CN114199915A - Nano plastic particle standard substance prepared by simulating natural conditions and development method thereof - Google Patents
Nano plastic particle standard substance prepared by simulating natural conditions and development method thereof Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/02—Investigating particle size or size distribution
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
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Abstract
The invention belongs to the field of material preparation, and relates to a nano plastic particle standard substance prepared by simulating natural conditions and a development method thereof. The preparation method comprises the following steps: carrying out simulated natural condition treatment on finished plastic, wherein the simulated natural condition treatment comprises the following steps: acid treatment, alkali treatment, protease treatment, water soaking treatment, drying treatment, ultraviolet irradiation treatment and grinding treatment. The particle size of the nano plastic particle standard substance provided by the invention is 10-1000 nm, the particles are irregular, the Zeta potential of the solution subjected to ultra-pure water ultrasonic dispersion is-30 to-20 mV, and is closer to the nano plastic particles formed under natural conditions.
Description
Technical Field
The invention belongs to the field of material preparation, and relates to a nano plastic particle standard substance prepared by simulating natural conditions and a development method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Since the 90 s of the 20 th century, researchers focused on the distribution, material, surface-adhering components, toxicology, and the like of micro-and nano-sized plastic particles present in the environment. Researchers define nano plastic particles as plastic particles with diameters less than 1 μm, and the existence of the nano plastic particles in nature is mostly predicted and analyzed according to the distribution of micro plastic.
Currently, most researchers use commercial nano plastic particles to perform related detection analysis, and research is concentrated on establishing a new detection method or researching the toxicity of the detection method. For example, the distribution of commercial fluorescent-labeled nano plastic particles in the root of Arabidopsis thaliana is explored. Some researchers also use the commercialized fluorescence labeled nano plastic particles to study the transportation and distribution conditions in animals. However, the inventors have found that the above-mentioned studies on nano plastic particles have the same outstanding problem, and whether commercial nano plastic particles can be used to replace naturally occurring nano plastic particles?
From the aspect of microscopic characterization: in reality, the existing nano plastic particles have different particle sizes, irregular shapes and complex surface components, and have various aggregation modes (aggregation among plastic particles, aggregation of plastic particles and various substances); the commercialized nano plastic particles are uniform in particle size and uniform and spherical in shape, and a surfactant is generally added into a solution, so that the monodisperse effect in ultrapure water is good. From the formation process: the nano plastic particles existing in nature are formed by aging and crushing through various natural condition factors such as weathering effect, ultraviolet irradiation and the like; the current commercialized nano plastic particles are synthesized by a plastic monomer through an emulsion synthesis method and do not undergo a natural aging process.
Due to the complex matrix interference, the separation and acquisition of the nano plastic particles from the natural environment are very difficult, and few researchers can really separate the nano plastic particles existing in the nature. The inventor thinks that the commercialized nano plastic particles used in the research on the nano plastic particles at present have great difference with the nano plastic particles existing in nature, and certain method errors are certainly caused when the commercialized nano plastic particles are used as standard products for carrying out related research.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the inventors believe that the use of a standard substance of nano plastic particles that is closer to the naturally occurring standard substance enables the results of research related to nano plastic to be more accurate, such as establishment of a nano plastic particle detection method and toxic effects of nano plastic particles on animals and plants. However, in the research field of nano plastics, the standard microspheres which are synthesized by using an emulsion polymerization method and have regular shapes are mostly different from nano plastic particles generated under natural conditions.
Therefore, the invention aims to provide a nano plastic particle standard substance prepared by simulating natural conditions and a development method. The method has research and industrial popularization significance, and if the mass production of the nano plastic particle standard substance which is close to the naturally existing standard substance is realized, the method can lay a foundation for improving the accuracy of the related research of the nano plastic particles.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the first hand, in a nano plastic particle standard substance prepared by simulating natural conditions, particles are irregular in a 10-1000 nm electron microscope picture; the Zeta potential of the solution after ultrasonic dispersion by adopting ultrapure water is-30 to-20 mV.
Researches show that the commercialized nano plastic particles and nano plastic particles prepared under simulated natural conditions have obvious differences in appearance rule degree, particle size distribution, Zeta potential, natural aggregation state and the like. When the nano plastic particles meet the requirements of irregular shape, wide particle size distribution, Zeta potential of-30 to-20 mV and the existence of aggregation plastic particles, the nano plastic particles are closer to the nano plastic particles formed under natural conditions, so the nano plastic particles can be used as a standard product for replacing the nano plastic particles formed under natural conditions.
