CN116284496A - Curcumin-carboxylated chitosan connector and preparation method and application thereof - Google Patents
Curcumin-carboxylated chitosan connector and preparation method and application thereof Download PDFInfo
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- CN116284496A CN116284496A CN202310299901.4A CN202310299901A CN116284496A CN 116284496 A CN116284496 A CN 116284496A CN 202310299901 A CN202310299901 A CN 202310299901A CN 116284496 A CN116284496 A CN 116284496A
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Abstract
The invention discloses a curcumin-carboxylated chitosan connector, a preparation method and application thereof, wherein a new binding site is introduced by modifying chitosan, so that grafting modification with curcumin is realized, the purposes of improving the water solubility and stability of curcumin while coupling curcumin are achieved.
Description
Technical Field
The invention belongs to the technical field of modification of bioactive substances, and particularly relates to a curcumin-carboxylated chitosan connector and a preparation method and application thereof.
Background
With the improvement of the living standard and the enhancement of the safety consciousness of people, some natural additives which are safe, nontoxic and green are more and more favored by people.
Curcumin (Cur, C) 21 H 20 O 6 ) Is a natural fat-soluble compound with low relative molecular weight extracted from turmeric, is a rare pigment with diketone in plant kingdom, is a diketone chemical, and is currently commonly applied in the fields of food and medicines, such as:
curcumin is orange yellow crystal powder, has slightly bitter taste, is insoluble in water, is a natural yellow pigment, and is mainly used for coloring sausage products, cans, marinated products and the like in food production;
curcumin also has various nutrition and pharmacological functions such as anti-inflammatory, anti-tumor, antioxidant, antiviral, anti-infection, anticoagulation, anti-hepatic fibrosis, antibacterial, anti-atherosclerosis and the like, so that the curcumin can be widely applied in the fields of medicines, foods and the like;
however, curcumin has low solubility, so that it has low absorption in vivo and low bioavailability, and can be degraded due to the change of certain conditions in the food processing process, so that the application of curcumin in foods and medicines is severely limited.
Chitosan is a natural ionic polymer obtained by deacetylation of chitin, is an alkaline polysaccharide with positive charges on the surface, has good biocompatibility and biodegradability, is nontoxic, and has-NH 2 and-OH, which can be modified in a variety of ways.
In view of the defects of curcumin, the invention provides a preparation method of a curcumin-chitosan connector, which enhances the water solubility and stability of the curcumin-chitosan connector and the oxidation resistance in water, so that the curcumin-chitosan connector has better utilization value in the fields of medicine, food, cosmetics, agriculture and the like.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a curcumin-carboxylated chitosan connector, wherein the curcumin-chitosan connector has a chemical structural formula shown in a formula A;
wherein x=0.1, y=0.9, and R1 is-CH 2 OH, -COOH or curcumin group, wherein the structural formula of the curcumin group is shown as a formula B;
the invention further aims to overcome the defects in the prior art and provide a preparation method of the curcumin-carboxylated chitosan connector.
In order to solve the technical problems, the invention provides the following technical scheme: comprising the steps of (a) a step of,
dissolving carboxylated chitosan in dimethyl sulfoxide aqueous solution, stirring, and adding a catalyst to obtain carboxylated chitosan solution;
dissolving curcumin in dimethyl sulfoxide aqueous solution, and stirring to obtain curcumin aqueous solution;
adding curcumin water solution into carboxylated chitosan solution, performing esterification reaction, filtering after the reaction is finished, discarding precipitate, sequentially dialyzing supernatant in dimethyl sulfoxide and deionized water, freezing, and drying to obtain curcumin-chitosan connector.
As a preferred scheme of the preparation method of the curcumin-carboxylated chitosan connector, the preparation method comprises the following steps: the preparation method of the carboxylated chitosan comprises the steps of,
dissolving 2, 6-tetramethyl piperidine-1-oxygen free radical and sodium bromide in deionized water, adding chitosan, stirring to obtain suspension, adding sodium hypochlorite, mixing, carboxylating, centrifuging after the reaction is finished, discarding precipitate, dialyzing supernatant in deionized water, freezing, and drying to obtain carboxylated chitosan.
As a preferred scheme of the preparation method of the curcumin-carboxylated chitosan connector, the preparation method comprises the following steps: the carboxylation reaction is carried out at the reaction temperature of 20-35 ℃ for 2.5-4 h.
As a preferred scheme of the preparation method of the curcumin-carboxylated chitosan connector, the preparation method comprises the following steps: the catalyst is compounded by N, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine.
