Peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, preparation method and application thereof

Abstract

The invention discloses peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres and a preparation method thereof. 1 part by weight of hyperbranched peach gum polysaccharide, 0.5-5 parts by weight of cinnamic acid, 0.1-1 parts by weight of 4-dimethylaminopyridine, and 0.5-2 parts by weight of N,N-dicyclohexylcarbodiimide are dissolved in anhydrous N,N-dimethylformamide under a nitrogen atmosphere, reacted at room temperature for 24-48 hours, added with ice ethanol for precipitation, washed 3 times, and dried to constant weight in a 60-degree oven to obtain an amphiphilic hyperbranched peach gum polysaccharide-cinnamic acid copolymer. Subsequently, the copolymer is dissolved in an organic solvent, and when completely dissolved, water equivalent to 4-9 times the volume of the organic solvent is slowly dripped, and then dialyzed for 8-24 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres. The present invention also discloses the use of the peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres for loading chemotherapeutic drugs, photodynamic therapy agents or bioactive ingredients, and as delivery carriers of molecules and / or nanoparticles in the fields of food, cosmetics and medicine.

Description

Technical Field

[0001] The invention belongs to the field of nanotechnology, and particularly relates to peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, a preparation method and application thereof. Background Art

[0002] Natural polymer nanospheres have shown good application prospects in drug delivery, environmental governance, food, cosmetics and other fields due to their excellent biocompatibility and rich surface groups. Peach gum polysaccharide is a typical natural polysaccharide with similar characteristics to other polysaccharides, namely, good biocompatibility, biodegradability, rich reactive groups, etc., and is suitable for preparing nanospheres that can load functional substances (such as drug molecules, food additives, fluorescent molecules, etc.). my country's peach gum polysaccharide resources are very rich, but only a very small part of peach gum polysaccharide is used, and the waste of peach gum polysaccharide resources is very serious. So far, there are few reports on the use of peach gum polysaccharide to prepare nanospheres. Therefore, the invention of the preparation method of peach gum polysaccharide nanospheres will greatly improve the practicality and added value of peach gum polysaccharide, and effectively promote the development and application of peach gum resources. Summary of the invention

[0003] Based on this, the purpose of the present invention is to provide a peach gum polysaccharide-cinnamic acid anti-ultraviolet nanosphere, a preparation method and application thereof.

[0004] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0005] (1) dissolving 1 part by weight of hydrolyzed peach gum polysaccharide, 0.5-5 parts by weight of cinnamic acid, 0.1-1 parts by weight of 4-dimethylaminopyridine, and 0.5-2 parts by weight of N,N-dicyclohexylcarbodiimide in anhydrous N,N-dimethylformamide under a nitrogen atmosphere, reacting at room temperature for 24-48 hours, adding icy ethanol for precipitation, washing 3 times, and drying in an oven at 60 degrees to constant weight to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer;

[0006] (3) dissolving 1 part by weight of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in step (1) in an organic solvent, slowly dripping water equivalent to 4-9 times the volume of the organic solvent after it is completely dissolved, and then dialyzing for 8-24 hours to obtain UV-resistant hyperbranched peach gum polysaccharide nanospheres.

[0007] In one embodiment, the molecular weight of the hydrolyzed peach gum polysaccharide is 3500-50000 Daltons.

[0008] In one embodiment, the organic solvent is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide and tetrahydrofuran.

[0009] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps: firstly, using the terminal hydroxyl groups of natural hyperbranched peach gum polysaccharide macromolecules and the carboxyl groups on cinnamic acid molecules to prepare amphiphilic peach gum polysaccharide-cinnamic acid molecules through low-temperature esterification reaction, and then self-assembling in water to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0010] The invention discloses peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, which are prepared by any one of the above-mentioned preparation methods.

[0011] In one embodiment, the size of the peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres is 40-200 nanometers.

