CN117735555A - Fluorescent silicon nano-particles, preparation method thereof and water-soluble fluorescent anti-counterfeiting ink - Google Patents
Fluorescent silicon nano-particles, preparation method thereof and water-soluble fluorescent anti-counterfeiting ink Download PDFInfo
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Abstract
The application provides fluorescent silicon nano particles, a preparation method thereof and water-soluble fluorescent anti-counterfeiting ink, and relates to the technical field of silicon nano materials. The preparation method of the fluorescent silicon nano-particles comprises the following steps: mixing a silicon source, a reducing agent and water, and reacting to obtain the fluorescent silicon nano particles; wherein the silicon source comprises 3-aminopropyl triethoxysilane; the reducing agent comprises humic acid. The fluorescent silicon nano particles prepared by the method are green under the irradiation of 365nm ultraviolet light, and can be applied to water-soluble fluorescent anti-counterfeiting ink. The fluorescent silicon nano particles with excellent acid and alkali resistance, light resistance and salt resistance are prepared by using the preparation method which is low in cost, simple to operate, easy to obtain raw materials, quick and convenient and mild in condition, and can be applied to fluorescent anti-counterfeiting ink to obtain clear and bright fluorescent patterns.
Description
Technical Field
The application relates to the technical field of silicon nano materials, in particular to fluorescent silicon nano particles, a preparation method thereof and water-soluble fluorescent anti-counterfeiting ink.
Background
In recent years, information security and anti-counterfeiting have attracted attention, and the need for developing novel anti-counterfeiting materials and anti-counterfeiting technologies is also increasing. In order to distinguish the authenticity of the commodity, the most effective and direct method is to use anti-counterfeiting technology to distinguish. The fluorescent anti-counterfeiting technology based on the fluorescent material has the advantages of rapid identification, simplicity and convenience in operation, time saving, strong anti-counterfeiting performance and the like, and is widely applied. At present, the commonly used fluorescent anti-counterfeiting materials mainly comprise semiconductor quantum dots, carbon quantum dots, polymer fluorescent materials, rare earth complex fluorescent nanoparticles and the like. Although these excellent fluorescent materials achieve good anti-counterfeit applications, they have non-negligible disadvantages such as poor photostability, high toxicity, cumbersome preparation, and high price.
Compared with the traditional luminescent semiconductor quantum dots and organic fluorescent dyes, the water-soluble fluorescent silicon nanoparticles (Si NPs) are a new research hot spot in the field of fluorescent nanomaterials. The fluorescent material has abundant and cheap resources, excellent biocompatibility and biodegradability, low toxicity, high fluorescence intensity, excellent fluorescence stability/photobleaching resistance and easy surface modification, and is considered to be an ideal fluorescent material, and is widely applied to the fields of fluorescence sensing, biological imaging, disease diagnosis and the like. For example, si NPs have been successfully used to detect dopamine, heparin, tetracycline, intracellular pH, reactive oxygen species, and the like. More importantly, si NPs can be biodegraded in a mouse model, and the degradation product orthosilicic acid is well compatible with many biological tissues, eventually excreted outside the body through renal clearance, while not producing significant toxicity to the mouse. This suggests that Si NPs have good biocompatibility and biosafety, lower toxicity. Therefore, the Si NPs with low cost, no toxicity and good light stability are designed and prepared, so that the Si NPs are applied to fluorescent anti-counterfeiting materials, and the Si NPs are the technical problems which are urgently needed to be solved at present.
Disclosure of Invention
The purpose of the application is to provide fluorescent silicon nano particles, a preparation method thereof and water-soluble fluorescent anti-counterfeiting ink. The fluorescent silicon nano particles with excellent acid and alkali resistance, light resistance and salt resistance are prepared by using the preparation method which has the advantages of low cost, simple operation, readily available raw materials, rapidness, convenience and mild condition, and can be applied to fluorescent anti-counterfeiting ink to obtain clear and bright fluorescent patterns.
