CN111879753B - Noble metal nano cone SERS substrate for detecting novel coronaviruses and preparation method - Google Patents
Noble metal nano cone SERS substrate for detecting novel coronaviruses and preparation method Download PDFInfo
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- CN111879753B CN111879753B CN202010778334.7A CN202010778334A CN111879753B CN 111879753 B CN111879753 B CN 111879753B CN 202010778334 A CN202010778334 A CN 202010778334A CN 111879753 B CN111879753 B CN 111879753B
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Abstract
The invention belongs to the technical field of laser Raman spectroscopy and virus detection, and particularly relates to a noble metal nano-cone SERS substrate for detecting novel coronaviruses and a preparation method thereof. The SERS substrate comprises a base, a nano cone array positioned on the base, and a noble metal film coated on the surfaces of the nano cones and the base where the nano cones are positioned, wherein the nano cones forming the nano cone array are radial from the center of the substrate to the periphery, the included angles between the adjacent nano cones are gradually changed, the effective capturing of coronaviruses with the size of 60-140nm can be realized, the compatibility is stronger, and the capturing efficiency can be greatly improved when the viruses contact the substrate and slide on the surface. The preparation method of the invention comprises the following steps: the preparation method is simple, and the prepared noble metal nano cone has three-dimensionally distributed SERS hot spots and high SERS sensitivity.
Description
Technical Field
The invention relates to the technical field of laser Raman spectroscopy and virus detection, in particular to a noble metal nano-cone SERS substrate for detecting novel coronaviruses and a preparation method thereof.
Background
2019 novel coronavirus (2019-nCOV) can be transmitted through respiratory tract droplets, contact, aerosols, etc., and after infection, symptoms of a person are mainly fever, cough, shortness of breath and dyspnea, and serious people can lead to renal failure and even death. Because of the lack of specific drugs, the physical isolation of suspected and diagnosed cases is an effective way to prevent further exacerbation of epidemic situation. Therefore, it is important to rapidly screen patients who have been infected with new pneumonia from the population. At present, the common screening and detection technology is mainly a reverse transcription-polymerase chain reaction (RT-PCR) method, so that the diagnosis process takes a long time (about 3 hours for single detection), and the detection kit has a high false negative rate due to poor sensitivity. Therefore, in order to effectively block the transmission of the novel coronavirus, development of a novel on-site rapid detection technology is highly demanded.
The detection technology based on the Surface Enhanced Raman Scattering (SERS) effect has the advantages of simple operation, short detection time, low detection limit, fingerprint identification and the like, and has the ultrasensitive detection capability of single molecules. Meanwhile, with the gradual maturity of portable laser raman spectroscopy technology, SERS has evolved into a rapid, trace, non-destructive, in-situ field detection technique. At present, a great deal of research has shown that SERS can analyze the base sequence, composition and interaction between proteins or ligands of nucleic acids with DNA, RNA, proteins and other biomolecules as detection targets, and can recognize and detect different RNA or DNA virus cells with high performance. For example, wang Lianhui (Talanta, 205,2019) from the university of south Beijing post gave silver nanorod arrays on glass substrates by oblique angle deposition, enabling SERS detection of H7 and N9 subtype influenza viruses. However, in order to achieve the Capture of viruses, it is necessary to design an auxiliary reagent containing a substitution chain, a Capture chain and a Probe chain based on the viral gene sequence, and it is necessary to co-culture the detection sample with the auxiliary reagent at a certain temperature, and this "bio-linked" capturing method is cumbersome and time-consuming in steps. Meanwhile, the traditional noble metal cone SERS substrate has a determined nano cone distance and a determined nano cone gap, can only capture viruses with smaller size distribution, has lower capture efficiency, and causes weaker characteristic Raman signal intensity required by detection.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a noble metal nano-cone SERS substrate for detecting novel coronaviruses.
Another technical problem to be solved by the invention is to overcome the defects in the prior art and provide a preparation method of a noble metal nano-cone SERS substrate for detecting novel coronaviruses.
