CN110054723B - Preparation and application of multi-wavelength regulated optical switch fluorescent polymer nanoparticles - Google Patents
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Abstract
The invention discloses preparation and application of a multi-wavelength-regulated optical switch fluorescent polymer nano particle, which is prepared by taking Methyl Methacrylate (MMA), green light switch fluorescent dye (SP-PDI) and photochromic compound diarylethene (DTE-BA) as main raw materials and adopting a miniemulsion polymerization method by utilizing a Fluorescence Resonance Energy Transfer (FRET) principle. The nano particles have small particle size and good water dispersibility, and can show the characteristics of a rapid and reversible fluorescence switch under the irradiation of two ultraviolet lights and visible lights. Compared with the existing optical switch fluorescent polymer nano particles, the optical switch fluorescent polymer nano particles obtained by the invention have the advantages of multi-level optical switch capability, lower input cost, simple synthetic route and the like, are suitable for amplification synthesis and practical production application, and have huge application prospects in the technical fields of logic gates, display materials and the like.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation and display materials, in particular relates to preparation and application of a multi-wavelength regulated optical switch material, and particularly relates to preparation and application of reversible optical switch fluorescent polymer nanoparticles based on a diarylethene compound DTE-BA containing a green light switch fluorescent dye SP-PDI and having photochromic characteristics.
Background
The photoswitch fluorescent polymer nanoparticles adjust the color or light/dark state of the fluorescence by introducing a fluorescent chromophore or a photoswitch compound. The polymer nano particle with the core-shell structure provides a hydrophobic environment for organic dye molecules, is favorable for increasing the concentration of the organic dye molecules in a water phase so as to improve the fluorescence intensity of the organic dye molecules in a water phase system, can also reduce the toxicity possibly generated in biological application, and has the advantages of small particle size, good water dispersibility, good biocompatibility and the like.
The optical switch fluorescent polymer nano-particle has great application potential in the fields of chemical sensing, fluorescence microscope technology, display materials and the like. For the optical switch monochromatic fluorescent polymer nanoparticles, the signal depends on the contrast ratio of fluorescence light and dark, and is greatly influenced by the outside. In order to overcome the problems, the compound with the optical switch property and the fluorescent donor dye with the energy level matching are combined into the polymer nano particle to prepare the optical switch fluorescent polymer nano particle, so that the change of the double-color optical switch fluorescence can be realized. For a two-color fluorescent switch system with partially overlapped emission spectra, the two-color fluorescence obviously cannot meet the current requirements, another compound with the photoswitch property is required to be introduced to serve as an acceptor, so that reversible regulation of the bright-dark state of the fluorescence is realized, and an effective way is provided for the appearance of the diarylethene-based photoswitch fluorescent polymer nanoparticles regulated and controlled by multiple wavelengths.
The diarylethene compounds have excellent optical switching performance, so that research on the diarylethene compounds is in the hot direction of researchers. Scientists have now made continuous attempts to develop certain diarylethene compounds with logic gate function. Setaria et al, respectively, impart fluorescence properties to the molecule and increase water solubility thereof by introducing derivatives of naphthalimide and piperazine and D-galactose groups on diarylethene. The molecule can realize light and pH value regulation and control of molecular fluorescence color through ultraviolet light/visible light and trifluoroacetic acid/triethylamine, and the authors further apply the molecule to a 'forbidden' gate logic circuit (X. Chai, Y. X. Fu, T.D. James, J.Zhang, X.P. He, H.Tian, Photochromysm and molecular gate operation of a water-compatible bis-glycidyl. chem. Commun.,2017,53,9494-9497.) with fluorescence signal as output. Soo Young Park et al utilizes a photoswitch fluorescent compound diarylethene CF3-BPDBTEO and a temperature sensitive sol-gel molecule CN-TFMBE to blend to obtain a mixed sol-gel system. The molecule can realize the fluorescent color and state of light and temperature regulation molecules through ultraviolet light/visible light and high/low temperature, and the authors further apply the molecule to a composite logic circuit (d.kim, j.e.kwon, s.y.park, adv.funct.mater.2018,28,1706213.) which takes a fluorescent signal as output. However, the logic gates based on the diarylethene small molecules are applied, and different fluorescent colors or states can be achieved by adopting different stimulation conditions (light, pH and temperature), so that the problem of how to develop a material of an all-optical switch fluorescent polymer system with the function of the logic gates becomes a breakthrough.