In order to achieve the above object, the technical scheme of the present application is as follows:
the application provides a preparation method of fluorescent silicon nano particles, which comprises the following steps:
mixing a silicon source, a reducing agent and water, and reacting to obtain the fluorescent silicon nano particles;
the silicon source comprises 3-aminopropyl triethoxysilane;
the reducing agent comprises humic acid.
Preferably, the mixing comprises:
and after dissolving the reducing agent in alkali liquor to prepare a reducing agent solution, adding the silicon source and the reducing agent solution into the water.
Optionally, when the reducing agent is humic acid, the alkali liquor is 1wt% sodium hydroxide solution; the concentration of humic acid in the reducing agent solution is 5mmol/L-20mmol/L.
Further preferably, the silicon source, the reducing agent solution and the water are mixed in a volume ratio of (0.5 to 0.8): (1.0-2.5): (2.5-3).
Preferably, the reaction comprises:
after the mixed solution is obtained by mixing, the mixed solution is continuously stirred at the rotation speed of 800rpm-1200rpm under the standard atmospheric pressure and the temperature of 10-40 ℃ for reaction, and the reaction time is 20-40 min.
Preferably, after the reaction is finished, the method further comprises:
and transferring the solution after the reaction is finished into a dialysis bag of 500Da-1000Da for dialysis to obtain the purified fluorescent silicon nano particles.
Preferably, after the fluorescent silicon nano particles are obtained, the fluorescent silicon nano particle solution is obtained by dilution with water and is stored in an environment of 2-6 ℃.
The application also provides fluorescent silicon nanoparticles, which are prepared by adopting the preparation method of the fluorescent silicon nanoparticles.
Preferably, the fluorescent silicon nanoparticles appear green under 365nm ultraviolet light irradiation;
the particle size of the fluorescent silicon nano particles is 2.2nm-3.0nm.
The application also provides water-soluble fluorescent anti-counterfeiting ink, which comprises the fluorescent silicon nanoparticles prepared by the preparation method of the fluorescent silicon nanoparticles.
The beneficial effects of this application:
according to the preparation method of the fluorescent silicon nano particles, humic acid is used as a reducing agent, the silicon nano particles with obvious fluorescent effect are prepared through one-step synthesis, the preparation cost is low, the operation is simple, the method is rapid and convenient, the condition is mild, the raw materials are easy to obtain, no further chemical modification is needed, and no complex and expensive instrument is needed.
The fluorescent silicon nano particles have excellent light stability and chemical stability after being irradiated by an ultraviolet lamp with the wavelength of 365nm for a long time, in an environment with high concentration of salt or in an acidic and alkaline environment with the pH value of 3-12, and can be used for fluorescent anti-counterfeiting technology in a complex external environment.