In a second aspect, a development method of a nano plastic particle standard product prepared by simulating natural conditions simulates natural aging treatment of finished plastic, wherein the simulated natural aging treatment comprises the following steps: acid treatment, alkali treatment, protease treatment, water soaking treatment, drying treatment, ultraviolet irradiation treatment and grinding treatment.
The invention utilizes various existing finished plastics to simulate natural aging for treatment to obtain a nano plastic particle standard product, compares the current commercialized nano plastic particles and nano plastic particles prepared under simulated natural conditions with naturally existing nano plastic particles, and finds that the nano plastic particles prepared under simulated natural aging are closer to the nano plastic particles generated under natural conditions than the commercialized nano plastic particles. In addition, the method for preparing the nano plastic particles by simulating natural conditions can stably produce the nano plastic particles with different particle size distributions under laboratory conditions, can realize production from 50-100 nm, 100-200 nm and the like, and can be realized by only increasing filter membranes with corresponding pore sizes if more accurate particle size distribution is needed. Verification proves that the nano plastic particles with different materials can be obtained by replacing the initial plastic with different materials.
In a third aspect, a characterization method of the nano plastic particle standard substance prepared by simulating natural conditions adopts a scanning electron microscope, a particle size analyzer and surface enhanced raman spectroscopy for detection.
The nano plastic particles prepared by the method are basically consistent with the characterization results of the nano plastic particles generated under natural conditions in all aspects, including the degree of shape regulation, particle size distribution, Zeta potential, natural aggregation state and the like. The method has the outstanding advantages that the prepared nano plastic particles are closer to nano plastic particles generated under natural conditions than commercial nano plastic particles, and the method provides a standard substance closer to an object to be measured for related research of nano plastic. The method has the advantages that raw materials are easy to obtain, the crushing process can be correspondingly adjusted according to natural conditions needing to be simulated, the grinding means is replaced by an analytical ball mill, the large-scale production can be realized, and the method has important scientific research value.
In a fourth aspect, the nano plastic particle standard substance prepared by simulating natural conditions is applied to any one of the following items:
a. the application in detecting naturally-produced nano plastic particles;
b. the application in researching the toxicity of the nano particles;
c. the application in preparing and screening the medicine for treating the damage of the naturally generated nano plastic particles to animals and plants;
d. the application of the nano plastic in researching the behavior change of the nano plastic in the environment is disclosed.
The nano plastic particle standard substance prepared by simulating natural conditions is applied to the establishment of the detection method of the naturally generated nano plastic particles, so that the behavior change and the appearing response signal of the naturally generated nano plastic particles in the detection process can be restored to the maximum extent; the method is applied to the toxicological research of the nano plastic particles, can simulate the damage process and pathogenic mechanism of the naturally generated nano plastic particles to animals and plants to the maximum extent, and can be particularly applied to the preparation and screening of medicaments for treating the damage of the naturally generated nano plastic particles to the animals and plants; the method is applied to the research on the behavior change of the nano plastic in the environment, and can simulate the behavior dynamics characteristics of aggregation, distribution, adsorption and the like of naturally generated nano plastic particles to the maximum extent.
Compared with the prior art, the invention has the beneficial effects that:
1. in view of the difference between the commercialized nano plastic particles obtained by the existing preparation method of nano plastic particles and naturally produced nano plastic particles, the field of preparing the nano plastic particles simulating natural conditions is blank. The nano plastic particles prepared by simulating natural conditions are closer to naturally produced nano plastic particles than commercial nano plastic particles. The nano plastic particles prepared by the method have almost no difference from naturally generated nano plastic particles in the aspects of forming process, surface roughness, particle size distribution range, physical and chemical properties and the like. The standard substance can be used for related scientific research work of the nano plastic particles, such as establishment of a nano plastic particle detection method, research on influence of the nano plastic particles on organisms, distribution change of the nano plastic particles in the environment and the like, and the accuracy of the research is improved.
2. The preparation method utilizes the conditions of grinding, ultraviolet light, acid and alkali, protease and the like to treat, and reduces the influence of the conditions of wind action, ultraviolet irradiation, acid and alkali erosion and the like on plastics in natural conditions to a greater extent, so that the nano plastic particles generated under the conditions close to the natural conditions are stably prepared under the laboratory conditions, and the batch production of the nano plastic particles with different materials can be realized only by changing the initial plastic material.
