex/anhydrous pyridine solution or sodium aminotrisulfonate aqueous solution; wherein, the chlorosulfonic acid/anhydrous pyridine solution, the sulfur trioxide pyridine complex/anhydrous pyridine solution and the sodium aminotrisulfonate aqueous solution respectively obtain the rice straw xylan sulfate with the substitution degrees of 0.233, 1.276 and 1.566.
Wherein, the running water dialysis adopts the running water dialysis of a dialysis bag with the molecular cut-off of 3500 Da.
The application of the rice straw xylan sulfate in the production of cosmetic raw materials is provided.
The technical scheme of the invention has the following beneficial effects:
(1) the method has the characteristics of no need of an organic solvent (reaction in a water phase), simple and convenient operation, high substitution degree of the sulfuric acid product, high yield and the like;
(2) the rice straw xylan is subjected to sulfation modification, and the rice straw xylan sulfate with different degrees of substitution can be obtained by changing factors such as reaction temperature, reaction time, addition of an esterification reagent and the like. Then, the products are used for antioxidant activity research, and the antioxidant activity of the sulfated xylan is greatly enhanced compared with that of rice straw xylan, and the antioxidant activity of the sulfated xylan is equivalent to that of vitamin C-OH scavenging capacity under the same concentration, so that a foundation is laid for the development and application of rice straw xylan sulfate as a novel cosmetic raw material in future.
Drawings
FIG. 1 is a standard curve of sulfate salt in example 2;
FIG. 2 is an IR spectrum of xylan extracted from rice straw in example 3;
FIG. 3 is the IR spectrum of xylan sulfate by the sodium aminotrisulfonate method of example 3;
FIG. 4 is the NMR spectrum of rice straw xylan 13C in example 4;
FIG. 5 shows the sulfate xylan by the sodium aminotrisulfonate process of example 4 13 C NMR spectrum.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The embodiment of the invention provides rice straw xylan sulfate, which has the following structural formula:
the invention also provides a preparation method of the rice straw xylan sulfate, which comprises the following steps:
s1, extracting and preparing rice straw xylan: extracting xylan from the rice straw powder by an alkali extraction, alcohol precipitation and dialysis method, and dialyzing the xylan in running water;
s2, preparation of rice straw xylan sulfate: and (S1) carrying out sulfation reaction on the rice straw xylan obtained in the step (S1), and dialyzing with running water to obtain the rice straw xylan sulfate.
The grain size of the rice straw powder is 80 meshes, and the preparation of the rice straw powder comprises the following steps: collecting rice straws, cleaning with clear water to remove dirt on the surface, draining water, drying, pulverizing, and sieving with 80 mesh sieve.
The step S1 includes the following steps:
s1.1, alkali extraction: pouring the rice straw powder into a NaOH solution with the mass fraction of 5% -10%, and reacting for 30 min-1 h at 50-60 ℃ and the microwave power of 300-800W to obtain an alkali extraction reaction solution;
s1.2, alcohol precipitation: cooling, standing and filtering the alkali extraction reaction solution obtained in the step S1.1, adjusting the filtrate to be neutral by using HCl, and standing overnight in 2-2.5 times of volume of absolute ethyl alcohol with the temperature of 4 ℃ to obtain a rice straw xylan crude product;
s1.3, dialysis: and (3) carrying out running water dialysis on the rice straw xylan crude product obtained in the step (S1.2) for 24-48 h through a dialysis bag, and carrying out vacuum freeze drying to obtain the rice straw xylan.
The step of step S2 is: slowly adding the rice straw xylan into a sulfation reagent, and carrying out sulfation reaction for 2.5-4 h under the stirring condition, wherein the reaction temperature is 45-65 ℃; and after the reaction is finished, cooling to room temperature, adding 2-2.5 times of volume of absolute ethyl alcohol, standing for 8-24 h at 4 ℃, performing suction filtration to obtain a filter cake, and performing dialysis and freeze-drying to obtain the rice straw xylan sulfate.
During the sulfation reaction, the mass ratio of the rice straw xylan to the esterification reagent is 1: 5-10; the sulfation reagent is chlorosulfonic acid/anhydrous pyridine solution, sulfur trioxide pyridine complex/anhydrous pyridine solution or sodium aminotrisulfonate aqueous solution, wherein the chlorosulfonic acid/anhydrous pyridine solution, the sulfur trioxide pyridine complex/anhydrous pyridine solution and the sodium aminotrisulfonate aqueous solution respectively obtain sulfated rice straw xylan with substitution degrees of 0.233, 1.276 and 1.566, namely: the xylan sulfate is prepared from rice straw.
The technical scheme of the invention is further illustrated by the following specific examples.
