Nitrite intelligent response type hydrogel nanomaterial FMs (at) SHNM as well as preparation method and application thereof

Abstract

The invention provides a nitrite intelligent response type hydrogel nanomaterial FMs (at) SHNM as well as a preparation method and application thereof, and relates to the field of algaecide, antidote and material synthesis and the technical field of water pollution treatment. The preparation method of the material comprises the following steps: dissolving an acrylic acid analogue, an acrylamide analogue and a to-be-wrapped host molecule in water, and adding a cross-linking agent to obtain a mixed solution; and adding an accelerator and a catalyst, and carrying out constant-temperature polymerization to obtain the material. The host molecule wrapped by the nitrite response type hydrogel nanomaterial is the algicide, the algicide can be intelligently released, cyanobacterial bloom and algal toxin pollution can be accurately treated, meanwhile, the dosage and implementation cost of the algicide are reduced, the algae killing efficiency is improved, and cyanobacterial bloom outbreak and algal toxin pollution are effectively controlled.

Description

Technical Field

[0001] The present invention relates to the fields of algaecides, detoxifiers, material synthesis and water pollution treatment technology, and in particular to a nitrite intelligent response hydrogel nanomaterial FMs@SHNM and a preparation method and application thereof. Background Art

[0002] Algal bloom refers to the phenomenon of algae multiplying and gathering in large numbers under suitable conditions, including marine red tide and freshwater cyanobacteria bloom. Once an algae bloom occurs, a layer of algae cells covers the water surface, blocking the sunlight. This phenomenon usually occurs in eutrophic water bodies. At the same time, during algae blooms, a large number of algae release algal toxins, seriously polluting the water body, damaging water quality, and devastating the river, lake, and marine ecosystems.

[0003] The main reasons for the outbreak of algae blooms include eutrophication of water bodies and climate warming. Eutrophication refers to excessive nutrients such as nitrogen and phosphorus in water bodies, which leads to abnormal reproduction of algae. These nutrients mainly come from the loss of agricultural fertilizers, the discharge of industrial wastewater and domestic sewage, and the release of bait in aquaculture. Algae reproduce rapidly through vegetative reproduction and spore reproduction, forming algae blooms. The hazards of algae blooms include deterioration of water quality, oxygen depletion, and destruction of ecosystems. Algae blooms can cause water to become turbid, affect water transparency and light penetration, and thus affect the photosynthesis of aquatic plants and the survival of other aquatic organisms. In addition, algae consume a lot of oxygen during the decomposition process, resulting in hypoxia in the water body, which can cause the death of fish and other aquatic organisms in severe cases.

[0004] As the climate warms, harmful algal blooms are becoming more common in freshwater areas, and the frequent occurrence of algal blooms has caused serious environmental consequences and economic losses. Direct addition of algaecides is currently the most commonly used method for algae control, but due to non-intelligent and non-precise delivery, the amount of algaecides delivered is large, but the algaecide effect is poor and it is easy to cause secondary pollution, which leads to further deterioration of water quality. Summary of the invention

[0005] The purpose of the present invention is to provide a nitrite intelligent response hydrogel nanomaterial (Functional Molecules@Smart Hydrogel Nano-Materials, FMs@SHNM) and its preparation method and application, which relates to the fields of algaecides, detoxifiers, material synthesis and water pollution treatment technology. The hydrogel nanomaterial FMs@SHNM can release different concentrations of nitrite ions according to the different degrees of cyanobacterial blooms, intelligently respond and release algaecides, achieve the goal of accurately and effectively controlling cyanobacterial blooms and algal toxin pollution, greatly reduce the amount of algaecides and implementation costs, and improve the use efficiency and safety of algaecides.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a method for preparing a nitrite-responsive hydrogel nanomaterial FMs@SHNM, comprising the following steps:

[0008] The acrylic acid analog, the acrylamide analog and the main molecule to be encapsulated are dissolved in water, and a cross-linking agent is added and mixed evenly to obtain a mixed solution. The pH value of the mixed solution is adjusted until the pH is greater than 9.0, and then an accelerator and a catalyst are added, and the mixture is polymerized at a constant temperature and finally dried to obtain the nitrite smart responsive hydrogel nanomaterial FMs@SHNM.

[0009] In a second aspect, the present invention provides a nitrite-responsive hydrogel nanomaterial FMs@SHNM, which is prepared by the method of the first aspect.

