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CN112321731B - Photoactivated tea sapogenin cellulose nano material and preparation method and application thereof - Google Patents

Photoactivated tea sapogenin cellulose nano material and preparation method and application thereof Download PDF

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CN112321731B
CN112321731B CN202011008429.7A CN202011008429A CN112321731B CN 112321731 B CN112321731 B CN 112321731B CN 202011008429 A CN202011008429 A CN 202011008429A CN 112321731 B CN112321731 B CN 112321731B
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phenanthroline
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CN112321731A (en
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叶勇
刘泽宇
黄传庆
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South China University of Technology SCUT
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Abstract

本发明公开了一种光活化茶皂苷元纤维素纳米材料及其制备方法与应用。该方法包括：将邻菲咯啉通过混酸氧化得到1,10‑邻菲咯啉‑5,6‑二酮，与邻羧基苯甲醛和醋酸铵反应得到2‑(2‑羧基苯基)咪唑并[4,5‑f]‑1,10菲咯啉；邻菲咯啉与钌在氯化锂作用下可结合生成邻菲咯啉钌配合物，再与上述产物连接得到菲咯啉并苯基咪唑钌配合物；纤维素与N‑叔丁氧羰基甘氨酸在催化剂作用下生成甘氨酸‑纤维素酯，再与菲咯啉并苯基咪唑钌配合物连接生成甘氨酸‑纤维素酯并菲咯啉钌配合物，最后其氨基与茶皂苷元醛基反应生成所述光活化茶皂苷元纤维素纳米材料。该材料在蓝光照射下具有抗耐药菌活性，可用于抗菌辅料或药物载体。

Figure 202011008429

The invention discloses a light-activated tea saponin cellulose nanomaterial and a preparation method and application thereof. The method comprises: oxidizing o-phenanthroline with mixed acid to obtain 1,10-o-phenanthroline-5,6-dione, reacting with o-carboxybenzaldehyde and ammonium acetate to obtain 2-(2-carboxyphenyl) imidazoline [4,5-f]-1,10 phenanthroline; o-phenanthroline and ruthenium can combine under the action of lithium chloride to form o-phenanthroline ruthenium complex, and then connect with the above product to obtain phenanthroline acyl group Imidazole ruthenium complex; cellulose and N-tert-butoxycarbonylglycine generate glycine-cellulose ester under the action of a catalyst, and then connect with phenanthroline phenylimidazole ruthenium complex to generate glycine-cellulose ester and phenanthroline ruthenium The complex, and finally its amino group reacts with the teasapogenin aldehyde group to form the light-activated teasapogenin cellulose nanomaterial. The material has antibacterial activity under blue light irradiation, and can be used as antibacterial excipients or drug carriers.

Figure 202011008429

Description

Photoactivated tea sapogenin cellulose nano material and preparation method and application thereof
Technical Field
The invention belongs to the field of medicines, and particularly relates to a photoactivated tea sapogenin cellulose nano material as well as a preparation method and application thereof.
Background
Due to the abuse of antibiotics, more and more drug-resistant bacteria pose great threats to human health, and efforts are made to develop antibiotic substitutes in order to solve the above problems. Natural products contain a large amount of active ingredients, have an inhibitory effect on bacteria, and are not easily tolerated by bacteria, so natural products are an important source of antibiotic substitutes.
Tea saponin is an active ingredient in tea seeds and has the function of inhibiting bacteria and fungi (Huangweiwen, etc., research on bacteriostatic effect of tea saponin, economic forest research, 2002, 20 (1): 17-19), but the tea saponin has low antibacterial activity compared with antibiotics. The transition metal ruthenium pyridine complex has a stable structure, fluorescence, low toxicity and easy absorption and metabolism, can induce the chain breaking of DNA through singlet oxygen under the excitation of light, has an antibacterial effect (Liu Han Jie, preparation and characterization of the polypyridine ruthenium complex and antibacterial mechanism research, Master's academic thesis of southwest university, 2016), can enhance the antibacterial activity of tea saponin, but the tea saponin is difficult to react with the ruthenium pyridine complex to form a stable compound.
