A method for preparing iron-doped polymer self-assembled nanoparticles and nanoparticles prepared thereby

Abstract

The application discloses a preparation method of iron-doped polymer self-assembled nanoparticles and the nanoparticles prepared by the method. The preparation method comprises the following steps: mixing a mixed solution containing a polymer, an iron salt and a solvent I with a solvent II to obtain the iron-doped polymer self-assembled nanoparticles. The preparation method is simple, low in cost, short in period and high in yield; the iron-doped polymer self-assembled nanoparticles are stable in structure, adjustable in catalytic oxidation capacity, free of strong acid and strong base, and green and environment-friendly.

Description

Technical Field

[0001] This application relates to a method for preparing iron-doped polymer self-assembled nanoparticles and the prepared nanoparticles, belonging to the field of functional nanomaterials. Background Technology

[0002] In recent years, numerous studies have reported that carbon nanomaterials possess high catalytic oxidation capabilities similar to natural enzymes, making them potential substitutes for natural enzymes in fields such as biomedicine. Catalytic oxidation refers to an oxidation reaction carried out by a catalyst using air, oxygen, ozone, or other oxidants under specific pressure and temperature conditions. However, natural enzymes and most nanozymes suffer from problems such as variability, high cost, difficult preparation, and inability to be mass-produced. Therefore, the search for a novel catalytic oxidation nanozyme material that is simple to synthesize, has high yield, and high activity has become a new research hotspot.

[0003] Metal-doped polymer self-assembled nanoparticles can serve as a novel type of nanozyme to address this problem. By exposing more active sites, they significantly enhance catalytic oxidation performance. Self-assembly refers to the spontaneous formation of unique structures through intermolecular forces, enabling individual molecules to form oriented and ordered structures. The orderly connection of building blocks via non-covalent bonds to form assemblies with specific structures or functions has already demonstrated enormous application potential in fields such as biomedicine and environmental monitoring. Summary of the Invention

[0004] Iron-based polymer self-assembled nanoparticles exhibit several advantages. Firstly, the polymer chains can self-assemble through hydrogen bonding and van der Waals forces, bringing iron ions into the self-assembled structure. Secondly, in the excited state, electron delocalization occurs, generating free radicals (such as superoxide anion radicals and hydroxyl radicals), which can be captured by ferric ions and reduced to ferrous ions, forming a Fenton-like catalytic oxidation system to oxidize organic matter near the nanoparticles. Therefore, metal-doped polymer self-assembled nanoparticles have significant application value in photocatalytic degradation, bacterial detection, sterilization and bacteriostasis, food preservation, and wound healing.

[0005] According to one aspect of this application, a method for preparing iron-doped polymer self-assembled nanoparticles is provided, comprising the following steps:

[0006] A mixed solution containing polymer, iron salt and solvent I is mixed with solvent II to obtain the iron-doped polymer self-assembled nanoparticles.

[0007] The molecular weight of the polymer is 7000~15000 Da;

[0008] The end-capping group of the polymer is a carboxyl group;

[0009] The polymer contains carboxyl side groups.

[0010] The iron salt is selected from at least one of ferric chloride, ferric nitrate, and ferric sulfate;

[0011] Solvent I is selected from at least one of DMSO, methanol, ethanol, water, and acetone;

[0012] The mass ratio of the polymer to the iron salt is 1:0.1~50;

[0013] The mass ratio of the polymer to solvent I is 0.01~1:10.

[0014] Solvent II is selected from at least one of ethanol, chloroform, acetone, acetonitrile, toluene, and n-hexane;

[0015] The volume ratio of solvent II to the mixed solution is 0.1~1:10.

[0016] The polymer is obtained by the following method:

[0017] Includes the following steps:

[0018] A mixture containing polycarboxylic acids and polyamines is reacted and dried to obtain the non-conjugated dehydrated polymer.

[0019] The polycarboxylic acid is selected from at least one of oxalic acid, trimalic acid, succinic acid, 1,2,4-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, glutaric acid, adipic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid;

[0020] The polyamine is selected from at least one of ethylenediamine, propanetriamine, 1,3-propanediamine, and phenylenediamine;

[0021] The reaction temperature is 80~260℃;

[0022] The reaction atmosphere is a non-reactive gas atmosphere.

[0023] The molar ratio of the polycarboxylic acid and the polyamine is 1:10 to 10:1.

[0024] The reaction is a molten polymerization reaction.

[0025] The reaction time is 0.5 to 6 hours.

[0026] The inactive gas atmosphere is selected from at least one of nitrogen, helium, and argon.

[0027] The polymer is a non-conjugated dehydrated polymer with a molecular weight of 1000~15000 Da.