Therefore, the invention provides a simple, low-cost and fully-optically-controlled reversible optical switch fluorescent polymer nanoparticle with quite important practical significance and application prospect, and the invention is provided in view of the above characteristics.
Disclosure of Invention
The technical problem to be solved by the present invention is to overcome the defects of the prior art, and to provide a multi-wavelength controlled optical switch fluorescent polymer nanoparticle and application thereof in a logic gate, in order to solve the technical problem, the basic concept of the technical scheme adopted by the present invention is as follows:
the preparation method of the multi-wavelength regulated optical switch fluorescent polymer nano particle comprises the following steps: methyl methacrylate, a green light switch fluorescent dye SP-PDI, a diaryl ethylene compound DTE-BA with photochromic characteristics, n-hexadecane, azodiisobutyronitrile, hexadecyl trimethyl ammonium chloride and trimethylolpropane trimethacrylate are taken as raw materials, and after mixing, miniemulsion polymerization is carried out to obtain the multi-wavelength regulated light switch fluorescent polymer nano particle.
The method specifically comprises the following steps:
(1) methyl methacrylate, a green light switch fluorescent dye SP-PDI, a diarylethene compound DTE-BA with photochromic characteristics, n-hexadecane, azobisisobutyronitrile and trimethylolpropane trimethacrylate are mixed according to the mass ratio of 1: 0.004: 0.02: 0.125: 0.05: 0.316 to form a solution;
(2) preparing a hexadecyl trimethyl ammonium chloride reagent into an aqueous solution with the concentration of 0.005-0.015 g/mL;
(3) mixing and stirring the solutions prepared in the step (1) and the step (2) for 5 minutes to form a pre-emulsion;
(4) carrying out ultrasonic emulsification on the pre-emulsion formed in the step (3) in an ultrasonic cell crusher for 10 minutes to form a miniemulsion;
(5) and (4) introducing nitrogen into the miniemulsion formed in the step (4) to remove oxygen for 10 minutes, heating to 75 ℃, and reacting for 4 hours to obtain the multi-wavelength regulated optical switch fluorescent polymer nanoparticles.
In the preparation of the multi-wavelength-regulated photoswitch fluorescent polymer nanoparticle, the green fluorescent dye SP-PDI in the step (1) has the following structural formula:
in the step (1), the diarylethene compound bis (4- (acryloyloxy) butyl) 4,4' - (octafluorocyclopentene-1, 2-yl) bis (5-methylthiophene-2-carboxyl), i.e., DTE-BA, having photochromic properties is prepared from the following structural formula:
after the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
(1) The invention successfully prepares the multi-wavelength regulated optical switch polymer fluorescent nano-particle by adopting a one-step emulsion polymerization method, and the polymer nano-particle has good water dispersibility and smaller particle size (about 85 nm).
(2) The multi-wavelength regulated optical switch polymer fluorescent nano particle prepared by the invention adopts spiropyran and diarylethene as photosensitizers to regulate and control the color and the light and shade state of fluorescence under the condition of full light control, and the synthesis and preparation processes are simpler.
(3) The multi-wavelength regulated optical switch polymer fluorescent nano particle prepared by the invention can realize reversible conversion from green light to red light emission to fluorescence quenching and from green light to fluorescence quenching under the action of two ultraviolet lights and visible lights by regulating the irradiation time of the two ultraviolet lights and the visible lights. The multi-wavelength regulated optical switch polymer fluorescent nano particle has very important application prospect in the fields of logic gates and the like.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention to its proper form. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
fig. 1 is a graph of the particle size of the nanoparticles prepared.
FIG. 2 is a diagram of the ultraviolet-visible absorption spectrum of the prepared nanoparticles under the action of different external lights.
FIG. 3 is a fluorescence emission spectrum of the prepared nanoparticles under different external light effects.