Cellulose is a natural compound widely existing in the nature, and can be used as a drug carrier because the cellulose has a large number of hydroxyl groups on the surface, and has hydrophilicity, modifiability and biocompatibility. The cellulose is connected with the tea saponin and ruthenium pyridine complex to construct a new compound, the synergistic effect of the three can be exerted, and a relatively stable photoactivation antibacterial material is formed, and the research on the aspect is not reported.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary object of the invention is to provide a photoactivated theasapogenin cellulose nano material (theasapogenin cellulose phenanthroline ruthenium complex).
The invention also aims to provide a preparation method of the photoactivated tea sapogenin cellulose nano material.
The invention further aims to provide application of the photoactivated tea sapogenin cellulose nano material.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a photoactivated tea sapogenin cellulose nano material, which has the following molecular structural formula:
Figure BDA0002696759510000021
the invention provides a method for preparing the photoactivated theasapogenin cellulose nano material, which comprises the following steps:
(1) mixing phenanthroline and potassium bromide to obtain a mixture, adding a mixed solution of concentrated sulfuric acid and concentrated nitric acid, heating to perform a reflux reaction, cooling to room temperature to obtain a reaction solution, adding the reaction solution into water, uniformly mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to be neutral, filtering to obtain a filtrate, extracting (preferably extracting with trichloromethane), and removing a solvent (evaporating the solvent) to obtain a product 1;
(2) mixing the product 1 obtained in the step (1), o-carboxybenzaldehyde and ammonium acetate to obtain a mixture, adding the mixture into glacial acetic acid, heating to perform a reflux reaction, cooling to room temperature to obtain a reaction liquid, then adding the reaction liquid into water to obtain a mixed liquid, adjusting the pH of the mixed liquid to be neutral, filtering to obtain a precipitate, and obtaining a product 2;
(3) mixing phenanthroline, lithium chloride and ruthenium trichloride to obtain a mixture, adding dimethyl amide, heating to perform a reflux reaction, adding acetone until a precipitate is separated out, standing, filtering to obtain a precipitate, and obtaining a product 3;
(4) mixing the product 2 and the product 3 to obtain a mixture, then adding an ethanol aqueous solution, heating to perform a reflux reaction, adding a saturated sodium perchlorate solution until a precipitate is separated out, and filtering to obtain a precipitate to obtain a product 4;
(5) adding cellulose into dimethyl amide, adding N-tert-butyloxycarbonyl glycine, triethylamine, diimine hydrochloride and 4-dimethylamino pyridine to obtain a mixture, reacting at room temperature, adding water, filtering to obtain a filtrate, dialyzing, collecting a retention solution, and freeze-drying to obtain a product 5
(6) Adding the product 5 in the step (5) into dimethyl amide, uniformly dispersing, adding the product 4, N' -diisopropylcarbodiimide and 1-hydroxybenzotriazole, mixing to obtain a mixture, reacting at room temperature, adding water, filtering to obtain a filtrate, dialyzing, taking a retention solution, and freeze-drying to obtain a product 6;
(7) and (3) adding the product 6 obtained in the step (6) into methanol, adding theasapogenin, heating for reflux reaction, removing the methanol (evaporating the methanol), and crystallizing by using chloroform and absolute ethyl alcohol to obtain the photoactivated theasapogenin cellulose nano material.
Further, the mass ratio of the phenanthroline to the potassium bromide in the step (1) is 1: 1-1: 1.5; the mass of the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 6-10 times of that of the mixture of phenanthroline and potassium bromide, and the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of concentrated sulfuric acid and concentrated nitric acid is (1-3) to 1; the temperature of the reflux reaction is 80-110 ℃, and the time of the reflux reaction is 2-4 h; the volume of the water is 2-5 times of the volume of the reaction liquid; the extraction is carried out by adopting trichloromethane, and the volume of the trichloromethane is 1-5 times of the volume of the filtrate.
Preferably, in the mixed solution of concentrated sulfuric acid and concentrated nitric acid in the step (1), the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 2: 1.
Preferably, in step (1), the pH of the mixed solution is adjusted to neutral by using a saturated sodium hydroxide solution.
Further, the mass ratio of the product 1 in the step (2) to the o-carboxybenzaldehyde is (1-3) to 1; the mass of the ammonium acetate is 5-10 times of that of the product 1; the mass of the glacial acetic acid is 5-10 times of the mass of the mixture of the product 1, the o-carboxybenzaldehyde and the ammonium acetate; the temperature of the reflux reaction is 80-120 ℃, and the time of the reflux reaction is 2-4 h; the volume of the water is 2-5 times of the volume of the glacial acetic acid.
