CN115044251A - Multicolor fluorescent ink based on light-controlled nanoparticles and preparation method thereof - Google Patents
Multicolor fluorescent ink based on light-controlled nanoparticles and preparation method thereof Download PDFInfo
- Publication number
- CN115044251A CN115044251A CN202210275788.1A CN202210275788A CN115044251A CN 115044251 A CN115044251 A CN 115044251A CN 202210275788 A CN202210275788 A CN 202210275788A CN 115044251 A CN115044251 A CN 115044251A
- Authority
- CN
- China
- Prior art keywords
- solution
- light
- fluorescent dye
- polyethyleneimine
- fluorescent ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The invention discloses a fluorescent ink based on light-operated nanoparticles, which is an aqueous solution containing a photoacid compound, polyethyleneimine and a fluorescent dye; under the irradiation of light with the wavelength of 420 +/-10 nm, the photoacid compound and the polyethyleneimine are polymerized to form spherical nano particles, fluorescent dye molecules are wrapped in the spherical nano particles, after the irradiation of the light is removed, the solution is placed in a dark place to be protected from light, and the structure of the nano particles formed by the photoacid compound and the polyethyleneimine is reversely changed. The invention also discloses a preparation method of the fluorescent ink based on the light-operated nanoparticles. The fluorescent ink has double excitation response, firstly the fluorescent ink can trigger color development after being irradiated by 420nm light, and then the color can be seen through 365nm ultraviolet excitation, so that the safety anti-counterfeiting grade can be obviously improved when the fluorescent ink is applied to the anti-counterfeiting field.
Description
Technical Field
The invention relates to multicolor fluorescent ink based on light-operated nano particles and a preparation method of the fluorescent ink.
Background
As an important information safety protection measure, the anti-counterfeiting technology plays an important role in national defense, economy and daily life. The anti-counterfeiting technology used at present mainly comprises: fluorescence anti-counterfeiting, nuclear track anti-counterfeiting, laser holographic anti-counterfeiting, magnetic anti-counterfeiting and the like, and the anti-counterfeiting technology is widely applied to currency circulation, labels and important documents. The fluorescent anti-counterfeiting has the advantages of good stability, simple printing, low cost and the like, and is the most common anti-counterfeiting measure. Fluorescent ink based on fluorescent anti-counterfeiting technology is an important component of fluorescent anti-counterfeiting technology. The traditional fluorescent anti-counterfeiting ink is often prepared by methods such as organic phase solvent synthesis, nanocrystal instrument wrapping and the like, and has the problem of complex manufacturing process. The anti-counterfeiting mechanism is based on a single-stage anti-counterfeiting technology, namely, the ink marks cannot be seen under natural light and can be displayed under ultraviolet or near-infrared excitation light, and the encryption mode is easily replaced by fluorescent materials with similar emission characteristics, so that the encryption grade is reduced, and the anti-counterfeiting performance is lower. And the traditional fluorescent anti-counterfeiting ink is usually only in a fixed form, has no processes of developing and erasing, and is easy to crack and identify.
Disclosure of Invention
The purpose of the invention is as follows: one of the purposes of the invention is to provide fluorescent ink with double excitation response and high anti-counterfeiting performance, and the fluorescent ink can excite color development when color development is needed and can not carry out fluorescent color development when color development is not needed; the invention also aims to provide a preparation method of the fluorescent ink.
The technical scheme is as follows: the multicolor fluorescent ink based on the light-operated nano particles is an aqueous solution containing a photoacid compound, polyethyleneimine and a fluorescent dye; under the irradiation of light with the wavelength of 420 +/-10 nm, the photoacid compound and the polyethyleneimine are polymerized to form spherical nano particles, fluorescent dye molecules are wrapped in the spherical nano particles, after the irradiation of the light is removed, the solution is placed in a dark place to be protected from light, and the structure of the nano particles formed by the photoacid compound and the polyethyleneimine is reversely changed.