[0028] Optionally, the polymer is selected from at least one of poly(3-phenyl)-2-carboxymethylimide-succinimide, poly(N-ethyl-2-carboxymethylimide-succinimide), polyphenyloxalate diimide, polyethyloxalate diimide, polyethylglutarate diimide, polyphenylglutarate diimide, polyethylsuccinate diimide, and polyphenylsuccinate diimide.

[0029] Specifically,

[0030] A low molecular weight non-conjugated polyimide with carboxylic acid groups as side groups and end groups having self-assembly function is dispersed with ferric ions in a first solvent and stirred uniformly.

[0031] The second solvent is gradually added until a precipitate is formed. The precipitate is then filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0032] According to another aspect of this application, iron-doped polymer self-assembled nanoparticles prepared by the above-described method are provided.

[0033] In the first solvent, the imide in the polymer and the carbonyl oxygen of the carboxylic acid can complex with iron ions. Upon the addition of a second solvent, self-assembly occurs due to hydrogen bonds and van der Waals forces between the polymer chains, bringing iron ions into the self-assembled structure and forming iron-based polymer self-assembled nanoparticles. The catalytic oxidation principle lies in the fact that the self-assembled non-conjugated polyimide can undergo electron delocalization in the excited state. When ferric ions are nearby, the generated free electrons can be captured by the ferric ions, generating ferrous ions. Meanwhile, the valence state of the ferric ions complexed with the carboxyl group in the self-assembled nanoparticle remains unchanged. At this point, ferrous ions, ferric ions, and unbound imide coexist within the self-assembled nanoparticle, forming a Fenton-like catalytic oxidation system that oxidizes organic matter near the nanoparticle.

[0034] According to another aspect of this application, an application of the above-mentioned iron-doped polymer self-assembled nanoparticles is provided for use in the fields of photocatalysis and bactericidal / bacteriostatic reactions.

[0035] The beneficial effects that this application can produce include:

[0036] (1) The preparation method is simple, low-cost, short-cycle, and has a high yield;

[0037] (2) The iron-doped polymer self-assembled nanoparticles have a stable structure, adjustable catalytic oxidation ability, and are environmentally friendly as they do not require strong acids or bases. Attached Figure Description

[0038] Figure 1 The image shows the XRD pattern of the nanoparticles produced in Example 1.

[0039] Figure 2a The image shows a scanning electron microscope (SEM) image of the nanoparticles in Example 1, with a scale of 25 μm.

[0040] Figure 2b The image shows the XRF mapping of the nanoparticles in Example 1, with a scale of 25 μm.

[0041] Figure 3 The absorption spectrum is shown in Example 1 when oligomers, iron-doped nanoparticles, and tetramethylbenzidine (TMB) coexist.

[0042] Figure 4 The image shows a control group after 15 days of storage, consisting of gels without (left) and gels with (right) iron-doped nanoparticles. Detailed Implementation

[0043] The present invention will be further described below with reference to embodiments, so that those skilled in the art can better understand the present invention, but this does not limit the present invention.

[0044] Example 1

[0045] At room temperature, 0.2 g of poly(3-phenyl)-2-carboxymethylimide-succinimide with an average molecular weight of 8000 Da was dissolved in 3 mL of water and stirred evenly. Then, 0.7 g of ferric chloride was added and stirring continued. Then, 50 mL of acetonitrile was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0046] Take 1.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3- ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0047] Figure 1 The image shows the XRD pattern of the nanoparticles produced in Example 1. It can be seen from the image that doping did not change the amorphous nature of the nanoparticles, and that iron was dispersed within the nanoparticles in ionic form rather than in oxide form.

[0048] Figure 2a The image shows a scanning electron microscope (SEM) image of the nanoparticles in Example 1, with a scale of 25 μm. The image shows that the nanoparticles can be deposited relatively smoothly on the silicon wafer.

[0049] Figure 2b This is a topological map of the iron element in the nanoparticles of Example 1, at a scale of 25 μm. The map shows that iron ions are uniformly distributed throughout the nanoparticle layer.

[0050] Figure 3The image shows the absorption spectra of oligomers, iron-doped nanoparticles, and tetramethylbenzidine (TMB) in Example 1. The figure shows that iron doping effectively oxidizes TMB, increasing its absorbance.

[0051] Figure 4 The image shows a control group (left) of gelatin gels containing (right) iron-doped nanoparticles after 15 days. The figure shows that the presence of iron-doped nanoparticles generates superoxide radicals, which effectively inhibit bacterial growth in the gelatin.