Preferably, the mass ratio of the product 1 to the o-carboxybenzaldehyde in the step (2) is 1: 1.
Preferably, in step (2), the pH of the mixed solution is adjusted to neutral, and ammonia water may be used for adjustment.
Further, the mass ratio of the phenanthroline to the lithium chloride in the step (3) is (1-3) to 1; the mass ratio of the o-phenanthroline to the ruthenium trichloride is (1-3) to 1; the mass of the dimethyl amide is 3-6 times of the mass of the mixture of the phenanthroline, the lithium chloride and the ruthenium trichloride; the temperature of the reflux reaction is 120-150 ℃, and the time of the reflux reaction is 3-6 h; the standing time is 8-24h, and the standing temperature is 0-10 ℃.
Preferably, the mass ratio of the phenanthroline to the lithium chloride in the step (3) is 1: 1.
Preferably, the mass ratio of the phenanthroline to the ruthenium trichloride in the step (3) is 1: 1.
Further, the molar ratio of the product 2 to the product 3 in the step (4) is (1-3): 1; the volume percentage concentration of the ethanol aqueous solution is 30-50%, and the mass of the ethanol aqueous solution is 6-12 times of that of the mixture of the product 2 and the product 3; the temperature of the reflux reaction is 80-120 ℃, and the time of the reflux reaction is 4-6 h.
Preferably, the molar ratio of the product 2 to the product 3 in the step (4) is 1: 1.
Preferably, the ethanol aqueous solution in the step (3) has a concentration of 30% by volume.
Further, the mass of the dimethyl amide in the step (5) is 10-20 times of that of the cellulose; the mass of the N-tert-butyloxycarbonyl glycine, the triethylamine, the diimine hydrochloride and the 4-dimethylaminopyridine is 1/5-1/10 of that of the cellulose; the reaction time at room temperature is 24-72h, and the mass of the water is 1-3 times of that of the mixture; the molecular weight cut-off of the dialysis bag obtained in the dialysis use is 50-200kDa, the dialysis time is 24-72 hours, and the dialysate used in the dialysis is water.
Preferably, the cellulose in the step (5) is more than one of microcrystalline cellulose, plant cellulose and bacterial cellulose, and the molecular weight of the cellulose is 30-200 kDa.
Further, the mass of the dimethyl amide in the step (6) is 10-20 times of that of the product 5; the mass of the product 4, the N, N' -diisopropylcarbodiimide and the 1-hydroxybenzotriazole is 1/10-1/20 of the mass of the product 5; the reaction time at room temperature is 24-72 h; the mass of the water is 1-3 times of that of the mixture; the molecular weight cut-off of the dialysis bag obtained in the dialysis use is 50-200kDa, the dialysis time is 24-72 hours, and the dialysate used in the dialysis is water.
Further, the mass of the methanol in the step (7) is 10-20 times of that of the product 6; the weight of the tea sapogenin is 0.5-2 times of that of the product 6; the temperature of the reflux reaction is 50-70 ℃, and the time of the reflux reaction is 2-6 h.
The theasapogenin is a product of tea saponin after acid-base hydrolysis. The preparation of the tea sapogenin can be carried out according to the literature (populus, the preparation of the photoresponse tea sapogenin derivative cationic liposome and the antibacterial activity research thereof, master academic thesis of southern China university, 2018).
The theasapogenin is a product obtained by acid or alkali hydrolysis of theasaponin, is a pentacyclic triterpenoid with aldehyde group, and has a chemical formula C30H48O6。
The photoactivated tea sapogenin cellulose nano material provided by the invention can be applied to preparation of antibacterial auxiliary materials or drug carriers.
The photoactivated theasapogenin cellulose nano material provided by the invention has the activity of resisting drug-resistant bacteria under the irradiation of blue light.
