Preparation method and application of waste straw carbon quantum dots doped with trace copper ion preparation

Abstract

The present invention relates to the field of chemical materials technology, and discloses a preparation method and application of a waste straw carbon quantum dot-doped trace copper ion preparation. The method comprises the following steps: soaking agricultural and forestry waste straw in water, adding a copper-containing solution, adjusting the pH, heating, cooling, filtering, and dialyzing to obtain a preparation. The preparation is used in the prevention and treatment of plant viral diseases. The preparation is negatively charged and binds to the positively charged regions of the plant viral capsid protein. The efficient electron presentation efficiency of the carbon quantum dots enhances the redox activity of the copper ions, promoting the generation of reactive oxygen species. This achieves a highly efficient driving force for degradation of the plant viral capsid protein even under conditions of reduced copper ion concentration, thereby reducing the application of copper ions and increasing their efficiency, thereby lowering the environmental exposure level of copper ions.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and in particular to a preparation method and application of a waste straw carbon quantum dot-doped trace copper ion preparation. Background Art

[0002] Copper has been used in antibacterial and antiviral activities for thousands of years. Modern technology research shows that copper can induce the production of ROS (superoxide radicals, hydroxyl radicals, etc.) through its own redox process, destroying the biological molecules, RNA, DNA and proteins of viruses. Studies have shown that copper-based metal nanoparticles (NPs) can kill viruses by inducing degradation of viral capsid proteins through ROS. + With Cu 2+ The ratio determines the damage efficiency of the capsid protein.

[0003] Regarding copper-based antiviral drugs: Traditional commercially available anti-plant virus products use high concentrations of copper ions in exchange for high-efficiency redox activity. These heavy metal copper ions bring new environmental pressures.

[0004] As for other anti-plant virus drugs: drug types can be divided into metal salts, organic compounds, amino acids, vitamins, plant hormones, proteins, etc. Although these drugs can produce certain inhibitory effects on plant viruses, there are still the following challenges: (1) Low antiviral efficiency. Conventional anti-plant virus drugs are often not efficiently and accurately delivered to plant cells to perform antiviral actions, thus affecting the antiviral efficiency. (2) They are prone to secondary pollution. Many metal salts and organic compound drugs often introduce new pollutants while implementing anti-plant virus, causing new pressure on the environment. (3) They produce plant toxicity. Some drugs enhance the antiviral ability of plants by inducing acquired resistance in plants, thereby inhibiting the replication and proliferation of viruses; there are also drugs used as inhibitors of protein expression and nucleic acid replication to resist plant viruses. These mechanisms effectively resist plant viruses while causing serious damage to the normal growth of the plants themselves.

[0005] Therefore, a new formulation is urgently needed. Summary of the Invention

[0006] The purpose of the present invention is to overcome the problem that high concentrations of copper ions are used to resist plant viruses in the prior art, and excessive metal copper ions cause environmental pollution, and to provide a preparation method and application of a waste straw carbon quantum dot doped trace copper ion preparation.

[0007] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a waste straw carbon quantum dot doped trace copper ion preparation, wherein the method comprises the following steps:

[0008] The agricultural and forestry waste straw is soaked in water, and after adding a copper-containing solution, the pH is adjusted, heated, cooled, filtered and dialyzed to obtain a preparation.

[0009] The second aspect of the present invention provides a waste straw carbon quantum dot doped with trace copper ions prepared by the above preparation method;

[0010] Preferably, the content of copper ions in the preparation is 0.12-1.82 wt%.

[0011] The third aspect of the present invention provides the use of the above-mentioned waste straw carbon quantum dots doped with trace copper ions in the prevention and treatment of plant viral diseases.

[0012] Through the above technical solution, the preparation method and application of the waste straw carbon quantum dot doped trace copper ion preparation provided by the present invention have the following beneficial effects:

[0013] In the method for preparing a waste straw carbon quantum dot-doped trace copper ion preparation of the present invention, agricultural and forestry waste straw is soaked in water, poured into a reactor, and after adding a copper-containing solution, the pH is adjusted, heating, cooling, filtering, and dialyzing are performed to obtain the waste straw carbon quantum dot-doped trace copper ion preparation. The preparation is negatively charged and combines with the positively charged region in the plant virus capsid protein. The efficient electron presentation efficiency of the carbon quantum dots enhances the redox activity of the copper ions and can promote the generation of reactive oxygen species, thereby achieving a highly efficient driving force for degradation of the plant virus capsid protein while reducing the copper ion concentration, achieving reduced copper ion application and increased efficiency, and reducing the environmental exposure level of the copper ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is an AFM image of a waste straw carbon quantum dot doped with a trace amount of copper ion preparation prepared in Example 1 of the present invention;

[0015] Figure 2 This is a schematic diagram of the process of using the waste straw carbon quantum dots doped with trace copper ion preparation prepared in an embodiment of the present invention in the prevention and treatment of plant viral diseases;

[0016] Figure 3 This is an infrared spectrum of the waste straw carbon quantum dots doped with trace copper ions prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0017] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0018] The first aspect of the present invention provides a method for preparing a waste straw carbon quantum dot-doped trace copper ion preparation, wherein the method comprises the following steps:

[0019] The agricultural and forestry waste straw is soaked in water, and after adding a copper-containing solution, the pH is adjusted, heated, cooled, filtered and dialyzed to obtain a preparation.