Irradiating for 10 minutes under 420nm light to obtain spherical nano particles; and (3) putting the mixture in a dark place for 20 minutes, converting the spherical nano particles into square nano particles, wherein the chemical structural formula of the photoacid compound is as follows:
the photoacid compound is converted to an anionic amphiphilic compound after 420nm light irradiation, and the structural formula of the compound is changed as follows:
the reaction equation is:
the structural formula of polyethyleneimine is:
zwitterionic (having both positively and negatively charged ends) photoacid and cationic polyethyleneimine are initially present in free form in aqueous solution, and upon activation by 420nm light irradiation, the photoacid molecules isomerize to anionic sulfospiropyran compounds; due to strong electrostatic interaction between the negative photoacid isomeric molecules and the positive polyethyleneimine molecules and the hydrophilic and hydrophobic characteristics of the two molecules, the two molecules can construct unstable spherical supramolecular nanoparticles; removing 420nm light irradiation to place the solution in complete darkness, wherein the photoacid isomeric molecules spontaneously begin to be converted into starting photoacid molecules, but as polyethyleneimine molecules have higher-density positive charges, part of the photoacid isomeric molecules can still keep an isomeric state in the darkness, and the nanoparticles are not completely dissociated but are combined with one another to be converted into larger square nanoparticles; the assembled state of the nanoparticles in solution can be cycled between a spherical nanoparticle assembled state and a square nanoparticle assembled state after 420nm reciprocating light irradiation. The method comprises the steps of adding a fluorescent dye into a precursor solution before assembly, driving the assembly of the nano particles by 420nm illumination, wrapping dye molecules into the nano particles, enabling an assembly system loaded with the fluorescent dye molecules to emit fluorescence with corresponding colors (strong fluorescence intensity) under the excitation of 365nm, and after the illumination is removed, weakening the fluorescence intensity of the assembly system loaded with the fluorescent dye molecules along with the conversion of the nano particles, wherein no fluorescence with corresponding colors is emitted even under the excitation of 365 nm. In the self-assembly system, anions formed by isomerization of photoacid molecules and spherical nanoparticles formed by assembly of polyethyleneimine cations show stronger electronegativity, so that in the spherical nanoparticles, the charge transfer effect of fluorescent dye is smaller, and as the assembly forms a better hydrophobic environment, stronger fluorescence intensity is shown. In the square nano particles, the photoacid isomeric molecules are gradually recovered, the system is converted into electric neutrality, and at the moment, the charge transfer effect of the system is strong, so that the fluorescent dye is subjected to aggregation induced quenching, and the fluorescence is quenched. In fluorescent systems, charge transfer (a negatively charged system has a weaker charge transfer effect than a positively charged and neutrally charged system) typically results in fluorescence aggregation induced quenching or fluorescence red-shift.
Wherein, the fluorescent dye is composed of blue fluorescent dye and/or green fluorescent dye and/or red fluorescent dye.
The preparation method of the fluorescent ink based on the light-controlled nano particles comprises the following steps:
(1) preparing a light-operated nanoparticle precursor solution: dissolving a photoacid compound in acidic water, and adding a polyethyleneimine aqueous solution after ultrasonic dissolution to obtain a light-controlled nanoparticle precursor solution; at the moment, the photoacid compound and the polyethyleneimine in the solution are in a free state;
(2) adding a solution containing blue and/or red and/or green fluorescent dye into the precursor solution in the step (1), and irradiating at 420 +/-10 nm to obtain fluorescent ink with corresponding color; and after illumination, the photoacid compound and the polyethyleneimine in the precursor solution are polymerized and assembled into spherical nano particles, and fluorescent dye molecules are wrapped in the spherical nano particles.