3. The invention provides a characterization and detection method of nano plastic particles. In the process of preparing the nano plastic particles, an effective characterization and detection means of the nano plastic particles is established. The morphology of the nano-plastics can be observed through a scanning electron microscope, and the primary counting is carried out. And analyzing the particle size distribution and the Zeta potential of the nano plastic particles by using a particle size analyzer, and realizing qualitative detection of the nano plastic particles by using the surface enhanced Raman effect of the nano silver particles. Grinding for 20min under determined conditions, with a grinding mass of 0.6g, under scanning electron microscope to obtain at least 1.24 × 1010And (3) nano plastic particles with the particle size range meeting the expected purpose of classified filtration.
4. The nano plastic particle preparation method under the simulated natural condition is expected to be applied to scientific research work related to nano plastic, provides a more accurate nano plastic particle sample and a corresponding qualitative and quantitative method for the establishment of a nano plastic particle detection method, and provides a nano plastic particle standard substance closer to the natural state for the toxicological research of nano plastic particles.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic representation of nano plastic particles obtained by the preparation method of example 1 of the present invention, wherein a is a schematic representation of crushing an initial plastic under simulated natural conditions, b is a schematic representation of a graded filtering process after crushing the initial plastic, and c is a schematic representation of a detection and characterization process of the nano plastic particles;
FIG. 2 is a diagram of an optimization mirror for grinding time and quality conditions of ground samples for preparing nano plastic particles in example 1, wherein a is nano plastic particles with a particle size of 50-100 nm in a field of view after graded filtration, and b is a counting result of a scanning mirror;
fig. 3 shows the detection and characterization results of the nano plastic particles prepared in example 1 of the present invention, wherein a is the measurement of various morphological parameters of the prepared nano plastic particles, including the measurement results of the symmetrical angle, maximum length, width, and area, b is the result of particle size distribution, c is the result of Zeta potential, d and e are raman detection spectra, and f is the raman detection spectra;
FIG. 4 is a comparison of parameters of the nano plastic particles prepared in example 1 of the present invention with commercially available commercial nano plastic particles and naturally occurring nano plastic particles, a is a transmission electron microscope image of blank ultrapure water, b is a transmission electron microscope image of commercial fluorescent nano plastic particles, c is a transmission electron microscope image of commercial monodisperse nano plastic particles, d is a transmission electron microscope image of nano plastic particles prepared in example 1, e is a transmission electron microscope image of naturally occurring nano plastic particles, f is a scanning electron microscope image of blank ultrapure water, g is a scanning electron microscope image of commercial monodisperse nano plastic, h is a scanning electron microscope image of commercial fluorescent nano plastic particles, i is a scanning electron microscope image of nano plastic particles prepared in example 1, j is a scanning electron microscope image of naturally occurring nano plastic particles, and k is a parameter curve of commercial nano plastic particles, l is a parameter curve of the nano plastic particle prepared in example 1 of the present invention, m is a parameter curve of a naturally occurring nano plastic particle, n is a particle size distribution curve, o is a Zeta potential, and p is a raman spectrum.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular is intended to include the plural unless the context clearly dictates otherwise, and it should be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of features, steps, operations, devices, components, and/or combinations thereof.
The irregular shape refers to a three-dimensional shape with an nonstandard appearance, and the standard three-dimensional shape is a sphere, a cube, a cylinder, a cone, a prismoid, a regular tetrahedron and the like.
In view of the difference between the commercialized nano plastic and the nano plastic existing in nature, the commercialized nano plastic cannot be used as a standard substance for research, and the invention provides a nano plastic particle standard substance prepared by simulating natural conditions and a development method thereof.
In a typical embodiment of the invention, a nano plastic particle standard substance prepared by simulating natural conditions is provided, particles are irregular in a 10-1000 nm electron micrograph, and the Zeta potential of a solution subjected to ultrasonic dispersion by adopting ultrapure water is-30-20 mV.
On the other hand, the development method for preparing the nano plastic particle standard product by simulating natural conditions carries out simulated natural aging treatment on finished plastic, and comprises the following steps: acid treatment, alkali treatment, protease treatment, water soaking treatment, drying treatment, ultraviolet irradiation treatment and grinding treatment.