[0020] In the present invention, the preparation is negatively charged and combines with the positively charged region in the plant virus capsid protein. The efficient electron presentation efficiency of the carbon quantum dots enhances the redox activity of copper ions and can promote the generation of reactive oxygen species, thereby achieving a highly efficient driving force for degradation of plant virus capsid proteins while reducing the copper ion concentration, achieving reduced copper ion application and increased efficiency, and reducing the environmental exposure level of copper ions.

[0021] According to the present invention, the agricultural and forestry waste straw is 0.5-1.5 parts by weight.

[0022] In the present invention, when the content of the agricultural and forestry waste straw is less than 0.5 parts by weight, the relative content of copper ions bound thereto increases, bringing stress to the environment and plants. When the content of the agricultural and forestry waste straw is greater than 1.5 parts by weight, the relative content of copper ions bound thereto is too low, and the effect of degrading plant viruses cannot be achieved.

[0023] Furthermore, the mass of the agricultural and forestry waste straw is 0.8-1.2 parts by weight.

[0024] According to the present invention, the agricultural and forestry waste straw is selected from at least one of corn straw, soybean straw and rice straw.

[0025] According to the present invention, the copper-containing solution is selected from at least one of copper chloride dihydrate, copper nitrate and copper sulfate pentahydrate.

[0026] According to the present invention, the concentration of the copper-containing solution is 1-10 mM.

[0027] In the present invention, when the concentration of the copper-containing solution is less than 1 mM, plant viruses cannot be degraded, and when the concentration is greater than 10 mM, stress is brought to plants or the environment.

[0028] Furthermore, the concentration of the copper-containing solution is 1-5 mM.

[0029] According to the present invention, the volume of the water is 75-225 mL relative to 0.5-1.5 g of the agricultural and forestry waste straw.

[0030] Furthermore, relative to 0.5-1.5 g of the agricultural and forestry waste straw, the volume of the water is 120-170 mL.

[0031] According to the present invention, the water is selected from ultrapure water and / or deionized water.

[0032] According to the present invention, the soaking time is 30-60 minutes.

[0033] Furthermore, the soaking time is 40-50 minutes.

[0034] According to the present invention, the pH is 4-9.

[0035] In the present invention, a pH that is too high or too low is not conducive to the stability of the preparation and may cause precipitation under natural conditions.

[0036] Furthermore, the pH is 7-9.

[0037] According to the present invention, the conditions of the oven include: temperature of 120-240° C. and time of 8-16 hours.

[0038] Furthermore, the conditions of the oven include: temperature of 160-200° C. and time of 10-14 hours.

[0039] According to the present invention, the filtering conditions include: the pore size of the filter membrane is 0.1-0.22 μm.

[0040] Furthermore, the filtering conditions include: the pore size of the filter membrane is 0.13-0.19 μm.

[0041] According to the present invention, the dialysis conditions include: using a 200-400D dialysis bag for 48-72 hours.

[0042] Furthermore, the dialysis conditions include: using a 250-350D dialysis bag for 55-65 hours.

[0043] The second aspect of the present invention provides a waste straw carbon quantum dot doped with trace copper ions prepared by the above preparation method;

[0044] Preferably, the content of copper ions in the preparation is 0.12-1.82 wt%.

[0045] In the present invention, Figure 1 This is an AFM image of the waste straw carbon quantum dots doped with trace copper ions (Cu-CDs) prepared in Example 1 of the present invention; Figure 1 It can be seen that the Cu-CDs have uniform particle size distribution and good dispersion, and their particle size range is within 10 nm.

[0046] The third aspect of the present invention provides the use of the above-mentioned waste straw carbon quantum dots doped with trace copper ions in the prevention and treatment of plant viral diseases.

[0047] In the present invention, Figure 2The present invention is a schematic diagram of the process of using the waste straw carbon quantum dot-doped trace copper ion preparation prepared by the present invention in the prevention and treatment of plant viral diseases.

[0048] In the present invention, 0.5-1.5 L of the synthetic stock solution is diluted 5-10 times and used for spraying crops in sunny weather, and the spraying is repeated 2-4 times at intervals of 2-5 days.

[0049] In the present invention, plant viruses include tobacco mosaic virus (TMV), cucumber mosaic virus (CMV), potato virus X (PVX) and pepper mild mottle virus (PMMoV).