In the water-soluble fluorescent anti-counterfeiting ink, fluorescent writing and fluorescent pattern drawing imaging can be performed by using the fluorescent silicon nano particles prepared by the preparation method, clear and bright fluorescent patterns can be obtained under ultraviolet irradiation, and the water-soluble fluorescent anti-counterfeiting ink is particularly suitable for packaging and printing of edible products such as foods, beverages and medicines.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is an XRD pattern of fluorescent silicon nanoparticles prepared in example 1;
FIG. 2 is a TEM image of fluorescent silicon nanoparticles prepared in example 1;
FIG. 3 is a UV-Vis absorption spectrum of fluorescent silicon nanoparticles prepared in example 1;
FIG. 4 is a graph showing fluorescence excitation and emission spectra of fluorescent silicon nanoparticles prepared in example 1;
FIG. 5 is a bar graph of fluorescence intensity of silicon nanoparticles prepared using different amounts of humic acid;
FIG. 6 is a bar graph of fluorescence intensity of silicon nanoparticles produced using different reaction times;
FIG. 7 is a graphical representation of the silicon nanoparticle solutions prepared using different APTES dosages under 365nm UV lamp irradiation;
FIG. 8 is a graphical representation of the silicon nanoparticle solutions prepared using different silicon sources under 365nm UV lamp illumination;
FIG. 9 is a graphical representation of the silicon nanoparticle solutions prepared using different reducing agents under 365nm UV lamp irradiation;
FIG. 10 is a daylight image of the water-soluble fluorescent anti-counterfeit ink prepared in example 1 after air-drying of a butterfly pattern engraved on rice paper and a fluorescent image under a 365nm ultraviolet lamp;
FIG. 11 is a daylight image of the water-soluble fluorescent anti-counterfeit ink prepared in example 1 after air-drying the peony pattern re-engraved on rice paper and a fluorescent image under 365nm ultraviolet lamp;
FIG. 12 is a daylight image of the water-soluble fluorescent anti-forgery ink prepared in example 1 after air-drying the bamboo pattern re-engraved on Xuan paper and a fluorescent image under 365nm ultraviolet lamp;
FIG. 13 is a sunlight image of the water-soluble fluorescent anti-counterfeiting ink prepared in example 1 after air-drying of the two words "Gan Nong" written on rice paper and a fluorescent image under a 365nm ultraviolet lamp;
FIG. 14 is a graph showing fluorescence intensity test of fluorescent silicon nanoparticles prepared in example 1 in NaCl solutions of different concentrations;
FIG. 15 is a graph showing the fluorescence intensity test of fluorescent silicon nanoparticles prepared in example 1 in PBS buffer at pH 3-12;
FIG. 16 is a graph showing the fluorescence intensity test of fluorescent silicon nanoparticles prepared in example 1 continuously irradiated under a 446nm ultraviolet lamp for 60 minutes.
FIG. 17 is a graph showing fluorescence emission spectra of the fluorescent silicon nanoparticle solution prepared in example 1 after CRM was added at various concentrations;
FIG. 18 shows the fluorescence intensity difference F of the fluorescent silicon nanoparticle solution prepared in example 1 0 -a linear plot of F and CRM concentration.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus. The conjunction "consisting of … …" excludes any unspecified element, step or component.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The application provides a preparation method of fluorescent silicon nano particles, which comprises the following steps: and mixing and reacting a silicon source, a reducing agent and water to obtain the fluorescent silicon nano particles. Wherein the silicon source comprises aminopropyl triethoxysilane (APTES), and the reducing agent comprises humic acid.
In the preparation method of the present application, different silicon source substances and different reducing agent substances are used to react, so that fluorescent silicon nanoparticles with different fluorescent effects can be prepared. For example, 3-aminopropyl trimethoxysilane (APTMS) or N- [3- (trimethoxysilyl) propyl ] ethylenediamine (DAMO) is used for mixing reaction with humic acid, and the fluorescent silicon nanoparticles prepared by DAMO have the smallest fluorescent effect, hardly see fluorescence, but APTMS has the fluorescent effect, but does not have the good fluorescent effect prepared by APTES.
In one embodiment of the present application, the mixing comprises: after dissolving the reducing agent in the alkaline solution to prepare a reducing agent solution, the silicon source and the reducing agent solution are added to the water.
Further preferably, when the reducing agent is humic acid, the alkali liquor is 1wt% sodium hydroxide solution.
Humic acid is dissolved in a NaOH solution with the weight percent of 1 to prepare a humic acid solution, and then the silicon source 3-aminopropyl triethoxysilane and the humic acid solution are added into water for mixing and stirring.
It is specifically noted that the water of the present application is preferably ultrapure water or deionized water.
In one embodiment of the present application, the concentration of humic acid in the reducing agent solution is 5mmol/L-20mmol/L, and may be, for example, 5mmol/L, 10mmol/L, 15mmol/L, 20mmol/L, or any value between 5mmol/L and 20mmol/L. More preferably, an aqueous solution of humic acid with a concentration of 10mmol/L is selected.
