CN112362622A - Flexible fluorescence enhancement substrate and preparation method and application thereof - Google Patents
Flexible fluorescence enhancement substrate and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
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Abstract
The invention provides a flexible fluorescence-enhanced substrate and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) integrating noble metal colloidal particles on the surface of the porous metal oxide template to obtain an array of noble metal colloidal particles; (2) compounding the noble metal colloidal particle array obtained in the step (1) with a flexible polymer to obtain a noble metal colloidal particle array/flexible polymer composite film; (3) and (3) chemically etching the composite film obtained in the step (2) to remove the residual metal of the porous metal oxide to obtain the flexible fluorescence enhanced substrate. According to the invention, the high-efficiency flexible fluorescence enhanced substrate is obtained through large-scale rapid integration and flexible transfer of noble metal colloid particles. The method has the advantages of low cost, simple and convenient operation and excellent enhancement effect on the fluorescence signal, and lays a foundation for the wide application of the fluorescence spectrum analysis technology in practice.
Description
Technical Field
The invention belongs to the field of integration and transfer of nano materials, and particularly relates to a flexible fluorescence enhancement substrate and a preparation method and application thereof.
Background
Fluorescence spectroscopy is an important part of modern spectroscopy, and in the nineties of the last century, scientists found that rough metal surfaces can have a significant enhancement effect on the fluorescence of fluorescent molecules, thereby attracting general attention of the academia. At present, the fluorescence spectrum analysis technology is mainly applied to the fields of pollutant detection, optical sensing, biology and medical treatment.
Recent studies have found that the surface plasmon effect of the noble metal nanoparticles can produce a great enhancement effect on the fluorescence of fluorescent molecules, and this enhancement effect is extremely related to the distance between the molecules and the noble metal nanoparticles and the distance between the noble metal nanoparticles and the particles.
The fluorescence is enhanced by the surface plasmon, and a specific fluorescence enhancement substrate is required for realization. At present, two types of commonly used fluorescence enhancement substrates are available, one type is a substrate with a specific structure prepared by a micro-nano processing mode, and CN106350058A discloses a preparation method of a fluorescence enhancement substrate based on nano porous gold. The substrate has a certain fluorescence enhancement effect, the signal deviation in different areas is small, the repeatability is high, but the micro-nano processing cost is high, the process steps are complicated, and the micro-nano detection method is difficult to be widely applied to detection. The other is that noble metal colloid particles are directly spread on a substrate, and a "hot spot" of surface plasmon is generated by aggregation between the colloid particles to generate an enhancement effect. CN105136757A discloses a flower-shaped silver nanoparticle fluorescence enhancement substrate and a preparation method thereof, wherein the method comprises the steps of reacting a silver nitrate solution, polyvinylpyrrolidone and ascorbic acid, and repeatedly performing ultrasonic dispersion and centrifugation on reactants to obtain a flower-shaped silver nanoparticle ethanol dispersion liquid so as to manufacture the substrate. The substrate has good local enhancement effect, but the hot spots are not uniformly distributed and have poor repeatability, and the deviation of signals in different areas is large, so the substrate is not beneficial to wide practical application. In addition, the current fluorescence-enhanced substrates based on these two methods are rigid and do not meet the requirements for bending, stretching, etc. that may be encountered in practical assays.
Based on the method, a simple, efficient and low-cost flexible fluorescence enhancement substrate is researched, and the method has important significance for wide application of a fluorescence spectrum analysis technology in practice.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a flexible fluorescence-enhanced substrate, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a method for preparing a flexible fluorescence-enhanced substrate, comprising the steps of:
(1) integrating noble metal colloidal particles on the surface of the porous metal oxide template to obtain an array of noble metal colloidal particles;
(2) compounding the noble metal colloidal particle array obtained in the step (1) with a flexible polymer to obtain a noble metal colloidal particle array/flexible polymer composite film;
(3) and (3) chemically etching the composite film obtained in the step (2) to remove the residual metal of the porous metal oxide template, thereby obtaining the flexible fluorescence enhanced substrate.
The preparation method is a strategy combining top-down and bottom-up, and finally obtains the flexible fluorescence enhancement substrate by quickly integrating and flexibly transferring the noble metal colloid particles. Compared with the substrate prepared by the traditional micro-nano processing method, the preparation method has the advantages of low cost, rapidness, high efficiency and the like; the prepared flexible fluorescence enhancement substrate has the advantages of large area, high particle integration level, high response and the like. The flexible fluorescence enhancement substrate has wide application prospect in the aspects of rapid detection of low-concentration fluorescent molecules and optical sensors.