In the step (1), the acidic water is obtained by adding dilute hydrochloric acid into water to make the pH value of the water 5-6, and if the pH value of the initially used deionized water is 8, adding 1 microliter of 1mM dilute hydrochloric acid into 10mL of water can adjust the pH value of the water to 5-6. The structure of the photoacid molecule can be damaged under the alkaline condition, so that the photoinduced isomerization characteristic is lost, and the isomerization performance of the photoacid molecule is good only when the pH value of the solution is 5-6.
Wherein in the step (1), the concentration of the polyethyleneimine in the polyethyleneimine aqueous solution is 1mg/mL, and the weight-average molecular weight of the polyethyleneimine is 10000. Only when the molecular weight of the polyethyleneimine is 10000, the photoacid and the polyethyleneimine have a good assembly effect.
Wherein, in the step (1), the concentration of polyethyleneimine in the precursor solution is 5 mug/mL; the concentration of the photoacid compound was 0.225 mM.
The concentration of photoacid compound was increased from 0.05mM to 0.325mM in steps of 0.025mM, and the critical aggregation concentration CAC found by linear fitting of the change in UV transmission at 650nm after 420nm light irradiation was 0.1521mM, thereby determining the optimal assembly concentration of photoacid compound to be 0.225 mM. The concentration of the prepared photoacid compound was fixed at 0.225mM, the concentration of polyethyleneimine was from 0.5. mu.g/mL to 7.5. mu.g/mL, the step size was increased by 0.5. mu.g/mL, and the optimum assembly concentration of polyethyleneimine was 5. mu.g/mL by the change in ultraviolet transmittance at 650nm after 420nm light irradiation.
In the step (2), the blue fluorescent dye solution is a DMSO (dimethyl sulfoxide) solution of scoparone, only the DMSO solution of scoparone is added into the precursor solution, and after light irradiation of 420 +/-10 nm, blue fluorescent ink is obtained, wherein the emission wavelength is 425 nm; the concentration of scoparone in the mixed solution is 0.001 mM; the red fluorescent dye solution is a sulforhodamine 101 aqueous solution, only the sulforhodamine 101 aqueous solution is added into the precursor solution, and the red fluorescent ink is obtained after the irradiation of light with the wavelength of 420 +/-10 nm, wherein the emission wavelength is 606 nm; the concentration of sulforhodamine 101 in the mixed solution is 0.006 mM; the green fluorescent dye solution is a DMSO solution of 5(6) -carboxyfluorescein diacetate, only the DMSO solution of 5(6) -carboxyfluorescein diacetate is added into the precursor solution, and after the mixture is irradiated by light of 420 +/-10 nm, green fluorescent ink is obtained, and the emission wavelength is 520 nm; the concentration of 5(6) -carboxyfluorescein diacetate in the mixture was 0.01 mM.
In the step (2), adding the blue fluorescent dye solution and the red fluorescent dye solution into the precursor solution at the same time, or adding the green fluorescent dye solution and the red fluorescent dye solution at the same time, or adding the blue fluorescent dye solution and the green fluorescent dye solution at the same time, adding the blue fluorescent dye solution, the red fluorescent dye solution and the green fluorescent dye solution at the same time, and adjusting the mixing ratio of the fluorescent dye solutions to obtain the fluorescent ink with the required color after light irradiation of 420 +/-10 nm. The method specifically comprises the following steps: adding a DMSO solution of scoparone and a sulforhodamine 101 aqueous solution into the precursor solution at the same time to prepare a solution with scoparone concentration of 0.0003mM and sulforhodamine 101 concentration of 0.006mM, and irradiating for 10 minutes at 420nm to obtain pink fluorescent ink; adding 5(6) -DMSO solution of carboxyfluorescein diacetate and sulforhodamine 101 aqueous solution into the precursor solution at the same time to prepare a solution with the concentration of 5(6) -carboxyfluorescein diacetate being 0.02mM and the concentration of sulforhodamine 101 being 0.003mM, and irradiating for 10 minutes at 420nm to obtain yellow fluorescent ink; adding a DMSO solution of scoparone and a DMSO solution of 5(6) -carboxyfluorescein diacetate into the precursor solution at the same time to prepare a solution with scoparone concentration of 0.0001mM and 5(6) -carboxyfluorescein diacetate concentration of 0.03mM, and irradiating for 10 minutes at 420nm to obtain cyan fluorescent ink; adding a DMSO solution of scoparone, a DMSO solution of 5(6) -carboxyfluorescein diacetate and a sulforhodamine 101 aqueous solution into the precursor solution at the same time to prepare a solution with the scoparone concentration of 0.0002mM, the 5(6) -carboxyfluorescein diacetate concentration of 0.025mM and the sulforhodamine 101 concentration of 0.004mM, and irradiating for 10 minutes at 420nm to obtain the white fluorescent ink.