In order to solve the technical problem of the invention, the adopted technical scheme is that the noble metal nano-cone SERS substrate for detecting the novel coronavirus comprises a substrate, a nano-cone array positioned on the substrate and a noble metal film coated on the surfaces of the nano-cone array and the substrate where the nano-cone array is positioned, wherein the thickness of the noble metal film is 10-50nm, and the noble metal film is made of noble metal with Raman activity; the nanometer cone array comprises a plurality of nanometer cone rings with different diameters, the nanometer cone rings are formed by circumferentially surrounding a plurality of nanometer cones with the nanometer cones perpendicular to a substrate as the center, an included angle alpha formed between the central axis of the nanometer cones and the substrate is 30-90 degrees, the included angle alpha is gradually reduced from the inner ring nanometer cone ring to the outer ring nanometer cone ring, the height of the nanometer cones is 200-300nm, the diameter of the root is 50-300nm, the diameter of the tip of the cone is 20-50nm, the tip angle of the tip of the cone is 10-60 degrees, and the distance between adjacent nanometer cones is 80-150nm.
As a further technical scheme of the noble metal nano-cone SERS substrate for detecting novel coronaviruses, the following is adopted:
preferably, the substrate and the nanopyramid are the same material and are flexible materials that can be bent.
Further preferably, the substrate and the nano-cone are made of one of polyimide and polyethylene terephthalate.
Preferably, the noble metal thin film is formed by stacking noble metal nano particles with the size of 10-30 nm.
Preferably, the noble metal film is made of one of gold, silver and copper.
Preferably, in the nano cone array, the intervals between adjacent nano cones are not completely equal or completely unequal.
In order to solve another technical problem of the invention, the adopted technical scheme is that the preparation method of the noble metal nano-cone SERS substrate for detecting the novel coronavirus comprises the following steps:
s1, covering a single-layer polystyrene microsphere on the surface of a substrate by a self-assembly method, wherein the diameter of the polystyrene microsphere is 80-150nm;
s2, smoothly bending the periphery of the substrate for 5-30 degrees towards the center of the surface where the polystyrene microspheres are located, and then placing the bent substrate in a reactive ion etching device;
s3, performing reactive ion etching on the substrate surface where the polystyrene microspheres are positioned under the conditions of 10-50sccm of gas flow rate, 5-20 Pa of cavity pressure and 100-250 watts of etching power by using sulfur hexafluoride as reaction gas until nano cones are formed on the surface of the substrate and the polystyrene microspheres are thoroughly removed;
and S4, keeping the bending state of the substrate, depositing noble metal nano particles on the surface of the substrate where the nano cone is positioned by a magnetron sputtering method to form a noble metal film, and then flattening the bent substrate to obtain the noble metal nano cone SERS substrate for detecting the novel coronavirus.
The preparation method of the noble metal nano cone SERS substrate for detecting the novel coronavirus is further characterized by comprising the following steps:
preferably, the diameters of the polystyrene microspheres in step S1 are not identical or are not identical.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention discloses a noble metal nano-cone SERS substrate for detecting novel coronaviruses, wherein the surface of a SERS detection chip is provided with rough conical protrusions, the nano-cone is provided with gradual radial directions from the middle to the periphery, and an included angle formed between the central axis of the nano-cone and a substrate is gradually enlarged. When used for detecting novel coronaviruses by SERS technology, compared with the common nano cone with fixed included angle, the method has the remarkable advantages of two points: firstly, the gap and the angle between the substrate nanocones have the characteristic of gradual change, can effectively capture the novel coronavirus with the size of 60-140nm, and have stronger compatibility; secondly, the orientation of the nano cone (namely, the opening direction of the cone gap) is radial from the center of the substrate to the periphery, and when viruses contact with the substrate and slide on the surface, the capturing efficiency can be greatly improved. The efficient and firm capture of viruses on the surface of a substrate is a key for obtaining stable Raman detection signals. Particularly, when virus detection is performed through expiration, false negative caused by too small amount of captured viruses can be effectively avoided, and compared with a particle membrane or a conventional nano cone array, the method has higher capture efficiency and detection accuracy for novel coronaviruses.
