CN108383928B - Tetrabutylammonium-based inulinum and preparation method and application thereof - Google Patents
Tetrabutylammonium-based inulinum and preparation method and application thereof Download PDFInfo
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- CN108383928B CN108383928B CN201810275668.5A CN201810275668A CN108383928B CN 108383928 B CN108383928 B CN 108383928B CN 201810275668 A CN201810275668 A CN 201810275668A CN 108383928 B CN108383928 B CN 108383928B
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- 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
- C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
- C08B37/0054—Inulin, i.e. beta-2,1-D-fructofuranan; Derivatives thereof
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- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
Abstract
The invention relates to the field of daily chemicals and the pharmaceutical industry, in particular to tetrabutylammonium inulin carbamate and a preparation method and application thereof. The structural formula of the tetrabutylammonium inulin urethane is shown as a formula (1), wherein the value range of the average polymerization degree n is 2-60. The method has the advantages of high reaction efficiency, easy popularization and easy obtainment of required equipment and raw materials. Research shows that the synthesized tetrabutylammonium inulin carbamate has good water solubility and excellent antioxidant activity, and can be widely applied to the fields of daily chemicals and medicines.
Description
Technical Field
The invention relates to the field of daily chemicals and the pharmaceutical industry, in particular to tetrabutylammonium inulin carbamate and a preparation method and application thereof.
Background
Inulin (Inulin), also known as Inulin or cornstarch, is a plant polysaccharide, and is widely found in nature, and mainly exists in 36000 various plant bodies in the form of polysaccharide reserve, such as Jerusalem artichoke, chicory, dahlia, yacon tubers, salsify and the like.
The urethane compounds are very common in the fields of medicine and functional materials, such as styrene-acrylic urethane, polyurethane, various polyurethane materials and the like. The urethane can be used as a bioactive group and a link between active groups, and is grafted to an inulin molecule to obtain the inulin derivative with certain bioactivity. However, the functional group of the urethane (-OCONH-) is a hydrophobic group, and the water solubility of the urethane compounds is generally poor. Further, it is desired to provide a method for further enhancing the activity of inulin.
Disclosure of Invention
The invention aims to provide tetrabutylammonium inulin carbamate with better antioxidant activity and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a tetrabutylammonium inulin urethane, the structural formula of which is shown as a formula (1),
wherein the average polymerization degree n ranges from 2 to 60.
A preparation method of tetrabutylammonium inulin carbamate comprises the following steps:
firstly, activating hydroxyl on inulin molecules by using N, N' -Carbonyl Diimidazole (CDI), and then reacting with tetrabutylammonium glycinate to obtain a product tetrabutylammonium inulin carbamate shown in a formula (1);
the molar weight of the N, N' -Carbonyldiimidazole (CDI) is 1.0-1.5 times of that of the inulin; the molar weight of tetrabutylammonium glycinate is 1.0-2.0 times of that of inulin.
The tetrabutylammonium glycinate is prepared by dropwise adding tetrabutylammonium hydroxide into 0.6-0.8mol/L glycine aqueous solution, stirring at room temperature for 12-16h, evaporating the aqueous solution obtained by the reaction at 55-60 ℃ under reduced pressure, adding the obtained liquid into excessive mixed solution, stirring vigorously, filtering, and drying the obtained filtrate with anhydrous magnesium sulfate to obtain the tetrabutylammonium glycinate; wherein the molar ratio of tetrabutylammonium hydroxide to glycine is 1: 1-1.2; the mixed solution is acetonitrile with the volume ratio of 8:2-9: 1: and (4) mixing the solution with methanol.
Dissolving the inulin in excessive dimethyl sulfoxide, adding N, N' -carbonyldiimidazole with the molar weight of 1.0-1.5 times of that of the inulin, reacting for 8-10h at 40-50 ℃, adding tetrabutylammonium glycinate with the molar weight of 1.0-2.0 times of that of the inulin, reacting for 12-24h at 40-50 ℃, washing, cooling and drying to obtain the tetrabutylammonium inulinum.
Use of tetrabutylammonium inuiinate for the preparation of an antioxidant.
The invention has the advantages that:
(1) after the tetrabutylammonium inulin carbamate is prepared by the method, the biological activity is improved, such as: antioxidant activity.