Preferably, the noble metal in the noble metal colloidal particles of step (1) is an alloy formed by any one or a combination of at least two of Au, Ag, Cu, or Pt.
Preferably, the colloidal particles in the noble metal colloidal particles in step (1) are any one of or a combination of at least two of noble metal nanospheres, noble metal nanocubes or noble metal nanocubes synthesized by a solution method and having a size of 20-500nm (e.g., 20nm, 50nm, 80nm, 100nm, 120nm, 150nm, 200nm, 300nm, 400nm or 500 nm).
Preferably, the porous metal oxide template in the step (1) is any one of a porous anodic aluminum oxide template, a porous anodic titanium oxide template and a porous anodic iron oxide template
Preferably, the porous anodized aluminum template of step (1) is a hard template having a pore size of 20 to 550nm (e.g., 20nm, 50nm, 80nm, 100nm, 120nm, 150nm, 200nm, 300nm, 400nm, or 550nm) prepared by a three-step anodization method.
Preferably, the porous anodized titanium template is a hard template having a pore size of 20 to 550nm (e.g., 20nm, 50nm, 80nm, 100nm, 120nm, 150nm, 200nm, 300nm, 400nm, or 550nm) prepared by a three-step anodization method.
Preferably, the porous anodic iron oxide template is a hard template with a pore size of 20-550nm (e.g., 20nm, 50nm, 80nm, 100nm, 120nm, 150nm, 200nm, 300nm, 400nm, or 550nm) prepared by a three-step anodic oxidation process.
Preferably, step (1) is integrated into a process of trapping noble metal colloidal particles inside the pores of the porous metal oxide template. Preferably, the integration process is: the method comprises the following steps of uniformly spreading an aqueous solution or an alcoholic solution of noble metal colloid particles on the surface of a porous metal oxide template, enabling the noble metal colloid particles to enter a pore channel of the template under the action of surface tension and a template confinement effect, carrying out an integration process at a gas-liquid-solid three-phase interface, moving the three-phase interface along with volatilization of liquid, and further completing the integration process on the surface of the whole template.
Preferably, in the present invention, the array of noble metal colloidal particles in step (1) is a single-layer array with hexagonal ordered arrangement, the integration rate is higher than 95%, and the particle density is higher than 1010Per square centimeter.
Preferably, in the present invention, the flexible polymer in step (2) is any one of Polyethylene (PE), polymethyl methacrylate (PMMA), Polydimethylsiloxane (PDMS), or polyethylene terephthalate (PET).
Preferably, the compounding method in step (2) is as follows: and (3) paving the flexible high polymer solution on the surface of the noble metal colloidal particle array, and fully forming a film to obtain the composite film.
Preferably, the concentration of the flexible polymer solution is 5 wt% to 20 wt% (e.g., 5 wt%, 10 wt%, 15 wt%, or 20 wt%).
Preferably, the film forming temperature is 80 ℃ to 150 ℃ (e.g., 80 ℃, 100 ℃, 125 ℃ or 150 ℃) and the film forming time is 4 to 24 hours (e.g., 4 hours, 8 hours, 12 hours, 16 hours, 20 hours or 24 hours).
In the invention, the porous metal oxide template refers to a metal with a layer of oxide layer formed on the surface of the metal after anodic oxidation, so that residual metal exists and needs to be removed by chemical etching in subsequent steps.
In the invention, the etching solution for the chemical etching in the step (3) is a saturated aqueous solution of copper chloride or tin chloride, the etching temperature is room temperature, and the etching time is 1-5 hours, such as 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.
In another aspect, the present invention provides a flexible fluorescence-enhanced substrate prepared by the preparation method as described above.
In the present invention, the flexible fluorescence-enhanced substrate is composed of three parts: the flexible polymer film support layer at the bottommost part, the precious metal colloid particle array in hexagonal ordered arrangement in the middle part and the metal oxide barrier layer at the topmost layer.
Preferably, the metal oxide barrier layer has a thickness of 5-40nm, such as 5nm, 8nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm or 40 nm.
Preferably, the flexible fluorescence enhancing substrate has a thickness of 1-1000 μm, such as 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 30 μm, 50 μm, 80 μm, 100 μm, 300 μm, 500 μm, 700 μm, 900 μm or 1000 μm.
