CN103980888B - Zinc oxide fluorescence enhancing method based on layer-by-layer assembling technology - Google Patents
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002708 enhancing effect Effects 0.000 title claims description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- 239000004038 photonic crystal Substances 0.000 claims abstract description 24
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 14
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 53
- 239000006228 supernatant Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 10
- 239000007850 fluorescent dye Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- -1 polypropylene ammonium chloride Polymers 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 4
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明公开了一种基于层层组装技术的氧化锌荧光增强的方法，在利用氧化锌进行增强同时，在体系中引入一维光子晶体，以提高对荧光分子的增强效果。本发明方法简单有效，操作简便，且所需时间短。本发明具有良好的荧光增强效果，相较于单纯的一维光子晶体和氧化锌纳米颗粒，其荧光增强倍数更大。本发明成本低，相较于使用贵金属的荧光增强，本发明采用廉价的氧化锌材料，成本更低。
The invention discloses a zinc oxide fluorescence enhancement method based on layer-by-layer assembly technology. While using zinc oxide for enhancement, a one-dimensional photonic crystal is introduced into the system to improve the enhancement effect on fluorescent molecules. The method of the invention is simple and effective, and the operation is simple and convenient, and the required time is short. The invention has a good fluorescence enhancement effect, and compared with simple one-dimensional photonic crystals and zinc oxide nanoparticles, the fluorescence enhancement ratio is larger. The invention has low cost. Compared with the fluorescence enhancement using precious metals, the invention adopts cheap zinc oxide material, and the cost is lower.
Description
技术领域technical field
本发明属于荧光增强的技术领域，具体公开了一种基于层层组装技术的氧化锌荧光增强的方法。The invention belongs to the technical field of fluorescence enhancement, and specifically discloses a zinc oxide fluorescence enhancement method based on layer-by-layer assembly technology.
背景技术Background technique
自从1850年Herschel和Stokes发表了第一篇关于荧光的论文，荧光一直是科学家研究的热点方向之一。在G.weber的先驱性贡献基础上，荧光技术自从1950就被广泛的应用在生物学研究中。现在荧光光谱探测是在生物学、化学和物理学中常用的分析探测技术。荧光光谱法是利用荧光强度和波长之间进行定量、定性分析的方法。Since Herschel and Stokes published the first paper on fluorescence in 1850, fluorescence has been one of the hot research directions of scientists. Based on the pioneering contribution of G. Weber, fluorescence technology has been widely used in biological research since 1950. Fluorescence spectroscopy is now a common analytical detection technique in biology, chemistry, and physics. Fluorescence spectroscopy is a method of quantitative and qualitative analysis using fluorescence intensity and wavelength.
利用光子晶体的特殊光学性质实现对荧光分子的增强检测是近年来兴起的一个新的方法。当光子晶体的带隙与染料的激发或者发射光谱匹配时，涂在光子晶体表面的染料的光检测信号会极大增强。带隙若是与激发光谱匹配时，其增强作用主要取决于慢光子效应。若是与发射光谱匹配时，其增强作用主要是由于光子晶体的光禁阻效应可以使染料分子的发射信号定向收集加强。因为目前几乎所有的荧光探测都是依赖荧光物质光子的自发辐射，这种自发辐射没有特定的辐射取向，在空间沿各个方向随机分布。Using the special optical properties of photonic crystals to realize enhanced detection of fluorescent molecules is a new method emerging in recent years. When the band gap of the photonic crystal matches the excitation or emission spectrum of the dye, the photodetection signal of the dye coated on the surface of the photonic crystal can be greatly enhanced. If the band gap matches the excitation spectrum, its enhancement mainly depends on the slow photon effect. If it matches the emission spectrum, the enhancement is mainly due to the photon barrier effect of the photonic crystal can enhance the directional collection of the emission signal of the dye molecules. Because almost all current fluorescence detection relies on the spontaneous emission of photons of fluorescent substances, this spontaneous emission has no specific radiation orientation and is randomly distributed in all directions in space.
此外，现有的一些关于金属增强荧光的研究通常是将金属与荧光物质人为地隔开一定距离，并探讨距离对金属增强荧光效果的影响。常用的隔离方法有利用二氧化硅、DNA、大分子蛋白质以及多层膜作为中间的隔层。其中构建多层膜材料的常用方法是利用L-B-L(layer-by-layer)自组装方法或是LB(Langmuir-Blodgett)生长的薄膜。In addition, some existing studies on metal-enhanced fluorescence usually artificially separate metals and fluorescent substances by a certain distance, and explore the effect of distance on the effect of metal-enhanced fluorescence. Commonly used isolation methods include the use of silica, DNA, macromolecular proteins, and multilayer membranes as interlayers. The common method for constructing multilayer film materials is to use the L-B-L (layer-by-layer) self-assembly method or the thin film grown by LB (Langmuir-Blodgett).