Has the beneficial effects that: (1) the fluorescent ink with various colors can be obtained by utilizing the invention, the light-controlled nano particles are obtained by self-assembling photoacid molecules and polyethyleneimine molecules, at least one fluorescent dye molecule in blue, green and red is wrapped in the nano particles, and the fluorescent ink with various colors can be prepared by randomly mixing the three colors of blue, green and red; (2) the fluorescent ink has double excitation response, firstly the fluorescent ink can trigger color development after being irradiated by light of 420nm, and then the color can be seen through the excitation of 365nm ultraviolet light, so that the safety anti-counterfeiting grade can be obviously improved when the fluorescent ink is applied to the anti-counterfeiting field; (3) the fluorescent ink can excite color development when color development is needed, and can also realize non-fluorescent color development when color development is not needed.
Drawings
FIG. 1 is a graph of UV transmission titrations with fixed polyethyleneimine concentration of 5. mu.g/mL, photoacid concentration from 0.05mM to 0.325mM, in incremental steps of 0.025 mM;
FIG. 2 is a graph of UV transmission titration with a fixed photoacid concentration of 0.225mM, polyethyleneimine concentration from 0.5 μ g/mL to 7.5 μ g/mL, in incremental steps of 0.5 μ g/mL;
FIG. 3 is a transmission electron microscope image of spherical nanoparticles;
FIG. 4 is a transmission electron micrograph of square nanoparticles;
FIG. 5 shows the change of fluorescence intensity of 0.001mM scoparone under excitation of 340nm before and after 420nm illumination;
FIG. 6 shows the change of fluorescence intensity at 440nm excitation before and after irradiation with 0.01mM5(6) -carboxyfluorescein diacetate at 420 nm;
FIG. 7 shows the change of fluorescence intensity under excitation of 585nm before and after irradiation with 0.005mM sulforhodamine 101 and 420nm light;
FIG. 8 shows cyan color coordinates of seven fluorescent inks, i (0.0001mM scoparone, 0.03mM 5(6) -carboxyfluorescein diacetate), pink color ii (0.0003mM scoparone, 0.006mM sulforhodamine 101), yellow color iii (0.02mM 5(6) -carboxyfluorescein diacetate, 0.003mM sulforhodamine 101), white color iv (0.0002mM scoparone, 0.025mM 5(6) -carboxyfluorescein diacetate, 0.004mM sulforhodamine 101), blue color v (0.001mM scoparone), green color vi (0.01mM 5(6) -carboxyfluorescein diacetate), and red color vii (0.006mM sulforhodamine 101), after excitation at 420nm, corresponding to color coordinates on the CIE chromaticity diagram;
FIG. 9 is a photograph of the fluorescence of the three fluorescent inks after excitation;
FIG. 10 is an actual fluorescent photograph of four fluorescent inks, pink yellow, cyan and white, after excitation;
FIG. 11 is a photograph of 96-well plates filled with different fluorescent inks according to a design under natural light;
FIG. 12 is a photograph of 96-well plates filled with different fluorescent inks according to a design pattern under 365nm light excitation;
FIG. 13 is a photograph of 96-well plates filled with different fluorescent inks according to a designed pattern under 365nm light excitation after 420nm light irradiation; s is a site filled with blue fluorescent ink, E is a site filled with red fluorescent ink, and U is a site filled with green fluorescent ink.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The fluorescent ink based on the light-controlled nano particles is an aqueous solution containing a photoacid compound, polyethyleneimine and a fluorescent dye; under the irradiation of light of 420nm, the photoacid compound and the polyethyleneimine are polymerized to assemble spherical nano particles, fluorescent dye molecules are wrapped in the spherical nano particles, after the irradiation of the light is removed, the solution is placed in a dark place to be protected from light, and the structure of the nano particles assembled by the photoacid compound and the polyethyleneimine is reversely changed.