The development method of the invention avoids the interference of other substances except plastics to the maximum extent, and simulates the influence of natural conditions on plastics to the maximum extent. For example: after entering the environment, the plastic is affected by a damp environment, such as a dustbin or a garbage pile damp and warm environment, or enters a marine environment, the pH range is 4.0-10.0, and the process is simulated by acid and alkali treatment; the plastic can be directly irradiated by sunlight, and the process is simulated by drying and ultraviolet irradiation; plastics are also subject to weathering in natural conditions, and this process is simulated by grinding.
In some examples of this embodiment, the acid treatment is carried out at a pH of 3.5 to 4.5 for 2 to 24 hours. The acid can be hydrochloric acid, sulfuric acid, nitric acid or mixed acid.
In some examples of the embodiment, the pH of the alkali is 9.5-10.5, and the treatment time is 2-24 h. The alkali can be sodium hydroxide, potassium hydroxide or mixed alkali.
In some examples of this embodiment, the protease treatment time is 12 to 36 hours. The protease used may be trypsin. The trypsin can effectively degrade the biological residual protein substances attached to the surface.
In some examples of this embodiment, the water soaking time is 12 to 36 hours. The water used may be ultrapure water. The ultrapure water serves to avoid the influence of other impurities in the tap water or river water.
In some examples of this embodiment, the drying temperature is room temperature. The room temperature refers to the indoor environment temperature, and is generally 15-30 ℃. The drying time is 12-36 h.
In some examples of this embodiment, the UV irradiation treatment time is 12 to 36 hours.
In some examples of this embodiment, the grinding process employs an agate mortar. In the experimental process, impurities generated by the glass mortar body influence the preparation of the nano plastic particles, so that the agate mortar with harder texture is selected to replace the glass mortar.
In some examples of this embodiment, the milling treatment time is not less than 20 min. When ground for 20min, the increase in grinding time did not significantly increase the abundance of nano-plastic particles. The grinding time is therefore preferably 20 min.
In some examples of the embodiment, the natural simulation treatment is followed by classification filtration, so that nano plastic particles with different particle size distributions can be stably produced.
In a third embodiment of the present invention, a characterization method of the nano plastic particle standard substance simulating the above natural conditions is provided, and an electron microscope, a particle size analyzer and a surface enhanced raman spectroscopy are adopted for detection.
In some embodiments of this embodiment, the electron microscope is a scanning electron microscope and/or a transmission electron microscope.
In some examples of this embodiment, the nano plastic particle standard prepared by simulating natural conditions is added to ultrapure water and ultrasonically dispersed to obtain an aqueous dispersion, and the aqueous dispersion is detected by using a transmission electron microscope, a particle size analyzer and surface enhanced raman spectroscopy.
In one or more embodiments, the aqueous dispersion is mixed with the colloidal silver solution, the magnesium sulfate solution is added and mixed uniformly, and then the mixture is added dropwise to the raman spectroscopy substrate for raman spectroscopy scanning.
In a fourth embodiment of the present invention, there is provided an application of the above standard nano plastic particles prepared by simulating natural conditions in any one of the following applications:
a. the application in detecting naturally-produced nano plastic particles;
b. the application in researching the toxicity of the nano particles;
c. the application in preparing and screening the medicine for treating the damage of the naturally generated nano plastic particles to animals and plants;
d. the application of the nano plastic in researching the behavior change of the nano plastic in the environment is disclosed.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
Crushing and separating of polypropylene material
As shown in FIG. 1, polypropylene takeaway packaging box was subjected to hydrochloric acid (pH 4.0) treatment for 24h, sodium hydroxide solution (pH 10.0) treatment for 24h, trypsin solution (concentration 0.25%) treatment for 24h, ultra pure water soaking for 24h, room temperature drying for 24h, ultraviolet irradiation for 24h, and preliminary crushing with scissors to 1mm2And (3) taking 0.6g of the small blocks, grinding the small blocks in an agate mortar for 20min, and flushing the small blocks into a beaker by using ultrapure water after grinding to obtain a sample. Filtering with 400nm, 200nm, 100nm and 50nm filter membranes respectively, and retaining nanometer plastic particles on the filter membranes with 200nm, 100nm and 50nm pore diametersThe particle size distribution is 200-400 nm, 100-200 nm, 50-100 nm. And reserving the central parts of the filter membranes with the diameters of 5mm multiplied by 5mm, spraying gold, observing the sample by using a scanning electron microscope, putting the rest parts into a beaker, adding 5mL of ultrapure water, and carrying out ultrasonic treatment for 30min to Promote Polypropylene (PP) nano plastic particles to be dispersed into the ultrapure water, so as to obtain the ultrapure water dispersed sample of the PP nano plastic particles with different particle sizes.