Fig. 4 is a graph of the photo-response of the prepared nanoparticles to 365nm ultraviolet light, 254nm ultraviolet light and visible light.
FIG. 5 is a graph of reversible cycling of the prepared nanoparticles for 365nm UV and visible light.
Fig. 6 is a graph of the photo-response of the prepared nanoparticles to 254nm uv and visible light.
Fig. 7 is a graph of reversible cycling of prepared nanoparticles for 254nm uv and visible light.
FIG. 8 is a graph showing the photo-response of the prepared nanoparticles to 254nm UV light and 365nm UV light.
FIG. 9 is a graph of reversible cycling of prepared nanoparticles to 254nm UV light and 365nm UV light.
FIG. 10 is a graph showing the change of fluorescence intensity at 550nm of the prepared nanoparticles under different input signals.
FIG. 11 is a graph showing the change of fluorescence intensity at 650nm of the prepared nanoparticles under different input signals.
Fig. 12 is a truth table of the logic operation of the prepared nanoparticles.
FIG. 13 is a schematic of a logic circuit of the prepared nanoparticles.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1: the preparation method of the multi-wavelength regulated optical switch polymer fluorescent nanoparticles comprises the following specific steps:
0.5g of methyl methacrylate, 0.002g of green light switch fluorescent dye SP-PDI, 0.010g of diarylethene compound DTE-BAhaving photochromic property, 0.075g of n-hexadecane, 0.025g of azodiisobutyronitrile and 0.158g of trimethylolpropane trimethacrylate are mixed and stirred uniformly, dispersed in 10mL of hexadecyltrimethylammonium chloride aqueous solution with the concentration of 0.005g/mL, and ultrasonically emulsified to form stable and uniform miniemulsion, and reacted for 4 hours at 75 ℃ to obtain the green light switch fluorescent polymer nano-particle with multi-wavelength regulation and control.
Example 2: the preparation method of the multi-wavelength regulated optical switch polymer fluorescent nanoparticles comprises the following specific steps:
0.5g of methyl methacrylate, 0.002g of green light switch fluorescent dye SP-PDI, 0.010g of diarylethene compound DTE-BA0.010g with photochromic property, 0.075g of n-hexadecane, 0.025g of azodiisobutyronitrile and 0.158g of trimethylolpropane trimethacrylate are mixed and stirred uniformly, dispersed in 10mL of hexadecyltrimethylammonium chloride aqueous solution with the concentration of 0.01g/mL, and ultrasonically emulsified to form stable and uniform miniemulsion, and reacted for 4 hours at 75 ℃ to obtain the green light switch fluorescent polymer nano-particle with multi-wavelength regulation and control.
Example 3: the preparation method of the multi-wavelength regulated optical switch polymer fluorescent nanoparticles comprises the following specific steps:
0.5g of methyl methacrylate, 0.002g of green light switch fluorescent dye SP-PDI, 0.010g of diarylethene compound DTE-BAhaving photochromic property, 0.075g of n-hexadecane, 0.025g of azodiisobutyronitrile and 0.158g of trimethylolpropane trimethacrylate are mixed and stirred uniformly, dispersed in 10mL of hexadecyltrimethylammonium chloride aqueous solution with the concentration of 0.015g/mL, and ultrasonically emulsified to form stable and uniform miniemulsion, and reacted for 4 hours at 75 ℃ to obtain the green light switch fluorescent polymer nano-particle with multi-wavelength regulation and control.
Example 4: the ultraviolet-visible absorption spectra of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in example 2 under different external light effects were tested.
The specific test instrument is as follows: shimadzu UV-2501PC ultraviolet-visible absorption spectrometer, the concentration tested is 0.29 wt% of solid content, the temperature tested is 25 ℃.
Fig. 2 is a graph of the ultraviolet-visible absorption spectrum of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in example 2 in the range of 300nm to 700 nm. As can be seen from FIG. 2, after the nanoparticles are irradiated by 525nm visible light, an obvious absorption characteristic peak of perylene imide appears at 520nm, then after the nanoparticles are irradiated by 365nm ultraviolet light, the nanoparticles appear an obvious absorption characteristic peak of spiropyran at 570nm, and then after the nanoparticles are irradiated by 254nm ultraviolet light, the nanoparticles appear obvious absorption characteristic peaks of diarylethene at 380nm and 590 nm.