As a preferred scheme of the preparation method of the curcumin-carboxylated chitosan connector, the preparation method comprises the following steps: the molar ratio of the N, N' -dicyclohexylcarbodiimide, the 4-dimethylaminopyridine and the curcumin is 1:0.25:0.1-0.15.
As a preferred scheme of the preparation method of the curcumin-carboxylated chitosan connector, the preparation method comprises the following steps: the mass ratio of the carboxylated chitosan to the curcumin is 5-10:1.
As a preferred scheme of the preparation method of the curcumin-carboxylated chitosan connector, the preparation method comprises the following steps: the esterification reaction is heated by water bath, wherein the reaction temperature is 35-40 ℃ and the reaction time is 12h.
As a preferred embodiment of the curcumin-carboxylated chitosan linker of the present invention, wherein: the curcumin-carboxymethyl chitosan connector is a water-soluble material and has stability and antioxidant activity.
It is a further object of the present invention to overcome the deficiencies of the prior art and to provide the use of curcumin-carboxylated chitosan conjugates, including, the conjugates which can be used in the medical, food, cosmetic and agricultural fields for food coloring, antibacterial, antioxidant.
The invention has the beneficial effects that:
(1) The invention provides a curcumin-carboxylated chitosan connector, which adopts aqueous-organic phase biphasic reaction, realizes grafting of curcumin on carboxylated chitosan molecules for the first time through DCC/DMAP-mediated catalytic reaction, obtains a curcumin water-soluble material, achieves the purposes of coupling curcumin and improving curcumin water solubility and stability, and has better stability compared with physical loading of curcumin by chitosan.
(2) The curcumin-carboxymethyl chitosan connector is a water-soluble material, has excellent stability and antioxidant activity, solves the defects of low curcumin solubility, low in vivo absorption, low bioavailability and limited application in the prior art, and greatly expands the application range of curcumin.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is an infrared spectrum of carboxylated chitosan in example 1 of the present invention.
FIG. 2 is an infrared spectrum of curcumin-carboxylated chitosan conjugate in example 1 of the present invention.
FIG. 3 is a carboxylated chitosan according to example 1 of the present invention 1 H NMR chart.
FIG. 4 shows curcumin-carboxylated chitosan in example 1 of the present invention 1 H NMR chart.
FIG. 5 is a reaction scheme of curcumin-carboxylated chitosan of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The molecular weight of the chitosan used in the invention is 50000Da, the deacetylation degree is 90%, and the other raw materials are all commonly and commercially available unless specified.
Example 1
1) Preparing carboxylated chitosan:
dissolving 0.040g of 2, 6-tetramethylpiperidine-1-oxygen free radical and 0.800g of sodium bromide in 100mL of deionized water, adding 2.000g of chitosan, stirring to obtain suspension, adding 40mL of sodium hypochlorite, carrying out carboxylation reaction at 25 ℃ after mixing, finishing the reaction after 4 hours, centrifuging, discarding the precipitate, dialyzing the supernatant in deionized water for 72 hours, freezing and drying to obtain carboxylated chitosan;
2) Preparing curcumin-carboxylated chitosan linker:
the mass ratio of the carboxylated chitosan to the curcumin is 10:1;
dissolving 0.200g of carboxylated chitosan in a mixed solution of dimethyl sulfoxide and water, stirring to obtain a carboxylated chitosan solution, adding 0.148g of N, N' -dicyclohexylcarbodiimide and 0.022g of 4-dimethylaminopyridine, and reacting for 2 hours at 35 ℃ to activate carboxyl;
0.020g of curcumin is dissolved in dimethyl sulfoxide, added into the activated carboxylated chitosan solution, mixed, stirred in a water bath at 35 ℃ for reaction in a dark place for 12 hours for esterification reaction, filtered after the reaction is finished, the precipitate is removed, and the supernatant is dialyzed, frozen and dried in sequence in dimethyl sulfoxide and deionized water to obtain the curcumin-carboxylated chitosan connector, which is denoted as COCS-Cur-1.
The linker prepared in this embodiment was characterized using infrared spectroscopy and nuclear magnetic resonance hydrogen spectroscopy.
FIG. 1 is an infrared spectrum of carboxylated chitosan used in this example, at 1618cm -1 And 1403cm -1 Two new bands were observed at this point, which were carboxyl groups (COO - ) Characteristic peaks of symmetrical and asymmetrical modes of stretching vibration. At the same time, since the primary hydroxyl group at the C-6 position is converted into C-6 carboxyl group by oxidation, COCS can be seen at 2929cm -1 The reduction in C-H stretch bands at the sites, both demonstrated successful synthesis of COCS.