[0052] Example 2

[0053] 0.2 g of poly(N-ethyl-2-carboxymethylimide-succinimide) with an average molecular weight of 8000 Da was dissolved in 3 mL of dimethyl sulfoxide (DMSO) at room temperature and stirred evenly. Then, 0.8 g of ferric nitrate was added and stirring continued. Then, 30 mL of ethanol was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0054] Take 1.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3- ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0055] Example 3

[0056] 0.3 g of polyphenyloxalic acid diimide with an average molecular weight of 7000 Da was dissolved in 5 mL of methanol at room temperature and stirred evenly. Then, 0.6 g of ferric sulfate was added and stirring continued. Then, 30 mL of toluene was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0057] Take 1.0 mg of the nanoparticles and add them to 2.0 mL of 10 mg / mL 3,3-dimethylformamide. ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0058] Example 4

[0059] 0.3 g of polyethyl oxalate diimide with an average molecular weight of 7000 Da was dissolved in 5 mL of ethanol at room temperature and stirred evenly. Then, 0.5 g of ferric sulfate was added and stirring continued. Then, 50 mL of chloroform was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0060] Take 1.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3- ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0061] Example 5

[0062] 0.2 g of polyethylglutaric acid diimide with an average molecular weight of 7500 Da was dissolved in 3 mL of acetone at room temperature and stirred evenly. Then, 0.7 g of ferric sulfate was added and stirring continued. Then, 30 mL of n-hexane was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0063] Take 1.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3- ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0064] Example 6

[0065] 0.2 g of polyphenylglutaric acid diimide with an average molecular weight of 7500 Da was dissolved in 3 mL of ethanol at room temperature and stirred evenly. Then, 0.6 g of ferric chloride was added and stirring continued. Then, 30 mL of acetone was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0066] Take 1.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3- ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0067] Example 7

[0068] 0.2 g of polyethyl succinic diimide with an average molecular weight of 8000 Da was dissolved in 5 mL of dimethyl sulfoxide (DMSO) at room temperature and stirred evenly. Then, 0.5 g of ferric chloride was added and stirring continued. Then, 50 mL of ethanol was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0069] Take 2.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3-dimethylformamide. ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0070] Example 8

[0071] 0.3 g of polyphenyl succinic diimide with an average molecular weight of 8000 Da was dissolved in 5 mL of methanol at room temperature and stirred evenly. Then, 0.3 g of ferric chloride was added and stirring continued. Then, 30 mL of acetonitrile was added to produce a precipitate. The precipitate was filtered and dried to obtain iron-based polymer self-assembled nanoparticles with catalytic oxidation properties.

[0072] Take 2.0 mg of the nanoparticles and add them to 2.0 mL of 100 mg / mL 3,3-dimethylformamide. ， ,5,5 ， In aqueous solution of tetramethylbenzidine hydrochloride, the solution quickly turns blue, indicating that the obtained nanoparticles possess good oxidizing properties.

[0073] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing iron-doped polymer self-assembled nanoparticles, characterized in that, Includes the following steps: A mixed solution containing polymer, iron salt and solvent I is mixed with solvent II to obtain the iron-doped polymer self-assembled nanoparticles. The molecular weight of the polymer is 7000~15000 Da; The end-capping group of the polymer is a carboxyl group; The polymer contains carboxyl side groups; The polymer is obtained by the following method: A polycarboxylic acid and a polyamine are mixed and subjected to a melt polymerization reaction at 80-260°C for 0.5-6 hours under an inert gas atmosphere, followed by drying to obtain the polymer. The polycarboxylic acid is selected from at least one of oxalic acid, trimalonic acid, succinic acid, 1,2,4-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, glutaric acid, adipic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid. The polyamine is selected from at least one of ethylenediamine, propanetriamine, 1,3-propanediamine, and phenylenediamine; The inactive gas atmosphere is selected from at least one of nitrogen, helium, and argon; The molar ratio of the polycarboxylic acid and the polyamine is 1:10 to 10:1; The iron salt is selected from at least one of ferric chloride, ferric nitrate, and ferric sulfate; Solvent I is selected from at least one of DMSO, methanol, ethanol, water, and acetone; the mass ratio of the polymer to the iron salt is 1:0.1~50; The mass ratio of the polymer to solvent I is 0.01 to 1:10; Solvent II is selected from at least one of ethanol, chloroform, acetone, acetonitrile, toluene, and n-hexane; The volume ratio of solvent II to the mixed solution is 0.1 to 1:

10.

2. Iron-doped polymer self-assembled nanoparticles prepared by the method of claim 1.

3. An application of the iron-doped polymer self-assembled nanoparticles according to claim 2, characterized in that, Used in photocatalysis, sterilization and bacteriostasis.

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