(2) The synthesis method has the following advantages in synthesis process: the method has the advantages of simple synthesis steps, easily obtained required equipment and raw materials, low cost, easy popularization and high product yield which can reach more than 60%. The product obtained by the invention can be widely used in the fields of biology, medicine, food, chemical industry and the like.
Drawings
FIG. 1 shows an IR spectrum of tetrabutylammonium glycinate at 2958.27, 2877.27 and 1473.35cm according to an embodiment of the invention-1The absorption peak at (A) is the absorption peak of butyl, 1392.35cm-1The absorption peak of carboxylic acid anion is shown.
FIG. 2 is an infrared spectrum of inulin.
FIG. 3 is an IR spectrum of tetrabutylammonium inulinum according to the present invention, and FIG. 3 shows the raw material of inulinIn contrast, 2962.13, 2877.27, 1465.64cm-1The absorption peak at (A) is the absorption peak of butyl, 1712.48cm-1Is shown as the absorption peak of urethane, 1396.21cm-1The absorption peak of carboxylic acid negative ions is shown, and the above analysis data proves that the synthesis of tetrabutylammonium inulin carbamate is successful.
Detailed Description
The invention is further illustrated by the following examples and combinations.
The method firstly activates hydroxyl on inulin molecules by using N, N' -Carbonyldiimidazole (CDI), then reacts with synthesized tetrabutylammonium glycinate to obtain tetrabutylammonium inulin urethane, and researches the scavenging capacity of the tetrabutylammonium inulin urethane on hydroxyl radicals and superoxide anion radicals. The derivatives are simple and convenient to prepare and mild in condition, and provide a feasible idea for the development of the inulin antioxidant.
The synthetic route of tetrabutylammonium inulin carbamate is as follows:
wherein the average polymerization degree n ranges from 2 to 60.
Example 1
This example synthesizes tetrabutylammonium inulinum carbamate, the target compound, according to the above synthetic route.
1) Preparation of tetrabutylammonium glycinate: 0.9g of glycine was dissolved in 20mL of deionized water, and 6.48g of tetrabutylammonium hydroxide (40% aqueous solution) was added dropwise to the aqueous solution and stirred at room temperature for 12 hours. Then, all water was distilled off under reduced pressure at 55 ℃ and 90mL of acetonitrile and 10mL of methanol were poured into the resulting liquid, and after vigorously stirring for 20min, undissolved solids were filtered off. The obtained filtrate was dried over anhydrous magnesium sulfate, filtered, and acetonitrile and methanol were distilled off to obtain 2.25g of tetrabutylammonium glycinate (see fig. 1) for use.
2) Preparation of tetrabutylammonium inulin carbamate: 1.62g of inulin (see FIG. 2) was dissolved in 20mL of dimethyl sulfoxide (DMSO), and then 1.62g N, N' -Carbonyldiimidazole (CDI) was added, and the reaction was stirred at 40 ℃ for 10 hours. Then 3.16g tetrabutylammonium glycinate was added and reacted at 40 ℃ for 24 h. Then precipitating with excessive acetone, washing with acetone, and freeze drying to obtain target product tetrabutylammonium inulinum shown in formula (1) (see figure 3).
Example 2
The difference from the embodiment 1 is that:
1) preparation of tetrabutylammonium glycinate: 0.9g of glycine was dissolved in 15mL of deionized water, and 7.14g of tetrabutylammonium hydroxide (40% aqueous solution) was added dropwise to the aqueous solution and stirred at room temperature for 12 hours. Then, all water was distilled off under reduced pressure at 60 ℃ and 85mL of acetonitrile and 15mL of methanol were poured into the resulting liquid, and after vigorously stirring for 20min, undissolved solids were filtered off. The obtained filtrate was dried over anhydrous magnesium sulfate, filtered, and acetonitrile and methanol were distilled off to obtain 2.51g of tetrabutylammonium glycinate (see FIG. 1) for use.
2) Preparation of tetrabutylammonium inulin carbamate: 1.62g of inulin (see FIG. 2) was dissolved in 20mL of dimethyl sulfoxide (DMSO), and then 2.03g N, N' -Carbonyldiimidazole (CDI) was added, and the reaction was stirred at 40 ℃ for 10 hours. Then 4.74g tetrabutylammonium glycinate was added and reacted at 40 ℃ for 24 h. Then precipitating with excessive acetone, washing with acetone, and freeze drying to obtain target product tetrabutylammonium inulinum shown in formula (1) (see figure 3).