FIG. 2 is an infrared spectrum of a curcumin-carboxylated chitosan linker of this example, 3417cm -1 The peak at this point is sharper than chitosan due to the stretching vibration of the phenolic hydroxyl groups contained in part of curcumin, 2932cm -1 And 2863cm -1 The peak at 1216cm is the stretch of aliphatic C-H in curcumin -1 The peak at the position is attributed to the stretching vibration of C-O in the ester bond of the conjugate, which proves that the target product is successfully synthesized.
FIG. 3 is a carboxylated chitosan of this example 1 H NMR chart, δ=2.06 ppm ascribed to chemical shift of acetyl group on acetamido glucose residue, 3.16-4.55 ppm ascribed to chemical shift of hydrogen atom on chitosan glycoside ring.
FIG. 4 is a curcumin-chitosan conjugate of the present example 1 H NMR chart showing correlation of curcumin aromatic ring protons at 6-7ppmCharacteristic peaks prove the successful synthesis of the target product.
Example 2
The difference between this example and example 1 is that the mass ratio of carboxylated chitosan to curcumin is adjusted to 7:1, and the rest of the preparation process is the same as example 1, specifically:
1) Preparing carboxylated chitosan: the molecular weight of chitosan is 50000Da, and the deacetylation degree is 90%.
Dissolving 0.040g of 2, 6-tetramethylpiperidine-1-oxygen free radical and 0.800g of sodium bromide in 100mL of deionized water, adding 2.000g of chitosan, stirring to obtain suspension, adding 40mL of sodium hypochlorite, carrying out carboxylation reaction at 25 ℃ after mixing, finishing the reaction after 4 hours, centrifuging, discarding the precipitate, dialyzing the supernatant in deionized water for 72 hours, freezing and drying to obtain carboxylated chitosan;
2) Preparing curcumin-carboxymethyl chitosan connector:
the mass ratio of the carboxylated chitosan to the curcumin is 7:1.
Dissolving 0.200g of carboxylated chitosan in a mixed solution of dimethyl sulfoxide and water, stirring to obtain a carboxylated chitosan solution, and then adding 0.148g of N, N' -dicyclohexylcarbodiimide and 0.022g of 4-dimethylaminopyridine to react for 2 hours to activate carboxyl;
0.029g of curcumin is dissolved in dimethyl sulfoxide, added into the activated carboxylated chitosan solution, mixed, stirred in a water bath at 35 ℃ for reaction in a dark place for 12 hours for esterification reaction, filtered after the reaction is finished, the precipitate is discarded, and the supernatant is dialyzed, frozen and dried in dimethyl sulfoxide and deionized water in sequence to obtain a curcumin-carboxymethyl chitosan connector, which is denoted as COCS-Cur-2.
Example 3
The difference between this example and example 1 is that the mass ratio of carboxylated chitosan to curcumin is adjusted to 5:1, and the rest of the preparation process is the same as example 1, specifically:
1) Preparing carboxylated chitosan: the molecular weight of chitosan is 50000Da, and the deacetylation degree is 90%.
Dissolving 0.040g of 2, 6-tetramethylpiperidine-1-oxygen free radical and 0.800g of sodium bromide in 100mL of deionized water, adding 2.000g of chitosan, stirring to obtain suspension, adding 40mL of sodium hypochlorite, carrying out carboxylation reaction at 25 ℃ after mixing, finishing the reaction after 4 hours, centrifuging, discarding the precipitate, dialyzing the supernatant in deionized water for 72 hours, freezing and drying to obtain carboxylated chitosan;
2) Preparing curcumin-carboxymethyl chitosan connector:
the mass ratio of the carboxylated chitosan to the curcumin is 5:1.
Dissolving 0.200g of carboxylated chitosan in a mixed solution of dimethyl sulfoxide and water, stirring to obtain a carboxylated chitosan solution, and then adding 0.148g of N, N' -dicyclohexylcarbodiimide and 0.022g of 4-dimethylaminopyridine to react for 2 hours to activate carboxyl;
0.040g of curcumin is dissolved in dimethyl sulfoxide, added into the activated carboxylated chitosan solution, mixed, stirred in a water bath at 35 ℃ for reaction in a dark place for 12 hours for esterification, filtered after the reaction is finished, the precipitate is discarded, and the supernatant is dialyzed, frozen and dried in dimethyl sulfoxide and deionized water in sequence to obtain a curcumin-carboxymethyl chitosan connector, which is denoted as COCS-Cur-3.