Example 5: the fluorescence emission spectra of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in example 2 under different external light effects were tested.
The specific test instrument is as follows: edinburgh FLS920 steady state/transient state fluorescence spectrometer, test concentration is 0.29 wt% of solid content, test temperature is 25 ℃.
Fig. 3 is a fluorescence emission spectrum of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in example 2 under different external light effects. After the nano particles are irradiated by 525nm visible light, an obvious green fluorescence emission peak of perylene imide groups appears at 550nm, then after the nano particles are irradiated by 365nm ultraviolet light, the fluorescence intensity of perylene imide groups at 550nm is partially reduced, the fluorescence intensity of the spiropyran in an open-loop state at 650nm is increased, and the fluorescence color of the nano particles is changed from green to red. Then, after the irradiation of 254nm ultraviolet light, the fluorescence intensity of perylene bisimide and the spiropyran in an open-loop state in the nano particles is obviously reduced, and the quenching of fluorescence is realized.
Example 6: the light response experiment of the fluorescence emission spectrum of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in the test example 2 after the alternating irradiation of 365nm ultraviolet light, 254nm ultraviolet light and 525nm visible light is carried out.
Fig. 4 is a photoresponse graph of the fluorescence emission spectrum of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticle prepared in example 2 at 550nm after the alternating irradiation of 365nm ultraviolet light, 254nm ultraviolet light and 525nm visible light. As can be seen from FIG. 4, the fluorescence intensity of the sample at 550nm also changes regularly with the time of UV or visible light irradiation. After 2 minutes of 365nm UV irradiation, the fluorescence intensity at 550nm drops to a certain extent and is substantially constant, and then after 2 minutes of 254nm UV irradiation, the fluorescence intensity at 550nm drops to a minimum. Then, after visible light irradiation at 525nm for 10 minutes, the fluorescence intensity at 550nm can be substantially restored to the original state. Therefore, the multi-wavelength-regulated optical switch fluorescent polymer nanoparticles have higher optical response speed.
Example 7: the reversible photoswitch cycle experiment of the multi-wavelength-controlled photoswitch fluorescent polymer nanoparticles prepared in example 2 after alternating irradiation of 365nm ultraviolet light and 525nm visible light was tested.
FIG. 5 is a graph of the reversible cycle times of the multi-wavelength tuned optical switch fluorescent polymer nanoparticles prepared in example 2. The sample is placed in a quartz cuvette, and the fluorescence intensity of the sample at the position of 550nm is respectively tested after repeated alternate irradiation of 365nm ultraviolet light and 525nm visible light, as shown in figure 5, the result shows that the multi-wavelength regulated optical switch fluorescent polymer nano particle still has better reversible optical switch performance after ten optical switch cycle tests.
Example 8: the light response experiment of the fluorescence emission spectrum of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in the example 2 after the alternate irradiation of 254nm ultraviolet light and 525nm visible light is tested.
FIG. 6 is a graph of the photoresponse of the fluorescence emission spectrum of the multi-wavelength-modulated optical switch fluorescent polymer nanoparticles prepared in example 2 at 550nm after the alternate irradiation of 254nm ultraviolet light and 525nm visible light. As can be seen from FIG. 6, the fluorescence intensity of the sample at 550nm also changes regularly with the time of UV or visible light irradiation. After irradiation with 254nm UV light for 3 minutes, the fluorescence intensity at 550nm dropped to a minimum. Then, after 7 minutes of visible light irradiation at 525nm, the fluorescence intensity at 550nm was able to be substantially restored to the original state. Therefore, the multi-wavelength-regulated optical switch fluorescent polymer nanoparticles have higher optical response speed.
Example 9: the reversible photoswitch cycle experiment of the multi-wavelength-controlled photoswitch fluorescent polymer nanoparticles prepared in example 2 after alternating irradiation of 365nm ultraviolet light and 525nm visible light was tested.