[0010] In a third aspect, the present invention provides an application of the nitrite smart response hydrogel nanomaterial FMs@SHNM of the second aspect prepared by the first aspect in the field of algae bloom and algae toxin pollution control.

[0011] The principle of the nitrite intelligent response type hydrogel nanomaterial FMs@SHNM in the embodiment of the present invention to achieve nitrite intelligent response to release FMs to kill algae is: when cyanobacteria multiply in large quantities, the nitrate ion content in the water body will increase, and these nitrate ions react chemically with oxygen to generate a large amount of nitrite ions. The nitrite intelligent response type hydrogel nanomaterial FMs@SHNM obtained by the present invention reacts chemically with nitrite ions, thereby causing the hydrogel to cleave, and the encapsulated main molecule (benzalkonium bromide, BB) with algaecidal function is released in time, playing the role of intelligent and precise algaecidal function.

[0012] Compared with the prior art, the present invention has at least the following advantages or beneficial effects: the nitrite-responsive hydrogel nanomaterial FMs@SHNM prepared by the present invention can realize the intelligent release of the main molecule algaecide, greatly reduce the usage and implementation cost of algaecide products, improve the utilization efficiency of algaecide products, and can effectively control the outbreak of cyanobacteria blooms, solving the problem of large amount of algaecide products used during non-intelligent delivery.

[0013] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the technical solution of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0015] Figure 1 It is the standard curve of nitrite ion concentration in water.

[0016] Figure 2 This is a visual diagram of the effect of the algaecide benzalkonium bromide (BB group) on the growth of Microcystis aeruginosa 905.

[0017] Figure 3 This is the effect of benzalkonium bromide (BB) on the growth indicators of Microcystis aeruginosa 905.

[0018] Figure 4 This is a visual diagram of the effects of nanomaterials BB@SHNM-1 and SHNM group on the growth of Microcystis aeruginosa 905.

[0019] Figure 5 The effects of nanomaterials BB@SHNM-1 and SHNM group on the growth indicators of Microcystis aeruginosa 905.

[0020] Figure 6 This is a visual diagram of the effects of nanomaterials BB@HNM and HNM group on the growth of Microcystis aeruginosa 905.

[0021] Figure 7 The effects of nanomaterials BB@HNM and HNM group on the growth indicators of Microcystis aeruginosa 905. DETAILED DESCRIPTION

[0022] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0023] In a first aspect, the present invention provides a method for preparing a nitrite-responsive hydrogel nanomaterial (Functional Molecules@Smart Hydrogel Nano-Materials, FMs@SHNM), comprising the following steps:

[0024] The acrylic acid analog, acrylamide analog and the main molecule FMs to be encapsulated are dissolved in water, and a cross-linking agent is added and mixed evenly to obtain a mixed solution. The pH value of the mixed solution is adjusted until the pH is greater than 9.0, and then an accelerator and a catalyst are added, and the mixture is polymerized at a constant temperature of 50 to 100°C for 8 to 48 hours, and finally washed with water for 3 to 5 times, and dried at room temperature or freeze-dried for 12 to 48 hours to obtain the nitrite smart responsive hydrogel nanomaterial FMs@SHNM.

[0025] In the present invention, the acrylic acid analog is selected from one of acrylic acid, methacrylic acid, 2-ethylacrylic acid, butenedioic acid, propylene oxide, and propanesulfonic acid, preferably 2-ethylacrylic acid; the acrylamide analog is selected from one of 2-methylacrylamide and buteneamide, preferably 2-methylacrylamide.

[0026] The main molecule described in the present invention is a small molecule and / or a macromolecule with certain algaecidal and detoxification functions, and is selected from at least one of the following types: benzalkonium bromide (BB) and other quaternary ammonium salt algaecides, algae toxin degrading enzyme MlrA and its complex enzyme, algae toxin degrading enzyme MlrB and its complex enzyme, algae toxin degrading enzyme MlrC and its complex enzyme, preferably benzalkonium bromide BB.

[0027] In the present invention, the mass ratio of acrylic acid derivatives, acrylamide derivatives and main molecules is (1-10):(1-50):1.