Example 1: condition optimization for preparing rice straw xylan sulfate by using rice straws
S1: extracting and preparing rice straw xylan:
5g of rice straw powder (crushed and dried) was added into a three-necked flask containing 100mL of NaOH solution (10%) and reacted at 65 ℃ for 4.5 hours. Cooling, standing, filtering, adjusting the filtrate to neutral with HCl, concentrating, adding 200mL anhydrous ethanol into the concentrated solution, and standing overnight. And (4) carrying out suction filtration, and carrying out vacuum drying on a filter cake to obtain a crude product of xylan. Recrystallizing the crude xylan product by alkali solution and alcohol precipitation (10% NaOH solution, filtering, adjusting the filtrate to neutral, concentrating, and adding anhydrous ethanol into the concentrated solution) for 3 times. Dialyzing the dissolved crude xylan product for 48h by a 3500Da (molecular weight) dialysis bag, concentrating, and freeze-drying to obtain the rice straw xylan.
S2: preparation of xylan sulfate from rice straw (amino trisulfonic acid sodium method):
5g of NaHSO 3 Dissolved in 15mL of deionized water, and 10% NaNO was added slowly 2 And continuously stirring the solution for 1h to obtain the sodium aminotrisulfonate solution. The sodium aminotrisulphonate solution was adjusted to pH 10 with 5% NaOH. Adding 1g of rice straw xylan into the solution in batches, reacting at 45 ℃, concentrating reaction liquid after the reaction is finished, adding 50mL of acetone for settling, dissolving a filter cake in 20mL of deionized water, slowly dropwise adding 4mL of HCl solution (10%), stirring for 0.5h, slowly adding 75mL of cold acetone, standing overnight, and performing suction filtration to obtain a crude product of the esterification product. And dissolving the crude product, dialyzing, and freeze-drying to obtain the xylan sulfate.
Example 2: degree of substitution of xylan sulfates of three esterification systems
Sulfate radical content determination:
utilizing common BaCl in laboratory 2 Gelatin method to determine the sulfate content. Hydrolyzing xylan sulfate to form precipitate with Ba2+, and measuring absorbance (OD) at 360nm and SO in xylan sulfate 4 2- Standard curve of concentration.
And substituting the OD value of the sample into the equation to obtain the sulfate radical content of the 1mL sample, and recording the content as Xs.
The calculation formula is as follows:
the degree of sulfation of the polysaccharide is expressed in terms of Degree of Substitution (DS).
Calculated as one pentose residue:
the calculation formula for DS is therefore:
the absorbance values (360nm) of the potassium sulfate standard solutions were measured as shown in table 1 below:
TABLE 1 Absorbance value of sulfate Standard solution (360nm)
As shown in FIG. 1, a standard curve is prepared with the abscissa as the sulfate concentration (. mu.g/mL) and the ordinate as the absorbance value (360nm), and the regression equation of the standard curve is: y is 0.0018X +0.0055, and R2 is 0.9872. And substituting the measured absorbance values of the esterification products into an equation, respectively calculating the sulfate radical content of the three esterification systems, and calculating the substitution degree of the sulfuric acid.
The yield and the degree of substitution of sulfuric acid of xylan sulfate obtained in this experiment using three esterification systems are shown in table 2:
TABLE 2 yield and sulfate content of xylan sulfates in three esterification systems
Example 3: characterization of the Infrared Spectrum
Tabletting the dried xylan sulfate sample and potassium bromide at 400-4000 cm -1 Infrared spectrum scanning in wave number range with resolution of 3.2cm -1 。
As can be seen from FIG. 2, the product was found to be 3440cm -1 Has strong absorption peak, is O-H stretching vibration and is 1050cm -1 The absorption peak is the stretching vibration of C-O, which shows that the rice straw is hydrolyzed into xylan.
As shown in FIG. 3, the esterification product was found to be 1251cm -1 The absorption peak is S ═ O asymmetric stretching vibration at 805cm -1 The peak appears as a sharp absorption peak, which is the stretching vibration of the C-O-S bond, and the two absorption peaks are specific absorption peaks generated by sulfate radicals and are typical absorption peaks of the esterified polysaccharide. This indicates that xylan sulfates have been obtained.
Example 4: characterization of nuclear magnetic spectra
Process for preparation of xylan sulfates 13 C NMR was analyzed using a nuclear magnetic resonance spectrometer with a working frequency of 500MHz and dissolved in D 2 In O, the accumulation was 10h at 50 ℃.
As shown in FIG. 4, 102ppm is the chemical shift of xylan C1, and the chemical shifts of C2-C6 are centered around 63-77ppm, indicating that the rice straw has been hydrolyzed into xylan.
As shown in FIG. 5, of comparative xylans 13 C NMR charts, C2, C3, have their chemical shifts more complex and lower due to attachment of sulfate groups, and C4, C5 have higher chemical shifts due to attachment of sulfate groups, indicating that xylan sulfates have been obtained.