[0012] The invention discloses an application of peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, specifically, the peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres described in any one of the above items are used to load chemotherapeutic drugs, photodynamic therapy agents or bioactive ingredients, and are used as delivery carriers of molecules and / or nanoparticles in the fields of food, cosmetics and medicine.

[0013] The peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres involved in the method of the invention are prepared by taking natural peach gum polysaccharide with a hyperbranched structure as a matrix, have a large number of terminal functional groups that can be post-functionalized, excellent anti-ultraviolet performance, and an adjustable size between 40 and 200 nanometers. They are suitable for loading chemotherapeutic drugs, photodynamic therapy agents, bioactive ingredients, etc., and are used as delivery carriers of molecules and / or nanoparticles in the fields of food, cosmetics, medicine, etc. The preparation method of the invention has the advantages of cheap and readily available raw materials, simple preparation process, easy purification, little environmental pollution, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a photograph of peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres prepared in Example 1 of the present invention under normal light.

[0015] Figure 2 This is a TEM image of peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres prepared in Example 1 of the present invention.

[0016] Figure 3 This is the UV transmittance spectrum of peach gum polysaccharide-cinnamic acid anti-UV nanospheres prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0017] The invention provides a method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, comprising the following steps: firstly, using abundant terminal hydroxyl groups of natural hyperbranched peach gum polysaccharide macromolecules and carboxyl groups on cinnamic acid molecules to prepare amphiphilic peach gum polysaccharide-cinnamic acid molecules through low-temperature esterification reaction, and then self-assembling in water to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0018] In one embodiment, the preparation method of peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following specific steps:

[0019] (1) 1 part by weight of hydrolyzed peach gum polysaccharide, 0.5-5 parts by weight of cinnamic acid, 0.1-1 parts by weight of 4-dimethylaminopyridine, and 0.5-2 parts by weight of N,N-dicyclohexylcarbodiimide are dissolved in anhydrous N,N-dimethylformamide under a nitrogen atmosphere, reacted at room temperature for 24-48 hours, precipitated and washed three times with ice ethanol, and dried in an oven at 60 degrees to constant weight to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0020] (2) dissolving 1 part by weight of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in step (1) in an organic solvent, slowly dripping water equivalent to 4-9 times the volume of the organic solvent after it is completely dissolved, and then dialyzing for 8-24 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0021] The molecular weight of the hydrolyzed peach gum polysaccharide is 3500-50000 Daltons.

[0022] The organic solvents include dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, etc., all of which are chemically pure or above.

[0023] The invention discloses peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, which are prepared by any one of the above-mentioned preparation methods.

[0024] In one embodiment, the size of the peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres is 40-200 nanometers.

[0025] The invention discloses an application of peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, specifically, the peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres described in any one of the above items are used to load chemotherapeutic drugs, photodynamic therapy agents or bioactive ingredients, and are used as delivery carriers of molecules and / or nanoparticles in the fields of food, cosmetics and medicine.

[0026] Peach gum polysaccharide is the main component of peach gum, a secretion of peach trees. It is a hyperbranched heteropolysaccharide, and its monosaccharide composition includes arabinose (32-59%), galactose (27-42%), xylose (4.0-14%), uronic acid (1.6-20%), mannose (0.37-5.4%) and rhamnose (0-1.3%). Unlike most linear polysaccharides, peach gum polysaccharide presents a highly branched molecular structure, so it has the advantages of excellent water solubility, low viscosity, high reactivity, etc., and has a unique assembly structure and performance in the preparation of amphiphilic micelles.