层层自组装技术(Layer-by-Layerself-assembly)是近年来发展起来的制备有序薄膜的方法。它利用有机或无机阴阳离子的静电吸附特性，通过反离子体系的交替分子沉积形成薄膜。1991年D.Decher等人用层层吸附技术对构造有序薄膜进行了开创性研究。他们用两亲性有机阴阳离子(或者聚电解质)在离子化基片表面交替吸附制备多层膜。这种从二维到三维的技术转变，可以在金属或金属氧化物纳米颗粒的表面包裹特定组成、性质和厚度的多层聚合物材料，从而对荧光分子和金属之间的距离进行调控，达到荧光增强的效果。Layer-by-Layer self-assembly (Layer-by-Layerself-assembly) is a method developed in recent years to prepare ordered thin films. It utilizes the electrostatic adsorption properties of organic or inorganic anions and cations to form thin films by alternating molecular deposition of counter ion systems. In 1991, D. Decher et al. used layer-by-layer adsorption technology to conduct pioneering research on the structure of ordered films. They used amphiphilic organic anions and cations (or polyelectrolytes) to alternately adsorb on the surface of ionized substrates to prepare multilayer films. This transformation from two-dimensional to three-dimensional technology can wrap multilayer polymer materials with specific composition, properties and thickness on the surface of metal or metal oxide nanoparticles, so as to regulate the distance between fluorescent molecules and metals to achieve The effect of fluorescence enhancement.
常用的金属物质主要是价格比较昂贵的金属银和金，氧化锌材料是一种廉价的材料，最近多有利用氧化锌材料进行荧光增强的研究被报道。但是将这上述两种方法进行有效结合，即在利用氧化锌进行增强同时，在体系中引入一维光子晶体，以提高对荧光分子的增强效果，到目前尚未有人研究。Commonly used metal substances are mainly silver and gold, which are relatively expensive. Zinc oxide is a cheap material. Recently, many studies on the use of zinc oxide for fluorescence enhancement have been reported. However, the effective combination of the above two methods, that is, the use of zinc oxide for enhancement and the introduction of one-dimensional photonic crystals in the system to improve the enhancement effect on fluorescent molecules, has not been studied so far.
发明内容Contents of the invention
技术问题：本发明的目的在于提供一种基于层层组装技术的氧化锌荧光增强的方法。Technical problem: The purpose of the present invention is to provide a method for enhancing the fluorescence of zinc oxide based on layer-by-layer assembly technology.
技术方案：本发明提供了一种基于层层组装技术的氧化锌荧光增强的方法，具体方法如下：Technical solution: The present invention provides a method for enhancing the fluorescence of zinc oxide based on layer-by-layer assembly technology, the specific method is as follows:
1)以水为溶剂分别配制聚苯乙烯磺酸钠PSS和聚丙烯氯化铵PAH溶液，PSS和PAH浓度为0.5mg·mL-1～2mg·mL-1；1) Prepare polystyrene sulfonate sodium PSS and polypropylene ammonium chloride PAH solutions respectively with water as solvent, the concentrations of PSS and PAH are 0.5 mg·mL −1 ~ 2 mg·mL −1 ;
2)在氧化锌纳米颗粒中加入PSS溶液，振荡后以8000r·min-1～12000r·min-1的转速离心15min至25min，弃去上清，得到表面组装有PSS的氧化锌纳米颗粒；2) Add PSS solution to the zinc oxide nanoparticles, shake and centrifuge at a speed of 8000r·min -1 ~ 12000r·min -1 for 15min to 25min, discard the supernatant, and obtain zinc oxide nanoparticles with PSS assembled on the surface;
3)将表面组装有PSS的氧化锌纳米颗粒用纯水洗涤多次，每次洗涤后以8000r·min-1～12000r·min-1的转速离心15min至25min，弃去上清，得到已清洗的表面组装有PSS的氧化锌纳米颗粒；3) The zinc oxide nanoparticles with PSS assembled on the surface were washed with pure water for several times, centrifuged at a speed of 8000r·min -1 ~ 12000r·min -1 for 15min to 25min after each washing, and the supernatant was discarded to obtain the washed ZnO nanoparticles with PSS assembled on the surface;