Example 5: verification of antioxidant Activity
Using vitamin as positive control, sequentially adding 1mL of sample solution with different concentrations and 2.0mL of EDTA-FeSO into the test tube 4 (0.2mmol/L) solution, after being mixed uniformly, 1.5mL salicylic acid-ethanol (0.2mmol/L) solution is respectively added, the temperature is kept at 37 ℃ for reaction for 30min, the respective absorbance value is measured under the wavelength of 510nm, the absorbance is substituted into a sample clearance free radical formula, and the clearance free radical formula of the sample is as follows:
clearance D ═ 1- (OD1-OD2)/OD0 x 100%,
in the formula: OD1 is the absorbance value of the sample solution; OD2 is absorbance value without sodium salicylate; OD0 was a blank control.
The effect of xylan and sulfate on OH clearance of rice straw is shown in Table 3:
TABLE 3 Rice straw xylan and sulfate on OH scavenging action
According to the research results of the antioxidant activity of the compounds, the rice straw xylan and the sulfated products show antioxidant activity of different degrees. The sequence of the capacity of scavenging free radicals is vitamin C, rice straw xylan sulfate and rice straw xylan, which shows that the sulfation modification can improve the antioxidant activity of the rice straw xylan, the antioxidant activity of the sulfated xylan is greatly enhanced compared with that of the rice straw xylan, and the antioxidant activity of the sulfated xylan is equivalent to that of the vitamin C-OH scavenging capacity under the same concentration.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The rice straw xylan sulfate is characterized by having the following structural formula:
2. a preparation method of rice straw xylan sulfate is characterized by comprising the following steps:
s1, extraction and preparation of rice straw xylan: extracting the rice straw powder by an alkali extraction alcohol precipitation dialysis method, and dialyzing by running water to obtain rice straw xylan;
s2, preparation of rice straw xylan sulfate: and (S1) carrying out sulfation reaction on the rice straw xylan obtained in the step (S1), and dialyzing with running water to obtain the rice straw xylan sulfate.
3. The method for preparing rice straw xylan sulfate according to claim 2, wherein the particle size of the rice straw powder is 80 mesh, and the method for preparing rice straw powder comprises the following steps: collecting rice straw, cleaning with clear water to remove surface dirt, draining, oven drying, pulverizing, and sieving with 80 mesh sieve.
4. The method for preparing the rice straw xylan sulfate according to claim 2, wherein the step S1 comprises the following steps:
s1.1, alkali extraction: pouring the rice straw powder into a NaOH solution with the mass fraction of 5% -10%, and reacting for 30 min-1 h at 50-60 ℃ and the microwave power of 300-800W to obtain an alkali extraction reaction solution;
s1.2, alcohol precipitation: cooling, standing and filtering the alkali extraction reaction solution obtained in the step S1.1, adjusting the filtrate to be neutral by using HCl, and standing overnight in 2-2.5 times of volume of absolute ethyl alcohol with the temperature of 4 ℃ to obtain a rice straw xylan crude product;
s1.3, dialysis: and (3) carrying out running water dialysis on the rice straw xylan crude product obtained in the step (S1.2) for 24-48 h through a dialysis bag, and carrying out vacuum freeze drying to obtain the rice straw xylan.
5. The method for preparing rice straw xylan sulfate according to claim 2, wherein the step S2 is: slowly adding the rice straw xylan into a sulfation reagent, and carrying out sulfation reaction for 2.5-4 h under the stirring condition, wherein the reaction temperature is 45-65 ℃; and after the reaction is finished, cooling to room temperature, adding 2-2.5 times of volume of absolute ethyl alcohol, standing for 8-24 h at 4 ℃, performing suction filtration to obtain a filter cake, and performing dialysis and freeze-drying to obtain the rice straw xylan sulfate.
6. The preparation method of rice straw xylan sulfate according to claim 5, wherein the mass ratio of rice straw xylan to an esterification reagent is 1: 5 to 10.
7. The method for preparing rice straw xylan sulfate according to claim 5 or 6, wherein the sulfation agent is chlorosulfonic acid/anhydrous pyridine solution, sulfur trioxide-pyridine complex/anhydrous pyridine solution, or sodium aminotrisulfonate aqueous solution; wherein the chlorosulfonic acid/anhydrous pyridine solution, the sulfur trioxide pyridine complex/anhydrous pyridine solution and the sodium aminotrisulfonate aqueous solution respectively obtain the rice straw xylan sulfate with the substitution degrees of 0.233, 1.276 and 1.566.
8. The method for preparing the rice straw xylan sulfate according to claim 2, wherein a dialysis bag with a molecular cut-off of 3500Da is used for running water dialysis.
9. An application of xylan sulfate from rice straw in preparing cosmetic raw material.
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