[0027] Trans-cinnamic acid is a typical component of the cortex of the traditional spice cinnamon. It is a commercial natural molecule with multiple physiological activities such as anti-ultraviolet, antibacterial, anti-inflammatory, and antiviral. It has been approved as a food additive by multiple institutions such as the FAO / WHO Joint Expert Committee on Food Additives and is widely used in the fields of food and cosmetics. This application introduces trans-cinnamic acid to the surface of water-soluble hyperbranched peach gum polysaccharide to prepare an amphiphilic peach gum polysaccharide-cinnamic acid copolymer, thereby constructing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres. The cinnamic acid component in peach gum polysaccharide-cinnamic acid not only gives peach gum polysaccharide hydrophobicity and drives its self-assembly to form an assembly with a nanometer size, but also the double bonds in the cinnamic acid molecular structure can undergo [2+2] cross-linking under ultraviolet light to play a role in chemical anti-ultraviolet, thereby giving peach gum polysaccharide-cinnamic acid nanospheres excellent anti-ultraviolet properties.

[0028] Embodiment 1:

[0029] See also Figure 1-3 A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0030] 1 gram of hydrolyzed peach gum polysaccharide, 3 grams of cinnamic acid, 0.1 gram of 4-dimethylaminopyridine, and 1.5 grams of N,N-dicyclohexylcarbodiimide were added to 20 milliliters of N,N-dimethylformamide, and the mixture was reacted at room temperature under a nitrogen atmosphere for 48 hours to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0031] (2) After 1 g of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in (1) is completely dissolved in 100 ml of N,N-dimethylformamide, 500 ml of water is slowly added, and then dialyzed for 24 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0032] The molecular weight of the hydrolyzed peach gum polysaccharide is 35,000 Daltons.

[0033] The chemical reagents described are all of chemical purity or above.

[0034] Embodiment 2:

[0035] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0036] (1) 1 g of hydrolyzed peach gum polysaccharide, 1 g of cinnamic acid, 0.2 g of 4-dimethylaminopyridine, and 2 g of N,N-dicyclohexylcarbodiimide were added to 20 ml of N,N-dimethylformamide, and the mixture was reacted at room temperature under a nitrogen atmosphere for 24 hours to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0037] (2) After 1 g of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in (1) is completely dissolved in 100 ml of N,N-dimethylformamide, 600 ml of water is slowly added, and then dialyzed for 18 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0038] The molecular weight of the hydrolyzed peach gum polysaccharide is 5000 Daltons.

[0039] The chemical reagents described are all of chemical purity or above.

[0040] Embodiment 3:

[0041] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0042] (1) 1 g of hydrolyzed peach gum polysaccharide, 1.5 g of cinnamic acid, 0.25 g of 4-dimethylaminopyridine, and 2.5 g of N,N-dicyclohexylcarbodiimide were added to 20 ml of N,N-dimethylformamide, and the mixture was reacted at room temperature for 22 hours under a nitrogen atmosphere to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0043] (2) After 1 g of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in (1) is completely dissolved in 100 ml of N,N-dimethylformamide, 400 ml of water is slowly added, and then dialyzed for 20 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0044] The molecular weight of the hydrolyzed peach gum polysaccharide is 50,000 Daltons.

[0045] The chemical reagents described are all of chemical purity or above.

[0046] Embodiment 4:

[0047] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0048] (1) 1 g of hydrolyzed peach gum polysaccharide, 3 g of cinnamic acid, 0.3 g of 4-dimethylaminopyridine, and 3.5 g of N,N-dicyclohexylcarbodiimide were added to 20 ml of N,N-dimethylformamide, and the mixture was reacted at room temperature for 24 hours under a nitrogen atmosphere to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0049] (2) After 1 gram of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in (1) is completely dissolved in 50 ml of dimethyl sulfoxide, 450 ml of water is slowly added dropwise, and then dialyzed for 12 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0050] The molecular weight of the hydrolyzed peach gum polysaccharide is 10,000 Daltons.

[0051] The chemical reagents described are all of chemical purity or above.