In the preparation method provided by the invention, o-phenanthroline is oxidized by mixed acid to obtain 1, 10-o-phenanthroline-5, 6-diketone (product 1), and the 1, 10-o-phenanthroline reacts with o-carboxybenzaldehyde and ammonium acetate to obtain 2- (2-carboxyl phenyl) imidazo [4,5-f ] -1,10 phenanthroline (product 2); phenanthroline and ruthenium can be combined under the action of lithium chloride to generate phenanthroline ruthenium complex (product 3), and then the phenanthroline ruthenium complex is connected with the product 2 to obtain phenanthroline acenyl imidazole ruthenium complex (product 4); cellulose and N-tert-butyloxycarbonyl glycine generate glycine-cellulose ester (product 5) under the action of a catalyst, then are connected with product 4 to generate glycine-cellulose ester phenanthroline ruthenium complex (product 6), and finally, the amino group of the glycine-cellulose ester phenanthroline ruthenium complex reacts with theasapogenin aldehyde group to generate theasapogenin cellulose phenanthroline ruthenium complex (product 7).
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method of the photoactivated theasapogenin cellulose nano material, the theasapogenin and phenanthroline ruthenium complex are fixed on a cellulose carrier to form a new compound, so that the stability of the theasapogenin and the phenanthroline ruthenium complex is improved, and the theasapogenin and the phenanthroline ruthenium complex can be activated and released under the action of blue light, so that the photoactivated antibacterial effect is realized;
(2) the preparation method provided by the invention has the advantages of mild reaction conditions, simple preparation process and convenience for industrial production.
Drawings
FIG. 1 is a graph comparing the IR spectra of product 5 and product 6 with cellulose;
FIG. 2 is a comparison graph of infrared spectra of product 7 and theasapogenin.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
(1) 5g of phenanthroline and 5g of potassium bromide are mixed, 60g of mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio is 2:1) is added, the mixture is heated to 80 ℃ and refluxed for 4 hours, the mixture is cooled to room temperature, the mixed solution is poured into 120mL of water, saturated sodium hydroxide solution is added to adjust the solution to be neutral, the solution is filtered, 600mL of trichloromethane is used for extraction of filtrate, and the solvent of the extract is evaporated to obtain a product 1(5.8 g).
(2) 5g of product 1 together with 5g of o-carboxybenzaldehyde and 50g of ammonium acetate are dissolved in 600g of glacial acetic acid, heated to 80 ℃ under reflux for 4h, cooled to room temperature, the mixture is poured into 3000mL of water, the solution is neutralized with ammonia and filtered, and the precipitate is retained as product 2(8.2 g).
(3) 5g of phenanthroline, 5g of lithium chloride and 5g of ruthenium trichloride are mixed, 45g of dimethylamide is added, the mixture is heated to 120 ℃ for reflux reaction for 6h, acetone is added until precipitate is separated out, the mixture is placed at 10 ℃ for 24h, and the precipitate is filtered and is reserved as a product 3(7.6 g).
(4) 3.4g of product 2 were mixed with 5.3g of product 3, dissolved in 104g of a 30% strength by volume aqueous ethanol solution, refluxed at 120 ℃ for 4h, and then precipitated by addition of a saturated sodium perchlorate solution, and the precipitate was filtered to give product 4(8.5 g).
(5)5g of cellulose (microcrystalline cellulose with molecular weight of 30 kDa) is dispersed in 100g of dimethylformamide, 1g of N-tert-butoxycarbonylglycine, 1g of triethylamine, 1g of diimine hydrochloride and 1g of 4-dimethylaminopyridine are added, reaction is carried out at room temperature for 24h, 320mL of water is added, filtration is carried out, the filtrate is dialyzed with water for 24h (the molecular weight cut-off is 50kDa), and freeze drying is carried out to obtain a product 5(4.8 g).
(6) 3g of product 5 are dispersed in 60g of dimethylformamide, 0.3g of product 4, 0.3g of 0.3g N, N' -diisopropylcarbodiimide and 0.3g of 1-hydroxybenzotriazole are added, the reaction is carried out at room temperature for 24h, 190mL of water are added, filtration is carried out, the filtrate is dialyzed against water for 24h (molecular weight cut-off 50kDa) and the product 6(3.6g) is obtained by freeze-drying.
(7) Dispersing 3g of the product 6 in 60g of methanol, adding 1.5g of tea sapogenin, refluxing at 70 ℃ for 2h, evaporating the methanol, and crystallizing by using chloroform and absolute ethyl alcohol to obtain 4.2g of a final product (a product 7, a light-activated tea sapogenin cellulose nano material).