Characterization and detection of nano plastic particles
Carrying out scanning electron microscope observation (3kV) on the film sample, and representing the morphology and the particle abundance of the nano plastic particles; and (3) carrying out transmission electron microscope (8kV) observation and particle size instrument detection on the ultrapure water dispersion sample, further verifying the morphology and the size of the nano plastic particles, and analyzing the particle size distribution and the Zeta potential of the nano plastic particles. And (3) uniformly mixing 20 mu L of liquid sample with 1mL of colloidal silver solution, adding 10 mu L of magnesium sulfate solution with the concentration of 1mol/L, uniformly mixing, dropwise adding 5 mu L of mixture onto a clean silicon wafer, and scanning a Raman spectrum (633nm, 5%) to obtain Raman spectrum information.
The quantity of PP nano plastic particles with the particle size of 100-200 nm under a scanning electron microscope is shown in figure 2, under the same grinding condition, the grinding time is prolonged, and the richness of the PP nano plastic particles is not obviously increased; under the same grinding time, the plastic quality is increased, and the richness of the nano plastic particles is obviously increased. The histogram shows that five fields were randomly selected for simple counting, 0.6g plastic was ground for 20min to produce at least 6.2X 109And PP nano plastic particles. (formula: effective filtration area of Membrane (2. pi. mm)2) Scanning electron microscope observation Total area (5X 5 mm)2) Total area observed by X scanning electron microscope (5X 5 mm)2) Observation of actual area by scanning mirror (4X 10)-3×3×10-3mm2) Mean observation number (43). The effect is better when 0.6g of plastic is selected and the grinding time is 20min as the grinding condition.
The size parameters, the particle size distribution, the Zeta potential and the Raman spectrum data of the PP nano plastic particles with different particle sizes are shown in figure 3. In fig. 3a, the size of the prepared PP nanoplastic particles gradually decreases, but it appears irregular; in fig. 3b, the actual particle diameters of the prepared PP nano plastic particles with the particle diameters of 200-400 nm and 100-200 nm are 255nm and 122nm respectively, and the distribution is in accordance with the expectation, but the prepared PP nano plastic particles with the particle diameters of 50-100 nm are in an aggregation state, and the particles with the particle diameters of 164nm account for 23.4% and the particles with the particle diameter of 965nm account for 78.2%. As the particle size of the PP nano plastic particles is reduced, the absolute value of the Zeta potential of the PP nano plastic particles is reduced, and the particle dispersibility becomes unstable, so that the particles are aggregated. FIG. 3c shows that the final Zeta potential results of the PP nano plastic particles with three particle sizes are all about-30 mV. According to the relation between the Zeta potential of the particles and the stability of the particles in a dispersion system, the PP nano plastic particles with three particle sizes have moderate stability in ultrapure water, wherein the actual particle size of the prepared nano plastic particles with the particle size of 50-100 nm is 965nm and exists in a polymerization state.
And 3 d-f, detecting the prepared PP nano plastic particles by adopting a surface enhanced Raman method, mixing colloidal silver with a sample in an ultrapure water environment, adsorbing the colloidal silver onto the surfaces of the prepared PP nano plastic particles, and drying on a silicon wafer. Using PP nanometer plastic particles adsorbing colloidal silver as a condensation core, gathering the peripheral unadsorbed silver particles to form spots of about 1 mu m, and scanning the spots to obtain 841cm-1、971cm-1、1149 cm-1、1451cm-1Characteristic peaks of polypropylene.
The characterization result shows that the PP nano plastic particles with different particle sizes generated under the simulated natural condition are successfully prepared under the laboratory condition.