FIG. 7 is a graph of the reversible cycle times of the multi-wavelength tuned optical switch fluorescent polymer nanoparticles prepared in example 2. The sample is placed in a quartz cuvette, and the fluorescence intensity of the sample at the position of 550nm is respectively tested after multiple alternate irradiation of 254nm ultraviolet light and 525nm visible light, as shown in figure 7, the result shows that the multi-wavelength regulated optical switch fluorescent polymer nano particle still has better reversible optical switch performance after ten optical switch cycle tests.
Example 10: the light response experiment of the fluorescence emission spectrum of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in the test example 2 after the alternate irradiation of 254nm ultraviolet light and 365nm ultraviolet light is tested.
FIG. 8 is a photo-response graph of the fluorescence emission spectrum of the multi-wavelength-modulated optical switch fluorescent polymer nanoparticles prepared in example 2 at 650nm after the alternate irradiation of 254nm ultraviolet light and 365nm visible light. As can be seen from FIG. 8, the fluorescence intensity of the sample at 650nm also changes regularly with the time of UV or visible light irradiation. After 2 minutes of UV irradiation at 254nm, the fluorescence intensity at 650nm dropped to a minimum. Then, after 9 minutes of 365nm ultraviolet light irradiation, the fluorescence intensity at 650nm can be substantially restored to the original state. Therefore, the multi-wavelength-regulated optical switch fluorescent polymer nanoparticles have higher optical response speed.
Example 11: the reversible photoswitch cycle experiment of the multi-wavelength-controlled photoswitch fluorescent polymer nanoparticles prepared in example 2 after the alternating irradiation of 254nm ultraviolet light and 365nm ultraviolet light was tested.
FIG. 9 is a graph of the reversible cycle times of the multi-wavelength tuned optical switch fluorescent polymer nanoparticles prepared in example 2. The sample is placed in a quartz cuvette, and the fluorescence intensity of the sample at 650nm is respectively tested after multiple alternate irradiation of 254nm ultraviolet light and 365nm visible light, as shown in fig. 9, the result shows that the multi-wavelength regulated optical switch fluorescent polymer nano particle still has better reversible optical switch performance after ten optical switch cycle tests.
Example 12: the graph of the fluorescence intensity change of the fluorescence emission spectrum at 550nm of the multi-wavelength-modulated optical switch fluorescent polymer nanoparticles prepared in example 2 is tested at different input signals.
FIG. 10 is a graph showing the fluorescence intensity variation of the multi-wavelength tunable optical switch fluorescent polymer nanoparticles prepared in example 2 under different input signals. As shown in fig. 10, the output threshold of the nanoparticles was set to 0.7, and when the fluorescence intensity was lower than the output threshold, the output was "0"; when the fluorescence intensity is higher than the output threshold, the output is "1". Thus, a complex logic circuit consisting of NOR gates and OR gates is simulated with 365nm, 254nm, 525nm as input signals and different fluorescence intensity values at 550nm as outputs.
Example 13: the graph of the fluorescence intensity change of the fluorescence emission spectrum at 650nm of the multi-wavelength-modulated optical switch fluorescent polymer nanoparticles prepared in example 2 at different input signals was tested.
FIG. 11 is a graph showing the fluorescence intensity variation of the multi-wavelength tunable optical switch fluorescent polymer nanoparticles prepared in example 2 under different input signals. As shown in fig. 11, the output threshold of the nanoparticles was set to 0.7, and when the fluorescence intensity was lower than the output threshold, the output was "0"; when the fluorescence intensity is higher than the output threshold, the output is "1". Thus, 365nm, 254nm and 525nm are used as input signals, different fluorescence intensity values at 650nm are used as output, and a composite logic circuit consisting of an implication gate and a NOR gate is simulated.
Example 14: the truth table of the logical operation of the multi-wavelength-controlled optical switch fluorescent polymer nanoparticles prepared in example 2 was tested.
Fig. 12 is a truth table of the logic operation of the three-input and two-output combination of the prepared multi-wavelength-controlled optical switch fluorescent polymer nanoparticles. When three input signals are set as input 1(365nm), input 2(254nm) and input 3(525nm), the fluorescence intensities at 550nm and 650nm corresponding to the input nanoparticles are used as output signals. Defining the fluorescence emission spectrum to have an output logic value of "1" at output fluorescence intensities I >0.7 at 550nm and 650 nm. Otherwise, the output logic value is "0".