In one embodiment of the present application, the silicon source, the reducing agent solution and the water are mixed in a volume ratio of (0.5-0.8): (1.0-2.5): (2.5-3), for example, may be 0.5:1.0:2.5, 0.6:1.2:2.7, 0.7:1.5:3.0, 0.8:1.5:2.7, 0.8:2.0:3.0, 0.8:2.5:2.7 or (0.5-0.8): (1.0-2.5): any value between (2.5-3), more preferably 0.8:1.5:2.7.
in one embodiment of the present application, the conditions required for the reaction include: at standard atmospheric pressure, a temperature of 10℃to 40℃may be, for example, 10℃15℃20℃25℃30℃40℃or any value between 10℃and 40 ℃; the mixed solution is continuously stirred using a rotation speed of 800rpm to 1200rpm, and may be, for example, 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm or any value between 800rpm and 1200 rpm; the reaction time is 20min-40min, and can be, for example, 20min, 25min, 30min, 35min, 40min or any value between 20min-40min.
More preferably, the reaction is carried out at a temperature of 25℃to 30℃with continuous stirring at 1000rpm for 30min.
In one embodiment of the present application, after the reaction is completed, the method further comprises: and transferring the solution after the reaction to a dialysis bag of 500Da-1000Da for dialysis to obtain the purified fluorescent silicon nano particles.
Specifically, 0.8mL of 3-aminopropyl triethoxysilane and 1.5mL of 10mM humic acid solution are added into a round-bottomed flask containing 2.7mL of ultrapure water, and the mixture is stirred by a magnetic stirrer at a stirring speed of 1000rpm for 30min, and dialyzed after the reaction is completed, so that purified fluorescent silicon nanoparticles are obtained. The silicon nano-particles prepared are diluted by water to obtain a silicon nano-particle solution, and the silicon nano-particle solution is stored at the temperature of 2-6 ℃ for standby, and more preferably at the temperature of 4 ℃ for standby.
The preparation method has the advantages of simple process, readily available raw materials, capability of reacting at normal temperature and normal pressure, and short reaction time, thereby greatly reducing the preparation cost of the fluorescent silicon nano particles and improving the preparation efficiency of the product.
The application also provides fluorescent silicon nanoparticles, which are prepared by adopting the preparation method of the fluorescent silicon nanoparticles.
It can be understood that, because the preparation method is carried out in water, the prepared nano-particles have the characteristic of water solubility, namely, the fluorescent silicon nano-particles are water-soluble fluorescent silicon nano-particles.
In one embodiment of the present application, the fluorescent silicon nanoparticles appear green under 365nm ultraviolet light.
In one embodiment of the present application, the fluorescent silicon nanoparticles have a particle size of 2.2nm to 3.0nm, the particles have a spherical structure, and the average particle size is 2.6nm.
The application also provides water-soluble fluorescent anti-counterfeiting ink which comprises the fluorescent silicon nano particles.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a fluorescent silicon nanoparticle, and the specific preparation method comprises the following steps:
0.8mL of 3-aminopropyl triethoxysilane (APTES) and 1.5mL of 10mM humic acid solution were added to a round-bottomed flask containing 2.7mL of ultrapure water at normal temperature and pressure, and the mixture was stirred at 1000rpm for 30 minutes at normal temperature and pressure using a magnetic stirrer. After the reaction, transferring the reacted solution into a dialysis bag with the molecular weight of 1000Da for dialysis to obtain purified fluorescent silicon nano particles, adding water for dilution by 50 times to obtain a silicon nano particle solution, and placing the silicon nano particle solution at the temperature of 4 ℃ for sealing and preserving for later use.
The embodiment provides a water-soluble fluorescent anti-counterfeiting ink, which comprises: the silicon nanoparticle solution prepared as described above in this example.