2) The method comprises the steps of covering a single-layer polystyrene microsphere template on a substrate, bending the substrate towards the center of the surface of the polystyrene microsphere template, performing reactive ion etching on the surface of the polystyrene microsphere in the substrate, performing reactive etching on the substrate and the microsphere template by ionized fluorine free radicals, completely removing the microspheres on the surface layer after the microspheres play a role of mask protection and the like, forming a noble metal film by depositing noble metal nano particles on the surface of the substrate where the conical protrusions are located by a magnetron sputtering method, and then flattening the bent substrate to obtain the noble metal nano cone SERS substrate with nano cones with different opening angles and directions. The preparation method is simple, the prepared noble metal nano cone can be used as an active substrate for surface enhanced Raman scattering, has three-dimensional distributed SERS hot spots, and has high SERS sensitivity.
Drawings
FIG. 1 is a flow chart of the preparation of a noble metal nanopyramid SERS substrate of the present invention;
fig. 2 is a graph of raman spectral characterization of noble metal nanopyramid SERS substrates prepared in comparative example 1 and example 1.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, wherein all other examples, which are obtained by a person skilled in the art without making any inventive effort, are included in the scope of the present invention.
Comparative example 1
S1, covering a single-layer polystyrene microsphere on the surface of a substrate by a self-assembly method, wherein the diameter of the polystyrene microsphere is 100nm, and the diameters of the polystyrene microspheres in the same batch are highly consistent and the standard deviation of the particle size is less than 5%;
s2, placing the substrate covered with the polystyrene microspheres in a reactive ion etching device;
s3, performing reactive ion etching on the substrate surface where the polystyrene microspheres are positioned under the conditions of gas flow rate of 30sccm, cavity pressure of 15 Pa and etching power of 150 watts by using sulfur hexafluoride as a reaction gas until nano cones are formed on the surface of the substrate and the polystyrene microspheres are thoroughly removed;
and S4, depositing noble metal nano particles on the surface of the substrate where the nano cone is positioned by a magnetron sputtering method to form a noble metal film, thus obtaining the common noble metal nano cone SERS substrate.
Example 1
S1, covering a single-layer polystyrene microsphere on the surface of a substrate by a self-assembly method, wherein the diameter of the polystyrene microsphere is 100nm, and the diameters of the polystyrene microspheres in the same batch are highly consistent and the standard deviation of the particle size is less than 5%;
s2, smoothly bending the periphery of the substrate for 20 degrees towards the center of the surface where the polystyrene microspheres are located, and then placing the bent substrate in a reactive ion etching device;
s3, performing reactive ion etching on the substrate surface where the polystyrene microspheres are positioned under the conditions of gas flow rate of 30sccm, cavity pressure of 15 Pa and etching power of 150 watts by using sulfur hexafluoride as a reaction gas until nano cones are formed on the surface of the substrate and the polystyrene microspheres are thoroughly removed;
and S4, keeping the bending state of the substrate, depositing noble metal nano particles on the surface of the substrate where the nano cone is positioned by a magnetron sputtering method to form a noble metal film, and then flattening the bent substrate to obtain the noble metal nano cone SERS substrate for detecting the novel coronavirus.
The 10 microgram of polystyrene colloid microsphere with 100nm diameter is blown out at the gas flow rate of 100sccm, meanwhile, the two noble metal nano cone SERS substrates prepared in comparative example 1 and example 1 are adopted for capturing and collecting, and after washing for 10 seconds, raman spectrum characterization is carried out, as shown in the following figure 2, a curve I, II is respectively a raman spectrum obtained by a common noble metal nano cone SERS substrate and a noble metal nano cone SERS substrate for detecting novel coronaviruses, and as can be seen from the figure 2, the raman spectrum obtained by the noble metal nano cone SERS substrate with different opening directions and opening sizes prepared by the preparation method provided by the invention has stronger characteristic peaks, which shows that the raman spectrum has higher capturing efficiency.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (3)