Example 15: a schematic logic circuit diagram of the multi-wavelength tunable optical switch fluorescent polymer nanoparticles prepared in test example 2 was tested.
FIG. 13 is a schematic of a logic circuit of the prepared nanoparticles. In eight combinations of input 1(365nm), input 2(254nm), and input 3(525nm) as input signals at 550nm of the fluorescence emission spectrum, the output signal is "1" in the initial state or when the input signal of 525nm exists, and the output signal is "0" in the remaining cases. Thus, a complex logic circuit consisting of NOR gates and OR gates is simulated with 365nm, 254nm, 525nm as input signals and different fluorescence intensity values at 550nm as outputs. Similarly, in eight combinations of 365nm (input 1), 254nm (input 2) and 525nm (input 3) as input signals at 650nm of the fluorescence emission spectrum, the output signal is "1" when only the 365nm input signal exists, and the output signals are all "0" in other cases, so that a composite logic circuit consisting of an "implication" gate and a "not or" gate is simulated.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A preparation method of multi-wavelength regulated optical switch fluorescent polymer nanoparticles is characterized in that methyl methacrylate, a green light switch fluorescent dye SP-PDI, a diaryl ethylene compound DTE-BA with photochromic property, n-hexadecane, azobisisobutyronitrile, hexadecyltrimethylammonium chloride and trimethylolpropane trimethacrylate are taken as raw materials, mixed and polymerized in miniemulsion to obtain the multi-wavelength regulated optical switch fluorescent polymer nanoparticles;
the green light switch fluorescent dye SP-PDI has a structural formula as follows:
the structural formula of the diarylethene compound DTE-BA with photochromic characteristic is as follows:
2. the method for preparing the multi-wavelength-regulated optical switch fluorescent polymer nanoparticle as claimed in claim 1, wherein the specific steps are as follows:
step 1, mixing methyl methacrylate, a green light switch fluorescent dye SP-PDI, a diarylethene compound DTE-BA with photochromic property, n-hexadecane, azodiisobutyronitrile and trimethylolpropane trimethacrylate according to the mass ratio of 1: 0.004: 0.02: 0.125: 0.05: 0.316 to form a solution;
step 2, preparing a hexadecyl trimethyl ammonium chloride reagent into an aqueous solution with the concentration of 0.005-0.015 g/mL;
step 3, mixing and stirring the solutions prepared in the step 1 and the step 2 for 5 minutes to form a pre-emulsion;
step 4, carrying out ultrasonic emulsification on the pre-emulsion formed in the step 3 in an ultrasonic cell crusher for 10 minutes to form a miniemulsion after completion;
and 5, introducing nitrogen into the miniemulsion formed in the step 4 to remove oxygen for 10 minutes, heating to 75 ℃, and reacting for 4 hours to obtain the multi-wavelength regulated optical switch fluorescent polymer nanoparticles.
3. The multi-wavelength modulated optical switch fluorescent polymer nano-particles prepared by the method of claim 1 or 2.
4. The application of the multi-wavelength-regulated optical switch fluorescent polymer nanoparticles prepared by the preparation method according to claim 1 or 2 in logic gates.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104140489A (en) * | 2014-07-23 | 2014-11-12 | 湖南科技大学 | Amphipathy photoswitch fluorescent polymer nano particles and preparing method thereof |
| CN107389636A (en) * | 2017-07-13 | 2017-11-24 | 湖南科技大学 | A kind of preparation and application of the water soluble fluorescence sensor that endogenous glutathione can be detected in cancer cell |
| CN107417849A (en) * | 2017-08-23 | 2017-12-01 | 湖南科技大学 | A kind of near infrared light switch fluorescent polymer nano-particle prepares and its application |
| CN108084326A (en) * | 2017-12-19 | 2018-05-29 | 湖南科技大学 | The preparation of series adjustable composition polymer nanosphere from white light to primaries |
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