Example 4
The present example was used to determine the antioxidant activity of curcumin-carboxymethyl chitosan conjugate prepared in the present invention, including the in vitro scavenging effect of the conjugate on DPPH radicals and ABTS radicals, by the following method:
test method for in vitro scavenging test of DPPH free radical:
dissolving curcumin-carboxymethyl chitosan connector in water, uniformly mixing to obtain curcumin-carboxymethyl chitosan solution, adding 1mL of curcumin-carboxymethyl chitosan connector solution with the concentration of 2.1mg/mL into 1mL of DPPH solution with the concentration of 0.06mg/mL as a liquid to be detected, vibrating and uniformly mixing, incubating for 30min at room temperature in the dark, and measuring absorbance at 517 nm.
The curcumin-carboxymethyl chitosan linker in the blank group was replaced with 1mL of water, and all operations were performed at room temperature in the dark.
DPPH free clearance (%) = (a-B)/a×100. Wherein A is the absorbance of the blank control group, and B is the absorbance of the liquid to be measured.
Test method for in vitro scavenging test of ABTS free radicals:
1mL of 7mM ABTS solution and 3mL of 2.45mM potassium persulfate solution are incubated for 16h in dark place, ABTS+ is generated by the reaction, a probe stock solution is obtained, and then the stock solution is diluted with water until the absorbance at 734nm is 0.7+/-0.1. In the experiment, the curcumin-carboxymethyl chitosan connector is dissolved in water, uniformly mixed to obtain curcumin-chitosan connector solution, 1mL of the curcumin-carboxymethyl chitosan connector solution with the concentration of 2.1mg/mL is added into 1mL of diluted stock solution to be used as a liquid to be detected, after shaking and uniformly mixing, the mixture is incubated in the dark at room temperature for 8min, and then the absorbance at 734nm is measured.
The curcumin-chitosan conjugate was replaced with 1mL of water in the blank, and all procedures were performed at room temperature in the dark.
ABTS radical clearance (%) = (a-B)/a×100. Wherein A is the absorbance of the blank control group, and B is the absorbance of the liquid to be measured.
The test results of the above test are shown in table 1.
Table 1 antioxidant Activity of the products
As can be seen from Table 1, the curcumin-carboxymethyl chitosan connector prepared by the invention has good antioxidant activity at different concentrations. And along with the increase of the coupling proportion of curcumin, the antioxidation activity of the connector is also continuously increased, but along with the increase of the grafting proportion, the enhancement amplitude of the antioxidation activity is weakened, and the COCS-Cur-2 is the best choice for realizing good effect in consideration of the problems of cost waste and the like.
Example 5
This example was used to determine the stability of curcumin-carboxymethyl chitosan linker:
the stability of curcumin-carboxymethyl chitosan conjugate was measured at different temperatures (30 ℃, 50 ℃, 80 ℃) and under light (ultraviolet, dark, natural light) conditions. Curcumin-carboxymethyl chitosan conjugate is dissolved in water, and after incubation for 12 hours under corresponding conditions, ultraviolet absorption of the sample at 425nm is measured, so that the curcumin retention rate is obtained, and the result is shown in table 2.
TABLE 2 Retention of curcumin under different conditions
As can be seen from Table 2, the curcumin-carboxymethyl chitosan prepared by the invention has excellent thermal stability and photostability compared with curcumin, and the connectors can still maintain higher stability along with the rising of the coupling ratio of curcumin.
Example 6
This example was used to determine the solubility of curcumin-carboxymethyl chitosan linker in water:
weighing excessive m 1 Adding the curcumin-chitosan connector into a centrifuge tube filled with 5mL of ultrapure water and dried in advance to constant weight, so that the solution is in a supersaturated state, and marking the mass of an empty centrifuge tube as m 0 g, continuously oscillating the mixed solution for 12 hours at room temperature, then reserving sediment through centrifugation, drying the sediment and a centrifuge tube to constant weight, and recording the total mass at the moment as m 2 g. The test was set up in triplicate. The solubility of the sample in water was calculated as follows:
S＝(m 0 +m 1 -m 2 )×20
wherein S is the solubility of the sample in water, g/100mL H2O; m is m 0 G is the mass of the centrifuge tube; m is m 1 G is the mass of a sample to be detected; m is m 2 G is the mass of the centrifuge tube and undissolved sample.
TABLE 3COCS-Cur yield and Water solubility
As can be seen from Table 3, all three COCS-Cur obtained by the invention show good water solubility compared with curcumin, and the water solubility of the connector is obviously reduced along with the increase of the coupling ratio of curcumin. When tables 1 to 3 are combined, COCS-Cur-2 is the best choice when the stability is not greatly different.
