CN115594772B - Coumarin starch derivative and preparation and application thereof - Google Patents
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Abstract
The invention relates to the field of biological medicine, and particularly relates to a coumarin starch derivative, and a preparation method and application thereof. The coumarin starch derivative is shown in a formula (1). The method has the advantages of simple reaction process, mild conditions, cheap and easily-obtained reaction materials, and easy popularization and industrial application, and researches prove that the prepared coumarin starch derivative has good bacteriostatic activity while ensuring good water solubility, enhances the biological activity of the starch, expands the application range of the starch, and can be widely applied to the fields of food, health care products and daily chemicals.
Formula (1).
Description
Technical Field
The invention relates to the field of biological medicine, and particularly relates to a coumarin starch derivative, and a preparation method and application thereof.
Background
Starch (starch) is a polysaccharide substance formed by the polycondensation of glucose and is the main storage form of carbohydrates in cells. The starch is a natural polysaccharide which has rich sources, is reproducible, has no toxic or side effect, has good biocompatibility and degradability, can be widely applied to the fields of food, medicine, packaging and the like, and has no toxicity or pollution. However, starch does not contain amino groups, carboxyl groups and other groups with biological activities such as antibiosis, bacteriostasis and the like, so that the activity of the starch is low, and the starch is easy to breed bacteria, thereby limiting the expansion of the application range and the improvement of the application value.
Disclosure of Invention
The invention aims to provide a coumarin starch derivative and a preparation method and application thereof.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a coumarin starch derivative is shown in formula (1),
In the formula (1)
wherein n represents polymerization degree, and the average value range of n is 5-12000.
The preparation method of the coumarin starch derivative comprises the steps of carrying out bromination reaction on starch and N-bromosuccinimide to obtain 6-bromostarch; 6-ethyl amino starch is prepared by the reaction of 6-bromo starch and ethylenediamine; and then 6-ethylaminostarch and substituted hydroxycoumarin react in the presence of a solvent to obtain the coumarin starch derivative shown in the formula (1).
The 6-bromostarch is as follows: dissolving starch in N, N-dimethylformamide, stirring at 120 ℃ for 1-3h, cooling to 90 ℃, adding lithium bromide, cooling to 0 ℃, adding N-bromosuccinimide and triphenylphosphine, reacting at 70-90 ℃ for 1-3h, precipitating with ethanol after reaction, washing the precipitate with ethanol, suction-filtering to obtain a filter cake, and drying to constant weight to obtain 6-bromostarch; wherein the adding amount of the lithium bromide is 2-4 times of the molar amount of the raw material starch, the adding amount of the N-bromosuccinimide is 5-10 times of the molar amount of the raw material starch, and the adding amount of the triphenylphosphine is 5-10 times of the molar amount of the raw material starch.
The 6-ethyl amino starch is as follows: dissolving 6-bromostarch in dimethyl sulfoxide, adding ethylenediamine, reacting at 70-90 ℃ for 16-24h, precipitating with acetone, washing the precipitate with acetone, vacuum-filtering to obtain a filter cake, and drying to constant weight to obtain 6-ethylaminostarch; wherein the addition amount of the ethylenediamine is 30-50 times of the molar amount of the 6-brominated starch.
The coumarin starch derivative shown in the formula (1) is as follows: dissolving the obtained 6-ethylamino starch and substituted hydroxycoumarin in dimethyl sulfoxide, reacting at 70-90 ℃ for 8-14h, precipitating with anhydrous acetone after reaction, washing the precipitate with ethanol, vacuum-filtering to obtain a filter cake, and drying to constant weight to obtain the coumarin starch derivative shown in formula (1); wherein the addition amount of the substituted hydroxycoumarin is 1.5 to 3 times of the molar amount of the 6-ethylaminostarch.
The substituted hydroxycoumarin is 4-hydroxycoumarin, 4-hydroxy-6-methylcoumarin, 4-hydroxy-6-chlorocoumarin or 4, 7-dihydroxycoumarin.
An application of coumarin starch derivatives, namely an application of a compound shown in a formula (1) in preparation of starch products with antibacterial properties.
The invention has the advantages that:
(1) Starch has the advantages of good biodegradability, biocompatibility, nontoxicity and the like, but has almost no antibacterial activity. The antibacterial starch is chemically modified, so that the antibacterial activity of the starch is improved while the advantages of the starch are kept; compared with starch, the activity of the coumarin starch derivative for inhibiting bacteria is greatly improved. The derivative can be developed into a starch product with antibacterial performance so as to solve the problems of potential toxicity and the like of chemical antibacterial agents to human health. Meanwhile, the method can be widely applied to the fields of food, medicine and the like.