[0028] The crosslinking agent (CL) in the present invention is prepared by the following method: dissolving allyl acetoacetate, undecenal and ammonium acetate in ethanol, adding catalyst triethylamine, mixing evenly, and reacting for 1 to 24 hours. Then, heating at 50 to 100°C and reflux for 12 to 48 hours, passing through a column, and spin drying. The molar ratio of allyl acetoacetate, undecenal and ammonium acetate is (1 to 5): 1: (1 to 20). The volume ratio of the mixed solution of allyl acetoacetate, undecenal and ammonium acetate to the catalyst triethylamine is (5 to 50): 1. The synthesis route of the crosslinking agent (CL) is as follows:

[0029]

[0030] The molar ratio of the accelerator to the catalyst is 1:(1-50). The accelerator is selected from one of diisopropyl-ethylenediamine (2-Diaminoethane), 1,3-propylenediamine (1,3-Diaminopropane), tetramethylethylenediamine (TMEDA), and triethylenetetraaminehexaacetic acid (TETA), preferably tetramethylethylenediamine (TMEDA). The catalyst is selected from one of sodium persulfate, potassium persulfate, and ammonium persulfate, preferably ammonium persulfate.

[0031] In a second aspect, the present invention provides a nitrite intelligent responsive hydrogel nanomaterial FMs@SHNM, characterized in that it is prepared by the method provided in the first aspect.

[0032] In the third aspect, the present invention provides an application of a nitrite-smart responsive hydrogel nanomaterial FMs@SHNM in the field of algae bloom and algae toxin pollution control. Algae include red algae and cyanobacteria. Preferably, the algae are cyanobacteria. When algae multiply in large numbers, the nitrite ion content in the water body will increase. FMs@SHNM intelligently responds to changes in nitrite ion concentration and releases the encapsulated main molecule algaecide benzalkonium bromide (BB), achieving the goal of intelligent and precise algae killing.

[0033] In order to make the purpose, technical scheme and technical advantages of the present invention clearer, the technical scheme, implementation effect and the like of the present invention are clearly and completely described below through examples. The reagents or instruments used without indicating the manufacturer are conventional products that can be purchased commercially. If the specific conditions are not indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer are followed.

[0034] It should be noted that the embodiments and features of the embodiments of the present invention can be combined with each other without conflict. The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0035] When cyanobacteria blooms occur, a large number of cyanobacteria cells consume dissolved oxygen and carbon dioxide in the water, causing the pH value of the water to rise, promoting denitrification of the water, and thus leading to the accumulation of nitrite. The present invention uses the aniline-α-naphthol spectrophotometric method to determine the content of nitrite in water samples. The principle is that aniline and nitrite are diazotized in a hydrochloric acid medium, and then react with α-naphthol in a NaOH solution to generate an orange-red coupling product. This method is used to determine the content of nitrite in water under different degrees of cyanobacteria blooms. Concentration (c The content of Figure 1 Therefore, the present invention uses the above principle to explore the law of the nanomaterial of the present invention responding to the change of nitrite concentration and the inhibitory effect of the released drug on algae.

[0036] Example 1

[0037] A method for preparing a nitrite-responsive hydrogel nanomaterial BB@SHNM-1 comprises the following steps:

[0038] S1. Preparation of crosslinking agent (CL): add allyl acetoacetate, undecenal, and ammonium acetate in a ratio of 1:1:2; then add ethanol (EtOH) to dissolve the raw materials; then add 1 mL of catalyst, preferably triethylamine, mix well, and react for 4 hours. Heat the mixture to 50°C, reflux for 12 hours, remove the solvent ethanol after completion, pass through a column, and spin dry to obtain a crosslinking agent (CL).

[0039] S2. Dissolve acrylic acid (AA), acrylamide (AM), and the main molecule benzalkonium bromide (BB) in a certain amount of distilled water at a mass ratio of AA:AM:BB=5:10:1, add the crosslinking agent (CL) synthesized by the present invention at a ratio of 10:1, and mix evenly; slowly drop NaOH solution to adjust the pH to 9.5. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), where TEMED:APS=1:5. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 4 hours to remove impurities, and dry for 24 hours to obtain the product BB@SHNM-1 of this embodiment.

[0040] Example 2

[0041] A method for preparing a nitrite smart responsive hydrogel nanomaterial BB@SHNM-2 comprises the following steps:

[0042] S1. Preparation of crosslinking agent (CL): add allyl acetoacetate, undecenal, and ammonium acetate in a ratio of 2:1:2; then add ethanol (EtOH) to dissolve the raw materials; then add 2 mL of catalyst, preferably triethylamine, mix well, and react for 4 hours. Heat the mixture to 60°C, reflux for 15 hours, remove the solvent ethanol after completion, pass through a column, and spin dry to obtain a crosslinking agent (CL).