Example 2
The preparation method of the fluorescent silicon nanoparticle of this example is the same as that of example 1, except that: the amount of 3-aminopropyl triethoxysilane added was changed from 0.8mL to 0.6mL.
Example 3
The preparation method of the fluorescent silicon nanoparticle of this example is the same as that of example 1, except that: the 10mM humic acid solution was replaced with 1.0mL from 1.5mL.
Example 4
The preparation method of the fluorescent silicon nanoparticle of this example is the same as that of example 1, except that: the 10mM humic acid solution was replaced with 2.0mL from 1.5mL.
Example 5
The preparation method of the fluorescent silicon nanoparticle of this example is the same as that of example 1, except that: the 10mM humic acid solution was replaced with 2.5mL from 1.5mL.
Example 6
The preparation method of the fluorescent silicon nanoparticle of this example is the same as that of example 1, except that: the time of the stirring reaction was replaced by 20min from 30min.
Example 7
The preparation method of the fluorescent silicon nanoparticle of this example is the same as that of example 1, except that: the time of the stirring reaction was replaced by 40min from 30min.
Comparative example 1
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the amount of 3-aminopropyl triethoxysilane added was changed from 0.8mL to 1.0mL.
Comparative example 2
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the amount of 3-aminopropyl triethoxysilane added was changed from 0.8mL to 1.5mL.
Comparative example 3
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the amount of 3-aminopropyl triethoxysilane added was changed from 0.8mL to 2.0mL.
Comparative example 4
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: 10mM humic acid solution was replaced with 0.5mL from 1.5mL.
Comparative example 5
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the 10mM humic acid solution was replaced with 3.0mL from 1.5mL.
Comparative example 6
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the time of the stirring reaction was replaced by 10min from 30min.
Comparative example 7
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the time of the stirring reaction was replaced by 50min from 30min.
Comparative example 8
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the time of the stirring reaction was replaced by 60min from 30min.
Comparative example 9
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: 3-aminopropyl triethoxysilane was replaced with 3-aminopropyl trimethoxysilane (APTMS).
Comparative example 10
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: aminopropyl triethoxysilane is replaced with N- [3- (trimethoxysilyl) propyl ] ethylenediamine (DAMO).
Comparative example 11
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the humic acid solution was replaced with sodium citrate solution.
Comparative example 12
The preparation method of the fluorescent silicon nanoparticle of the present comparative example is the same as in example 1, except that: the humic acid solution was replaced with bovine serum albumin solution.
The silicon nanoparticles prepared in each example and comparative example were subjected to XRD characterization test, and as a result, found that: the nanoparticle samples prepared in the examples and comparative examples of the present application are amorphous silicon. Figure 1 gives the XRD pattern of the fluorescent silicon nanoparticle of example 1.
Meanwhile, TEM characterization test is carried out on the fluorescent silicon nano-particles prepared in the example 1, and the result shows that: the silicon nanoparticles in the sample of example 1 have good monodispersity, a spherical structure, a particle size distribution of 2.2-3.0nm, and an average particle size of about 2.6nm, as shown in fig. 2.
The nano sample prepared in the example 1 is also subjected to a UV-Vis absorption spectrum test and a fluorescence excitation and emission spectrum test, and the results are shown in FIG. 3 and FIG. 4 respectively. As can be seen from fig. 3, the distinct absorption peaks at 300nm and 330nm belong to the pi-pi transition of c=c, and the absorption peak at 540nm belongs to the n-pi transition of c=o. As can be seen from fig. 4, the silicon nanoparticle has a maximum excitation wavelength of 446nm and a maximum emission wavelength of 504nm.