FIGS. 4a-f are morphology feature graphs of 80nm commercialized fluorescent PS microspheres and 80nm commercialized monodisperse PS microspheres under transmission electron microscope and scanning electron microscope. The results show that the 80nm commercial PS microspheres are uniform spheres and have good dispersibility regardless of fluorescence. This is because most of them are synthesized by emulsion polymerization, and have a surfactant on the surface to promote dispersion stability. FIGS. 4h and k are transmission electron microscope pictures of PP nano plastic particles with the particle size of 50-100 nm, and FIGS. 4i and l are scanning electron microscope pictures of PP nano plastic particles with the particle size of 50-100 nm, wherein the transmission electron microscope pictures and the scanning electron microscope pictures are irregular particles and have aggregation phenomena. The parameter analysis of fig. 4m, n, o shows that the prepared PP nano plastic particles are closer to naturally occurring nano plastic particles than commercial nano plastic particles.
The results of fig. 4n and o show that the particle size distribution of the commercial PS nano plastic particles is good and no aggregation phenomenon occurs, and the prepared nano plastic particles are similar to the naturally occurring nano plastic particles in distribution, and the aggregation phenomenon occurs, and the particle size of the nano plastic particles tends to be significantly increased. The Zeta potential result also shows that the Zeta potential of the commercialized PS nano plastic particles is significantly different from the Zeta potential of the prepared PP nano plastic particles, and the Zeta potential of the prepared PP nano plastic particles is not significantly different from the Zeta potential of the naturally existing nano plastic particles. Fig. 4p shows that the raman spectroscopy results are qualitatively for the corresponding material of the nano-plastic particles.
Therefore, by combining the particle size distribution and the Zeta potential of the three, the PP nano plastic particles prepared by the method are closer to naturally existing nano plastic particles.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nano plastic particle standard substance prepared by simulating natural conditions is characterized in that in an electron micrograph of 10-1000 nm, particles are irregular, and the Zeta potential of a solution subjected to ultrasonic dispersion by adopting ultrapure water is-30-20 mV.
2. A method for preparing a nano plastic particle standard substance by simulating natural conditions comprises the following steps of: acid treatment, alkali treatment, protease treatment, water soaking treatment, drying treatment, ultraviolet irradiation treatment, grinding treatment and graded filtration.
3. The method for preparing a nano plastic particle standard substance by simulating natural conditions as claimed in claim 2, wherein the pH of acid used for acid treatment is 3.5-4.5, and the treatment time is 2-24 h;
or, the pH value of alkali used for alkali treatment is 9.5-10.5, and the treatment time is 2-24 h;
or, the protease treatment time is 12-36 h;
or, the water soaking treatment time is 12-36 h;
or, the drying temperature is 15-15 ℃ at room temperature;
or, the ultraviolet irradiation treatment time is 12-36 h.
4. The method for preparing nano plastic particle standard substance by simulating natural conditions as claimed in claim 2, wherein the grinding treatment is carried out by means of agate mortar, ball mill and the like; or, the grinding treatment time is not less than 20 min.
5. The method as claimed in claim 2, wherein the natural conditions are simulated and nano-sized plastic particle standard is prepared by nano-scale classification filtration.
6. A characterization method of the nano plastic particle standard substance prepared by simulating natural conditions, which is obtained by the development method of claim 1 or any one of claims 2 to 5, is characterized in that a transmission electron microscope, a scanning electron microscope, a particle size and Zeta potential detector and a surface enhanced Raman spectrum are adopted for detection.
7. The characterization method according to claim 6, wherein the electron microscope is a scanning electron microscope and/or a transmission electron microscope.
8. The characterization method according to claim 6, wherein the nano plastic particle standard prepared by simulating natural conditions is added into ultrapure water, ultrasonic dispersion is carried out to obtain the aqueous dispersion, and the aqueous dispersion is detected by using a transmission electron microscope, a particle size analyzer and surface enhanced Raman spectroscopy.
9. The characterization method as claimed in claim 8, wherein the aqueous dispersion is mixed with the colloidal silver solution, then the magnesium sulfate solution is added and mixed uniformly, and then the mixture is dropped on the Raman spectrum substrate for Raman spectrum scanning.
10. The application of the nano plastic particle standard substance prepared by simulating natural conditions and obtained by the development method of claim 1 or any one of claims 2 to 5 in any one of the following applications:
a. the application in detecting naturally-produced nano plastic particles;
b. the application in researching the toxicity of the nano particles;
c. the application in preparing and screening the medicine for treating the damage of the naturally generated nano plastic particles to animals and plants;
d. the application of the nano plastic in researching the behavior change of the nano plastic in the environment is disclosed.
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