The preparation method of the fluorescent ink based on the light-controlled nanoparticles comprises the following steps:
(1) preparing a light-controlled nano particle precursor solution: dissolving a photoacid compound in water with a pH value of 5-6, performing ultrasonic full dissolution, and then adding a polyethyleneimine (polyethyleneimine weight average molecular weight is about 10000) water solution with a polyethyleneimine concentration of 1mg/mL to obtain a light-controlled nanoparticle precursor solution; in the precursor solution, the concentration of the photoacid compound was 0.225mM, and the concentration of polyethyleneimine was 5. mu.g/mL.
Irradiating for 10 minutes under 420nm light under the corresponding assembling concentration of a photoacid compound and polyethyleneimine to obtain spherical nanoparticles with the particle size of about 300 nm; the mixture is put in a dark place for recovering for 20 minutes, and spherical nano particles are converted into square nano particles with the particle size of about 600 nm;
the photo-acid molecule has a photo-isomerisation structural formula:
the structural formula of polyethyleneimine is:
preparing blue fluorescent ink: and (2) adding a DMSO solution of scoparone into the precursor solution in the step (1) to obtain a mixed solution with the scoparone concentration of 0.001mM, and irradiating for 10 minutes at 420nm to obtain the blue fluorescent ink, wherein as shown in FIG. 5, the maximum emission wavelength of the blue fluorescent ink is 425nm, the fluorescence intensity before and after the light irradiation is enhanced by 114 times, and the coordinate position of the blue fluorescent color on a CIE (circular arc element) diagram is (0.156, 0.0707).
Preparing green fluorescent ink: adding 5(6) DMSO solution of carboxyfluorescein diacetate into the precursor solution in the step (1) to obtain a mixed solution with the concentration of 5(6) carboxyfluorescein diacetate of 0.01mM, and irradiating the mixed solution for 10 minutes at 420nm to obtain the green fluorescent ink, wherein as shown in FIG. 6, the maximum emission wavelength of the green fluorescent ink is 520nm, the fluorescence intensity before and after the irradiation is enhanced by 358 times, and the coordinate position of the green fluorescent color on a CIE diagram is (0.2949, 0.6153).
Preparing red fluorescent ink: and (2) adding a sulforhodamine 101 aqueous solution into the precursor solution in the step (1) to obtain a mixed solution with the sulforhodamine 101 concentration of 0.006mM, and irradiating for 10 minutes at 420nm to obtain the red fluorescent ink, wherein as shown in FIG. 7, the maximum emission wavelength of the red fluorescent ink is 606nm, the fluorescence intensity before and after the light irradiation is enhanced by 4 times, and the coordinate position of the red fluorescent color on a CIE diagram is (0.6675, 0.3322). The light-operated nano particles have good reversible regulation and control effect on the fluorescence of the solution before and after light irradiation after loading the fluorescent dye.