[0043] S2. Dissolve acrylic acid (AA), acrylamide (AM), and benzalkonium bromide (BB, a main molecule with a specific algaecidal function) in a certain amount of distilled water at a mass ratio of AA:AM:BB=5:20:1, add the crosslinking agent (CL) synthesized by the present invention at a ratio of 15:1, and mix evenly; slowly add NaOH solution to adjust the pH to 9.5. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), where TEMED:APS=1:10. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 4 hours to remove impurities, and dry for 24 hours to obtain the product BB@SHNM-2 of this embodiment.

[0044] Example 3

[0045] A method for preparing a nitrite smart responsive hydrogel nanomaterial BB@SHNM-3 comprises the following steps:

[0046] S1. Preparation of crosslinking agent (CL): add allyl acetoacetate, undecenal, and ammonium acetate in a ratio of 3:1:2; then add ethanol (EtOH) to dissolve the raw materials; then add 3 mL of catalyst, preferably triethylamine, mix well, and react for 24 hours. Heat the mixture to 70°C and reflux for 24 hours. After completion, remove the solvent ethanol, pass through a column, and spin dry to obtain a crosslinking agent (CL).

[0047] S2. Dissolve acrylic acid (AA), acrylamide (AM), and benzalkonium bromide (BB, a main molecule with a specific algaecidal function) in a certain amount of distilled water at a mass ratio of AA:AM:BB=10:15:1, add the crosslinking agent (CL) synthesized by the present invention at a ratio of 20:1, and mix evenly; slowly drop NaOH solution to adjust the pH to 9.5. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), wherein TEMED:APS=1:15. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 4 hours to remove impurities, and dry for 24 hours to obtain the product BB@SHNM-3 of this embodiment.

[0048] Example 4

[0049] A method for preparing a nitrite smart responsive hydrogel nanomaterial BB@SHNM-4 comprises the following steps:

[0050] S1. Preparation of crosslinking agent (CL): add allyl acetoacetate, undecenal, and ammonium acetate in a ratio of 4:1:10; then add ethanol (EtOH) to dissolve the raw materials; then add 4 mL of catalyst, preferably triethylamine, mix well, and react for 24 hours. Heat the mixture to 75°C, reflux for 24 hours, remove the solvent ethanol after completion, pass through a column, and spin dry to obtain a crosslinking agent (CL).

[0051] S2. Dissolve acrylic acid (AA), acrylamide (AM), and benzalkonium bromide (BB, a main molecule with a specific algaecidal function) in a certain amount of distilled water at a mass ratio of AA:AM:BB=10:20:1, add the crosslinking agent (CL) synthesized by the present invention at a ratio of 30:1, and mix evenly; slowly drop NaOH solution to adjust the pH to a solution pH of 10. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), wherein TEMED:APS=1:20. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 8 hours to remove impurities, and dry for 24 hours to obtain the product BB@SHNM-4 of this embodiment.

[0052] Example 5

[0053] A method for preparing a nitrite-free smart responsive hydrogel nanomaterial SHNM, comprising the following steps:

[0054] S1. Preparation of crosslinking agent (CL): add allyl acetoacetate, undecenal, and ammonium acetate in a ratio of 5:1:15; then add ethanol (EtOH) to dissolve the raw materials; then add 5 mL of catalyst, preferably triethylamine, mix well, and react for 24 hours. Heat the mixture to 80°C and reflux for 36 hours. After completion, remove the solvent and spin dry through a column to obtain a crosslinking agent (CL).

[0055] S2. Dissolve acrylic acid (AA) and acrylamide (AM) in a certain amount of distilled water at a mass ratio of AA:AM=1:2, add the crosslinking agent (CL) synthesized by the present invention at a ratio of 50:1, and mix evenly; slowly drip NaOH solution to adjust the pH to 10.5. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), wherein TEMED:APS=1:5. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 4 hours to remove impurities, and dry for 24 hours to obtain the product SHNM of this embodiment.

[0056] Example 6

[0057] A method for preparing non-responsive functional hydrogel nanomaterials HNM and BB@HNM comprises the following steps:

[0058] S1. Select N,N-dimethylformamide as the cross-linking agent.

[0059] S2. Dissolve acrylic acid (AA) and acrylamide (AM) in a certain amount of distilled water at a mass ratio of AA:AM=1:2, add the crosslinking agent N,N-dimethylformamide synthesized by the present invention at a ratio of 50:1, and mix evenly; slowly drop NaOH solution to adjust the pH to 9.5. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), where TEMED:APS=1:20. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 4 hours to remove impurities, and dry for 24 hours to obtain the product HNM of this embodiment.