4)在已清洗的表面组装有PSS的氧化锌纳米颗粒中加入PAH溶液，振荡后以8000r·min-1～12000r·min-1的转速离心15min至25min，弃去上清，得到表面组装有PSS/PAH的氧化锌纳米颗粒；4) Add PAH solution to the cleaned surface-mounted zinc oxide nanoparticles with PSS, shake and centrifuge at a speed of 8000r·min -1 ~ 12000r·min -1 for 15min to 25min, discard the supernatant, and obtain surface-assembled Zinc oxide nanoparticles of PSS/PAH;
5)将表面组装有PSS/PAH的氧化锌纳米颗粒用纯水洗涤多次，每次洗涤后以8000r·min-1～12000r·min-1的转速离心15min至25min，弃去上清，得到已清洗的表面组装有PSS/PAH的氧化锌纳米颗粒；5) The zinc oxide nanoparticles with PSS/PAH assembled on the surface were washed with pure water for several times, centrifuged at a speed of 8000r·min -1 ~ 12000r·min -1 for 15min to 25min after each washing, and the supernatant was discarded to obtain ZnO nanoparticles assembled with PSS/PAH on the cleaned surface;
6)重复第2～5步多次从而得到表面组装有n层PSS/PAH的氧化锌纳米颗粒；6) repeat steps 2 to 5 multiple times to obtain zinc oxide nanoparticles with n layers of PSS/PAH assembled on the surface;
7)在一维光子晶体上滴加表面组装有n层PSS/PAH的纳米氧化锌溶液，以500r·min-1～1500r·min-1的转速旋转30s～60s；7) On the one-dimensional photonic crystal, drop the nano-zinc oxide solution with n layers of PSS/PAH assembled on the surface, and rotate at a speed of 500r·min -1 ~ 1500r·min -1 for 30s ~ 60s;
8)将步骤7)中旋涂有纳米氧化锌的一维光子晶体经过亲水处理后，再在其上沉积荧光染料；8) After the one-dimensional photonic crystal spin-coated with nano-zinc oxide in step 7) undergoes a hydrophilic treatment, a fluorescent dye is deposited thereon;
其中，in,
所述步骤6)中n＝2-8。n=2-8 in the step 6).
所述步骤7)中一维光子晶体表面经过亲水处理。In step 7), the surface of the one-dimensional photonic crystal is treated with hydrophilicity.
所述步骤7)和步骤8)中的一维光子晶体的光子禁带位置和荧光染料的激发或发射波长相匹配。The photonic band gap position of the one-dimensional photonic crystal in the step 7) and the step 8) matches the excitation or emission wavelength of the fluorescent dye.
所述步骤7)和步骤8)中的一维光子晶体的光子禁带位置和荧光染料的激发或发射波长在400nm～750nm之间。The photonic band gap position of the one-dimensional photonic crystal in the step 7) and the step 8) and the excitation or emission wavelength of the fluorescent dye are between 400nm and 750nm.
所述层层组装技术为基于正负电荷静电作用的自组装技术。所述基于层层组装技术的氧化锌纳米颗粒是在氧化锌纳米颗粒上交替组装有带负电荷的PSS和带正电荷的PAH。The layer-by-layer assembly technology is a self-assembly technology based on the electrostatic interaction of positive and negative charges. The zinc oxide nanoparticles based on layer-by-layer assembly technology are alternately assembled with negatively charged PSS and positively charged PAH on the zinc oxide nanoparticles.
有益效果：本发明具有以下优点：1.方法简单有效，操作简便，且所需时间短。2.本发明具有良好的荧光增强效果，相较于单纯的一维光子晶体和氧化锌纳米颗粒，其荧光增强倍数更大。3.成本低，相较于使用贵金属的荧光增强，本发明采用廉价的氧化锌材料，成本更低。Beneficial effects: the present invention has the following advantages: 1. The method is simple and effective, the operation is simple and the required time is short. 2. The present invention has a good fluorescence enhancement effect, and its fluorescence enhancement ratio is larger than that of simple one-dimensional photonic crystals and zinc oxide nanoparticles. 3. Low cost. Compared with the fluorescence enhancement using precious metals, the present invention uses cheap zinc oxide material, and the cost is lower.
附图说明Description of drawings
图1是实施例1的荧光增强谱图。Fig. 1 is the fluorescence enhancement spectrogram of embodiment 1.
图2是实施例2的荧光增强谱图。Fig. 2 is the fluorescence enhancement spectrogram of embodiment 2.
图3是实施例3的荧光增强谱图。Fig. 3 is the fluorescence enhancement spectrogram of embodiment 3.