In another aspect, the present invention provides an optical sensor comprising a flexible fluorescence-enhancing substrate as described above.
In another aspect, the present invention provides the use of a flexible fluorescence enhanced substrate or optical sensor as described above for the rapid detection of low concentrations of fluorescent molecules.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a high-efficiency flexible fluorescence-enhanced substrate is obtained through large-scale rapid integration and flexible transfer of noble metal colloid particles. Compared with the existing method, the method has the advantages of low cost, simple operation, excellent effect of enhancing fluorescence signal, and capability of enhancing the fluorescence signal with extremely low concentration (less than 10)-8M) fluorescence signal amplification of the fluorescence molecule is 10-100 times, which lays a foundation for the wide application of the fluorescence spectrum analysis technology in practice.
Drawings
FIG. 1 is a schematic cross-sectional view of a flexible fluorescence-enhanced substrate according to example 1.
Fig. 2 is a scanning electron micrograph of the gold nanosphere array after the integration step in example 1 was completed.
FIG. 3 is a scanning electron micrograph of the flexible fluorescence-enhanced substrate obtained in example 1.
FIG. 4 is 10-8Fluorescence spectra of M rhodamine fluorescent molecule on the flexible fluorescence-enhanced substrate described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a flexible fluorescence enhancement substrate based on a gold nanosphere with a diameter of 60nm, which comprises the following specific steps:
(1) the method comprises the following steps of dripping water solution of gold nanospheres with the diameter of 60nm on the surface of a porous anodic alumina template with the pore size of 66nm, enabling the gold nanospheres to enter pore channels of the template under the action of surface tension and template confinement effect, carrying out an integration process at a gas-liquid-solid three-phase interface, and moving the three-phase interface along with volatilization of liquid so as to finish the integration process on the surface of the whole template. Fig. 2 is a scanning electron micrograph of the gold nanosphere array after the integration step in example 1, and it can be seen from fig. 2 that the integrated gold nanosphere array is highly ordered and has a hexagonal arrangement.
(2) And (3) spreading a precursor solution of PDMS with the mass fraction of 20 wt% on the surface of the integrated gold nanosphere array, forming a film for 4 hours at 150 ℃, and fully forming the film to obtain the gold nanosphere array/PDMS composite film.
(3) And placing the gold nanosphere array/PDMS composite film in a saturated solution of copper chloride for etching for 2 hours, removing the residual aluminum, and cleaning to obtain the flexible fluorescence enhancement substrate based on the gold nanospheres with the diameter of 60nm, wherein the thickness of the flexible fluorescence enhancement substrate is 500 mu m.
The flexible fluorescence-enhanced substrate is composed of three parts: the flexible polymer film support layer at the bottommost part, the precious metal colloid particle array in hexagonal ordered arrangement in the middle part and the alumina barrier layer at the top layer. FIG. 1 is a schematic cross-sectional structure diagram of the flexible fluorescence-enhanced substrate, and the three parts can be visually seen from FIG. 1.
FIG. 3 is a scanning electron micrograph of the flexible fluorescence-enhanced substrate finally obtained in example 1. As can be seen from FIG. 3, the surface layer of the gold nanosphere array in hexagonal ordered arrangement has an alumina barrier layer with a thickness of 20 nm.
FIG. 4 is 10-8As can be seen from FIG. 4, the fluorescence spectrum of the rhodamine molecule of M on the flexible fluorescence-enhanced substrate obtained in example 1 is amplified by 20 times compared with the fluorescence signal on the glass substrate at a very low concentration of the rhodamine molecule.
Example 2
The embodiment provides a preparation method of a flexible fluorescence enhancement substrate based on a silver nanocube with the diameter of 70nm, which comprises the following specific steps:
(1) the method comprises the following steps of dripping 70 nm-diameter silver nanocubes into the surface of a porous anodic alumina template with the size of 77nm aperture, enabling the silver nanocubes to enter pore channels of the template under the action of surface tension and template confinement effect, carrying out an integration process at a gas-liquid-solid three-phase interface, and moving the three-phase interface along with volatilization of liquid so as to complete the integration process on the surface of the whole template.
(2) And (3) spreading a precursor solution of PMMA with the mass fraction of 5 wt% on the surface of the integrated silver nanocube array, and fully forming a film for 12 hours at 80 ℃ to obtain the silver nanocube array/PMMA composite film.