[0050] The present invention will be described in detail below by way of examples.

[0051] The production rate of active oxygen was measured by electron paramagnetic resonance spectrometer;

[0052] Cu 2+ :Cu + The ratio was measured using inductively coupled plasma mass spectrometry;

[0053] The charge of the preparation was measured using a Zeta potential instrument;

[0054] The anti-plant virus efficiency is calculated according to the formula:

[0055] The raw materials used in the examples and comparative examples are all commercially available products.

[0056] Example 1

[0057] Soak 1 g of rice straw in 150 mL of ultrapure water for 30 min, pour it into a reactor, add 0.1705 g of 1 mM copper chloride dihydrate, adjust the pH to 9, move to an oven at 180°C and heat for 12 h, cool to room temperature, filter with a 0.16 μm filter membrane, and place the filtrate in a 300D dialysis bag for 50 h to obtain Preparation A1.

[0058] Figure 1 This is an AFM image of the waste straw carbon quantum dots doped with trace copper ions (Cu-CDs) prepared in Example 1 of the present invention; Figure 1 It can be seen that the Cu-CDs have uniform particle size distribution and good dispersion, and their particle size range is within 10 nm.

[0059] Figure 3 This is the infrared spectrum of the waste straw carbon quantum dots doped with trace copper ion preparation (Cu-CDs) prepared in Example 1 of the present invention. Figure 3 It can be seen that at 1597cm -1 The peak centered on the C=O / C=N stretching vibration is derived from the stretching vibration of CC and CN, which appears at 1383 cm-1 and 1350cm -1 Nearby, at 1027cm -1 The peak at 618 cm is the stretching vibration of N-Cu-N. -1 The peak appearing at is Cu-O vibration.

[0060] Examples 2-5

[0061] Preparations were prepared according to the method of Example 1, except that the types and amounts of raw materials were different from those in Example 1, as shown in Table 1; and the process conditions were different from those in Example 1, as shown in Table 1. Preparations A2-A5 were prepared respectively.

[0062] Comparative Example

[0063] Preparations were prepared according to the method of Example 1, except that the types and amounts of raw materials were different from those in Example 1, as shown in Table 1; and the process conditions were different from those in Example 1, as shown in Table 1. Preparations D1-D4 were prepared respectively.

[0064] Table 1

[0065]

[0066]

[0067] Table 1 (continued)

[0068]

[0069] Test Example 1

[0070] The preparations in the above examples and comparative examples were tested for their anti-plant virus properties. The results are shown in Table 2.

[0071] Table 2

[0072]

[0073]

[0074] As shown in Table 2, compared with the comparative example, when the preparation prepared in the embodiment of the present invention is tested for anti-plant virus, the preparation is negatively charged, and the content of copper ions in the preparation is 0.12-1.82 wt%. When the preparation is used for anti-plant virus, the relative yield of active oxygen is 45-100%, and Cu 2+ :Cu + The mass ratio is (1-3):1, and the anti-plant virus efficiency is 50-94%, which has excellent anti-plant virus efficiency.

[0075] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A method for preparing a waste straw carbon quantum dot doped trace copper ion preparation, characterized in that: The method comprises the following steps: The waste agricultural and forestry straw is soaked in water, a copper solution is added, and then the pH is adjusted, heated, cooled, filtered and dialyzed to obtain a preparation. Wherein, the concentration of the copper-containing solution is 1-10mM; Wherein, the volume of the water is 75-225 mL relative to 0.5-1.5 g of the agricultural and forestry waste straw; Wherein, the pH is 4-9.

2. The preparation method according to claim 1, characterized in that The copper-containing solution is selected from at least one of copper chloride dihydrate, copper nitrate and copper sulfate pentahydrate.

3. The preparation method according to claim 1, characterized in that The water is selected from ultrapure water and / or deionized water.

4. The preparation method according to claim 1, characterized in that The soaking time is 30-60 minutes.

5. The preparation method according to any one of claims 1 to 4, characterized in that The heating conditions include: temperature of 120-240° C. and time of 8-16 hours.

6. The preparation method according to any one of claims 1 to 4, characterized in that The filtering conditions include: the pore size of the filter membrane is 0.1-0.22 μm.

7. The preparation method according to any one of claims 1 to 4, characterized in that The dialysis conditions include: using a 200-400D dialysis bag for 48-72 hours.

8. A waste straw carbon quantum dot-doped trace copper ion preparation prepared by the preparation method according to any one of claims 1 to 7.

9. The waste straw carbon quantum dot doped trace copper ion preparation according to claim 8, characterized in that: The content of copper ions in the preparation is 0.12-1.82 wt %.

10. Use of the waste straw carbon quantum dot-doped trace copper ion preparation according to claim 8 in the prevention and treatment of plant viral diseases.

Images