WO2019100231A1 - 一种基于壳层隔绝纳米粒子的三维热点拉曼检测芯片 - Google Patents
一种基于壳层隔绝纳米粒子的三维热点拉曼检测芯片 Download PDFInfo
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- WO2019100231A1 WO2019100231A1 PCT/CN2017/112263 CN2017112263W WO2019100231A1 WO 2019100231 A1 WO2019100231 A1 WO 2019100231A1 CN 2017112263 W CN2017112263 W CN 2017112263W WO 2019100231 A1 WO2019100231 A1 WO 2019100231A1
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- raman spectroscopy
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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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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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
- G01N21/65—Raman scattering
Definitions
- the invention relates to a highly sensitive and highly stable three-dimensional hotspot Raman spectroscopy detection chip based on shell-insulated nanoparticles.
- Raman spectroscopy is a molecular spectroscopy technology with fingerprint recognition function, which can realize qualitative and quantitative analysis of samples without damage in milliseconds.
- ordinary Raman spectroscopy has low sensitivity and is not suitable for complex systems.
- Surface-enhanced Raman spectroscopy utilizes the electromagnetic field on the surface of gold and silver nanostructures to enhance the Raman signal of nearby molecules in millions of times, thereby enabling trace detection of substances (even to single-molecule levels).
- the portable Raman spectrometer has the characteristics of easy portability, simple operation, and real-time detection in the field. The test sample does not require special pre-processing and sample preparation work, but it is difficult to be applied to practical life due to sensitivity.
- SERS Surface-enhanced Raman spectroscopy
- Raman spectroscopy uses the electromagnetic field enhancement effect of gold-silver nano-materials to amplify the signal of the object to be measured by several million times, achieving high-sensitivity detection of trace targets by Raman spectroscopy. Its detection sensitivity can reach a single molecule level, which overcomes the problem of low sensitivity of Raman spectroscopy detection. Due to its extremely high surface sensitivity, surface-enhanced Raman spectroscopy has been widely used in surface chemistry, analytical chemistry, electrochemistry, biochemistry and materials science.
- the main limitation comes from the non-uniformity of nanoparticles and detection substrates, and the reproducibility is not high, which leads to it is usually only used for qualitative analysis, and it is difficult to perform quantitative analysis. Therefore, the key to the practical application of SERS is to obtain a highly enhanced, uniform and stable substrate.
- the preparation process of the chip is long, and the ion beam etching and the sputtering gold plating technology are very expensive and complicated, so the preparation cost of the chip is high, which brings about the widespread promotion of the portable surface enhanced Raman detection technology. difficult.
- an object of the present invention is to provide a three-dimensional hotspot Raman spectroscopy detection chip based on shell-insulating nanoparticles, which is suitable for manufacturing a uniform, uniform Raman spectrum enhancement substrate at low cost, and is used for Raman. Quantitative testing.
- the solution of the present invention is:
- a three-dimensional hot-spot Raman spectroscopy detection chip based on shell-insulating nanoparticles consists of two parts: one part is a hydrophobic substrate; the other part is a shell-separated nano-particle, and the shell-separated nano-particles form a three-dimensional hot-spot structure.
- the three-dimensional hot-spot Raman spectroscopy detection chip based on shell-insulated nanoparticles can be used for surface-enhanced Raman detection.
- the hydrophobic substrate is prepared by using a hydrophobic silicon wafer, a glass sheet, a polytetrafluoroethylene plastic substrate, a polytrifluoroethylene substrate, a polydimethylsiloxane film (PDMS), and a polymethacrylic acid.
- a methyl ester film (PMMA) or a ceramic substrate which is immersed in a mixed solution containing 0.5-3 wt.% of HF acid and 1-5 wt.% of NH 4 F to obtain a hydrophobic substrate.
- the shell-insulating nanoparticles are shell-insulated silver nanoparticles (for the synthesis method, see the invention patent CN201510287999.7, the publication number 104827029B, the announcement date 2017-07-11) or the shell layer isolating the gold nanoparticles.
- the three-dimensional hotspot structure is a multi-layer structure, and the two-dimensional hotspot structure of the planar structure has more hot spots and has higher Raman spectral signal enhancement capability.
- the three-layer hotspot Raman spectroscopy detection chip based on shell-insulated nanoparticles is used for liquid sample detection, and can be used for large-scale desktop Raman spectroscopy in laboratory, and can also be used for portable Raman spectroscopy, which greatly compensates for portable spectrometers compared with desktop computers. Inferiority in detection.
- the chip may be one detection point of one chip, or may be a larger chip having multiple detection sites.
- the detection chip of the invention can realize the enhanced detection effect on the Raman spectrum, and has a three-dimensional hotspot structure, has more hot spots, can more effectively increase the detection sensitivity, and has a good uniformity. Sex.
- the nanoparticle since the surface of the shell-insulating nanoparticle is covered with a thin layer of inert silica, the nanoparticle has good stability, resulting in a higher warranty period for the detection chip, which can be stored for a long time and more consistent. The characteristics of general goods.
- the Raman spectrum signal can be obtained by testing with a Raman spectrometer or even a portable Raman spectrometer.
- the method is very simple to apply, and requires the same liquid injection chromatography method, which greatly saves the detection time and has low requirements on the instrument, and can realize outdoor portable detection, real-time online monitoring of liquid and gaseous substances, and The inspectors do not need professional knowledge and training, and ordinary people can quickly master and carry out actual operations, which greatly saves time, material and labor costs.