In conclusion, the grafting of curcumin on carboxylated chitosan molecules is realized for the first time through the catalytic reaction mediated by DCC/DMAP, the curcumin water-soluble material is obtained, and compared with the prior art, the curcumin water-soluble material has higher stability in realizing physical load of curcumin by utilizing chitosan.
The curcumin-carboxymethyl chitosan connector is a water-soluble material, has excellent stability and antioxidant activity, solves the defects of low curcumin solubility, low in vivo absorption, low bioavailability and limited application in the prior art, and greatly expands the application range of curcumin.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A curcumin-carboxylated chitosan conjugate, characterized by: the curcumin-chitosan connector has a chemical structural formula shown in a formula A;
wherein x=0.1, y=0.9, and R1 is-CH 2 OH, -COOH or curcumin group, wherein the structural formula of the curcumin group is shown as a formula B;
2. a preparation method of a curcumin-carboxylated chitosan connector is characterized by comprising the following steps: comprising the steps of (a) a step of,
dissolving carboxylated chitosan in dimethyl sulfoxide aqueous solution, stirring, and adding a catalyst to obtain carboxylated chitosan solution;
dissolving curcumin in dimethyl sulfoxide aqueous solution, and stirring to obtain curcumin aqueous solution;
adding curcumin water solution into carboxylated chitosan solution, performing esterification reaction, filtering after the reaction is finished, discarding precipitate, sequentially dialyzing supernatant in dimethyl sulfoxide and deionized water, freezing, and drying to obtain curcumin-chitosan connector.
3. The method for preparing curcumin-carboxylated chitosan according to claim 2, characterized in that: the preparation method of the carboxylated chitosan comprises the steps of,
dissolving 2, 6-tetramethyl piperidine-1-oxygen free radical and sodium bromide in deionized water, adding chitosan, stirring to obtain suspension, adding sodium hypochlorite, mixing, carboxylating, centrifuging after the reaction is finished, discarding precipitate, dialyzing supernatant in deionized water, freezing, and drying to obtain carboxylated chitosan.
4. A method of preparing a curcumin-chitosan conjugate as claimed in claim 3, wherein: the carboxylation reaction is carried out at the reaction temperature of 20-35 ℃ for 2.5-4 h.
5. The method for preparing curcumin-carboxylated chitosan according to claim 2, characterized in that: the catalyst is compounded by N, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine.
6. A method of preparing a curcumin-carboxylated chitosan linker according to claim 2 or 3, characterized in that: the molar ratio of the N, N' -dicyclohexylcarbodiimide, the 4-dimethylaminopyridine and the curcumin is 1:0.25:0.1-0.15.
7. The method for preparing curcumin-carboxylated chitosan linker according to claim 2, characterized in that: the mass ratio of the carboxylated chitosan to the curcumin is 5-10:1.
8. The method for preparing curcumin-carboxylated chitosan linker according to claim 2, characterized in that: the esterification reaction is heated by water bath, wherein the reaction temperature is 35-40 ℃ and the reaction time is 12h.
9. The curcumin-carboxylated chitosan linker of claim 1, characterized in that: the curcumin-carboxymethyl chitosan connector is a water-soluble material and has stability and antioxidant activity.
10. Use of a curcumin-carboxylated chitosan linker according to claim 1 or 9, characterized in that: the connector can be applied to the fields of medicine, food, cosmetics and agriculture, and is used for food coloring, antibiosis and antioxidation.
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| CN102988999A (en) * | 2012-05-09 | 2013-03-27 | 中国药科大学 | Curcumin-polysaccharide conjugate as well as preparation method and application thereof |
| CN107952077A (en) * | 2017-12-15 | 2018-04-24 | 河南科技大学 | One kind improves the water miscible method of curcumin and application |
| CN114149516A (en) * | 2021-12-08 | 2022-03-08 | 齐鲁工业大学 | Chitosan derivative and preparation method and application thereof |
| CN114259466A (en) * | 2021-12-07 | 2022-04-01 | 华南理工大学 | Chitosan microemulsion for curcumin transdermal drug delivery and preparation method thereof |
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| CN102988999A (en) * | 2012-05-09 | 2013-03-27 | 中国药科大学 | Curcumin-polysaccharide conjugate as well as preparation method and application thereof |
| CN107952077A (en) * | 2017-12-15 | 2018-04-24 | 河南科技大学 | One kind improves the water miscible method of curcumin and application |
| CN114259466A (en) * | 2021-12-07 | 2022-04-01 | 华南理工大学 | Chitosan microemulsion for curcumin transdermal drug delivery and preparation method thereof |
| CN114149516A (en) * | 2021-12-08 | 2022-03-08 | 齐鲁工业大学 | Chitosan derivative and preparation method and application thereof |
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