Then, the silicon nanoparticle solutions prepared in example 1, examples 3 to 7 and comparative examples 4 to 8 were tested for fluorescence intensity, and the results are shown in fig. 5 and 6. FIG. 5 is a graph showing the effect of different humic acid levels on the fluorescence intensity of the silicon nanoparticles produced; FIG. 6 represents the effect of different reaction times on the fluorescence intensity of the produced silicon nanoparticles. From the graph, when the humic acid dosage is 1.0mL-2.5mL and the reaction time is 20min-40min, the fluorescence intensity of the prepared silicon nano particles is relatively high. More preferably, when the humic acid dosage is 1.5mL and the reaction time is 30min, the fluorescence intensity of the prepared silicon nano-particles reaches the highest.
The present application also tested the fluorescence effect of the silicon nanoparticle solutions prepared in examples 1-2 and comparative examples 1-3 under 365nm ultraviolet light irradiation, as shown in fig. 7, and the following steps are sequentially performed from left to right in fig. 7: APTES was used in an amount of 0.6mL, 0.8mL, 1mL, 1.5mL, 2mL. The silicon nanoparticle solutions prepared in comparative examples 9 to 10 and example 1 were tested for fluorescence effect under 365nm ultraviolet irradiation, as shown in fig. 8, and in fig. 8, the silicon source was APTMS, APTES, DAMO in order from left to right. The silicon nanoparticle solutions prepared in comparative examples 11 to 12 and example 1 were tested for fluorescence effect under 365nm ultraviolet irradiation, as shown in fig. 9, and in fig. 9, reducing agents of sodium citrate, bovine serum albumin, humic acid were sequentially added from left to right.
As is apparent from FIG. 7, the amount of 3-aminopropyl triethoxysilane as a silicon source was 0.6mL-0.8mL, and the fluorescence effect was relatively good, and particularly, the fluorescence effect was best when the amount was 0.8 mL. As is evident from fig. 8 and 9, compared with two silicon source materials, i.e., APTMS and DAMO, the fluorescence effect obtained by using 3-aminopropyl triethoxysilane (APTES) as the silicon source is the best; compared with two reducing agents, namely sodium citrate and serum albumin, the fluorescent effect obtained by using humic acid as the reducing agent is the best.
Aiming at the water-soluble fluorescent anti-counterfeiting ink prepared in each embodiment and comparative example, a small amount of ink solution is dipped by using a writing brush, patterns of butterfly, peony and bamboo are respectively selected to be re-carved on the rice paper according to the lines of the patterns, meanwhile, two words of Gan Nong are manually written on the rice paper, after the solution on the rice paper is naturally air-dried, light yellow marks appear on the surface of the rice paper in sunlight, and the light yellow marks are respectively shown in left diagrams in fig. 10, 11, 12 and 13.
Then, the air-dried image is irradiated under an ultraviolet lamp of 365nm, and the images under the ultraviolet irradiation are respectively shown in the right images in fig. 10, 11, 12 and 13, so that clear and complete patterns and writing of butterfly, peony, bamboo and Gan Nong can be seen, the patterns show obvious green fluorescence, the edges of the images are tidy, and important details are clearly visible.
The results after air-drying in combination with pattern engraving show that: the fluorescent silicon nano particles prepared by the method can be used as an excellent fluorescent material and used for manufacturing anti-counterfeiting labels.
In addition, the application also detects the salt resistance, acid and alkali resistance and light resistance of the fluorescent silicon nano particles. Specifically, the fluorescent silicon nanoparticles prepared in example 1 were added to NaCl solutions of different concentrations, and the fluorescence intensities in the NaCl solutions of different concentrations were tested as shown in fig. 14. As a result, it was found that the fluorescence intensity was not significantly changed, indicating that the fluorescent silicon nanoparticles have excellent salt stability and can be used in an environment of high ionic strength.
The fluorescent silicon nanoparticles prepared in example 1 were added to PBS buffer solutions of different pH (3-12), and fluorescence intensity was measured as shown in FIG. 15. As a result, the fluorescence intensity was found to remain substantially constant, indicating that it was very stable over a wide pH range.