Example 3
The difference from the embodiment 1 is that:
1) preparation of tetrabutylammonium glycinate: 0.9g of glycine was dissolved in 20mL of deionized water, and 7.78g of tetrabutylammonium hydroxide (40% aqueous solution) was added dropwise to the aqueous solution and stirred at room temperature for 16 hours. Then, all water was distilled off under reduced pressure at 60 ℃ and 80mL of acetonitrile and 20mL of methanol were poured into the resulting liquid, and after vigorously stirring for 20min, undissolved solids were filtered off. The obtained filtrate was dried over anhydrous magnesium sulfate, filtered, and acetonitrile and methanol were distilled off to obtain 2.63g of tetrabutylammonium glycinate (see fig. 1) for use.
2) Preparation of tetrabutylammonium inulin carbamate: 1.62g of inulin (see FIG. 2) was dissolved in 20mL of dimethyl sulfoxide (DMSO), and then 2.43g N, N' -Carbonyldiimidazole (CDI) was added, and the reaction was stirred at 50 ℃ for 8 hours. Then 6.32g tetrabutylammonium glycinate was added and reacted at 50 ℃ for 12 h. Then precipitating with excessive acetone, washing with acetone, and freeze drying to obtain target product tetrabutylammonium inulinum shown in formula (1) (see figure 3).
Application example 1
Determination of the hydroxyl radical scavenging capacity:
inulin and tetrabutylammonium inulinum carbamate prepared in the examples were prepared as mother liquors of 10mg/mL, respectively. 1mL of the sample solutions having different concentrations prepared in Table 1 and 1mL of the phosphate buffer (phosphate buffer preparation: 41.58g of Na was used respectively)2HPO4·12H2O、5.2887g NaH2PO4·2H2O, water is added to be dissolved to 1000mL), 1mL of saffron of 360 μ g/mL, 0.5mL of EDTA-Fe of 2mmol/L, and 1mL of 3% hydrogen peroxide are mixed in a test tube, and after reaction in a water bath at 37 ℃ for 30min, the absorbance of the sample at 520nm is measured, 1mL of distilled water in a blank group replaces the sample to be tested, 1.0mL of distilled water in a control group and 1mL of phosphate buffer solution replaces the sample and hydrogen peroxide (note: the samples to be measured were measured three times, and the average value was taken).
Ability to scavenge hydroxyl radical (%) [ (A)Sample 520nm-ABlank 520nm)/(AControl 520nm-ABlank 520nm)]×100
TABLE 1 hydroxyl radical scavenging ability of tetrabutylammonium inulinum and inulin (%)
Application example 2
Determination of the capability of scavenging superoxide anion radicals:
inulin and tetrabutylammonium inulinum carbamate prepared in the examples were prepared as mother liquors of 10mg/mL, respectively. And respectively taking 1.5mL of sample solution with different concentrations prepared in the table 2, 1mL of Tris-HCl buffer solution (preparing Tris-HCl buffer solution: respectively taking 1.9382g of Tris-hydroxymethyl aminomethane and 0.8mL of concentrated hydrochloric acid, adding water and fixing the volume to 1000mL), 0.5mL of NADH (preparing NADH: 36.57mg of reducing coenzyme I, adding buffer solution and fixing the volume to 100mL), 0.5mL of NBT (preparing NADH: 24.53mg of nitrotetrazolium blue, adding buffer solution and fixing the volume to 100mL), and 0.5mL of PMS (preparing PMS: 1.84mg of phenazine methyl sulfate, adding buffer solution and fixing the volume to 100 mL). The absorbance of the sample at 560nm was measured, with 1.5mL of buffer in the blank group replacing the test sample and 0.5mL of buffer in the control group replacing NADH (note: the samples tested were measured three times and averaged).