1. The noble metal nano-cone SERS substrate for detecting the novel coronavirus is characterized by comprising a base, a nano-cone array positioned on the base and a noble metal film coated on the surfaces of the nano-cone array and the base where the nano-cone array is positioned, wherein the thickness of the noble metal film is 10-50nm, and the noble metal film is made of noble metal with Raman activity; the nanometer cone array comprises a plurality of nanometer cone rings with different diameters, the nanometer cone rings are formed by circumferentially arranging a plurality of nanometer cones by taking the nanometer cone perpendicular to a substrate as a center, an included angle alpha formed between the central axis of the nanometer cone and the substrate is 30-90 degrees, the included angle alpha is gradually reduced from an inner ring nanometer cone ring to an outer ring nanometer cone ring, the height of the nanometer cone is 200-300nm, the diameter of the root is 50-300nm, the diameter of the tip of the cone is 20-50nm, the tip angle of the tip of the cone is 10-60 degrees, and the interval between adjacent nanometer cones is 80-150nm;
the substrate and the nano cone are made of the same material and are flexible materials which can be bent; the noble metal thin film is formed by stacking noble metal nano particles with the size of 10-30 nm; the spacing between adjacent nano cones is not completely equal or completely unequal;
the preparation method comprises the following steps:
s1, covering a single-layer polystyrene microsphere on the surface of a substrate by a self-assembly method, wherein the diameter of the polystyrene microsphere is 80-150nm; the diameters of the polystyrene microspheres are not identical or are not identical;
s2, smoothly bending the periphery of the substrate for 5-30 degrees towards the center of the surface where the polystyrene microspheres are located, and then placing the bent substrate in a reactive ion etching device;
s3, performing reactive ion etching on the substrate surface where the polystyrene microspheres are positioned under the conditions of 10-50sccm of gas flow rate, 5-20 Pa of cavity pressure and 100-250 watts of etching power by using sulfur hexafluoride as reaction gas until nano cones are formed on the surface of the substrate and the polystyrene microspheres are thoroughly removed;
and S4, keeping the bending state of the substrate, depositing noble metal nano particles on the surface of the substrate where the nano cone is positioned by a magnetron sputtering method to form a noble metal film, and then flattening the bent substrate to obtain the noble metal nano cone SERS substrate for detecting the novel coronavirus.
2. The noble metal nanopyramid SERS substrate for detecting a novel coronavirus according to claim 1, wherein the base and nanopyramid material is one of polyimide, polyethylene terephthalate.
3. The noble metal nanopyramid SERS substrate for detecting a novel coronavirus according to claim 1, wherein the noble metal thin film is one of gold, silver, copper.
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| CN113046708B (en) * | 2021-02-09 | 2023-11-14 | 杭州电子科技大学 | Preparation method and application of magnetic field regulation nano array structure |
| CN113252640B (en) * | 2021-06-03 | 2021-12-14 | 季华实验室 | Rapid virus screening and detecting method |
| CN113702352A (en) * | 2021-08-25 | 2021-11-26 | 山东智微检测科技有限公司 | SERS detection chip suitable for gas-phase erosive toxicant and preparation method thereof |
| CN114199854B (en) * | 2021-12-15 | 2024-01-12 | 曲阜师范大学 | Preparation method of SERS substrate constructed by flexible transparent cone ordered array |
| CN115684580B (en) * | 2022-09-27 | 2023-08-25 | 郑州大学 | Microsphere array chip based on magnetic control, detection assembly, detection system and method |
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| CN103398997A (en) * | 2013-08-07 | 2013-11-20 | 苏州扬清芯片科技有限公司 | Rapid preparation method of nano-grade conical SERS active substrate |
| CN111455319A (en) * | 2020-05-15 | 2020-07-28 | 中国科学院合肥物质科学研究院 | Gold-silver nanocone array with body-enhanced Raman scattering effect and preparation method and application thereof |
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| US7738096B2 (en) * | 2004-10-21 | 2010-06-15 | University Of Georgia Research Foundation, Inc. | Surface enhanced Raman spectroscopy (SERS) systems, substrates, fabrication thereof, and methods of use thereof |
| US20110037976A1 (en) * | 2009-08-17 | 2011-02-17 | Yiping Zhao | Flexible surface enhanced raman spectroscopy (sers) substrates, methods of making, and methods of use |
| DK2491372T3 (en) * | 2009-10-23 | 2021-10-18 | Univ Danmarks Tekniske | SURFACE IMPROVED RAMAN SPREADING SUBSTRATE CONSUMABLES FOR RAMAN SPECTROSCOPY |
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| CN103398997A (en) * | 2013-08-07 | 2013-11-20 | 苏州扬清芯片科技有限公司 | Rapid preparation method of nano-grade conical SERS active substrate |
| CN111455319A (en) * | 2020-05-15 | 2020-07-28 | 中国科学院合肥物质科学研究院 | Gold-silver nanocone array with body-enhanced Raman scattering effect and preparation method and application thereof |
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