Example 2
(1) 5g of phenanthroline and 7.5g of potassium bromide are mixed, 100g of mixed solution of concentrated sulfuric acid and concentrated nitric acid (volume ratio is 1:1) is added, the mixture is heated to 110 ℃ and refluxed for 2 hours, the mixture is cooled to room temperature, the mixed solution is poured into 500mL of water, saturated sodium hydroxide solution is added to adjust the solution to be neutral, the solution is filtered, the filtrate is extracted by 500mL of trichloromethane, and the solvent of the extract is evaporated to obtain a product 1(5.6 g).
(2) 5g of product 1, together with 2.5g of o-carboxybenzaldehyde and 100g of ammonium acetate, are dissolved in 538g of glacial acetic acid, heated to 120 ℃ under reflux for 2h, cooled to room temperature, the mixture is poured into 1100mL of water, the solution is neutralized with ammonia and filtered, and the precipitate is retained as product 2(8.5 g).
(3) 5g of phenanthroline, 2.5g of lithium chloride and 2.5g of ruthenium trichloride are mixed, 60g of dimethyl amide is added, the mixture is heated to 150 ℃ for reflux reaction for 3h, acetone is added until a precipitate is separated out, the mixture is placed at 0 ℃ for 8h, and the precipitate is filtered to obtain a product 3(7.8 g).
(4) 6.8g of product 2 were mixed with 5.3g of product 3, dissolved in 75g of 40% by volume aqueous ethanol, refluxed at 80 ℃ for 6h, and then precipitated by addition of saturated sodium perchlorate solution, and the precipitate was filtered to give product 4(8.3 g).
(5)5g of cellulose (bacterial cellulose with the molecular weight of 100kDa) is dispersed in 50g of dimethyl amide, 0.5g of N-tert-butyloxycarbonyl glycine, 0.5g of triethylamine, 0.5g of diimine hydrochloride and 0.5g of 4-dimethylaminopyridine are added, the mixture is reacted for 72h at room temperature, 177mL of water is added, the mixture is filtered, the filtrate is dialyzed for 72h (the molecular weight cut-off is 100kDa) with water, and the product 5(4.3g) is obtained by freeze drying.
(6) 3g of product 5 are dispersed in 30g of dimethylformamide, 0.15g of product 4, 0.15g of 0.15g N, N' -diisopropylcarbodiimide and 0.15g of 1-hydroxybenzotriazole are added, reaction is carried out at room temperature for 72h, 100mL of water are added, filtration is carried out, the filtrate is dialyzed against water for 72h (molecular weight cut-off 100kDa) and freeze-dried to give product 6(3.2 g).
(7) Dispersing 3g of product 6 in 30g of methanol, adding 6g of tea sapogenin, refluxing at 50 ℃ for 6h, evaporating the methanol, and crystallizing with chloroform and absolute ethanol to obtain a final product of 4.8g (product 7, light-activated tea sapogenin cellulose nano material).
Example 3
(1) 5g of phenanthroline and 6g of potassium bromide are mixed, 80g of mixed liquor of concentrated sulfuric acid and concentrated nitric acid (the volume ratio is 3:1) is added, the mixture is heated to 100 ℃ and refluxed for 3 hours, the mixture is cooled to room temperature, the mixed liquor is poured into 250mL of water, saturated sodium hydroxide solution is added to adjust the solution to be neutral, the solution is filtered, the filtrate is extracted by 750mL of trichloromethane, and the extract liquor is evaporated to remove the solvent to obtain a product 1(5.3 g).
(2) 5g of product 1 together with 1.7g of o-carboxybenzaldehyde and 40g of ammonium acetate are dissolved in 380g of glacial acetic acid, heated to 100 ℃ under reflux for 3h, cooled to room temperature, the mixture is poured into 1200mL of water, the solution is neutralized with ammonia water and filtered, and the precipitate is retained as product 2(7.5 g).
(3) 5g of phenanthroline, 1.7g of lithium chloride and 1.7g of ruthenium trichloride are mixed, 42g of dimethylamide is added, the mixture is heated to 140 ℃ for reflux reaction for 4 hours, acetone is added until a precipitate is separated out, the mixture is placed at 4 ℃ for 16 hours, and the precipitate is filtered and is reserved as a product 3(7.2 g).