具体实施方式Detailed ways
实施例1：Example 1:
一种基于层层组装技术的氧化锌荧光增强的方法，具体方法如下：A method for enhancing the fluorescence of zinc oxide based on layer-by-layer assembly technology, the specific method is as follows:
1)以水为溶剂分别配制聚苯乙烯磺酸钠(PSS)和聚丙烯氯化铵(PAH)溶液，PSS和PAH浓度为1mg·mL-1；1) Prepare polystyrene sulfonate sodium (PSS) and polypropylene ammonium chloride (PAH) solutions with water as solvent respectively, the concentrations of PSS and PAH are 1 mg·mL −1 ;
2)在氧化锌纳米颗粒中加入PSS溶液，振荡3min后以12000r·min-1的转速离心15min，弃去上清；2) Add PSS solution to the zinc oxide nanoparticles, shake for 3 minutes, centrifuge at a speed of 12000r min -1 for 15 minutes, and discard the supernatant;
3)将表面组装有PSS的氧化锌纳米颗粒用纯水洗涤三次，每次洗涤后以12000r·min-1的转速离心20min，弃去上清；3) Wash the zinc oxide nanoparticles with PSS assembled on the surface three times with pure water, centrifuge at a speed of 12000r min -1 for 20min after each washing, and discard the supernatant;
4)在已清洗的表面组装有PSS的氧化锌纳米颗粒中加入PAH溶液，振荡3min后以12000r·min-1的转速离心15min，弃去上清；4) Add PAH solution to the cleaned zinc oxide nanoparticles assembled with PSS on the surface, shake for 3 minutes, centrifuge at a speed of 12000r min -1 for 15 minutes, and discard the supernatant;
5)将表面组装有PSS/PAH的氧化锌纳米颗粒用纯水洗涤三次，每次洗涤后以12000r·min-1的转速离心20min，弃去上清；5) Wash the zinc oxide nanoparticles with PSS/PAH assembled on the surface three times with pure water, centrifuge at a speed of 12000r min -1 for 20min after each washing, and discard the supernatant;
6)重复第2～5步3次，从而得到表面具有4层PSS/PAH的氧化锌纳米颗粒。6) Repeat steps 2 to 5 for 3 times to obtain zinc oxide nanoparticles with 4 layers of PSS/PAH on the surface.
7)在经过亲水处理的禁带位置在599nm的一维光子晶体上滴加(PSS/PAH)4的纳米氧化锌溶液，以1000r·min-1的转速旋转60s；7) Add (PSS/PAH) 4 nanometer zinc oxide solution dropwise on the 599nm one-dimensional photonic crystal at the forbidden band position after hydrophilic treatment, and rotate at a speed of 1000r min -1 for 60s;
8)将步骤7)中旋涂有纳米氧化锌的一维光子晶体经过亲水处理后，再在其上沉积1mg·ml-1的罗丹明B溶液。8) After the one-dimensional photonic crystal spin-coated with nano-zinc oxide in step 7) is subjected to hydrophilic treatment, 1 mg·ml -1 of rhodamine B solution is deposited thereon.
荧光增强谱图见图1。The fluorescence enhancement spectrum is shown in Figure 1.
实施例2：Example 2:
一种基于层层组装技术的氧化锌荧光增强的方法，具体方法如下：A method for enhancing the fluorescence of zinc oxide based on layer-by-layer assembly technology, the specific method is as follows:
1)以水为溶剂分别配制聚苯乙烯磺酸钠(PSS)和聚丙烯氯化铵(PAH)溶液，PSS和PAH浓度为0.5mg·mL-1；1) Prepare polystyrene sulfonate sodium (PSS) and polypropylene ammonium chloride (PAH) solutions with water as solvent respectively, the concentrations of PSS and PAH are 0.5 mg·mL −1 ;
2)在氧化锌纳米颗粒中加入PSS溶液，振荡3min后以8000r·min-1的转速离心25min，弃去上清；2) Add PSS solution to the zinc oxide nanoparticles, shake for 3 minutes, centrifuge at a speed of 8000r·min −1 for 25 minutes, and discard the supernatant;
3)将表面组装有PSS的氧化锌纳米颗粒用纯水洗涤三次，每次洗涤后以8000r·min-1的转速离心25min，弃去上清；3) Wash the zinc oxide nanoparticles with PSS assembled on the surface three times with pure water, centrifuge at a speed of 8000r min -1 for 25min after each washing, and discard the supernatant;
4)在已清洗的表面组装有PSS的氧化锌纳米颗粒中加入PAH溶液，振荡3min后以8000r·min-1的转速离心25min，弃去上清；4) Add PAH solution to the zinc oxide nanoparticles with PSS assembled on the surface that has been cleaned, shake for 3 minutes, centrifuge at a speed of 8000r min for 25 minutes, and discard the supernatant;
5)将表面组装有PSS/PAH的氧化锌纳米颗粒用纯水洗涤三次，每次洗涤后以8000r·min-1的转速离心25min，弃去上清；5) Wash the zinc oxide nanoparticles with PSS/PAH assembled on the surface three times with pure water, centrifuge at a speed of 8000r min -1 for 25min after each washing, and discard the supernatant;
6)重复第2～5步7次，从而得到表面具有7层PSS/PAH的氧化锌纳米颗粒。6) Repeat steps 2-5 7 times to obtain zinc oxide nanoparticles with 7 layers of PSS/PAH on the surface.