[0052] Embodiment 5:

[0053] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0054] (1) 1 g of hydrolyzed peach gum polysaccharide, 0.5 g of cinnamic acid, 0.1 g of 4-dimethylaminopyridine, and 1.5 g of N,N-dicyclohexylcarbodiimide were added to 20 ml of N,N-dimethylformamide, and the mixture was reacted at room temperature under a nitrogen atmosphere for 48 hours to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0055] (2) After 1 gram of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in (1) is completely dissolved in 200 ml of tetrahydrofuran, 800 ml of water is slowly added dropwise, and then dialyzed for 24 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0056] The molecular weight of the hydrolyzed peach gum polysaccharide is 5000 Daltons.

[0057] The chemical reagents described are all of chemical purity or above.

[0058] Embodiment 6:

[0059] A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres comprises the following steps:

[0060] (1) 1 g of hydrolyzed peach gum polysaccharide, 1 g of cinnamic acid, 0.2 g of 4-dimethylaminopyridine, and 1.5 g of N,N-dicyclohexylcarbodiimide were added to 20 ml of N,N-dimethylformamide, and the mixture was reacted at room temperature for 30 hours under a nitrogen atmosphere to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer.

[0061] (2) After 1 gram of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in (1) is completely dissolved in 25 ml of tetrahydrofuran, 225 ml of water is slowly added dropwise, and then dialyzed for 8 hours to obtain peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres.

[0062] The molecular weight of the hydrolyzed peach gum polysaccharide is 8000 Daltons.

[0063] The chemical reagents described are all of chemical purity or above.

[0064] The peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres involved in the method of the invention are prepared by taking natural peach gum polysaccharide with a hyperbranched structure as a matrix, have a large number of terminal functional groups that can be post-functionalized, excellent anti-ultraviolet performance, and an adjustable size between 40 and 200 nanometers. They are suitable for loading chemotherapeutic drugs, photodynamic therapy agents, bioactive ingredients, etc., and are used as delivery carriers of molecules and / or nanoparticles in the fields of food, cosmetics, medicine, etc. The preparation method of the invention has the advantages of cheap and readily available raw materials, simple preparation process, easy purification, little environmental pollution, etc.

[0065] For those skilled in the art, various other corresponding changes and deformations can be made according to the technical solutions and concepts described above, and all of these changes and deformations should fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, characterized in that: The preparation method comprises the following steps: (1) dissolving 1 part by weight of hydrolyzed peach gum polysaccharide with a molecular weight of 3500 to 50000 Daltons, 0.5 to 5 parts by weight of cinnamic acid, 0.1 to 1 parts by weight of 4-dimethylaminopyridine, and 0.5 to 2 parts by weight of N,N-dicyclohexylcarbodiimide in anhydrous N,N-dimethylformamide under a nitrogen atmosphere, reacting at room temperature for 24 to 48 hours, adding icy ethanol for precipitation, washing 3 times, and drying in an oven at 60 degrees to constant weight to obtain an amphiphilic peach gum polysaccharide-cinnamic acid copolymer; (2) dissolving 1 part by weight of the amphiphilic peach gum polysaccharide-cinnamic acid copolymer obtained in step (1) in at least one of dimethyl sulfoxide, N,N-dimethylformamide and tetrahydrofuran, and slowly dripping water equivalent to 4-9 times the volume of the organic solvent after the copolymer is completely dissolved, and then dialyzing for 8-24 hours to obtain UV-resistant hyperbranched peach gum polysaccharide nanospheres, wherein the size of the peach gum polysaccharide-cinnamic acid UV-resistant nanospheres is 40-200 nanometers.

2. A peach gum polysaccharide-cinnamic acid anti-ultraviolet nanosphere, characterized in that: The peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres are prepared by the preparation method as claimed in claim 1.

3. An application of peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres, characterized in that: The peach gum polysaccharide-cinnamic acid anti-ultraviolet nanospheres as described in claim 2 are used to load chemotherapeutic drugs, photodynamic therapy agents or bioactive ingredients, and are used as delivery carriers of molecules and / or nanoparticles in the fields of food, cosmetics, and medicine.

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