(4) 10.2g of product 2 were mixed with 5.3g of product 3, dissolved in 155g of a 30% strength by volume aqueous ethanol solution, refluxed at 100 ℃ for 5h, and then precipitated by addition of a saturated sodium perchlorate solution, and the precipitate was filtered to give product 4(8.1 g).
(5)5g of cellulose (plant cellulose with molecular weight of 200kDa) is dispersed in 75g of dimethylformamide, 0.75g of N-tert-butyloxycarbonylglycine, 0.75g of triethylamine, 0.75g of diimine hydrochloride and 0.75g of 4-dimethylaminopyridine are added, the mixture is reacted for 48h at room temperature, 170mL of water is added, the mixture is filtered, the filtrate is dialyzed for 48h (molecular weight cut-off is 200kDa) with water, and the product 5(4.5g) is obtained by freeze drying.
(6) 3g of product 5 are dispersed in 45g of dimethylformamide, 0.2g of product 4, 0.2g of 0.2g N, N' -diisopropylcarbodiimide and 0.2g of 1-hydroxybenzotriazole are added, reaction is carried out at room temperature for 48h, 100mL of water are added, filtration is carried out, the filtrate is dialyzed against water for 48h (molecular weight cut-off 200kDa) and freeze-dried to give product 6(3.5 g).
(7) Dispersing 3g of the product 6 in 45g of methanol, adding 3g of tea sapogenin, refluxing at 60 ℃ for 4h, evaporating the methanol, and crystallizing by using chloroform and absolute ethyl alcohol to obtain 4.5g of a final product (a product 7, a light-activated tea sapogenin cellulose nano material).
Example 4
The method comprises the following steps: 300g of the final product obtained in example 1 was taken and mixed with 300kg of chicken or pig feed for feeding 30 chickens (300 + -30 g) suffering from bacterial enteritis and 10 pigs (2 + -0.2 kg) suffering from bacterial enteritis at a dose of 0.1g of the final product/100 g of the final product and 0.5g of the final product/kg of the pigs per day, and continuously fed for 10 days and irradiated with blue light (400-450nm) for 60 min. The untreated group and the blue control group (only blue light was irradiated, but the final product prepared in example 1 was not fed) were set. The animal status and weight changes before and after treatment were compared.
As a result: the results are shown in Table 1. After the final product of the example 1 is fed and irradiated with light, diarrhea, inactive feeding and cachexia of animals can be eliminated, the weight gain is obvious, and the control group has no obvious change, which shows that the final product of the example 1 can effectively prevent and treat enteritis and promote the growth of chickens or pigs.
TABLE 1 control of enteritis in chickens and pigs by the final product of example 1
Figure BDA0002696759510000081
Example 5
And (3) adding 1000mL of water into 10g of the final product prepared in the embodiment 1-3 to prepare emulsion, adding 1g of antibacterial peptide, stirring at 3000 r/min for 10min, and freeze-drying to obtain the antibacterial peptide drug-loaded nanoparticles.
Test 1
Structural characterization of the products obtained in examples 1-3
The method comprises the following steps: the products 1 to 7 obtained in examples 1 to 3 were structurally characterized by infrared and nuclear magnetic resonance.
As a result: the products 1 to 7 are successfully synthesized, and the molecular structure of the target product is obtained.
Product 1: IR (KBr): 3060, 1683, 1575, 1560, 1460, 1413, 1311, 1290, 1203, 1115, 1008, 923, 875, 802, 737cm-1.1HNMR(DMSO-d6,400MHz)：9.0(s,2H)，8.4(dd,2H)，7.68(s,2H).
And (3) a product 2: IR (KBr): 3428, 2971, 2895, 1693, 1572, 1465, 1414, 1302, 1297cm-1；1H NMR(DMSO-d6,400MHz)：7.65(m,1H)，7.74(m,1H)，7.83(m,2H)，7.94(m,2H)，8.82(s，2H)，8.83(s,2H)，9.03(d,2H).
And (3) a product: IR (KBr): 3409, 2977, 2396, 2351, 1423, 1049cm-1.