[0060] S3. Dissolve acrylic acid (AA), acrylamide (AM), and benzalkonium bromide (BB, a main molecule with a specific algaecidal function) in a certain amount of distilled water at a mass ratio of AA:AM:BB=10:20:1, add the cross-linking agent N,N-dimethylformamide synthesized by the present invention at a ratio of 50:1, and mix evenly; slowly add NaOH solution to adjust the pH to 9.5. Stir magnetically at room temperature for 30 minutes, then add accelerators tetramethylethylenediamine (TEMED) and ammonium persulfate (APS), wherein TEMED:APS=1:20. Polymerize in a 50°C constant temperature incubator for 24 hours, soak the obtained product in distilled water for 4 hours to remove impurities, and dry for 24 hours to obtain the product BB@HNM of this embodiment.

[0061] Example 7

[0062] The Microcystis aeruginosa 905, which has the highest frequency and amplitude of cyanobacterial blooms, was selected as the algae killing experiment object in the amplification system. In the 100 mL culture system, the cyanobacterial cell density was cultured to 1×10 8 When the algae solution was 12h, 24h, 36h, 48h, 60h, 72h and 84h after treatment, the OD of algae solution was measured at 12h, 24h, 36h, 48h, 60h, 72h and 84h after treatment. 680 The values ​​were used to verify the algicidal activity of BB@SHNM-1.

[0063] Take the Microcystis aeruginosa 905 algae solution and dilute it with BG11 culture medium to a cyanobacterial cell density of 1×10 8 / L, pH = 8.02, set up the experiment according to Table 1, a total of 12 groups, repeated once in parallel.

[0064] Table 1

[0065]

[0066]

[0067] In the table, BG11 is a blank control, and BB is a main molecule benzalkonium bromide with algaecidal function, which is used as a positive control. BB@SHNM-1 is a nitrite-smart responsive hydrogel nanomaterial (the preparation method is shown in Example 1), and SHNM is a nitrite-responsive hydrogel nanomaterial without a functional main molecule (the preparation method is shown in Example 5). BB@HNM (with functional main molecule BB) and HNM (without functional main molecule BB) are hydrogel nanomaterials without responsive function, and HNM is a hydrogel nanomaterial without a functional main molecule (the preparation method is shown in Example 6).

[0068] The results are as follows Figure 2 to Figure 7 shown.

[0069] in Figure 2 This is a visual diagram of the effect of algaecide benzalkonium bromide (BB group) on the growth of Microcystis aeruginosa 905. Figure 3 The effect of algaecide benzalkonium bromide (BB group) on the growth index of Microcystis aeruginosa 905. Figure 2 and Figure 3 It can be seen that the algaecidal effect of BB with the same concentration is consistent under different nitrite concentrations. In other words, the algaecidal effect of BB is not affected by nitrite concentration.

[0070] Figure 4 This is a visual diagram of the effect of nanomaterials BB@SHNM-1 and SHNM group on the growth of Microcystis aeruginosa 905. Figure 5 The effects of nanomaterials BB@SHNM-1 and SHNM group on the growth indicators of Microcystis aeruginosa 905. Figure 4 and Figure 5 It can be seen that the hydrogel nanomaterial SHNM without algaecidal functional molecules has no algaecidal ability. The hydrogel nanomaterial BB@SHNM-1 loaded with algaecidal functional molecules BB has intelligent nitrite concentration response ability. As the nitrite concentration increases, BB@SHNM-1 shows stronger algaecidal ability earlier. The higher the nitrite concentration, the more BB is released in BB@SHNM-1, and the stronger the algaecidal ability, so it shows a faster onset phenomenon, indicating that the hydrogel nanomaterial BB@SHNM-1 prepared by the present invention has nitrite response performance.

[0071] Figure 6 This is a visual diagram of the effect of nanomaterials BB@HNM and HNM group on the growth of Microcystis aeruginosa 905. Figure 7 The effects of nanomaterials BB@HNM and HNM group on the growth indexes of Microcystis aeruginosa 905. Figure 6 and Figure 7It can be seen that the hydrogel nanomaterial HNM without algaecidal functional molecules has no algaecidal ability. The hydrogel nanomaterial BB@HNM loaded with algaecidal functional molecules BB has a certain algaecidal ability, but it is not as obvious as BB@SHNM-1. As the nitrite concentration increases, the algaecidal ability of each group of BB@HNM is basically similar, and as the nitrite concentration increases, the algaecidal ability of BB@HNM does not increase significantly, indicating that BB@HNM does not have nitrite response performance or its response ability is extremely weak.