Preparing pink fluorescent ink: and (2) adding a DMSO solution of scoparone and a sulforhodamine 101 aqueous solution into the precursor solution in the step (1) at the same time to obtain a mixed solution with the scoparone concentration of 0.0003mM and the sulforhodamine 101 concentration of 0.006mM (the DMSO solvent content in the mixed solution is 0.5%, a small amount of DMSO is doped into the mixed solution, the system taking water as a fluorescent ink solvent is not influenced, and the DMSO content basically has no influence on the assembly process), and irradiating for 10 minutes by light at 420nm to obtain pink fluorescent ink.
Preparing yellow fluorescent ink: and (2) adding 5(6) -DMSO solution of carboxyfluorescein diacetate and sulforhodamine 101 aqueous solution into the precursor solution in the step (1) at the same time to obtain a mixed solution of 5(6) -carboxyfluorescein diacetate with the concentration of 0.02mM and sulforhodamine 101 with the concentration of 0.003mM, and irradiating for 10 minutes at 420nm to obtain the yellow fluorescent ink.
Preparing cyan fluorescent ink: and (2) adding a DMSO solution of scoparone and a DMSO solution of 5(6) -carboxyfluorescein diacetate into the precursor solution in the step (1) at the same time to obtain a mixed solution with the scoparone concentration of 0.0001mM and the 5(6) -carboxyfluorescein diacetate concentration of 0.03mM, and irradiating for 10 minutes at 420nm to obtain the cyan fluorescent ink.
Preparing white fluorescent ink: adding a DMSO solution of scoparone, a DMSO solution of 5(6) -carboxyfluorescein diacetate and a sulforhodamine 101 aqueous solution into the precursor solution in the step (1) at the same time to obtain a mixed solution of scoparone with the concentration of 0.0002mM, 5(6) -carboxyfluorescein diacetate with the concentration of 0.025mM and sulforhodamine 101 with the concentration of 0.004mM, and irradiating for 10 minutes at 420nm to obtain the white fluorescent ink.
Table 1 shows three fluorescent dyes of blue, green and red as three primary colors, which are orthogonally mixed and added into the precursor solution in the step (1), and the mixture is irradiated for 10 minutes at 420nm to obtain fluorescent inks with different colors:
the traditional fluorescent encryption mode is that the color is not developed under natural light and is developed under ultraviolet light. As can be seen from comparison of FIGS. 11 to 13, the fluorescent ink of the present invention has an additional encryption means of 420nm light irradiation, and does not develop color under natural light before 420nm light irradiation (FIG. 11), does not develop color even under 365nm ultraviolet light (FIG. 12), and does not see encrypted content, and only after 420nm light irradiation, the fluorescent ink can show a predetermined pattern as shown in FIG. 13, thereby completely showing the double encryption process. Therefore, the fluorescent ink does not develop color under the excitation of ultraviolet light when not irradiated by 420nm light, and displays the pre-designed fluorescent color under the excitation of the ultraviolet light after the irradiation of 420nm light, so the fluorescent ink has double anti-counterfeiting effects of light-operated assembly and fluorescence excitation, has a self-erasing function when the irradiation of 420nm light is removed, and has wide application prospects in the aspects of information encryption and anti-counterfeiting identification.
Claims (9)
1. The multicolor fluorescent ink based on the light-controlled nano particles is characterized by being an aqueous solution containing a photoacid compound, polyethyleneimine and a fluorescent dye; under the irradiation of light with the wavelength of 420 +/-10 nm, the photoacid compound and the polyethyleneimine are polymerized to form spherical nano particles, fluorescent dye molecules are wrapped in the spherical nano particles, after the irradiation of the light is removed, the solution is placed in a dark place to be protected from light, and the structure of the nano particles formed by the photoacid compound and the polyethyleneimine is reversely changed.
2. The light-controlling nanoparticle-based multicolor fluorescent ink according to claim 1, characterized in that: the chemical structural formula of the photoacid compound is:
3. the light-controlling nanoparticle-based multicolor fluorescent ink according to claim 1, characterized in that: the fluorescent dye is composed of blue fluorescent dye and/or green fluorescent dye and/or red fluorescent dye.