(3) And (3) placing the silver nanocube array/PMMA composite film in a saturated solution of copper chloride for etching for 2 hours, removing the residual aluminum, and cleaning to obtain the flexible fluorescence enhancement substrate based on the silver nanocubes with the diameter of 70nm, wherein the thickness of the flexible fluorescence enhancement substrate is 1 micrometer.
Example 3
The embodiment provides a preparation method of a flexible fluorescence-enhanced substrate based on 20 nm-diameter platinum nanospheres, which comprises the following specific steps:
(1) the method is characterized in that water solution of platinum nanospheres with the diameter of 20nm is dripped on the surface of a porous anodic iron oxide template with the pore size of 22nm, the platinum nanospheres enter pores of the template under the action of surface tension and a template confinement effect, the integration process is carried out at a gas-liquid-solid three-phase interface, and along with the volatilization of liquid, the three-phase interface moves, so that the integration process is completed on the surface of the whole template.
(2) And (3) spreading a PE precursor solution with the mass fraction of 10 wt% on the surface of the integrated platinum nanosphere array, and fully forming a film for 10 hours at 100 ℃ to obtain the platinum nanosphere array/PE composite film.
(3) And (3) placing the platinum nanosphere array/PE composite film in a saturated solution of copper chloride for etching for 2 hours, removing residual iron, and cleaning to obtain the flexible fluorescence-enhanced substrate based on the platinum nanospheres with the diameter of 70nm, wherein the thickness of the flexible fluorescence-enhanced substrate is 200 microns.
Example 4
The embodiment provides a preparation method of a flexible fluorescence enhancement substrate based on a copper nanometer triangular plate with the diameter of 200nm, which comprises the following specific steps:
(1) the method comprises the following steps of dripping water solution of copper nanometer triangular plates with the diameter of 200nm on the surface of a porous anodic alumina template with the aperture of 220nm, enabling the copper nanometer triangular plates to enter pore channels of the template under the action of surface tension and template confinement effect, carrying out an integration process at a gas-liquid-solid three-phase interface, and moving the three-phase interface along with volatilization of liquid so as to finish the integration process on the surface of the whole template.
(2) And (3) flatly spreading a PET precursor solution with the mass fraction of 15 wt% on the surface of the integrated copper nano triangular plate array, and fully forming a film for 16 hours at 80 ℃ to obtain the copper nano triangular plate array/PET composite film.
(3) And (3) placing the copper nano triangular plate array/PET composite film in a saturated solution of tin chloride for etching for 2 hours, removing the residual aluminum, and cleaning to obtain the flexible fluorescence enhancement substrate based on the copper nano triangular plate with the diameter of 200nm, wherein the thickness of the flexible fluorescence enhancement substrate is 1000 microns.
Example 5
The embodiment provides a preparation method of a flexible fluorescence enhancement substrate based on gold nanospheres with the diameter of 500nm, which comprises the following specific steps:
(1) dropping a 500 nm-diameter gold nanosphere aqueous solution on the surface of a porous anodic titanium oxide template with the size of 550nm aperture, enabling a copper nano triangular plate to enter a pore channel of the template under the action of surface tension and a template confinement effect, carrying out an integration process at a gas-liquid-solid three-phase interface, and moving the three-phase interface along with volatilization of liquid so as to complete the integration process on the surface of the whole template.
(2) And (3) spreading a precursor solution of PDMS with the mass fraction of 15 wt% on the surface of the integrated gold nanosphere array, and forming a film at 125 ℃ for 8 hours to obtain the gold nanosphere array/PDMS composite film.
(3) And placing the gold nanosphere array/PDMS composite film in a saturated solution of tin chloride for etching for 2 hours, removing the residual titanium, and cleaning to obtain the flexible fluorescence enhancement substrate based on the gold nanospheres with the diameter of 500nm, wherein the thickness of the flexible fluorescence enhancement substrate is 300 mu m.
The preparation method of the flexible fluorescence-enhanced substrate is simple and low in cost, and the obtained flexible fluorescence-enhanced substrate has excellent enhancement effect on fluorescence signals and canFor very low concentration (less than 10)-8M) fluorescence signal amplification is 10-100 times, can be used for rapid detection of low concentration fluorescence molecule.