[0072] In summary, the nitrite-responsive drug-loaded hydrogel BB@SHNMs and its preparation method and application according to the embodiment of the present invention have the following advantages:

[0073] In the embodiment of the present invention, a cross-linking agent and an algaecide detoxifier are mixed in a certain proportion, and an appropriate amount of water is added under the conditions of acrylic acid and acrylamide to synthesize a hydrogel nanomaterial (BB@SHNMs) with nitrite response function. BB@SHNMs can intelligently and slowly release the encapsulated main functional molecule algaecide BB according to the different nitrite ion concentrations during the outbreak of cyanobacteria blooms, so as to achieve the goal of accurately treating cyanobacteria blooms, greatly reduce the dosage and implementation cost of algaecides, improve the use efficiency and safety of algaecides, and can efficiently control the outbreak of cyanobacteria blooms and effectively improve the safety of algaecides.

[0074] The embodiments described above are part of the embodiments of the present invention, rather than all of the embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the application claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

Claims

1. A method for preparing nitrite intelligent responsive hydrogel nanomaterial FMs@SHNM, characterized in that: The following steps are involved: The acrylic acid analog, the acrylamide analog and the main molecule to be encapsulated are dissolved in water, and a cross-linking agent is added and mixed evenly to obtain a mixed solution; the pH value of the mixed solution is adjusted until the pH is greater than 9.0, and then an accelerator and a catalyst are added, and the mixture is polymerized at a constant temperature of 50 to 100° C. for 8 to 48 hours, and then washed with water and dried for 12 to 48 hours to obtain the nitrite smart responsive hydrogel nanomaterial FMs@SHNM.

2. The method for preparing a nitrite smart responsive hydrogel nanomaterial FMs@SHNM according to claim 1, characterized in that: The acrylic acid analogue is selected from one of acrylic acid, methacrylic acid, 2-ethylacrylic acid, butenedioic acid, propylene oxide, and propanesulfonic acid; the acrylamide analogue is selected from one of 2-methylacrylamide and buteneamide; the mass ratio of the acrylic acid derivative, the acrylamide derivative, and the main molecule is (1-10):(1-50):

1.

3. The method for preparing a nitrite smart responsive hydrogel nanomaterial FMs@SHNM according to claim 1, characterized in that: The main molecule is a small molecule and / or a macromolecule with algaecidal and detoxifying functions, and is selected from at least one of the following types: benzalkonium bromide and other quaternary ammonium salt algaecides, algae toxin degrading enzyme MlrA and its complex enzyme, algae toxin degrading enzyme MlrB and its complex enzyme, and algae toxin degrading enzyme MlrC and its complex enzyme.

4. The method for preparing a nitrite smart responsive hydrogel nanomaterial FMs@SHNM according to claim 1, characterized in that: The cross-linking agent is prepared by the following method: allyl acetoacetate, undecenal and ammonium acetate are dissolved in ethanol, and then a catalyst triethylamine is added, mixed evenly, and reacted for 1 to 24 hours; then, heated at 50 to 100° C. and refluxed for 12 to 48 hours, passed through a column, and dried by spin drying to remove the solvent ethanol; the molar ratio of allyl acetoacetate, undecenal and ammonium acetate is (1 to 5):1:(1 to 20); the volume ratio of the mixed solution of allyl acetoacetate, undecenal and ammonium acetate to the catalyst triethylamine is (5 to 50):

1.

5. The method for preparing a nitrite smart responsive hydrogel nanomaterial FMs@SHNM according to claim 1, characterized in that: The accelerator is selected from one of diisopropylethylenediamine, 1,3-propylenediamine, tetramethylethylenediamine, and triethylenetetraminehexaacetic acid; the catalyst is selected from one of sodium persulfate, potassium persulfate, and ammonium persulfate; the added molar ratio of the accelerator and the catalyst is 1: (1-50).

6. A nitrite-responsive hydrogel nanomaterial FMs@SHNM, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 5.

7. An application of the nitrite smart response hydrogel nanomaterial FMs@SHNM as claimed in claim 6 as a water treatment agent in the field of algae bloom water environment pollution control.

8. A use according to claim 7, characterized in that The algae blooms include red tides and cyanobacterial blooms.

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