4. The method for preparing multicolor fluorescent ink based on light-controlled nanoparticles as claimed in claim 1, characterized by comprising the following steps:
(1) dissolving a photoacid compound in acidic water, and adding a polyethyleneimine aqueous solution after ultrasonic dissolution to obtain a light-controlled nanoparticle precursor solution; at the moment, the photoacid compound and the polyethyleneimine in the solution are in a free state;
(2) adding a solution containing blue and/or red and/or green fluorescent dye into the precursor solution in the step (1), and irradiating at 420 +/-10 nm to obtain fluorescent ink with corresponding color; and after illumination, the photoacid compound and the polyethyleneimine in the precursor solution are polymerized to form spherical nanoparticles, and fluorescent dye molecules are wrapped in the spherical nanoparticles.
5. The method of claim 4, wherein the method comprises: in the step (1), the pH value of the acidic water is 5-6.
6. The method of claim 4, wherein the method comprises: in the step (1), the concentration of polyethyleneimine in the polyethyleneimine aqueous solution is 1mg/mL, and the weight-average molecular weight of polyethyleneimine is 10000.
7. The method of claim 4, wherein the method comprises: in the step (1), the concentration of polyethyleneimine in the precursor solution is 5-5.5 mug/mL; the concentration of the photoacid generator is 0.225 to 0.226 mM.
8. The method of claim 4, wherein the method comprises: in the step (2), the blue fluorescent dye solution is a DMSO solution of scoparone, only the DMSO solution of scoparone is added into the precursor solution, and the blue fluorescent ink is obtained after light irradiation of 420 +/-10 nm; the red fluorescent dye solution is a sulforhodamine 101 aqueous solution, only the sulforhodamine 101 aqueous solution is added into the precursor solution, and the red fluorescent ink is obtained after the irradiation of light with the wavelength of 420 +/-10 nm; the green fluorescent dye solution is a DMSO solution of 5(6) -carboxyfluorescein diacetate, only the DMSO solution of 5(6) -carboxyfluorescein diacetate is added into the precursor solution, and after the mixture is irradiated by light of 420 +/-10 nm, the green fluorescent ink is obtained.
9. The method for preparing a multicolor fluorescent ink based on light-controlled nanoparticles according to claim 8, characterized in that: in the step (2), adding the blue fluorescent dye solution and the red fluorescent dye solution into the precursor solution at the same time, or adding the green fluorescent dye solution and the red fluorescent dye solution at the same time, or adding the blue fluorescent dye solution and the green fluorescent dye solution at the same time, and adding the blue fluorescent dye solution, the red fluorescent dye solution and the green fluorescent dye solution at the same time, and adjusting the mixing ratio of the fluorescent dye solutions to obtain the fluorescent ink with the required color respectively after the fluorescent ink is irradiated by light of 420 +/-10 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210275788.1A CN115044251B (en) | 2022-03-11 | 2022-03-11 | Multicolor fluorescent ink based on light-operated nano particles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210275788.1A CN115044251B (en) | 2022-03-11 | 2022-03-11 | Multicolor fluorescent ink based on light-operated nano particles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115044251A true CN115044251A (en) | 2022-09-13 |
| CN115044251B CN115044251B (en) | 2023-09-29 |
Family
ID=83158248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210275788.1A Active CN115044251B (en) | 2022-03-11 | 2022-03-11 | Multicolor fluorescent ink based on light-operated nano particles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115044251B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031477A (en) * | 2014-06-25 | 2014-09-10 | 吉林大学 | Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles |
| CN112175449A (en) * | 2020-11-16 | 2021-01-05 | 武汉理工大学 | Super-stable printable aqueous fluorescent anti-counterfeiting ink and preparation method thereof |