The applicant states that the present invention is illustrated by the above examples of the flexible fluorescence enhancement substrate of the present invention and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A method of making a flexible fluorescence-enhanced substrate, comprising the steps of:
(1) integrating noble metal colloidal particles on the surface of the porous metal oxide template to obtain an array of noble metal colloidal particles;
(2) compounding the noble metal colloidal particle array obtained in the step (1) with a flexible polymer to obtain a noble metal colloidal particle array/flexible polymer composite film;
(3) and (3) chemically etching the composite film obtained in the step (2) to remove the residual metal of the porous metal oxide to obtain the flexible fluorescence enhanced substrate.
2. The method according to claim 1, wherein the noble metal in the noble metal colloidal particles of step (1) is an alloy of any one or a combination of at least two of Au, Ag, Cu, or Pt.
3. The method of claim 1 or 2, wherein the noble metal colloidal particles of step (1) are any one of or a combination of at least two of noble metal nanospheres, noble metal nanocubes or noble metal nanoprisms synthesized by a solution method and having a size of 20-500 nm.
4. The preparation method according to any one of claims 1 to 3, wherein the porous metal oxide template in step (1) is any one of a porous anodic aluminum oxide template, a porous anodic titanium oxide template, and a porous anodic iron oxide template;
preferably, the porous anodized aluminum template in the step (1) is a hard template with the pore size of 20-550nm prepared by a three-step anodization method;
preferably, the porous anodic titanium oxide template is a hard template with the pore size of 20-550nm prepared by a three-step anodic oxidation method;
preferably, the porous anodic iron oxide template is a hard template with the pore size of 20-550nm prepared by a three-step anodic oxidation method.
5. The production method according to any one of claims 1 to 4, wherein the step (1) is integrated into a process of trapping noble metal colloidal particles inside the pores of a porous metal oxide template;
preferably, the integration process is: the method comprises the following steps of uniformly spreading an aqueous solution or an alcoholic solution of noble metal colloid particles on the surface of a porous metal oxide template, enabling the noble metal colloid particles to enter a pore channel of the template under the action of surface tension and a template confinement effect, carrying out an integration process at a gas-liquid-solid three-phase interface, moving the three-phase interface along with volatilization of liquid, and further completing the integration process on the surface of the whole template.
6. The method according to any one of claims 1 to 5, wherein the array of noble metal colloidal particles of step (1) is a monolayer array with hexagonal ordered arrangement, the integration rate is higher than 95%, and the particle density is higher than 1010Per square centimeter.
7. The method according to any one of claims 1 to 6, wherein the flexible polymer in step (2) is any one of polyethylene, polymethyl methacrylate, polydimethylsiloxane and polyethylene terephthalate;
preferably, the compounding method in step (2) is as follows: paving a flexible polymer solution on the surface of the noble metal colloidal particle array, and fully forming a film to obtain the composite film;
preferably, the concentration of the flexible polymer solution is 5 wt% -20 wt%;
preferably, the film forming temperature is 80-150 ℃, and the film forming time is 4-24 hours;
preferably, the etching solution for chemical etching in step (3) is a saturated aqueous solution of copper chloride or tin chloride, the etching temperature is room temperature, and the etching time is 1-5 hours.
8. A flexible fluorescence-enhanced substrate produced by the production method according to any one of claims 1 to 7;
preferably, the flexible fluorescence-enhancing substrate is composed of three parts: the flexible polymer film supporting layer at the bottommost part, the precious metal colloid particle array in hexagonal ordered arrangement in the middle and the metal oxide barrier layer at the surface layer;
preferably, the thickness of the metal oxide barrier layer is 5-40 nm;
preferably, the flexible fluorescence enhancing substrate has a thickness of 1 to 1000 μm.
9. An optical sensor comprising a flexible fluorescence-enhanced substrate according to any one of claims 1 to 7.
10. Use of the flexible fluorescence-enhanced substrate according to claim 8 or the optical sensor according to claim 9 for the rapid detection of low concentrations of fluorescent molecules.
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| CN102001619A (en) * | 2010-10-19 | 2011-04-06 | 东南大学 | Substrate for fluorescence labeling cell imaging and preparation method and application thereof |
| CN105067524A (en) * | 2015-08-12 | 2015-11-18 | 苏州大学 | Micro device for enhancing fluorescence of fluorescent molecules |
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| CN102001619A (en) * | 2010-10-19 | 2011-04-06 | 东南大学 | Substrate for fluorescence labeling cell imaging and preparation method and application thereof |
| CN105067524A (en) * | 2015-08-12 | 2015-11-18 | 苏州大学 | Micro device for enhancing fluorescence of fluorescent molecules |
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Application publication date: 20210212 |