The fluorescent silicon nanoparticle solution prepared in example 1 was continuously irradiated under a 446nm ultraviolet lamp for 60 minutes, and the fluorescence intensity was tested, as shown in fig. 16. As a result, the fluorescence intensity was found to remain unchanged all the time, indicating that the fluorescent silicon nanoparticles have excellent photobleaching resistance.
The results show that the fluorescent silicon nano-particles have good photo-temperature property and chemical stability.
The present application also tested fluorescent silicon nanoparticles for carmine testing. Specifically, equal volumes of carmine solutions of different concentrations were added to the silicon nanoparticle solutions prepared in example 1, and the final carmine concentrations were 0, 10, 20, 30, 40, 50, 60, 70, 80, 90. Mu. Mol/L, and the fluorescence intensity values of the resulting solutions were measured, and the results are shown in FIGS. 17 and 18.
As can be seen from fig. 17: after adding different concentrations of carmine solution to the silicon nanoparticle solution, a significant quenching of the fluorescence intensity occurred. As the concentration of carmine solution increases, the fluorescence intensity of the silicon nanoparticle solution decreases.
Based on this, a new method of fluorescence detection of carmine was established as shown in fig. 18. When the carmine solution concentration is in the range of (0-90) mu mol/L, F 0 There is a good linear relationship between F and the concentration c of the carmine solution, and the linear fitting equation is F 0 -F= -6.1453+4.3537c (μmol/L), correlation coefficient R 2 =0.9980, the lowest limit of detection (LOD) is 0.056 μmol/L, which is well below the allowable addition amount specified by the country.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, any of the above-described claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for preparing fluorescent silicon nanoparticles, comprising:
mixing a silicon source, a reducing agent and water, and reacting to obtain the fluorescent silicon nano particles;
the silicon source comprises 3-aminopropyl triethoxysilane;
the reducing agent comprises humic acid.
2. The method of preparing as claimed in claim 1, wherein said mixing comprises:
and after dissolving the reducing agent in alkali liquor to prepare a reducing agent solution, adding the silicon source and the reducing agent solution into the water.
3. The method according to claim 2, wherein when the reducing agent is humic acid, the alkali solution is 1wt% sodium hydroxide solution;
the concentration of humic acid in the reducing agent solution is 5mmol/L-20mmol/L.
4. The method of claim 3, wherein the silicon source, the reducing agent solution, and the water are mixed in a volume ratio of (0.5-0.8): (1.0-2.5): (2.5-3).
5. The method of preparation of claim 1, wherein the reaction comprises:
after the mixed solution is obtained by mixing, the mixed solution is continuously stirred at the rotation speed of 800rpm-1200rpm under the standard atmospheric pressure and the temperature of 10-40 ℃ for reaction, and the reaction time is 20-40 min.
6. The method of claim 1, wherein after the reaction is completed, further comprising:
and transferring the solution after the reaction is finished into a dialysis bag of 500Da-1000Da for dialysis to obtain the purified fluorescent silicon nano particles.
7. The method of any one of claims 1 to 6, wherein after obtaining the fluorescent silicon nanoparticles, the fluorescent silicon nanoparticles are diluted with water to obtain a fluorescent silicon nanoparticle solution, and the fluorescent silicon nanoparticle solution is stored in an environment of 2 ℃ to 6 ℃.
8. A fluorescent silicon nanoparticle prepared by the method of any one of claims 1-7.
9. The fluorescent silicon nanoparticle of claim 8, wherein the fluorescent silicon nanoparticle appears green under 365nm ultraviolet light irradiation;
the particle size of the fluorescent silicon nano particles is 2.2nm-3.0nm.
10. The water-soluble fluorescent anti-counterfeiting ink is characterized by comprising the fluorescent silicon nanoparticles prepared by the preparation method of the fluorescent silicon nanoparticles in any one of claims 1-7.
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