7)在经过亲水处理的禁带位置在599nm的一维光子晶体上滴加(PSS/PAH)8的纳米氧化锌溶液，以500r·min-1的转速旋转60s；7) Add (PSS/PAH) 8 nanometer zinc oxide solution dropwise on the 599nm one-dimensional photonic crystal at the forbidden band position after hydrophilic treatment, and rotate at a speed of 500r min −1 for 60s;
8)将步骤7)中旋涂有纳米氧化锌的一维光子晶体经过亲水处理后，再在其上沉积1mg·ml-1的罗丹明B溶液。8) After the one-dimensional photonic crystal spin-coated with nano-zinc oxide in step 7) is subjected to hydrophilic treatment, 1 mg·ml -1 of rhodamine B solution is deposited thereon.
荧光增强谱图见图2。The fluorescence enhancement spectrum is shown in Figure 2.
实施例3：Example 3:
一种基于层层组装技术的氧化锌荧光增强的方法，具体方法如下：A method for enhancing the fluorescence of zinc oxide based on layer-by-layer assembly technology, the specific method is as follows:
1)以水为溶剂分别配制聚苯乙烯磺酸钠(PSS)和聚丙烯氯化铵(PAH)溶液，PSS和PAH浓度为2mg·mL-1；1) Prepare polystyrene sodium sulfonate (PSS) and polypropylene ammonium chloride (PAH) solutions with water as solvent respectively, the concentrations of PSS and PAH are 2 mg·mL −1 ;
2)在氧化锌纳米颗粒中加入PSS溶液，振荡3min后以10000r·min-1的转速离心20min，弃去上清；2) Add PSS solution to the zinc oxide nanoparticles, shake for 3 minutes, centrifuge at a speed of 10000r min -1 for 20 minutes, and discard the supernatant;
3)将表面组装有PSS的氧化锌纳米颗粒用纯水洗涤三次，每次洗涤后以10000r·min-1的转速离心20min，弃去上清；3) Wash the zinc oxide nanoparticles with PSS assembled on the surface three times with pure water, centrifuge at a speed of 10000r min -1 for 20min after each washing, and discard the supernatant;
4)在已清洗的表面组装有PSS的氧化锌纳米颗粒中加入PAH溶液，振荡3min后以10000r·min-1的转速离心20min，弃去上清；4) Add PAH solution to the cleaned zinc oxide nanoparticles assembled with PSS on the surface, shake for 3 minutes, centrifuge at a speed of 10000r min -1 for 20 minutes, and discard the supernatant;
5)将表面组装有PSS/PAH的氧化锌纳米颗粒用纯水洗涤三次，每次洗涤后以10000r·min-1的转速离心20min，弃去上清；5) Wash the zinc oxide nanoparticles with PSS/PAH assembled on the surface three times with pure water, centrifuge at a speed of 10000r min -1 for 20min after each washing, and discard the supernatant;
6)重复第2～5步1次，从而得到表面具有2层PSS/PAH的氧化锌纳米颗粒。6) Repeat steps 2-5 once to obtain zinc oxide nanoparticles with 2 layers of PSS/PAH on the surface.
7)在经过亲水处理的禁带位置在599nm的一维光子晶体上滴加(PSS/PAH)2的纳米氧化锌溶液，以1000r·min-1的转速旋转60s；7) Add (PSS/PAH) 2 nanometer zinc oxide solution dropwise on the 599nm one-dimensional photonic crystal at the forbidden band position after hydrophilic treatment, and rotate at a speed of 1000r min -1 for 60s;
8)将步骤7)中旋涂有纳米氧化锌的一维光子晶体经过亲水处理后，再在其上沉积1mg·ml-1的四磺基苯基卟啉溶液。8) After the one-dimensional photonic crystal spin-coated with nano-zinc oxide in step 7) is subjected to hydrophilic treatment, 1 mg·ml −1 tetrasulfophenylporphyrin solution is deposited thereon.
荧光增强谱图见图3。The fluorescence enhancement spectrum is shown in Figure 3.
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be It is regarded as the protection scope of the present invention.
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