- the invention can be applied in the fields of food safety testing, water environment testing, atmospheric environment testing, production process monitoring, daily cosmetics, etc., and can provide an effective rapid screening method for quality inspection departments, enterprises, testing institutions and the like. It has become a supplement to traditional laboratories, improving operational efficiency, reducing testing costs, and promising to become a standard means of detection.
- Figure 1 is a schematic view of the microstructure of the present invention
- FIG. 2 is a schematic view of silver nanoparticles of a silica shell layer encapsulating different shell thicknesses
- Figure 3 is a schematic diagram of a contact angle test of a hydrophobic substrate
- FIG. 4 is a schematic view of a shell-insulating nanoparticle droplet on a hydrophobic substrate
- Figure 5 is a schematic view showing the formation of a 'particle cake' on a hydrophobic substrate by shell-insulating nanoparticles
- Figure 6 is a particle stacking structure inside the chip
- Figure 7 is a graph showing the Raman spectral uniformity of the chip of the present invention.
- Figure 8 is a graph showing the standard operating curve for pyrithione using the chip of the present invention.
- FIG. 1 A schematic diagram of the low-light structure of the Raman spectroscopy detecting chip based on the shell-insulating nanoparticle of the present invention is shown in FIG. 1.
- the shell-insulating nanoparticle 2 On a hydrophobic substrate 1, the shell-insulating nanoparticle 2 is closely packed on the three-dimensional structure. Between the particles and the particles, a high-density hot-spot structure is formed. After the molecules of the analyte enter the hot spot, the Raman spectral signal is greatly enhanced, which increases the detection sensitivity.
- the shell layer isolates the synthesis of gold or silver nanoparticles.
- the nanoparticles used to enhance the Raman spectral signal are shell-isolated gold or silver nanoparticles, which are coated with a dense silica shell on the surface of 150 nm gold or silver nanoparticles.
- For the synthesis method see Patent No. CN201010579701. 7 and CN201510287999.7.
- the synthesized particles are shown in Figure 2.
- the water droplets drip on the substrate and did not spread out, forming a water droplet with a contact angle of 116°, which has a good Hydrophobic effect.
- the method is very simple to implement, the acid used can be reused, the cost is low, and large-scale environmental pollution is not caused.
- the detection chip of the invention can effectively solve the problems of the prior art.
- the invention synthesizes shell-insulating nanoparticles with adjustable size and shape and high uniformity, and then assembles them into uniform enhanced Raman nanochips with three-dimensional hot-spot structure, which makes the sensitivity, reproducibility and stability of Raman detection.
- the performance is greatly improved, and surface-enhanced Raman detection analysis is realized.
- the chip preparation process does not require complicated processes, and has many advantages such as low preparation cost, simple method, convenient use, good stability, good reproducibility, and reliable results.
- the chip is simple to fabricate and is used for surface-enhanced Raman spectroscopy. It has higher stability and sensitivity, and the chip is very simple to apply. It only needs to drop the liquid sample to be tested on the chip. It can be tested with a Raman spectrometer and can be quantitatively tested.
- the invention can have great commercial application prospects.
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Abstract
Description
Claims (5)
- 一种基于壳层隔绝纳米粒子的三维热点拉曼光谱检测芯片,其特征在于:由两部分组成:一部分是疏水基底;另一部分是壳层隔绝纳米粒子,壳层隔绝纳米粒子堆积构成三维热点结构。
- 根据权利要求1所述的一种基于壳层隔绝纳米粒子的三维热点拉曼光谱检测芯片,其特征在于:所述疏水基底的制备方法是:其材料可以为疏水的硅片、玻璃片、聚四氟乙烯塑料基底、聚三氟乙烯基底、聚二甲基硅氧烷膜PDMS、聚甲基丙烯酸甲酯薄膜PMMA或陶瓷基底,将上述材料浸入含有0.5-3wt.%HF酸和1-5wt.%NH4F的混合溶液中获得疏水基底。
- 根据权利要求1所述的一种基于壳层隔绝纳米粒子的三维热点拉曼光谱检测芯片,其特征在于:所述壳层隔绝纳米粒子为壳层隔绝银纳米粒子或壳层隔绝金纳米粒子。
- 根据权利要求1所述的一种基于壳层隔绝纳米粒子的三维热点拉曼光谱检测芯片,其特征在于:所述三维热点结构为多层结构。
- 根据权利要求1所述的一种基于壳层隔绝纳米粒子的三维热点拉曼光谱检测芯片,其特征在于:所述芯片是一个芯片有一个检测位点,或者是一个芯片具有多个检测位点。
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Cited By (4)
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CN113049569A (zh) * | 2021-03-22 | 2021-06-29 | 厦门赛纳斯科技有限公司 | 一种用于毒品快速检测的芯片制备方法及其应用 |
CN113624739A (zh) * | 2021-08-10 | 2021-11-09 | 中国人民解放军军事科学院军事医学研究院 | 用于生物样本中季铵盐肟类重活化剂快速检测的检测方法和试剂盒 |
CN113702348A (zh) * | 2021-04-30 | 2021-11-26 | 中国农业科学院茶叶研究所 | 一种具有三维热点表面增强拉曼基底及其制备方法 |
CN114149585A (zh) * | 2021-11-29 | 2022-03-08 | 北京工业大学 | 一种光致聚合超疏水表面的制备方法及其sers应用 |
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CN114149585A (zh) * | 2021-11-29 | 2022-03-08 | 北京工业大学 | 一种光致聚合超疏水表面的制备方法及其sers应用 |
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