Capacity (%) of scavenging superoxide anion radical 1- [ (A)Sample 560nm-AControl 560nm)/ABlank 560nm]×100
TABLE 2 ability of tetrabutylammonium inulinum with inulin to scavenge superoxide anion radical (%)
The experimental results are as follows: the abilities of eliminating hydroxyl radicals and superoxide anion radicals of tetrabutylammonium inulin urethane and inulin synthesized by the method are shown in tables 1 and 2, the abilities of eliminating the hydroxyl radicals and the superoxide anion radicals of the inulin are very weak, the effect of eliminating the hydroxyl radicals is almost not realized at low concentration, and the elimination rate of the superoxide anion radicals is not more than 10% at high concentration. The tetrabutylammonium inulin urethane synthesized by the method has far stronger scavenging capacity to the two free radicals than inulin, the scavenging rate to the hydroxyl free radical under low concentration reaches more than 60%, and the scavenging rates to the hydroxyl free radical and the superoxide anion free radical under high concentration respectively reach more than 95% and more than 55%.
Claims (3)
1. Tetrabutylammonium inulin carbamate, characterized in that: the structural formula of the tetrabutylammonium inulin urethane is shown as a formula (1),
wherein the average polymerization degree n ranges from 2 to 60.
2. A method of preparing tetrabutylammonium inulinum according to claim 1, wherein:
dissolving inulin in excessive dimethyl sulfoxide, adding N, N' -carbonyldiimidazole with the molar weight of 1.0-1.5 times of that of inulin, reacting at 40-50 ℃ for 8-10h, adding tetrabutylammonium glycinate with the molar weight of 1.0-2.0 times of that of inulin, reacting at 40-50 ℃ for 12-24h, washing, cooling and drying to obtain tetrabutylammonium inulinate shown in formula (1);
the tetrabutylammonium glycinate is prepared by dropwise adding tetrabutylammonium hydroxide into 0.6-0.8mol/L glycine aqueous solution, stirring at room temperature for 12-16h, evaporating the aqueous solution obtained by the reaction at 55-60 ℃ under reduced pressure, and adding excessive acetonitrile with the volume ratio of 8:2-9:1 into the obtained liquid: the methanol mixed solution is stirred vigorously, and then the filtrate obtained by filtering is dried by anhydrous magnesium sulfate to obtain tetrabutylammonium glycinate; wherein the molar ratio of tetrabutylammonium hydroxide to glycine is 1: 1-1.2.
3. Use of tetrabutylammonium inulinputaminate according to claim 1, characterized in that: the tetrabutylammonium inulinum carbamate is used for preparing an antioxidant.
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| CN101367880A (en) * | 2008-09-05 | 2009-02-18 | 烟台海岸带可持续发展研究所 | Inulin quaternary ammonium salt, preparation and uses thereof |
| CN102060942A (en) * | 2010-11-22 | 2011-05-18 | 中国科学院烟台海岸带研究所 | 6-amino-6-deoxyinulin as well as preparation and application thereof |
| CN102952208A (en) * | 2012-11-06 | 2013-03-06 | 中国科学院烟台海岸带研究所 | Amphiphilic amido inulin and preparation method thereof |
| CN105418803A (en) * | 2015-12-30 | 2016-03-23 | 山东天晟生物科技有限公司 | Esterification method for hyaluronic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367880A (en) * | 2008-09-05 | 2009-02-18 | 烟台海岸带可持续发展研究所 | Inulin quaternary ammonium salt, preparation and uses thereof |
| CN102060942A (en) * | 2010-11-22 | 2011-05-18 | 中国科学院烟台海岸带研究所 | 6-amino-6-deoxyinulin as well as preparation and application thereof |
| CN102952208A (en) * | 2012-11-06 | 2013-03-06 | 中国科学院烟台海岸带研究所 | Amphiphilic amido inulin and preparation method thereof |
| CN105418803A (en) * | 2015-12-30 | 2016-03-23 | 山东天晟生物科技有限公司 | Esterification method for hyaluronic acid |
Non-Patent Citations (3)
| Title |
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| Chemical hydrophobic modification of inulin in aqueous media: Synthesis of β-hydroxyalkyl ethers of inulin;Jordi Morros等;《Carbohydrate Polymers》;20100330;第81卷;第681–686页 * |
| 卤代苯取代菊糖衍生物的合成及抑真菌活性研究;陈源 等;《烟台大学学报( 自然科学与工程版)》;20180131;第31卷(第1期);第14-18页 * |
| 菊粉季铵盐的合成及性能;赵伟等;《精细化工》;20090415(第04期);第336-339页 * |
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