And (3) a product 4:1HNMR(DMSO-d6,400MHz)：7.49(s,1H)，7.61(s,1H)，7.77(s,4H)，7.94(m,1H)，8.08(s，2H)，8.14(s,1H)，8.20(d,2H)，8.22(d,2H)，8.40(s,3H)，8.73(m，1H)，8.76(d，2H)，8.86(d，1H).
product 5 had a depth of 3350cm-1And 3280cm-1Characteristic peak of amino group, 1745cm-1Characteristic peak of carbon-oxygen double bond, 1160cm-1And 1056cm-1Symmetric and asymmetric stretching vibration of carbon-oxygen-carbon. Thus, glycine successfully esterified with nanocellulose. Product 6 had a depth of 3340cm-1Nitrogen-hydrogen stretching vibration peak, 1745cm-1Characteristic peak of carbon-oxygen double bond, 1546cm-1Characteristic peak of carbon-carbon double bond of 1370cm-1And imidazole characteristic peaks show that a product 5 is connected with a product 4 through amidation reaction to synthesize the target compound. See figure 1.
The product 7 is at 3250-3450cm-1The absorption peaks of the regions are mainly hydroxyl absorption peaks and N-H stretching vibration peaks on imidazole and amido bonds. 2920cm-1Characteristic peak of methyl group, 1774cm-1And 1750cm-1Is a characteristic peak of ester bonds and amido bonds, and is 1685-1560 cm-1Is the stretching vibration peak of C-N and C-C, 1430-1320 cm-1Bending vibration peak of C-CH and C-N stretching vibration peak on imidazole ring, 1160-1030 cm-1Is the C-O-H bending vibration peak. The product 6 is successfully connected with the theasapogenol to synthesize the target compound. See figure 2.
Test 2
Drug-resistant bacterium resistance test of end product 7 obtained in example 1
The method comprises the following steps:
adding amoxicillin-resistant staphylococcus aureus liquid (final concentration is 1 × 10) into a 96-well 2-plate8CFU/mL), 100 μ L per well, a total of 144 wells; coli solution (final concentration 1X 10) was added to another 2-well 96-well plate8CFU/mL), a total of 144 wells were added; amoxicillin, theasapogenin and the final product 7 prepared in example 1 were added to wells containing amoxicillin-resistant staphylococcus aureus solutions, respectively, at final concentrations of 128, 64, 32, 16, 8, 4, 2 and 0 μmol/L for each drug, and at 6 wells for each concentration. The medicines are respectively added into the holes filled with the escherichia coli liquid, and the concentration setting and the number of the medicine adding holes are the same as those of the holes filled with the amoxicillin-resistant staphylococcus aureus liquid;
the experiment is divided into 6 groups, namely an experiment group of amoxicillin, theasapogenin and a final product 7 prepared in example 1 under the illumination condition and an experiment group without the illumination condition, each group is provided with 12 holes, wherein 6 holes are inoculated with amoxicillin-resistant staphylococcus aureus bacterial liquid (3 are cultured under the illumination condition, the other 3 are cultured under the non-illumination condition), 6 holes are inoculated with escherichia coli bacterial liquid (3 are cultured under the illumination condition, and the other 3 are cultured under the non-illumination condition)Cultured under the same conditions). After adding the drug, incubating for 0.5h at 37 ℃ in a constant temperature oscillator. Then, 40. mu.L of the mixture (culture medium) was taken from each well, and diluted 10 times with PBS buffer6And (4) respectively inoculating the bacterial colonies to MHA agar plates, culturing the bacterial colonies for 24 hours at 37 ℃ in the dark, and observing the growth condition of the bacterial colonies, wherein the minimum inhibitory concentration is aseptic growth.
As a result: the amoxicillin can not inhibit the growth of bacteria under both illumination and non-illumination, the minimum inhibitory concentration of the theasapogenin to escherichia coli and staphylococcus aureus under both illumination and non-illumination is 128 mu mol/L, while the minimum inhibitory concentration of the product 7 under non-illumination is 64 mu mol/L, and under illumination is 8 mu mol/L. The product of the invention has the function of photo-activation and drug-resistant bacteria resistance.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (2)

1.一种光活化茶皂苷元纤维素纳米材料，其特征在于，分子结构式如下所示：1. a light-activated tea saponin cellulose nanomaterial, is characterized in that, molecular structural formula is as follows:
Figure FDA0003144884010000011
Figure FDA0003144884010000011
 2.权利要求1所述的光活化茶皂苷元纤维素纳米材料在制备抗菌辅料或药物载体中的应用。2. The application of the photoactivated teasapogenin cellulose nanomaterial of claim 1 in the preparation of antibacterial adjuvants or drug carriers.
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