(2) The invention adopts the sugar modification method to modify hydroxyl on the polysaccharide so as to obtain the derivative with high antioxidant activity, the preparation process is simple, and the cost of the used material is low.
Drawings
FIG. 1 is a scheme for synthesizing a derivative represented by formula (1) according to an embodiment of the present invention.
FIG. 2 is an infrared spectrum of starch provided by an embodiment of the present invention.
FIG. 3 is an infrared spectrum of 6-ethylamino starch provided in example 1 of the present invention.
Fig. 4 is an infrared spectrum of a coumarin starch derivative provided in example 1 of the present invention.
Fig. 5 is an infrared spectrum of a coumarin starch derivative provided in example 2 of the present invention.
Fig. 6 is an infrared spectrum of a coumarin starch derivative provided in example 3 of the present invention.
Fig. 7 is an infrared spectrum of a coumarin starch derivative provided in example 4 of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are only for purposes of illustration and explanation and are not intended to be limiting.
Example 1
The coumarin starch derivative prepared as shown in figure 1 is a derivative shown in a formula (1):
(1) Preparation of 6-bromostarch: 3.24 g (20 mmol) of starch are weighed out and dissolved in 80mLN, N-dimethylformamide, stirred for 1 h at 120 ℃, cooled to 90 ℃, then 3.47 g (40 mmol) of lithium bromide are added, cooled to 0 ℃, 17.8 g (100 mmol) of N-bromosuccinimide and 26.2 g (100 mmol) of triphenylphosphine are added, and the reaction is carried out for 3h at 70 ℃. After the reaction, the reaction solution was poured into 200 mL of anhydrous ethanol to precipitate a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate with ethanol, and drying at 65 ℃ to obtain the 6-bromostarch.
(2) Dissolving 0.45 g (2 mmol) of the 6-bromostarch obtained in the step (1) into 2 mL of dimethyl sulfoxide, adding 4 mL of ethylenediamine, and reacting at 70 ℃ for 24 h. After the reaction is finished, excessive acetone is used for precipitation, the precipitation is filtered, washed and precipitated by acetone, and dried at 65 ℃ to obtain the 6-ethylaminostarch (see figure 3).
(3) 204 g (1 mmol) of 6-ethylaminostarch obtained in the step (2) and 324 g (2 mmol) of 4-hydroxycoumarin are dissolved in 2 mL of dimethyl sulfoxide and reacted at 70 ℃ for 14h, and after the reaction is finished, the reaction solution is poured into 20 mL of acetone to separate out a precipitate. Filtering the precipitate, washing the precipitate with acetone, and drying at 65 deg.C to obtain coumarin starch derivatives (see figure 4), wherein R is 1 And R 2 Is hydrogen. The obtained product is brown powder, and is easily soluble in water.
FIG. 2 is an infrared spectrum of raw starch.FIG. 3 is an infrared spectrum of 6-ethylaminostarch: 1569cm -1 The bending vibration absorption peak of the amino group. FIG. 4 is an infrared spectrum of a coumarin starch derivative according to example 1 of the present invention, which is 1659cm from FIG. 4 -1 Is the stretching vibration peak of C = O on coumarin, 1605cm -1 Is the stretching vibration peak of C = C on the benzene ring, 760cm -1 The above analysis data shows that R is the deformation vibration peak of the benzene ring C-H 1 And R 2 The coumarin starch derivatives which are hydrogen are successfully synthesized.
Example 2
This example synthesizes R according to the above synthetic route 1 Is methyl, R 2 Coumarin starch derivatives which are hydrogen. The difference from the example 1 is that:
(1) Preparation of 6-bromostarch: 3.24 g (20 mmol) of starch are weighed out and dissolved in 80mLN, N-dimethylformamide, stirred for 2 h at 120 ℃, cooled to 90 ℃, then 4.34 g (50 mmol) of lithium bromide are added, cooled to 0 ℃, then 21.36 g (120 mmol) of N-bromosuccinimide and 31.44 g (120 mmol) of triphenylphosphine are added, and the reaction is carried out for 2 h at 80 ℃. After the reaction, the reaction solution was poured into 200 mL of anhydrous ethanol to precipitate a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate by using ethanol, and drying at 65 ℃ to obtain the 6-bromostarch.
(2) Dissolving 0.45 g (2 mmol) of the 6-bromostarch obtained in the step (1) into 2 mL of dimethyl sulfoxide, adding 5mL of ethylenediamine, and reacting at 80 ℃ for 22 h. After the reaction is finished, excessive acetone is used for precipitation, the precipitation is filtered, washed and precipitated by acetone, and dried at 65 ℃ to obtain the 6-ethylaminostarch (see figure 3).
(3) 204 g (1 mmol) of 6-ethylaminostarch obtained in the step (2) and 264 g (1.5 mmol) of 4-hydroxy-6-methylcoumarin are dissolved in 2 mL of dimethyl sulfoxide, the mixture reacts for 12 h at 80 ℃, and after the reaction is finished, the reaction solution is poured into 20 mL of acetone to separate out a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate with acetone, and drying at 65 ℃ to obtain the coumarin starch derivative (see figure 5). The obtained product is brown powder, and is easily soluble in water.
FIG. 5 is an infrared spectrum of a coumarin starch derivative according to example 2 of the present invention, which is 1651cm from FIG. 5 -1 Is the C = O stretching vibration peak on coumarin, 1618cm -1 Is the stretching vibration peak of C = C on benzene ring, 816cm -1 And 763cm -1 The above analysis data shows that R is the deformation vibration peak of the benzene ring C-H 1 Is methyl, R 2 The coumarin starch derivatives which are hydrogen are successfully synthesized.
Example 3
This example synthesizes R according to the above synthetic route 1 Is chlorine, R 2 Coumarin starch derivatives which are hydrogen. The difference from the embodiment 1 is that:
(1) Preparation of 6-bromostarch: 3.24 g (20 mmol) of starch are weighed out and dissolved in 80mLN, N-dimethylformamide, stirred for 3h at 120 ℃, cooled to 90 ℃, then 5.21 g (60 mmol) of lithium bromide are added, cooled to 0 ℃, 24.92 g (140 mmol) of N-bromosuccinimide and 36.68 g (140 mmol) of triphenylphosphine are added, and the reaction is carried out for 1 h at 90 ℃. After the reaction, the reaction solution was poured into 200 mL of anhydrous ethanol to precipitate a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate with ethanol, and drying at 65 ℃ to obtain the 6-bromostarch.
(2) Dissolving 0.45 g (2 mmol) of the 6-bromostarch obtained in the step (1) in 2 mL of dimethyl sulfoxide, adding 6 mL of ethylenediamine, and reacting at 90 ℃ for 16 h. After the reaction is finished, excessive acetone is used for precipitation, and the precipitate is filtered, washed by acetone and dried at 65 ℃ to obtain the 6-ethylaminostarch (see figure 3).
(3) 204 g (1 mmol) of 6-ethylaminostarch obtained in the step (2) and 588 g (3 mmol) of 4-hydroxy 6-chlorocoumarin are dissolved in 2 mL of dimethyl sulfoxide, the mixture reacts for 8 hours at 90 ℃, and after the reaction is finished, the reaction solution is poured into 20 mL of acetone to separate out a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate with acetone, and drying at 65 ℃ to obtain the coumarin starch derivative (see figure 6). The obtained product is brown powder, and is easily soluble in water.
FIG. 6 is an infrared spectrum of coumarin starch derivative according to example 3 of the present invention, which is 1647cm from FIG. 6 -1 Is the C = O stretching vibration peak on coumarin, 1606cm -1 815cm, which is the stretching vibration peak of C = C on the benzene ring -1 The above analysis data shows that R is the deformation vibration peak of the benzene ring C-H 1 Is chlorine, R 2 The coumarin starch derivatives which are hydrogen are successfully synthesized.
Example 4
This example synthesizes R according to the above synthetic route 1 Is hydrogen, R 2 Coumarin starch derivatives which are hydroxyl groups. The difference from the embodiment 1 is that:
(1) Preparation of 6-bromostarch: 3.24 g (20 mmol) of starch are weighed out and dissolved in 80ml N-dimethylformamide, stirred for 2.5 h at 120 ℃, cooled to 90 ℃, 6.94 g (80 mmol) of lithium bromide are added, cooled to 0 ℃, 35.6 g (200 mmol) of N-bromosuccinimide and 52.4 g (200 mmol) of triphenylphosphine are added and reacted for 2 h at 70 ℃. After the reaction, the reaction mixture was poured into 200 mL of anhydrous ethanol to precipitate a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate with ethanol, and drying at 65 ℃ to obtain the 6-bromostarch.
(2) Dissolving 0.45 g (2 mmol) of the 6-bromostarch obtained in the step (1) in 2 mL of dimethyl sulfoxide, adding 7mL of ethylenediamine, and reacting at 80 ℃ for 20 h. After the reaction is finished, excessive acetone is used for precipitation, the precipitation is filtered, washed and precipitated by acetone, and dried at 65 ℃ to obtain the 6-ethylaminostarch (see figure 3).
(3) 204 g (1 mmol) of 6-ethylaminostarch obtained in the step (2) and 445 g (2.5 mmol) of 4, 7-dihydroxycoumarin are dissolved in 2 mL of dimethyl sulfoxide and reacted at 80 ℃ for 10 h, and after the reaction is finished, the reaction solution is poured into 20 mL of acetone to separate out a precipitate. And (3) carrying out suction filtration on the precipitate, washing the precipitate with acetone, and drying at 65 ℃ to obtain the coumarin starch derivative (see figure 7). The obtained product is brown powder, and is easily soluble in water.
FIG. 7 is an infrared spectrum of coumarin starch derivative according to example 4 of the present invention, as shown in FIG. 7, 1616cm -1 Is C = O stretching vibration peak on coumarin and C = C stretching vibration peak on benzene ring, 852cm -1 And 808cm -1 The above analysis data shows that R is the deformation vibration peak of the benzene ring C-H 1 Is hydrogen, R 2 The coumarin starch derivatives which are hydroxyl groups are successfully synthesized.
Application example
Determination of the ability to inhibit E.coli and S.flavus:
respectively measuring the Minimum Inhibitory Concentrations (MIC) of the synthesized coumarin starch derivative or starch shown in the formula (1) for inhibiting escherichia coli and staphylococcus aureus by adopting a trace broth dilution method, and respectively comparing: firstly, culturing bacteria in 37 deg.C nutrient solution for 18 hr to obtain bacterial suspension, and diluting the bacterial suspension with sterile nutrient solution to 10 5 -10 6 Per ml of individual cells. Then, the coumarin starch derivative and the experimental starch prepared in the examples were lyophilized in vacuum to a constant weight, and then prepared into a 32 mg/mL sample aqueous solution using water as a solvent, 100 μ L of sterile water was added to each well of the 96-well plate, then 100 μ L of the sample solution was added to the first row of wells of the 96-well plate, and after repeated mixing, 100 μ L of each row of wells was sequentially aspirated and transferred to the next row of wells, and the mixture was continuously diluted 11-fold at concentrations of 8 mg/mL, 4 mg/mL, 2 mg/mL, 1 mg/mL, 0.5 mg/mL, 0.25 mg/mL, 0.125 mg/mL, 0.0625 mg/mL, 0.03125 mg/mL, 0.015625 mg/mL, 0.00781 mg/mL and 0.00391 mg/mL, and then 100 μ L of the bacterial suspension was added to each well, and incubated at 37 ℃ for 18 hours. Ionized water was used as a blank. The MIC is the lowest concentration of sample solution that is visually observed to completely inhibit the growth of visible bacteria. After the MIC assay was completed, 100. Mu.L of medium without significant bacterial growth was plated on agar plates and incubated at 37 ℃ for 8h for the determination of the minimal lethal concentration (MBC). MBC is defined as the lowest concentration of 99.9% reduction of viable bacteria in the experimental sample.
The experimental results are as follows: the ability of the synthesized coumarin starch derivative and starch to inhibit staphylococcus aureus is shown in table 1, and the ability of the synthesized coumarin starch derivative and starch to inhibit escherichia coli is shown in table 2. The analysis of the experimental results shows that: under very low concentration, the coumarin starch derivative synthesized by the invention has good inhibiting and killing effects on staphylococcus aureus and escherichia coli.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions and combinations which are consistent with the essence and principle of the present invention shall be considered as equivalent replacement modes, and all the modifications, substitutions and combinations shall fall within the protection scope of the present invention.
TABLE 1 ability of starch and coumarin starch derivatives to inhibit Staphylococcus aureus
TABLE 2 ability of starch and coumarin starch derivatives to inhibit E.coli
Claims (7)
1. A coumarin starch derivative is characterized in that: the coumarin starch derivative is shown in a formula (1),
In the formula (1)
wherein n represents polymerization degree, and the average value range of n is 5-12000.
2. A process for the preparation of coumarin starch derivatives according to claim 1, characterized in that: carrying out bromination reaction on starch and N-bromosuccinimide to obtain 6-bromostarch; 6-ethyl amino starch is prepared by the reaction of 6-bromo starch and ethylenediamine; and then 6-ethylaminostarch and substituted hydroxycoumarin react in the presence of a solvent to obtain the coumarin starch derivative shown in the formula (1).
3. A process for the preparation of coumarin starch derivatives according to claim 2, characterized in that: the 6-bromostarch is as follows: dissolving starch in N, N-dimethylformamide, stirring at 120 ℃ for 1-3h, cooling to 90 ℃, adding lithium bromide, cooling to 0 ℃, adding N-bromosuccinimide and triphenylphosphine, reacting at 70-90 ℃ for 1-3h, precipitating with ethanol after reaction, washing the precipitate with ethanol, suction-filtering to obtain a filter cake, and drying to constant weight to obtain 6-bromostarch; wherein, the adding amount of the lithium bromide is 2 to 4 times of the molar amount of the raw material starch, the adding amount of the N-bromosuccinimide is 5 to 10 times of the molar amount of the raw material starch, and the adding amount of the triphenylphosphine is 5 to 10 times of the molar amount of the raw material starch.
4. A process for the preparation of coumarin based starch derivatives according to claim 2, wherein: the 6-ethyl amino starch is as follows: dissolving 6-bromostarch in dimethyl sulfoxide, adding ethylenediamine, reacting at 70-90 deg.C for 16-24h, precipitating with acetone, washing the precipitate with acetone, vacuum filtering to obtain filter cake, and oven drying to constant weight to obtain 6-ethylaminostarch; wherein the addition amount of the ethylenediamine is 30-50 times of the molar amount of the 6-brominated starch.
5. A process for the preparation of coumarin starch derivatives according to claim 2, characterized in that: the coumarin starch derivative shown in the formula (1) is prepared by dissolving the obtained 6-ethylaminostarch and substituted hydroxycoumarin in dimethyl sulfoxide, reacting at 70-90 ℃ for 8-14h, precipitating with anhydrous acetone after reaction, washing the precipitate with ethanol, vacuum-filtering to obtain a filter cake, and drying to constant weight to obtain the coumarin starch derivative shown in the formula (1); wherein the addition amount of the substituted hydroxycoumarin is 1.5 to 3 times of the molar amount of the 6-ethylaminostarch.
6. A process for the preparation of coumarin starch derivatives according to claim 2, characterized in that: the substituted hydroxycoumarin is 4-hydroxycoumarin, 4-hydroxy-6-methylcoumarin, 4-hydroxy-6-chlorocoumarin or 4, 7-dihydroxycoumarin.
7. Use of the coumarin-based starch derivative according to claim 1, wherein: the application of the compound shown in the formula (1) in preparing starch products with antibacterial property.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011383A (en) * | 2007-02-05 | 2007-08-08 | 福建广生堂药业有限公司 | Dispersible tablet of coumarin derivative and its preparation method |
| JP2009102230A (en) * | 2007-10-19 | 2009-05-14 | Shingo Kikuchi | Immunostimulator and cancer-inhibiting agent of sasa senanensis extract |
| DE102010023790A1 (en) * | 2010-06-15 | 2011-12-15 | Heinrich-Heine-Universität Düsseldorf | Wash active composition |
| EP3556779A1 (en) * | 2018-04-20 | 2019-10-23 | Roquette Freres | Cross-linked starch-based polymers for drug-delivery |
| CN114869919A (en) * | 2022-06-29 | 2022-08-09 | 江西中医药大学 | Application of seaweed and seaweed extract in preparation of anti-neuritis medicine and anti-neuritis medicine |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101011383A (en) * | 2007-02-05 | 2007-08-08 | 福建广生堂药业有限公司 | Dispersible tablet of coumarin derivative and its preparation method |
| JP2009102230A (en) * | 2007-10-19 | 2009-05-14 | Shingo Kikuchi | Immunostimulator and cancer-inhibiting agent of sasa senanensis extract |
| DE102010023790A1 (en) * | 2010-06-15 | 2011-12-15 | Heinrich-Heine-Universität Düsseldorf | Wash active composition |
| EP3556779A1 (en) * | 2018-04-20 | 2019-10-23 | Roquette Freres | Cross-linked starch-based polymers for drug-delivery |
| CN114869919A (en) * | 2022-06-29 | 2022-08-09 | 江西中医药大学 | Application of seaweed and seaweed extract in preparation of anti-neuritis medicine and anti-neuritis medicine |
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