| CN113755057A (en) * | 2021-07-30 | 2021-12-07 | 哈尔滨工业大学（深圳） | Water-based fluorescent ink, preparation method thereof and application thereof in full-color printing and encryption anti-counterfeiting |
-
2022
- 2022-03-11 CN CN202210275788.1A patent/CN115044251B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031477A (en) * | 2014-06-25 | 2014-09-10 | 吉林大学 | Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles |
| CN112175449A (en) * | 2020-11-16 | 2021-01-05 | 武汉理工大学 | Super-stable printable aqueous fluorescent anti-counterfeiting ink and preparation method thereof |
| CN113755057A (en) * | 2021-07-30 | 2021-12-07 | 哈尔滨工业大学（深圳） | Water-based fluorescent ink, preparation method thereof and application thereof in full-color printing and encryption anti-counterfeiting |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115044251B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tan et al. | Upconversion nanoparticles@ carbon Dots@ Meso-SiO2 sandwiched core–shell nanohybrids with tunable dual-mode luminescence for 3D anti-counterfeiting barcodes | |
| Li et al. | Carbon dots‐in‐matrix boosting intriguing luminescence properties and applications | |
| Zhuang et al. | Organic photoresponsive materials for information storage: a review | |
| Lin et al. | Photoswitchable ultrahigh-brightness red fluorescent polymeric nanoparticles for information encryption, anti-counterfeiting and bioimaging | |
| Liu et al. | A strategy to achieve efficient dual‐mode luminescence of Eu3+ in lanthanides doped multifunctional NaGdF4 nanocrystals | |
| Miliani et al. | Acidichromic effects in 1, 2‐di‐and 1, 2, 4‐tri‐hydroxyanthraquinones. A spectrophotometric and fluorimetric study | |
| CN111320199B (en) | Anti-counterfeiting fluoride nanoparticle composite material and preparation method thereof | |
| US9187668B2 (en) | Photochromic inks | |
| Chiang et al. | Construction of emission-tunable nanoparticles based on a TICT-AIEgen: Impact of aggregation-induced emission versus twisted intramolecular charge transfer | |
| Chen et al. | Self-assembled supramolecular artificial light-harvesting nanosystems: construction, modulation, and applications | |
| CN104031477A (en) | Panchromatic fluorescent anti-counterfeiting ink based on conjugated polymer nano-particles | |
| Bhaumik et al. | Cucurbituril based luminescent materials in aqueous media and solid state | |
| CN110408396A (en) | NaLuF based on lanthanide ion doping4/Y2O3Double mode fluorescent material, anti-forgery ink and preparation method and application | |
| Li et al. | Design and assembly of AIE-active fluorescent organic nanoparticles for anti-counterfeiting fluorescent hydrogels and inks | |
| Yan et al. | Self-quenching-resistant solid-state carbon dots for mechanism and applications | |
| CN102703061A (en) | Method for performing fluorescent anti-counterfeit by ZnO quantum dots | |
| CN111681532B (en) | Multi-stage anti-counterfeiting material with three-primary-color orthogonal up-conversion fluorescence characteristic and application thereof | |
| Guerrero‐Martínez et al. | Microcontainers with fluorescent anisotropic zeolite L cores and isotropic silica shells | |
| CN111484846B (en) | Chameleon-like rare earth inorganic material, preparation method thereof and application thereof in fluorescence anti-counterfeiting | |
| CN113388402B (en) | Double-excitation multicolor luminous rare earth up-conversion nanoparticles and preparation method thereof | |
| Bao et al. | pH-responsive dual fluorescent core–shell microspheres fabricated via a one-step emulsion polymerization | |
| CN115044251A (en) | Multicolor fluorescent ink based on light-controlled nanoparticles and preparation method thereof | |
| CN112500740B (en) | Time-response color-changing phosphorescent carbon dot ink and preparation method and application thereof | |
| CN104672990A (en) | Water-based visible ultraviolet excited ink and preparation method thereof | |
| CN111892843B (en) | Preparation method of red, green and blue three-primary-color orthogonal up-conversion fluorescent safety ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |